JP3962327B2 - Detergency composition - Google Patents

Abstract

A hard-surface cleaning composition for removing cooked-, baked-, or burnt-on food soil from cookware and tableware, the composition being in sprayable form and comprising an organic solvent system having a volatile organic content above 1 mm Hg of less than about 50% and an odor masking perfume or perfume base, said perfume or perfume base comprising at least about 20% by weight thereof of non-volatile perfume materials having a boiling point above 250°C at 1 atmosphere pressure. The composition can be used as pretreatment prior to the dishwashing process. The composition provides excellent removal of polymerised grease from metal and glass substrates and has a very pleasant odor.

Description

【００４７】
Ｒ¹は平均約７〜約１２個の炭素原子を有する直鎖アルキル炭化水素であり、Ｒ²は約１〜約４個の炭素原子を有する直鎖アルキル炭化水素であり、Ｒ³は約１〜約４個の炭素原子を有する直鎖アルキル炭化水素であり、ｘは約１〜約６の整数、ｙは約４〜約１５の整数及びｚは約４〜約２５の整数である。
その他の低曇点非イオン性界面活性剤は、以下の式を有するエーテル末端保護ポリ（オキシアルキル化）である。
Ｒ_IＯ（Ｒ_IIＯ）_nＣＨ（ＣＨ₃）ＯＲ_III
Ｒ_Iは約７〜約１２個の炭素原子を有する直鎖又は分岐鎖、飽和又は不飽和、置換型又は非置換型、脂肪族又は芳香族の炭化水素基から成る群から選択され、Ｒ_IIは同じ基でも異なる基でもよく、上記のいずれかの分子のうち、分岐鎖又は直鎖状Ｃ₂〜Ｃ₇のアルキレンから成る群から独立して選択され、ｎは１〜約３０の数であり、Ｒ_IIIは以下の群から選択される。
【００４８】
（ｉ）１〜３個のヘテロ原子を有する４〜８員環の置換型又は非置換型複素環、及び
（ｉｉ）約１〜約３０個の炭素原子を有する直鎖又は分岐鎖、飽和又は不飽和、置換型又は非置換型、環式又は非環式、脂肪族又は芳香族の炭化水素基。
（ｂ）Ｒ²が（ｉｉ）の場合、（Ａ）Ｒ¹の少なくとも１つがＣ₂〜Ｃ₃アルキレン以外のものであるか、あるいは（Ｂ）Ｒ²が６〜３０個の炭素原子を有し、更にＲ²が８〜１８個の炭素原子を有する場合、ＲはＣ₁〜Ｃ₅アルキル以外のものである。
【００４９】
本明細書に好適なその他の成分には、分散性、再付着防止性、汚れ放出性又はその他の洗浄特性の発明を有する有機ポリマーが含まれる。その割合は、組成物の約０．１重量％〜約３０重量％、好ましくは約０．５重量％〜約１５重量％、最も好ましくは約１重量％〜約１０重量％である。本明細書において好ましい再付着防止ポリマーには、ポリマー含有アクリル酸（例えば、SokalanＰＡ３０、ＰＡ２０、ＰＡ１５、ＰＡ１０及びSokalanＣＰ１０（BASF GmbH）、Acusol４５Ｎ、４８０Ｎ、４６０Ｎ（Rohm and Haas））、アクリル酸／マレイン酸コポリマー（例えば、SokalanＣＰ５）、及びアクリル／メタクリルコポリマーが含まれる。本明細書において好ましい汚れ放出ポリマーには、アルキル及びヒドロキシアルキルセルロース（米国特許第４，０００，０９３号）、ポリオキシエチレン、ポリオキシプロピレン及びこれらのコポリマー、並びにエチレングリコール、プロピレングリコール及びこれらの混合物のテレフタレートエステルに基づく非イオン性及びアニオン性ポリマーが含まれる。
【００５０】
重金属イオン封鎖剤及び結晶成長阻害剤は、一般に組成物の約０．００５重量％〜約２０重量％、好ましくは約０．１重量％〜約１０重量％、更に好ましくは約０．２５重量％〜約７．５重量％、最も好ましくは約０．５重量％〜約５重量％の割合で本明細書に用いるのに好適である。これらには、例えば、ジエチレントリアミンペンタ（メチレンホスホネート）、エチレンジアミンテトラ（メチレンホスホネート）、ヘキサメチレンジアミンテトラ（メチレンホスホネート）、エチレンジホスホネート、ヒドロキシエチレン−１，１−ジホスホネート、ニトリロトリアセテート、エチレンジアミノテトラアセテート、エチレンジアミン−Ｎ，Ｎ’−ジサクシネートの塩及び遊離酸の形態が挙げられる。
【００５１】
本明細書における組成物は、腐食防止剤を含有することができる。これには、例えば、組成物の約０．０５重量％〜約１０重量％、好ましくは約０．１重量％〜約５重量％の割合で含有される有機銀コーティング剤（とりわけ、Wintershall（ドイツ、ザルツバーゲン）から市販されているWinog７０などのパラフィン）、窒素含有腐食防止剤化合物（例えば、ベンゾトリアゾール及びベンズイマダゾール−英国特許第１，１３７，７４１号参照）、及び組成物の約０．００５重量％〜約５重量％、好ましくは約０．０１重量％〜約１重量％、更に好ましくは約０．０２重量％〜約０．４重量％の割合で含有されるＭｎ（ＩＩ）化合物（とりわけ、有機配位子のＭｎ（ＩＩ）塩）が挙げられる。
【００５２】
本明細書におけるその他の好適な成分には、着色剤、約０．０１％〜約５％の割合で含有される水溶性ビスマス化合物（例えば、酢酸ビスマス及びクエン酸ビスマス）、約０．０１％〜約６％の割合で含有される酵素安定剤（例えば、カルシウムイオン、ホウ酸、プロピレングリコール及び塩素漂白剤捕捉剤）、石灰石鹸分散剤（ＷＯ−Ａ−９３／０８８７７号参照）、石鹸泡抑制剤（ＷＯ−Ａ−９３／０８８７６号及び欧州特許第０，７０５，３２４号参照）、ポリマー染料転移阻害剤、光学的光沢剤、香料、充填剤及び粘土が含まれる。
液体洗剤組成物は、キャリアとして水及びその他の揮発性溶媒を含有することができる。本発明の液体洗剤には、少量の低分子量一級又は二級アルコール（例えば、メタノール、エタノール、プロパノール及びイソプロパノール）を使用することができる。少量で使用されるその他の好適なキャリア溶媒には、グリセロール、プロピレングリコール、エチレングリコール、１，２−プロパンジオール、ソルビトール及びこれらの混合物が含まれる。
【００５３】
臭いマスキングベース
臭いマスキングベース（この単語には、完全処方の臭いマスキング香料又はその中に使用するベース組成物が含まれる）は、イオノン、ジャコウ及び高揮発性香料の混合物であることが好ましい。臭いマスキングベースの濃度は、組成物の約０.００１重量％〜約３重量％、好ましくは約０．００６重量％〜約２．５重量％、更に好ましくは約０．００７５重量％〜約１重量％の範囲であることが好ましい。
【００５４】
臭いマスキングベースのイオノン、ジャコウ及び高揮発性香料は、各成分の沸点の範囲に１つの特徴を有する。イオノン及びジャコウは、１気圧において約２５０℃超過の沸点を有することが好ましい。一方、高揮発性香料成分は、１気圧において約２５０℃未満の沸点を有する。多くの香料物質の沸点は、例えば、「Perfume and Flavor Chemicals（Aroma Chemicals）」（S. Arctander、著者出版、１９６９年）に開示されている。その他の沸点は、種々の化学ハンドブック及びデータベース（例えば、the Beilstein Handbook、Lange's Handbook of Chemistry、及びthe CRC Handbook of Chemistry and Physics）から得ることができる。異なる圧力（通常、１標準気圧より低い圧力）における沸点だけが提示されている場合、標準圧又は外気圧における沸点は、沸点−圧力計算図表を使用して概算することができる。この沸点−圧力計算図表には、例えば「The Chemist's Companion」（A. J. Gordon及びR. A. Ford、John Wiley & Sons Publishers、１９７２年、３０〜３６頁）に記載されているものがある。適用可能な場合には、沸点を分子構造データに基づいてコンピュータプログラムで計算することもできる。このようなプログラムには、例えば「Computer-Assisted Prediction of Normal Boiling Points of Pyrans and Pyrroles」（D. T.Stantonら、J. Chem. Inf. Comput. Sci.、３２、１９９２年、３０６〜３１６頁）、「Computer-Assisted Prediction of Normal Boiling Points of Furans, Tetrahydrofurans, and Thiophenes」（D. T. Stantonら、J. Chem. Inf. Comput. Sci.、３１、１９９２年、３０１〜３１０頁）及びこれらの中で引用している参照文献、並びに「Predicting Physical Properties from Molecular Structure」（R. Muruganら、Chemtech、１９９４年６月、１７〜２３頁）に記述されているものがある。
臭いマスキングベースのイオノン香料、高揮発性香料及びジャコウ成分の各成分について、以下に詳細に記述する。
【００５５】
高揮発性香料
臭いマスキングベースの高揮発性香料は、悪臭溶媒と競合して鼻のレセプター受容体部に到達する香料物質を含有する。これらの高揮発性香料は、脳に最初に認識され、識別される臭いであり、嗅覚における溶媒認識を阻害又はマスクすることに役立つ。高揮発性香料の濃度は、臭いマスキングベースの約１５重量％〜約８５重量％、好ましくは約２０重量％〜約８０重量％、更に好ましくは約３５重量％〜約７５重量％、より好ましくは約４５重量％〜約６５重量％である。
高揮発性香料は、臭いマスキングベースのイオノン及びジャコウ成分より揮発性が高く、１気圧において約２５０℃未満、好ましくは約２３０℃未満、更に好ましくは約２２０℃未満の沸点を有する。これらの高揮発性香料は、約２〜１５個の炭素原子を有するアルデヒド、約３〜１５個の炭素原子を有するエステル、約４〜１２個の炭素原子を有するアルコール、約４〜１３個の炭素原子を有するエーテル、約３〜１２個の炭素原子を有するケトン又はこれらの組み合わせとして分類される。
【００５６】
好適なアルデヒドの例には、ｎ−デシルアルデヒド、１０−ウンデセン−１−アル、ドデカナール、３，７−ジメチル−７−ヒドロキシオクタン−１−アル、２，４−ジメチル−３−シクロヘキセンカルボキシアルデヒド、ベンズアルデヒド、アニスアルデヒド及びこれらの混合物が含まれるが、これらに限定されない。
好適なエーテルの例には、エチルアセテート、シス−３−ヘキセニルアセテート、２，６−ジメチル−２，６−オクタジエン−８−イルアセテート、ベンジルアセテート、１，１−ジメチル−２−フェニルアセテート、２−ペンチルオキシアリルエステル、アリルヘキサノエート、メチル−２−アミノベンゾエート及びこれらの混合物が含まれるが、これらに限定されない。
【００５７】
好適なアルコールの例には、ｎ−オクチルアルコール、β−γ−ヘキセノール、２−トランス−６−シス−ノナジエン−１−オル、３，７−ジメチル−トランス−２，６−オクタジエン−１−オル、３，７−ジメチル−６−オクテン−１−オル、３，７−ジメチル−１，６−オクタジエン−３−オル、２，６−ジメチル−７−オクテン−２−オル、２−フェニルエチルアルコール、２−シス−３，７−ジメチル−２，６−オクタジエン−１−オル、１−メチル−４−イソプロピル−１−シクロヘキセン−８−オル及びこれらの混合物が含まれるが、これらに限定されない。
好適なエーテルの例には、アミルクレゾールオキシド、４−エトキシ−１−メチル−ベンゾール、４−メトキシ−１−メチルベンゼン、メチルフェニルエチルエーテル及びこれらの混合物が含まれるが、これらに限定されない。
【００５８】
好適なケトンの例には、ジメチルアセトフェノン、エチル−ｎ−アミルケトン、２−ヘプタノン、２−オクタノン、３−メチル−２−（シス−２−ペンテン−１−イル）−２−シクロペンテン−１−オン、１−１−メチル−４−イソプロペニル−６−シクロヘキセン−２−オン、パラ−第三級アミルシクロヘキサノン及びこれらの混合物が含まれるが、これらに限定されない。
好ましい高揮発性香料には、２−ペンチルオキシアリルエステル（Allyl Amyl Glycolateの商標でInternational Flavors and Fragrances, Inc.（米国ニューヨーク州ニューヨーク）から市販されている）、ベンズアルデヒド（Amandolの商標でRhone-Poulenc, Inc（米国ニュージャージー州プリンストン）から市販されている）、シス−３−ヘキセニルアセテート（Verdural extraの商標でInternational Flavors and Fragrances, Inc.（米国ニューヨーク州ニューヨーク）から市販されている）、２，６−ジメチル−７−オクテン−２−オル（Dihydromyrcenolの商標でInternational Flavors and Fragrances, Inc.（米国ニューヨーク州ニューヨーク）から市販されている）、パラ−第三級アミルシクロヘキサノン（Orivoneの商標でInternational Flavors and Fragrances, Inc.（米国ニューヨーク州ニューヨーク）から市販されている）、ｎ−デシルアルデヒド（Decyl Aldehydeの商標でAceto, Corp.（米国ニューヨーク州レークサクセス）から市販されている）及びこれらの混合物が含まれる。
好適な高揮発性香料の例及びそれらの１気圧における沸点は、米国特許第５，９１９，４４０号に開示されているが、これらに限定されない。
【００５９】
イオノン
臭いマスキングベースは、イオノン香料成分（つまり、イオノン又はイオノン混合物）を、臭いマスキングベースの約１５重量％〜約８０重量％、好ましくは約１６重量％〜約６０重量％、更に好ましくは約１６重量％〜約４０重量％の濃度で含有することが好ましい。イオノンは、天然油に由来するか、合成的に作られる香料化学物質においてよく知られた種類であり、典型的に無色又は淡黄色の液体で、森林スミレのような香りを呈する。
【００６０】
臭いマスキングベースに使用するイオノン香料は、１気圧において約２５０℃超過、好ましくは約２５５℃超過、更に好ましくは約２６０℃超過の沸点を有し、このときイオノン香料は、メチルイオノン、αイオノン、βイオノン、γイオノン又はこれらの組み合わせから選択されることが好ましい。
好適なイオノンの例には、１−（２，６，６−トリメチル−２−シクロヘキセン−１−イル）−１，６−ヘプタジエン−３−−オン、２−アリル−パラ−メンテン−（４（８））−オノ−３、擬似アリル−α−イオノン、α−シトリリデンシクロペンタノン、５−（２，６，６−トリメチル−２−シクロヘキセン−１−イル）−４−メチル−４−ペンテン−３−オン、６−（２，６，６−トリメチル−２−シクロヘキセン−１−イル）−１−メチル−５−ヘキセン−４−オン、２，６，６−トリメチルシクロヘキシル−１−ブテノン−３、ジヒドロ−α−イオノン、４−（２，６，６−トリメチルシクロヘキセン−１−イル）−ブタン−２−オン、４−（２−メチレン−６，６−ジメチルシクロヘキシル）−ブタン−２−オン、１−（２，５，６，６−テトラメチル−２−シクロヘキセニル）−ブタン−３−オン、ジヒドロ−β−イロン、ジヒドロ−γ−イロン、５−（２，６，６−トリメチル−２−シクロヘキセニル）−ペンタン−３−オン、シヒドロ−イソ−メチル−β−イオノン、６−（２，６，６−トリメチル−２−シクロヘキセン−１−イル）−５−ヘキセン−４−オン、α−エチル−２，２，６−トリメチルシクロヘキサンブチルアルデヒド、４−メチル−６−（１，１，３−トリメチル−２’−シクロヘキセン−２’−イル）−３，５−ヘキサジエン−２−オン、６，１０−ジメチルウンデカン−２−オン、６−（２，６，６−トリメチル−１−シクロヘキセン−１−イル）−１−メチル−２，５−ヘキサジエン−４−オン、６−（２，６，６−トリメチル−２−シクロヘキセン−１−イル）−１−メチル−２，５−ヘキサジエン−４−オン、４−（２，２，６−トリメチル−２−シクロヘキセン−１−イル）−３−ブテン−２−オン、４−（２，６，６−トリメチル−１−シクロヘキセン−１−イル）−３−ブテン−２−オン、４−（２−メチレン−６，６−ジメチルシクロヘキシル）−３−ブテン−２−オン、エポキシ−２，３−β−イオノン、エチル−２，３−エポキシ−３−メチル−５−（２，６，６−トリメチル−２−シクロヘキセニル）−４−ペンテノエート、α−イオノンアントラニル酸メチル、メチル−２，３−エポキシ−３−メチル−５−（２，６，６−トリメチル−２−シクロヘキセニル）−４−ペンテノエート、４−（２，５，６，６−テトラメチル−２−シクロヘキセン−１−イル）−３−ブテン−２−オン、６−メチル−β−イオノン、６−メチル−γ−イオノン、４−（２，６，６−トリメチル−２−シクロヘキセニル）−２，３−ジメチル−２−ブテン−１−アル、４−（２，６，６−トリメチル−２−シクロヘキセン−１−イル）−３−メチル−３−ブテン−２−オン、５−（２，６，６−トリメチル−２−シクロヘキセン−１−イル）−４−ペンテン−３−オン、５−（２，６，６−トリメチル−１−シクロヘキセン−１−イル）−４−ペンテン−３−オン、４−（２，６，６−トリメチル−３−シクロヘキセン−１−イル）−３−メチル−３−ブテン−２−オン、５−（２−メチレン−６，６−ジメチルシクロヘキシル）−４−ペンテン−３−オン、４−（２−メチレン−６，６−ジメチルシクロヘキシル）−３−メチル−３−ブテン−２−オン、４−（２，３，６，６−テトラメチル−２−シクロヘキセン−１−イル）−３−ブテン−２−オン、４−（２，４，６，６−テトラメチル−２−シクロヘキセン−１−イル）−３−ブテン−２−オン、４−（２，４，６，６−テトラメチル−１−シクロヘキセン−１−イル）−３−ブテン−２−オン、５−メチル−１−（３−メチル−３−シクロヘキセニル）−１，３−ヘキサンジオン、２−メチル−４−（２，６，６−トリメチル−２−シクロヘキセニル）−３−ブテン−１−アル、３−メチル−４−（２，４，６−トリメチル−３−シクロヘキセニル）−３−ブテン−２−オン、４−（２−メチル−５−イソ−プロペニル−１−シクロペンテン−１−イル）−２−ブタノン、４−（２，６，６−トリメチル−７−シクロヘプテニル）−３−ブテン−２−オン、４−（２，６，６−トリメチル−４−シクロヘキセニル）−３−ブテン−２−オン、２，６−ジメチルウンデカ−２，６，８−トリエン−１０−オン、２，６，１２−トリメチル−トリデカ−２，６，８−トリエン−１０−オン、２，６−ジメチルドデカ−２，６，８−トリエン−１０−オン、２，６，９−トリメチルウンデカ−２，６，８−トリエン−１０−オン、４−（２，６，６−トリメチル−２−シクロヘキセン−１−イル）−３−メチル−３−ブテン−２−オン、４−（２，４，６−トリメチル−３−シクロヘキセン−１−イル）−３−ブテン−２−オン、５−（２−メチレン−６，６−ジメチルシクロヘキシル）−４−ペンテン−３−オン及びこれらの混合物が含まれるが、これらに限定されない。
【００６１】
好ましいイオノンには、４−（２，６，６−トリメチル−３−シクロヘキセン−１−イル）−３−メチル−３−ブテン−２−オン（Isoraldeineの商標でGivaudan Roure, Corp.（米国ニュージャージー州ティーネック）から市販されている）、５−（２−メチレン−６，６−ジメチルシクロヘキシル）−４−ペンテン−３−オン（γ−メチルイオノンの商標でGivaudan Roure, Corp.（米国ニュージャージー州ティーネック）から市販されている）、４−（２，２，６−トリメチル−２−シクロヘキセン−１−イル）−３−ブテン−２−オン（α−イオノンの商標でInternational Flavors and Fragrances, Inc.（米国ニューヨーク州ニューヨーク）から市販されている）、４−（２，６，６−トリメチル−１−シクロヘキセン−１−イル）−３−ブテン−２−オン（β−イオノンの商標でInternational Flavors and Fragrances, Inc.（米国ニューヨーク州ニューヨーク）から市販されている）、４−（２，６，６−トリメチル−２−シクロヘキセン−１−イル）−３−メチル−３−ブテン−２−オン（メチルイオノンの商標でBush Boake Allen, Inc.（米国ニュージャージー州モントベール）から市販されている）及びこれらの混合物が含まれる。
【００６２】
イオノンは、１つ以上の個別の香料化学物質として、あるいはイオノン香料化学物質を含む香料化学物質の組み合わせから構成される特定香料として、臭いマスキングベースに添加することができる。イオノン特定香料の例には、Alvanone Extra（International Flavors and Fragrances, Inc.（米国ニューヨーク州ニューヨーク）から市販されている）、Irisia Base（Firmenich, Inc.（米国ニュージャージー州プリンストン）から市販されている）、Irival（International Flavors and Fragrances, Inc.（米国ニューヨーク州ニューヨーク）から市販されている）、Iritone（International Flavors and Fragrances, Inc.（米国ニューヨーク州ニューヨーク）から市販されている）及びこれらの混合物が含まれるが、これらに限定されない。
本明細書に用いるのに好適なその他のイオノン含有物質は、例えば、オジギソウ、スミレ、アヤメ、ニオイイリス及びこれらの混合物などの天然物質である。
【００６３】
臭いマスキングベースに使用するジャコウ及び高揮発性香料も、１つ以上の個別の香料化学物質として、あるいは香料化学物質の組み合わせから構成される特定香料として、臭いマスキングベースに添加することができる。好ましい高揮発性特定香料の例には、Cassis Base３４５−Ｂ（Firmenich, Inc.（米国ニュージャージー州プリンストン）から市販されている）が含まれるが、これに限定されない。N好適なイオノン香料の例及びそれらの１気圧における沸点は、米国特許第５，９１９，４４０号に開示されているが、これらに限定されない。
【００６４】
ジャコウ
臭いマスキングベースは、ジャコウ成分を、臭いマスキングベースの約５重量％〜約７０重量％、好ましくは約１５重量％〜約５０重量％、更に好ましくは約２０重量％〜約３５重量％の濃度で含有することが好ましい。ジャコウは香料化学物質のよく知られた種類であり、典型的に無色又は淡黄色の物質で、特有のジャコウようの香りを有する。
臭いマスキングベースに使用するジャコウ成分は、１気圧において約２５０℃超過、好ましくは約２５５℃超過、更に好ましくは約２６０℃超過の沸点を有する必要があり、このときジャコウ成分は、多環式ジャコウ、大環状ジャコウ、ニトロ環式ジャコウ又はこれらの組み合せであることが好ましい。また、ジャコウ成分はそれぞれ、約１２個超過、好ましくは約１３個超過、更に好ましくは約１５個超過の炭素原子を有することが好ましい。
【００６５】
好適な多環式ジャコウには、５−アセチル−１，１，２，３，３，６−ヘキサメチルインダン、４−アセチル−１，１−ジメチル−６−第三級ブチルインダン、７−アセチル−１，１，３，４，４，６−ヘキサメチル−１，２，３，４−テトラヒドロナフタレン、１，１，４，４−テトラメチル−６−エチル−７−アセチル−１，２，３，４−テトラヒドロナフタレン、１，３，４，６，７，８−ヘキサヒドロ−４，６，６，７，８，８−ヘキサメチル−シクロペンタ−γ−２−ベンゾピラン及びこれらの混合物が含まれる。
好適な大環状ジャコウには、シクロペンタデカノリド、シクロペンタデカノロン、シクロペンタデカノン、３−メチル−１−シクロペンタデカノン、シクロヘプタデセン−９−オン−１、シクロヘプタデカノン、シクロヘキサデセン−７−オリド、シクロヘキサデセン−９−オリド、シクロヘキサデカノリド、エチレントリデカンジオエート、１０−オキサヘキサデカノリド、１１−オキサヘキサデカノリド、１２−オキサヘキサデカノリド及びこれらの混合物が含まれる。
【００６６】
好適なニトロ環式ジャコウには、１，１，３，３，５−ペンタメチル−４，６−ジニトロインダン、２，６−ジニトロ−３−メトキシ−１−メチル−４−第三級ブチルベンゼン、２，６−ジメチル−３，５−ジニトロ−４−第三級ブチル−アセトフェノン、２，６−ジニトロ−３，４，５−トリメチル−第三級ブチルベンゼン、２，４，６−トリニトロ−１，３−ジメチル−５−第三級ブチルベンゼン及びこれらの混合物が含まれる。
好ましいジャコウには、１，３，４，６，７，８−ヘキサヒドロ−４，６，６，７，８，８−ヘキサメチル−シクロペンタ−γ−２−ベンゾピラン（Galaxolideの商標でInternational Flavors and Fragrances, Inc.（米国ニューヨーク州ニューヨーク）から市販されている）、シクロペンタデカノリド（Exaltolideの商標でFirmenich, Inc.（米国ニュージャージー州プリンストン）から市販されている）、エチレントリデカンジオエート（Ethylene Brassylateの商標でFragrance Resource, Inc.（米国ニュージャージー州キーポート）から市販されている）、７−アセチル−１，１，３，４，４，６−ヘキサメチル−１，２，３，４−テトラヒドロナフタレン（Tonalidの商標でGivaudan 好適なジャコウの例及びそれらの１気圧における沸点は、米国特許第５，９１９，４４０号に開示されているが、これらに限定されない。
【００６７】
（実施例）
実施例に使用されている略語
実施例において、成分名の略語は次の意味を有する。
【００６８】
【表１】

