JP2004504925A - Long-lasting coatings for modifying hard surfaces and methods of application - Google Patents

Abstract

Disclosed are materials, coating compositions, methods and articles of manufacture for coatings that include or employ nanoparticle systems that confer the benefit of modifying the surface for all types of inanimate hard surfaces. In some embodiments, dispersing the nanoparticles in a suitable carrier medium allows for creating coating compositions, methods, and articles of manufacture that create versatile benefits on the modified hard surface. Such surface modifications can produce long lasting or semi-permanent versatile benefits, including improved surfaces compared to hard surfaces that have not been modified with such nanoparticle systems, such as: Properties: Wet and sheet forming, quick drying, uniform drying, stain removal, self-cleaning, anti-speckle, anti-stain, more clean appearance, enhanced gloss, enhanced color, repair of small surface defects, smoothness Anti-fog, reduced surface friction, release of actives, and at least one of transparency. Increase the durability of hard surface coatings using aggressive curing of the coating composition on the hard surface, including, but not limited to, radially heating the air around the hard surface with the coating thereon be able to.

Description

【００７２】
１−プロパンアミニウム、３−［（８−クロロ−２，２，３，３，４，４，５，５，６，６，７，７，８，８−テトラデカフルオロ−１−オキソオクチル）アミノ］−Ｎ，Ｎ，Ｎ−トリメチル−、硫酸メチル（９ＣＩ）が挙げられる。
【００７３】
【化２】

【００７４】
シリコーンを基にした界面活性剤には：１−プロパンアミニウム、Ｎ，Ｎ，Ｎ，−トリメチル−３−［１，３，３、３−テトラメチル−１−［（トリメチルシリル）オキシ］ジシロキサニル］−、ブロミド（９ＣＩ）が挙げられる。
【００７５】
【化３】

【００７６】
脂肪族双極性界面活性剤には：１−ドデカアミニウム、Ｎ−（２−ヒドロキシ−３−スルホプロピル）−Ｎ，Ｎ−ジメチル−、内部塩（９ＣＩ）が挙げられる。
【００７７】
【化４】

【００７８】
ヘキサデシルジメチルアミン酸化物のような脂肪族アミン酸化物類も包含される。脂肪族アニオン界面活性剤には：オレイル硫酸ナトリウム；オレイン酸カリウム；ドデシルベンゼンスルホン酸ナトリウム；キソジウム（ｘｏｄｉｕｍ）テトラデシル硫酸；及び二ナトリウム２−ヘキサデセニルブタンジオエートが挙げられる。
【００７９】
界面活性剤
界面活性剤は本発明の任意成分である。界面活性剤は、硬質表面上におけるナノ粒子の分散を円滑にする湿潤剤として、本被覆組成物では本質的に有用である。被覆組成物の噴霧特性を高め、ナノ粒子を含む被覆組成物をさらに均一に分布させるために、被覆組成物が疎水性の硬質表面を処理するのに用いられる場合又は被覆組成物が噴霧散布器で適用される場合に、界面活性剤は別の方法として包含される。被覆組成物の拡散はそれをさらに速く乾燥させることができるので、処理された物質がさらに素早く使用に供される。濃縮組成物において、界面活性剤は、濃縮された水性組成物中の抗菌活性物質及び香料のような多数の添加成分の分散を促進する。本発明で有用な好適な界面活性剤は、アニオン界面活性剤、カチオン界面活性剤、ノニオン界面活性剤、両性界面活性剤、双極性界面活性剤及びこれらの混合物から成る群から選択される界面活性剤である。
【００８０】
本発明の被覆組成物において界面活性剤を用いる場合、それは、本明細書で記載される１以上の利益を提供するような、典型的に、使用組成物の約０．０１重量％〜約５重量％、あるいは約０．０１重量％〜約３重量％、あるいは約０．０１重量％〜約０．５重量％の有効量で添加される。
【００８１】
界面活性剤の代替型は、エチレン酸化物の脂肪族アルコール、脂肪酸、脂肪族アミンなどとの付加生成物のようなエトキシル化界面活性剤である。任意で、エチレン酸化物とプロピレン酸化物の混合物の脂肪族アルコール、脂肪酸、及び脂肪族アミンとの付加生成物を用いることができる。エトキシル化界面活性剤は次一般式を有する化合物を包含する：
Ｒ^８−Ｚ−（ＣＨ_２ＣＨ_２Ｏ）_ｓＢ
式中Ｒ^８は、約６〜約２０の炭素原子、あるいは約８〜約１８、あるいは約１０〜約１５の炭素原子を有する一級、二級及び分枝鎖のアルキルヒドロカルビル基、一級、二級及び分枝鎖のアルケニルヒドロカルビル基、及び／又は一級、二級及び分枝鎖のアルキル−及びアルケニル−置換フェノールヒドロカルビル基から成る群から選択されるアルキル基又はアルキルアリール基であり；ｓは、約２〜約４５、あるいは約２〜約２０、あるいは約２〜約１５の整数であり；Ｂは、水素、カルボキシレート基、又はサルフェート基であり；連結基Ｚは、−Ｏ−、−Ｃ（Ｏ）Ｏ−、又は−Ｃ（Ｏ）Ｎ（Ｒ）−、及びこれらの混合物であり、Ｒは、存在する場合、Ｒ^８又は水素である。
【００８２】
ノニオン界面活性剤は本明細書では、５〜２０、あるいは６〜１５のＨＬＢ（親水性−親油性バランス）を特徴とする。
【００８３】
代替のエトキシル化界面活性剤の非限定例は：
−Ｒ^８がＣ_８〜Ｃ_１８、あるいはＣ_１０〜Ｃ_１４のアルキル及び／又はアルケニル基であり、ｓが約２〜約８である直鎖、一級アルコールエトキシレート；
−Ｒ^８がＣ_８〜Ｃ_１８のアルキル及び／又はアルケニル、例えば、３−ヘキサデシル、２−オクタデシル、４−エピコサニル、及び５−エピコサニルであり、ｓが約２〜約１０である直鎖、二級アルコールエトキシレート；
−アルキルフェノールが一級、二級又は分枝鎖の配置において３〜２０の炭素原子、あるいは６〜１２の炭素原子を含有するアルキル又はアルケニル基を有し、ｓが約２〜約１２であるアルキルフェノールエトキシレート類；
−例えば、周知の「オキソ」工程又はその改変から利用可能である分枝鎖一級及び二級アルコール（又はゲルベットアルコール類）がエトキシル化される分枝鎖アルコールエトキシレート類である。
【００８４】
代替のエトキシル化界面活性剤のその他の例には、Ｒ^８が約１２〜約１６の炭素原子を有し、ｓが約５〜約１３であるエーテルカルボキシレートとしても知られるカルボキシル化アルコールエトキシレート；ＰＥＧ−５ココモニウムメトサルフェート、ＰＥＧ−１５塩化ココモニウム、ＰＥＧ−１５塩化オレアンモニウム及びビス（ポリエトキシエタノール）タロー塩酸アンモニウムのようなエトキシル化四級アンモニウム界面活性剤が挙げられる。
他の好適なノニオンエトキシル化界面活性剤は、エチレン酸化物と疎水性のアルキルアミンとの縮合により得られるエトキシル化アルキルアミンであり、Ｒ^８は、約８〜約２２の炭素原子を有し、Ｓは約３〜約３０である。
【００８５】
また、本明細書に用いるのに好適なノニオンエトキシル化界面活性剤には、米国特許第４，５６５，６４７号（レナド（Ｌｌｅｎａｄｏ）、１９８６年１月２１日発行）に開示されており、約８〜約３０の炭素原子、あるいは約１０〜約１６の炭素原子を含有する疎水性基及び多糖類、例えば、ポリグリコシド、約１．３〜約１０、あるいは約１．３〜約３を含有する親水性基を有するアルキル多糖類が挙げられる。５又は６の炭素原子を含むいかなる還元性のサッカライドも使用でき、例えばグルコース、ガラクトースであり、ガラクトシル部分はグルコシル部分で置換されていてもよい。サッカライド間結合は、例えば、付加させるサッカライド単位のどれかの位置と、元のサッカライド単位の２−、３−、４−、及び／又は６−位との間で形成させることができる。代替のアルキルポリグリコシド類は次式を有する：
Ｒ^２Ｏ（Ｃ_ｎＨ_２ｎＯ）ｔ（グリコシル）_ｘ
式中、Ｒ^２は、アルキル、アルキルフェニル、ヒドロキシアルキル、ヒドロキシアルキルフェニル、及びこれらの混合物から成る群から選択され、その際、アルキル基は１０〜１８、あるいは１２〜１４の炭素原子を含有し；ｎは２又は３であり、ｔは０〜約１０であり；ｘは１．３〜あるいは約１０である。グリコシルはあるいはグルコースから誘導される。
【００８６】
シリコーン潤滑剤及び／又はシリコーンを含有する添加剤形状保持コポリマーを可溶化する及び／又は分散するための、本発明の被覆組成物の配合において有用であるもう１つの部類の代替の界面活性剤は、シリコーン界面活性剤である。シリコーン超湿潤剤としても知られる。それらは単独で用いることができ、及び／又はあるいは本明細書で上述した代替のアルキルエトキシレート界面活性剤と組み合わせて用いることができる。シリコーン界面活性剤の非限定例は、ジメチルポリシロキサン疎水部分及び１以上の親水性のポリアルキレン側鎖を有し、次の一般式を有するポリアルキレン酸化物ポリシロキサン類である：
Ｒ^１−（ＣＨ_３）_２ＳｉＯ−［（ＣＨ−_３）_２ＳｉＯ］_ａ−［（ＣＨ_３）（Ｒ^１）ＳｉＯ］_ｂ−Ｓｉ（ＣＨ_３）_２−Ｒ^１
式中、別の方法としてはａ＋ｂは約１〜約５０であり、Ｒ^１はそれぞれ同一であるか、又は異なっており、メチル及び次の一般式を有するポリ（エチレン酸化物／プロピレン酸化物）コポリマー群から成る群から選択される：
−（ＣＨ_２）_ｎＯ（Ｃ_２Ｈ_４Ｏ）_ｃ（Ｃ_３Ｈ_６Ｏ）_ｄＲ^２
式中、ｎは３又は４であり；（全てのポリアルキレンオキシ側基の）ｃの合計は１〜約１００、あるいは約６〜約１００であり；ｄの合計は０〜約１４；あるいはｄは０であり；ｃ＋ｄの合計の値は約５〜約１５０、あるいは約９〜約１００であり、そして各Ｒ^２は同一であるか又は異なり、水素、１〜４個の炭素原子を有するアルキル基、及びアセチル基、あるいは水素及びメチル基から成る群から選択される。各ポリアルキレン酸化物ポリシロキサンは、ポリ（エチレン酸化物／プロピレン酸化物）コポリマー基である少なくとも１個のＲ^１基を有する。
【００８７】
この種類の界面活性剤の非限定的な実施例は、ＯＳｉスペシャルティ（ＯＳｉ Ｓｐｅｃｉａｌｔｉｅｓ、Ｉｎｃ．）（コネティカット州ダンベリー）から入手可能なシルウェット（Ｓｉｌｗｅｔ）（登録商標）界面活性剤である。エチレンオキシ（Ｃ_２Ｈ_４Ｏ）基だけを含有する代表的なシルエット（Ｓｉｌｗｅｔ）界面活性剤は以下のとおりである。
【００８８】
【表１】

【００８９】
ポリアルキレンオキシ基（Ｒ^１）の分子量は、約１０、０００未満又はそれに同等である。あるいは、ポリアルキレンオキシ基の分子量は約８，０００未満又はそれに同等、最も別の方法としては約３００〜約５，０００の範囲である。したがって、ｃ及びｄの値は、これらの範囲の分子量を与える数であり得る。しかしながら、ポリエーテル鎖（Ｒ^１）中のエチレンオキシ単位（−Ｃ_２Ｈ_４Ｏ）の数は、ポリアルキレン酸化物ポリシロキサンを水分散性又は水溶性にするのに十分な値でなければならない。ポリアルキレンオキシ鎖にプロピレンオキシ基が存在するとき、それらは鎖中にランダムに分布するか、又はブロックとして存在し得る。エチレンオキシ基を持たず、プロピレンオキシ基のみを含有する界面活性剤は好ましくない。代替のシルウェット界面活性剤は、Ｌ−７７、Ｌ−７２８０、Ｌ−５５５０、Ｌ−７２８０、Ｌ７６０８、Ｌ７６０７、及びこれらの混合物である。
【００９０】
この種類の界面活性剤のもう１つの非限定例は、ダウ・コーニングから入手可能なシリコーン超湿潤剤であり、シリコーングリコールコポリマー（例えばＱ２−５２１１及びＱ２−５２１２）のようなシリコーン超湿潤剤として販売されている。
【００９１】
その他の有用なシリコーン界面活性剤は、疎水部分及び例えば、アニオン、カチオン、及び両向性の基を含む親水性のイオン基を有するものである。アニオンシリコーン界面活性剤の非限定例は、それぞれ米国特許第４，７１７，４９８号；同第４，９６０，８４５号；同第５，１４９，７６５及び同第５，２９６，４３４号に開示されているようなシリコーンスルホスクシネート、シリコーンサルフェート、シリコーンホスフェート、シリコーンカルボキシレート、及びこれらの混合物である。カチオンシリコーン界面活性剤の非限定例は、それぞれ米国特許第５，０９８，９７９号；同第５，１３５，２９４及び同第５，１９６，４９９号に開示されているようなシリコーンアルキル四級化物（四級アンモニウム）、シリコーンアミド四級化物、シリコーンイミダゾリン四級化物、及びこれらの混合物である。両向性シリコーン界面活性剤の非限定例は、それぞれ米国特許第４，６５４，１６１号；同第５，０７３，６１９号及び同第５，２３７，０３５に開示されるシリコーンベタイン、シリコーンアミノプロプリオネート、シリコーンホスホベタイン、及びこれらの混合物である。これらの全ての特許を参考として本明細書に組み入れる。
【００９２】
自動食器洗浄サイクルで使用すべき本発明の被覆組成物は、一般の洗剤とともに用いることができるし、実際にすすぎ又は乾燥のサイクルにてすすぎ助剤として用いることができる。本発明に基づいた被覆組成物は、ナノ粒子システム及び任意で界面活性剤又は界面活性剤システムを含み、その際、界面活性剤は、ノニオン及び／又はアニオン及び／又はカチオン及び／又は両性及び／又は双極性及び／又は半極性ノニオンの界面活性剤から選択される。
界面活性剤は典型的に、約０．０１重量％〜約５重量％のレベルにて存在する。組み込みのさらに別の方法としてのレベルは、本発明に基づいた被覆組成物の約０．０１重量％〜約３重量％、最もあるいは０．０１重量％〜０．５重量％である。
【００９３】
界面活性剤は、あるいは、被覆組成物に存在するナノ粒子システム、好適な担体媒質及び任意の添加成分に相容性であるように配合される。
好適なノニオン、アニオン、カチオン、両性、双極性及び半極性ノニオンの界面活性剤の例は、米国特許第５，７０７，９５０号及び同第５，５７６，２８２号に開示されており、参考として本明細書に組み入れる。
【００９４】
ノニオン界面活性剤のその他の非限定例は、次式のポリヒドロキシ脂肪酸アミド界面活性剤である：
Ｒ^２−Ｃ（Ｏ）−Ｎ（Ｒ^１）−Ｚ、
式中、Ｒ^１は、Ｈ、又はＣ^１ _１〜_４のヒドロカルビル、２−ヒドロキシエチル、２−ヒドロキシプロピル又はそれらの混合物であり、Ｒ^２は、Ｃ_５〜_３１のヒドロカルビルであり、及びＺは、鎖に直接結合した少なくとも３つのヒドロキシルを持つ線状ヒドロカルビルを有するポリヒドロキシヒドロカルビル、又はそのアルコキシル化誘導体である。あるいは、Ｒ^１はメチルであり、Ｒ^２は直鎖Ｃ_１１〜_１５のアルキル又はＣ_１６〜_１８のアルキル又はアルケニル鎖、例えばココナッツアルキル又はその混合物であり、Ｚは、還元型アミノ化反応におけるグルコース、フルクトース、マルトース、ラクトースのような還元糖に由来する。
【００９５】
あるいは、アニオン界面活性剤としては、アルキルアルコキシル化スルフェート界面活性剤が挙げられ、これは式ＲＯ（Ａ）_ｍＳＯ３Ｍの水溶性塩又は酸で、式中ＲはＣ_１０〜Ｃ_２４アルキル成分、あるいはＣ_１２〜Ｃ_２０アルキル又はヒドロキシアルキル、あるいはＣ_１２〜Ｃ_１８アルキル又はヒドロキシアルキルを有する非置換Ｃ_１０〜Ｃ_２４アルキル又はヒドロキシアルキル基であり、Ａはエトキシ又はプロポキシ単位、ｍは０より大きく典型的には約０．５〜約６、あるいは約０．５〜約３、及びＭはＨ又は例えば金属カチオン（例えばナトリウム、カリウム、リチウム、カルシウム、マグネシウムなど）、アンモニウム又は置換されたアンモニウムカチオンであることができるカチオンである。アルキルエトキシル化スルフェート類並びにアルキルプロポキシル化スルフェート類について本明細書において考慮した。
【００９６】
その中に包含される場合、本発明の被覆組成物は典型的に、約０．０１重量％〜約５重量％、あるいは約０．０１重量％〜約３重量％のかかるアニオン系界面活性剤を含む。
代替のカチオン界面活性剤は、本組成物で有用な次式を有する水溶性の第四級アンモニウム化合物である：
Ｒ_１Ｒ_２Ｒ_３Ｒ_４Ｎ^＋Ｘ⁻
式中、Ｒ_１は、Ｃ_８〜Ｃ_１６のアルキルであり、Ｒ_２、Ｒ_３及びＲ_４はそれぞれ独立してＣ_１〜Ｃ_４のアルキル、Ｃ_１〜Ｃ_４のヒドロキシアルキル、ベンジル、及び−（Ｃ_２Ｈ_４０）_ｘＨであり、その際、ｘは２〜５の値を有し、Ｘはアニオンである。１を超えないＲ_２、Ｒ_３又はＲ_４がベンジルであるべきである。
【００９７】
その中に包含される場合、本発明の被覆組成物は典型的に、０．０１重量％〜約１５重量％、あるいは約０．０１重量％〜約３重量％のかかるカチオン界面活性剤を含む。
その中に包含される場合、本発明の被覆組成物は典型的に、０．０１重量％〜約１５重量％、あるいは約０．０１重量％〜約３重量％のかかる両性界面活性剤を含む。
その中に包含される場合、本発明の被覆組成物は典型的に、約０．０１重量％〜約１５重量％、あるいは約０．０１重量％〜約５重量％のかかる双極性界面活性剤を含む。
【００９８】
その中に包含される場合、本発明の被覆組成物は典型的に、約０．０１重量％〜約１５重量％、あるいは約０．０１重量％〜約５重量％のかかる半極性ノニオン界面活性剤を含む。
本発明の洗剤組成物は、一級アミン又は第三級アミンの群から選択される補助界面活性剤をさらに含むことができる。
本明細書に用いるのに好適な第１級アミン類には、式Ｒ_１ＮＨ_２に基づくアミン類が挙げられ、式中、Ｒ_１は、Ｃ_６〜Ｃ_１２、あるいはＣ_６〜Ｃ_１０のアルキル鎖又はＣ_４Ｘ（ＣＨ_２）ｎであり、その際、Ｘは−Ｏ−、−Ｃ（Ｏ）ＮＨ−又は−ＮＨ−であり、Ｒ_４は、Ｃ_６〜Ｃ_１２のアルキル鎖ｎは１〜５の間であり、あるいは３である。Ｒ_１のアルキル鎖は、直鎖又は分枝状であることができ、１２までの、あるいは５未満のエチレン酸化物部分を割りこませることができる。
【００９９】
本明細書の上述の式による代替のアミン類はｎ−アルキルアミン類である。本明細書の使用に好適なアミンは１−へキシルアミン、１−オクチルアミン、１−デシルアミン及びラウリルアミンから選択することができる。その他の代替一級アミンとしてはＣ８−Ｃ１０オキシプロピルアミン、オクチルオキシプロピルアミン、２−エチルへキシル−オキシプロピルアミン、ラウリルアミドプロピルアミン及びアミドプロピルアミンが挙げられる。
本明細書に用いるのに好適な第三級アミンには、式Ｒ_１Ｒ_２Ｒ_３Ｎを有する第３級アミンが挙げられ、式中、Ｒ_１及びＲ_２がＣ_１〜Ｃ_８のアルキル鎖又は
【０１００】
【化５】

【０１０１】
Ｒ_３が、Ｃ_６〜Ｃ_１２、あるいはＣ_６〜Ｃ_１０のアルキル鎖のいずれかであり、又はＲ_３が、Ｒ_４Ｘ（ＣＨ_２）ｎであり、その際、Ｘが−Ｏ−、−Ｃ（Ｏ）ＮＨ−又は−ＮＨ−であり、Ｒ_４がＣ_４〜Ｃ_１２であり、ｎが１〜５、あるいは２〜３の間であり、Ｒ_５が、Ｈ又はＣ_１〜Ｃ_２のアルキルであり、ｘが１〜６である。
Ｒ_３及びＲ_４は線状又は分枝状であることができ；Ｒ_３のアルキル鎖は１２まで、あるいは５未満のエチレン酸化物部分を割りこませることができる。
代替の第三級アミンは、Ｒ_１Ｒ_２Ｒ_３Ｎであり、その際、Ｒ_１はＣ_６〜Ｃ_１２のアルキル鎖であり、Ｒ_２及びＲ_３はＣ_１〜Ｃ_３のアルキルであり、又は
【０１０２】
【化６】