【００６９】
以下の実施例では、割合はすべて重量で表す。
【００７０】
実施例１〜１６
実施例１〜１６は、食品の調理汚れ、焼きつき汚れ及び焦げつき汚れを除去しやすくするために、食器洗い前に使用する前処理用組成物について説明する。実施例の組成物を洗い物に適用する。洗い物は、１４０℃で２時間焼いたパイレックス容器のラザーニャ、１５０℃で２時間調理したステンレススチール容器のラザーニャ、１５０℃で２時間調理したステンレススチール容器のポテトとチーズ、１５０℃で２時間調理したステンレススチール容器の卵黄及び１２０℃で１時間調理した後、１８０℃で１時間調理したソーセージといった異なる汚れと異なる基材から構成される。洗い物を実施例の組成物に１０分間浸け置きした後、冷たい水道水ですすぐ。その後、典型的な食器洗い用洗剤組成物で、洗い物を手で、あるいは自動食器洗い機（例えば、Bosch６０３２食器洗い機）で洗浄する（５５℃、下洗いは行わない）。典型的な食器洗い用洗剤組成物は、例えば、アルカリ性成分、ビルダー、酵素、漂白剤、漂白剤触媒、非イオン性界面活性剤、石鹸泡抑制剤、銀腐食防止剤、汚れ懸濁化ポリマーなどを含有する。洗い物を実施例の組成物で処理し、その後、食器洗い機で洗浄したところ、食品の調理汚れ、焼きつき汚れ及び焦げつき汚れがきれいに除去された。
【００７１】
【表２】

【００７２】
【表３】

【００７３】
【表４】

【００７４】
【表５】

【００７５】
実施例はすべて、２５℃における液体表面張力が２４．５ｍＮ／ｍ未満、ｐＨが１２以上及びステンレススチール基材上の重合油脂汚れにおける４５分間の汚れ膨潤指数が少なくとも２００％である。
マスキング香料組成物を以下の表に示す。
【００７６】
【表６】

[0001]
(Industrial application fields)
The present invention is an invention in the field of hard surface cleaning compositions, and in particular to products and methods suitable for removing cooking, burnt and burnt stains from cookware and tableware.
[0002]
(Background of the Invention)
Cooking stains, burn-in stains and burnt stains are among the most difficult to remove from the surface. Traditionally, removing cooked, burnt and burnt stains from cookware and tableware requires soaking the soiled article in water prior to mechanical cleaning. It is considered difficult to sufficiently remove cooking stains, burn-in stains, and burnt stains only by the method using an automatic dishwasher. The method of washing dishes by hand requires strong rubbing to remove cooking stains, burn-in stains and burnt stains, which can be detrimental to safety and the condition of the cookware / tableware.
[0003]
It is known in the art to use detersive compositions containing solvents to facilitate removal of cooked, burned and burnt stains. For example, U.S. Pat. No. 5,102,573 presents a method of treating hard surfaces soiled with cooking soil, burnt soil, or dried food residue. In this method, the pre-spot composition is dropped onto a soiled article. The composition to be dropped contains a surfactant, a builder, an amine and a solvent. U.S. Pat. No. 5,929,007 presents an aqueous detergency composition for hard surfaces to remove deposits of oil stains that are hardened, dried or baked. The composition contains a nonionic surfactant, a chelating agent, a corrosive agent, a glycol ether solvent system, an organic amine and an anti-redeposition agent. WO-A-94 / 28108 discloses an aqueous detergent concentrate composition that can be diluted to create a more viscous use solution. This use solution has an effective consistency due to the hooked micelle thickener composition, the low molecular weight alkyl glycol ether solvent and the hard sequestering agent. As an example of its application, it describes a method for cleaning a cooking preparation device having at least one essentially vertical surface covered with a burn-in stain of food. However, in fact, none of the inventions has been confirmed to be very effective in removing dirt that has burned and polymerized from metals or other substrates.
Accordingly, there remains a cleansing composition and method that can be used prior to cleaning cooking soils, burnt or burnt food utensils, and table utensils to facilitate cleaning of food residues that are difficult to remove. It has been demanded. There also remains a need for detergency compositions and methods that are more effective in removing burn-in stains.
[0004]
(Summary of Invention)
In the first aspect of the present invention, cooking stains, burnt stains and burnt stains (oils and fats, meats, dairy products, fruits, pasta and other foods that are particularly difficult to remove after cooking) are used as cooking utensils and table utensils. Provided is a hard surface detersive composition for removal from (including stainless steel, glass, plastic, wood and earthenware articles), the composition containing an organic amine solvent. Generally, the composition has a liquid surface tension of less than about 26 mN / m, preferably less than about 25 mN / m, more preferably less than about 24.5 mN / m, more preferably less than about 24 mN / m. When measured as a% distilled aqueous solution, it has a pH of at least 10.5. The organic amine solvent is present in an effective amount in the compositions herein. This effective amount is an amount that can functionally remove cooking stains, burn-in stains, and burnt stains. In situations where the liquid surface tension is low and the pH is high, the organic amine solvent can act as a swelling agent, wettable powder or other solvating agent for cooking stains, burnt stains and burnt stains, and in this context. Demonstrate the effect. In this specification, the term “stain swelling agent” means that when a substrate on which cooking dirt, burn-in dirt, and burnt dirt are deposited is treated with a dirt swelling agent, these dirt can be swollen without applying external frictional force. It is considered a substance or composition. The soil swelling effect can be expressed by a soil swelling index.
[0005]
The compositions of the present invention preferably have a pH of at least about 10.5, preferably from about 11 to about 14, more preferably from about 11.5 to about 13.5, when measured as a 10% distilled aqueous solution. When cleaning cooking stains, burn-in stains and burnt stains, the cleaning performance is related to some extent to the high pH of the detersive composition. However, some acidic soils such as cooking oil are preferably pre-alkaline in order to keep the pH high. On the other hand, it is necessary that the preliminary alkalinity is not too high so as not to damage the user's skin. Accordingly, it is preferred that the compositions of the present invention have a pre-alkaline of less than about 5, preferably less than about 4, especially less than about 3. “Preliminary alkalinity” as used herein refers to the ability of a composition to keep the pH alkaline even in the presence of acid. This is related to the fact that the pH can be maintained by treating an acid to which a composition having sufficient reserve alkali is added. More specifically, preliminary alkalinity is defined as grams of NaOH per 100 cc of products with a pH greater than 9.5. The preliminary alkalinity of the solution is measured by the following method.
[0006]
The pH 4, 7, and 10 buffers (or buffers in the expected pH range) are used to calibrate the auto titrator Mettler DL77 with the glass pH electrode Mettler DG115-SC. Prepare a 1% solution of the composition to be measured using distilled water. Record the weight of the sample. Measure the pH of the 1% solution and titrate the solution using 0.25N HCl solution until the pH is 9.5. The preliminary alkalinity (RA) is calculated by the following method.
RA = NaOH ratio × specific gravity
Ratio of NaOH = ml of HCl × normality of HCl × 40 × 100 / weight of aliquoted sample (g) × 1000
In the composition of the present invention, a surfactant selected from anionic surfactants, amphoteric surfactants, bipolar surfactants, nonionic surfactants, semipolar surfactants and mixtures thereof is reduced. When added at a concentration, the cleaning action is enhanced, which also helps protect the user's skin. Preferred surfactant concentrations are from about 0.05% to about 10%, preferably from about 0.09% to about 5%, more preferably from about 0.1% to about 2%. Preferred surfactants for use herein are amine oxide surfactants.
[0007]
The soil swelling index (SSI) is a value obtained by measuring the increased thickness of the soil by treating the soil with a substance or composition and comparing the thickness of the soil before and after the treatment. Without being limited by theory, it is believed that the increase in soil thickness is due, at least in part, to soil hydration or solvation. When the dirt swells, the dirt can be easily removed without applying a force or with a minimum force. This minimum force includes, for example, wiping, rinsing, manual or automatic dishwashing. The change in dirt thickness is measured and expressed as SSI.
[0008]
The amount of material or composition required to swell the soil will depend on the nature of the material or composition and can be determined by routine experimentation. Other conditions that affect soil swelling (eg, pH, temperature, and treatment time) can also be determined by routine experimentation. However, the preferred materials or compositions herein are organic amines, which are effective in swelling cooked, burned and burnt stains such as polymerized fats and carbohydrate stains on glass and metal substrates. When the organic amine is contacted with the soil at 20 ° C. within 45 minutes, preferably within 30 minutes, more preferably within 20 minutes, at least about 15%, preferably at least about 20 in a 5% aqueous solution, pH 12.8. %, More preferably at least about 30%, especially at least about 50%. It is also preferred to select the organic amine so that the final composition has an SSI of at least about 100%, preferably at least about 200%, more preferably at least about 500%. At this time, the SSI of the final composition is measured as an undiluted stock solution under the same processing time and temperature conditions as described above. Highly preferred soil swelling agents and final compositions herein are those that meet the SSI values required for polymerized oil soils when following the methods described below.
[0009]
In this specification, SSI is measured by optical visual inspection, for example, using a Zygo NewView 5030 scanning white light interferometer. Prepare a sample of polymerized oil. This sample is a stainless steel metal piece coated with a polymerized fat with a brush, and the sample preparation method will be described later in the section on the measurement of the polymerized fat removal index. Next, an optical appearance inspection is performed on a small droplet oil sample having an end thickness of about 10 μm. An image by scanning white light interferometry is taken and processed (S_i) And after processing (S_f) Measure the thickness of the dirty droplet. The interferometer (Zygo NewView 5030 with a Mirau 20x objective lens) separates the incident light into light rays that are directed toward the reference surface inside the interferometer and rays that are directed toward the sample. After the rays are reflected, they recombine inside the interferometer and strengthen each other (architectural interference) or cancel each other (destructive interference), resulting in bright and dark interference fringes. Data is recorded using a CCD (Charge Coupled Device) camera, frequency domain analysis is performed with interferometer software, and the data is processed. Thereafter, the obtained image size (pixel) is converted into an actual size (μm or mm). Dirt thickness on stainless steel metal strip (S_i) Is measured, the stainless steel metal piece is immersed in the composition of the present invention at room temperature for a certain time, and the above method is repeated to obtain the thickness of the soil (S_f). If necessary, repeat the procedure with a sufficient number of droplets and samples to give statistical significance.
[0010]
The SSI is calculated by the following method.
SSI = [(S_f-S_i) / S_i] × 100
The compositions herein are characterized by very low liquid surface tension and contact angle on polymer oil coated substrates. In a preferred embodiment of the present invention, the composition has an advancing contact angle of less than about 20 °, preferably less than about 10 °, more preferably less than about 5 ° at 25 ° C. on a glass substrate coated with polymerized oil. Select as shown.
[0011]
The contact angle measurement method is as follows. A sample plate (a preparation method will be described later) is immersed in a liquid and then pulled up, and the contact angle is calculated according to the Wilhelmy method. The force applied to the sample is measured according to the submerged depth (using software called KrussK12 and SystemK121 of the surface tension meter). This force is proportional to the contact angle of the liquid on the solid surface. The sample plate is prepared as follows. Spray 30-50 g of canola oil into a beaker. A glass slide (3 × 9 × 0.1 cm) is immersed in canola oil to completely cover the surface. This creates a layer of oil that is uniformly dispersed on the surface. Adjust the weight of product formed on the surface of the glass slide until approximately 0.5 g of oil has been released and the oil has spread evenly. After the adjustment, the slide glass is baked at 250 ° C. for 20 minutes and allowed to cool to room temperature.
In another aspect of the present invention, there is provided a hard surface detersive composition that removes cooking stains, burn-in stains and burnt stains from cookware and tableware, the composition comprising an organic amine solvent, Shows an advancing contact angle at 25 ° C. of less than about 20 °, preferably less than about 10 °, and more preferably less than about 5 ° on a glass substrate coated with a polymerized fat.
[0012]
The composition of the present invention may further contain a diffusion aid. Since the diffusion aid serves to reduce the interfacial tension between the organic amine and the soil, the organic amine can increase the wettability of the soil. When a diffusion aid is added to the composition herein, the diffusion aid can reduce the surface tension of the composition. At this time, the diffusion aid is preferably one that can lower the surface tension of the composition than the surface tension of the diffusion aid itself. Particularly useful diffusion aids are those that can reduce the surface tension to less than about 26 mN / m, preferably less than about 24.5 mN / m, more preferably less than about 24 mN / m, especially less than about 23.5 mN / m. It is. Surface tension is measured herein at 25 ° C.
While not wishing to be bound by theory, it is believed that organic amines penetrate soil and hydrate the soil. Diffusion aids promote the interfacial action between the organic amine and the soil and help the soil swell. It is considered that the bonding force between the dirt and the substrate is weakened by the penetration and swelling of the dirt. The resulting composition is particularly effective in removing baked polymer soils from the metal substrate.
[0013]
The diffusion aid used herein can generally be selected from organic solvents, wetting agents and mixtures thereof. In preferred embodiments, the liquid surface tension of the diffusion aid is less than about 30 mN / m, preferably less than about 28 mN / m, more preferably less than about 26 mN / m, and most preferably less than about 24.5 mN / m. Suitable organic solvents that can function as diffusion aids include alcohol solvents, glycols and glycol derivatives, and mixtures thereof. A preferred diffusion aid for use herein is a mixture of diethylene glycol monobutyl ether and propylene glycol butyl ether.
Herein, wetting agents suitable for use as diffusion aids are surfactants, which include anionic surfactants, amphoteric surfactants, bipolar surfactants, nonionic surfactants. Activators and semipolar surfactants are included. Preferred nonionic surfactants include silicone surfactants such as Silwet copolymers. Preferred Silwet copolymers include Silwet L-8610, Silwet L-8600, Silwet L-77, Silwet L-7657, Silwet L-7650, Silwet L-7607, Silwet L-7604, Silwet L-7600, Silwet L-7280 and mixtures thereof. Preferred for use herein is Silwet L-77.
[0014]
Other suitable wetting agents include organic amine surfactants, such as amine oxide surfactants. The amine oxides preferably contain an average of 12 to 18 carbon atoms in the alkyl moiety, and highly preferred herein are dodecyldimethylamine oxide, tetradecyldimethylamine oxide, hexadecyldimethylamine oxide and these It is a mixture.
Highly preferred hard surface detersive compositions herein contain a mixed solvent system, which is based on an organic amine solvent in combination with a cosolvent that acts as a diffusion aid. Also, from the standpoint of optimal removal of baked polymerized soils, a highly preferred composition is preferably a solvent having limited water miscibility (in this case a coupling). Called solvent). Both solvents are preferably present in the composition at a certain concentration. In another aspect of the present invention, there is provided a hard surface cleansing composition that removes cook, burnt and burnt stains from cookware and tableware, the composition comprising from about 10% to about 40. %, Preferably from about 12% to about 20% organic solvent, including about 1% to about 15% organic amine solvent and about 7% to about 30% solvent acting as a diffusion aid, It further contains at least about 3.5% water miscible solvent and at least about 3.5% coupling solvent with limited water miscibility.
[0015]
As used herein, a water-miscible solvent is a solvent that can be miscible with water in any proportion at 25 ° C. A coupling solvent having limited miscibility is a solvent that is miscible with water at a certain ratio at 25 ° C., but is immiscible depending on the ratio. The solvent preferably has a water solubility at 25 ° C. of less than about 30% by weight, preferably less than about 20% by weight. Also, the solubility of water in the solvent is preferably less than about 30% by mass, preferably less than about 20% by mass at 25 ° C.
Preferred diffusion aids herein include a mixture of a water miscible enough organic solvent and a limited water miscible coupling organic solvent, wherein the ratio of the water miscible organic solvent to the coupling organic solvent is About 4: 1 to about 1:20, preferably about 2: 1 to about 1: 6, more preferably about 1.5: 1 to about 1: 3. Other suitable diffusion aids are wetting agents having a liquid surface tension of less than about 30 mN / m, preferably less than about 28 mN / m, more preferably less than about 26 mN / m, more preferably less than about 24.5 mN / m. Containing. A preferred wetting agent is amine oxide. A highly preferred diffusion aid contains a mixture of coupling solvent and wetting agent.