【０１０３】
式中、Ｒ_５は、Ｈ又はＣＨ_３であり、ｘ＝１〜２である。
代替は、次式のアミドアミン類である：
【０１０４】
【化７】

【０１０５】
式中、Ｒ_１はＣ_６〜Ｃ_１２のアルキルであり；ｎは２〜４であり、あるいはｎは３であり；Ｒ_２及びＲ_３は、Ｃ_１〜Ｃ_４である。
本発明の代替のアミン類には、１−オクチルアミン、１−ヘキシルアミン、１−デシルアミン、１−ドデシルアミン、Ｃ８〜１０オキシプロピルアミン、Ｎココ１−３ジアミノプロパン、ココナッツアルキルジメチルアミン、ラウリルジメチルアミン、ラウリルビス（ヒドロキシエチル）アミン、ココビス（ヒドロキシエチル）アミン、２モルプロポキシル化されたラウリルアミン、２モルプロポキシル化されたオクチルアミン、ラウリルアミドプロピルジメチルアミン、Ｃ８〜１０のアミドプロピルジメチルアミン及びＣ１０のアミドプロピルジメチルアミンが挙げられる。
【０１０６】
本明細書の被覆組成物で使用するための代替のアミン類は１−ヘキシルアミン、１−オクチルアミン、１−デシルアミン、１−ドデシルアミンである。とりわけ望ましいのはｎ−ドデシルジメチルアミン及びビスヒドロキシエチルココナツアルキルアミン及びオレイルアミン７倍エトキシ化、ラウリルアミドプロピルアミン及びココアミドプロピルアミンである。
【０１０７】
代替の添加物質
アミノカルボキシレートキレート化剤
例えば、エチレンジアミン四酢酸（ＥＤＴＡ）、ヒドロキシエチレン−ジアミン三酢酸、ジエチレントリアミン五酢酸、及びその他のアミノカルボキシレートキレート化剤、及びこれらの混合物、及びそれらの塩、及びこれらの混合物のようなキレート化剤は、グラム陰性細菌、特にシュードモナス（Ｐｓｅｕｄｏｍｏｎａｓ）種に対する抗菌剤及び防腐剤の有効性を高めるために任意で用いることができる。ＥＤＴＡ及び他のアミノカルボキシレートキレート化剤への感度は、主にシュードモナス属の特徴であるが、他の細菌属もキレート化剤に対して高い感度を有し、これらにはアクロモバクター属、アルカリゲネス属、アゾトバクター属、エシェリキア属、サルモネラ属、スピリルム属、及びビブリオ属が挙げられる。真菌及びイースト菌を包含する、他の微生物の群もまた、これらのキレート化剤に対して高い感度を示す。その上、アミノカルボキシレートキレート化剤は、例えば製品の透明性の保持、芳香及び香料成分の保護、及び酸敗及び悪臭の防止を援助し得る。
【０１０８】
これらのアミノカルボキシレートキレート化剤は、それ自体は効き目のある殺生物剤ではないかもしれないが、本発明の被覆組成物の、他の抗菌剤／防腐剤の性能を改善する強化剤として機能する。アミノカルボキシレートキレート化剤は、多くのカチオン、アニオン、及びノニオン抗菌剤／防腐剤、フェノール化合物、及びイソチアゾリノンであって、本発明の被覆組成物において抗菌剤／防腐剤として用いられるものの性能を強化することができる。溶液中のアミノカルボキシレートキレート化剤により強化されるカチオンの抗菌剤／防腐剤の非限定例には、クロルヘキシジン塩（ジグルコン酸塩、ジ酢酸塩、及びジヒドロクロリド塩が挙げられる）、及びまたダウィシル（Ｄｏｗｉｃｉｌ）２００、ダウィサイド（Ｄｏｗｉｃｉｄｅ）Ｑ、プリベントール（Ｐｒｅｖｅｎｔｏｌ）Ｄ１としても知られクアテルニウム−１５（Ｑｕａｔｅｒｎｉｕｍ−１５）、塩化ベンザルコニウム、セトリモニウム、ミリスタリコニウムクロリド（ｍｙｒｉｓｔａｌｋｏｎｉｕｍ ｃｈｌｏｒｉｄｅ）、塩化セチルピリジニウム、塩化ラウリルピリジニウムなどがある。アミノカルボキシレートキレート化剤により強化される、有用なアニオンの抗菌剤／防腐剤の非限定例は、ソルビン酸及びソルビン酸カリウムである。アミノカルボキシレートキレート化剤により強化される、有用なノニオンの抗菌剤／防腐剤の非限定例は、ＤＭＤＭヒダントイン、フェネチルアルコール、モノラウリン、イミダゾリジニル尿素、及びブロノポール（２−ブロモ−２−ニトロプロパン−１，３，−ジオール）である。
【０１０９】
これらのキレート化剤により強化される、有用なフェノール性抗菌剤／防腐剤の例は、クロルオキシレノール（ｃｈｌｏｒｏｘｙｌｅｎｏｌ）、フェノール、ｔ−ブチルヒドロキシアニソール、サリチル酸、レゾルシノール、及びソジウムオルト−フェニルフェナート（ｓｏｄｉｕｍ ｏ−ｐｈｅｎｙｌ ｐｈｅｎａｔｅ）である。アミノカルボキシレートキレート化剤により強化される、イソチアゾリノン抗菌剤／防腐剤の非限定例は、カトン（Ｋａｔｈｏｎ）、プロキセル（Ｐｒｏｘｅｌ）及びプロメキサル（Ｐｒｏｍｅｘａｌ）である。
任意のキレート化剤は本発明に抗細菌の効果を提供するために、典型的に使用組成物の約０．０１重量％〜約０．３重量％、あるいは約０．０２重量％〜約０．１重量％の濃度で、本発明の被覆組成物中に存在する。
【０１１０】
抗菌剤の効果を強化するため、遊離した、非錯体型のアミノカルボキシレートキレート化剤が必要である。そのため、アルカリ土類（特にカルシウム及びマグネシウム）、及び遷移金属（鉄、マンガン、銅、及びその他）が存在する場合、遊離したキレート化剤が利用できず、そして抗細菌の強化も見られない。水の硬度が高い、又は遷移金属が利用される場合、又は製品の美観から特別なキレート化剤の濃度が必要である場合は、抗細菌／防腐剤強化剤として機能する、遊離した、非錯体型のアミノカルボキシレートキレート化剤の利用可能性に合った、より高い濃度が必要とされるかもしれない。
【０１１１】
その他の任意成分
本発明の被覆組成物は、臭気抑制添加物質、キレート化剤、静電気防止剤、及び防虫防蛾剤、着色剤、青味剤、酸化防止剤、並びにこれらの混合物を、環状シリコーン分子に加えて、任意で含有することができる。これらの任意成分は、これ以前に具体的に記載した他の成分を除外する。臭気抑制添加物質を組み込むことにより、シクロデキストリンが臭気を抑制する能力を高め、並びに抑制し得る臭気の種類、及び分子の大きさの範囲を広げることができる。かかる物質には、例えば、金属塩、ゼオライト類、水溶性重炭酸塩類、抗菌防腐剤、ＵＶ吸収剤、及びこれらの混合物が挙げられるが、これに限定されない。
【０１１２】
抗菌防腐剤
任意で、しかし別の方法として、組成物を保護するために、抗菌防腐剤、あるいは可溶化する、水溶性、抗菌防腐剤を本発明の被覆組成物に加えることができる。被覆組成物における微生物の増殖は、いかなる時間の長さにおいても硬質表面被覆溶液の保存安定性の問題を招き得る。特定の微生物による汚染とその後の細菌の成長により、溶液は見苦しく及び／又は悪臭がひどくなる。硬質表面における細菌の増殖は、それが生じた場合には極めて好ましくないことであり、あるいは透明、水性を含有する硬質表面被覆組成物の保存安定性を高めるために、抗菌防腐剤、あるいは、細菌の増殖を抑制及び／又は調節するのに有効な可溶性、水溶性の抗菌防腐剤を包含することは極めて好ましい。
【０１１３】
広域スペクトルの防腐剤、例えば、バクテリア（グラム陰性及びグラム陽性の両方）及びカビの両方に有効な防腐剤を使用することが好ましい。スペクトルの限定された防腐剤、例えば単一の微生物群、例えばカビにしか有効ではない防腐剤は、優れた活性及び／又は補足する活性を有する、広域スペクトル防腐剤又はその他のスペクトルの限定された防腐剤と組み合わせて使用し得る。広域スペクトル防腐剤の混合物も又使用し得る。汚染微生物の特定の群が（グラム陰性のように）問題がある場合には、アミノカルボキシレートキレート化剤を単独で又は強化剤として、その他の防腐剤とともに使用し得る。例えば、エチレンジアミン四酢酸（ＥＤＴＡ）、ヒドロキシエチレンジアミン三酢酸、ジエチレントリアミン五酢酸、及びその他のアミノカルボキシレートキレート化剤、及びそれらの混合物、及びそれらの塩を含むこれらのキレート化剤、及びそれらの混合物は、グラム陰性バクテリア、とりわけシュードモナス（Ｐｓｅｕｄｏｍｏｎａｓ）属に対する防腐剤の有効性を増大する。
【０１１４】
本発明に有効な抗菌防腐剤には、殺菌性化合物すなわち殺微生物物質、又は生物静力学的化合物すなわち微生物の増殖を阻害する及び／又は抑制する物質が含まれる。好適な防腐剤は、米国特許第５，５３４，１６５号、第５，５７８，５６３号；第５，６６３，１３４号；第５，６６８，０９７号；第５，６７０，４７５号；及び第５，７１４，１３７号（トリン（Ｔｒｉｎｈ）ら、各々１９９６年７月９日発行；１９９６年１１月２６日発行、１９９７年９月２日発行；１９９７年９月１６日発行；１９９７年９月２３日発行；及び１９９８年２月３日発行）に開示されており、前記特許のすべては参考として、以前に本明細書に組み入れられている。本明細書の上記で提供された抗菌活性物質の項で多数の抗菌防腐剤が提供されている。パラベン及びトリクロサンのような水不溶性の抗菌防腐剤は本発明の被覆組成物において有用ではあるが、前記防腐剤を効果的に液状組成物に分配するには界面活性剤及び／又はシクロデキストリンのような可溶化剤、乳化剤、分散剤などの使用を必要とする。代替の抗菌防腐剤は、水溶性であって、低濃度で有効なものである。本発明に有効な水溶性防腐剤は、１００ｍｌの水に少なくとも約０．３ｇの水への溶解性、すなわち、室温で約０．３％より大きい、あるいは室温で約０．５％より大きい水への溶解性を有する防腐剤である。
【０１１５】
本発明の水溶性抗細菌防腐剤は、有効量にて包含される。本明細書において定義される「有効量」という用語は、具体的な期間の間、腐敗を防止、又は不適切にも添加された微生物の成長を防止するのに十分な濃度を意味する。換言すれば、防腐剤は、微生物により生成された臭気を除くために、被覆組成物が付着する面上の微生物を殺すのに用いられるのではない。その代わり、別の方法としてはそれは、被覆組成物の貯蔵寿命を増やすためには硬質表面被覆組成物の腐敗を防ぐのに用いられている。防腐剤の別の方法としての濃度は使用組成物の約０．０００１重量％〜約０．５重量％、あるいは約０．０００２重量％〜約０．２重量％、あるいは約０．０００３重量％〜約０．１重量％である。
【０１１６】
防腐剤は硬質表面の見かけを損なう、例えば変色、着色、漂白を生じないであろう、いかなる有機防腐剤物質であることもできる。別の方法としての水溶性防腐剤には、有機イオウ化合物、ハロゲン化合物、環状有機窒素化合物、低分子量のアルデヒド、四級アンモニウム化合物、デヒドロ酢酸、フェニル化合物、及びフェノール化合物、及びそれらの混合物が含まれる。
本発明の防腐剤は、広範囲の微生物を抑制するために、混合物として使用し得る。
静菌効果は、水性組成物において、被覆組成物のｐＨを酸のｐＨ、例えばｐＨ約４未満、あるいはｐＨ約３未満、又は塩基のｐＨ、例えばｐＨ約１０より大きく、あるいはｐＨ約１１より大きく調整することにより得られることもある。
【０１１７】
ＵＶ吸収剤
理論により制限されないが、ＵＶ吸収剤は、硬質表面に沈着した被覆を、ＵＶに曝すことから保護することにより、機能する。ＵＶ光が自動酸化過程を開始することは既知であり、そしてＵＶ吸収剤は、ＵＶ光を硬質表面及び不飽和脂肪物質から遮るように硬質表面上に付着し、それにより、自動酸化の開始を妨げることができる。
【０１１８】
酸化安定剤
酸化安定剤は本発明の被覆組成物中に存在することができ、酸化過程におけるスカベンジャーとして作用し、自動酸化を防止及び／又は終了するか、又は酸化を反転させて、黄ばみも反転させることにより、黄ばみを防止する。本明細書で用いる場合、「酸化安定剤」という用語には、酸化防止剤及び還元剤が包含される。これらの剤は、酸化防止剤としては０％〜約２％、あるいは約０．０１％〜約０．２％、あるいは約０．０３５％〜約０．１％の濃度で、及びあるいは還元剤としては約０．０１％〜約０．２％の濃度で存在する。
【０１１９】
本発明の被覆組成物及び製法に添加し得る酸化防止剤の例には、アスコルビン酸、アスコルビン酸パルミチン酸塩、没食子酸プロピルの混合物が挙げられ、イーストマン・ケミカル・プロダクツ社（Ｅａｓｔｍａｎ Ｃｈｅｍｉｃａｌ Ｐｒｏｄｕｃｔｓ，Ｉｎｃ．）より商品名テノックス（Ｔｅｎｏｘ（登録商標））ＰＧ、及びテノックス（Ｔｅｎｏｘ（登録商標））Ｓ−１として入手可能であり；ＢＨＴ（ブチル化ヒドロキシトルエン）、ＢＨＡ（ブチル化ヒドロキシアニソール）、没食子酸プロピル、及びクエン酸の混合物が挙げられ、イーストマン・ケミカル・プロダクツ社（Ｅａｓｔｍａｎ Ｃｈｅｍｉｃａｌ Ｐｒｏｄｕｃｔｓ、Ｉｎｃ．）より商品名テノックス（Ｔｅｎｏｘ（登録商標））−６として入手可能であり；ブチル化ヒドロキシトルエンが挙げられ、ＵＯＰプロセス・ディヴィジョン（ＵＯＰ Ｐｒｏｃｅｓｓ Ｄｉｖｉｓｉｏｎ）より商品名サスタン（Ｓｕｓｔａｎｅ（登録商標））ＢＨＴとして入手可能であり；ｔ−ブチルヒドロキノンが挙げられ、イーストマン・ケミカル・プロダクツ社（Ｅａｓｔｍａｎ Ｃｈｅｍｉｃａｌ Ｐｒｏｄｕｃｔｓ、Ｉｎｃ．）より商品名テノックス（Ｔｅｎｏｘ（登録商標））ＴＢＨＱとして入手可能であり；天然のトコフェロールが挙げられ、イーストマン・ケミカル・プロダクツ社（Ｅａｓｔｍａｎ Ｃｈｅｍｉｃａｌ Ｐｒｏｄｕｃｔｓ、Ｉｎｃ．）より商品名テノックス（Ｔｅｎｏｘ（登録商標））ＧＴ−１／ＧＴ−２として入手可能であり；及びブチル化ヒドロキシアニソールが挙げられ、イーストマン・ケミカル・プロダクツ社（Ｅａｓｔｍａｎ Ｃｈｅｍｉｃａｌ Ｐｒｏｄｕｃｔｓ、Ｉｎｃ．）よりのＢＨＡであり；長鎖エステル（Ｃ_８〜Ｃ_２２）の没食子酸、例えば没食子酸ドデシルが挙げられ；イルガノックス（Ｉｒｇａｎｏｘ（登録商標））１０１０；イルガノックス（Ｉｒｇａｎｏｘ（登録商標））１０３５；イルガノックス（Ｉｒｇａｎｏｘ（登録商標））Ｂ１１７１；イルガノックス（Ｉｒｇａｎｏｘ（登録商標））１４２５；イルガノックス（Ｉｒｇａｎｏｘ（登録商標））３１１４；イルガノックス（Ｉｒｇａｎｏｘ（登録商標））３１２５；及びこれらの混合物が挙げられ、あるいはイルガノックス（Ｉｒｇａｎｏｘ（登録商標））３１２５；イルガノックス（Ｉｒｇａｎｏｘ（登録商標））１４２５；イルガノックス（Ｉｒｇａｎｏｘ（登録商標））３１１４；及びこれらの混合物が挙げられ、あるいはイルガノックス（Ｉｒｇａｎｏｘ（登録商標））３１２５で、単独で、又はクエン酸及び／又は他のキレート化剤との混合によるものが挙げられ、この他のキレート化剤は、例えばクエン酸イソプロピル、モンサント（Ｍｏｎｓａｎｔｏ）より化学名１−ヒドロキシエチリデン−１，１−ジホスホン酸（エチドロン酸）として入手可能なデクエスト（Ｄｅｑｕｅｓｔ（登録商標））２０１０、及びコダック（Ｋｏｄａｋ）より化学名４，５−ジヒドロキシ−ｍ−ベンゼン−スルホン酸／ナトリウム塩として入手可能なチロン（Ｔｉｒｏｎ（登録商標）、及びアルドリッチ（Ａｌｄｒｉｃｈ）より化学名ジエチレントリアミン五酢酸として入手可能なＤＴＰＡ（登録商標）である。
工程のいかなる時点においても酸化安定剤を添加することができる。これらによって長期の保存条件下における良好な臭気安定性が確保される。
【０１２０】
着色剤
着色剤、染料、及び青味剤は、視覚訴求及び性能の印象のため、被覆組成物に任意に添加することができる。着色剤が用いられる場合は、硬質表面に染みが付くのを避けるため、極めて低い濃度で用いられる。本組成物に用いるための代替の着色剤は、高度に水溶性の染料であり、例えばリキチント（Ｌｉｑｕｉｔｉｎｔ（登録商標））染料であり、ミリケン・ケミカル社（Ｍｉｌｌｉｋｅｎ Ｃｈｅｍｉｃａｌ Ｃｏ．）より入手できる。好適な染料の非限定例は、リキチント・ブルーＨＰ（Ｌｉｑｕｉｔｉｎｔ Ｂｌｕｅ ＨＰ（登録商標））、リキチント・ブルー６５（Ｌｉｑｕｉｔｉｎｔ Ｂｌｕｅ ６５（登録商標））、リキチント・パテント・ブルー（Ｌｉｑｕｉｔｉｎｔ Ｐａｔｅｎｔ Ｂｌｕｅ（登録商標））、リキチント・ロイヤル・ブルー（Ｌｉｑｕｉｔｉｎｔ Ｒｏｙａｌ Ｂｌｕｅ（登録商標））、リキチント・イクスペリメンタル・イエロー８９４９−４３（Ｌｉｑｕｉｔｉｎｔ Ｅｘｐｅｒｉｍｅｎｔａｌ Ｙｅｌｌｏｗ ８９４９−４３（登録商標））、リキチント・グリーンＨＭＣ（Ｌｉｑｕｉｔｉｎｔ Ｇｒｅｅｎ ＨＭＣ（登録商標））、リキチント・イエローＩＩ（Ｌｉｑｕｉｔｉｎｔ Ｙｅｌｌｏｗ ＩＩ（登録商標））、及びこれらの混合物であり、あるいは、リキチント・ブルーＨＰ（Ｌｉｑｕｉｔｉｎｔ Ｂｌｕｅ ＨＰ（登録商標））、リキチント・ブルー６５（Ｌｉｑｕｉｔｉｎｔ Ｂｌｕｅ ６５（登録商標））、リキチント・パテント・ブルー（Ｌｉｑｕｉｔｉｎｔ Ｐａｔｅｎｔ Ｂｌｕｅ（登録商標））、リキチント・ロイヤル・ブルー（Ｌｉｑｕｉｔｉｎｔ Ｒｏｙａｌ Ｂｌｕｅ（登録商標））、リキチント・イクスペリメンタル・イエロー８９４９−４３（Ｌｉｑｕｉｔｉｎｔ Ｅｘｐｅｒｉｍｅｎｔａｌ Ｙｅｌｌｏｗ ８９４９−４３（登録商標））、及びこれらの混合物である。
【０１２１】
ビルダー
本発明に基づいた被覆組成物はさらに、特に被覆組成物のためのビルダー又はビルダーシステムを含むことができる。アルミノシリケート物質、シリケート類、ポリカルボキシレート類、アルキル−又はアルケニル−コハク酸及び脂肪酸、例えば、エチレンジアミン四酢酸、ジエチレントリアミンペンタメチレン酢酸のような物質、例えば、アミノポリホスフォネート、特に、エチレンジアミンテトラメチレンホスホン酸及びジエチレントリアミンペンタメチレンホスホン酸のような金属イオン封鎖剤を含む従来のいかなるビルダーシステムも本明細書に用いるのに好適である。ホスフェートビルダーも本明細書で使用することができる。　本発明は、好適なビルダー又は洗浄性の塩を包含することができる。洗浄性の塩／ビルダーの濃度は被覆組成物の最終用途及び所望の物理的形態によって幅広く変化することができる。存在する場合、被覆組成物は典型的に、少なくとも約１重量％のビルダー、さらに典型的に約１０重量％〜約８０重量％、一層さらに典型的に約１５重量％〜約５０重量％のビルダーを含む。しかしながら、さらに低い又はさらに高い濃度が除外されることを意味しない。
【０１２２】
無機又はリン含有洗浄性塩には、ポリホスフェート類（トリポリホスフェート類、ピロホスフェート類、及びガラス状の高分子メタ−ホスフェート類が例示される）、ホスホネート類、フィチン酸、シリケート類、カーボネート類（重炭酸塩類及びセスキカーボネート類を含む）、スルフェート類、及びアルミノシリケート類のアルカリ金属、アンモニウム及びアルカノールアンモニウム塩が挙げられるが、これに限定されない。しかしながら、ある地域では非ホスフェート塩類が求められる場合もある。重要なことに、クエン酸塩のようないわゆる「弱い」ビルダー（リン酸塩に比べて）の存在下でも、ゼオライト又は層状珪酸塩ビルダーとともに生じる可能性があるいわゆる「増進下」の状況でも、驚くべきことに本明細書における被覆組成物は上手く機能する。
【０１２３】
本発明の目的に好適な有機洗浄性ビルダーには、多種多様なポリカルボキシレート化合物が挙げられるが、これに拘束されない。本明細書で使用するとき、「ポリカルボキシレート」は、複数のカルボキシレート基、あるいは少なくとも３つのカルボキシレート基を有する化合物をいう。ポリカルボキシレートビルダーは一般に酸性形態で被覆組成物に添加することができるが、中和された塩の形態で加えることもできる。塩の形態で利用する場合、ナトリウム、カリウム、及びリチウムのようなアルカリ金属、又はアルカノールアンモニウム塩が代替である。
好適なシリケートビルダー、カーボネート塩類、アルミノシリケートビルダー、ポリカルボキシレートビルダー、シトレートビルダー、３，３−ジカルボキシ−４−オキサ−１，６−ヘキサンジオエートビルダー及び米国特許第４，５６６，９８４号（ブッシュ（Ｂｕｓｈ））に開示されている関連する化合物、コハク酸ビルダー、リンを基にしたビルダー及び脂肪酸の例は、米国特許第５，５７６，２８２号、同第５，７２８，６７１号同第５，７０７，９５０号に開示されている。
【０１２４】
追加の好適なビルダーは、無機イオン交換物質、一般に無機水和アルミノシリケート物質、さらに詳しくは水和ゼオライトＡ、Ｘ、Ｂ、ＨＳ又はＭＡＰのような水和合成ゼオライトであることができる。
【０１２５】
本発明に好適な具体的なポリカルボキシレート類は、ベルギー特許第８３１，３６８号、同第８２１，３６９号及び同第８２１，３７０号に開示されているような、乳酸、グリコール酸及びそのエーテル誘導体を含むカルボキシル基を１つ含有するポリカルボキシレート類である。２つのカルボキシル基を含有するポリカルボキシレート類には、コハク酸、マロン酸、（エチレンジオキシ）二酢酸、マレイン酸、ジグリコール酸、酒石酸、タルトロン酸及びフマル酸の水溶性塩、並びにドイツ仮出願（Ｏｆｆｅｎｌｅｇｅｎｓｃｈｒｉｆｔ）第２，４４６，６８６号及び同第２，４４６，６８７号及び米国特許第３，９３５，２５７号に記載されるエーテルカルボキシレート類並びにベルギー特許第８４０，６２３号に記載されるスルフィニルカルボキシレート類が挙げられる。３つのカルボキシ基を含有するポリカルボキシレートには、特に、水溶性シトレート、アコニトレート及びシトラコネート、並びに英国特許第１，３７９，２４１号に記載されるカルボキシメチルオキシスクシネートのようなスクシネート誘導体、及びオランダ特許第７２０５８７３号に記載されるラクトキシスクシネート、及び英国特許第１，３８７，４４７号に記載される２−オキサ−１，１，３−プロパントリカルボキシレートのようなオキシポリカルボキシレート物質が挙げられる。
【０１２６】
４つのカルボキシ基を含有するポリカルボキシレート類には、英国特許第１，２６１，８２９号で開示されたオキシジスクシネート、１，１，２，２−エタンテトラカルボキシレート類、１，１，３，３−プロパンテトラカルボキシレート類及び１，１，２，３−プロパンテトラカルボキシレート類が挙げられる。ホスホン置換基を含有するポリカルボキシレート類は、英国特許第１，４３９，０００号に開示されている一方、スルホ置換基を含有するポリカルボキシレート類には、英国特許第１，３９８，４２１号及び同第１，３９８，４２２号及び米国特許第３，９３６，４４８号に開示されているスルホスクシネート誘導体、及び英国特許第１，０８２，１７９号に記載されるスルホン化熱分解シトレート類が挙げられる。
【０１２７】
脂環族及び複素環のポリカルボキシレート類には、シクロペンタン−シス、シス、シス−テトラカルボキシレート類、シクロペンタジエニドペンタカルボキシレート類、２，３，４，５−テトラヒドロフラン−シス、シス、シス−テトラカルボキシレート類、２，５−テトラヒドロフラン−シス−ジカルボキシレート類、２，２，５，５−テトラヒドロフラン−テトラカルボキシレート類、１，２，３，４，５，６−ヘキサン−ヘキサカルボキシレート類、並びにソルビトール、マニトール及びキシリトールのような多価アルコールのカルボキシメチル誘導体が挙げられる。芳香族ポリカルボキシレートには、英国特許第１，４２５，３４３号で開示されたメリト酸、ピロメリト酸、及びフタル酸誘導体が挙げられる。
【０１２８】
前記の中で、代替のポリカルボキシレート類は、分子当り３つまでのカルボキシ基を含有するヒドロキシカルボキシレート類であり、さらに特にはシトレート類である。
本組成物で使用するためのビルダーシステムには、ゼオライトＡ、又は層状シリケート（ＳＫＳ−６）のような水不溶性のアルミノシリケートビルダーとクエン酸のような水溶性カルボキシレート−キレート化剤の混合物を包含する。
ビルダーシステムには、ゼオライトＡのような水不溶性のアルミノシリケートビルダーとクエン酸のような水溶性カルボキシレート−キレート化剤の混合物を包含する。本発明の液状被覆組成物で使用するためのビルダーシステムは石鹸及びポリカルボキシレート類である。
【０１２９】
その他の好適な水溶性有機塩類は、ホモポリマー性又はコポリマー性の酸又はその塩であって、その際ポリカルボン酸は２つ以下の炭素原子で互いに分離された少なくとも２つのカルボキシル基を含む。この種類のポリマーは英国特許Ａ１，５９６，７５６に開示されている。そのような塩類の例は、分子量が２０００〜５０００のポリアクリレート及びそれらの無水マレイン酸とのコポリマーであり、そのようなコポリマーは分子量が２０，０００〜７０，０００、特に約４０，０００である。
洗浄性ビルダー塩は普通、被覆組成物の５重量％〜８０重量％、あるいは１０重量％〜７０重量％、最も通常では３０重量％〜６０重量％の量にて包含される。
【０１３０】
泡抑制剤
もう１つの任意成分は、シリコーン、及びシリカ−シリコーン混合物で例示される泡抑制剤である。好適な泡抑制剤の例は、米国特許第５，７０７，９５０号及び同第５，７２８，６７１に開示される。このような泡抑制剤は普通、被覆組成物の０．００１重量％〜２重量％、あるいは０．０１重量％〜１重量％のレベルで用いられる。
【０１３１】
酵素
例えば洗濯中の染料の移行防止及び布修復のため、タンパク質を主とした、炭水化物を主とした、又はトリグリセリドを主とした染みを織物又は食器のような表面から取り除くことを含む、種々の目的で、本洗剤組成物中に酵素を包含することができる。好適な酵素には、植物性、動物性、細菌性、真菌性、及び酵母性起源質のような好適な起源物質からのプロテアーゼ、アミラーゼ、リパーゼ、セルラーゼ、ペルオキシダーゼ、及びこれらの混合物が含まれる。別の方法としての選択は、ｐＨ−活性及び／又は安定性の最適条件、熱安定性、及び活性のある洗剤、ビルダーなどに対する安定性のような因子によって影響される。この点に関して、細菌又は真菌の酵素は、例えば、細菌のアミラーゼ類及びプロテアーゼ、並びに真菌のセルラーゼのように代替である。
【０１３２】
本明細書で使用するとき、「洗浄性酵素」とは洗濯洗剤組成物中で、洗浄、汚れの除去、又は他の有益な効果を有する任意の酵素を意味する。別の方法としての洗浄性酵素は、プロテアーゼ、アミラーゼ及びリパーゼのような加水分解酵素である。洗濯の目的上、別の方法としての酵素には、プロテアーゼ、セルラーゼ、リパーゼ、及びペルオキシダーゼが含まれるが、これらに限定されない。
【０１３３】
酵素は通常、「洗浄−有効量」を提供するのに十分なレベルにて洗剤組成物又は洗剤添加組成物に組み入れられる。「洗浄有効量」という用語は、布地、食器などのような基材において、洗浄、染みの除去、汚れの除去、漂白、脱臭、又は新品度を上げる効果を与えることができるいずれかの量を意味する。現在の商業的製剤に関する現実の問題として、典型的な量は、約５重量ｍｇまでであり、さらに典型的には、洗剤組成物のグラムあたり０．０１重量ｍｇ〜３重量ｍｇの活性酵素である。別の言い方をすれば、本明細書における組成物は典型的に、０．００１重量％〜５重量％、あるいは０．０１重量％〜１重量％の市販の酵素製剤を含む。プロテアーゼ酵素は、通常、組成物のグラム当り０．００５〜０．１アンソン単位（ＡＵ）の活性を提供するのに十分なレベルでこのような市販の製剤に存在する。濃縮度の高い洗剤処方物ではさらに高い活性レベルが望ましい可能性もある。
【０１３４】
好適な酵素の例としては、ヘミセルラーゼ類、ペルオキシダーゼ類、プロテアーゼ類、セルラーゼ類、キシラナーゼ類、リパーゼ類、ホスホリパーゼ類、エステラーゼ類、クチナーゼ類、ペクチナーゼ類、ケラタナーゼ（ｋｅｒａｔａｎａｓｅ）類、レダクターゼ類、オキシダーゼ類、フェノールオキシダーゼ類、リポキシゲナーゼ類、リグニナーゼ類、プルラナーゼ類、タンナーゼ類、ペントサナーゼ類、マラナーゼ（ｍａｌａｎａｓｅ）類、βグルカナーゼ類、アラビノシダーゼ類、ヒアルロニダーゼ類、コンドロイチナーゼ類、ラッカーゼ類、マンナナーゼ（ｍａｎｎａｎａｓｅｓ）類、より好ましくは植物細胞壁分解酵素類及び非細胞壁分解酵素類（ＷＯ９８／３９４０３Ａ）が挙げられるがこれらに限定されず、より詳細には、ペクチナーゼ（ＷＯ９８／０６８０８Ａ，ＪＰ１００８８４７２Ａ、ＪＰ１００８８４８５Ａ）；ペクトリアーゼ（ＷＯ９８／０６８０５Ａ１）；その他のペクチン酵素を含まないペクチンリアーゼ（ＷＯ９８０６８０７Ａ１）；コンドリオチナーゼ（ＥＰ７４７，４６９Ａ）；キシラナーゼ（ＥＰ７０９，４５２Ａ、ＷＯ９８／３９４０４Ａ、ＷＯ９８／３９４０２Ａ）（マイクロテトラスポラフレクソーサ（ｍｉｃｒｏｔｅｔｒａｓｐｏｒａ ｆｌｅｘｕｏｓａ）から誘導されたもの（ＵＳ５６８３９１１）を含む）；イソペプチダーゼ（ＷＯ９８／１６６０４Ａ）；ケラチナーゼ（ＥＰ７４７，４７０Ａ、ＷＯ９８／４０４７３Ａ）；リパーゼ（ＧＢ２，２９７，９７９Ａ；ＷＯ９６／１６１５３Ａ；ＷＯ９６／１２００４Ａ；ＥＰ６９８，６５９Ａ；ＷＯ９６／１６１５４Ａ）；セルラーゼ又はエンドグルカナーゼ（ＧＢ２，２９４，２６９Ａ；ＷＯ９６／２７６４９Ａ；ＧＢ２，３０３，１４７Ａ；ＷＯ９８／０３６４０Ａ）；（ＷＯ９８１５６３３Ａに開示されているクリソスポリウムラクノウェンス（ｃｈｒｙｓｏｓｐｏｒｉｕｍ ｌｕｃｋｎｏｗｅｎｓｅ）株ＶＫＭＦ−３５００Ｄから誘導された中性又はアルカリ性セルラーゼ類も参照のこと）；ポリガラクツロナーゼ（ＷＯ９８／０６８０９Ａ）；ミコデキストラナーゼ（ｍｙｃｏｄｅｘｔｒａｎａｓｅ）（ＷＯ９８／１３４５７Ａ）；サーミターゼ（ｔｈｅｒｍｉｔａｓｅ）（ＷＯ９６／２８５５８Ａ）；コレステロールエステラーゼ（ＷＯ９８２８３９４Ａ）；又はこれらの任意の組み合わせ；及び既知のアミラーゼ類；酸化還元酵素類；オキシダーゼ類又はそれを含むコンビネーションシステム（ＤＥ１９５２３３８９Ａ１）；変異体青色銅オキシダーゼ類（ＷＯ９７０９４３１Ａ１）、ペルオキシダーゼ類（例えば、ＵＳ５，６０５，８３２、ＷＯ９７／３１０９０Ａ１参照）、マンナナーゼ（ｍａｎｎａｎａｓｅｓ）類（ＷＯ９７１１１６４、ＷＯ９９／０９１２６、ＰＣＴ／ＵＳ００／００８３９）；キシログルカナーゼ類（ＷＯ９８／５０５１３、ＰＣＴ／ＵＳ／００／００８３９、ＷＯ９９／０２６６３）；ラッカーゼ類ＷＯ９８３８２８７Ａ１又はＷＯ９８３８２８６Ａ１、例えば、ＷＯ９８２７１９７Ａ１に記載されているミセリオフトラ（ｍｙｃｅｌｉｏｐｈｔｈｏｒａ）又はスキタリジウム（ｓｃｙｔａｌｉｄｉｕｍ）ラッカーゼ（類）中にアミノ酸変化を有するラッカーゼ変異株又はＤＥ１９６１２１９３Ａ１に記載されている媒介されたラッカーゼシステム、又はヒトヨタケ（ｃｏｐｒｉｎｕｓ）株から誘導されるもの（例えば、ＷＯ９８／１００６０Ａ１又はＷＯ９８／２７１９８Ａ１参照）、フェノールオキシダーゼ又はポリフェノールオキシダーゼ（ＪＰ１０１７４５８３Ａ）又は媒介されたフェノールオキシダーゼシステム（ＷＯ９７／１１２１７Ａ）；増強されたフェノールオキシダーゼシステム（ＷＯ９７／２５４６８Ａ、ＷＯ９７／２５４６９Ａ）；セルロ−ス結合ドメインを有するアミノ酸配列に融合したフェノールオキシダーゼ類（ＷＯ９７／４０１２７Ａ１、ＷＯ９７／４０２２９Ａ１）又はその他のフェノールオキシダーゼ類（ＷＯ９７／０８３２５Ａ、ＷＯ９７／２８２５７Ａ１）、又はスーパー酸化物ジスムターゼ類を挙げることができる。ＷＯ９８／０７８１６Ａで教示されるように、酸化還元酵素及び／又はそれに関連する抗体を例えば、Ｈ_２Ｏ_２とともに用いることができる。組成物の種類によって、その他のレドックス活性酵素、例えば、カタラーゼ類（例えばＪＰ０９３１６４９０Ａを参照のこと）を用いることができる。
【０１３５】
プロテアーゼの好適な例はサブチリシンであり、Ｂ．サブチリス（Ｂ．ｓｕｂｔｉｌｉｓ）、及びＢ．リケニフォームス（Ｂ．ｌｉｃｈｅｎｉｆｏｒｍｓ）の特別な株から得られる。１つの好適なプロテアーゼは、ｐＨ８−１２の範囲で最大活性を有するバシルス株から得られ、デンマークのノボ・インダストリーズ（Ｎｏｖｏ Ｉｎｄｕｓｔｒｉｅｓ）Ａ／Ｓ（本明細書において以降ノボと呼ぶ）によってエスペラス（ＥＳＰＥＲＡＳＥ）（登録商標）として開発及び販売されている。この酵素及び類似酵素の調製は、ノボへの英国特許第１，２４３，７８４号に記載されている。その他の好適なプロテアーゼ類には、ノボ（Ｎｏｖｏ）のアルカラーゼ（ＡＬＣＡＬＡＳＥ）（登録商標）及びサビナーゼ（ＳＡＶＩＮＡＳＥ）（登録商標）、並びにインターナショナル・バイオシンセティックス社（Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｂｉｏ−Ｓｙｎｔｈｅｔｉｃｓ，Ｉｎｃ．）（オランダ）のマキサターゼ（ＭＡＸＡＴＡＳＥ）（登録商標）；並びにＥＰ１３０，７５６Ａ（１９８５年１月９日）に開示されているプロテアーゼＡ、及びＥＰ３０３，７６１Ａ（１９８７年４月２８日）及びＥＰ１３０，７５６Ａ（１９８５年１月９日）に開示されているプロテアーゼＢが挙げられる。ノボのＷＯ９３１８１４０Ａに記載されているバチルスｓｐ．ＮＣＩＭＢ４０３３８に由来するｐＨの高いプロテアーゼも参照のこと。プロテアーゼ、１以上のその他の酵素、及び可逆的プロテアーゼ阻害剤を含む酵素的洗剤は、ノボのＷＯ９２／０３５２９Ａに記載されている。その他の択一的なプロテアーゼには、プロクター＆ギャンブルのＷＯ９５／１０５９１Ａのものが挙げられる。所望であれば、低下した吸収及び上昇した加水分解を有するプロテアーゼは、プロクター＆ギャンブルのＷＯ９５／０７７９１に記載されているように入手可能である。本明細書で好適な洗剤のための組換えのトリプシン様プロテアーゼは、ノボへのＷＯ９４／２５５８３に記載されている。
【０１３６】
さらに詳細には、「プロテアーゼＤ］といわれる択一的なプロテアーゼは、天然には見い出されないアミノ酸配列を有するカルボニルヒドロラーゼ変異体であり、双方とも１９９４年１０月１３日に出願された米国特許出願出願番号０８／３２２，６７６号を有するＡ．ベック（Ｂａｅｃｋ）らの表題「プロテアーゼ含有清浄組成物」及び米国特許出願番号０８／３２２，６７７を有するＣ．ゴーシュ（Ｇｈｏｓｈ）らの表題「プロテアーゼ酵素を含む漂白組成物」に記載されるようなバチルス・アミロリクエファシエンス（Ｂａｃｉｌｌｕｓ ａｍｙｌｏｌｉｑｕｅｆａｃｉｅｎｓ）のサブチリシンの番号付けに従って、部位＋７６と同等の前記カルボニルヒドロラーゼの部位において、あるいは、＋９９、＋１０１、＋１０３、＋１０４、＋１０７、＋１２３、＋２７、＋１０５、＋１０９、＋１２６、＋１２８、＋１３５、＋１５６、＋１６６、＋１９５、＋１９７、＋２０４、＋２０６、＋２１０、＋２１６、＋２１７、＋２１８、＋２２２、＋２６０、＋２６５、及び／又は＋２７４から成る群から選択されるものに同等の１以上のアミノ酸残基部位との組み合わせにおいて、複数のアミノ酸残基について異なったアミノ酸を置換することによる前駆体カルボニルヒドロラーゼに由来する
択一的プロテアーゼ、「プロテアーゼＥ」は、自然界には見られないアミノ酸配列を有するカルボニル加水分解酵素変異型であり、それは、前記カルボニル加水分解酵素のバチルス・アミロリクエファシエンス（Ｂａｃｉｌｌｕｓ ａｍｙｌｏｌｉｑｕｅｆａｃｉｅｎｓ）サブチリシンの１０３の位置に相当する位置で、異なるアミノ酸を、複数のアミノ酸残基と置換することと、アミノ酸残基をもう１つの自然発生するアミノ酸残基と、バチルス・アミロリクエファシエンス（Ｂａｃｉｌｌｕｓ ａｍｙｌｏｌｉｑｕｅｆａｃｉｅｎｓ）サブチリシンの１、３、４、８、９、１０、１２、１３、１６、１７、１８、１９、２０、２１、２２、２４、２７、３３、３７、３８、４２、４３、４８、５５、５７、５８、６１、６２、６８、７２、７５、７６、７７、７８、７９、８６、８７、８９、９７、９８、９９、１０１、１０２、１０４、１０６、１０７、１０９、１１１、１１４、１１６、１１７、１１９、１２１、１２３、１２６、１２８、１３０、１３１、１３３、１３４、１３７、１４０、１４１、１４２、１４６、１４７、１５８、１５９、１６０、１６６、１６７、１７０、１７３、１７４、１７７、１８１、１８２、１８３、１８４、１８５、１８８、１９２、１９４、１９８、２０３、２０４、２０５、２０６、２０９、２１０、２１１、２１２、２１３、２１４、２１５、２１６、２１７、２１８、２２２、２２４、２２７、２２８、２３０、２３２、２３６、２３７、２３８、２４０、２４２、２４３、２４４、２４５、２４６、２４７、２４８、２４９、２５１、２５２、２５３、２５４、２５５、２５６、２５７、２５８、２５９、２６０、２６１、２６２、２６３、２６５、２６８、２６９、２７０、２７１、２７２、２７４及び２７５の位置に相当する１つ以上のアミノ酸残基の位置で置換することと組み合わせて、前駆体カルボニル加水分解酵素から導かれ；前記プロテアーゼ変異型が、１０３及び７６の位置に相当する位置でのアミノ酸残基の置換を包含するとき、バチルス・アミロリクエファシエンス（Ｂａｃｉｌｌｕｓ ａｍｙｌｏｌｉｑｕｅｆａｃｉｅｎｓ）サブチリシンの２７、９９、１０１、１０４、１０７、１０９、１２３、１２８、１６６、２０４、２０６、２１０、２１６、２１７、２１８、２２２、２６０、２６５、又は２７４の位置に相当するアミノ酸残基の位置以外の１つ以上のアミノ酸残基の位置の置換もあり；及び１つ以上の洗浄性添加物質の、アミノ酸残基の置換もある。
【０１３７】
上記に列挙したアミノ酸置換のいかなる組合せも使用してよいが、本発明に有用な好ましいプロテアーゼ変異型酵素は、以下の組合せでアミノ酸残基の置換、除去、又は挿入を含む：
（１）１０３の位置及び以下の２３６及び２４５の位置の１つ以上のアミノ酸残基の置換を包含するプロテアーゼ変異型；
（２）１０３及び２３６の位置及び以下の：１２、６１、６２、６８、７６、９７、９８、１０１、１０２、１０４、１０９、１３０、１３１、１５９、１８３、１８５、２０５、２０９、２１０、２１１、２１２、２１３、２１５、２１７、２３０、２３２、２４８、２５２、２５７、２６０、２７０及び２７５の位置の１つ以上のアミノ酸残基の置換を含むプロテアーゼ変異型；
（３）１０３及び２４５の位置及び以下の：１２、６１、６２、６８、７６、９７、９８、１０１、１０２、１０４、１０９、１３０、１３１、１５９、１７０、１８３、１８５、２０５、２０９、２１０、２１１、２１２、２１３、２１５、２１７、２２２、２３０、２３２、２４８、２５２、２５７、２６０、２６１、２７０及び２７５の位置の１つ以上のアミノ酸残基の置換を含むプロテアーゼ変異型；及び
（４）１０３、２３６、及び２４５の位置、並びに以下の：１２、６１、６２、６８、７６、９７、９８、１０１、１０２、１０４、１０９、１３０、１３１、１５９、１８３、１８５、２０５、２０９、２１０、２１１、２１２、２１３、２１５、２１７、２３０、２３２、２４３、２４８、２５２、２５７、２６０、２７０、及び２７５の位置での１つ以上のアミノ酸残基の置換を含むプロテアーゼ変異型であって、Ｃ．ゴッシュ（Ｃ．Ｇｈｏｓｈ）らの特許出願であって、「複数置換プロテアーゼ変異型を含有する洗浄性組成物」と称される米国特許出願番号０９／５２９９０５（１９９８年１０月２３日出願）に記載されているプロテアーゼ変異型。
【０１３８】
特に、自動食器洗浄目的のための、しかしこれに限定されない本明細書で好適なアミラーゼ類には、例えば、ノボへの英国特許第１，２９６，８３９号に記載されたα−アミラーゼ、インターナショナル・バイオシンセティクス社のラピダーゼ（ＲＡＰＩＤＡＳＥ）（登録商標）、及びノボのターマミル（ＴＥＲＭＡＭＹＬ）（登録商標）が挙げられる。ノボからのファンガミル（ＦＵＮＧＡＭＹＬ）（登録商標）が特に有用である。安定性、例えば、酸化安定性を改善するための酵素工学は既知である。例えば、ジャーナル・オブ・バイオロジカル・ケミストリー（Ｊ．Ｂｉｏｌｏｇｉｃａｌ Ｃｈｅｍ．）の第２６０巻、１１号（１９８５年６月）６５１８〜６５２１頁を参照のこと。本明細書で別の方法としてのこのようなアミラーゼは、「安定性が強化された」アミラーゼであるという特徴を共有しており、最低限、：例えば、ｐＨ９〜１０にて緩衝溶液中の過酸化水素／テトラアセチルエチレンジアミンに対する酸化安定性、例えば、約６０℃のような通常の洗濯温度における熱安定性、又は、例えば、約８〜約１１のｐＨにて、前記で確認された基準点アミラーゼに対して測定されるアルカリ安定性の１以上における測定可能な改善を特徴とする。当該技術が開示した技術試験のいかなるものを使用しても安定性を測定することができる。例えば、ＷＯ９４／０２５９７で開示されている参考文献を参照のこと。安定性を高めたアミラーゼは、ノボ又はジェネンコールインターナショナルから入手することができる。本明細書で別の方法としてのアミラーゼの部類の１つは、１、２又は複数のアミラーゼ株が直接の前駆体であるかどうかに関係なく部位特異的突然変異誘発を用いて、１以上のバチルス（Ｂａｃｃｉｌｌｕｓ）のアミラーゼ、特にバチルスのα−アミラーゼに由来するという共通性を有する。前記で確認された基準アミラーゼに対して酸化安定性が強化されたアミラーゼは、本明細書の塩素漂白、洗剤組成物を除外して特に漂白における使用、あるいは酸素漂白における使用に選択的である。かかるもう１つの方法としてのアミラーゼには、（ａ）前記で組み入れられたＷＯ９４／０２５９７（１９９４年２月３日、ノボ）に基づいた、アラニン又はスレオニン、もう１つの方法としてはスレオニンを用いて、Ｂ．リケニフォルミン（Ｂ．ｌｉｃｈｅｎｉｆｏｒｍｉｓ）のアルファ−アミラーゼの１９７位に位置するメチオニン残基の置換を行った突然変異体によりさらに説明される、ターマミル（ＴＥＲＭＡＭＹＬ）（登録商標）として知られるアミラーゼ、又はＢ．ａｍｙｌｐｌｏｑｕｅｆａｃｉｅｎｓ、Ｂ．ｓｕｂｔｉｌｉｓ又はＢ．ｓｔｅａｒｏｔｈｅｒｍｏｐｈｉｌｕｓのような類似する母型アミラーゼの相同位置変異体、（ｂ）第２０７回全米化学会総会（１９９４年３月１３〜１７日）にてＣ．ミチンソン（Ｍｉｔｃｈｉｎｓｏｎ）により提示された「酸化耐性アルファアミラーゼ」と題する論文中でジェネンコール・インターナショナルによって記載された安定性が強化されたアミラーゼが挙げられる。メチオニン（Ｍｅｔ）が最も改変し易い残基であることが同定された。８、１５、１９７、２５６、３０４、３６６及び４３８位にてＭｅｔを一度に置換し、特別の変異体を作製したが、特に重要なのは、Ｍ１９７Ｌ及びＭ１９７Ｔであり、Ｍ１９７Ｔ変異体は最も安定的に発現された変異体である。その他のもう１つの方法としての酸化安定性を高めるアミラーゼには、ジェネンコール・インターナショナルへのＷＯ９４／１８３１４号及びノボへのＷＯ９４／０２５９７号に記載されるものが挙げられる。例えば、既知のキメラハイブリッドからの部位特異的突然変異誘発又は利用可能なアミラーゼの単純な変異母型に由来するような、その他の酸化安定性を高めるいかなるアミラーゼも使用することができる。その他のもう１つの方法としての酵素の修飾は、入手可能である。ノボへのＷＯ９５／０９９０９Ａを参照のこと。
【０１３９】
本発明に使用可能なセルラーゼには、バクテリア及び真菌の両方の種類が包含され、あるいはまたｐＨの至適条件が５〜９．５である。米国特許第４，４３５，３０７号（バーベスゴード（Ｂａｒｂｅｓｇｏａｒｄ）ら、１９８４年３月６日発行）は、ヒューミコラ・インソレンス（Ｈｕｍｉｃｏｌａ ｉｎｓｏｌｅｎｓ）又はヒューミコラ（Ｈｕｍｉｃｏｌａ）株ＤＳＭ１８００由来の好適な真菌セルラーゼ又はセルラーゼ２１２を生成するアエロモナス属に属する真菌、及び海洋軟体動物、ドラベラ・オーリクラ・ソランダー（Ｄｏｌａｂｅｌｌａ Ａｕｒｉｃｕｌａ Ｓｏｌａｎｄｅ）の肝膵より抽出されたセルラーゼを開示する。好適なセルラーゼは、英国特許出願Ａ−２，０７５，０２８号、英国特許出願Ａ−２，０９５，２７５号及びドイツ特許ＯＳ−２，２４７，８３２号にも開示されている。カレザイム（ＣＡＲＥＺＹＭＥ）（登録商標）（ノボ）が特に有用である。ノボへのＷＯ９１１７２４３も参照のこと。
【０１４０】
洗剤用途に好適なリパーゼ酵素は、英国特許第１，３７２，０３４号で開示されている、Ｐｓｅｕｄｏｍｏｎａｓ　ｓｔｕｔｚｅｒｉ（ＡＴＣＣ１９．１５４号）のようなシュードモナス群の微生物により生成されるものが挙げられる。日本の特許出願、５３，２０４８７（１９７８年２月２４日公開）のリパーゼも参照のこと。このリパーゼは、商品名リパーゼＰ「アマノ」又は「アマノＰ」のもとで日本の名古屋、天野製薬株式会社から入手可能である。その他の好適な市販のリパーゼには、アマノ−ＣＥＳ、クロモバクタービスコスム（Ｃｈｒｏｍｏｂａｃｔｅｒ ｖｉｓｃｏｓｕｍ）のリパーゼ、例えば日本の田方、東洋醸造株式会社のクロモバクタービスコスムｖａｒ．リポリチカム（ｌｉｐｏｌｙｔｉｃｕｍ）ＮＲＲＬＢ３６７３；米国、ＵＳバイオケミカルコーポレーション（Ｂｉｏｃｈｅｍｉｃａｌ Ｃｏｒｐ．）、及びオランダディソイス社（Ｄｉｓｏｙｎｔｈ Ｃｏ．）のクロモバクタービスコスムのリパーゼ、及びシュードモナスグラジオリ（Ｐｓｅｕｄｏｍｏｎａｓ ｇｌａｄｉｏｌｉ）のリパーゼが挙げられる。ヘミコララヌギノサ（Ｈｕｍｉｃｏｌａ ｌａｎｕｇｉｎｏｓａ）に由来し、ノボから市販され、欧州特許３４１，９４７を参照する、リポラーゼ（ＬＩＰＯＬＡＳＥ）（登録商標）酵素は、本明細書で使用するもう１つの方法としてのリパーゼである。ペルオキシダーゼ酵素に対して安定化されたリパーゼ及びアミラーゼの変異体は、ノボのＷＯ９４／１４９５１Ａに記載されている。ＷＯ９２／０５２４９及びＲＤ９４３５９０４４も参照のこと。
【０１４１】
本明細書での使用に好適なクチナーゼ酵素は、ジェネンコールのＷＯ８８／０９３６７Ａに記載されている。
ペルオキシダーゼ酵素は、酸素供給源、例えば、過炭酸塩、過ホウ酸塩、過酸化水素などと組み合わせて用いられる。それらは、「溶液漂白」のため、又は、洗浄操作中に基材から除かれた染料もしくは色素が洗浄溶液中に存在するその他の基材に移行するのを妨げるために用いられる。既知のペルオキシダーゼには、西洋ワサビペルオキシダーゼ、リグニナーゼ、及びクロロ−又はブロモ−ペルオキシダーゼのようなハロペルオキシダーゼが挙げられる。ペルオキシダーゼを含有する洗剤組成物は、ＷＯ８９／０９９８１３Ａ（１９８９年１０月１９日、ノボ）及びノボのＷＯ８９／０９８１３Ａに開示されている。
【０１４２】
合成洗剤組成物に組み込まれる酵素物質の範囲及びその手段もジェネンコールのＷＯ９３／０７２６３Ａ及びＷＯ９３／０７２６０Ａ、ノボのＷＯ８９／０８６９４Ａ、並びに米国特許第３，５５３，１３９号（マッカーティ（ＭｃＣａｒｔｙ）ら、１９７１年１月５日発行、）に開示されている。酵素はさらに、米国特許第４，１０１，４５７号（プレイス（Ｐｌａｃｅ）ら、１９７８年７月１８日発行）及び米国特許第４，５０７，２１９号（ヒュージ（Ｈｕｇｈｅｓ）、１９８５年３月２６日）に開示されている。液状の洗剤配合に有用な酵素物質及びかかる配合へのそれらの組み入れは、米国特許第４，２６１，８６８号（ホラ（Ｈｏｒａ）ら、１９８１年４月１４日発行）に記載されている。種々の技法によって洗剤で使用する酵素を安定化することができる。酵素の安定化技術は、米国特許第３，６００，３１９号（ゼドゲ（Ｇｅｄｇｅ）ら、１９７１年８月１７日発行）、欧州特許第１９９，４０５号及び欧州特許第２００，５８６号（ベネガス（Ｖｅｎｅｇａｓ）、１９８６年１０月２９日）に開示されており、例示されている。酵素の安定化システムは、例えば、米国特許第３，５１９，５７０号にも記載されている。プロテアーゼ、キシラナーゼ及びセルラーゼを提供する有用なバチルスｓｐ．ＡＣ１３は、ＷＯ９４／０１５３２Ａ（ノボ）に記載されている。
【０１４３】
その他の物質