[0016]
Another aspect of the present invention provides a hard surface detersive composition that removes cooking stains, burnt stains and burnt stains from utensils and tableware, the composition comprising an organic amine solvent, limited A water-miscible coupling solvent and wetting agent and having a liquid surface tension of less than about 26 mN / m, preferably less than about 24.5 mN / m.
The compositions herein further have the characteristic of exhibiting properties that reduce surface tension. This property is considered to be important for ensuring optimum removal performance against polymerized soil. In another aspect of the present invention, there is provided a hard surface detersive composition that removes cooking stains, burnt stains and burnt stains from cookware and tableware, the composition comprising an organic solvent system and a wetting agent. Containing. At this time, the organic solvent system contains at least an organic amine solvent component, and the wetting agent is effective in reducing the surface tension of the solvent system by at least 1 mN / m from the surface tension of the wetting agent.
[0017]
The compositions of the present invention preferably have a surface tension of less than about 24 mN / m, preferably less than about 23.5 mN / m.
Suitable organic amine solvents for use herein include alkanolamines, alkylamines, alkyleneamines and mixtures thereof.
[0018]
The composition of this invention has the characteristics which show the removal performance outstanding with respect to polymer fats and oils. The composition of the present invention preferably has a polymerized oil removal index of at least 25%, preferably at least 50%, more preferably at least 75%. The polymerized oil removal index is a measured value of the amount of dirt removed from the surface by treatment with the composition of the present invention. A dishwasher without the use of detergents or rinsing agents after soaking the soiled substrate in the composition of the present invention for about 45 minutes, preferably within about 30 minutes, more preferably within about 20 minutes at room temperature. Wash with. The substrate is then dried and weighed, and the removed soil is determined by gravimetric analysis. The soiled substrate is prepared as follows. Thoroughly wash the stainless steel piece / slide with the product of the invention and rinse thoroughly with water. If necessary, place the slide in a 50 ° C. room and let it dry. The metal piece / slide is allowed to cool to room temperature (approximately 30 minutes). Measure the weight of the metal piece / slide. Spray canola oil into a small beaker or pour in 3 portions (20-30 ml of canola oil in a 100 ml beaker). Soak 1 inch brush in canola oil. Rotate the dipped brush and gently press it 4-4 times against the side of the container to remove excess canola oil from both sides of the brush. Apply a thin layer of canola oil on the surface of the metal piece / slide. Then gently wipe each slide with a dry brush so that only a thin coating of canola oil is applied (wiping twice evenly will remove the excess). It is believed that 0.1 to 0.2 g of dirt is applied to the metal piece / slide by this method. Place the metal piece / slide on a completely horizontal cookie sheet or oven rack and place in an oven heated to 245 ° C. The slide / metal piece is baked for 20 minutes and then allowed to cool to room temperature (about 45 minutes). After standing to cool, the weight of the metal piece / slide is measured.
[0019]
The solvent-based composition of the present invention is characterized by excellent removal performance when applied directly to dirty cooking utensils and tableware. Desirably, the organic solvent system comprises at least one solvent component that acts as a soil swell agent and has a liquid surface tension of less than about 27 mN / m, preferably less than about 26 mN / m, more preferably less than about 25 mN / m. Furthermore, the organic solvent system contains a plurality of solvent components, the concentration of which is the advancing contact angle of an equivalent composition containing the individual components of the solvent system on a glass substrate coated with polymerized oil. The concentration is preferably such that it has a lower advancing contact angle. Such solvent systems and compositions are formulated to be optimal for removing burnt soils with high carbon content from cookware and tableware. The composition is preferably in the form of a liquid or gel having a pH of greater than about 9, preferably greater than 10.5, more preferably greater than about 11, when measured at 25 ° C.
[0020]
Apart from the solvent parameters described above, the compositions of the present invention must also meet certain rheological parameters and other performance parameters. These parameters include both the properties that allow spraying and the properties that can adhere to the surface. For example, when spraying a product onto a vertical stainless steel surface, it is desirable for the product to have a flow rate of less than about 1 cm / s, preferably less than about 0.1 cm / s. In this case, the product is in the form of a shear thinning fluid, with a shear of about 0 to about 0.8, preferably about 0.3 to about 0.7, more preferably about 0.4 to about 0.6. It has an index (n) (Herschel-Bulkey type). Highly preferred are shear thinning liquids having a shear index of 0.5 or less. On the other hand, the fluid consistency index is about 0.1 to about 50 Pa.s. sⁿOf about 1 Pa. sⁿIt is preferable that it is less than. A more preferred fluid consistency index is from about 0.20 to about 0.15 Pa. sⁿIt is. The product is about 0.1 to about 200 Pa s, preferably about 0.3 to about 20 Pa s at a speed of 3 rpm when measured with a cylinder viscometer Brookfield (LVDII type) using a 10 ml sample and an S-31 spindle. It is preferable to have a consistency of Particularly useful compositions for use herein are greater than about 1 Pas at a speed of 6 rpm, preferably from about 2 to about 4 Pas, less than about 2 Pas at a speed of 30 rpm, preferably from about 0.8 to about 1. It has a consistency of less than about 1 Pas, preferably about 0.3 to about 0.5 Pas at 2 Pas and a speed of 60 rpm. Rheology is measured at room temperature (25 ° C.).
[0021]
Suitable thickener components for use herein include viscoelastic and thixotropic thickener components, the concentration of which is from about 0.1% to about 10%, preferably about 0%. From about 25 wt% to about 5 wt%, most preferably from about 0.5 wt% to about 3 wt%. Suitable thickener components include polymers having a molecular weight of about 500,000 to about 10,000,000, preferably about 750,000 to about 4,000,000. Preferred cross-linked polycarboxylate polymers are preferably carboxyvinyl polymers. Such compounds are disclosed in US Pat. No. 2,798,053 (issued July 2, 1957, Brown). This patent also discloses a method for producing a carboxyvinyl polymer. Carboxyvinyl polymers are substantially insoluble in volatile liquid organic hydrocarbons and are dimensionally stable when exposed to air.
[0022]
Other suitable thickener components include inorganic clays (eg, laponite, aluminum silicate, bentonite, fumed silica). Preferred clay thickener components may be natural or synthetic. Preferred synthetic clays include synthetic smectite-type clays that are commercially available from Southern Clay Products, Inc under the name Laponite ™. Particularly useful are gel-forming grades such as Laponite RD and sol-forming grades such as Laponite RDS. Naturally occurring clays include certain types of smectites and attapulgite clays. Mixtures of clay and polymeric thickener are also suitable for use herein. Preferred for use herein are compatible smectite-type clays (eg, Laponite and other compatible clays) having an average platelet size with a maximum diameter of less than about 100 nm. Laponite has a layered structure, and when dispersed in water, the layered structure takes the form of a disk-shaped crystal having a thickness of about 1 nm and a diameter of about 25 nm. As used herein, platelet size is important to provide excellent sprayability, stability, rheology and adhesion, and desirable aesthetic value.
[0023]
Other types of thickening agents that can be used in the composition include natural rubbers such as xanthan gum, locust bean gum, guar gum and the like. For cellulose type thickeners, hydroxyethyl and hydroxymethylcellulose (ETHOCEL and METHOCEL® commercially available from Dow Chemical) can also be used. Natural rubbers are believed to affect droplet size when spraying the composition. It has been found that when measured using a TSIAerosizer, the droplets have a geometrically equal average diameter of about 3 to about 10 μm, preferably about 4 to about 7 μm, to help reduce odor. . A preferred natural rubber for use herein is xanthan gum.
[0024]
Highly preferred herein is a mixture of Laponite and xanthan gum in view of sprayability, adhesion, stability and soil penetration performance. In addition, a mixture of Laponite and xanthan gum increases the aesthetic value of the product while also reducing the solvent odor.
[0025]
In a preferred embodiment, the hard surface cleaning composition comprises an organic solvent system comprising a solvent component that acts as at least one soil swell agent, wherein the organic solvent system is an alcohol, amine, ester, glycol ether, glycol. , Terpenes and mixtures thereof, containing at least one organic amine solvent component. Suitable organic solvents include organic amine solvents, alkanolamines, alkylamines, alkyleneamines, and mixtures thereof, aromatic alcohols, aliphatic alcohols (preferably C_Four~ C_Ten), An alcohol solvent containing a cycloaliphatic alcohol, and mixtures thereof, C₂~ C_Three(Poly) alkylene glycols, glycol ethers, glycol esters, and mixtures thereof, and glycols and glycol derivatives, and mixtures selected from organic amine solvents, alcohol solvents, glycols and glycol derivatives. Highly preferred organic amine solvents include 2-aminoalkanol solvents as disclosed in US Pat. No. 5,540,846.
[0026]
In a preferred composition of the invention, the organic solvent contains an organic amine (especially alkanolamine) solvent and a glycol ether solvent, preferably in a weight ratio of about 3: 1 to about 1: 3. At this time, the glycol ether solvent is ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, ethylene glycol phenyl. Selected from ethers and mixtures thereof. Preferred organic amines for use herein are alkanolamines, especially monoethanolamine, methylamine ethanol and 2-amino-2-methylpropanol. In a preferred composition, the glycol ether is a mixture of diethylene glycol monobutyl ether and propylene glycol butyl ether, and the weight ratio is preferably from about 1: 2 to about 2: 1.
[0027]
Preferred organic solvent systems for use herein have a volatile organic content of greater than 1 mmHg and less than about 50%, preferably less than about 20%, more preferably less than about 10%. Preferably, the organic solvent is essentially free of solvent components having a boiling point less than about 150 ° C., a flash point less than about 50 ° C., preferably less than about 100 ° C., or a vapor pressure greater than about 1 mmHg. Highly preferred organic solvent systems have a volatile organic content of greater than 0.1 mmHg and less than about 50%, preferably less than about 20%, more preferably less than about 10%, more preferably less than about 4%.
Regarding solvent parameters, the organic solvent can be selected from the following a) to e).
[0028]
a) at least 20 (Mpa)^1/2Hansen solubility parameter of at least 7 (Mpa)^1/2, Preferably at least 12 (Mpa)^1/2Polarity parameters of at least 10 (Mpa)^1/2A polar hydrogen-bonding solvent having the following hydrogen-bonding parameters:
b) at least 20 (Mpa)^1/2Hansen solubility parameter of at least 7 (Mpa)^1/2, Preferably at least 12 (Mpa)^1/2Polarity parameters of 10 and 10 (Mpa)^1/2A polar non-hydrogen bonding solvent having a hydrogen bonding parameter of less than
c) 20 (Mpa)^1/2Hansen solubility parameter of less than 7, at least 7 (Mpa)^1/2Polarity parameters of at least 10 (Mpa)^1/2An amphiphilic solvent having the following hydrogen bonding parameters:
d) 7 (Mpa)^1/2Less than polar parameters and 10 (Mpa)^1/2A nonpolar solvent having a hydrogen bonding parameter of less than
e) Mixtures of these.
[0029]
When an organic solvent is used in the cleaning composition, a solvent odor is generally a problem. Many consumers do not like solvent odors and consider these odors as “bad odors”. If a high concentration of perfume is used, such a composition can be made more acceptable to consumers. Adding a high concentration of perfume can change or reduce all of the unpleasant properties of the composition, but often results in an undesirable result of the perfume scent disappearing. Even if high-concentration perfumes properly alter, mask or mask the malodor of the composition, these high-concentration perfumes do not necessarily improve the essence or duration of the perfume, so that the perfume volatilizes. It will return to the original odor.
[0030]
It is now known that the combination of perfume substances defined herein can be selected and added to the composition of the present invention to effectively suppress or mask malodors when solvents are used in the composition. Yes. Accordingly, in another aspect, the present invention provides a hard surface detergency composition comprising the organic amine solvent described above and a solvent odor masking fragrance or fragrance base. In general, odor masking fragrances or fragrance bases contain a mixture of volatile and non-volatile fragrance materials, where the concentration of non-volatile fragrance materials (boiling point at 250 ° C. at 1 atm) exceeds about 20% by weight. It is preferable that In a preferred embodiment, the perfume or perfume base contains at least 0.001% by weight of ionone or a mixture of ionones (including α, β and γ ionone). Preferred ionones are selected from γ-methyl ionone, Alvanone Extra, Irisia Base, Cassis Base 345-B and mixtures thereof. The perfume or perfume base may further contain musk. The musk preferably has a boiling point above about 250 ° C. Preferred musk is selected from Exaltolide Total, Habonolide, and mixtures thereof. The masking perfume or perfume base may further contain a mixture of highly volatile perfume ingredients or ingredients having a boiling point of less than about 250 ° C. Preferred highly volatile perfume ingredients are selected from decyl aldehyde, benzaldehyde, cis-3-hexenyl acetate, allyl amyl glycolate, dihydromyrsenol and mixtures thereof.
[0031]
The composition can further contain a cyclodextrin to assist in controlling the malodor of the solvent. Cyclodextrins suitable for use herein are those that can selectively absorb molecules that cause the odor of a solvent without adversely affecting odor masking molecules or perfume molecules. The compositions used herein contain about 0.1% to about 3%, preferably about 0.5% to about 2%, by weight of the composition of cyclodextrin. The term “cyclodextrin” as used herein refers to unsubstituted cyclodextrins containing 6-12 glucose units, in particular α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin and / or their Includes any known cyclodextrins such as derivatives and / or mixtures thereof. α-cyclodextrin consists of 6 glucose units, β-cyclodextrin consists of 7 glucose units, and γ-cyclodextrin consists of 8 glucose units arranged in a donut shaped ring. Due to the unique binding and arrangement of glucose units, cyclodextrins have a unique volume cavity and an inflexible conical molecular structure. Since the “lining” of the inner cavity is formed by hydrogen atoms and glycosidic oxygen atoms, this surface is completely hydrophobic. The unique shape and physicochemical properties of the cavity allow the cyclodextrin molecule to absorb (with it form an inclusion complex) an organic molecule or part of an organic molecule that can be incorporated into the cavity. ing. Malodorous molecules can be incorporated into the cavity.
[0032]
Preferred cyclodextrins are those that are highly water soluble and include, for example, α-cyclodextrin and derivatives thereof, γ-cyclodextrin and derivatives thereof, derivatized β-cyclodextrin and / or mixtures thereof. Cyclodextrin derivatives mainly consist of molecules in which some of the OH groups are converted to OR groups. Cyclodextrin derivatives include, for example, those having a short-chain alkyl group and R being a methyl group or an ethyl group (eg, methylated cyclodextrin and ethylated cyclodextrin), having a hydroxyalkyl substituent, and R being -CH₂-CH (OH) -CH_ThreeOr -CH₂CH₂-OH (eg, hydroxypropyl cyclodextrin and / or hydroxyethyl cyclodextrin), branched cyclodextrin (eg, maltose-linked cyclodextrin), cationic cyclodextrin (eg, 2-hydroxy-3- ( CH containing dimethylamino) propyl ether and R being a cation at low pH₂-CH (OH) -CH₂-N (CH_Three)₂), Quaternary ammonium (for example, 2-hydroxy-3- (trimethylammonio) propyl ether chloride group), and R is CH₂-CH (OH) -CH₂-N⁺(CH_Three)_ThreeCl^-Anionic cyclodextrins (eg carboxymethylcyclodextrin, cyclodextrin sulfate and cyclodextrin succinate), amphoteric cyclodextrins (eg carboxymethyl / quaternary ammonium cyclodextrin), at least one glucopyranose A cyclodextrin having a unit having a 3-6-anhydro-cyclomalto structure (for example, mono-3-6-anhydrocyclodextrin), and “Optimal Performances with Minimal Chemical Modification of Cyclodextrins” (F. Diedaini-Pilard and B. Perly, 7th International Cyclodextrin Symposium Summary, April 1994, p. 49) and mixtures thereof. Other cyclodextrin derivatives are US Pat. No. 3,426,011, US Pat. No. 3,453,257, US Pat. No. 3,453,258, US Pat. No. 3,453,259, US Pat. US Pat. No. 3,453,260, US Pat. No. 3,459,731, US Pat. No. 3,553,191, US Pat. No. 3,565,887, US Pat. No. 4,535,152, US Pat. No. 4,616,008, U.S. Pat. No. 4,678,598, U.S. Pat. No. 4,638,058 and U.S. Pat. No. 4,746,734.
[0033]
A highly water-soluble cyclodextrin has a water solubility of at least about 10 g in 100 ml water at room temperature, preferably at least about 20 g in 100 ml water, more preferably at least about 25 g in 100 ml water at room temperature. It is a certain cyclodextrin. Examples of preferred water-soluble cyclodextrin derivatives suitable for use herein are hydroxypropyl α-cyclodextrin, methylated α-cyclodextrin, methylated β-cyclodextrin, hydroxyethyl β-cyclodextrin and hydroxypropyl β -Cyclodextrin. The hydroxyalkyl cyclodextrin derivative preferably has a degree of substitution of about 1 to about 14, more preferably about 1.5 to about 7, wherein the total number of OR groups per cyclodextrin is defined as the degree of substitution. Methylated cyclodextrin derivatives usually have a degree of substitution of about 1 to about 18, preferably about 3 to about 16. A known methylated β-cyclodextrin is heptakis-2,6-di-O-methyl-β-cyclodextrin, commonly known as DIMEB, where each glucose unit is about 2 with a degree of substitution of about 14. Having a methyl group. A more readily available preferred methylated β-cyclodextrin is a randomly methylated β-cyclodextrin having a degree of substitution of about 12.6. Preferred cyclodextrins are commercially available from, for example, the American Maize-Products Company and Wacker Chemicals (USA), Inc.
[0034]
The compositions of the present invention are particularly useful when applied directly in pre-treating cooking utensils or tableware utensils that are soiled with cooking debris, burn-in, or burnt (or other dry soil). The composition is applied to the soiled substrate in the form of a spray or foam before washing, rinsing or wiping dishes automatically or manually. Pre-treated cooking utensils or table utensils are very slippery and as a result may be difficult to handle during and after rinsing. This can be solved by using a divalent cation. Such divalent cations include, for example, magnesium salts and calcium salts, and magnesium chloride is particularly suitable for use herein. About 0.01 wt.% To about 5 wt.%, Preferably about 0.1 wt.% To about 3 wt.%, More preferably about 0.4 wt.% To about 2 wt. The slippery properties of the cooking utensil or tableware surface can be eliminated without adversely affecting the stability of the physical properties of the composition. The composition of the present invention can also be used as an automatic dishwashing detergent composition or a component thereof.
[0035]
In a method aspect, the present invention provides a method for removing cooking stains, burn-in stains and burnt stains from cooking utensils and tableware, which is cooked with the hard surface cleaning composition of the present invention. Including processing utensils / table utensils. Also provided is a method for removing polymer oil or carbohydrate cooking stains, burn-in stains and scorch stains from metal cookware and tableware, which is cooked with the hard surface cleaning composition of the present invention. Including processing utensils / table utensils. These methods include pre-treating the cookware / tableware with the composition of the present invention before automatically or manually washing the dishes. If desired, after applying the cleaning composition of the present invention, the soiled substrate is covered with a cling film and the soil is swollen to facilitate the process of removing cooked, burned and burnt soils. Can do. The cling film is preferably applied for about 1 hour or more, preferably for about 6 hours or more.
[0036]
(Detailed description of the invention)
The present invention contemplates hard surface detersive compositions for pretreating cookware and tableware utensils that are soiled with cooked, burned and burnt stains and facilitate subsequent cleaning. These effects are obtained mainly by adding an organic amine solvent that swells dirt to the composition. The present invention also contemplates a method for removing the aforementioned dirt.
The soil swelling agent is a substance or composition having an effect of swelling cooking soil, burnt soil and burnt soil as described above. Preferred soil swelling agents for use herein include organic amine solvents.
A diffusion aid is a substance or composition having the property of reducing the surface tension as described above. Suitable diffusion aids for use herein include surfactants such as silicone surfactants and amine oxide surfactants (especially those having a surface tension of less than about 25 mN / m), organic solvents and these A mixture of
[0037]
In general, the organic solvent used herein should be selected to be compatible with the various components of a cookware / tableware or automatic dishwasher. Further, the solvent system is less than about 50%, preferably less than about 30%, more preferably less than about 10%, more preferably about 4% by weight of the solvent system at greater than 1 mmHg (preferably greater than 0.1 mmHg). Since it has a volatile organic content of less than 1%, it must be used efficiently and safely. Also, the odor of the solvent system needs to be extremely mild and comfortable. The individual organic solvents used herein generally have a boiling point greater than about 150 ° C., a flash point greater than about 50 ° C., preferably less than 100 ° C., and less than about 1 mm Hg, preferably less than 0.1 mm Hg and atmospheric pressure at 25 ° C. Have a vapor pressure of less than. Furthermore, each organic solvent is about 500 cm.^Three/ Mol, preferably about 250 cm^Three/ Mole, more preferably about 200 cm^ThreePreferably having a molar volume of less than / mole. These molar volumes are preferred from the standpoint of optimally penetrating the soil and causing the soil to swell.
[0038]
Solvents that can be used in the present specification include the following i) to v). i) Alcohol. For example, benzyl alcohol, 1,4-cyclohexanedimethanol, 2-ethyl-1-hexanol, furfuryl alcohol, 1,2-hexanediol and other similar materials. ii) amines. For example, alkanolamines (for example, primary alkanolamines (monoethanolamine, monoisopropanolamine, diethylethanolamine, ethyldiethanolamine, β-aminoalkanol), secondary alkanolamines (diethanolamine, diisopropanolamine, 2- (methylamino) ethanol) ), Tertiary alkanolamine (triethanolamine, triisopropanolamine)), alkylamine (primary alkylamine (monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, cyclohexylamine), secondary alkylamine ( Dimethylamine)), alkyleneamines (primary alkyleneamines (ethylenediamine, propylenediamine)) and other similar substances. iii) Esters. For example, ethyl lactate, methyl ester, ethyl acetoacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and other similar materials. iv) Glycol ether. For example, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol butyl ether and other similar materials. v) Glycol. For example, propylene glycol, diethylene glycol, hexylene glycol (2-methyl-2,4-pentanediol), triethylene glycol, compositions and dipropylene glycol and other similar materials and mixtures thereof.
[0039]
Preferred solvents for use herein as soil swell agents include alkanolamines (especially monoethanolamine), β-aminoalkanols (especially 2-amino-2-methylpropanol (β-having an amine group at the third carbon). Among the amino alkanols, the lowest molecular weight, thus minimizing the reactivity of the amine groups)) and mixtures thereof.
Preferred solvents for use herein as diffusion aids include glycols and glycol ethers, especially diethylene glycol monobutyl ether, propylene glycol butyl ether and mixtures thereof.
[0040]
Apart from the soil swelling agent and diffusion aid, the hard surface detergency composition herein can contain additional components. This includes surfactants other than the wetting agents described above, builders, enzymes, bleaching agents, alkaline components, thickeners, stabilizing components, perfumes, abrasives, and the like. The composition may also contain an organic solvent having a carrier or dilution function (as opposed to soil swelling or diffusion) or other specific functions. The composition can be provided from any suitable container. Examples of such containers include bottles (bottles with pumps, squeeze bottles), paste dispensers, capsules, pouches, and multi-compartment pouches.
[0041]
Surfactant
In the compositions and methods of the present invention used for automatic dishwashing, the detergent surfactant is preferably low foaming, either alone or in combination with other ingredients (ie soap suds suppressor). In the compositions and methods of the present invention, detergent surfactants are foamable for direct application and low foaming for use in automatic dishwashing for use in hard surface cleaning or dishwashing pretreatment. It is preferable that Suitable surfactants herein include anionic surfactants (eg, alkyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, alkyl glyceryl sulfonates, alkyl and alkenyl sulfonates, alkyl ethoxy carboxylates, N-acyls). There are sarcosinates, N-acyl taurates, alkyl succinates and sulfosuccinates, where the alkyl, alkenyl or acyl moiety is C_Five~ C₂₀, Preferably C_Ten~ C₁₈Straight chain or branched chain), cationic surfactants (eg, chlorine esters (US Pat. No. 4,228,042, US Pat. No. 4,239,660, and US Pat. No. 4,260)). , No. 529) and Mono C₆~ C₁₆N-alkyl or alkenyl ammonium surfactants, and the remaining N-position is substituted with a methyl group, hydroxyethyl group or hydroxypropyl group), low cloud point and high cloud point nonionic surfactant And mixtures thereof (eg, nonionic alkoxylated surfactants (especially C₆~ C₁₈Ethoxylates derived from primary alcohols), ethoxylated to propoxylated alcohols (eg, Poly-Tergent® SLF18 from Olin Corporation), epoxy end-protected poly (oxyalkylated) alcohols (eg, from Olin Corporation). Poly-Tergent® SLF18B, see WO-A-94 / 22800), ether-terminated protected poly (oxyalkylated) alcohol surfactants and block polyoxyethylene-polyoxypropylene polymer compounds (eg BASF-Wyandotte PLURONIC®, REVERSED PLURONIC®, and TETRONIC®, commercially available from Corp. (Wyandotte, Mich.), Amphoteric surfactants (eg, C₁₂~ C₂₀Alkylamine oxides (preferred amine oxides for use herein include lauryl dimethylamine oxide and hexadecyldimethylamine oxide) and alkyl amphoteric carboxylic acid surfactants (eg, Miranol ™ C2M) ), Zwittersurfactants (eg betaine and sultaines) and mixtures thereof. Suitable surfactants herein are, for example, U.S. Pat. No. 3,929,678, U.S. Pat. No. 4,259,217, EP 0,414,549, WO-A-93 / 08876. No., and WO-A-93 / 08874. The surfactant is typically from about 0.2% to about 30%, more preferably from about 0.5% to about 10%, most preferably from about 1% to about 5% by weight of the composition. Present at a rate of. Preferred surfactants for use herein in automatic dishwashing are low foaming, low cloud point nonionic surfactants, and high foaming and low cloud point nonionic surfactants (this In the case of a soap foam inhibitor).
[0042]
builder
Suitable builders for use in the detersive compositions herein include water soluble builders (eg, citrate, carbonate and polyphosphate (eg, sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, tripolylin Potassium acid and sodium tripolyphosphate and potassium mixtures)) and partially water-soluble or insoluble builders (eg, crystalline layered silicates (European Patent Nos. 0,164,514 and 0,293,640)) and Aluminosilicates such as zeolite A, B, P, X, HS, and MAP). Builders are typically present in a proportion of about 1% to about 80%, preferably about 10% to about 70%, most preferably about 20% to about 60% by weight of the composition.
Preferred compositions for use herein contain silicates to prevent damage to aluminum and certain painted surfaces. SiO₂: Na₂Amorphous sodium silicate having an O ratio of 1.8 to 3.0, preferably 1.8 to 2.4, and most preferably 2.0 can also be used herein. However, from the viewpoint of long-term storage stability, highly preferred is a composition containing less than about 22%, preferably less than about 15% of total silicate (amorphous and crystalline).
[0043]
enzyme
Suitable enzymes herein include bacterial and fungal cellulases (eg, Carezyme and Celluzyme (Novo Nordisk A / S)), peroxidases, lipases (eg, Amano-P (Amano Pharmaceutical Co.), M1 Lipase®). And Lipomax® (Gist-Brocades), and Lipolase® and Lipolase Ultra® (Novo)), cutinases, proteases (eg, Esperase®, Alcalase®, Durazym ( (Registered trademark), and Savinase (registered trademark) (Novo), and Maxatase (registered trademark), Maxacal (registered trademark), Properase (registered trademark), and Maxapem (registered trademark) (Gist-Brocades)), α and β amylase (For example, Purafect Ox Am® (Genencor) and Termamyl®, Ban®, Fungamyl®, Duramyl® and Natalase® (Novo) And mixtures thereof. Enzymes are preferably added herein in the form of small spheres, granules, or co-grains and are typically present as pure enzymes in a proportion of from about 0.0001% to about 2% by weight of the composition. .
[0044]
bleach
Suitable bleaching agents herein include chlorine bleaches and oxygen bleaches, especially inorganic perhydrate salts (eg sodium perborate monohydrate and tetrahydrate and controlled release rate). Optionally coated sodium percarbonate) (for example, see British Patent No. 1,466,799 for sulfate / carbonate coatings), organic peroxoacid bleach precursors and / or transition metal coating bleaches Included are preformed organic peroxo acids with agent catalysts (especially manganese or cobalt) and mixtures thereof. The inorganic perhydrate salt is typically a proportion of about 1% to about 40%, preferably about 2% to about 30%, more preferably about 5% to about 25% by weight of the composition. Add in. Preferred peroxoacid bleach precursors for use herein include perbenzoic acid and substituted perbenzoic acid precursors, cationic peroxoacid precursors, peracetic acid precursors (eg, TAED, acetoxy Sodium benzenesulfonate and pentaacetylglucose), pernonanoic acid precursors (eg, sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS) and sodium nonanoyloxybenzenesulfonate (NOBS)), Amide-substituted alkyl peroxoacid precursors (European Patent No. 0,170,386) and benzoxazine peroxoacid precursors (European Patent No. 0,332,294 and European Patent No. 0,482,807) Is included. The bleach precursor is typically added at a rate of about 0.5% to about 25%, preferably about 1% to about 10% by weight of the composition. On the other hand, the preformed organic peroxoacid is typically added at a rate of about 0.5% to about 25%, preferably about 1% to about 10% by weight of the composition. Preferred bleach catalysts for use herein include triazacyclononane manganese and related complexes (US Pat. No. 4,246,612, US Pat. No. 5,227,084), bispyridylamine Co, Cu , Mn, Fe and related complexes (US Pat. No. 5,114,611), and pentamine acetate cobalt (III) and related complexes (US Pat. No. 4,810,410).
[0045]
Low cloud point nonionic surfactant and soap foam inhibitor
Suitable soap suds suppressors for use herein include nonionic surfactants having a low cloud point. “Cloud point”, as used herein, is a known property of a nonionic surfactant that occurs in a surfactant that becomes less soluble as the temperature increases, and refers to the temperature at which different phases appear. Called “cloud point” (see Kirk Othmer, pages 360-362). As used herein, “low cloud point” nonionic surfactants are less than 30 ° C., preferably less than about 20 ° C., more preferably less than about 10 ° C., and most preferably less than about 7.5 ° C. Defined as a nonionic surfactant system component having a cloud point of Typical low cloud point nonionic surfactants include nonionic alkoxylated surfactants (especially ethoxylates derived from primary alcohols) and polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO). / PO) Reverse block polymers are included. These low cloud point nonionic surfactants also include, for example, ethoxylated to propoxylated alcohols (eg, Poly-Tergent® SLF18 from Olin Corporation) and epoxy end-protected poly (oxyalkylated). Alcohols (eg, Poly-Tergent® SLF18B series from Olin Corporation, described in US Pat. No. 5,576,281 as non-ionic materials) are included.
A preferred low cloud point surfactant is an ether end-protected poly (oxyalkylated) soap foam inhibitor having the formula:
[0046]
[Chemical 1]