本組成物に任意で包含される洗浄性成分又は添加剤は、組成物を処理する性能、清浄されるべき基材の処理を助ける又は高めるための、又は組成物の審美性を改善するように設計された１以上の物質を包含することができる。本発明の組成物に使用するのに従来技術で確立されたレベル（一般に、添加剤は全体において組成物約３０重量％〜約９９．９重量％、あるいは約７０重量％〜約９５重量％含まれる）で包含されることができる添加剤には、米国特許第５，７０５，４６４号；同第５，７１０，１１５号；同第５，６９８，５０４号；同第５，６９５，６７９号；同第５，６８６，０１４号；同第５，５７６，２８２号；及び同第５，６４６，１０１号に記載されるような光活性のある無機金属酸化物、カラースペックル、サビ防止剤、腐食止め剤、アルカリ性供給源、ヒドロトロープ、酸化防止剤、有機溶媒、界面活性剤、ポリマー、ビルダー、漂白剤、漂白活性化剤、漂白剤触媒、非活性化酵素、酵素安定化システム、キレート剤、光学的光沢剤、汚れ放出ポリマー、湿潤剤、染料付着剤、分散剤、泡抑制剤、染料、着色剤、充填剤塩、光活性化剤、蛍光剤、コンディショナー、加水分解可能な補助界面活性剤、防腐剤、縮み防止剤、殺菌剤、殺真菌剤、シルバーケア、可溶化剤、担体、加工助剤、顔料、及びｐＨ調節剤のようなその他の有効成分が挙げられる。
【０１４４】
ＩＩ．使用方法
有効量の光活性のないナノ粒子及び好適な水性担体媒質、及び任意で界面活性剤、１以上の荷電した官能化表面分子、有効量の光活性のあるナノ粒子、及び任意で、例えば、添加物の有機溶媒、界面活性剤、ポリマー、キレート剤、ビルダー、漂白剤、漂白活性化剤、漂白剤触媒、非活性化酵素、酵素安定化システム、光学的光沢剤、汚れ放出ポリマー、湿潤剤、染料移行剤、分散剤、泡抑制剤、染料、香料、着色剤、充填剤塩、屈水性誘発物質、光活性化剤、蛍光剤、コンディショナー、親水化可能な補助界面活性剤、防腐剤、酸化防止剤、収縮防止剤、殺菌剤、殺カビ剤、カラースペックル、シルバーケア、サビ防止剤及び又は腐食防止剤、アルカリ源、安定化剤、担体、加工助剤、色素、及びｐＨ調節剤、など及びそれらの混合物によるナノ粒子システムを含有する被覆組成物は、（ａ）前記ナノ粒子を好適な担体媒質中で混合して前記被覆組成物を形成すること；（ｂ）任意で、好適な担体媒質に分散された前記ナノ粒子を添加成分と混合して前記被覆組成物を形成すること；（ｃ）任意で、好適な担体媒質に分散された前記ナノ粒子を界面活性剤と混合して前記被覆組成物を形成すること；（ｄ）任意で、好適な担体媒質に分散された前記ナノ粒子を添加成分及び界面活性剤と混合して前記被覆組成物を形成すること；（ｅ）前記被覆組成物を前記硬質表面に適用すること；（ｆ）前記被覆組成物を乾燥させること、又は被覆組成物を積極的に乾燥すること、又はさもなければ被覆組成物を硬化すること；及び（ｇ）任意で、必要に応じて工程（ａ）から（ｆ）のいずれかを反復することによって用いることができる。
【０１４５】
被覆組成物の分配は、噴霧装置、浸漬容器、噴霧ホース取り付け具、又は、布地、スポンジ、ローラー、パッドなどのようなアプリケータ、あるいは噴霧ディスペンサーを用いて達成することができる。ナノ粒子システムを含有する、本発明の被覆組成物及び本発明の物品は、あらゆる硬質表面を処理するのに使用し、以下の耐久性の利益：改善された硬質表面の濡れ及びシート形成、速乾、均一な乾燥、汚れ落し、自浄、斑点防止、汚れ沈着防止、さらに清潔な外観、強化された光沢、強化された色彩、表面の小さな欠陥の修復、滑らかさ、曇り防止、表面摩擦の緩和、活性物質の放出、摩擦への軽減された損傷及び改善された透明性の少なくとも１つを提供することができる。
【０１４６】
本発明の１つの態様では、本発明の有効量の液状被覆組成物はあるいは：室内及び室外のガラス窓、壁及びドア；自動車の車体、トラック、列車、船及び飛行機を含むが、これに限定されない乗り物の車体の外面；陶器のタイル、床及び壁；風呂場及び台所の台；器具；金属備品、サイディング及び屋根葺き；食器；木製の家具、床及び壁の処理；石のタイル及び壁；アスファルトの屋根、サイディング及び道路；宝石；建物の外壁；塗装された及び被覆された表面などを含むが、これに限定されない硬質表面及び／又は硬質表面物品の上に噴霧される。被覆組成物が硬質表面に噴霧されると、有効量のナノ粒子システムが硬質表面に沈着され、硬質表面がーティング組成物で濡らされ、全体として飽和されるようになるべきである。浸漬容器においてロール被覆、カーテン被覆、浸漬及び／又は浸しの工程を介して本発明の硬質表面被覆組成物を硬質表面に適用することもできる。いかなる適用工程も乾燥工程又は硬化工程がその後に続くことができる。
【０１４７】
本発明の非限定的態様の１つでは、自動車のような乗り物の表面に耐久性の被覆を適用するのに本発明の被覆組成物を用いる。被覆組成物を適用する工程には、被覆組成物を適用する工程に加えて以下の１つ以上を含むことができる：予備洗浄工程；泡を生じるために石鹸やスポンジを伴うような洗浄工程；すすぎ工程；活性化されたすすぎ工程；本明細書に記載された被覆組成物を適用するための工程；及び乾燥工程。自動車ケアキットのようなキットの形態で、工程を実行するのに必要な構成要素を提供されれば、家庭にて消費者によってこのような工程を実行することができる。説明書を提供することができる。あるいは、洗車のような商業的な操作で工程を実行することができ、それは自動種類又は「セルフサービス」種類であってもよく、その際、消費者は洗車場を使ってクルマをスプレー洗浄する。
いかなる好適な気温においても硬質表面被覆組成物を硬質表面に適用することができる。硬質表面被覆組成物は、凍結するより高いいかなる温度でも適用できることが判っている。例えば、１℃、５℃、１０℃、又は１５℃ほどに低い温度で被覆組成物を適用することができる。
【０１４８】
次いで、被覆組成物を硬化又は乾燥することができるような条件に硬質表面をさらすことができる。乾燥工程は、周囲条件における風乾を含むことができる。あるいは、乾燥工程は、乾燥又は硬化の過程を加速するために知られているいかなる技術を利用することによっても被覆組成物を積極的に乾燥する又は硬化することを含むことができる。本明細書で使用されるとき、「積極的に硬化すること」という用語は、被覆組成物を周囲条件下で単に乾燥させることを超えて硬化過程を加速するのに用いられるいかなる技術もいう。例えば、それを硬化するのに既知の架橋剤を組成物に組み入れることができる。種々の硬化法を用いてもよいが、熱による又は加熱硬化、又は加熱乾燥が好ましい。硬質表面被覆組成物は、室温より高いいかなる気温においても加熱乾燥することができる（乾燥の気温が、例えば、０℃より上又はそれに同等の約５度上昇以上でもよい）。一般に、放射熱源によって提供されるもののような上昇した温度に被覆された表面をさらすことによって熱硬化を達成する。かかる技術には、送風機による乾燥、送風乾燥などのような動いている（又は強制された）風による乾燥、又は熱の適用（例えば、放射熱源、例えば、オーブンによる乾燥など）、又は動いている又は強制された風による乾燥と熱の適用の両方（例えば、熱風乾燥）を挙げてもよい。
【０１４９】
硬質表面被覆組成物を熱乾燥すると、硬質表面被覆の耐久性を大きく高めることができることが判っている。本発明の硬質表面被覆組成物の耐久性における増加量は、実際、まったく予想外に高い。
例えば、実施形態の中には、硬質表面被覆組成物を硬質表面に適用し、室温にて風乾した場合、以下の試験方法の項に記載される機械的磨き方法の１又は２回の決まりきった／サイクルにさらした後、硬質表面被覆は本明細書で記載される利益（又は少なくともかかる利益の一部）を提供することができることが判っているものもある。このことは、週に約１回表面を洗浄することを含めた、戸外の環境における約２〜４週間の表面の保護及び改質と解釈されると考えられる。
【０１５０】
しかしながら、硬質表面被覆組成物が室温（穏かな外気温又は建物の室内気温の場合約２０〜２２℃であってもよい）より上で熱乾燥されると、表面上に形成された硬質表面被覆は高められた耐久性を有することが判っているので、さらに持続性の利益が提供される。本明細書で使用されるとき、「長く続く」という用語は、試験方法に記載される磨き方法の１回以上のサイクルの後、本明細書で記載される利益の少なくとも一部を提供することができる被覆をいう。本発明の硬質表面被覆組成物は、約５０℃より上又はそれに同等の及び５０℃から上の５度ずつの区切り（例えば、８０℃）のいかなる温度にても熱乾燥し、長く続く利益を提供することができる。しかしながら、これは反応促進剤、すなわち、溶媒及び架橋剤によって影響され得る。被覆される硬質表面に溶解、ブロッキングなどのような変化を起こす温度に近づくが、好ましくはそれを超えない温度にて硬質表面被覆組成物を風乾することができる。非限定的実施形態の１つでは、本発明の硬質表面被覆組成物を自動車の車体に適用し、次いで約１４５℃〜約１６０℃、又はその間の５度ずつの区切りの風温にて熱乾燥することができる。かかる熱乾燥工程で乾燥された被覆は５００回以上の機械的磨き試験のサイクルに耐えることが判っている。もう１つの非限定的実施形態では、硬質表面被覆組成物を自動車の車体に適用し、次いで約１３５℃の風温にて熱乾燥することができる。かかる熱乾燥工程で乾燥した被覆は、５０回以上の機械的磨き試験のサイクルに耐えられることが判っている。
【０１５１】
もう１つの非限定的実施形態では、硬質表面被覆組成物を自動車のガラスに適用し、次いで約１３５℃の風温にて熱乾燥することができる。かかる熱乾燥工程で乾燥した被覆は、５０回以上の機械的磨き試験のサイクルに耐えられることが判っている。
乾燥させた硬質表面被覆は、好ましくは実質的に親水性である。乾燥させた硬質表面は、実施形態によっては、約６０未満又はそれと同等の；又は別の方法としては、６０未満の５ずつの区切り（例えば、約５０、４５、４０、．．．、２０、．．．、１０以下など）未満又はそれと同等の水との接触角を有してもよい。実施形態によっては、適用又は乾燥の温度が高ければ高いほど、より高い最初の接触角を生じ、適用又は乾燥の温度が低ければ低いほど、より低い最初の接触角を生じる。しかしながら接触角は、被覆の間にわたって変化することができる。実施形態によっては、表面を５００秒間水和した後に、乾燥させた硬質表面被覆の外観を改善することができる。視覚的改善は、表面被覆上での改善された水のシート形成又は幕張として特徴付けられる。
【０１５２】
工業的適用における硬質表面及び／又は仕上り物品での大規模な工程によって、又は製造物品の使用により消費者の家庭において、本発明の硬質表面被覆組成物の適用を行うことができる。
態様の１つでは、自動車の製造及び／又は塗装操作において本発明の方法を用い、自動車の外側に耐久性の仕上げを提供することができる。図４は、自動車の車体外板の外側を塗装し、それに透明塗料仕上げを適用する非限定例の１つを示すフローチャートである。透明塗料組成物は、米国ミシガン州サウスフィールドのＢＡＳＦの商品名ウレクリア（ＵＲＥＣＬＥＡＲ）（登録商標）で入手可能であるようなカーバメートとメラミン組成物の重合から生成されるポリウレタンを含む。
【０１５３】
図４に示される例では、自動車の車体外板を塗装する第１の工程は、塗りの間にフラッシュ時間（有機溶媒の蒸発のための経過時間）を挟まないで下塗剤の２度塗りを適用することである。これに続いて、下塗剤を１０分間フラッシュする（最初低い温度で乾燥して溶媒の大半を追い出し、次いでさらに高い温度でそれを硬化する；これによって起泡を防ぐ）。次いで１２９℃にて３０分間、外板を焼く。この後、塗りの間に６０秒間のフラッシュを挟んで下地塗り（塗装）の２度塗りを適用する。次いで、塗りの間に６０秒間のフラッシュを挟んで透明塗料の２度塗りを適用する。次いで、８２℃にて１０分間、外板を加熱する。この加熱工程を１３２℃まで上げ、その温度を２５分間保つ。最終工程は、外板を１６０℃のオーブンに５分間入れることである。当然、その他の方法では、いかなる好適な方式においても温度及び時間を変えることができる。例えば、ＡＣＴラボラトリーズ社（米国ミシガン州、ヒルスデール）によって用いられ、自動車車体の外板を調べる自動車産業で用いられる方法を試験方法の項に記載する。
【０１５４】
図４に示されるように、自動車車体の外板に透明塗料仕上げを適用する方法における多数の異なった工程に、本明細書に記載された硬質表面被覆組成物を適用することができる。前記１以上の塗料の塗りが前記自動車車体の部品に適用された後；１以上の透明塗料を前記自動車車体の部品に適用する工程の間；又は前記１以上の透明塗料が前記自動車車体の部品に適用された後、本明細書に記載された硬質表面被覆組成物を適用することができる。
その他の実施形態では、粉末の形態にてナノ粒子を用いることが望ましい。ナノ粒子は単独で用いることができるし、その他の物質と組み合わせて組成物を形成することもできる。透明塗料組成物は、かかる実施形態では、液体及び粉末を含むがこれに限定されないいかなる好適な形態においても提供されることができる。粉末の透明塗料とともにナノ粘土を含む粉末の硬質表面被覆組成物を使用することが望ましい実施形態では、適用手順を変更することが望ましい。多数の様々な方法において適用手順を変更することができる。所望のいかなる実施形態においても、それへのナノ粒子の吸引及び密着を促進するために、粉末の被覆が沈着されるべき表面を帯電させることができる。
【０１５５】
例えば、静電気的沈着技術又は流動床技術又は一般に実践されるその他のかかる技術によって先ず、透明な被覆粉末組成物を適用し、次いで静電気的沈着技術又は流動床技術又は一般に実践されるその他のかかる技術によってナノ粘土被覆組成物を適用する。次いで表面を加熱して適当な硬化を提供することができる。
もう１つの実施形態では、先ず透明塗料粉末組成物をナノ粘土を含む粉末化した硬質表面被覆で被膜することができる。これに続いて、ナノ粘土を含む粉末の硬質表面被覆で被膜された透明な塗料粉末組成物を所望の表面へ静電気的沈着技術若しくは流動床技術又は一般に実践されるその他のかかる技術によって適用することができる。次いで表面を加熱して適当な硬化を提供することができる。
【０１５６】
もう１つの実施形態では、静電気的沈着技術若しくは流動床技術又は一般に実践されるその他のかかる技術によって、透明な被覆粉末組成物及びナノ粘土を含む粉末の硬質表面被覆を所望の表面に同時に適用することができる。次いで表面を加熱して適当な硬化を提供することができる。
その他の実施形態では、自動車車体の修復事業のようなものでは、自動車の別の部分を損傷することなく、先行段落に記載したような温度に車体の外板を加熱することが可能ではないような場合、６０℃（暑い日にクルマの表面が達する温度）より上の温度のようなかなり低い温度で硬質表面被覆組成物を適用することができる。かかる実施形態では、所望に応じて反応促進剤を用いることができる。
【０１５７】
有機透明塗料とともにナノ粘土を含む水性の硬質表面被覆組成物を使用することが望ましい実施形態では、適用手順を変更することが望ましい。例えば、先ず透明塗料組成物を適用し、次いで、当業者に既知の技術を用いて濡れた透明塗料の上に「スキム」又はフィルムを形成する（透明塗料組成物は一般に、その上方部分から下方に向かって乾燥し、乾燥するとややべとつくようになる）。硬質表面被覆組成物をスキムの上に載せることができ、次いでその上に硬質表面被覆組成物を伴った透明塗料を一緒に加熱する。
本明細書に記載される実施形態のいかなるものにおいても、本明細書に記載される硬質表面のいかなるものにも複数層の硬質表面被覆組成物を適用することができる。このような複数層の硬質表面被覆組成物はすべて同一の化学的組成を有することができ、又はそれらは異なった化学的組成を有することができる。
【０１５８】
自動車車体の外板に本明細書で記載される硬質表面被覆組成物を適用することに加えて、本発明の硬質表面被覆組成物は、ガラス、プラスチック、又はゴムに適用することができる。例えば、自動車の窓ガラスに本発明の硬質表面被覆組成物を適用することができる。窓ガラスの製造又は自動車の製造のいかなる工程においても、本発明の硬質表面被覆組成物を自動車の窓ガラスに適用することができる。
その他の実施形態では、本明細書で記載される硬質表面被覆組成物の適用方法を飛行機、船、建物などの構成成分に適用して、さらに耐久性のある表面被覆を提供することができる。
【０１５９】
本発明はまた、濃縮された液体又は固体の被覆組成物を含み、それは、「使用条件」での使用のために、上文で提供されたように希釈され、使用濃度の組成物を形成する。濃縮組成物は、濃縮被覆組成物の典型的に約０．１重量％〜約５０重量％、あるいは約０．５重量％〜約４０重量％、あるいは約１重量％〜約３０重量％の、高いレベルのナノ粒子濃度を含む。
濃縮組成物はより安価な製品を提供するために用いられる。濃縮生成物はあるいは、被覆組成物の１，０００部の好適な担体媒質、あるいは１００部の好適な担体媒質、及びあるいは１０部の好適な担体媒質で希釈される。
【０１６０】
本発明のもう１つの実施形態では、自動食器洗浄機のすすぎ工程で食器を処理するために、（ａ）有効量の光活性のないナノ粒子；（ｂ）任意で界面活性剤；（ｃ）任意で前記ナノ粒子表面に会合させた、親水性、疎水性及びこれらの混合から成る群から選択される特性を示す１以上の官能化させた表面分子；（ｄ）任意で、有効量の光活性のあるナノ粒子；（ｅ）任意で１以上の添加成分；及び（ｆ）好適な担体媒質を含む液状被覆組成物、あるいは濃縮された液体を用いる方法が提供される。すすぎ水は典型的に、約０．０００５％〜約１％、あるいは約０．０００８％〜約０．１％、あるいは約０．００１％〜約０．０２％のナノ粒子を含有すべきである。
【０１６１】
もう１つの代替の方法は、乾燥サイクルの開始時及び／又はその途中にてスプレー器から散布された被覆組成物による食器の処理を含む。どの利益を達成することができ、そのような利益をいかに最良に入手するかを消費者が確実に知るように、処理は使用説明書に従って行うことが好ましい。
もう１つの代替の方法は、所望の利益を付与するために使用説明書に従って、外来物質（すなわち、汚れ、染み残留物、食物など）の層を除くために機械的又は化学的な手段を用いて処理された硬質表面上の透明な被覆から少なくとも一層のナノ粒子を剥ぎ取ることを含み、その際、機械的又は化学的手段とは、天候又は任意で表面の通常の使用を除外するものではない。理論に限定されずに、本方法の剥ぎ取り可能なフィルムのメカニズムを図１〜３に示す。
【０１６２】
図１〜３において、硬質表面は参照番号２０によって表される。個々のナノ粒子は参照番号２２によって表し、それによって形成される層は参照番号２４によって表す。ナノ粒子上に沈着した汚れは参照番号２６によって表す。本発明の実施形態の１つでは、かかる自動車、建物の外面又は食器表面への適用として、有効量のナノ粒子の被覆を目に見えないフィルムとして沈着し、汚れ２６が硬質表面２０に付着するのを妨げる（図１）。ナノ粒子の被覆は、利益を提供するナノ粒子シートの複数の有効な層２４から成る。風化する、洗浄する又は剥ぎ取る処理工程の間に、ナノ粒子被覆の少なくとも１枚の一番上の層２４が取り除かれ、それと共に汚れ２６を取る（図２及び３）。
【０１６３】
ＩＩＩ．製造物品
本発明はまた、所望の結果、すなわち、改善された硬質表面の濡れ及びシート形成、速乾、均一な乾燥、汚れ落し、自浄、斑点防止防止、汚れ沈着防止、さらに清潔な外観、強化された光沢、強化された色彩、表面の小さな欠陥の修復、改良された滑らかさ、曇り防止、表面摩擦の緩和、活性物質の放出、磨耗への軽減された損傷及び改善された透明性及びそれらの混合から成る改善された多目的の利益を得るために、硬質表面を正しく処理するための被覆組成物の使い方に関する説明書と関連して、包装に硬質表面被覆組成物を含む製造物品に関する。代替の製造物品は、例えば、スプレーすべき組成物の方式及び／又は量、及び本明細書の以下でさらに詳細に記載されるような被覆組成物を適用する代替方法を含む、正しく硬質表面を処理するための被覆組成物の使い方に関する説明書に関連して、噴霧ディスペンサーの中に前記組成物を含む。説明書はできるだけ簡単で明瞭であることが重要なので、絵及び／又は絵記号を使用することが望ましい。
【０１６４】
噴霧ディスペンサー
本明細書の製造物品は噴霧散布器を含む。被覆組成物は硬質表面に散布するため噴霧ディスペンサーの中に設置される。液体の液滴の噴霧を形成するための前記噴霧ディスペンサーは、当該技術分野で既知のいかなる手動操作の手段、例えば被覆組成物で小さい硬質表面積及び／又は少数の基材を処置するための制動型、ポンプ型、非エアゾール自己加圧型、及びエアゾール型噴霧手段、並びに、被覆組成物で大きい硬質表面積及び／又は多数の基材を都合良く処置するための非手動操作動力付き噴霧器であり得る。本明細書の噴霧ディスペンサーは、透明な水性の被覆組成物を実質的に形成するものは普通は包含しない。さらに小さな粒子液滴を提供することは性能を高めることが見い出された。望ましくは、ザウタ（Ｓａｕｔｅｒ）平均粒径は、約１０μｍ〜約１２０μｍ、あるいは約２０μｍ〜約１００μｍである。被覆利益は例えば、特に界面活性剤が存在する場合には小さい粒子（液滴）を提供することにより改善される。
【０１６５】
噴霧ディスペンサーはエアゾールディスペンサーであり得る。前記エアゾールディスペンサーは容器を具備し、この容器はエアゾール容器を組み立てるのに用いられているいかなる従来の物質により構造され得る。このディスペンサーは、約２０〜約１１０ｐ．ｓ．ｉ．ｇ．、あるいは約２０〜約７０ｐ．ｓ．ｉ．ｇ．の範囲内の内圧に耐えることができなくてはならない。ディスペンサーに関する１つの重要な要件は、ディスペンサーがバルブ部材を備えており、このバルブ部材により、ディスペンサーに含有される、透明で、水性の被覆組成物が、非常に微細な噴霧又は、超微粒子状の粒子又は液滴の形態において散布されることである。エアゾールディスペンサーは加圧封入容器を使用し、この容器から透明で水性の被覆組成物が特別な作動装置／バルブ部品を介して加圧下で散布される。その中に組み込むことによって、一般に噴射剤として知られるガス状成分がエアゾールディスペンサーを加圧する。一般的なエアゾール噴射剤、例えばイソブタンなどのガス状炭化水素、及びハロゲン化炭化水素を混合したものを用い得る。ハロゲン化炭化水素噴射剤、例えばクロロフルオロ炭化水素は問題の原因になるとされており、代替ではない。シクロデキストリンが存在する場合、炭化水素噴射剤は代替ではないが、それは炭化水素噴射剤がシクロデキストリン分子と錯体を形成し、それにより、臭気吸収のための非錯体型シクロデキストリン分子の利用可能性を減少するためである。代替の噴射剤は、圧縮空気、窒素、不活性ガス、二酸化炭素などである。市販のエアゾール−噴霧ディスペンサーのさらに完全な記載は、米国特許第３，４３６，７７２号（ステビンズ（Ｓｔｅｂｂｉｎｓ）、１９６９年４月８日発行）；及び同第３，６００，３２５号（カウフマン（Ｋａｕｆｍａｎ）ら、１９７１年８月１７日発行）に見られ；前記参照を双方とも参考として本明細書に組み入れる。
【０１６６】
あるいは、噴霧ディスペンサーは、自己加圧型、非エアゾール容器であることが可能であり、この容器は回旋状のライナー（内張り）及びエラストマースリーブを有する。前記自己加圧型ディスペンサーは、ライナー／スリーブ部品を含み、この部品は本質的に円筒形のエラストマースリーブ内部に、厚さ約０．０１０〜約０．０２０インチの、薄い、柔軟性のある、放射状に拡張できる回旋状のプラスチックライナーを含有する。ライナー／スリーブはかなりの量の被覆組成物を保持することができ、前記組成物を散布することができる。自己加圧型噴霧ディスペンサーのより完全な記述は米国特許番号第５，１１１，９７１号（ワイナー（Ｗｉｎｅｒ）、１９９２年５月１２日発行）、及び米国特許番号第５，２３２，１２６号（発行ワイナー（Ｗｉｎｅｒ）、１９９３年８月３日）に見出され、前記参考文献の両方を参考として本明細書に組み入れる。別の種類のエアゾール噴霧散布器は、障壁が被覆組成物を噴射剤（あるいは圧縮空気又は窒素である）から分離するものであり、米国特許番号第４，２６０，１１０号（１９８１年４月７日発行）に開示されており、参考として本明細書に組み入れる。こうしたディスペンサーはニュージャージー州イースト・ハノーバー（Ｅａｓｔ Ｈａｎｏｖｅｒ）のＥＰスプレー・システムズ（ＥＰ Ｓｐｒａｙ Ｓｙｓｔｅｍｓ）より入手できる。
【０１６７】
あるいは、噴霧ディスペンサーは非エアゾールであり、手動操作の、ポンプ噴霧ディスペンサーである。前記ポンプ噴霧ディスペンサーは、容器及びポンプ機構を含み、このポンプ機構は安定して、容器上で回転又はスナップする。容器は散布される水性の被覆組成物を含有する容器を含む。
ポンプ機構は、実質的に固定された体積のポンプチャンバーを含み、このポンプチャンバーは、その内部末端に開口部を有する。ポンプチャンバー内には、ポンプ茎部が設置され、このポンプ茎部はその末端にピストンを有しポンプチャンバー内の逆運動を防止する。ポンプ茎部は通路を有し、その外側末端には通路から通じた散布用出口があり、及びその内側には軸性注入口ポートが位置する。
【０１６８】
容器及びポンプ機構は、ポンプ噴霧ディスペンサーを作るのに使用される、いかなる従来物質により構成されることが可能であり、その従来物質には：ポリエチレン；ポリプロピレン；ポリエチレンテレフタレート；ポリエチレン、ビニルアセテート、及びゴム・エラストマーのブレンドが挙げられるが、これらに限定されない。代替容器は透明の、例えば、ポリエチレンテレフタレートから作製される。他の物質にはステンレス鋼を挙げることができる。市販の散布装置のより完全な開示は、米国特許番号第４，８９５，２７９号（シュルツ（Ｓｃｈｕｌｔｚ）、１９９０年１月２３日発行）；米国特許番号第４，７３５，３４７号（シュルツ（Ｓｃｈｕｌｔｚ）、１９８８年４月５日発行）；米国特許番号第４，２７４，５６０号（カーター（Ｃａｒｔｅｒ）、１９８１年６月２３日発行）に見られ、前記参考文献のすべてを参考として本明細書に組み入れる。
【０１６９】
あるいは、噴霧ディスペンサーは手動操作の制動型噴霧ディスペンサーである。前記制動型噴霧ディスペンサーは、容器及び制動機を含み、両方共が制動型噴霧ディスペンサーを作るのに使用される、いかなる従来物質により構成されることが可能であり、その従来物質には：ポリエチレン；ポリプロピレン；ポリアセタール、ポリカーボネート；ポリエチレンテレフタレート；ポリ塩化ビニル；ポリスチレン；ポリエチレン、ビニルアセテート、及びゴム・エラストマーの混合が挙げられるが、これらに限定されない。他の物質にはステンレス鋼、及びガラスを挙げることができる。代替容器は透明の、例えば、ポリエチレンテレフタレートから作製される。制動型噴霧ディスペンサーは噴射剤ガスを臭気吸収組成物に組み込まず、あるいは被覆組成物を形成するであろうものを包含しない。本明細書の制動型噴霧散布器は典型的に、ピストン又は折りたたみ式ベローズの手段により、被覆組成物自体の個々の量について作用するものであるが、この折りたたみ式ベローズは被覆組成物をノズルから移動させ、薄い液体の噴霧を生成する。前記制動型噴霧ディスペンサーは典型的にポンプチャンバーを有し、このポンプチャンバーはピストン又はベローズのいずれかを有し、これは前記ポンプチャンバーの体積により変化する、制動機への限られた打撃応答を通して可動できる。このポンプチャンバー又はベローズチャンバーは、散布用の製品を収集し、保持することができる。制動型噴霧チャンバーは典型的に、ノズルを通した流体の伝達及び流れを遮断するように出口点検バルブを有し、及びチャンバー内の圧力に反応する。ピストン型の制動型ディスペンサーの場合は、制動機が圧縮されると、チャンバー内の流体及びばねに作用し、流体への圧力を高める。ベローズ噴霧ディスペンサーの場合は、ベローズが圧縮されると流体への圧力が高まる。いずれの種類の制動型噴霧器の場合も流体の圧力の増加は上端の出口点検バルブを開くように作用する。上端のバルブにより製品は、渦流室を通過してノズルの外に出され、放出型を形成する。調整可能なノズルキャップは散布される流体の型を変化させるために用い得る。
【０１７０】
ピストン噴霧ディスペンサーの場合は、制動機が開放されると、ばねはピストンに元の位置に戻るように作用する。ベローズ噴霧ディスペンサーの場合は、ベローズが、ばねのように元の位置に戻るように作用する。この作用によりディスペンサー内が真空になる。応答する流体は、入り口バルブを開き製品を貯蔵槽からディスペンサー内に引き込む一方で、出口バルブを閉じるように作用する。
市販の散布装置のより完全な開示は、米国特許番号第４，０８２，２２３号（ノザワ（Ｎｏｚａｗａ）、１９７８年４月４日発行）；米国特許番号第４，１６１，２８８号（マッキンニー（ＭｃＫｉｎｎｅｙ）、１９８５年７月１７日発行）；米国特許番号第４，４３４，９１７号（サイトウ（Ｓａｉｔｏ）ら、１９８４年３月６日発行）；米国特許番号第４，８１９，８３５号（タサキ（Ｔａｓａｋｉ）、１９８９年４月１１日発行）；及び米国特許番号第５，３０３，８６７号（ピーターソン（Ｐｅｔｅｒｓｏｎ）、１９９４年４月１９日発行）に見られ、前記参考文献のすべてを参考として本明細書に組み入れる。
【０１７１】
広範囲の制動型噴霧器又は指ポンプ噴霧器は、本発明の被覆組成物と共に用いるのに好適である。これらは供給元、例えば、カルフォルニア州工業団地（Ｃｉｔｙ ｏｆ Ｉｎｄｕｓｔｒｙ）のカルマー社（Ｃａｌｍａｒ、Ｉｎｃ．）；ミズーリー州セント・ピーターズ（Ｓｔ．Ｐｅｔｅｒｓ）のＣＳＩ（コンチネンタル・スプレイヤーズ社（Ｃｏｎｔｉｎｅｎｔａｌ Ｓｐｒａｙｅｒｓ、Ｉｎｃ．））；インディアナ州エバンスビレ（Ｅｖａｎｓｖｉｌｌｅ）のベリー・プラスティックス社（Ｂｅｒｒｙ Ｐｌａｓｔｉｃｓ Ｃｏｒｐ．）、グァラ（Ｇｕａｌａ（登録商標））噴霧器の配給業者；又はイリノイ州キャリー（Ｃａｒｙ）のシークエスト・ディスペンシング（Ｓｅａｑｕｅｓｔ Ｄｉｓｐｅｎｓｉｎｇ）より容易に入手可能である。
【０１７２】
制動型噴霧器の非限定例は、微細で均一な噴霧特性、噴霧容量、及びパターン大きさのゆえにベリープラスチックス社（Ｂｅｒｒｙ Ｐｌａｓｔｉｃｓ Ｃｏｒｐ．）から入手可能なブルーインサーテッド（ｂｌｕｅ ｉｎｓｅｒｔｅｄ）グアラ（Ｇｕａｌａ）（登録商標）噴霧器、又はカルマー社（Ｃａｌｍａｒ，Ｉｎｃ）から入手可能なカルマ−（Ｃａｌｍａｒ）ＴＳ８００−１Ａ（登録商標）、ＴＳ１３００（登録商標）、及びＴＳ−８００−２（登録商標）である。代替には、先行圧縮機能、及びより微細な噴霧の特徴、及び均一散布を有する噴霧器、例えば日本のヨシノ噴霧器（Ｙｏｓｈｉｎｏ ｓｐｒａｙｅｒｓ）が挙げられる。制動型噴霧器とともにいかなる好適なビン又は容器も用いることができ、代替のビンは、シンク（Ｃｉｎｃｈ）（登録商標）ビンの形状に類似する良好な人間工学的１７ｆｌ−ｏｚ（約５００ｍｌ）のビンである。それはいかなる物質、例えば高密度ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ポリエチレンテレフタレート、ガラス又はビンを形成するいかなる他の物質より製造し得る。あるいは、それは高密度ポリエチレン又は透明なポリエチレンテレフタレートより製造される。
【０１７３】
より小さい流体のオンスサイズ（例えば１〜８オンス）については、密閉容器又は円筒形ビンと共に指ポンプを用い得る。本出願についての代替のポンプは、シークエスト・ディスペンシング（Ｓｅａｑｕｅｓｔ Ｄｉｓｐｅｎｓｉｎｇ）からの円筒形のユーロミストＩＩ（Ｅｕｒｏｍｉｓｔ ＩＩ（登録商標））である。
本明細書の製造物品はまた、非手動操作の噴霧ディスペンサーを含み得る。「非手動操作」とは、噴霧ディスペンサーは手動で作動することは可能であるが、被覆組成物を散布するのに必要な力は、別の非手動の手段により提供されることを意味する。非手動操作の噴霧器には、動力付き噴霧器、空気吸入噴霧器、液体吸入噴霧器、静電気噴霧器、及び霧吹き式噴霧器が挙げられるが、これらに限定されない。被覆組成物は硬質表面に散布するため噴霧ディスペンサーの中に設置される。
【０１７４】
動力付き噴霧器には、自蔵型動力ポンプであって水性の被覆組成物を加圧し、ノズルを通して散布し液体の液滴の噴霧を形成するものが挙げられる。動力付き噴霧器は、水性の被覆組成物を保持する貯蔵槽（例えばビン）にパイプ／チューブを用いて、直接的に又は間接的に取り付けられる。動力付き噴霧器には、遠心式又は容積移送式の設計を挙げることができるがこれらに限定されない。動力付き噴霧器は、使い捨て電池（例えば市販のアルカリ電池）又は蓄電池ユニット（市販のニッケル・カドミウム電池ユニット）のいずれかによる携帯用ＤＣ電流により動力を供給されることが好ましい。動力付き噴霧器はまた、大部分の建物で利用可能な標準ＡＣ電源により動力を供給されることも可能である。具体的な噴霧の特徴（例えば噴霧の直径及び粒径）を作り出すため、放出ノズルの設計は異なる可能性がある。異なる噴霧の特徴のため、複数の噴霧ノズルを有することも可能である。ノズルは、調整可能なノズルの覆いを含有してもしなくてもよいが、この覆いにより噴霧の特徴は代わる。
【０１７５】
市販の動力付き噴霧器の非限定例は、米国特許番号第４，８６５，２５５号（ルビソット（Ｌｕｖｉｓｏｔｔｏ）、１９８９年９月１２日発行）に開示されており、参考として本明細書に組み入れる。代替の動力付き噴霧器は供給元、例えばバージニア州ニューポート・ニューズ（Ｎｅｗｐｏｒｔ Ｎｅｗｓ）のソロ（Ｓｏｌｏ）（例えばソロ・スプレイスター（Ｓｏｌｏ Ｓｐｒａｙｓｔａｒ）（商標）充電式噴霧器、手動部品番号：ＵＳ ４６０　３９５として記載）、及びミネソタ州ミネアポリスのマルチ・スプレイヤー・システムズ（Ｍｕｌｔｉ−ｓｐｒａｙｅｒ Ｓｙｓｔｅｍｓ）（例えばモデル：スプレイ１（Ｓｐｒａｙ １））より容易に入手可能である。
【０１７６】
空気吸入噴霧器には総称的に「エア・ブラシ」として分類されるものが挙げられる。加圧された空気の流れは水性の被覆組成物を引き上げ、これをノズルから散布して、液体の噴霧を作り出す。被覆組成物は、別々のパイプ／チューブを介して供給されるか、又はより一般的には吸入噴霧器が取り付けられている瓶に含有される。
【０１７７】
市販の空気吸入噴霧器の非限定例は、米国特許番号第１，５３６，３５２号（マレイ（Ｍｕｒｒａｙ）、１９２４年４月２２日発行）；及び米国特許番号第４，２２１，３３９号（ヨシカワ（Ｙｏｓｈｉｋａｗａ）、１９８０年９月９日発行）に見られ、前記参考文献のすべてを参考として本明細書に組み入れる。空気吸入噴霧器は供給元、例えばイリノイ州フランクリン・パーク（Ｆｒａｎｋｌｉｎ Ｐａｒｋ）のバジャー・エアー・ブラシ社（Ｂａｄｇｅｒ Ａｉｒ−Ｂｒｕｓｈ Ｃｏ．）（例えばモデル番号：１５５）より、及びイリノイ州ウッドリッジ（Ｗｏｏｄｒｉｄｇｅ）のウィルトン・エアー・ブラシ・イクウィップメント（Ｗｉｌｔｏｎ Ａｉｒ Ｂｒｕｓｈ Ｅｑｕｉｐｍｅｎｔ）（例えばストック番号：４１５−４０００、４１５−４００１、４１５−４１００）より容易に入手可能である。
【０１７８】
液体吸入噴霧器は園芸用化学薬品の噴霧に広く使用されている多種多様なものの典型である。水性の被覆組成物は、ヴェンチュリ効果により作り出される吸引手段により、流体の流れの中に引き込まれる。高度な乱流が水性の被覆組成物と流体の流れ（典型的に、水）を混合し、均一な混合物／濃度を提供する。この方法により、本発明の水性濃縮被覆組成物を散布するための送達が可能であり、次いで送達流により組成物を選択した濃度に希釈する。
液体吸入噴霧器は、供給元、例えばニューヨーク州バタビア（Ｂａｔａｖｉａ）のチャピン・マニファクチャリング・ワークス（Ｃｈａｐｉｎ Ｍａｎｕｆａｃｔｕｒｉｎｇ Ｗｏｒｋｓ）（例えばモデル番号：６００６）より容易に入手可能である。
【０１７９】
静電気噴霧器は、水性被覆組成物に高電位を介してエネルギーを付与する。このエネルギーは、水性の被覆組成物を霧状にし、帯電させるように働き、微細な帯電した粒子の噴霧を作り出す。帯電した粒子が噴霧器から放出されると、それらの共通の電荷により互いに反発するようになる。これは噴霧が目標に到達する前に２つの効果を有する。第一に、噴霧の霧全体が膨張する。これは、かなり遠くの大きな領域に噴霧する場合には特に重要である。第二の効果は元の粒径の保持である。なぜなら粒子が互いに反発すると、帯電していない粒子がするように、大きな、より重い粒子へと共に集合することに抵抗するからである。これは、重力の影響を小さくし、帯電した粒子が目標に到達するのを早める。負に帯電した粒子の大部分が目標に近づくと、それらは電子を目標内部に内側に向かって押すため、目標の剥き出しの面全てが一時的に正の電荷を帯びる。結果として粒子と目標の間が引き合うことになり、これにより重力及び慣性の影響を無効にする。各粒子は目標に付着するにつれて、目標上のその点は中和され、もはや引き付けない。そのため、次の遊離粒子がすぐ隣りの点に引き付けられ、そして目標の全ての面が覆われるまでこの順番が継続する。それ故に、帯電した粒子は散布を高め、滴りを減らす。
【０１８０】
市販の静電気噴霧器の非限定例は、米国特許番号第５，２２２，６６４号（ノークス（Ｎｏａｋｅｓ）、１９９３年６月２９日発行）；米国特許番号第４，９６２，８８５号（コーフィー（Ｃｏｆｆｅｅｒ）、１９９０年１０月１６日発行）；米国特許番号第２，６９５，００２号（ミラー（Ｍｉｌｌｅｒ）、１９５４年１１月発行）；米国特許番号第５，４０５，０９０号（グリーン（Ｇｒｅｅｎｅ）、１９９５年４月１１日発行）；米国特許番号第４，７５２，０３４号（クン（Ｋｕｈｎ）、１９８８年６月２１日発行）；米国特許番号第２，９８９，２４１号（バジャー（Ｂａｄｇｅｒ）、１９６１年６月発行）に見られ、前記特許のすべてを参考として本明細書に組み入れる。静電気噴霧器は、供給元、例えば韓国のタエ・イン・テク社（Ｔａｅ Ｉｎ Ｔｅｃｈ Ｃｏ）、及びテキサス州ヒューストンのスペクトラム（Ｓｐｅｃｔｒｕｍ）より、容易に入手可能である。
【０１８１】
霧吹き式噴霧器は、水性の被覆組成物に変換器を介して超音波エネルギーを付与する。このエネルギーは、結果として水性の被覆組成物を霧状にする。多様な種類の霧吹き器には、加熱、超音波、ガス、ヴェンチュリ、及び詰め替え式霧吹き器が挙げられるが、これらに限定されない。
市販の霧吹き式噴霧器の非限定例は、米国特許番号第３，９０１，４４３号（ミツイ（Ｍｉｔｓｕｉ）、１９７５年８月２６日発行）；米国特許番号第２，８４７，２４８号（シュミット（Ｓｃｈｍｉｔｔ）、１９５８年８月発行）；米国特許番号第５，５１１，７２６（グリーンスパン（Ｇｒｅｅｎｓｐａｎ）、１９９６年４月３０日発行）号に見られ、前記特許のすべてを参考として本明細書に組み入れる。霧吹き式噴霧器は、供給元、例えばカリフォルニア州ミルピタス（Ｍｉｌｐｉｔａｓ）のＡ＆Ｄエンジニアリング社（Ａ＆Ｄ Ｅｎｇｉｎｅｅｒｉｎｇ，Ｉｎｃ．）（例えばモデルＡ＆ＤＵｎ−２３１超音波携帯噴霧器（ｕｌｔｒａｓｏｎｉｃ ｈａｎｄｙ ｎｅｂｕｌｉｚｅｒ））、及びペンシルバニア州スプリング・シティ（Ｓｐｒｉｎｇ Ｃｉｔｙ）のアミーチ社（Ａｍｉｃｉ，Ｉｎｃ．）（モデル：スワラ霧吹き器（ｓｗｉｒｌｅｒ ｎｅｂｕｌｉｚｅｒ））より、容易に入手可能である。
【０１８２】
本明細書の代替の製造物品は、水性の被覆組成物を含有する非手動操作の噴霧器、例えば電池動力付き噴霧器を含む。あるいは、製造物品は非手動操作の噴霧器、及び水性の被覆組成物の別の容器を含み、これは使用前に噴霧器に加えられ、及び／又は充填／詰め替えのため分離される。別の容器は使用する組成物、又は濃縮組成物を含有することが可能であり、この濃縮組成物は使用前に希釈されるか、及び／又は希釈する噴霧器、例えば本明細書で上に記載したように液体吸入噴霧器と共に使用される。
【０１８３】
また、上記のように別の容器は噴霧器の残りの部分と一致するような構造を有し、動作、衝撃などの後でさえも、及び未経験の消費者が取り扱った場合でも、漏れがないようにしっかりと固着する必要がある。噴霧器は望ましくはまた、取り付けシステムを有し、この取り付けシステムは、安全で、あるいは液体容器が充填された別の容器と置き換えられるように設計されている。例えば、充填された容器が流体容器に取って代わることができる。これにより、噴霧器及び容器の両方について、適切な組み合わせ及びシーリング手段が存在すれば、漏れを最小にすることを包含する、充填に伴う問題は最小になる。望ましくは、噴霧器は覆いを含有することができ、この覆いは適切な配置を確実にし、及び／又は置換する容器上に薄い壁の使用を許す。これは、再循環される及び／又は廃棄される物質の量を最小にする。パッケージのシーリング又は組み合わせシステムはネジによる閉合（噴霧器）であることが可能であり、現在の閉合を、充填された、ネジ付き容器と置き換える。ガスケットは、追加のシール安全性を提供し、漏れを最小にするため、望ましくは追加される。ガスケットは、噴霧器の閉合動作により壊れる可能性がある。これらのネジによるシーリングシステムは業界基準に基づく可能性がある。しかしながら適切な噴霧器／ビンの組み合わせが常に確実に用いられるように、規格外の寸法を有するネジによるシーリングシステムを用いることは極めて望ましい。噴霧器がその意図する目的のために用いられる場合に、この流体は散布されるはずであるから、これにより毒性である流体の使用が防止できる。
【０１８４】
別のシーリングシステムは、１以上の連結突起及び溝に基づいてもよい。こうしたシステムは一般に「差込み」システムと呼ばれる。こうしたシステムは、多種多様な構造に製造することが可能であり、従ってより確実に適切な置換流体が用いられるようにする。便宜上、ロック・システムもまた、詰め替えビンの「チャイルドプルーフ」キャップの対策を可能にするものであり得る。この「ロック及びキー」型のシステムはそのため極めて望ましい安全機能を提供する。こうしたロック及びキーのシーリングシステムの設計には、多種多様な方法がある。
しかしながら、充填及びシーリング操作が困難になり過ぎないように注意しなくてはならない。望むなら、ロック及びキーはシーリングメカニズムにとって完全である可能性がある。しかしながら、正確な再充填又は詰め替えを用いることを確実にする上で、連結部はシーリングシステムより分離されてもよい。例えば、覆い及び容器は適合性があるように設計される。こうした訳で、容器の特異な設計のみが、適切な再充填／詰め替えが用いられる確たる保証となり得る。
【０１８５】
ネジによる閉合及び差込みシステムの例は米国特許第４，７８１，３１１号、１９８８年１１月１日（選択的スナップ−回転容器結合を伴う角度で位置を合わせる制動型噴霧器（Ａｎｇｕｌａｒ Ｐｏｓｉｔｉｏｎｅｄ Ｔｒｉｇｇｅｒ Ｓｐｒａｙｅｒ ｗｉｔｈ Ｓｅｌｅｃｔｉｖｅ Ｓｎａｐ−Ｓｃｒｅｗ Ｃｏｎｔａｉｎｅｒ Ｃｏｎｎｅｃｔｉｏｎ）、クロロックス（Ｃｌｏｒｏｘ））、米国特許第５，５６０，５０５号、１９９６年１０月１日（相対的回転により共に固定される容器及び止め具部品とその使用（Ｃｏｎｔａｉｎｅｒ ａｎｄ Ｓｔｏｐｐｅｒ Ａｓｓｅｍｂｌｙ Ｌｏｃｋｅｄ Ｔｏｇｅｔｈｅｒ ｂｙ Ｒｅｌａｔｉｖｅ Ｒｏｔａｔｉｏｎ ａｎｄ Ｕｓｅ Ｔｈｅｒｅｏｆ）、セーバルＳＡ（Ｃｅｂａｌ ＳＡ））、及び米国特許第５，７２５，１３２号、１９９８年３月１０日（スナップ−固定容器結合を伴う散布器（Ｄｉｓｐｅｎｓｅｒ ｗｉｔｈ Ｓｎａｐ−Ｆｉｔ Ｃｏｎｔａｉｎｅｒ Ｃｏｎｎｅｃｔｉｏｎ）センチコ・インターナショナル（Ｃｅｎｔｉｃｏ Ｉｎｔｅｒｎａｔｉｏｎａｌ））に見出すことができる。前記特許のすべてを参考として本明細書に組み入れる。
【０１８６】
本発明はまた、消費者が確実に少なくとも有効量のナノ粒子システム及び／又は被覆組成物を適用し、所望の硬質表面の多目的利益を提供するために使用するための説明書に関連して提供される、過剰量の被覆組成物が屋外環境に放出されるのを妨げるような方式にて硬質表面又は物品全体を噴霧する及び／又はそれに霧を吹き付けるのに使用するための被覆組成物を含む製造物品にも関する。
自動食器洗浄法、例えば、予備洗浄、洗浄サイクル、すすぎサイクル、及び乾燥サイクルの様々な工程で食器のような硬質表面を処理するのに用いるための本発明のその他の被覆組成物は、望ましい硬質表面被覆成果、すなわち、改善された多目的硬質表面の濡れ及びシート形成、速乾、均一な乾燥、汚れ落し、自浄、斑点防止、汚れ沈着防止、さらに清潔な外観、強化された光沢、強化された色彩、表面の小さな欠陥の修復、改善された滑らかさ、曇り防止、表面摩擦の緩和、活性物質の放出、磨耗への軽減された損傷及び改善された透明性を得るために、正しく食器を処理するための被覆組成物の使い方に関する説明書と関連して包装されることができる。
【０１８７】
使用説明書を伴った製品
本発明は、本発明の被覆組成物の使用説明書を、被覆組成物を含有するパッケージ又は被覆組成物の販売又は使用に関連する他の広告形態とともに包含することも含む。説明書は消費製品製造又は供給企業によって典型的に使用されるいずれかの手法において包含されていてもよい。例としては被覆組成物を保持する容器に貼付されるラベル；容器に貼付されるか又は購入時に渡されるシート上での説明書き；又は広告、実演、及び／又は被覆組成物の購入若しくは使用につながるかもしれないその他の文章又は口頭による説明における説明書の提供が挙げられる。
【０１８８】
具体的に、説明書は、被覆組成物の使用、例えば、噴霧すること、浸漬すること又は擦ることが適当であれば、硬質表面又は物品を被覆するために使用する組成物の推奨量、硬質表面に適用する組成物の推奨量の記載を包含する。
本発明の被覆組成物は、あるいは製品に包含される。製品はあるいは、本発明に基づいた硬質表面被覆組成物を含み、さらに、被覆組成物が１以上の所望の硬質表面被覆の利益を硬質表面に付与するように、処理の必要な硬質表面を有効量の被覆組成物と接触させることによって硬質表面を洗濯する製品を使用するための説明書を含む。
以下の実施例は本発明の例示であり、その範囲を限定することも、制限することも意味しない。本明細書で使用されるあらゆる部、パーセンテージ及び比率は特に指示がないかぎり重量％として表される。
自動車や建物の構成成分の製造におけるような硬質表面の工業的改質のために本発明の組成物及び方法を用いることができる。
【０１８９】
（実施例）
以下は本発明のいくつかの非限定的実施例を提供する。
実施例１
米国ミシガン州サウスフィールドのＢＡＳＦコーポレーションから入手されるウレクリア（ＵＲＥＣＬＥＡＲ）（登録商標）透明塗料６８グラムを含む組成物を米国テキサス州ゴンサレスのサザンクレイプロダクツ（Ｓｏｕｔｈｅｒｎ Ｃｌａｙ Ｐｒｏｄｕｃｔｓ，Ｉｎｃ．）から入手される合成ヘクトライトである、ラポナイト（商標）のようなナノ粘土の０．１〜２５グラムと混ぜ合わせる。このような２つの成分を撹拌のもとで混合し、１５グラムのメチルイソアミルケトンメチル−２−ヘキサノンを加える。
電気塗装で下塗りした自動車車体の外板の上の極めて堅い下塗り上に濡れたものに濡れたもの（ｗｅｔ−ｏｎ−ｗｅｔ）で透明塗料組成物を噴霧する。室温にて１０分間、外板をフラッシュし、次いで、２７０°Ｆ（１３２．２０℃）にて２０分間硬化する。
【０１９０】
実施例２〜１５
本発明に基づいた液状被覆組成物は、以下のとおりであり、残部は水である：
【０１９１】
【表２】