[0047]
R¹Is a straight chain alkyl hydrocarbon having an average of about 7 to about 12 carbon atoms and R²Is a linear alkyl hydrocarbon having from about 1 to about 4 carbon atoms and R^ThreeIs a linear alkyl hydrocarbon having from about 1 to about 4 carbon atoms, x is an integer from about 1 to about 6, y is an integer from about 4 to about 15, and z is an integer from about 4 to about 25. is there.
Other low cloud point nonionic surfactants are ether-terminated protected poly (oxyalkylated) having the formula:
R_IO (R_IIO)_nCH (CH_Three) OR_III
R_IIs selected from the group consisting of linear or branched, saturated or unsaturated, substituted or unsubstituted, aliphatic or aromatic hydrocarbon groups having from about 7 to about 12 carbon atoms, R_IIMay be the same or different groups, and of any of the above molecules, a branched or straight chain C₂~ C₇Independently selected from the group consisting of alkylene, n is a number from 1 to about 30, and R_IIIIs selected from the following group:
[0048]
(I) a 4- to 8-membered substituted or unsubstituted heterocycle having 1 to 3 heteroatoms, and
(Ii) a linear or branched, saturated or unsaturated, substituted or unsubstituted, cyclic or acyclic, aliphatic or aromatic hydrocarbon group having from about 1 to about 30 carbon atoms.
(B) R²Is (ii), (A) R¹At least one of C₂~ C_ThreeOther than alkylene or (B) R²Has 6 to 30 carbon atoms and R²When R has 8 to 18 carbon atoms, R is C₁~ C_FiveOther than alkyl.
[0049]
Other ingredients suitable herein include organic polymers having inventions of dispersibility, anti-redeposition, soil release or other cleaning properties. The proportion is from about 0.1% to about 30%, preferably from about 0.5% to about 15%, most preferably from about 1% to about 10% by weight of the composition. Preferred anti-redeposition polymers herein include polymer-containing acrylic acid (eg, Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 (BASF GmbH), Acusol 45N, 480N, 460N (Rohm and Haas)), acrylic acid / maleic acid Copolymers (eg Sokalan CP5) and acrylic / methacrylic copolymers are included. Preferred soil release polymers herein include alkyl and hydroxyalkyl cellulose (US Pat. No. 4,000,093), polyoxyethylene, polyoxypropylene and copolymers thereof, and ethylene glycol, propylene glycol and mixtures thereof. Nonionic and anionic polymers based on these terephthalate esters are included.
[0050]
Heavy sequestering agents and crystal growth inhibitors are generally from about 0.005% to about 20%, preferably from about 0.1% to about 10%, more preferably about 0.25% by weight of the composition. Suitable for use herein in a proportion of ˜7.5 wt%, most preferably about 0.5 wt% to about 5 wt%. These include, for example, diethylenetriaminepenta (methylenephosphonate), ethylenediaminetetra (methylenephosphonate), hexamethylenediaminetetra (methylenephosphonate), ethylenediphosphonate, hydroxyethylene-1,1-diphosphonate, nitrilotriacetate, ethylenediaminotetraacetate , Ethylenediamine-N, N′-disuccinate salts and free acid forms.
[0051]
The compositions herein can contain a corrosion inhibitor. This includes, for example, organic silver coating agents (particularly Wintershall (Germany) contained in a proportion of from about 0.05% to about 10%, preferably from about 0.1% to about 5% by weight of the composition. Paraffins such as Winog 70, commercially available from Salzbergen), nitrogen-containing corrosion inhibitor compounds (see, for example, benzotriazole and benzimidazole-British Patent No. 1,137,741), and about 0. 005% to about 5% by weight, preferably about 0.01% to about 1% by weight, more preferably about 0.02% to about 0.4% by weight of Mn (II) compound (Especially Mn (II) salts of organic ligands).
[0052]
Other suitable ingredients herein include colorants, water-soluble bismuth compounds (eg, bismuth acetate and bismuth citrate) contained in a proportion of about 0.01% to about 5%, about 0.01% Enzyme stabilizer (for example, calcium ion, boric acid, propylene glycol and chlorine bleach scavenger), lime soap dispersant (see WO-A-93 / 08877), soap foam, contained in a proportion of ~ 6% Inhibitors (see WO-A-93 / 08876 and EP 0,705,324), polymeric dye transfer inhibitors, optical brighteners, fragrances, fillers and clays.
The liquid detergent composition can contain water and other volatile solvents as a carrier. A small amount of a low molecular weight primary or secondary alcohol (eg, methanol, ethanol, propanol and isopropanol) can be used in the liquid detergent of the present invention. Other suitable carrier solvents used in small amounts include glycerol, propylene glycol, ethylene glycol, 1,2-propanediol, sorbitol and mixtures thereof.
[0053]
Odor masking base
The odor masking base (which includes the fully formulated odor masking fragrance or the base composition used therein) is preferably a mixture of ionone, musk and high volatility fragrance. The concentration of the odor masking base is from about 0.001% to about 3%, preferably from about 0.006% to about 2.5%, more preferably from about 0.0075% to about 1% of the composition. It is preferably in the range of% by weight.
[0054]
Odor masking-based ionone, musk and highly volatile fragrances have one characteristic in the range of boiling points of each component. Ionone and musk preferably have a boiling point above about 250 ° C. at 1 atmosphere. On the other hand, highly volatile perfume ingredients have a boiling point of less than about 250 ° C. at 1 atmosphere. The boiling points of many perfume materials are disclosed, for example, in “Perfume and Flavor Chemicals (Aroma Chemicals)” (S. Arctander, Author Publishing, 1969). Other boiling points can be obtained from various chemical handbooks and databases (eg, the Beilstein Handbook, Lange's Handbook of Chemistry, and the CRC Handbook of Chemistry and Physics). If only boiling points at different pressures (usually pressures below 1 standard pressure) are presented, boiling points at standard pressure or ambient pressure can be approximated using a boiling point-pressure calculation chart. This boiling-pressure calculation chart includes, for example, those described in “The Chemist's Companion” (A. J. Gordon and R. A. Ford, John Wiley & Sons Publishers, 1972, pp. 30-36). Where applicable, boiling points can also be calculated by computer programs based on molecular structure data. Such programs include, for example, “Computer-Assisted Prediction of Normal Boiling Points of Pyrans and Pyrroles” (DTStanton et al., J. Chem. Inf. Comput. Sci., 32, 1992, pages 306-316), “ Computer-Assisted Prediction of Normal Boiling Points of Furans, Tetrahydrofurans, and Thiophenes "(DT Stanton et al., J. Chem. Inf. Comput. Sci., 31, 1992, 301-310) and references therein. As well as those described in “Predicting Physical Properties from Molecular Structure” (R. Murugan et al., Chemtech, June 1994, pp. 17-23).
The components of the odor masking base ionone fragrance, the highly volatile fragrance and the musk component are described in detail below.
[0055]
High volatile flavor
Odor masking-based highly volatile perfumes contain perfume materials that compete with malodorous solvents and reach the nasal receptor receptor. These highly volatile fragrances are odors that are first recognized and identified by the brain and serve to inhibit or mask solvent recognition in the olfaction. The concentration of the highly volatile perfume is from about 15% to about 85%, preferably from about 20% to about 80%, more preferably from about 35% to about 75%, more preferably from the odor masking base. About 45% to about 65% by weight.
High volatility perfumes are more volatile than the odor masking based ionone and musk components and have boiling points at 1 atmosphere of less than about 250 ° C, preferably less than about 230 ° C, more preferably less than about 220 ° C. These highly volatile perfumes include aldehydes having about 2-15 carbon atoms, esters having about 3-15 carbon atoms, alcohols having about 4-12 carbon atoms, about 4-13 Classified as ethers having carbon atoms, ketones having about 3-12 carbon atoms, or combinations thereof.
[0056]
Examples of suitable aldehydes include n-decyl aldehyde, 10-undecen-1-al, dodecanal, 3,7-dimethyl-7-hydroxyoctane-1-al, 2,4-dimethyl-3-cyclohexene carboxaldehyde, This includes, but is not limited to, benzaldehyde, anisaldehyde and mixtures thereof.
Examples of suitable ethers include ethyl acetate, cis-3-hexenyl acetate, 2,6-dimethyl-2,6-octadien-8-yl acetate, benzyl acetate, 1,1-dimethyl-2-phenyl acetate, 2 -Including but not limited to pentyloxyallyl ester, allyl hexanoate, methyl-2-aminobenzoate and mixtures thereof.
[0057]
Examples of suitable alcohols include n-octyl alcohol, β-γ-hexenol, 2-trans-6-cis-nonadien-1-ol, 3,7-dimethyl-trans-2,6-octadien-1-ol. 3,7-dimethyl-6-octen-1-ol, 3,7-dimethyl-1,6-octadien-3-ol, 2,6-dimethyl-7-octen-2-ol, 2-phenylethyl alcohol , 2-cis-3,7-dimethyl-2,6-octadien-1-ol, 1-methyl-4-isopropyl-1-cyclohexen-8-ol, and mixtures thereof, but are not limited thereto.
Examples of suitable ethers include, but are not limited to, amyl milk resole oxide, 4-ethoxy-1-methyl-benzol, 4-methoxy-1-methylbenzene, methylphenylethyl ether and mixtures thereof.
[0058]
Examples of suitable ketones include dimethylacetophenone, ethyl-n-amyl ketone, 2-heptanone, 2-octanone, 3-methyl-2- (cis-2-penten-1-yl) -2-cyclopenten-1-one , 1-1-methyl-4-isopropenyl-6-cyclohexen-2-one, para-tertiary amylcyclohexanone, and mixtures thereof.
Preferred highly volatile fragrances include 2-pentyloxyallyl ester (commercially available from International Flavors and Fragrances, Inc. (New York, NY) under the trademark Allyl Amyl Glycolate), benzaldehyde (Rhone-Poulenc under the Amandol trademark) , Inc (commercially available from Princeton, NJ), cis-3-hexenyl acetate (commercially available from International Flavors and Fragrances, Inc. (New York, NY)), 2,6 -Dimethyl-7-octen-2-ol (commercially available from International Flavors and Fragrances, Inc. (New York, NY)), para-tertiary amylcyclohexanone (International Flavors and Commercially available from Fragrances, Inc. (New York, NY, USA) And has), (Aceto under the trademark Decyl Aldehyde, Corp. (NY Lake Success) n- decyl aldehyde commercially available from) and mixtures thereof.
Examples of suitable highly volatile perfumes and their boiling points at 1 atmosphere are disclosed in, but not limited to, US Pat. No. 5,919,440.
[0059]
Ionon
The odor masking base contains the ionone perfume component (ie, ionone or ionone mixture) from about 15% to about 80%, preferably from about 16% to about 60%, more preferably about 16% by weight of the odor masking base. It is preferably contained at a concentration of from about 40% to about 40% by weight. Ionone is a well-known type of perfume chemical derived from natural oils or made synthetically, and is typically a colorless or light yellow liquid with a forest-like scent.
[0060]
The ionone fragrance used in the odor masking base has a boiling point of greater than about 250 ° C., preferably greater than about 255 ° C., more preferably greater than about 260 ° C. at 1 atmosphere. It is preferably selected from ionone, gamma-ionone or combinations thereof.
Examples of suitable ionones include 1- (2,6,6-trimethyl-2-cyclohexen-1-yl) -1,6-heptadien-3-one, 2-allyl-para-menten- (4 ( 8))-Ono-3, pseudoallyl-α-ionone, α-citrilidenecyclopentanone, 5- (2,6,6-trimethyl-2-cyclohexen-1-yl) -4-methyl-4-pentene -3-one, 6- (2,6,6-trimethyl-2-cyclohexen-1-yl) -1-methyl-5-hexen-4-one, 2,6,6-trimethylcyclohexyl-1-butenone- 3, dihydro-α-ionone, 4- (2,6,6-trimethylcyclohexen-1-yl) -butan-2-one, 4- (2-methylene-6,6-dimethylcyclohexyl) -butane-2- ON, 1- (2, 5, , 6-Tetramethyl-2-cyclohexenyl) -butane-3-one, dihydro-β-iron, dihydro-γ-iron, 5- (2,6,6-trimethyl-2-cyclohexenyl) -pentane-3 -One, cihydro-iso-methyl-β-ionone, 6- (2,6,6-trimethyl-2-cyclohexen-1-yl) -5-hexen-4-one, α-ethyl-2,2,6 -Trimethylcyclohexanebutyraldehyde, 4-methyl-6- (1,1,3-trimethyl-2'-cyclohexen-2'-yl) -3,5-hexadien-2-one, 6,10-dimethylundecane-2 -One, 6- (2,6,6-trimethyl-1-cyclohexen-1-yl) -1-methyl-2,5-hexadien-4-one, 6- (2,6,6-trimethyl-2- Cyclohe Xen-1-yl) -1-methyl-2,5-hexadien-4-one, 4- (2,2,6-trimethyl-2-cyclohexen-1-yl) -3-buten-2-one, 4 -(2,6,6-trimethyl-1-cyclohexen-1-yl) -3-buten-2-one, 4- (2-methylene-6,6-dimethylcyclohexyl) -3-buten-2-one, Epoxy-2,3-β-ionone, ethyl-2,3-epoxy-3-methyl-5- (2,6,6-trimethyl-2-cyclohexenyl) -4-pentenoate, methyl α-ionone anthranilate Methyl-2,3-epoxy-3-methyl-5- (2,6,6-trimethyl-2-cyclohexenyl) -4-pentenoate, 4- (2,5,6,6-tetramethyl-2- Cyclohexen-1-yl) -3 -Buten-2-one, 6-methyl-β-ionone, 6-methyl-γ-ionone, 4- (2,6,6-trimethyl-2-cyclohexenyl) -2,3-dimethyl-2-butene- 1-al, 4- (2,6,6-trimethyl-2-cyclohexen-1-yl) -3-methyl-3-buten-2-one, 5- (2,6,6-trimethyl-2-cyclohexene -1-yl) -4-penten-3-one, 5- (2,6,6-trimethyl-1-cyclohexen-1-yl) -4-penten-3-one, 4- (2,6,6) -Trimethyl-3-cyclohexen-1-yl) -3-methyl-3-buten-2-one, 5- (2-methylene-6,6-dimethylcyclohexyl) -4-penten-3-one, 4- ( 2-methylene-6,6-dimethylcyclohexyl) -3-me Tyl-3-buten-2-one, 4- (2,3,6,6-tetramethyl-2-cyclohexen-1-yl) -3-buten-2-one, 4- (2,4,6, 6-tetramethyl-2-cyclohexen-1-yl) -3-buten-2-one, 4- (2,4,6,6-tetramethyl-1-cyclohexen-1-yl) -3-butene-2 -One, 5-methyl-1- (3-methyl-3-cyclohexenyl) -1,3-hexanedione, 2-methyl-4- (2,6,6-trimethyl-2-cyclohexenyl) -3- Buten-1-al, 3-methyl-4- (2,4,6-trimethyl-3-cyclohexenyl) -3-buten-2-one, 4- (2-methyl-5-iso-propenyl-1- Cyclopenten-1-yl) -2-butanone, 4- (2,6,6-trimethyl) 7-cycloheptenyl) -3-buten-2-one, 4- (2,6,6-trimethyl-4-cyclohexenyl) -3-buten-2-one, 2,6-dimethylundeca-2,6 8-trien-10-one, 2,6,12-trimethyl-tridec-2,6,8-trien-10-one, 2,6-dimethyldodec-2,6,8-trien-10-one, 2, , 6,9-trimethylundeca-2,6,8-trien-10-one, 4- (2,6,6-trimethyl-2-cyclohexen-1-yl) -3-methyl-3-butene-2 -One, 4- (2,4,6-trimethyl-3-cyclohexen-1-yl) -3-buten-2-one, 5- (2-methylene-6,6-dimethylcyclohexyl) -4-pentene- 3-one and mixtures thereof are included, But it is not limited to these.
[0061]
Preferred ionones include 4- (2,6,6-trimethyl-3-cyclohexen-1-yl) -3-methyl-3-buten-2-one (Givaudan Roure, Corp. under the trademark Isoraldeine, NJ, USA) Commercially available from Teaneck), 5- (2-methylene-6,6-dimethylcyclohexyl) -4-penten-3-one (Givaudan Roure, Corp. under the trademark γ-methylionone, Teaneck, NJ, USA) ), 4- (2,2,6-trimethyl-2-cyclohexen-1-yl) -3-buten-2-one (trade name of International Flavors and Fragrances, Inc. Commercially available from New York, NY), 4- (2,6,6-trimethyl-1-cyclohexen-1-yl) -3-buten-2-one (β-iono) ), Commercially available from International Flavors and Fragrances, Inc. (New York, NY, USA), 4- (2,6,6-trimethyl-2-cyclohexen-1-yl) -3-methyl-3-butene 2-one (commercially available from Bush Boake Allen, Inc. (Montvale, NJ, USA) under the methyl ionone trademark) and mixtures thereof.
[0062]
Ionone can be added to the odor masking base as one or more individual perfume chemicals or as a specific perfume composed of a combination of perfume chemicals including ionone perfume chemicals. Examples of ionone-specific fragrances include Alvanone Extra (commercially available from International Flavors and Fragrances, Inc. (New York, NY), Irisia Base (commercially available from Firmenich, Inc. (Princeton, NJ, USA)) , Irival (commercially available from International Flavors and Fragrances, Inc. (New York, NY, USA)), Iritone (commercially available from International Flavors and Fragrances, Inc. (New York, NY, USA)) and mixtures thereof However, it is not limited to these.
Other ionone-containing materials suitable for use herein are natural materials such as, for example, hydrangea, violet, iris, squirrels and mixtures thereof.
[0063]
The musk and highly volatile fragrances used in the odor masking base can also be added to the odor masking base as one or more individual fragrance chemicals or as a specific fragrance comprised of a combination of fragrance chemicals. Examples of preferred highly volatile specific fragrances include, but are not limited to, Cass Base 345-B (commercially available from Firmenich, Inc. (Princeton, NJ, USA)). Examples of suitable ionone perfumes and their boiling points at 1 atmosphere are disclosed in US Pat. No. 5,919,440, but are not limited thereto.
[0064]
Musk
The odor masking base contains musk ingredients at a concentration of about 5% to about 70%, preferably about 15% to about 50%, more preferably about 20% to about 35% by weight of the odor masking base. It is preferable to contain. Musk is a well-known type of perfume chemical, typically a colorless or pale yellow material with a unique musk-like scent.
The musk component used in the odor masking base should have a boiling point of greater than about 250 ° C., preferably greater than about 255 ° C., more preferably greater than about 260 ° C. at 1 atmosphere, and the musk component is a polycyclic musk , Macrocyclic musk, nitrocyclic musk, or a combination thereof. Also, each musk component preferably has more than about 12, preferably more than about 13, more preferably more than about 15 carbon atoms.
[0065]
Suitable polycyclic musks include 5-acetyl-1,1,2,3,3,6-hexamethylindane, 4-acetyl-1,1-dimethyl-6-tert-butylindane, 7-acetyl -1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene, 1,1,4,4-tetramethyl-6-ethyl-7-acetyl-1,2,3 , 4-tetrahydronaphthalene, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-γ-2-benzopyran and mixtures thereof.
Suitable macrocyclic musks include cyclopentadecanolide, cyclopentadecanolone, cyclopentadecanone, 3-methyl-1-cyclopentadecanone, cycloheptadedec-9-one-1, cycloheptadecanone, Cyclohexadecene-7-olide, cyclohexadecene-9-olide, cyclohexadecanolide, ethylene tridecandioate, 10-oxahexadecanolide, 11-oxahexadecanolide, 12-oxahexadecanolide and These mixtures are included.
[0066]
Suitable nitro cyclic musks include 1,1,3,3,5-pentamethyl-4,6-dinitroindane, 2,6-dinitro-3-methoxy-1-methyl-4-tertiary butylbenzene, 2,6-dimethyl-3,5-dinitro-4-tert-butyl-acetophenone, 2,6-dinitro-3,4,5-trimethyl-tert-butylbenzene, 2,4,6-trinitro-1 , 3-dimethyl-5-tert-butylbenzene and mixtures thereof.
Preferred musks include 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-γ-2-benzopyran (Galaxolide trademark International Flavors and Fragrances, Inc. (commercially available from New York, NY, USA), cyclopentadecanolide (commercially available from Firmenich, Inc. (Princeton, NJ, USA) under the trademark Exaltolide), ethylene tridecandioate (Ethylene Brassylate) 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene, commercially available from Fragrance Resource, Inc. (Keyport, NJ, USA) (Examples of Givaudan preferred musk under the Tonalid trademark and their boiling point at 1 atmosphere are disclosed in US Pat. No. 5,919,440. To have, but are not limited to these.
[0067]
(Example)
Abbreviations used in the examples
In the examples, the abbreviations of the component names have the following meanings.
[0068]
[Table 1]