【０１９２】
１．ナノ粘土は、例えば、サザンクレイプロダクツ（Ｓｏｕｔｈｅｒｎ Ｃｌａｙ Ｐｒｏｄｕｃｔｓ）社から入手可能なラポナイト（商標）のような入手可能な合成のヘクトライト粘土のいかなるものであることもできる。
２．ジスペラル（Ｄｉｓｐｅｒａｌ）Ｐ２（商標）はコンデア（Ｃｏｎｄｅａ）社のベーマイトアルミナである。
【０１９３】
実施例１６〜１９
以下の実施例では、硬質表面被覆組成物を水道水で製造できるようにナノ粘土及び界面活性剤で分散剤を配合しした：
【０１９４】
【表３】

【０１９５】
１．ナノ粘土は、例えば、サザンクレイプロダクツ（Ｓｏｕｔｈｅｒｎ Ｃｌａｙ Ｐｒｏｄｕｃｔｓ）社のラポナイト（商標）のような入手可能な合成のヘクトライト粘土のいかなるものであることもできる。
２．ＭＡ：ＡＡ＝４：６、ＭＷ＝１１，０００。
【０１９６】
実施例２０〜２７
残部が水であり、被覆組成物を表面に適用することができ、任意で前記被覆組成物を水で希釈して０．１％のナノ粒子の被覆組成物を達成する、本発明に基づいた液状被覆組成物は以下のとおりである：
【０１９７】
【表４】

【０１９８】
１．ナノ粘土は、例えば、サザンクレイプロダクツ（Ｓｏｕｔｈｅｒｎ Ｃｌａｙ Ｐｒｏｄｕｃｔｓ）社から入手可能なラポナイト（商標）のような入手可能な合成のヘクトライト粘土のいかなるものであることもできる。
２．ジスペラル（Ｄｉｓｐｅｒａｌ）Ｐ２（商標）はコンデア（Ｃｏｎｄｅａ）社のベーマイトアルミナである。
３．ＭＡ：ＡＡ＝４：６、ＭＷ＝１１，０００。
【０１９９】
ソロ（Ｓｏｌｏ）噴霧器を用い、０．１％のナノ粘土／０．０７５％のネオドール（Ｎｅｏｄｏｌ）９１−６界面活性剤で外板を処理し、垂直に風乾した。表１に指定した温度にて２５分間オーブンの中で外板を加熱し、次いで冷却する。加熱後の性能を評価し、外板を磨き（シーンウエットアブラシオンスクラブテスター（Ｓｈｅｅｎ Ｗｅｔ Ａｂｒａｓｉｏｎ Ｓｃｒｕｂ Ｔｅｓｔｅｒ）、５００ｇの全重量、希釈したＤＡＷＮ（登録商標）食器洗浄液溶液で飽和したスポンジ）、性能を再評価した。加熱する前、加熱した後、及び磨いた後、接触角の測定を行った。Ｃ／２°の発光体を備えたミニスキャンＸＥ（米国バージニア州レストンのハンターアソシエーツラボラトリ社（Ｈｕｎｔｅｒ Ａｓｓｏｃｉａｔｅｓ Ｌａｂｏｒａｔｏｒｙ、Ｉｎｃ．））を用いて、加熱後、外板の色（ＣＩＥ　Ｌ＊ａ＊ｂ＊色基準）を測定した。チオニンカチオン染料（５００ｐｐｍ）で一部の外板を処理して被覆組成物の寿命を視覚的に評価した。
^ａ３日間硬化した黒色の外板
結果
【０２００】
【表５】

【０２０１】
実施例２８〜２９
硬質表面上での頑固な食物の汚れ落とし効果を改善するために噴霧ビンに入れられ、スプレーオン配合として送達されることができる、本発明に基づいた液状硬質表面被覆組成物は以下のとおりである：
【０２０２】
【表６】

【０２０３】
１．ナノ粘土は、例えば、サザンクレイプロダクツ（Ｓｏｕｔｈｅｒｎ Ｃｌａｙ Ｐｒｏｄｕｃｔｓ）社のラポナイトＲＤ（商標）又はＢ（商標）のような入手可能な合成のヘクトライト粘土のいかなるものであることもできる。
２．エーテルでキャップしたポリ（オキシアルキル化）アルコールはノニオン湿潤剤として作用する。
３．残部について水を使用する。
【０２０４】
硬質表面に適用するとき、上記被覆組成物は硬質表面を改質し、前記硬質表面被覆組成物で処理されていない硬質表面と比べて、次の改善された硬質表面からなる多目的の利益：濡れ及びシート形成、速乾、均一な乾燥、汚れ落し、自浄、斑点防止、汚れ沈着防止、さらに清潔な外観、強化された光沢、強化された色彩、表面の小さな欠陥の修復、滑らかさ、曇り防止、表面摩擦の緩和、活性物質の放出、磨耗及び透明性への軽減された損傷の少なくとも１つを示す。
特定の様態では、硬質表面被覆は、透過性試験に従って測定される約７５％より上又はそれに同等の光に対する透過性を有する。すなわち、かかる態様では、少なくとも７５％の入射光線が硬質表面被覆を透過し、２５％の入射光線が硬質表面被覆を透過しない。もう１つの態様では、硬質表面被覆は、硬質表面被覆で被覆された表面が硬質表面被覆で被覆されていない表面に比べてヒトの裸眼で実質的に変化していないと見えるように透明性を有する。
【０２０５】
本発明で記載された被覆が潜在的にその他の利益を提供することも可能である。確認条件で、本明細書に記載された被覆は、スキー、及び自動車、飛行機、船などのような動いている乗り物のような動いている物品において抗力を減らすこと、並びに飛行機の翼における氷の蓄積を防ぐこと及び、流体の移動を円滑にするためにパイプの内側における屑のような沈着物の蓄積を防ぐことのような硬質表面における物質の蓄積を防ぐことにおいて潜在的に有用であると考えられている。被覆の予防的目的の非限定例の１つは、排水管洗浄液の性質で被覆組成物を利用することである。かかる組成物を排水管の中に注ぎ、管の中での沈着物の蓄積、又はさらなる蓄積を防止することができる。
【０２０６】
この詳細な説明で記載された実施形態のいかなる場合も、特に指示されない限り、積極的な硬化工程の有無にかかわらず被覆を硬質表面に適用することができる。積極的な硬化工程は、被覆に追加の耐久性を提供すると考えられているので有用であることが理解される。それが製造される硬質表面の種類であれば硬質表面の製造中又は製造後を含む硬質表面のいかなる好適な時期においても本明細書に記載された被覆を適用することができる。保護的目的、予防的目的、又はその他のいかなる目的についてもいつでも硬質表面に被覆を適用することができる。
【０２０７】
試験方法
特に指示されない限り、試験はすべて通常の実験室条件（湿度５０％及び７３°Ｆ（２３℃））で行う。
【０２０８】
被覆の耐久性の測定手順
方法：
１．清浄な表面：適用された所望の被覆を受け入れる際、４ｉｎ×１２ｉｎの自動車外板を用いる。Ｘ線蛍光（ＸＲＦ）分析を行うならば、外板を１ｉｎ×１．５ｉｎ（２．５×３．８ｃｍ）の長方形に切断し、磨き試験で使用する前に、エタノールですすいで清浄し、次いで、米国オハイオ州シンシナティのプロクター＆ギャンブルカンパニーから入手可能なＤＡＷＮ（登録商標）食器洗浄液で洗浄し、脱イオン水ですすぐ。
２．自動車の外板が完全に濡れるまで手動のポンプ型噴霧器で製品を適用し、風乾する（最低２時間）。
３．オーブンにて２５分間（所望の温度、例えば、表４に列記される温度の１つにて）加熱し、室温に冷却する。
４．接触角を測定する。
５．視機能を評価する。
６．磨き試験を行う。
７．視機能を評価する。
８．いったん外板が乾いたら接触角を測定する。
９．色素又はＸＲＦ分析を行う。
【０２０９】
自動車の外板の仕様：試験外板、下塗剤及び下塗組成物はＡＣＴラボラトリーズ社（米国ミシガン州、ヒルスデール）から入手する。その調製方法は以下のとおりである。塗りの間にフラッシュ時間を持たずに２度塗りで下塗剤を噴霧する。次いで、下塗剤を１０分間フラッシュする。２６５°Ｆ（１２９℃）（この温度は基材又は外板の温度である）にて３０分間、オーブンの中で基材を焼く。フィルム形成範囲＝０．９〜１．１ｍｉｌｓ（２２．９〜２７．９μｍ）。いったん下塗剤が乾燥したら、塗りの間に６０秒間のフラッシュを伴って下塗りを２度塗りで適用し、０．６〜０．８ｍｉｌｓ（１５．２〜２０．３μｍ）のフィルムを形成する。下塗りを２分間フラッシュした後、塗りの間に６０秒間のフラッシュを伴ってウレクリア（ＵＲＥＣＬＥＡＲ）（登録商標）透明塗料を適用し、１．９〜２．１ｍｉｌｓ（４８．３〜５３．３μｍ）のフィルムを形成する。図４に示されるように、方法のいかなる工程においても硬質表面被覆を外板に適用することができる。次いで、外板を２０分間フラッシュし、その後、最終的にオーブンにて焼く：１８０°Ｆ（８２℃）にて１０分間、次いで温度を２５分間、２７０°Ｆ（１３２℃）（基材の温度）に上げる。
【０２１０】
視覚的機能評価
外板を水平に対して９０°に保持しながら、基材を水ですすぎ、次いで基材がシート形成、幕張またはビーズ化を示すかどうかを決定するために外板を判定する。「シート形成」は均一な水のフィルムが基材を覆い、フィルムを破損することなく緩やかに乾燥する場合である。「幕張」は、水が緩やかに中央に集まり、基材からはける場合である。機能は、水が表面に対して親和性を示さず、速やかに基材から流れ去る場合である「ビーズ化」であると判断される。
【０２１１】
耐久性の測定のための磨き方法
１ガロン当り１０グレインの添加硬度（Ｃａ^２＋：Ｍｇ^２＋のモル比３：１）を持つ脱イオン水中の３０ｍＬの０．２％のＤＡＷＮ（登録商標）食器洗浄液で飽和した４〜３．２５ｉｎ×１．５ｉｎ×１．７５ｉｎ（８．２５ｃｍ×３．８ｃｍ×４．４ｃｍ）のスポンジにシーン濡れ磨耗磨きテスタ（Ｓｈｅｅｎ Ｗｅｔ Ａｂｒａｓｉｏｎ Ｓｃｒｕｂ Ｔｅｓｔｅｒ）（モデル９０３ＰＧ、英国、キングストンのシーンインスツルメンツ社（Ｓｈｅｅｎ Ｉｎｓｔｒｕｍｅｎｔｓ Ｌｔｄ．））を取り付ける。それぞれ３００ｇの担体アームに２００ｇの錘で担体アーム当り合計５００ｇを伴って１分当り３０サイクルに装置を設定する。磨きレベル：０、１０、５０、１００、５００磨き。
【０２１２】
接触角
脱イオン水（２５μＬ）をピペットで被覆された基材に載せ、角度計（日本のオリンパス光学株式会社のオリンパスＴＧＨＭ光源を取り付けた米国ニュージャージ州、マウンテンレイクのレメ・ハート社（Ｒｅｍｅ−Ｈａｒｔ Ｉｎｃ．）のＮＲＬＣ．Ａ．モデル＃１００−００１１５）を用いて接触角を測定する。３回の測定を行い、調べた各試料について平均する。
【０２１３】
色素分析
この分析には白色の表面のみを使うことができる。チオニンカチオン色素（脱イオン水中で５００ｐｐｍ）の溶液で表面を十分にすすぎ、次いで水ですすいで過剰の色素を落とす。同一種類の処理していない表面を対照として用いる。視覚評価又はハンターミニスキャン（Ｈｕｎｔｅｒ Ｍｉｎｉｓｃａｎ）ＸＥ測定によって合成ヘクトライト被覆の表面被覆率を評価することができる。
【０２１４】
Ｘ線蛍光分析
Ｘ線蛍光（ＸＲＦ）は、試料における又は試料の表面における要素の濃度を評価する非破壊的且つ非侵食的技術である。米国、マサチューセッツ州のフィリップスアナリティカル（Ｐｈｉｌｌｉｐｓ Ａｎａｌｙｔｉｃａｌ）、ＰＷ２４０４連続「４０００Ｗ」Ｘ線スペクトロメーターシステム製造番号ＤＹ７３５を用いて分析を行う。装置の設定及びＸＲＦ分析の仕様は、以下の表６で設定する。
【０２１５】
測定手順：
１）所望の基材上で既知の濃度の標準をピペッティングすることによって、装置の反応を検体濃度に関係付ける較正曲線を構築する。測定を行う前に標準をゆっくり乾燥させる。
２）表を下にして試料を試料カップに入れ、試料カップをスペクトロメーターに設置し、データ獲得手順を開始することによって標準又は試料を評価する。合成ヘクトライト被覆の場合、Ｍｇ及びＳｉの要素ラインを測定するが、Ａｌに関する要素ラインはアルミニウム酸化物被覆に用いる。
３）標準に対する較正曲線から試料の濃度を決定する。
【０２１６】
【表７】

【０２１７】
透過性試験
ＡＳＴＭ法Ｄ１００３−００を用いて透過性を測定する。透過性は、調べられる物品を通過する入射光線の量を表す比率として表現される。
【０２１８】
粘度試験
米国マサチューセッツ州、ストートンのブルックフィールドエンジニアリングラボズ社（Ｂｒｏｏｋｆｉｅｌｄ Ｅｎｇｉｎｅｅｒｉｎｇ Ｌａｂｓ）から入手可能なブルックフィールドＲＶＤＶＩＩ＋回転粘度計によってあらゆる測定を行った。推奨される方法は、以下の例外を伴う以下のようである。さらに小さな容器を用い、保護脚を外すことによって推奨手順を変える。グリセリン（１４００ｃｐ）及びオリーブ油（８０ｃｐ）の入った６００ｍｌの低い形状のグリフィン型ビーカーを用い、１００ＲＰＭにて較正を行うべきである。それに続く測定はすべて適当なスピンドルと共に１００ＲＰＭにて５０ｍｌのビーカーで行う。
主題発明の特定の実施形態を記載したが、本発明の精神及び範囲から逸脱することなく、主題発明の様々な変形形態や修正形態が可能であることは熟練技術者には明らかである。本発明の範囲内にあるこうした全ての変更については、添付の特許請求の範囲において扱うつもりである。
【図面の簡単な説明】
本明細書の結論は、本発明を形成すると見なす主題を特に指摘して明確に請求する請求項に示すが、本発明は添付図面と関連させた次の説明でさらに充分に理解されると考えられる。
【図１】その上に被覆を形成し、ナノ粒子被覆の一部を汚す数層のナノ粒子を伴った硬質表面の概略的側面図である。
【図２】ナノ粒子の一番上の層の除去が被覆上に沈着された汚れをいかにして取り除いてもよいかのみを示す図１に類似する概略的側面図である。
【図３】除去方法におけるさらなる工程を示す図１及び図２に類似する概略的側面図である。
【図４】自動車産業において使用するための透明塗料の適用方法の実施形態の１つにおける工程を示すフローチャートである。[0001]
(Cross reference with related applications)
This application claims the priority of the filing date of PCT Application No. US 00/16349 (filed June 14, 2000) and US Provisional Patent Application No. 60 / 265,059 (filed January 30, 2001). I do.
[0002]
(Field of the Invention)
The present invention relates to coatings, compositions, methods and articles of manufacture comprising or employing nanoparticle systems that confer the benefit of modifying the surface for all types of inanimate hard surface applications.
The use of nanoparticles without photoactivity allows for the creation of coatings, compositions, methods and articles of manufacture that create the benefits of versatile applications for modifying hard surfaces. Such surface modifications can provide the benefits of durable, long lasting or semi-permanent versatile applications, including the following compared to hard surfaces that have not been modified with such nanoparticle systems: Improved surface properties: wetting and sheeting, quick drying, uniform drying, de-smearing, self-cleaning, anti-stain, anti-stain, more clean appearance, enhanced gloss, enhanced color, fine surface scratches At least one of the following: repair, smoothness, anti-fog, modification of surface friction, release of active substance, and transparency (for example, in the case of glass, etc.).
[0003]
(Background of the Invention)
Providing a beneficial layer with desirable properties, limits to single-use protection, insufficient coating, roughness and / or peeling of the coating during use, or, in contrast, cannot be removed once applied (see Concomitant with developing a hard surface coating that minimizes drawbacks, such as the limitations of the surface that can be modified, surface damage and deterioration due to photoactivity, if a temporary coating is desired). There were a number of challenges.
[0004]
The current approach to solving the coating problem is through the use of surfactants, film-forming polymer coatings, clay-containing film-forming polymer coatings, and photoactive inorganic metal oxide coatings. However, film-forming polymers such as alkoxylated silicones, poly (N-vinyl-2-pyrrolidones, poly (N-vinylimidazoles, poly (ethylene oxide) and poly (lactide) diblock copolymers)) The effectiveness of wetting / sheeting is short-lived because of the poor substantivity of water, soaks during one or two rinses, exposure to elements (e.g., rain, etc.), or conditions (e.g., water in the shower) / Residues return to negative. Elevating the level of polymers is not a solution to this problem, because increasing the level of polymers may cause unacceptable residual problems on automobile surfaces, This is especially evident in residential windows, building exteriors, shower units and dishes.In the case of a coating of a film-forming polymer containing clay, Nanoparticles are rheological agents for formulation and do not themselves provide the disclosed benefits.One approach is to use a US patent entitled "Organoclay Containing Two or More Cations and One or More Organic Anions" No. 5,429,999, the preparation and use of organophilic clay gelling agents in non-aqueous systems to provide improved rheological properties in paints, inks, And other related patents include: U.S. Patent No. 05,785,749 entitled "Methods of Making Rheological Additives and Coating Compositions Incorporating It". US Patent No. 5,780,376 entitled "Organoclay Composition"; US Patent No. entitled "Organoclay Product Containing Branched Alkyl Quaternary Ammonium Ions" U.S. Pat. No. 5,739,087; U.S. Pat. No. 05,728,764 entitled "Formulations Containing Improved Organoclay Compositions"; and U.S. Pat. No. 06,036 entitled "Organoclay Compositions and Preparation Methods". 765.
[0005]
Another approach to this problem is disclosed in U.S. Pat. No. 4,597,886, entitled "Dishwashing Compositions", which reduces the formation of stains and films on cleaned objects. Discloses the inclusion of effective levels of layered clay (eg, synthetic hectorite) in enzymatic dishwashing compositions. U.S. Pat. No. 4,591,448 entitled "Dishwashing Compositions" discloses a non-enzymatic tableware with a pH reduced to 9-11 to provide reduced stains and film formation on cleaned articles. Disclosed is the use of a layered clay in a cleaning composition. See also U.S. Patent No. 4,591,449. EP 139,330 B1, entitled "Rinse Aid", uses layered clay as a rinse aid or rinse component for the aqueous rinse step in a machine dishwashing process to provide a stain prevention benefit. It is disclosed that. In the aforesaid dishwashing patent, layered clay is introduced into a machine dishwashing detergent or rinse aid as a single use application to prevent the formation of stains and films during that particular wash cycle. Such patents, unlike the present invention, do not disclose the requirement of a nanoparticle coating system that is virtually preventive. Furthermore, they do not disclose the benefits of multi-purpose applications, such as anti-staining, anti-fog, scouring, and repair of fine scratches on the surface, without additional treatment between uses.
[0006]
Zinc oxide (ZnO₂) And titanium dioxide (TiO 2)₂Photo-active metal oxides using nanoparticles such as) have severe limitations and harmful and toxic surface effects to overcome. TiO on functionalized hard surface₂The possibilities for using are limited to (1) surfaces exposed to outdoor UV levels and (2) require special surface safety precautions to protect against light-activated damage mechanisms. In addition, TiO₂Are difficult to apply to the surface and often require specialized surface treatment.
[0007]
TiO₂In the case of thin films of the following, the approach used in Japanese Patent No. 11181339A2 entitled "Hydrophilic coating composition" is to use photocatalytic titanium oxide particles having a particle size of 1 to 100 nm and tin oxide having a particle size of 1 to 100 nm. An aqueous fluid containing pH 8-12 or pH 0-5, and a coating formed on a substrate, which is irradiated with ultraviolet rays at a wavelength of 200-400 nm and shows hydrophilicity when titanium oxide as a photocatalyst is photoexcited. A room temperature configurable coating composition comprising a film is disclosed. Other related patents which disclose methods and articles for use in the above-described titanium oxide coating composition include a Japanese patent entitled "Hydrophilic Member, Method for Hydrophilizing / Maintaining Hydrophilicity of Member Surface and Hydrophilic Coating Composition". Patent No. 11172239A2; Japanese Patent No. 10297436A2 entitled "Method of Manufacturing Mirror for Vehicle with Enhancing Visibility in Rainy Weather"; Japanese Patent No. 10046759A2 entitled "Roofing with Anti-Ice and Snow Adhesion Prevention Property"; Japanese Patent No. 09056549A2; Japanese Patent No. 00128672A2 entitled "Porcelain and its manufacturing method"; Japanese Patent No. 00996800A2 entitled "Anti-fouling building material and its manufacturing method"; "Method for cleaning composite material and self-cleaning composite" Japanese Patent No. 11300303A2 entitled "Reactivity Mechanism"; Japanese Patent No. 10223731A2; Japanese Patent No. 10212809A2 entitled “Building Materials for Exterior Walls”; Japanese Patent No. 09230107A2 entitled “Anti-fogging Glass Lens and its Anti-fog Method”; and Japanese Patent entitled “Outdoor Installation Members” No. 092228072A2. In the aforementioned patent, the hydrophilic TiO₂The film can provoke light and chemical degradation of the organic primer and any rubber or plastic in contact with it, requiring specialized means of application and processing.
[0008]
U.S. Pat. No. 4,164,509 entitled "Method for Preparing Ultrafine Hydrophobic Oxide Particles" discloses a method for preparing metal oxide and / or metal oxide by chemically bonding hydrocarbon radicals to the surface of the oxide particles. A method for preparing hydrophobic ultrafine particles of silicon oxide is disclosed.
[0009]
The various properties of any hard surface, including but not limited to fiberglass, plastics, metals, glass, ceramics, wood, stone, concrete, asphalt, minerals, and painted surfaces, can be used in coating compositions, methods of use, and manufacture. Clearly, there is a continuing need to improve through articles, and one or more of the following highly desirable modified surface properties, such as improved surface wetting and sheeting, fast drying, uniform Drying, dirt removal, self-cleaning, anti-speckle, anti-stain, even cleaner appearance, enhanced gloss, enhanced color, repair of small surface defects, improved smoothness, anti-fog properties, reduced surface friction It produces a hard surface with reduced release of actives, reduced damage to abrasion and improved transparency. Only light-activated coatings (e.g., TiO.sub.2) are used so that these modified surface benefits last longer than the polymer patented approach or are more likely to empathize with consumer applications.₂There is a continuing need to be more permanent than approaches that use
[0010]
Nanoparticles have been used for a number of purposes in general coatings, but have not been used for the aforementioned benefits. One example is disclosed in U.S. Pat. No. 4,173,480 entitled "Photographic Sheets with Synthetic Hectorite Antistatic Additives as Sizing or Subbing", wherein the support of the polymer film is Coated with synthetic hectorite clay, specifically Laponite S ™. The binder is gelatin, starch or carboxymethylcellulose. The main benefit here is to impart antistatic properties to the surface. In the present invention, no binder is required to apply the nanoparticles to the surface.
Another example is disclosed in U.S. Pat. No. 4,868,048, entitled "Conductive Sheet Material with Aqueous Conductive Composition," which uses it as a coating with a non-epoxy binder. Previously, certain fractions (ie, nevolite) were removed from the synthetic hectorite. The main advantage here is to provide charge conduction to the surface. In the present invention, no binder is required to apply the nanoparticles to the surface.
[0011]
Another example is disclosed in Japanese Patent No. 8053558 A2 entitled "Anti-fogging Agricultural Synthetic Resin Film", wherein colloidal alumina, colloidal silica, anionic surfactant, organic electrolyte and The inorganic layered compound forms a film that exhibits fog resistance properties that are persistent at low and high temperatures. Another example is disclosed in Japanese Patent No. 04353438A2 entitled "Transparent Film with Excellent Drip-Proof Property and Blocking Property", which is useful for greenhouses, book covers, business card holders and the like. -Discloses a Mg-Na silicate layer. See also EP 0732287 entitled "Fogging compositions and agricultural films coated therewith".
[0012]
Another example is disclosed in U.S. Pat. No. 4,786,558 entitled "Composite Films Containing Swellable Inorganic Silicate and Antistatic Composite Films," wherein the inorganic nanoparticles are treated with various ions. To provide a composite film having an antistatic benefit that includes an expandable inorganic silicate.
Another example is disclosed in PCT Publication No. WO 99/00457 A1 entitled "Coating Agent for Reducing Wall Soiling Process", which invention is used to reduce building wall soiling processes. Related to the preparation of the system. Here, a layered silicate is disclosed as a gelling agent and is not only concerned with the benefit of reducing surface contamination.
[0013]
Another approach is disclosed in U.S. Pat. No. 5,853,809 (issued to Campbell et al.) Entitled "Scratch Resistant Transparent Coating Containing Surface Reactive Fine Particles and Method Therefor". I have. This patent is directed to a coating composition of a transparent coating comprising an outermost layer on the body of an automobile after application. Reactive inorganic microparticles are added to the coating composition to improve scratch resistance.
Another approach utilized is U.S. Patent No. 6,020,419 entitled "Transparent coating composition containing nanoscale particles and having improved scratch resistance", wherein the transparency Specific combinations of properties in the coating, such as wear and abrasion resistance, may be obtained by using nanoparticles.
[0014]
The present invention relates to materials, coatings, compositions, methods, and articles of manufacture that provide the versatile benefits of some important hard surfaces that are long-lasting or semi-permanent. The benefits of such multiple use include the following: improved surface wetting and sheeting, quick drying, uniform drying, scouring, self-cleaning, anti-spotting, anti-staining, even cleaner appearance, enhancement Enhanced gloss, enhanced color, repair of minor surface imperfections, improved smoothness, anti-fog properties, reduced surface friction, release of actives, reduced damage to abrasion, and materials, coatings, or Improved transparency (in the case of surfaces such as glass, etc.) compared to transparent surfaces not treated with anti-fog agents for coating compositions and for surfaces designed to be reflective (eg mirrors) At least one such surface, especially after such a surface has been soiled or contacted with water).
[0015]
(Summary of the Invention)
In one embodiment of the present invention, a material for coating a hard surface is provided. Materials for coating hard surfaces can include a plurality of non-photoactive nanoparticles, or can include a hard surface coating composition. Such coating compositions include: (a) an effective amount of non-photoactive nanoparticles; (b) optionally a surfactant; (c) optionally hydrophilic, hydrophobic and One or more functionalized surface molecules exhibiting properties selected from the group consisting of: a mixture of (d) optionally one or more additional components; and (e) optionally a suitable carrier medium.
In another embodiment of the present invention, comprising applying an effective amount of a material comprising non-photoactive nanoparticles to a hard surface; and actively processing the material to form a coating on the hard surface. : Provides a method of applying a substantially transparent coating to hard surfaces.
[0016]
In another embodiment of the present invention, (a) mixing the nanoparticles in a suitable carrier medium to form the coating composition; (b) optionally dispersing in a suitable carrier medium. Mixing the nanoparticles with additional components to form the coating composition; (c) optionally mixing the nanoparticles dispersed in a suitable carrier medium with a surfactant to form the coating composition. (D) mixing the nanoparticles, optionally dispersed in a suitable carrier medium, with an additive component and a surfactant to form the coating composition; (e) applying the coating composition to a hard surface (F) drying the coating composition or drying the coating composition; and (g) optionally repeating any of steps (a)-(f) as necessary. A method of using an object is disclosed.
The drying step can include air drying at ambient conditions and can include actively drying the coating composition by utilizing any known technique to accelerate the drying step. It has been found that heat drying a hard surface coating composition can generally increase the durability of the hard surface coating.
[0017]
Another embodiment of the present invention comprises a spray dispenser, a dipping vessel, a hose spray dispenser fitting, an applicator such as a textile or sponge; and (a) a coating composition, wherein the liquid, liquid Said coating composition in physical form selected from the group consisting of concentrates, gels, powders, tablets, granules and mixtures thereof; (b) optionally a source of water or deionized water; and (c) optional Providing an article of manufacture including instructions for dispensing the coating composition from the spray dispenser to the hard surface at the hard surface.
[0018]
Another embodiment of the invention provides a treated hard surface coated with a coating composition. Substrates treated with the beneficial agent materials of the present invention have better wetting and sheeting, faster drying, uniform drying, scouring, self-cleaning, spotting than substrates treated without such beneficial agent materials. Prevention, dirt deposition prevention, more clean appearance, enhanced gloss, enhanced color, repair of small surface defects, improved smoothness, anti-fog, reduced surface friction, release of active substances, abrasion to wear It shows even greater improvements in reduced damage and improved clarity.
In another embodiment of the present invention, there is provided a treated hard surface coated with a coating composition, wherein the coating composition is peelable. Substrates treated with the beneficial agent materials of the present invention are more soiled and self-cleaning than substrates treated without such beneficial agent materials after at least one effective nanoparticle layer has been stripped. It shows even greater improvements in spotting prevention, dirt deposition prevention and cleaner appearance.
[0019]
These and other objects, features and advantages will become apparent from the following detailed description, examples and appended claims.
All percentages, ratios and ratios herein are based on the weight of the product unless otherwise indicated. All documents cited herein are hereby incorporated by reference.
[0020]
(Detailed description of the invention)
Lifeless hard surface
Fiberglass surfaces include resins, polymers, reinforced fabrics and fibers. Hard surfaces made of fiberglass include, but are not limited to, bathtubs, boats, motorcycles, car bodies, canoes, airplanes, model airplanes, jet skis, sculptures, and traditional industrial molded and modeled articles Not done.
Seven basic types including polyethylene terephthalate (PET), high density polyethylene (HDPE), polyvinyl chloride (PVC), low density polyethylene (LDPE), polypropylene (PP), polystyrene (PS), polymers and mixtures thereof There are hard surface plastics. Manufacturers are not limited in the number and type of articles that can be made from plastic. Carbon fibers and graphite fibers are high-strength substances used as reinforcing agents in plastic composites. Examples of plastic articles include bottles, jars, mugs, bags, covers, pipes, furniture, containers, lids, cups, trays, aircraft fuselage and wings, spacecraft structures, and sports equipment.
[0021]
Both ferrous and non-ferrous metal surfaces are available for use with the present invention. These include aluminum, brass, bronze, chromium, copper, tin, zinc, iron, stainless steel and steel. Examples of metal surfaces include (e.g., buildings, doors, window frames, automobiles, ships, structures, and too many to mention).
There are three basic types: glass sheets, plates, and floats. Changing such basic glass types to meet the recent requirements for comfort, security, safety and architectural needs by adding chemicals or other ingredients during manufacturing and processing. Can be.
[0022]
A number of different dish surface types are available. Tableware includes glass, ceramic, plastic, wooden and metal dishes. Examples of tableware include enameled ironware, basalt, bisque, bone porcelain, cauliflower pottery, cream pottery, Delft ware, earthenware, flambe, hard porcelain, hard porcelain, jackfield, jasper, glossy ware, majolica ware, marble pattern, parian , Pattesul putty, pearl tableware, porcelain, red tableware, salt glaze, slip wear, snow porcelain, soft porcelain, spatter wear, staffordshire figurine, stoneware, tortoiseshell, and moving tableware. Kitchenware can be made from any of the above substances.
Ceramic surfaces include decorative tiles, mosaic tiles, and quarry tiles. Applications for ceramic tiles include countertops, walls, floors, ceilings and utensils.
[0023]
Other types of surfaces, such as sinks, bathtubs, and toilets, may be made of porcelain, ceramic, or other materials.
There are many types of wood surfaces available. Examples of certain types of wood include han trees, ash, poplar trees, beech, birch, bocote, bubinga, butternut, cedar, cherry, cocobolo, canary wood, cypress, ebony, hickory, ilex, rosewood, Porcupine, False acacia, Mahogany, Maple, Oak, Osage, Parawood, Indian rose, Pecan, Oyster, Poplar, Purple, Red, Rosewood, Spanish cedar, Fig, Teak, Yulinoki, Walnut, Wenji, Zebra tree, Siam Wood surfaces selected from the group consisting of persimmons. Articles made from wood include furniture, baseball bats, chairs, stools, furniture, handles, auto parts, barrels and baskets, sports and sports equipment, sleepers, veneers, flooring, and decks, siding, wooden boxes, And treated lumber, such as those used for interior finishing.
[0024]
There are three basic types of stone surfaces available-igneous, metamorphic and sedimentary. Some of these surfaces include granite, marble, slate, sandstone, serpentine, gneiss, quartzite, sandstone, limestone and natural stone. Stone is often used for building buildings, roads, walls, fireplaces and monuments. There are many types of concrete available as well. Such surfaces include unreinforced concrete, reinforced concrete, cast-in-place concrete, precast concrete, post-tension concrete, and prestressed concrete. Examples of concrete surfaces include building components, bridge components, walls, streets, curbs and gutters. Asphalt works with four types of hot mix asphalt, cold mix asphalt, glass asphalt and rubberized asphalt. Asphalt is used on road surfaces, walls, roofs and sports trucks. There are numerous mineral surfaces available. Minerals include metal ore and other natural materials that can be mined. Examples of mineral surfaces may include jewelry, furniture, building components and many others. Finally, coated and painted surfaces are also examples of hard surfaces that can be modified according to the present invention to provide the desired benefits.
[0025]
Nanoparticle system
The nanoparticle system serves the common purpose of hard surface modification, with improved wetting and sheeting, quick drying, uniform drying, scouring, self-cleaning, anti-spotting, anti-soil deposition, more clean appearance, enhanced Desired luster, enhanced color, repair of small surface imperfections, improved smoothness, anti-fog properties, reduced surface friction, release of actives, reduced damage to abrasion and improved clarity , Compositions, devices, instruments, procedures, methods, conditions, etc. that provide the versatile benefits of
[0026]
Nanoparticles, defined as particles having a diameter of about 400 nm or less, have been utilized to produce structures, coatings and devices that have new and useful properties due to the extremely small size of their particulate components. So technically enough. Nanoparticles having a particle size ranging from about 2 nm to about 400 nm can be produced economically. The size distribution of the nanoparticles of the present invention can be anywhere from about 1 nm or less to less than 400 nm, or alternatively from about 2 nm to less than about 100 nm, or alternatively from about 2 nm to less than about 50 nm. For example, the silicates that synthesize the layers can have an average particle size of about 25 nanometers, but the particle size distribution can generally vary between about 10 nm to about 40 nm. Alternatively, the nanoparticles can include crystalline or amorphous particles having a particle size from about 1 or less to about 100 nanometers, or alternatively from about 2 to about 50 nanometers. Nanotubes can include structures having a particle size of up to 1 centimeter in length, or alternatively from about 1 or less to about 50 nanometers.
[0027]
The coating composition comprises a nanoparticle; optionally, a surfactant; and optionally, one or more functionalized surfaces associated with the nanoparticle and exhibiting properties selected from the group consisting of hydrophilicity, hydrophobicity, and mixtures thereof. A transparent coating is formed on the hard surface, including the molecule; optionally, one or more additional components; and a suitable carrier medium.
[0028]
Inorganic nanoparticles generally exist as oxides, silicates, carbonates and hydroxides. Some of the layered clay minerals and inorganic metal oxides can also be examples of nanoparticles. Layered clay minerals suitable for use in the present invention include the geological classes of smectite, kaolin, illite, chlorite, attapulgite and mixed layered clays. Typical examples of specific clays belonging to this class are smectite, kaolin, illite, chlorolite, attapulgite and mixed layered clays. Smectites include, for example, montmorillonite, bentonite, pyrophyllite, hectorite, saponite, saukonite, nontronite, talc, beidellite, vorconscoite, and vermiculite. Kaolins include kaolinite, dickite, nacrite, antigorite, anauxite, halloysite, indelite and chrysotile. Illites include bravasite, muscovite, paragonite, phlogopite and biotite. Chlorites include collensite, peninite, donbasite, sudoite, pennine and clinoclaw. Attapulgites include sepiolite and polygorskite. Mixed layered clays include alvaldite and vermicritebiotite. Such variants and isomorphous substitutes for layered clay minerals offer unique applications.
[0029]
The layered clay mineral of the present invention may be a natural material or a synthetic material. One example of an embodiment of the present invention employs natural or synthetic hectorite, montmorillonite and bentonite. Another embodiment uses commercially available hectorite clay, with a typical source of commercially available hectorite being Laponite from Southern Clay Products, USA; T. Vegum Pro and Vegum F from Vanderbilt; and Barasyms, Macaroids and Propaloids from Barroid Division of National Read Comp., USA. is there.
The inorganic metal oxides of the present invention may be nanoparticles based on natural or synthetic silica or alumina. Aluminum can be found in many natural resources such as kaolinite and bauxite. The natural resources of alumina are processed by the Hall method or the Bayer method to obtain the desired and required type of alumina. Various forms of alumina are commercially available from manufacturers such as Condea in the form of Gibbsite, Diaspore, and Boehmite.
[0030]
Natural Clay-Natural clay minerals typically exist as layered silicate minerals and are not as common as amorphous minerals. Layered silicate minerals consist of SiO arranged in a two-dimensional network.₄It has a tetrahedral sheet. The 2: 1 type layered silicate mineral has a laminated structure of several to several tens of silicate sheets having a three-layer structure, in which a magnesium octahedral sheet or an aluminum octahedral sheet is two silica tetrahedrons. It is sandwiched between sheets.
The sheet of expandable layered silicate has a negative charge, which is neutralized by the presence of alkali metal cations and / or alkaline earth metal cations. Smectite or expandable mica can be dispersed in water to form a thixotropic sol. In addition, smectite clay complex variants can be formed by reaction with various cationic organic or inorganic compounds. As an example of such an organic complex, an organophilic clay into which dimethyldioctadecyl ammonium ion (quaternary ammonium ion) is introduced by cation exchange is industrially produced and used as a gelling agent for coating.
[0031]
Synthetic Clay-With proper process control, the process of producing synthetic nanoscale powders (ie, synthetic clay) yields primary particles that are actually nanoscale. However, the particles are not normally present in the form of discrete particles, but instead appear to be primarily in the form of agglomerates due to sintering of the primary particles. Because such agglomerates can reach thousands of nanometers in diameter, the desired properties associated with the nanoscale nature of the particles cannot be achieved. For example, the particles may be deflocculated by milling as described in European Patent Application A 637,616 or by dispersing in a suitable carrier medium such as water or water / alcohol and mixtures thereof.
The production of nanoscale powders such as layered hydrosilicates, layered hydrous aluminum silicates, fluorosilicates, mica-montmorillonite, hydrotalcite, lithium magnesium silicate and lithium magnesium fluorosilicate is customary. As an example of a substituted variant of lithium magnesium silicate, the hydroxyl group is partially replaced by fluorine. Lithium and magnesium may also be partially replaced by aluminum. Indeed, the lithium magnesium silicate may be isomorphously replaced by any selected from the group consisting of magnesium, aluminum, lithium, iron, chromium, zinc and mixtures thereof.
[0032]
Synthetic hectorite was first synthesized in the early 1960's and is now commercially available from Southern Clay Products, Inc. under the trade name Laponite ™. There are many grades or variants and isomorphous substitutions of Laponite ™ commercially available. Examples of commercially available hectorites are Lucentite SWN ™, Laponite S ™, Laponite XLS ™, Laponite RD ™ and Laponite RDS ™. One embodiment of the present invention uses Laponite XLS ™ with the following characteristics: Analytical (dry basis) SiO₂59.8%, MgO 27.2%, Na₂O 4.4%, Li₂O0.8%, structure H₂O 7.8%, more tetrasodium pyrophosphate (6%); specific gravity 2.53; bulk density 1.0.
[0033]
Synthetic hectorites such as Laponite RD ™ do not contain any fluorine. Isomorphous replacement of the hydroxyl group by fluorine results in a synthetic clay called sodium magnesium lithium fluorosilicate. Such sodium magnesium lithium fluorosilicate, marketed as Laponite ™ and Laponite S ™, contains approximately 5% by weight of fluoride ions. Laponite B ™ has an average particle size of about 25 nanometers in length and about 1 nanometer in thickness. Another variant, called Laponite S ™, contains about 6% tetrasodium polyphosphate as an additive.
[0034]
Laponite ™ has the formula:
[Mg_wLi_xSi₈O₂₀OH_4-yF_y]^z-
Where w = 3-6, x = 0-3, y = 0-4, z = 12-2 w-x, the overall negative lattice charge is balanced by the counterion; Na⁺, K⁺, NH₄ ⁺, Cs⁺, Li⁺, Mg⁺⁺, Ca⁺⁺, Ba⁺⁺, N (CH₃)₄ ⁺And mixtures thereof.
[0035]
Depending on the application, the use of Laponite ™ variants and isomorphous substitutes provides great flexibility in manipulating the desired properties of the coating compositions of the present invention. The individual particles of Laponite ™ are negatively charged at the surface and retain a high concentration of surface bound water. When applied to hard surfaces, the hard surfaces are hydrophilically modified and surprising and fully improved wetting and sheeting, quick drying, uniform drying, scouring, self-cleaning, anti-spotting, anti-staining, and more Clean appearance, enhanced gloss, enhanced color, repair of small surface defects, improved smoothness, anti-fog, reduced surface friction, release of actives, reduced damage to abrasion and improved Shows transparency. In addition, surfaces modified with Laponite ™ may have non-lasting “self-cleaning” properties (rinsing with water, eg, soiling through rainfall) and / or soil release benefits (surface layering through gentle mechanical action). Peel off).
[0036]
The benefits provided by Laponite ™ over hydrophilicity modification by organic polymers, whether alone or in combination with a charged modifier, are even longer lasting. For example, the benefit of preventing sheeting / staining is that for surfaces coated with current hydrophilic polymer technology, after multiple rinses for a single rinse with tap water or rain, the automotive Is maintained on the vehicle body and glass windows.
Inorganic metal oxides-Inorganic metal oxides generally fall into two groups, photoactive and non-photoactive nanoparticles. Common examples of photoactive metal oxide nanoparticles include zinc oxide and titanium oxide. The photoactive metal oxide nanoparticles can be either visible (eg, zinc oxide) or ultraviolet (TiO 2).₂) Requires activation by light from either. Zinc oxide coatings are commonly used as antibacterial or antifouling agents.
[0037]
The titanium dioxide must be rutile, anatase and amorphous titanium dioxide having a particle size of 1 to 100 nm, or 1 to 10 nm, or titanium dioxide having a particle size in the above-mentioned state in a dispersed form. Interesting industrial application range for such titanium dioxide particles: transparency due to small particle size is a particularly preferred feature of the particles, as a photoreactive UV screening agent in cosmetics, plastics, silicone resins and lacquers; French Patent No. 2,682,369 As flame retardants and to increase the refractive index of silicones and plastics; in preventing photocatalytic degradation of organic pollutants, including halogenated pollutants, in wastewater; To accelerate; as a support for novel dye solar cells, for example as described in WO 93/20569; SiO produced in the same way₂At the same time, as a component of special glass (Japanese Patent No. 10,297,436A2), it has begun to appear.
[0038]
Non-photoactive metal oxide nanoparticles do not use UV or visible light to produce the desired effect. Examples of non-photoactive metal oxide nanoparticles include silica and alumina.
Using the sol / gel method, it is possible to produce particles having an average diameter of less than 50 nm by controlling the increase in molecular weight, starting from the metal alkoxide. Such systems are used, for example, as coating compositions or as active substance precursors, as described, for example, in the Encyclopedia of Polymeric Materials (Vol. 6, 1996, pp. 4782-4792 et seq.).
[0039]
Nanoscale metal oxide sols typically comprise 10-50% of metal oxides (Si, Al, Ti, Zr, Ta, Sn, Zn) having an average particle size of 2 to about 50 nm in aqueous or organic media. It is a colloidal solution. Alumina (Al) for processing aqueous-alcoholic suspensions of metal oxide particles₂O₃), Silica (SiO₃), Titanium (TiO₂The organophilic particles of the metal oxide selected from the above) do not have pores with a diameter of less than 5 nm on the surface. It is possible to prevent such metal oxide sols from agglomerating by electrical and / or electrostatic stabilization of the particle surface. For example, prepared from an alkaline solution by an ion exchange method (e.g., Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, A23, VCH-Verlag, Weinheim, 1993, pp. 614-629). Particular mention may be made of aqueous silica sols which may be present. Such products are commercially available, for example, under the trade name Levasil (Bayer).
Boehmite alumina is a water-dispersible inorganic metal oxide having an average particle size of about 25 nanometers in length and about 2 to 4 nanometers in thickness. Such products are commercially available, for example, under the trade name Disperal P2 ™.
[0040]
The prior art disclosure has shown that it is possible to coat cellulosic materials with sols of colloidal silica. In the past, dilute aqueous solutions of colloidal silica and urea for non-slip surfaces, generally for paper products, especially for cardboard containing recycled paper fibers, have been disclosed in US Pat. No. 4,418,111 and US Pat. No. 4,452,723 to Carstens (assigned to KeyTech Corporation) The use of colloidal silica sol to coat paper to provide slip resistance is disclosed in US Pat. And U.S. Pat. Nos. 2,643,048 and 2,872,094.
Inorganic metal oxide nanoparticles offer the additional benefit that concentrated sols of inorganic metal oxides can be prepared on layered clays without gelling. This is particularly advantageous for applications where a dilution step is utilized prior to the application of the coating composition. In addition, inorganic metal oxide nanoparticles use hard water in the preparation of nanoparticle dispersions, dilution of the nanoparticle dispersion composition, and application of the nanoparticle composition when the surface contains hard water ions. Can withstand.
[0041]
Treatment of paper as disclosed in U.S. Pat. Nos. 2,883,661; 2,801,938; 2,980,558 and other patents generally to impart rigidity to the paper. In contrast, sols of colloidal silica have been used.
[0042]
Charged functionalized molecules
In the present invention, the one or more charged functionalized surface molecules may include at least two different types of functionalized surface molecules. Further, the charged functionalized surface molecule is selected from the group consisting of polymers, copolymers, surfactants and mixtures thereof. The functionalized surface molecule is Ca⁺², Mg⁺², Ba⁺², Al⁺³, Fe⁺², Fe⁺³, Cu⁺²And a mixture of polyvalent inorganic salts consisting of a mixture thereof, using a suitable anion to balance the charges.
In applications, hydrophilic modification can be enhanced through the use of Laponite ™ as a primer or primer as a two-step method, followed by treating the negatively charged surface with functionalized charged molecules. . Specifically, sequential layering of Laponite ™ and ethoxylated, quaternized oligoamines results in reduced contact angles and enhanced sheeting / wetting of the treated surface. Further, if the charged functionalized species has a lipophilic component, the laponite treated surface can be hydrophobically modified. The combination of charged functionalized molecules on the net, nanoclay, offers a new technology for tailoring the hydrophilic / lipophilic characteristics of hard surfaces.
[0043]
Similarly, hydrophilic modification can be enhanced through the use of alumina as a primer or primer as a two-step method, followed by treating the positively charged surface with functionalized charged molecules. Specifically, sequential layering of alumina and a hydrophilic anionic polymer results in sheeting / wetting enhancement of the treated surface. Furthermore, if the charged functionalized species has a lipophilic component, the alumina treated surface can be hydrophobically modified. The combination of charged functionalized molecules in addition to nets, inorganic metal oxides, offers new techniques for tailoring the hydrophilic / lipophilic characteristics of hard surfaces.
[0044]
I. Composition
If the coating is in the form of a composition, the coating composition may be in any form, for example, liquid (aqueous or non-aqueous), granules, pastes, powders, sprays, foams, tablets, gels. Granular compositions can be in "consolidated" form, and liquid compositions can be in "concentrated" form. The coating compositions of the present invention include, but are not limited to, fiberglass, plastic, metal, glass, ceramic, wood, stone, concrete, asphalt, minerals, coated surfaces, painted surfaces, and mixtures thereof. Includes compositions used on any of the suitable hard surfaces.
In one embodiment, the hard surface coating composition comprises: (a) an effective amount of non-photoactive nanoparticles; (b) optionally one or more additional components; and (c) optionally a suitable carrier medium.
[0045]
In another embodiment, the hard surface coating composition comprises: (a) an effective amount of non-photoactive nanoparticles; (b) a surfactant; (c) optionally one or more additional components; and (d) a suitable A suitable carrier medium.
In another embodiment, the hard surface coating composition comprises: (a) an effective amount of a non-photoactive nanoparticle; (b) a surfactant; (c) a hydrophilic, hydrophobic, associated with the nanoparticle surface. And one or more functionalized surface molecules exhibiting properties selected from the group consisting of: and (d) optionally one or more additional components; and (e) a suitable carrier medium.
In another embodiment, the hard surface coating composition comprises: (a) an effective amount of a non-photoactive nanoparticle; (b) a surfactant; (c) a hydrophilic, hydrophobic, associated with the nanoparticle surface. One or more functionalized surface molecules exhibiting properties selected from the group consisting of: and (d) an effective amount of photoactive nanoparticles; (e) optionally one or more additional components; and (f) Includes a suitable carrier medium.
[0046]
Alternatively, an effective amount of one or more of the above nanoparticles is included in a composition useful for coating various hard surfaces in need of treatment. As used herein, "an effective amount of one or more nanoparticles" refers to the above-described nanoparticle of the present invention required to impart a desired hard surface coating benefit in a particular composition. Refers to the amount of particles. Such effective amounts are readily ascertained by those skilled in the art and include, for example, the particular nanoparticles used, the specific composition of the hard surface coating application, the hard surface coating composition, and the liquid or dry (eg, granules, powders, etc.). ) Based on a number of factors, such as whether a composition is needed.
Effective amounts of the non-photoactive nanoparticles in the present invention, such as natural clays, synthetic clays or inorganic metal oxides, require that at least 10% of the target surface be modified to achieve the desired benefit. I do.
[0047]
The concentration of the nanoparticles in the substances or compositions described herein always ranges up to 100%. A non-limiting example of the use of nanoparticles at such high concentrations would be where the nanoparticles are applied alone in powder form to the surface to be treated.
In one non-limiting aspect of the invention, the concentration of the nanoparticles in the coating composition before applying to the hard surface is less than or equal to about 50% by weight of the coating composition, or 50% by weight of the coating composition. % (For example, less than or equal to about 20% if the coating composition is a liquid to be sprayed on a hard surface; or alternatively, less than or equal to about 0.5% or even about 0%). 0.1% or less).
[0048]
In one aspect of the invention, the coating composition is prepared by dispersing dry nanoparticles in deionized water to form a 1% concentration mixture. This is then used to deliver at least 10% and / or at least 30% and / or at least 50% and / or at least 80% and / or at least 100% of the coating over the surface, in particular a transparent coating. The mixture is applied to the surface either by spraying, dipping, smearing, wiping, or otherwise.
In another embodiment of the present invention, the coating composition is prepared by diluting the gel of nanoparticles with deionized water to form a 1% strength mixture. This mixture is then sprayed to deliver a transparent coating over at least 10% and / or at least 30% and / or at least 50% and / or at least 80% and / or at least 100% of the surface. Applying, dipping, painting, wiping, or otherwise applying to the surface.
[0049]
In another embodiment of the present invention, a 10% strength boehmite alumina (e.g., Condea Disperal P2 (TM)) coating composition is diluted with deionized water to a 0.1% strength. A coating composition is prepared by forming a mixture. Then, to deliver a coating, especially a transparent coating, covering at least 10% and / or at least 30% and / or at least 50% and / or at least 80% and / or at least 100% of said surface The mixture is applied to the surface either by spraying, dipping, smearing, wiping, or in any other manner.
In another embodiment of the present invention, a 1% strength sodium magnesium lithium fluorosilicate (e.g., Laponite B (TM) from Southern Clay Products) coating composition is diluted with deionized water to a concentration of 0.1%. The coating composition is prepared by forming a 1% strength mixture. This is then used to deliver at least 10% and / or at least 30% and / or at least 50% and / or at least 80% and / or at least 100% of the coating over the surface, in particular a transparent coating. The mixture is applied to the surface either by spraying, dipping, smearing, wiping, or otherwise.
[0050]
In another embodiment of the present invention, a 1% strength lithium magnesium sodium silicate (eg, Lucentite SWN ™ from Kobo Products) coating composition is diluted with deionized water to a 0.1% strength. A coating composition is prepared by forming a mixture. This is then used to deliver at least 10% and / or at least 30% and / or at least 50% and / or at least 80% and / or at least 100% of the coating over the surface, in particular a transparent coating. The mixture is applied to the surface either by spraying, dipping, smearing, wiping, or otherwise.
In another embodiment of the present invention, the coating composition is prepared by dispersing the dry nanoparticle powder in deionized water to form a 0.1% strength mixture. Then, to deliver a coating, especially a transparent coating, covering at least 10% and / or at least 30% and / or at least 50% and / or at least 80% and / or at least 100% of said surface The mixture is applied to the surface either by spraying, dipping, smearing, wiping, or in any other manner.
[0051]
In other embodiments, the use of deionized water is not required as the coating composition is prepared by dispersing the dried nanoparticles with a surfactant and placing the dispersion in tap water. Two non-limiting examples of such coating compositions are provided in the Examples section at the end of this description. Examples of other suitable dispersants are: poly (acryl / allyl alcohol), poly (acryl / maleic), poly (a-hydroxyacrylic acid), poly (tetramethylene-1,2-dicarboxylic acid), poly (4 -Methoxy-tetramethylene-1,2-dicarboxylic acid) -sodium tripolyphosphate, pyrophosphate, and other dispersants and builders described herein, but are not limited to. This is then used to deliver at least 10% and / or at least 30% and / or at least 50% and / or at least 80% and / or at least 100% of the coating over the surface, in particular a transparent coating. The mixture is applied to the surface either by spraying, dipping, smearing, wiping, or otherwise.
[0052]
In one non-limiting aspect, an effective amount of charged functionalized surface molecule that provides hydrophobic properties to the nanoparticle surface generally comprises from about 1% to about 100% of the nanoparticle surface or coating composition. Modify from 0.01% to about 5% by weight.
[0053]
In other embodiments, charged functionalized molecules can be used to help deliver the nanoparticles to the surface to be coated, rather than to modify the characteristics of the surface to be coated. For example, in one non-limiting embodiment, if the coating of the nanoparticles is difficult to combine with another carrier medium, or if it is difficult to apply the nanoparticles to a particular surface, the surface to be coated Surfactants can be mixed with the nanoparticles to help deliver the nanoparticles. For example, if the nanoparticles are to be used with an organic clear coating composition, it is difficult to suspend the nanoparticles in the clear coating composition or to apply a nanoparticle coating to the surface of such a clear coating composition there is a possibility. In such cases, the addition of a relatively small amount of surfactant to the nanoparticles (eg, virtually any amount of surfactant or functionalized molecule, eg, stoichiometric amount) overcomes this difficulty. Help. In such cases, the amount of charged functionalized molecules can be less than about 0.01% of the coating composition.
[0054]
Some non-limiting examples of various coatings and coating compositions in which the nanoparticles of the present invention can be used are discussed in further detail below. The coating composition may also include from about 0.001% to about 99.999% by weight of the coating composition, or alternatively from about 0.01% to about 99.99% by weight of the additive material.
As used herein, coatings and "coating compositions" refer to additive coatings, additive compositions and compositions suitable for use in immersing and / or pretreating dirty or stained hard surfaces. And manual and machine applied coatings and compositions, including articles. The coatings, coating compositions and / or methods and / or articles of manufacture of the present invention are for any use, including manufacturing, sales, factory, research, agricultural and / or domestic applications. Where a coating composition is formulated as a composition suitable for use in the enumerated methods or articles of manufacture, the coating composition of the present invention may alternatively comprise a nanoparticle comprising both an effective amount of nanoparticles and a suitable carrier medium. A particle system may be formed and optionally include one or more of: a surfactant, some one or more charged functionalized surface molecules, photoactive nanoparticles, and one or more additional components.
[0055]
The coating composition of the present invention can also be used as a detergent additive product in solid or liquid form. Such additive products are intended to complement or enhance the performance of conventional coating compositions used to clean hard surfaces, and can be added at any stage of the cleaning process, while The addition of a transparent hard surface coating composition to the surface is more effective.
The aqueous liquid coating composition according to the present invention can also be in "concentrated form", in which case the concentrated liquid, coating composition according to the present invention can be compared to a conventional liquid coating composition. And a small amount of a suitable carrier medium. Typically, the content of a suitable carrier medium in the hard surface coating composition of the concentration system is alternatively from 99.99% to 50% by weight of the coating composition.
[0056]
The aqueous liquid, coating composition according to the invention can also be in "concentrated form" which is compatible with "tap water", in which case the concentrated liquid, coating according to the invention The composition contains a smaller amount of a suitable carrier medium than conventional liquid coating compositions and dispersants. Typically, the content of a suitable carrier medium in the hard surface coating composition of the concentration system is alternatively 99.99% to 50% by weight of the coating composition. Typically, the content of dispersant in the hard surface coating composition of the concentration system is alternatively 0.001% to 10%.
The present invention includes a liquid (compatible carrier) coating composition or an aqueous liquid (compatible carrier) coating composition. The aqueous liquid coating composition may alternatively comprise, in addition to the nanoparticle system described above, from about 50% to about 99.99%, alternatively from about 80% to about 99.99%, by weight of an alcohol and / or Or a liquid carrier such as water or a suitable carrier medium.
[0057]
The aqueous liquid, coating composition of the present invention may also alternatively include one or more additional materials. As used herein, the term "additive" is selected for an aqueous liquid coating composition or is compatible with other components present in the aqueous liquid coating composition of the present invention. Means any liquid, solid or gaseous substance that is neutral.
The specific choice of additive material is easily made by considering the surface to be cleaned. Examples of suitable additive materials include U.S. Pat. Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, and 5,539,679. Nos. 686,014 and 5,646,101, surfactants, builders, bleaching agents, bleaching activators, bleaching catalysts, enzymes, enzyme stabilizer systems, chelating agents, optical brighteners, stains Release polymers, dye adhering agents, dispersants, foam inhibitors, dyes, fragrances, coloring agents, filler salts, hydrotropes, photoactivators, phosphors, conditioners, curing agents, hydrolytic surfactants, Preservatives, antioxidants, anti-wrinkle agents, bactericides, fungicides, color speckles, silvercare, rust inhibitors and / or anticorrosives, alkalinity sources, solubilizers, Carrier, processing Auxiliaries, pigments, pH control agents include, but are not limited to. Specific additional substances will be illustrated in detail below.
[0058]
If the additive is not compatible with the other components present in the aqueous liquid, coating composition of the present invention, then the incompatible additive is used until the combination of the two components is appropriate. Any suitable method of keeping the other components separately (not in contact with each other) can be used. A suitable method can be any known method such as gel cap, capsule encapsulation, tablet, physical separation and the like.
The coating compositions of the present invention include: (a) an effective amount of non-photoactive nanoparticles; (b) optionally a surfactant; (c) hydrophilic, hydrophobic and optionally associated with the nanoparticle surface. One or more functionalized surface molecules exhibiting properties selected from the group consisting of: (d) optionally an effective amount of photoactive nanoparticles; (e) optionally one or more additional components; and (f) Includes a suitable carrier medium.
[0059]
The coating compositions of the present invention can also be used as detergent additive products in liquid form for automatic dishwashers. Such additive products are intended to complement or enhance the performance of conventional coating compositions and can be added at any stage of the dishwashing process, but best results are achieved with a rinse cycle .
Furthermore, the coating composition according to the invention may be an isotropic liquid, an aqueous gel, a liquid composition with separated phases and / or a colored liquid composition.
The coating composition according to the present invention may have any suitable viscosity. The viscosity of the coating composition should be such that it can be effectively applied to the surface to be coated. Thus, for example, if the coating composition is applied to a hard surface having a sloped portion, the slope having a vertical component, the hard surface coating composition will run off the surface to which the coating composition is to be coated. It should not have such a low viscosity. Non-limiting examples of suitable viscosities are less than or equal to about 1,000 Cps at 100 rpm, including, but not limited to, 100 Cps, 40 Cps and 1 Cps (the latter being the viscosity of water). . The method for determining the viscosity of the coating composition is described in the test method section.
[0060]
The dry coating composition of the present invention comprises: (a) an effective amount of non-photoactive nanoparticles; (b) optionally a surfactant; (c) optionally hydrophilic, hydrophobic and One or more functionalized surface molecules exhibiting properties selected from the group consisting of these mixtures; (d) optionally one or more additional components; and (e) a suitable carrier medium.
The dry coating composition of the present invention can also be used as a detergent additive product in powder, granule, or tablet form for automatic dishwashers. Such additive products are intended to complement or enhance the performance of conventional coating compositions and can be added at any stage of the dishwashing process, but best results are achieved with a rinse cycle. You.
Furthermore, the coating composition according to the invention may be in the form of a powder, granules, tablets or a complex comprising a capsule.
[0061]
Suitable carrier medium
Suitable carrier media include liquids, solids and gases. One suitable carrier medium is water, which can be distilled and deionized, or tap water. Water is valuable because of its low cost, convenience, safety and compatibility. Aqueous carrier media are more common than dry, non-aqueous media, but the present invention can exist as a dry powder, granules, or in the form of a tablet or encapsulated complex.
Optionally, in addition to water, the carrier can contain a low molecular weight organic solvent that is highly soluble in water, such as, for example, ethanol, methanol, propanol, isopropanol, and the like, and mixtures thereof. Low molecular weight alcohols can dry treated hard surfaces more quickly. Any water-soluble low molecular weight solvent can comprise up to about 50%, typically from about 0.1% to about 25%, alternatively from about 2% to about 15%, or alternatively from about 50% by weight of a suitable carrier medium. It can be used at a level of about 5% to about 10% by weight. When combining high levels of solvent with a suitable carrier medium, factors that need to be considered are odor, flammability, dispersibility of the nanoparticles, and environmental impact.
[0062]
In one non-limiting embodiment, the carrier can include any known clear coating composition. U.S. Pat. No. 5,853,809 describes one non-limiting example of a clear coating composition.
In other embodiments, the carrier can be an air stream. For example, in addition to a stream of moving air through a substance or composition, air can carry nanoparticles that are not photoactive to the surface to be treated.
In other embodiments, the coating material or composition can simply be dropped onto the surface to be treated via air by gravity (one example is by sieving solid material to the surface).
[0063]
Class of functionalized surface molecules
Polymer classes and examples
Polymers and copolymers containing functionality wherein at least one segment or group of the polymer serves to anchor or enhance adsorption at the surface of the nanoparticles. Such polymers also include at least one segment or group that, when adsorbed on the nanoparticles, serves to provide the polymer with either a hydrophilic or a hydrophobic character. Note also that the tethering segment may also serve as a hydrophilicizing segment.
Examples of tethering segments or groups include: polyamines, quaternized polyamines, amino groups, quaternized amino groups, and the corresponding amine oxides; bipolar polymers; polycarboxylates; Ethers; polyhydroxylated polymers; polyphosphonates and polyphosphates; and polymeric chelators.
[0064]
Examples of segments or groups that render hydrophilic include: water-soluble polyethers; water-soluble polyhydroxylated groups or polymers, including sugars and polysaccharides; water-soluble carboxylates and polycarboxylates; carboxylate, sulfonate, sulfate , Phosphates, phosphonates and polymers thereof; water-soluble amines, quaternized compounds, amine oxides and polymers thereof; water-soluble dipolar groups and polymers thereof; water-soluble acid amides and polyamides; And water-soluble polymers and copolymers of vinylimidazole and vinylpyrrolidone.
Examples of hydrophobizing segments or groups include: alkyl, alkylene, and aryl groups, and high molecular weight aliphatic or aromatic hydrocarbons; fluorocarbons and polymers containing fluorocarbons; silicones; poly (styrene oxide) , Poly (propylene oxide), poly (butene oxide), poly (tetramethylene oxide), and hydrophobic polyethers such as poly (dodecylglycidyl ether); and polycaprolactone and poly (3-hydroxycarboxylic acid). (Acids).
[0065]
Hydrophilic surface polymer
Hexamethylenediamine with a degree of ethoxylation of 3 to 100 at each NH site; bis (hexamethylenetriamine) with a degree of ethoxylation of 3 to 100 at each NH site; tetraethylenepentane with a degree of ethoxylation of 3 to 100 at each NH site Min; MW 300-25,000, polyethyleneimine with a degree of ethoxylation of 3-100 per NH or alkoxylated with propylene or butylene oxide and fully ethoxylated to impart hydrophilicity; MW 200-25,000 MW 200-25,000, polyallylamine with a degree of ethoxylation of 2-100 per NH; quaternized with at least one nitrogen, methyl chloride, dimethyl sulfate, benzyl Chloride and ethylene or propylene acid Things and ethoxylated or alkoxylated polyamines including the analogs that have been quaternized alkylating agents such as mixtures thereof. In addition, quaternization may not be sufficient if the level of hydrophobic groups so introduced is not sufficient to render the surface of the nanoparticles onto which the polymer is adsorbed hydrophobic, such as dodecyl bromide. Sulfated, carboxylated, or phosphorylated analogs as described above having at least one of the terminal OH groups derived to introduce anionic functionality; at least one amine group being oxidized to an amine oxide Amine oxide analogs of ethoxylated or alkoxylated polyamines; ethoxylation or alkoxylation in which at least one amine group is quaternized by an agent such as chloroacetate propane sultone or allyl chloride which is subsequently sulfonated Betaine and sulfobetaine analogs of polyamines; and optionally in combination with the above .
[0066]
Polycarboxylated polyamines include: the reaction products of polyethyleneimine with maleic acid, fumaric acid or chloroacetate. These may also include ethoxylated segments. See U.S. Patent No. 5,747,440, which is incorporated by reference.
Polycarboxylates include: copolymers with polyacrylic acid and polymethacrylic acid and maleic acid; copolymers containing maleic acid, fumaric acid or maleic anhydride together with polymaleic acid and another monomer such as methyl vinyl ether or lower alkene And graft copolymers of the above polycarboxylates further comprising ethoxylated fragments such as those derived from the monomethyl ether of polyethylene glycol. The polycarboxylate polymers may also be hydrophobic, such as esters of butanol or 2-ethylhexanol, provided that the level is not sufficient to render the surface of the nanoparticles onto which the polymer adsorbs hydrophobic. May be included.
[0067]
Polyethers include: block copolymers of ethylene oxide with propylene oxide, butylene oxide, tetramethylene oxide, styrene oxide, phenylglycidyl ether, or fatty glycidyl ether; polydimethylsiloxane segment and polyoxyethylene segment; In particular, mention may be made of block silicone copolyols containing those with small siloxane segments.
For polyhydroxy materials: methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose and hydrophobically modified analogues, provided that the hydrophobic substitution is not sufficient to render the nanoparticles onto which the polymer adsorbs hydrophobic Polyvinyl acetate with sufficient hydrolysis to provide hydrophilicity; and polyvinyl, provided that the level of hydrophobic material is not sufficient to render the nanoparticles onto which the polymer adsorbs hydrophobic. Alcohol and hydrophobically modified polyvinyl alcohol.
Also included are polyphosphates such as polyphosphates and phosphonates.
[0068]
Hydrophobic surface polymer
Alkylated polyamines include: polyethyleneimines alkylated with a fatty alkylating agent such as dodecyl bromide, octadecyl bromide, oleyl chloride, dodecyl glycidyl ether and benzyl chloride or mixtures thereof; and such as methyl dodecanoate and oleyl chloride Polyethyleneimine acylated by a fatty acylating agent.
Silicones include: polydimethylsiloxanes having pendant aminopropyl or aminoethylaminopropyl groups.
Fluorinated polymers: include, as monomers, polymers containing (meth) acrylate esters of perfluorinated or highly fluorinated alkyl groups.
[0069]
Non-polymeric substance
A molecule comprising a functionality wherein at least one segment or group serves to connect or enhance adsorption on the surface of the nanoparticles. Such molecules also include at least one segment or group that, when adsorbed to the nanoparticles, helps to provide the molecule with either a hydrophilic or a hydrophobic character. Note also that the tethering segment may also serve as a hydrophilicizing segment.
Examples of tethering segments or groups that also serve as hydrophilizing segments include amino groups, quaternized amino groups, and the corresponding amine oxide groups; and dipolar groups.
Examples of hydrophobizing segments or groups include alkyl, aryl, alkaryl, and fluoroalkyl surfactants with a cationic, dipolar, semipolar, nonionic, or anionic head group.
[0070]
Examples of non-polymeric surface modifiers
Aliphatic amines and quaternaries include: ditallow dimethyl ammonium chloride; octadecyl trimethyl ammonium bromide; dioleyl amine; and benzyl tetradecyl dimethyl ammonium chloride.
Examples of fluorocarbon-based surfactants include: 1-propanaminium, 3-[[(heptadecafluorooctyl) sulfonyl] amino] -N, N, N-trimethyl-, iodide (9CI)
[0071]
Embedded image