[0069]
In the following examples, all percentages are expressed by weight.
[0070]
Examples 1-16
Examples 1-16 describe pretreatment compositions used prior to dishwashing to facilitate the removal of food cooking stains, burn-in stains and burnt stains. The example composition is applied to the wash. Washings were Pyrex lasagna baked at 140 ° C for 2 hours, lasagna in stainless steel container cooked at 150 ° C for 2 hours, potato and cheese in stainless steel container cooked at 150 ° C for 2 hours, cooked at 150 ° C for 2 hours It consists of different stains and different substrates such as egg yolk in a stainless steel container and sausage cooked at 180 ° C for 1 hour after cooking at 120 ° C. The wash is soaked in the example composition for 10 minutes and then rinsed with cold tap water. The wash is then washed with a typical dishwashing detergent composition by hand or in an automatic dishwasher (eg, Bosch 6032 dishwasher) (55 ° C., no washing down). Typical dishwashing detergent compositions include, for example, alkaline ingredients, builders, enzymes, bleaches, bleach catalysts, nonionic surfactants, soap foam inhibitors, silver corrosion inhibitors, soil suspending polymers, and the like. contains. When the washing was treated with the composition of the example and then washed with a dishwasher, the cooking stains, burn-in stains and scorch stains of the food were removed cleanly.
[0071]
[Table 2]