[0072]
1-propanaminium, 3-[(8-chloro-2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1-oxooctyl ) Amino] -N, N, N-trimethyl-, methyl sulfate (9CI).
[0073]
Embedded image

[0074]
Silicone-based surfactants include: 1-propanaminium, N, N, N, -trimethyl-3- [1,3,3,3-tetramethyl-1-[(trimethylsilyl) oxy] disiloxanyl] -, Bromide (9CI).
[0075]
Embedded image

[0076]
Aliphatic zwitterionic surfactants include: 1-dodecaaminium, N- (2-hydroxy-3-sulfopropyl) -N, N-dimethyl-, internal salt (9CI).
[0077]
Embedded image

[0078]
Aliphatic amine oxides such as hexadecyldimethylamine oxide are also included. Aliphatic anionic surfactants include: sodium oleyl sulfate; potassium oleate; sodium dodecylbenzenesulfonate; oxodium tetradecyl sulfate; and disodium 2-hexadecenyl butanediate.
[0079]
Surfactant
Surfactants are an optional component of the present invention. Surfactants are inherently useful in the present coating compositions as wetting agents that facilitate the dispersion of nanoparticles on hard surfaces. When the coating composition is used to treat a hydrophobic hard surface to enhance the spray properties of the coating composition and distribute the coating composition containing the nanoparticles more evenly, or when the coating composition is a spray disperser Surfactants are included as an alternative when applied in. The diffusion of the coating composition allows it to dry faster, so that the treated material is more quickly available for use. In concentrated compositions, the surfactant facilitates the dispersion of a number of additional ingredients, such as antimicrobial actives and fragrances, in the concentrated aqueous composition. Suitable surfactants useful in the present invention are surfactants selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof. Agent.
[0080]
When a surfactant is used in the coating composition of the present invention, it typically provides from about 0.01% to about 5% by weight of the use composition, such as to provide one or more of the benefits described herein. %, Alternatively from about 0.01% to about 3%, alternatively from about 0.01% to about 0.5% by weight.
[0081]
An alternative type of surfactant is an ethoxylated surfactant, such as the addition product of ethylene oxide with aliphatic alcohols, fatty acids, aliphatic amines, and the like. Optionally, the addition products of a mixture of ethylene oxide and propylene oxide with aliphatic alcohols, fatty acids, and aliphatic amines can be used. Ethoxylated surfactants include compounds having the general formula:
R⁸-Z- (CH₂CH₂O)_sB
Where R⁸Is a primary, secondary, and branched alkylhydrocarbyl group having about 6 to about 20 carbon atoms, or about 8 to about 18, or about 10 to about 15 carbon atoms, primary, secondary, and branched Alkenyl hydrocarbyl groups and / or alkyl or alkylaryl groups selected from the group consisting of primary, secondary and branched alkyl- and alkenyl-substituted phenol hydrocarbyl groups; s is from about 2 to about 45 Or an integer from about 2 to about 20, alternatively from about 2 to about 15; B is hydrogen, carboxylate, or sulfate; and the linking group Z is -O-, -C (O) O- Or -C (O) N (R)-, and mixtures thereof, wherein R is⁸Or hydrogen.
[0082]
Nonionic surfactants are herein characterized by an HLB (hydrophilic-lipophilic balance) of 5-20, or 6-15.
[0083]
Non-limiting examples of alternative ethoxylated surfactants are:
-R⁸Is C₈~ C₁₈Or C₁₀~ C₁₄A linear, primary alcohol ethoxylate wherein s is from about 2 to about 8;
-R⁸Is C₈~ C₁₈Alkyl and / or alkenyl, such as 3-hexadecyl, 2-octadecyl, 4-epicosanyl, and 5-epicosanyl, wherein s is about 2 to about 10; a linear, secondary alcohol ethoxylate;
Alkylphenol ethoxy, wherein the alkylphenol has an alkyl or alkenyl group containing 3 to 20 carbon atoms, or 6 to 12 carbon atoms in a primary, secondary or branched configuration, and s is from about 2 to about 12 Rates;
-For example, branched alcohol ethoxylates in which the branched primary and secondary alcohols (or gelvet alcohols) available from the well-known "oxo" process or modifications thereof are ethoxylated.
[0084]
Other examples of alternative ethoxylated surfactants include R⁸Has about 12 to about 16 carbon atoms and s is about 5 to about 13; carboxylated alcohol ethoxylates, also known as ether carboxylates; PEG-5 cocomonium methosulfate, PEG-15 cocomonium chloride, PEG Ethoxylated quaternary ammonium surfactants such as -15 oleammonium chloride and bis (polyethoxyethanol) tallow ammonium hydrochloride.
Other suitable nonionic ethoxylated surfactants are ethoxylated alkylamines obtained by condensation of ethylene oxide with a hydrophobic alkylamine;⁸Has about 8 to about 22 carbon atoms and S is about 3 to about 30.
[0085]
Nonionic ethoxylated surfactants suitable for use herein are also disclosed in U.S. Pat. No. 4,565,647 (Llenado, issued January 21, 1986), Contains hydrophobic groups and polysaccharides containing from 8 to about 30 carbon atoms, alternatively from about 10 to about 16 carbon atoms, such as polyglycosides, from about 1.3 to about 10, or from about 1.3 to about 3. Alkyl polysaccharides having a hydrophilic group. Any reducing saccharide containing 5 or 6 carbon atoms can be used, such as glucose, galactose, where the galactosyl moiety may be replaced by a glucosyl moiety. Intersaccharide linkages can be formed, for example, between any position of the saccharide unit to be added and the 2-, 3-, 4-, and / or 6-position of the original saccharide unit. Alternative alkyl polyglycosides have the formula:
R²O (C_nH_2nO) t (glycosyl)_x
Where R²Is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl group contains 10 to 18, or 12 to 14 carbon atoms; 3, t is from 0 to about 10; x is from 1.3 to about 10 Glycosyl is alternatively derived from glucose.
[0086]
Another class of alternative surfactants useful in formulating the coating compositions of the present invention for solubilizing and / or dispersing silicone lubricants and / or additive-containing silicone-containing copolymers is , A silicone surfactant. Also known as silicone superwetting agent. They can be used alone and / or in combination with the alternative alkyl ethoxylate surfactants described herein above. Non-limiting examples of silicone surfactants are polyalkylene oxide polysiloxanes having a dimethylpolysiloxane hydrophobic moiety and one or more hydrophilic polyalkylene side chains and having the general formula:
R¹− (CH₃)₂SiO-[(CH-₃)₂SiO]_a-[(CH₃) (R¹) SiO]_b-Si (CH₃)₂-R¹
Wherein, alternatively, a + b is from about 1 to about 50;¹Are each the same or different and are selected from the group consisting of methyl and poly (ethylene oxide / propylene oxide) copolymers having the general formula:
− (CH₂)_nO (C₂H₄O)_c(C₃H₆O)_dR²
Wherein n is 3 or 4; the sum of c (of all polyalkyleneoxy side groups) is 1 to about 100, or about 6 to about 100; the sum of d is 0 to about 14; Is 0; the sum of c + d is about 5 to about 150, or about 9 to about 100;²Are the same or different and are selected from the group consisting of hydrogen, alkyl groups having 1-4 carbon atoms, and acetyl groups, or hydrogen and methyl groups. Each polyalkylene oxide polysiloxane has at least one R which is a poly (ethylene oxide / propylene oxide) copolymer group.¹Having a group.
[0087]
A non-limiting example of this type of surfactant is Silwet® surfactant, available from OSi Specialties, Inc. (Danbury, Conn.). Ethyleneoxy (C₂H₄Representative Silwet surfactants containing only the O) group are as follows:
[0088]
[Table 1]

[0089]
Polyalkyleneoxy group (R¹)) Is less than or equal to about 10,000. Alternatively, the molecular weight of the polyalkyleneoxy group is less than or equal to about 8,000, and most preferably ranges from about 300 to about 5,000. Thus, the values of c and d can be numbers that give a molecular weight in these ranges. However, the polyether chains (R¹) In the ethyleneoxy unit (-C₂H₄The number of O) must be sufficient to render the polyalkylene oxide polysiloxane water-dispersible or water-soluble. When propyleneoxy groups are present on the polyalkyleneoxy chain, they may be randomly distributed in the chain or may be present as blocks. A surfactant having no ethyleneoxy group and containing only a propyleneoxy group is not preferred. Alternative silwet surfactants are L-77, L-7280, L-5550, L-7280, L7608, L7607, and mixtures thereof.
[0090]
Another non-limiting example of this type of surfactant is a silicone superwetting agent available from Dow Corning, as a silicone superwetting agent such as silicone glycol copolymers (eg, Q2-5211 and Q2-5212). Sold.
[0091]
Other useful silicone surfactants are those having a hydrophobic moiety and a hydrophilic ionic group including, for example, anionic, cationic, and amphoteric groups. Non-limiting examples of anionic silicone surfactants are disclosed in U.S. Patent Nos. 4,717,498; 4,960,845; 5,149,765 and 5,296,434, respectively. Such as silicone sulfosuccinates, silicone sulfates, silicone phosphates, silicone carboxylate, and mixtures thereof. Non-limiting examples of cationic silicone surfactants include silicone alkyl quaternaries as disclosed in U.S. Patent Nos. 5,098,979; 5,135,294 and 5,196,499, respectively. (Quaternary ammonium), silicone amide quaternary, silicone imidazoline quaternary, and mixtures thereof. Non-limiting examples of amphoteric silicone surfactants include the silicone betaines and silicone aminopros disclosed in U.S. Patent Nos. 4,654,161; 5,073,619 and 5,237,035, respectively. Prionates, silicone phosphobetaines, and mixtures thereof. All of these patents are incorporated herein by reference.
[0092]
The coating composition of the present invention to be used in an automatic dishwashing cycle can be used with common detergents or can be used as a rinse aid in a rinsing or drying cycle. The coating composition according to the invention comprises a nanoparticle system and optionally a surfactant or a surfactant system, wherein the surfactant is nonionic and / or anionic and / or cationic and / or amphoteric and / or Or dipolar and / or semipolar nonionic surfactants.
The surfactant is typically present at a level from about 0.01% to about 5% by weight. Yet another level of incorporation is from about 0.01% to about 3%, most preferably 0.01% to 0.5% by weight of the coating composition according to the present invention.
[0093]
The surfactant may alternatively be formulated to be compatible with the nanoparticle system present in the coating composition, a suitable carrier medium and any additional ingredients.
Examples of suitable nonionic, anionic, cationic, amphoteric, zwitterionic and semipolar nonionic surfactants are disclosed in U.S. Patent Nos. 5,707,950 and 5,576,282 and are incorporated by reference. Incorporated herein.
[0094]
Another non-limiting example of a nonionic surfactant is a polyhydroxy fatty acid amide surfactant of the formula:
R²-C (O) -N (R¹) -Z,
Where R¹Is H or C¹ ₁~₄A hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof;²Is C₅~₃₁And Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl having at least three hydroxyls directly attached to the chain, or an alkoxylated derivative thereof. Alternatively, R¹Is methyl and R²Is linear C₁₁~_FifteenAlkyl or C₁₆~₁₈Wherein Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose in a reductive amination reaction.
[0095]
Alternatively, anionic surfactants include alkyl alkoxylated sulfate surfactants, which have the formula RO (A)_mA water-soluble salt or acid of SO3M, wherein R is C₁₀~ C₂₄Alkyl component, or C₁₂~ C₂₀Alkyl or hydroxyalkyl, or C₁₂~ C₁₈Unsubstituted C with alkyl or hydroxyalkyl₁₀~ C₂₄An alkyl or hydroxyalkyl group, where A is an ethoxy or propoxy unit, m is greater than 0, typically about 0.5 to about 6, or about 0.5 to about 3, and M is H or a metal cation ( For example, cations which can be sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cations. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates have been considered herein.
[0096]
When included therein, the coating compositions of the present invention typically comprise from about 0.01% to about 5%, alternatively from about 0.01% to about 3%, by weight of such anionic surfactant. including.
An alternative cationic surfactant is a water-soluble quaternary ammonium compound having the formula useful in the present composition:
R₁R₂R₃R₄N⁺X⁻
Where R₁Is C₈~ C₁₆And R is₂, R₃And R₄Are each independently C₁~ C₄Alkyl, C₁~ C₄Of hydroxyalkyl, benzyl, and-(C₂H₄₀)_xH, wherein x has a value of 2 to 5, and X is an anion. R not more than 1₂, R₃Or R₄Should be benzyl.
[0097]
When included therein, the coating compositions of the invention typically comprise from 0.01% to about 15%, alternatively from about 0.01% to about 3%, by weight of such cationic surfactants. .
When included therein, the coating compositions of the present invention typically comprise from 0.01% to about 15%, alternatively from about 0.01% to about 3%, by weight of such amphoteric surfactants. .
When included therein, the coating compositions of the present invention typically comprise from about 0.01% to about 15%, alternatively from about 0.01% to about 5%, by weight of such a zwitterionic surfactant. including.
[0098]
When included therein, the coating compositions of the present invention typically comprise from about 0.01% to about 15%, alternatively from about 0.01% to about 5%, by weight of such semipolar nonionic surfactants. Agent.
The detergent composition of the present invention may further include a co-surfactant selected from the group of primary amines or tertiary amines.
Primary amines suitable for use herein include those of the formula R₁NH₂Amines based on₁Is C₆~ C₁₂Or C₆~ C₁₀Alkyl chain or C₄X (CH_{2) n}Wherein X is —O—, —C (O) NH— or —NH—;₄Is C₆~ C₁₂The alkyl chain n is between 1 and 5, alternatively 3. R₁The alkyl chain of can be straight or branched and can have up to 12 or less than 5 ethylene oxide moieties.
[0099]
Alternative amines according to the above formula herein are n-alkylamines. Suitable amines for use herein can be selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other alternative primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl-oxypropylamine, laurylamidopropylamine and amidopropylamine.
Tertiary amines suitable for use herein include those of the formula R₁R₂R₃Tertiary amines having N, wherein R is₁And R₂Is C₁~ C₈An alkyl chain of
[0100]
Embedded image

[0101]
R₃But C₆~ C₁₂Or C₆~ C₁₀Or any of the alkyl chains of R₃Is R₄X (CH_{2) n}Wherein X is -O-, -C (O) NH- or -NH-, and R₄Is C₄~ C₁₂And n is between 1 and 5, or between 2 and 3, R₅Is H or C₁~ C₂And x is 1-6.
R₃And R₄Can be linear or branched; R₃Can have up to 12 or less than 5 ethylene oxide moieties.
An alternative tertiary amine is R₁R₂R₃N, where R₁Is C₆~ C₁₂An alkyl chain of₂And R₃Is C₁~ C₃Is an alkyl, or
[0102]
Embedded image

[0103]
Where R₅Is H or CH₃And x = 1 to 2.
Alternatives are amidoamines of the formula:
[0104]
Embedded image

[0105]
Where R₁Is C₆~ C₁₂N is 2-4, or n is 3; R₂And R₃Is C₁~ C₄It is.
Alternative amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C8-10 oxypropylamine, Ncoco 1-3 diaminopropane, coconut alkyldimethylamine, lauryl Dimethylamine, laurylbis (hydroxyethyl) amine, cocobis (hydroxyethyl) amine, 2 mole propoxylated lauryl amine, 2 mole propoxylated octylamine, lauramidopropyldimethylamine, C8-10 amidopropyldimethyl Amines and C10 amidopropyldimethylamine.
[0106]
Alternative amines for use in the coating compositions herein are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especially preferred are n-dodecyldimethylamine and bishydroxyethyl coconut alkylamine and oleylamine 7-fold ethoxylated, laurylamidopropylamine and cocoamidopropylamine.
[0107]
Alternative additives
Amino carboxylate chelating agent
For example, chelating agents such as ethylenediaminetetraacetic acid (EDTA), hydroxyethylene-diaminetriacetic acid, diethylenetriaminepentaacetic acid, and other aminocarboxylate chelators, and mixtures thereof, and salts thereof, and mixtures thereof. Can optionally be used to enhance the effectiveness of antimicrobial and preservatives against Gram-negative bacteria, especially Pseudomonas species. Sensitivity to EDTA and other aminocarboxylate chelators is primarily a feature of the genus Pseudomonas, but other bacterial genera also have high sensitivity to chelators, including Achromobacter, Alcaligenes, Azotobacter, Escherichia, Salmonella, Spirylum, and Vibrio. Other groups of microorganisms, including fungi and yeast, also show high sensitivity to these chelating agents. In addition, aminocarboxylate chelators can help, for example, maintain product clarity, protect aroma and fragrance components, and prevent rancidity and odor.
[0108]
These aminocarboxylate chelators may not themselves be effective biocides, but function as enhancers to improve the performance of other antimicrobial / preservatives of the coating compositions of the present invention. I do. Aminocarboxylate chelators enhance the performance of many cation, anion, and nonionic antimicrobial / preservatives, phenolic compounds, and isothiazolinones used as antimicrobial / preservatives in the coating compositions of the present invention. can do. Non-limiting examples of cationic antimicrobial agents / preservatives that are enhanced by aminocarboxylate chelators in solution include chlorhexidine salts (including digluconate, diacetate, and dihydrochloride salts), and also Davisil. (Dowicil) 200, Dowiside Q, also known as Preventol D1, Quaternium-15, benzalkonium chloride, cetrimonium chloride, myristalkonium chloride, cetylpyridinium chloride. And laurylpyridinium chloride. Non-limiting examples of useful anionic antimicrobial / preservatives that are enhanced by aminocarboxylate chelators are sorbic acid and potassium sorbate. Non-limiting examples of useful nonionic antimicrobial / preservatives that are enhanced by aminocarboxylate chelators include DMDM hydantoin, phenethyl alcohol, monolaurin, imidazolidinyl urea, and bronopol (2-bromo-2-nitropropane-1). , 3, -diol).
[0109]
Examples of useful phenolic antimicrobial / preservatives that are enhanced by these chelating agents include chloroxylenol, phenol, t-butylhydroxyanisole, salicylic acid, resorcinol, and sodium ortho-phenylphenate (sodium). o-phenyl phenate). Non-limiting examples of isothiazolinone antimicrobial agents / preservatives that are enhanced by aminocarboxylate chelators are Kathon, Proxel and Promexal.
The optional chelating agent will typically provide from about 0.01% to about 0.3%, alternatively from about 0.02% to about 0% by weight of the use composition to provide an antibacterial effect to the present invention. At a concentration of 0.1% by weight in the coating composition of the present invention.
[0110]
A free, uncomplexed aminocarboxylate chelator is required to enhance the effectiveness of the antimicrobial agent. Thus, in the presence of alkaline earths (especially calcium and magnesium) and transition metals (iron, manganese, copper, and others), no free chelating agent is available and no antibacterial enhancement is seen. Free, uncomplexed, which acts as an antibacterial / preservative enhancer when the hardness of the water is high or when transition metals are utilized, or when the aesthetics of the product require special chelating agent concentrations. Higher concentrations may be required to suit the availability of the type of aminocarboxylate chelator.
[0111]
Other optional ingredients
The coating composition of the present invention comprises an odor control additive, a chelating agent, an antistatic agent, and a moth repellent, a coloring agent, a bluing agent, an antioxidant, and a mixture thereof, in addition to the cyclic silicone molecule. Can be optionally contained. These optional components exclude the other components specifically described previously. By incorporating odor control additives, the ability of cyclodextrins to control odors can be increased, as well as the range of odor types and molecular sizes that can be controlled. Such materials include, but are not limited to, for example, metal salts, zeolites, water-soluble bicarbonates, antimicrobial preservatives, UV absorbers, and mixtures thereof.
[0112]
Antimicrobial preservative
Optionally, but alternatively, an antimicrobial preservative, or a solubilizing, water-soluble, antimicrobial preservative, can be added to the coating composition of the present invention to protect the composition. Microbial growth in the coating composition can lead to storage stability problems of the hard surface coating solution for any length of time. Due to contamination by certain microorganisms and the subsequent growth of bacteria, the solution becomes unsightly and / or malodorous. Bacterial growth on hard surfaces is highly undesirable when it occurs, or antimicrobial preservatives, or bacteria, to increase the storage stability of transparent, aqueous-containing hard surface coating compositions. It is highly preferred to include a soluble, water-soluble, antimicrobial preservative effective to inhibit and / or regulate the growth of spores.
[0113]
It is preferred to use a broad spectrum preservative, for example, a preservative effective against both bacteria (both Gram negative and Gram positive) and mold. Preservatives with a limited spectrum, such as preservatives that are only effective against a single group of microorganisms, such as mold, are broad-spectrum preservatives or other spectrum-limited preservatives that have excellent and / or complementary activity. It may be used in combination with a preservative. Mixtures of broad spectrum preservatives may also be used. If a particular group of contaminating microorganisms is problematic (such as Gram-negative), aminocarboxylate chelators, alone or as enhancers, may be used with other preservatives. For example, these chelating agents, including ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and other aminocarboxylate chelators, and mixtures thereof, and salts thereof, and mixtures thereof, Increase the effectiveness of preservatives against gram-negative bacteria, especially Pseudomonas.
[0114]
Antimicrobial preservatives useful in the present invention include bactericidal compounds, ie, microbicides, or biostatic compounds, ie, substances that inhibit and / or inhibit the growth of microorganisms. Suitable preservatives are described in U.S. Patent Nos. 5,534,165; 5,578,563; 5,663,134; 5,668,097; 5,670,475; No. 5,714,137 (Trinh et al., Issued July 9, 1996; issued November 26, 1996, issued September 2, 1997; issued September 16, 1997; September 1997, respectively). Issued on February 23, and issued on February 3, 1998), all of which are incorporated herein by reference. A number of antimicrobial preservatives are provided herein in the Antimicrobial Actives section provided above. Although water-insoluble antimicrobial preservatives such as parabens and triclosan are useful in the coating compositions of the present invention, such preservatives as surfactants and / or cyclodextrins can be effectively distributed into the liquid composition. Requires the use of suitable solubilizers, emulsifiers, dispersants and the like. Alternative antimicrobial preservatives are water-soluble and effective at low concentrations. Water-soluble preservatives useful in the present invention are soluble in at least about 0.3 g of water in 100 ml of water, ie, greater than about 0.3% at room temperature or greater than about 0.5% at room temperature. It is a preservative having solubility in water.
[0115]
The water-soluble antibacterial preservative of the present invention is included in an effective amount. The term "effective amount" as defined herein means a concentration sufficient to prevent spoilage or prevent the growth of inappropriately added microorganisms for a specific period of time. In other words, preservatives are not used to kill microorganisms on the surface to which the coating composition adheres, to remove odors generated by the microorganisms. Instead, it has been used to prevent spoilage of hard surface coating compositions to increase the shelf life of the coating composition. An alternative concentration of preservative is from about 0.0001% to about 0.5%, alternatively from about 0.0002% to about 0.2%, alternatively from about 0.0003% by weight of the use composition.約 about 0.1% by weight.
[0116]
The preservative can be any organic preservative substance that will not impair the appearance of the hard surface, eg, will not cause discoloration, coloration, or bleaching. Alternative water-soluble preservatives include organic sulfur compounds, halogen compounds, cyclic organic nitrogen compounds, low molecular weight aldehydes, quaternary ammonium compounds, dehydroacetic acid, phenyl compounds, and phenol compounds, and mixtures thereof. It is.
The preservatives of the present invention can be used as a mixture to control a wide range of microorganisms.
The bacteriostatic effect is to increase the pH of the coating composition in an aqueous composition by the pH of an acid, eg, less than about pH 4, or less than about pH 3, or the pH of a base, eg, greater than about pH 10, or greater than about pH 11. It may be obtained by adjusting.
[0117]
UV absorber
Without being limited by theory, UV absorbers work by protecting coatings deposited on hard surfaces from exposure to UV. It is known that UV light initiates the autoxidation process, and UV absorbers adhere to hard surfaces to block UV light from hard surfaces and unsaturated fatty substances, thereby preventing the initiation of autoxidation. Can be hindered.
[0118]
Oxidation stabilizer
Oxidation stabilizers can be present in the coating compositions of the present invention and act as scavengers in the oxidation process, preventing and / or terminating autoxidation, or by reversing oxidation and also reversing yellowing. Prevents yellowing. As used herein, the term "oxidation stabilizer" includes antioxidants and reducing agents. These agents may be present in antioxidants at concentrations from 0% to about 2%, alternatively from about 0.01% to about 0.2%, alternatively from about 0.035% to about 0.1%, and / or as reducing agents. Is present at a concentration of about 0.01% to about 0.2%.
[0119]
Examples of antioxidants that may be added to the coating compositions and processes of the present invention include ascorbic acid, a mixture of ascorbic acid palmitate, and propyl gallate, and include Eastman Chemical Products, Eastman Chemical Products, Inc. Inc.) under the tradenames Tenox® PG and Tenox® S-1; BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), And mixtures of propyl gallate and citric acid, available from Eastman Chemical Products, Inc. under the trade name Tenox®-6; butylated hydride. Loxytoluene, available from UOP Process Division under the tradename Sustain® BHT; t-butylhydroquinone, including Eastman Chemical Products (Eastman). Available from Chemical Products, Inc. under the trade name Tenox® TBHQ; includes natural tocopherols, trade name Tenox from Eastman Chemical Products, Inc. (Tenox®) GT-1 / GT-2; and butylated hydroxyanisole; -Products Company (. Eastman Chemical Products, Inc) be from the BHA; long chain ester (C₈~ C₂₂) Gallic acid, such as dodecyl gallate; Irganox® 1010; Irganox® 1035; Irganox® B1171; Irganox. Irganox® 3114; Irganox® 3125; and mixtures thereof, or Irganox® 3125; Irganox® 3125; Irganox® 3125; Irganox® 3125; and Irganox® 3125; Irganox® 3125; Nox (Irganox®) 1425; Irganox® 3114; and mixtures thereof, or Irganox® 3125. These include alone or by mixing with citric acid and / or other chelating agents, such as isopropyl citrate, the chemical name 1-hydroxyethylidene-1, from Monsanto. Dequest (R) 2010 available as 1-diphosphonic acid (etidronic acid), and Tiron available as the chemical name 4,5-dihydroxy-m-benzene-sulfonic acid / sodium salt from Kodak. (Tiron® and DTPA® available under the chemical name diethylenetriaminepentaacetic acid from Aldrich).
An oxidation stabilizer can be added at any point in the process. These ensure good odor stability under long-term storage conditions.
[0120]
Colorant
Colorants, dyes, and bluing agents can optionally be added to the coating composition for visual appeal and performance impression. If a colorant is used, it is used at a very low concentration to avoid staining the hard surface. Alternative colorants for use in the present compositions are highly water-soluble dyes, such as Liquitint® dyes, available from Milliken Chemical Co. Non-limiting examples of suitable dyes include Liquidint Blue HP (R), Liquidint Blue 65 (R), Liquidin Patent Blue (R). ), Liquitint Royal Blue (registered trademark), Liquitint Experimental Yellow 8949-43 (Liquitint Experimental Yellow 8949-43 (registered trademark)), Liquitint Green HMC (Liquitin GMC) Trademark)), Liquitint Yellow II (registered trademark), and mixtures thereof. , Liquitint Blue HP (registered trademark), Liquitint Blue 65 (registered trademark), Liquitint Patent Blue (registered trademark), and Liquitint Royal Blue (registered trademark). Liquidit Royal Blue (registered trademark)), Liquidint Expermental Yellow 8949-43 (Liquitint Experimental Yellow 8949-43 (registered trademark)), and a mixture thereof.
[0121]
builder
The coating composition according to the invention can further comprise a builder or builder system, in particular for a coating composition. Materials such as aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenyl-succinic acids and fatty acids, such as ethylenediaminetetraacetic acid, diethylenetriaminepentamethyleneacetic acid, such as aminopolyphosphonates, especially ethylenediaminetetramethylene Any conventional builder system including sequestering agents such as phosphonic acid and diethylenetriaminepentamethylenephosphonic acid is suitable for use herein. Phosphate builders can also be used herein. The present invention can include suitable builders or detersive salts. Detergent salt / builder concentrations can vary widely depending on the end use of the coating composition and the desired physical form. When present, the coating composition typically comprises at least about 1% by weight of builder, more typically about 10% to about 80%, even more typically about 15% to about 50% by weight of builder. including. However, it does not mean that lower or higher concentrations are excluded.
[0122]
Inorganic or phosphorus-containing detersive salts include polyphosphates (e.g., tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates ( (Including but not limited to, bicarbonates and sesquicarbonates), sulfates, and alkali metal, ammonium and alkanol ammonium salts of aluminosilicates. However, some areas may require non-phosphate salts. Importantly, even in the presence of so-called "weak" builders such as citrate (compared to phosphate), and in so-called "under-promotion" situations that can occur with zeolites or layered silicate builders, Surprisingly, the coating compositions herein function well.
[0123]
Organic detergency builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to a compound having multiple carboxylate groups, or at least three carboxylate groups. The polycarboxylate builder can generally be added to the coating composition in an acidic form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metal salts such as sodium, potassium, and lithium, or alkanolammonium salts are alternatives.
Suitable silicate builders, carbonate salts, aluminosilicate builders, polycarboxylate builders, citrate builders, 3,3-dicarboxy-4-oxa-1,6-hexanedioate builders and U.S. Pat. No. 4,566,984 Examples of related compounds, succinic acid builders, phosphorus-based builders and fatty acids disclosed in US Pat. No. 5,576,282 and US Pat. No. 5,728,671 are disclosed in US Pat. No. 5,707,950.
[0124]
Additional suitable builders can be inorganic ion exchange materials, generally inorganic hydrated aluminosilicate materials, and more particularly hydrated synthetic zeolites such as hydrated zeolites A, X, B, HS or MAP.
[0125]
Specific polycarboxylates suitable for the present invention include lactic acid, glycolic acid and ethers thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing one carboxyl group including derivatives. Polycarboxylates containing two carboxyl groups include succinic acid, malonic acid, (ethylenedioxy) diacetate, maleic acid, diglycolic acid, tartaric acid, tartronic acid and water-soluble salts of fumaric acid, The ether carboxylates described in Offenlegenschrift 2,446,686 and 2,446,687 and U.S. Pat. No. 3,935,257 and in Belgian Patent 840,623. And sulfinylcarboxylates. Polycarboxylates containing three carboxy groups include, among others, water-soluble citrates, aconitrates and citraconates, and succinate derivatives such as carboxymethyloxysuccinate described in GB 1,379,241. Oxypolycarboxylates such as lactoxysuccinate described in Dutch Patent 72058073 and 2-oxa-1,1,3-propanetricarboxylate described in British Patent 1,387,447 Substances.
[0126]
Polycarboxylates containing four carboxy groups include oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, 1,1,1 as disclosed in GB 1,261,829. Examples include 3,3-propanetetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing phosphon substituents are disclosed in British Patent 1,439,000, while polycarboxylates containing sulfo substituents are disclosed in British Patent 1,398,421. And the sulfosuccinate derivatives disclosed in US Pat. No. 1,398,422 and US Pat. No. 3,936,448, and the sulfonated pyrolytic citrates described in British Patent 1,082,179. Is mentioned.
[0127]
Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis Cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane- Hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include the melittic, pyromellitic, and phthalic acid derivatives disclosed in British Patent 1,425,343.
[0128]
Among the above, alternative polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, and more particularly citrates.
Builder systems for use in the present compositions include zeolite A or a mixture of a water-insoluble aluminosilicate builder such as layered silicate (SKS-6) and a water-soluble carboxylate-chelating agent such as citric acid. Include.
The builder system includes a mixture of a water-insoluble aluminosilicate builder such as zeolite A and a water-soluble carboxylate-chelating agent such as citric acid. Builder systems for use in the liquid coating compositions of the present invention are soaps and polycarboxylates.
[0129]
Other suitable water-soluble organic salts are homopolymeric or copolymeric acids or salts thereof, wherein the polycarboxylic acid contains at least two carboxyl groups separated from one another by no more than two carbon atoms. This type of polymer is disclosed in British Patent A1,596,756. Examples of such salts are polyacrylates having a molecular weight of 2000 to 5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 20,000 to 70,000, especially about 40,000. .
Detergent builder salts are usually included in amounts of 5% to 80%, alternatively 10% to 70%, most usually 30% to 60% by weight of the coating composition.
[0130]
Foam inhibitor
Another optional component is a suds suppressor, exemplified by silicones and silica-silicone mixtures. Examples of suitable suds suppressors are disclosed in U.S. Patent Nos. 5,707,950 and 5,728,671. Such suds suppressors are commonly used at levels of from 0.001% to 2%, alternatively from 0.01% to 1% by weight of the coating composition.
[0131]
enzyme
Various purposes, including removing protein-based, carbohydrate-based or triglyceride-based stains from surfaces such as textiles or dishes, for example to prevent dye transfer during laundry and to repair fabrics. Thus, an enzyme can be included in the present detergent composition. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof from suitable sources such as plant, animal, bacterial, fungal, and yeast sources. Alternative choices are influenced by factors such as pH-activity and / or stability optima, thermal stability, and stability to active detergents, builders, and the like. In this regard, bacterial or fungal enzymes are alternatives, such as, for example, bacterial amylases and proteases, and fungal cellulases.
[0132]
As used herein, "detergent enzyme" means any enzyme in a laundry detergent composition that has the ability to wash, remove stains, or have other beneficial effects. Alternative detersive enzymes are hydrolases such as proteases, amylases and lipases. Alternative enzymes for the purpose of washing include, but are not limited to, proteases, cellulases, lipases, and peroxidases.
[0133]
The enzyme is usually incorporated into the detergent composition or detergent additive composition at a level sufficient to provide a "wash-effective amount." The term "cleaning effective amount" refers to any amount that can provide the effect of washing, removing stains, removing stains, bleaching, deodorizing, or increasing the freshness of a substrate, such as fabric, tableware, and the like. means. As a practical matter with current commercial formulations, typical amounts are up to about 5 mg, more typically 0.01 to 3 mg of active enzyme per gram of detergent composition. is there. Stated another way, the compositions herein typically comprise from 0.001% to 5%, alternatively from 0.01% to 1% by weight of a commercially available enzyme preparation. Protease enzymes are usually present in such commercial formulations at levels sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher activity levels may be desirable in highly concentrated detergent formulations.
[0134]
Examples of suitable enzymes include hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases , Phenol oxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, mannanases And more preferably plant cell wall degrading enzymes and non-cell wall degrading enzymes (WO98 / 39403A), but more specifically, Pectinase (WO98 / 06805A1); Pectin lyase free from other pectin enzymes (WO98080607A1); Chondriotinase (EP747,469A); WO98 / 39402A) (including those derived from microtetraspora flexosa (US5683911)); isopeptidases (WO98 / 16604A); keratinases (EP747, 470A, WO98 / 40473G); lipases. 297, 979A; WO96 / 16153A; WO96 / 12004A; EP698. 659A; WO96 / 16154A); cellulase or endoglucanase (GB2,294,269A; WO96 / 27649A; GB2,303,147A; WO98 / 03640A); (Chrysosporium lacunowensknock strain disclosed in WO9815633A). See also neutral or alkaline cellulases derived from VKMF-3500D); polygalacturonase (WO98 / 06809A); mycodextranase (WO98 / 13457A); thermitase (WO96 / 28558A). Cholesterol esterase (WO9828394A); or any combination thereof; and known amilla Oxidases or a combination system containing the same (DE19523389A1); mutant blue copper oxidases (WO9709431A1), peroxidases (for example, see US Pat. No. 5,605,832, WO97 / 31090A1), mannanases (mannanases) ) (WO9711164, WO99 / 09126, PCT / US00 / 00839); xyloglucanases (WO98 / 50513, PCT / US / 00/00839, WO99 / 026663); laccases WO9838287A1 or WO9838286A1, such as those described in WO9827197A1. Myceliophthora or scytalidium laccase ( Laccase variants having an amino acid change in E. coli) or the mediated laccase system described in DE19612193A1, or those derived from the strain of Coprinus (see, for example, WO98 / 10060A1 or WO98 / 27198A1), phenol oxidase Or polyphenol oxidase (JP 10174583A) or mediated phenol oxidase system (WO97 / 11217A); enhanced phenol oxidase system (WO97 / 25468A, WO97 / 25469A); phenol oxidases fused to an amino acid sequence having a cellulose binding domain (WO97 / 40127A1, WO97 / 40229A1) or other phenol oxidases (WO97 / 08) 25A, WO97 / 28257A1), or super oxide dismutase compound can be mentioned. As taught in WO 98 / 07816A, oxidoreductases and / or antibodies related thereto can be used, for example, with H₂O₂Can be used with Depending on the type of composition, other redox-active enzymes, such as catalases (see, for example, JP09316490A) can be used.
[0135]
A preferred example of a protease is subtilisin; B. subtilis, and B. subtilis. Obtained from a special strain of B. licheniforms. One suitable protease is obtained from a Bacillus strain that has the greatest activity in the pH range of 8-12 and is available from Novo Industries A / S of Denmark (hereafter referred to as Novo) in Esperase. (Registered trademark). The preparation of this and similar enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include Novo's ALCALASE® and SAVINASE®, and International Bio-Synthetics, Inc. (Netherlands). MAXATASE®; and protease A disclosed in EP 130,756A (January 9, 1985), and EP 303,761A (April 28, 1987) and EP 130,756A (1985 Protease B disclosed on January 9). Bacillus sp. Described in Novo WO9318140A. See also the high pH protease from NCIMB 40338. Enzymatic detergents, including proteases, one or more other enzymes, and reversible protease inhibitors are described in Novo WO 92 / 03529A. Other alternative proteases include those of WO 95 / 10591A from Procter & Gamble. If desired, proteases with reduced absorption and increased hydrolysis are available as described in Procter & Gamble WO 95/07791. Recombinant trypsin-like proteases for detergents suitable herein are described in WO 94/25583 to Novo.
[0136]
More specifically, an alternative protease, referred to as "Protease D", is a carbonyl hydrolase variant having an amino acid sequence not found in nature, both of which are described in US patent application Ser. A. Baeck et al., Entitled "Protease-Containing Cleansing Composition," having Ser. No. 08 / 322,676; At the site of the carbonyl hydrolase equivalent to site +76, according to the subtilisin numbering of Bacillus amyloliquefaciens as described by Ghosh et al. In "Bleaching Compositions Containing Protease Enzymes". Or +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, and +260. Amino acids differing for a plurality of amino acid residues in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of: +265, and / or +274 From the precursor carbonyl hydrolase by substituting
An alternative protease, "Protease E", is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is a variant of the carbonyl hydrolase Bacillus amyloliquefaciens subtilisin. Substituting a different amino acid with a plurality of amino acid residues at a position corresponding to position 103, replacing the amino acid residue with another naturally occurring amino acid residue, and adding Bacillus amyloliquefaciens subtilisin 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57 , 58, 61, 62, 68, 72, 5, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 121, 123, 126, 128, 130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158, 159, 160, 166, 167, 170, 173, 174, 177, 181, 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205, 206, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 222, 224, 227, 228, 230, 232, 236, 237, 238, 240, 242, 243, 244, 245, 246, 247, 248, 249, 2 51, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 265, 268, 269, 270, 271, 272, 274, 275 Derived from the precursor carbonyl hydrolase in combination with substituting at amino acid residues; when the protease variant comprises substituting amino acid residues at positions corresponding to positions 103 and 76, Bacillus amyloliquefaciens subtilisins 27, 99, 101, 104, 107, 109, 123, 128, 166, 204, 206, 210, 216, 217, 218, 222, 260, 265, or 274 The position of the amino acid residue corresponding to the position There are also substitutions at one or more amino acid residue positions outside; and there are also substitutions of amino acid residues with one or more detersive additives.
[0137]
Although any combination of the above-listed amino acid substitutions may be used, preferred protease variant enzymes useful in the present invention include substitution, removal, or insertion of amino acid residues in the following combinations:
(1) a protease variant comprising a substitution at position 103 and one or more amino acid residues at positions 236 and 245 below;
(2) The positions of 103 and 236 and the following: 12, 61, 62, 68, 76, 97, 98, 101, 102, 104, 109, 130, 131, 159, 183, 185, 205, 209, 210, A protease variant comprising a substitution of one or more amino acid residues at positions 211, 212, 213, 215, 217, 230, 232, 248, 252, 257, 260, 270 and 275;
(3) The positions of 103 and 245 and the following: 12, 61, 62, 68, 76, 97, 98, 101, 102, 104, 109, 130, 131, 159, 170, 183, 185, 205, 209, A protease variant comprising a substitution of one or more amino acid residues at positions 210, 211, 212, 213, 215, 217, 222, 230, 232, 248, 252, 257, 260, 261, 270 and 275;
(4) The positions of 103, 236, and 245, and the following: 12, 61, 62, 68, 76, 97, 98, 101, 102, 104, 109, 130, 131, 159, 183, 185, 205, Protease variants comprising substitution of one or more amino acid residues at positions 209, 210, 211, 212, 213, 215, 217, 230, 232, 243, 248, 252, 257, 260, 270 and 275 And C.I. No. 09 / 529,905, filed Oct. 23, 1998, which is a patent application of C. Ghosh et al., Entitled "Detergent Composition Containing Multiple Substituted Protease Variants". Protease variants that have been used.
[0138]
In particular, amylases suitable herein for, but not limited to, automatic dishwashing purposes include, for example, α-amylases described in UK Patent No. 1,296,839 to Novo, International Biosynthetics, Inc. RAPIDASE® and Novo TERMAMYL®. FUNGAMYL® from Novo is particularly useful. Enzyme engineering to improve stability, eg, oxidative stability, is known. See, for example, Journal of Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521. Such amylases as alternatives herein share the feature of being "enhanced stability" amylases, and at a minimum: e.g. Oxidative stability to hydrogen oxide / tetraacetylethylenediamine, e.g., thermal stability at normal wash temperatures, such as about 60 <0> C, or the reference point amylase identified above, e.g., at a pH of about 8 to about 11 It is characterized by a measurable improvement in one or more of the alkali stability measured against. Stability can be measured using any of the technical tests disclosed in the art. See, for example, the references disclosed in WO 94/02597. Amylase with increased stability can be obtained from Novo or Genencor International. One class of amylases, as another method herein, uses site-directed mutagenesis to generate one or more amylase strains regardless of whether they are direct precursors. It has in common that it is derived from Bacillus amylase, particularly Bacillus α-amylase. Amylases having enhanced oxidative stability relative to the above-identified reference amylase are selective for use in bleaching, especially bleaching, or oxygen bleaching, except for the chlorine bleaching and detergent compositions herein. Such alternative amylases may include (a) alanine or threonine based on WO 94/02597 (November 3, 1994, Novo) incorporated above, or alternatively, threonine. , B. An amylase known as TERMAMYL®, or B. licheniformis, further described by a mutant that made a substitution for the methionine residue located at position 197 of the alpha-amylase, or B. licheniformis. amylploquefaciens, B.A. subtilis or B. subtilis; Homologous mutants of similar parental amylase such as stearothermophilus, (b) C. 207 at the 207th Annual Meeting of the American Chemical Society (March 13-17, 1994). Includes the enhanced stability amylase described by Genencor International in the article entitled "Oxidation Resistant Alpha Amylase" presented by Mitchinson. Methionine (Met) was identified as the most amenable residue. Met was substituted at positions 8, 15, 197, 256, 304, 366 and 438 all at once to create special mutants, but of particular importance are M197L and M197T, with the M197T mutant being the most stable. The mutant that was expressed. Amylases that enhance oxidative stability as another alternative include those described in WO 94/18314 to Genencor International and WO 94/02597 to Novo. Any other amylase that enhances oxidative stability can be used, for example, from site-directed mutagenesis from known chimeric hybrids or from simple mutant forms of available amylase. Modifications of enzymes as another alternative are available. See WO95 / 09909A to Novo.
[0139]
Cellulases that can be used in the present invention include both bacterial and fungal species, or have an optimal pH of 5 to 9.5. U.S. Patent No. 4,435,307 (Barbesgoard et al., Issued March 6, 1984) discloses suitable fungal cellulases or cellulases 212 from Humicola insolens or Humicola strain DSM1800. Disclosed are a fungus belonging to the genus Aeromonas and a cellulase extracted from the hepatopancreas of the marine mollusk, Dorabella Auriculara Solande. Suitable cellulases are also disclosed in British Patent Application A-2,075,028, British Patent Application A-2,095,275 and German Patent OS-2,247,832. CAREZYME® (Novo) is particularly useful. See also WO 9117243 to Novo.
[0140]
Lipase enzymes suitable for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri (ATCC 19.154) disclosed in British Patent No. 1,372,034. See also the lipase in Japanese Patent Application, 53,20487 (published February 24, 1978). This lipase is 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, a lipase of Chromobacter viscosum, such as Chromobacter viscosum var. Lipolyticum NRRLB 3673; United States, US Biochemical Corp., and the lipase of Chromobacter viscosum from Disynth Co., and Pseudomonas gladioli, including Pseudomonas gladioli. . The LIPOLASE® enzyme, derived from Humicola lanuginosa, commercially available from Novo and referring to EP 341 947, is a lipase as another method used herein. is there. Variants of lipase and amylase stabilized against peroxidase enzymes are described in Novo WO 94 / 14951A. See also WO92 / 05249 and RD94359044.
[0141]
Cutinase enzymes suitable for use herein are described in Genencor's WO 88 / 09367A.
Peroxidase enzymes are used in combination with an oxygen source such as percarbonate, perborate, hydrogen peroxide, and the like. They are used for "solution bleaching" or to prevent dyes or pigments removed from the substrate during the washing operation from migrating to other substrates present in the washing solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase. Detergent compositions containing peroxidase are disclosed in WO 89 / 099813A (November 19, 1989, Novo) and WO 89 / 09813A of Novo.
[0142]
The range and means of enzymatic substances incorporated into the detergent compositions are also described in Genencor's WO 93 / 07263A and WO 93 / 07260A, Novo's WO 89 / 08694A, and US Pat. No. 3,553,139 (McCarty et al., 1971). Issued January 5, 2008). Enzymes are further described in U.S. Pat. No. 4,101,457 (Place et al., Issued Jul. 18, 1978) and U.S. Pat. No. 4,507,219 (Hughes, Mar. 26, 1985). ). Enzymatic substances useful in liquid detergent formulations and their incorporation into such formulations are described in U.S. Pat. No. 4,261,868 (Hora et al., Issued Apr. 14, 1981). Various techniques can be used to stabilize enzymes used in detergents. Enzyme stabilization techniques are described in U.S. Pat. No. 3,600,319 (Gedge et al., Issued Aug. 17, 1971), EP 199,405 and EP 200,586 (Venegas ( Venegas), Oct. 29, 1986). Enzyme stabilization systems are also described, for example, in US Pat. No. 3,519,570. Useful Bacillus sp. To provide proteases, xylanases and cellulases AC13 is described in WO 94 / 01532A (Novo).
[0143]
Other substances
The detersive components or additives optionally included in the composition may help treat or enhance the performance of the composition, the treatment of the substrate to be cleaned, or improve the aesthetics of the composition. One or more designed materials can be included. Levels established in the prior art for use in the compositions of the present invention (generally, the additive comprises from about 30% to about 99.9%, or from about 70% to about 95%, by weight of the composition in total) Additives that can be included in US Pat. Nos. 5,705,464; 5,710,115; 5,698,504; 5,695,679. No. 5,686,014; No. 5,576,282; and No. 5,646,101. Photoactive inorganic metal oxides, color speckles, rust inhibitors. , Corrosion inhibitors, alkaline sources, hydrotropes, antioxidants, organic solvents, surfactants, polymers, builders, bleaches, bleach activators, bleach catalysts, deactivating enzymes, enzyme stabilization systems, chelates Agents, optical brighteners, stains Effluent polymer, wetting agent, dye adhering agent, dispersant, suds suppressor, dye, colorant, filler salt, photoactivator, fluorescent agent, conditioner, hydrolyzable auxiliary surfactant, preservative, anti-shrinkage Other active ingredients such as agents, fungicides, fungicides, silver care, solubilizers, carriers, processing aids, pigments, and pH modifiers.
[0144]
II. how to use
An effective amount of non-photoactive nanoparticles and a suitable aqueous carrier medium, and optionally a surfactant, one or more charged functionalized surface molecules, an effective amount of photoactive nanoparticles, and optionally, Organic solvents, surfactants, polymers, chelating agents, builders, bleaches, bleach activators, bleach catalysts, deactivating enzymes, enzyme stabilization systems, optical brighteners, soil release polymers, wetting agents, Dye transfer agent, dispersant, suds suppressor, dye, fragrance, colorant, filler salt, hydrotrope, photoactivator, fluorescent agent, conditioner, hydrophilizable auxiliary surfactant, preservative, oxidation Inhibitors, anti-shrink agents, fungicides, fungicides, color speckles, silver care, rust inhibitors and / or corrosion inhibitors, alkali sources, stabilizers, carriers, processing aids, pigments, and pH adjusters, Etc. and their mixtures A coating composition containing a nanoparticle system comprises: (a) mixing the nanoparticles in a suitable carrier medium to form the coating composition; (b) optionally dispersed in a suitable carrier medium. Mixing the nanoparticles with additional components to form the coating composition; (c) optionally mixing the nanoparticles dispersed in a suitable carrier medium with a surfactant to form the coating composition (D) optionally, mixing the nanoparticles dispersed in a suitable carrier medium with additional components and a surfactant to form the coating composition; (e) bonding the coating composition to the hard Applying to the surface; (f) drying the coating composition, or actively drying the coating composition, or otherwise curing the coating composition; and (g) optionally, Any of steps (a) to (f) depending on It can be used by repeating.
[0145]
Dispensing of the coating composition can be accomplished using a spray device, dipping vessel, spray hose fitting, or applicator such as a fabric, sponge, roller, pad, or the like, or a spray dispenser. The coating compositions of the invention and the articles of the invention containing nanoparticle systems can be used to treat any hard surface and have the following durability benefits: improved hard surface wetting and sheet formation, faster Dry, uniform drying, dirt removal, self-cleaning, anti-speckle, anti-stain, more clean appearance, enhanced gloss, enhanced color, repair of small surface defects, smoothness, anti-fog, reduced surface friction , At least one of active substance release, reduced damage to friction and improved clarity.
[0146]
In one embodiment of the present invention, the effective amount of the liquid coating composition of the present invention is alternatively: indoor and outdoor glass windows, walls and doors; including, but not limited to, car bodies, trucks, trains, ships and airplanes. Exterior of vehicle body not covered; ceramic tiles, floors and walls; bathroom and kitchen tables; utensils; metal fittings, siding and roofing; tableware; wooden furniture, floor and wall treatment; stone tiles and walls; Sprayed onto hard surfaces and / or hard surface articles including, but not limited to, asphalt roofs, sidings and roads; jewelry; building exterior walls; painted and coated surfaces and the like. When the coating composition is sprayed on the hard surface, an effective amount of the nanoparticle system should be deposited on the hard surface and the hard surface should be wetted with the coating composition and become totally saturated. The hard surface coating composition of the present invention can also be applied to hard surfaces through a roll coating, curtain coating, dipping and / or dipping process in a dipping vessel. Any application step can be followed by a drying step or a curing step.
[0147]
In one non-limiting aspect of the invention, the coating composition of the invention is used to apply a durable coating to the surface of a vehicle, such as an automobile. The step of applying the coating composition can include, in addition to the step of applying the coating composition, one or more of the following: a pre-cleaning step; a cleaning step involving soap or sponge to generate foam; A rinsing step; an activated rinsing step; a step for applying the coating composition described herein; and a drying step. Provided the components necessary to perform the process are provided in the form of a kit, such as a car care kit, such a process can be performed by a consumer at home. Instructions can be provided. Alternatively, the process can be performed in a commercial operation, such as a car wash, which may be of an automatic type or a "self-service" type, wherein the consumer sprays the car using a car wash. .
The hard surface coating composition can be applied to the hard surface at any suitable temperature. Hard surface coating compositions have been found to be applicable at any temperature above freezing. For example, the coating composition can be applied at temperatures as low as 1 ° C, 5 ° C, 10 ° C, or 15 ° C.
[0148]
The hard surface can then be exposed to conditions that allow the coating composition to cure or dry. The drying step can include air drying at ambient conditions. Alternatively, the drying step can include actively drying or curing the coating composition by utilizing any technique known to accelerate the drying or curing process. As used herein, the term "aggressive curing" refers to any technique used to accelerate the curing process beyond merely drying the coating composition under ambient conditions. For example, a known crosslinking agent can be incorporated into the composition to cure it. Various curing methods may be used, but heat or heat curing, or heat drying is preferred. The hard surface coating composition may be heat dried at any temperature above room temperature (the temperature of the drying may be, for example, above 0 ° C. or an equivalent increase of about 5 degrees or more). Generally, thermal curing is achieved by exposing the coated surface to an elevated temperature, such as that provided by a radiant heat source. Such techniques include moving (or forced) wind drying, such as blower drying, blast drying, etc., or the application of heat (eg, radiant heat sources, eg, oven drying, etc.) or moving. Or both forced air drying and the application of heat (eg hot air drying) may be mentioned.
[0149]
It has been found that heat drying the hard surface coating composition can greatly increase the durability of the hard surface coating. The increase in durability of the hard surface coating composition of the present invention is, in fact, quite unexpectedly high.
For example, in some embodiments, when a hard surface coating composition is applied to a hard surface and allowed to air dry at room temperature, one or two of the mechanical polishing methods described in the Test Methods section below. Some have been found that hard surface coatings can provide the benefits described herein (or at least some of such benefits) after exposure to heat / cycles. This would be interpreted as about 2 to 4 weeks of protection and modification of the surface in an outdoor environment, including cleaning the surface about once a week.
[0150]
However, when the hard surface coating composition is thermally dried above room temperature (which may be about 20-22 ° C. for moderate ambient or building room temperatures), the hard surface coating formed on the surface Has been found to have increased durability, thus providing further sustained benefits. As used herein, the term "long lasting" refers to providing at least some of the benefits described herein after one or more cycles of the polishing method described in the test method. Refers to a coating that can be The hard surface coating composition of the present invention can be thermally dried to any temperature above or equal to about 50 ° C. and in 5 degree increments above 50 ° C. (eg, 80 ° C.) to provide a lasting benefit. Can be provided. However, this can be affected by the accelerator, ie, solvent and crosslinker. The hard surface coating composition can be air dried at a temperature that approaches, but preferably does not exceed, a temperature that causes changes such as dissolution, blocking, etc., on the hard surface to be coated. In one non-limiting embodiment, the hard surface coating composition of the present invention is applied to a car body and then heat dried at about 145 ° C. to about 160 ° C., or 5 ° C. intervals therebetween. can do. Coatings dried in such a heat drying process have been found to withstand more than 500 mechanical polishing test cycles. In another non-limiting embodiment, the hard surface coating composition can be applied to a car body and then heat dried at a wind temperature of about 135 ° C. Coatings dried in such a heat drying process have been found to withstand more than 50 cycles of mechanical polish testing.
[0151]
In another non-limiting embodiment, the hard surface coating composition can be applied to automotive glass and then heat dried at an air temperature of about 135 ° C. Coatings dried in such a heat drying process have been found to withstand more than 50 cycles of mechanical polish testing.
The dried hard surface coating is preferably substantially hydrophilic. The dried hard surface may, in some embodiments, be less than or equal to about 60; or, alternatively, less than 60 quintuples (eg, about 50, 45, 40,. The contact angle with water may be less than or equal to 10 or less. In some embodiments, a higher application or drying temperature results in a higher initial contact angle, and a lower application or drying temperature results in a lower initial contact angle. However, the contact angle can vary over the course of the coating. In some embodiments, after hydrating the surface for 500 seconds, the appearance of the dried hard surface coating can be improved. Visual improvement is characterized as improved water sheeting or makuhari on the surface coating.
[0152]
The application of the hard surface coating composition of the present invention can be carried out in a consumer's home by a large-scale process on hard surfaces and / or finished articles in industrial applications or by the use of manufactured articles.
In one aspect, the method of the present invention can be used in the manufacture and / or painting operations of an automobile to provide a durable finish to the exterior of the automobile. FIG. 4 is a flowchart illustrating one non-limiting example of painting the outside of a vehicle body skin and applying a clear paint finish thereto. The clear coating composition comprises a polyurethane formed from the polymerization of a carbamate and melamine composition, such as that available under the trade name URECLEAR® from BASF of Southfield, Michigan.
[0153]
In the example shown in FIG. 4, the first step of coating the car body outer panel is to apply the primer twice without interposing a flash time (elapsed time for evaporating the organic solvent) between the coatings. Is to apply. Following this, the primer is flushed for 10 minutes (first drying at a low temperature to drive out most of the solvent and then curing it at a higher temperature; thus preventing foaming). Then bake the skin at 129 ° C. for 30 minutes. Thereafter, a double coat of a base coat (coating) is applied with a flash for 60 seconds between coats. Then, two coats of clear paint are applied with a 60 second flash between coats. The skin is then heated at 82 ° C. for 10 minutes. The heating step is raised to 132 ° C. and the temperature is maintained for 25 minutes. The final step is to place the skin in a 160 ° C. oven for 5 minutes. Of course, other methods may vary the temperature and time in any suitable manner. For example, a method used by ACT Laboratories, Inc. (Hillsdale, Michigan, USA) and used in the automotive industry to examine the skin of an automobile body is described in the Test Methods section.
[0154]
As shown in FIG. 4, the hard surface coating composition described herein can be applied to a number of different steps in a method of applying a clear paint finish to a car body skin. After the application of the one or more paints is applied to the vehicle body part; during the step of applying the one or more transparent paints to the vehicle body part; or the one or more transparent paints are applied to the vehicle body part. , The hard surface coating composition described herein can be applied.
In other embodiments, it is desirable to use nanoparticles in powder form. The nanoparticles can be used alone or in combination with other materials to form a composition. The clear coating composition may be provided in such embodiments in any suitable form, including but not limited to liquids and powders. In embodiments where it is desirable to use a powdered hard surface coating composition comprising a nanoclay with a powdered clear coating, it may be desirable to modify the application procedure. The application procedure can be modified in a number of different ways. In any desired embodiment, the surface on which the powder coating is to be deposited can be charged to facilitate the attraction and adherence of the nanoparticles thereto.
[0155]
For example, first by applying a transparent coating powder composition by electrostatic deposition or fluidized bed technology or other such technology commonly practiced, then electrostatic deposition or fluidized bed technology or other such technology commonly practiced. To apply the nanoclay coating composition. The surface can then be heated to provide a suitable cure.
In another embodiment, the clear coating powder composition can be first coated with a powdered hard surface coating containing nanoclay. This is followed by the application of a clear coating powder composition coated with a hard surface coating of the powder containing the nanoclay to the desired surface by electrostatic deposition or fluidized bed techniques or other such techniques commonly practiced. Can be. The surface can then be heated to provide a suitable cure.
[0156]
In another embodiment, a hard surface coating of a powder comprising a transparent coating powder composition and a nanoclay is simultaneously applied to a desired surface by electrostatic deposition or fluidized bed techniques or other such techniques commonly practiced. be able to. The surface can then be heated to provide a suitable cure.
In other embodiments, such as in a car body repair business, it may not be possible to heat the body skin to the temperature as described in the preceding paragraph without damaging another part of the car. In some cases, the hard surface coating composition can be applied at a much lower temperature, such as above 60 ° C. (the temperature reached by the surface of the car on a hot day). In such embodiments, a reaction accelerator can be used as desired.
[0157]
In embodiments where it is desirable to use an aqueous hard surface coating composition comprising nanoclay with an organic clearcoat, it is desirable to modify the application procedure. For example, a clear paint composition is first applied, and then a "skim" or film is formed over the wet clear paint using techniques known to those skilled in the art. To dry, it will become slightly sticky when dried). The hard surface coating composition can be placed on the skim, and then the clear coating with the hard surface coating composition is heated together.
In any of the embodiments described herein, multiple layers of the hard surface coating composition can be applied to any of the hard surfaces described herein. Such multiple layers of hard surface coating compositions can all have the same chemical composition, or they can have different chemical compositions.
[0158]
In addition to applying the hard surface coating composition described herein to the skin of an automotive body, the hard surface coating composition of the present invention can be applied to glass, plastic, or rubber. For example, the hard surface coating composition of the present invention can be applied to a window glass of an automobile. The hard surface coating composition of the present invention can be applied to automotive glazings in any process of manufacturing glazings or automobiles.
In other embodiments, the methods of applying the hard surface coating compositions described herein can be applied to components such as airplanes, ships, buildings, etc. to provide a more durable surface coating.
[0159]
The present invention also includes a concentrated liquid or solid coating composition, which is diluted as provided above to form a use concentration composition for use under "use conditions." . The concentrated composition typically comprises from about 0.1% to about 50%, alternatively from about 0.5% to about 40%, alternatively from about 1% to about 30%, by weight of the concentrated coating composition, Includes high levels of nanoparticle concentration.
Concentrated compositions are used to provide cheaper products. The concentrated product is alternatively diluted with 1,000 parts of a suitable carrier medium of the coating composition, alternatively 100 parts of a suitable carrier medium and / or 10 parts of a suitable carrier medium.
[0160]
In another embodiment of the present invention, (a) an effective amount of non-photoactive nanoparticles; (b) an optional surfactant; (c) for treating dishware in the rinsing step of an automatic dishwasher. One or more functionalized surface molecules, optionally associated with the nanoparticle surface, exhibiting properties selected from the group consisting of hydrophilicity, hydrophobicity, and mixtures thereof; (d) optionally, an effective amount of light. A method is provided for using a liquid coating composition comprising active nanoparticles; (e) optionally one or more additional components; and (f) a suitable carrier medium, or a concentrated liquid. The rinse water should typically contain from about 0.0005% to about 1%, alternatively from about 0.0008% to about 0.1%, or from about 0.001% to about 0.02% of the nanoparticles. is there.
[0161]
Another alternative method involves treating the dishes with a coating composition sprayed from a sprayer at the beginning and / or during the drying cycle. The process is preferably performed according to instructions to ensure that the consumer knows which benefits can be achieved and how to best obtain such benefits.
Another alternative is to use mechanical or chemical means to remove a layer of foreign material (ie, soil, stain residue, food, etc.) according to the instructions for use to impart the desired benefit. Stripping at least one layer of the nanoparticles from the transparent coating on the treated hard surface, wherein the mechanical or chemical means does not exclude the weather or optionally the normal use of the surface Absent. Without being limited by theory, the mechanism of the peelable film of the present method is shown in FIGS.
[0162]
1 to 3, the hard surface is designated by the reference numeral 20. The individual nanoparticles are represented by reference numeral 22 and the layers formed thereby are represented by reference numeral 24. Soil deposited on the nanoparticles is represented by reference numeral 26. In one embodiment of the present invention, such an application to an automobile, building exterior or tableware surface deposits an effective amount of the nanoparticle coating as an invisible film and soil 26 adheres to the hard surface 20. (Fig. 1). The nanoparticle coating consists of multiple active layers 24 of nanoparticle sheets that provide benefits. During the weathering, washing or stripping process step, at least one top layer 24 of the nanoparticle coating is removed and soil 26 is removed therewith (FIGS. 2 and 3).
[0163]
III. Manufactured goods
The present invention also provides the desired results, i.e., improved hard surface wetting and sheeting, quick drying, uniform drying, scouring, self-cleaning, anti-spot prevention, anti-soil deposition, more clean appearance, enhanced. Gloss, enhanced color, repair of small surface imperfections, improved smoothness, anti-fog, reduced surface friction, release of actives, reduced damage to abrasion and improved clarity and mixtures thereof The present invention relates to an article of manufacture comprising a hard surface coating composition in a package, in conjunction with instructions on how to use the coating composition to properly treat hard surfaces to obtain an improved versatile benefit consisting of: Alternative articles of manufacture can be used to properly coat hard surfaces, including, for example, the type and / or amount of the composition to be sprayed, and alternative methods of applying the coating composition as described in more detail herein below. Include said composition in a spray dispenser in connection with instructions on how to use the coating composition for processing. It is important that the instructions be as simple and clear as possible, so it is desirable to use pictures and / or pictograms.
[0164]
Spray dispenser
Articles of manufacture herein include spray dispersers. The coating composition is placed in a spray dispenser for spraying on a hard surface. The spray dispenser for forming a spray of liquid droplets may be any manually operated means known in the art, such as a damped mold for treating a small hard surface area and / or a small number of substrates with a coating composition. It can be a pump-type, non-aerosol self-pressurized and aerosol-type spraying means, and a non-manually operated powered sprayer for conveniently treating large hard surface areas and / or large numbers of substrates with the coating composition. The spray dispensers herein do not normally include those that substantially form a clear, aqueous coating composition. It has been found that providing smaller particle droplets enhances performance. Desirably, the Sauter mean particle size is from about 10 μm to about 120 μm, or from about 20 μm to about 100 μm. The coating benefit is improved, for example, by providing small particles (droplets), especially when a surfactant is present.
[0165]
The spray dispenser can be an aerosol dispenser. The aerosol dispenser comprises a container, which can be constructed of any conventional material used to assemble an aerosol container. This dispenser has a capacity of about 20 to about 110 p. s. i. g. Or about 20 to about 70 p. s. i. g. Must be able to withstand the internal pressure within the range. One important requirement for the dispenser is that the dispenser is provided with a valve member that allows the transparent, aqueous coating composition contained in the dispenser to be sprayed in very fine or fine particles. To be dispersed in the form of particles or droplets. Aerosol dispensers use a pressurized enclosure from which a clear, aqueous coating composition is sprayed under pressure via special actuator / valve components. By incorporating therein, the gaseous component commonly known as a propellant pressurizes the aerosol dispenser. A common aerosol propellant, for example, a mixture of a gaseous hydrocarbon such as isobutane and a halogenated hydrocarbon may be used. Halogenated hydrocarbon propellants, such as chlorofluorohydrocarbons, are said to cause problems and are not a replacement. Where cyclodextrins are present, hydrocarbon propellants are not a substitute, but they do form a complex with the cyclodextrin molecules, thereby making the uncomplexed cyclodextrin molecules available for odor absorption. This is to reduce. Alternative propellants are compressed air, nitrogen, inert gas, carbon dioxide, and the like. For a more complete description of commercially available aerosol-spray dispensers, see U.S. Pat. Nos. 3,436,772 (Stebbins, issued Apr. 8, 1969); and 3,600,325 (Kaufman). ) Et al., Issued August 17, 1971); both of which are incorporated herein by reference.
[0166]
Alternatively, the spray dispenser can be a self-pressurized, non-aerosol container having a convoluted liner (lining) and an elastomeric sleeve. The self-pressurizing dispenser includes a liner / sleeve part, which is a thin, flexible, radial, about 0.010 to about 0.020 inch thick, inside an essentially cylindrical elastomeric sleeve. Contains a convoluted plastic liner that can be expanded to The liner / sleeve can hold a significant amount of the coating composition and can spray the composition. More complete descriptions of self-pressurizing spray dispensers are given in U.S. Patent No. 5,111,971 (Winner, issued May 12, 1992) and U.S. Patent No. 5,232,126 (Issued Wiener). (Winner), Aug. 3, 1993), both of which are incorporated herein by reference. Another type of aerosol sprayer is one in which a barrier separates the coating composition from the propellant (or compressed air or nitrogen) and is disclosed in U.S. Pat. No. 4,260,110 (April 7, 1981). And published herein by reference. Such dispensers are available from EP Spray Systems, East Hanover, NJ.
[0167]
Alternatively, the spray dispenser is a non-aerosol, manually operated, pump spray dispenser. The pump spray dispenser includes a container and a pump mechanism that stably rotates or snaps on the container. Containers include those containing the aqueous coating composition to be sprayed.
The pumping mechanism includes a substantially fixed volume pump chamber having an opening at an internal end thereof. A pump stem is provided in the pump chamber and has a piston at its end to prevent reverse movement in the pump chamber. The pump stem has a passageway, the outer end of which has a sparging outlet through the passageway, and within which the axial inlet port is located.
[0168]
The container and pump mechanism can be composed of any conventional material used to make pump spray dispensers, including: polyethylene; polypropylene; polyethylene terephthalate; polyethylene, vinyl acetate, and rubber. -Including but not limited to blends of elastomers. Alternative containers are made of transparent, for example, polyethylene terephthalate. Other materials may include stainless steel. A more complete disclosure of commercially available spraying devices is disclosed in U.S. Patent No. 4,895,279 (Schultz, issued January 23, 1990); U.S. Patent No. 4,735,347 (Schultz). ), Issued April 5, 1988); U.S. Patent No. 4,274,560 (Carter, issued June 23, 1981), which is incorporated herein by reference in its entirety. Incorporate in.
[0169]
Alternatively, the spray dispenser is a manually operated braking spray dispenser. The damped spray dispenser can include any conventional material, including a container and a trigger, both of which are used to make the damped spray dispenser, including: polyethylene; Polypropylene; polyacetal, polycarbonate; polyethylene terephthalate; polyvinyl chloride; polystyrene; polyethylene, vinyl acetate, and mixtures of rubber and elastomers, but are not limited to. Other materials can include stainless steel and glass. Alternative containers are made of transparent, for example, polyethylene terephthalate. Braking spray dispensers do not incorporate propellant gas into the odor absorbing composition or include those that would form a coating composition. The braking sprayers herein typically operate on individual quantities of the coating composition itself, by means of a piston or collapsible bellows, which collapsible with the coating composition from the nozzle. Move to produce a thin liquid spray. The dampening spray dispenser typically has a pump chamber, which has either a piston or a bellows, through a limited impact response to the brake, which varies with the volume of the pump chamber. Can move. This pump chamber or bellows chamber can collect and hold the product for application. Damped spray chambers typically have an outlet check valve to shut off fluid flow and flow through the nozzle, and are responsive to pressure in the chamber. In the case of a piston type brake type dispenser, when the brake is compressed, it acts on the fluid and the spring in the chamber, increasing the pressure on the fluid. In the case of a bellows spray dispenser, the pressure on the fluid increases when the bellows is compressed. For any type of braking atomizer, the increase in fluid pressure acts to open the outlet check valve at the top. By means of the valve at the upper end, the product passes through the swirl chamber and out of the nozzle, forming a discharge mold. Adjustable nozzle caps can be used to change the type of fluid being dispensed.
[0170]
In the case of a piston spray dispenser, the spring acts on the piston to return to its original position when the brake is released. In the case of a bellows spray dispenser, the bellows acts like a spring to return to its original position. This action creates a vacuum in the dispenser. The responsive fluid acts to open the inlet valve and draw product from the reservoir into the dispenser while closing the outlet valve.
A more complete disclosure of commercially available spraying devices is disclosed in U.S. Pat. No. 4,082,223 (Nozawa, issued April 4, 1978); U.S. Pat. No. 4,161,288 (McKinney). ), Issued July 17, 1985); U.S. Patent No. 4,434,917 (Saito et al., Issued March 6, 1984); U.S. Patent No. 4,819,835 (Tasaki ( Tasaki), issued April 11, 1989); and U.S. Patent No. 5,303,867 (Peterson, issued April 19, 1994), which is incorporated by reference in its entirety. Incorporated herein.
[0171]
A wide range of braking sprays or finger pump sprays are suitable for use with the coating compositions of the present invention. These are suppliers such as, for example, Calmar, Inc. of the City of Industry; CSI of St. Peters, MO (Continental Sprayers, Inc.). )); Berry Plastics Corp., Evansville, Indiana; distributor of Guala® sprayers; or Seaquest, Cary, Illinois. Dispensing).
[0172]
A non-limiting example of a damped sprayer is the blue inserted Guala available from Berry Plastics Corp. due to its fine and uniform spray properties, spray volume, and pattern size. (Registered trademark) nebulizer, or Calmar TS800-1A (registered trademark), TS1300 (registered trademark), and TS-800-2 (registered trademark) available from Calmar, Inc. Alternatives include sprayers having a pre-compression function, and finer spray characteristics, and even distribution, such as Yoshino sprayers in Japan. Any suitable bottle or container can be used with the brake sprayer, and an alternative bottle is a good ergonomic 17 fl-oz (approximately 500 ml) bottle that resembles the shape of a Cinch® bottle. is there. It can be made from any material, such as high density polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyethylene terephthalate, glass or any other material that forms a bottle. Alternatively, it is made from high density polyethylene or clear polyethylene terephthalate.
[0173]
For smaller fluid ounce sizes (e.g., 1-8 ounces), a finger pump may be used with a closed container or cylindrical bottle. An alternative pump for the present application is the cylindrical Euromist II® from Seaquest Dispensing.
The article of manufacture herein may also include a non-manually operated spray dispenser. "Non-manual operation" means that the spray dispenser can be operated manually, but the force required to spray the coating composition is provided by another non-manual means. Non-manually operated nebulizers include, but are not limited to, powered nebulizers, air-inhaled nebulizers, liquid-inhaled nebulizers, electrostatic nebulizers, and atomized nebulizers. The coating composition is placed in a spray dispenser for spraying on a hard surface.
[0174]
Powered sprayers include self-contained powered pumps that pressurize an aqueous coating composition and spray through a nozzle to form a spray of liquid droplets. The powered sprayer is attached directly or indirectly to the storage tank (eg, bottle) holding the aqueous coating composition using a pipe / tube. Powered nebulizers can include, but are not limited to, centrifugal or positive displacement designs. Preferably, the powered sprayer is powered by a portable DC current from either a disposable battery (eg, a commercially available alkaline battery) or a storage battery unit (a commercially available nickel-cadmium battery unit). Powered nebulizers can also be powered by standard AC power supplies available in most buildings. The design of the discharge nozzle may be different to create specific spray characteristics (eg, spray diameter and particle size). It is also possible to have multiple spray nozzles due to different spray characteristics. The nozzle may or may not contain an adjustable nozzle cover, which alters the spray characteristics.
[0175]
A non-limiting example of a commercially available powered nebulizer is disclosed in U.S. Patent No. 4,865,255 (Lubisotto, issued September 12, 1989), which is incorporated herein by reference. Alternative powered nebulizers are available from suppliers such as Solo at Newport News, Virginia (eg, Solo Spraystar ™ rechargeable nebulizer, manual part number: US 460-395). And Multi-sprayer Systems, Minneapolis, MN (eg, Model: Spray 1).
[0176]
Air suction nebulizers include those generically classified as "air brushes." A stream of pressurized air draws up the aqueous coating composition, which is sparged from a nozzle, creating a liquid spray. The coating composition is supplied via a separate pipe / tube or, more usually, is contained in a bottle fitted with an inhalation nebulizer.
[0177]
Non-limiting examples of commercially available air inhalation nebulizers include U.S. Patent No. 1,536,352 (Murray issued April 22, 1924); and U.S. Patent No. 4,221,339 (Yoshikawa ( Yoshikawa), published September 9, 1980), all of which are incorporated herein by reference. Air inhalation nebulizers are available from sources such as Badger Air-Brush Co., Franklin Park, Illinois (e.g., model number: 155) and from Woodridge, Illinois. It is readily available from Wilton Air Brush Equipment (e.g., stock numbers: 415-4000, 415-4001, 415-4100).
[0178]
Liquid inhaler nebulizers are typical of a wide variety of widely used for spraying horticultural chemicals. The aqueous coating composition is drawn into the fluid stream by suction means created by the Venturi effect. High turbulence mixes the aqueous coating composition with the fluid stream (typically water) to provide a uniform mixture / concentration. In this manner, delivery for dispersing the aqueous concentrate coating composition of the present invention is possible, and then the composition is diluted to a selected concentration by the delivery stream.
Liquid inhalation nebulizers are readily available from suppliers such as Chapin Manufacturing Works of Batavia, NY (eg, Model Number: 6006).
[0179]
Electrostatic sprayers impart energy to aqueous coating compositions via a high potential. This energy serves to atomize and charge the aqueous coating composition, creating a spray of finely charged particles. As the charged particles are released from the nebulizer, they repel each other due to their common charge. This has two effects before the spray reaches the target. First, the entire spray mist expands. This is especially important when spraying large areas that are quite far away. The second effect is the retention of the original particle size. Because the particles repel each other, they resist aggregating together with larger, heavier particles, as do uncharged particles. This reduces the effects of gravity and speeds up the arrival of charged particles at the target. When most of the negatively charged particles approach the target, they push electrons inward into the target, so that all of the exposed surface of the target is temporarily positively charged. The result is an attraction between the particle and the target, which counteracts the effects of gravity and inertia. As each particle attaches to the target, that point on the target is neutralized and no longer attracts. Thus, the next free particle is attracted to the immediate neighbor, and this sequence continues until all faces of the target are covered. Hence, the charged particles enhance the dispersion and reduce dripping.
[0180]
Non-limiting examples of commercially available electrostatic sprayers are described in U.S. Patent No. 5,222,664 (Noakes, issued June 29, 1993); U.S. Patent No. 4,962,885 (Coffeeer). U.S. Pat. No. 2,695,002 (Miller, Nov. 1954); U.S. Pat. No. 5,405,090 (Green, 1995). U.S. Patent No. 4,752,034 (Kuhn, issued June 21, 1988); U.S. Patent No. 2,989,241 (Badger, 1961) , Issued June, 2000), all of which are incorporated herein by reference. Electrostatic sprayers are readily available from suppliers such as Tae In Tech Co, Korea and Spectrum, Houston, Texas.
[0181]
Spray nebulizers apply ultrasonic energy to aqueous coating compositions via a transducer. This energy causes the aqueous coating composition to atomize. Various types of nebulizers include, but are not limited to, heating, ultrasonic, gas, venturi, and refillable nebulizers.
Non-limiting examples of commercially available atomizers include U.S. Patent No. 3,901,443 (Mitsui, issued August 26, 1975); U.S. Patent No. 2,847,248 (Schmitt). ), Issued Aug. 1958); U.S. Pat. No. 5,511,726 (Greenspan, issued Apr. 30, 1996), which is incorporated herein by reference in its entirety. . Spray nebulizers are available from suppliers such as A & D Engineering, Inc. of Milpitas, California (e.g., model A & DUn-231 ultrasonic handheld nebulizer) and Spring City, PA. It is readily available from Amici, Inc. of Spring City (model: swirler nebulizer).
[0182]
Alternative articles of manufacture herein include non-manually operated sprayers containing an aqueous coating composition, such as battery powered sprayers. Alternatively, the article of manufacture comprises a non-hand operated sprayer and a separate container of the aqueous coating composition, which is added to the sprayer before use and / or separated for filling / refilling. Another container can contain the composition to be used, or the concentrated composition, which is diluted and / or diluted with a nebulizer prior to use, such as those described herein above. Used with liquid inhalation nebulizers as described.
[0183]
Also, as described above, another container has a structure that is consistent with the rest of the nebulizer so that it does not leak even after operation, impact, etc., and even when handled by inexperienced consumers. Need to be firmly fixed. The nebulizer also desirably has a mounting system, which is designed to be secure or to be replaced with another container filled with a liquid container. For example, a filled container can replace a fluid container. This minimizes the problems associated with filling, including minimizing leakage, if the proper combination and sealing means are present for both the nebulizer and the container. Desirably, the nebulizer may contain a shroud, which ensures proper placement and / or allows the use of thin walls on the container to be replaced. This minimizes the amount of material that is recycled and / or discarded. The package sealing or combination system can be a threaded closure (sprayer), replacing the current closure with a filled, threaded container. Gaskets are desirably added to provide additional seal security and minimize leakage. The gasket can be broken by the closing action of the atomizer. Sealing systems with these screws may be based on industry standards. However, it is highly desirable to use a screw sealing system with non-standard dimensions to ensure that the proper sprayer / bin combination is always used. If the atomizer is used for its intended purpose, this fluid should be sprayed on, thereby preventing the use of toxic fluids.
[0184]
Another sealing system may be based on one or more connecting projections and grooves. Such systems are commonly referred to as "plug-in" systems. Such a system can be manufactured in a wide variety of structures, thus ensuring that the proper replacement fluid is used. For convenience, the locking system may also allow for a “child-proof” cap on the refill bin. This "lock and key" type system therefore provides a highly desirable safety feature. There are many different ways to design such a lock and key sealing system.
However, care must be taken that the filling and sealing operations are not too difficult. If desired, locks and keys can be perfect for the sealing mechanism. However, the connection may be separated from the sealing system to ensure that accurate refilling or refilling is used. For example, covers and containers are designed to be compatible. For this reason, only the unique design of the container can be a reliable guarantee that a proper refill / refill is used.
[0185]
An example of a threaded closure and bayonet system is described in U.S. Pat. No. 4,781,311, Nov. 1, 1988 (Angular Positioned Trigger Sprayer with Selective). Snap-Screen Container Connection, Clorox), U.S. Pat. No. 5,560,505, Oct. 1, 1996 (Container and Stopper Parts Secured Together by Relative Rotation) Stopper Assembled Locked Tethered by Relative Rotation and Use Thereof, Cebal SA), and U.S. Patent No. , No. 725,132, March 10, 1998 - can be found in (snap dispenser with a fixation container coupling (Dispenser with Snap-Fit Container Connection) Senchiko International (Centico International)). All of said patents are incorporated herein by reference.
[0186]
The present invention is also provided in connection with instructions for use by a consumer to ensure that at least an effective amount of the nanoparticle system and / or coating composition is applied and to provide the desired multi-purpose benefit of a hard surface. A coating composition for use in spraying and / or spraying a hard surface or an entire article in such a manner as to prevent excessive amounts of the coating composition from being released into the outdoor environment. Also relates to articles of manufacture.
Other coating compositions of the present invention for use in treating hard surfaces such as tableware in various steps of automatic dishwashing processes, e.g., pre-washing, washing cycles, rinsing cycles, and drying cycles are desirable hard coatings. Surface coating results: improved multi-purpose hard surface wetting and sheeting, quick drying, uniform drying, scrubbing, self-cleaning, anti-spotting, anti-staining, more clean appearance, enhanced gloss, enhanced Treat dishes properly to obtain color, repair small surface imperfections, improve smoothness, prevent fogging, reduce surface friction, release actives, reduce damage to abrasion and improve clarity Can be packaged in conjunction with instructions on how to use the coating composition to perform the coating.
[0187]
Product with instructions for use
The present invention also includes the inclusion of instructions for using the coating composition of the present invention with a package containing the coating composition or other forms of advertising relating to the sale or use of the coating composition. The instructions may be included in any manner typically used by consumer product manufacturers or suppliers. Examples include a label affixed to a container holding the coating composition; an instruction on a sheet affixed to the container or provided at the time of purchase; or advertising, performance, and / or the purchase or use of the coating composition. Providing instructions in other sentences or verbal descriptions that may be connected.
[0188]
Specifically, the instructions indicate the use of the coating composition, e.g., the recommended amount of the composition to be used to coat the hard surface or article, if spraying, dipping, or rubbing is appropriate. Includes a description of the recommended amount of the composition applied to the surface.
The coating composition of the present invention is alternatively included in the product. The product may alternatively comprise a hard surface coating composition according to the present invention, and may further comprise a hard surface that requires treatment, such that the coating composition imparts one or more desired hard surface coating benefits to the hard surface. Includes instructions for using the product to wash hard surfaces by contacting with an amount of the coating composition.
The following examples are illustrative of the present invention and are not meant to limit or limit its scope. All parts, percentages and ratios used herein are expressed as weight percent unless otherwise indicated.
The compositions and methods of the present invention can be used for industrial modification of hard surfaces, such as in the manufacture of automotive and building components.
[0189]
(Example)
The following provides some non-limiting examples of the present invention.
Example 1
A composition comprising 68 grams of URECLEAR® clear paint obtained from BASF Corporation, Southfield, Michigan, USA was synthesized from Southern Clay Products, Inc. of Gonzales, Texas, USA. Combine with 0.1-25 grams of hectorite, a nanoclay such as Laponite ™. The two components are mixed under stirring and 15 grams of methyl isoamyl ketone methyl-2-hexanone are added.
The clear coating composition is sprayed wet-on-wet on a very hard undercoat on the outer skin of the car body primed with electrocoating. Flush the skin at room temperature for 10 minutes, then cure at 270 ° F (132.20 ° C) for 20 minutes.
[0190]
Examples 2 to 15
The liquid coating composition according to the present invention is as follows, with the balance being water:
[0191]
[Table 2]

[0192]
1. The nanoclay can be any of the available synthetic hectorite clays, such as, for example, Laponite ™ available from Southern Clay Products.
2. Disperal P2 ™ is boehmite alumina from Condea.
[0193]
Examples 16 to 19
In the following examples, a dispersant was formulated with a nanoclay and a surfactant so that a hard surface coating composition could be prepared in tap water:
[0194]
[Table 3]

[0195]
1. The nanoclay can be any of the available synthetic hectorite clays, such as, for example, Laponite ™ from Southern Clay Products.
2. MA: AA = 4: 6, MW = 11,000.
[0196]
Examples 20 to 27
According to the invention, the balance is water and the coating composition can be applied to the surface, optionally diluting said coating composition with water to achieve a 0.1% nanoparticle coating composition. The liquid coating composition is as follows:
[0197]
[Table 4]

[0198]
1. The nanoclay can be any of the available synthetic hectorite clays, such as, for example, Laponite ™ available from Southern Clay Products.
2. Disperal P2 ™ is boehmite alumina from Condea.
3. MA: AA = 4: 6, MW = 11,000.
[0199]
The skin was treated with 0.1% nanoclay / 0.075% Neodol 91-6 surfactant using a Solo sprayer and air dried vertically. Heat the skin in the oven for 25 minutes at the temperature specified in Table 1 and then cool. The performance after heating was evaluated and the skin was polished (Sheet Wet Abrasion Scrub Tester, 500 g total weight, sponge saturated with diluted DAWN® dishwashing solution) and the performance was evaluated. Re-evaluated. Before heating, after heating, and after polishing, the contact angle was measured. After heating using a Miniscan XE (Hunter Associates Laboratory, Inc., Reston, Virginia, USA) equipped with a C / 2 ° illuminant, the color of the skin (CIE @ L * a * b) * Color standard) was measured. Some skins were treated with a thionine cationic dye (500 ppm) to visually evaluate the life of the coating composition.
^aBlack skin cured for 3 days
result
[0200]
[Table 5]

[0201]
Examples 28 to 29
A liquid hard surface coating composition according to the present invention, which can be placed in a spray bottle and delivered as a spray-on formulation to improve the stubborn food degreasing effect on hard surfaces, is as follows: is there:
[0202]
[Table 6]

[0203]
1. The nanoclay can be any of the available synthetic hectorite clays such as, for example, Laponite RD (TM) or B (TM) from Southern Clay Products.
2. Ether-capped poly (oxyalkylated) alcohols act as nonionic wetting agents.
3. Use water for the rest.
[0204]
When applied to a hard surface, the coating composition modifies the hard surface and has the following versatile benefits of an improved hard surface compared to a hard surface that has not been treated with the hard surface coating composition: wetting. And sheet forming, quick drying, uniform drying, dirt removal, self-cleaning, anti-spotting, anti-staining, even cleaner appearance, enhanced gloss, enhanced color, repair of small surface defects, smoothness, anti-fog Exhibit at least one of reduced surface friction, active substance release, abrasion and reduced damage to clarity.
In certain aspects, the hard surface coating has a transmission for light of greater than or equal to about 75% as measured according to a transmission test. That is, in such an embodiment, at least 75% of the incident light is transmitted through the hard surface coating and 25% of the incident light is not transmitted through the hard surface coating. In another aspect, the hard surface coating has a transparency such that the surface coated with the hard surface coating appears to be substantially unchanged to the naked human eye compared to a surface not coated with the hard surface coating. Have.
[0205]
It is possible that the coatings described in the present invention could potentially provide other benefits. Under identified conditions, the coatings described herein reduce drag in moving articles such as skis and moving vehicles such as cars, airplanes, ships, and the like, as well as reduce ice drag on airplane wings. Potentially useful in preventing accumulation and preventing accumulation of material on hard surfaces, such as preventing accumulation of deposits such as debris inside the pipes to facilitate fluid movement. It is considered. One non-limiting example of a preventive purpose for coating is to utilize the coating composition in the nature of a drain flush. Such a composition can be poured into a drainpipe to prevent the accumulation or further accumulation of deposits in the pipe.
[0206]
In any of the embodiments described in this detailed description, unless otherwise indicated, a coating can be applied to a hard surface with or without an aggressive curing step. It is understood that an aggressive curing step is useful because it is believed to provide additional durability to the coating. The coating described herein can be applied at any suitable time on the hard surface, including during or after the manufacture of the hard surface, of the type of hard surface from which it is manufactured. The coating can be applied to the hard surface at any time for protective, preventive or any other purpose.
[0207]
Test method
Unless otherwise indicated, all tests are performed under normal laboratory conditions (50% humidity and 73 ° F. (23 ° C.)).
[0208]
Procedure for measuring coating durability
Method:
1. Clean Surface: Use a 4 in x 12 in automotive skin to receive the desired coating applied. If performing X-ray fluorescence (XRF) analysis, the skin should be cut into 1 in x 1.5 in (2.5 x 3.8 cm) rectangles and rinsed with ethanol before use in polishing tests, It is then washed with DAWN® dishwashing fluid available from Procter & Gamble Company of Cincinnati, Ohio, USA, and rinsed with deionized water.
2. Apply the product with a manual pump sprayer until the car skin is completely wet and air dry (minimum 2 hours).
3. Heat in an oven for 25 minutes (at the desired temperature, for example, one of the temperatures listed in Table 4) and cool to room temperature.
4. Measure the contact angle.
5. Evaluate visual function.
6. Perform a polish test.
7. Evaluate visual function.
8. Once the skin has dried, the contact angle is measured.
9. Perform dye or XRF analysis.
[0209]
Automotive skin specifications: Test skins, primers and primer compositions are obtained from ACT Laboratories, Inc. (Hillsdale, Michigan, USA). The preparation method is as follows. Spray the primer with two coats without flash time between coats. The primer is then flushed for 10 minutes. Bake the substrate in an oven at 265 ° F (129 ° C) (this temperature is the temperature of the substrate or skin) for 30 minutes. Film formation range = 0.9-1.1 mils (22.9-27.9 μm). Once the primer has dried, the primer is applied in two coats with a 60 second flash between coats to form a 0.6-0.8 mils (15.2-20.3 μm) film. After flashing the primer for 2 minutes, apply URECLEAR® clearcoat with a flash of 60 seconds between coats and apply 1.9-2.1 mils (48.3-53.3 μm). Form a film. As shown in FIG. 4, a hard surface coating can be applied to the skin at any step of the method. The skin is then flashed for 20 minutes and then finally baked in an oven: 180 ° F. (82 ° C.) for 10 minutes, then 25 minutes at 270 ° F. (132 ° C.) (substrate temperature ).
[0210]
Visual function evaluation
While holding the skin at 90 ° to horizontal, the substrate is rinsed with water and then the skin is determined to determine whether the substrate exhibits sheeting, makuhari or beading. "Sheet formation" is when a uniform water film covers the substrate and dries slowly without damaging the film. "Makuhari" refers to a case where water slowly gathers in the center and separates from the base material. The function is determined to be "beading", where water does not show affinity for the surface and flows off the substrate quickly.
[0211]
Polishing method for measuring durability
Addition hardness of 10 grains per gallon (Ca²⁺: Mg²⁺4 to 3.25 in x 1.5 in x 1.75 in (8.25 cm x 3.75 in) saturated with 30 mL of 0.2% DAWN® dishwashing water in deionized water having a molar ratio of 3: 1). Attach a Scene Wet Abrasion Scrub Tester (Model 903PG, Sheen Instruments Ltd., Kingston, UK) to an 8 cm x 4.4 cm sponge. The apparatus is set to 30 cycles per minute with a total of 500 g per carrier arm with a 200 g weight on each 300 g carrier arm. Polish level: 0, 10, 50, 100, 500 polish.
[0212]
Contact angle
Deionized water (25 μL) was placed on the pipette-coated substrate and a goniometer (Reme-Hart Inc., Mountain Lake, NJ, USA fitted with an Olympus TGHM light source from Olympus Optical Co., Japan). The contact angle is measured using the NRLC.A. model # 100-00115). Three measurements are taken and averaged for each sample examined.
[0213]
Dye analysis
Only white surfaces can be used for this analysis. Thoroughly rinse the surface with a solution of thionin cationic dye (500 ppm in deionized water), then rinse with water to remove excess dye. An untreated surface of the same type is used as a control. The surface coverage of the synthetic hectorite coating can be evaluated by visual evaluation or Hunter Miniscan XE measurement.
[0214]
X-ray fluorescence analysis
X-ray fluorescence (XRF) is a non-destructive and non-erosive technique for assessing the concentration of an element in a sample or at the surface of a sample. The analysis is performed using a PW2404 continuous “4000W” X-ray spectrometer system serial number DY735, Phillips Analytical, Mass., USA. The instrument settings and XRF analysis specifications are set in Table 6 below.
[0215]
Measurement procedure:
1) Construct a calibration curve relating instrument response to analyte concentration by pipetting a standard of known concentration on the desired substrate. Allow the standard to dry slowly before taking the measurement.
2) Evaluate the standard or sample by placing the sample face down into the sample cup, placing the sample cup on the spectrometer and initiating the data acquisition procedure. In the case of a synthetic hectorite coating, the element lines for Mg and Si are measured, while the element line for Al is used for aluminum oxide coating.
3) Determine the concentration of the sample from the calibration curve against the standard.
[0216]
[Table 7]

[0217]
Permeability test
The permeability is measured using ASTM method D1003-00. Transmittance is expressed as a ratio representing the amount of incident light passing through the article being examined.
[0218]
Viscosity test
All measurements were made with a Brookfield RVDVII + rotational viscometer available from Brookfield Engineering Labs, Stoughton, Mass., USA. The recommended method is as follows, with the following exceptions: Change the recommended procedure by using a smaller container and removing the protective feet. Calibration should be performed at 100 RPM using a 600 ml low profile Griffin-type beaker containing glycerin (1400 cp) and olive oil (80 cp). All subsequent measurements are taken in a 50 ml beaker at 100 RPM with a suitable spindle.
Although particular embodiments of the subject invention have been described, it will be apparent to those skilled in the art that various changes and modifications of the subject invention may be made without departing from the spirit and scope of the invention. All such modifications that fall within the scope of the invention are intended to be covered by the appended claims.
[Brief description of the drawings]
While the conclusions herein are set forth in the claims which particularly point out and distinctly claim the subject matter regarded as forming the invention, it is believed that the invention will be more fully understood from the following description taken in conjunction with the accompanying drawings. Can be
FIG. 1 is a schematic side view of a hard surface with several layers of nanoparticles forming a coating thereon and fouling a portion of the nanoparticle coating.
FIG. 2 is a schematic side view similar to FIG. 1 showing only how removal of the top layer of nanoparticles may remove dirt deposited on the coating.
FIG. 3 is a schematic side view similar to FIGS. 1 and 2 showing further steps in the removal method.
FIG. 4 is a flowchart illustrating the steps in one embodiment of a method for applying a clear paint for use in the automotive industry.

Claims (19)

A method of forming a substantially transparent hard surface coating on a hard surface, comprising:
(A) including an effective amount of a non-photoactive nanoparticulate material, applying a material to the hard surface to coat the hard surface; and (b) actively curing the material on the hard surface. A method comprising: The method of claim 1, wherein a substantially transparent, hydrophilic coating is formed on the hard surface. The step (a) comprises:
(I) applying a plurality of non-photoactive nanoparticles directly to said hard surface; or (ii) applying a plurality of non-photoactive nanoparticles to said hard surface via use of a carrier medium. The method of claim 1. 4. The method of claim 3, wherein the carrier medium comprises: a gas or a liquid, and, if the carrier medium is a liquid carrier medium, any one of an aqueous liquid or a non-aqueous liquid. The method of claim 1, wherein the substance applied in step (a) comprises a hard surface coating composition comprising an effective amount of non-photoactive nanoparticles and a carrier medium. 4. The method of claim 3, wherein the hard surface is charged to promote attraction and adhesion of the non-photoactive nanoparticles thereto. The method of claim 1, wherein said step (b) of actively curing said material on said hard surface comprises one of the following:
Thermally curing the substance; or the step of actively curing the substance, wherein the substance applied in step (a) comprises an agent incorporated therein to accelerate the curing of the substance. (B) that the substance is cured by the agent. The method of claim 5, wherein the hard surface coating composition of step (a) comprises one of the following:
A premix solution; or (i) providing a concentrated hard surface coating composition; (ii) a composition formed by diluting the concentrated hard surface coating composition. A composition is formed by diluting the concentrated hard surface coating composition: and said step (ii) comprises diluting said concentrated hard surface composition with deionized water; or a hard surface coating 9. The method of claim 8, wherein the composition comprises a dispersant, and step (ii) comprises diluting the concentrated hard surface composition with tap water. The step (b), wherein the substance is applied at room temperature and the substance is thermally cured, comprises:
8. Heating the material and the air around the hard surface above room temperature or equivalently; or heating the material and the air around the hard surface above 50 ° C. or equivalently. The method described in. 11. The method of claim 10, wherein the temperature at which the air surrounding the substance is heated does not exceed 180 <0> C. The concentration of nanoparticles in the coating composition before applying to the hard surface is less than 50% by weight of the coating composition;
The coating composition is in the form of a liquid for spraying upon application, wherein the concentration of nanoparticles in the coating composition before applying to the hard surface is less than 20% by weight of the coating composition; or An article according to claim 5, wherein the article is in the form of a liquid for spraying upon application, wherein the concentration of nanoparticles in the coating composition before application to the hard surface is less than 0.5% by weight of the coating composition. Method. The method of claim 5, wherein the viscosity of the coating composition is less than or equal to 1,000 Cps, or alternatively, less than or equal to 100 Cps, or alternatively, less than or equal to 40 Cps. The method of claim 1, wherein the hard surface is selected from the group consisting of fiberglass, plastic, metal, glass, tableware, ceramic, wood, rock, concrete, asphalt, minerals, painted surfaces, and mixtures thereof. The method of claim 1, wherein the hard surface is selected from the group consisting of an automotive skin, an aircraft skin, a ship skin, glass, skis, and inside a pipe. 16. The method according to claim 15, wherein the substance is applied before, during or after the process of painting and / or applying a transparent coating to the car skin. 17. The method of claim 16, wherein the processing comprises painting a car skin, followed by applying a transparent coating, and wherein the processing comprises one or more of the following:
(I) applying one or more primer coats to the exterior skin of said passenger car;
(Ii) applying one or more coatings of paint to the skin of the passenger car;
(Iii) applying one or more coatings of a transparent coating to the skin of the passenger car; and (iv) applying the one or more coatings of the undercoating, the paint coating, or the transparent coating to the passenger car. Heating the outer plate. 18. The method of claim 17, wherein the substance is applied in one or more of the following steps:
After applying the one or more coatings to the skin of the passenger car;
During step (iii) of applying one or more of the transparent coatings to the car skin; and after applying one or more of the transparent coatings to the car skin. a) providing a hard surface coating composition comprising an effective amount of non-photoactive nanoparticles, tap water, and a dispersant; and b) applying the coating composition to modify the hard surface. A method for treating a hard surface comprising:

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