[0072]
[Table 3]

[0073]
[Table 4]

[0074]
[Table 5]

[0075]
All examples have a liquid surface tension at 25 ° C. of less than 24.5 mN / m, a pH of 12 or higher, and a 45 minute soil swell index for polymerized oil soils on stainless steel substrates of at least 200%.
The masking fragrance composition is shown in the table below.
[0076]
[Table 6]

Claims (10)

A hard surface cleaning composition for removing cooking stains, burnt stains or burnt stains from cooking utensils and tableware, wherein the composition comprises:
(A) 10% to 40% by weight of an organic solvent system containing the following i) and ii) :
i) 1-15 % by weight of an organic amine solvent selected from alkanolamines, alkylamines, alkyleneamines and mixtures thereof ;
ii) ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, ethylene glycol phenyl ether and mixtures thereof here glycol ether solvent selected from, the weight ratio of organic amine solvent and glycol ether solvent is 3: 1 to 1: is 3;
(B ) a surfactant selected from anionic surfactants, amphoteric surfactants, zwitterionic surfactants, nonionic surfactants, semipolar surfactants and mixtures thereof ; 10% by weight and having a liquid surface tension of less than 24.5 mN / m.   The composition of claim 1 having a pH of at least 10.5 when measured as a 10% distilled aqueous solution.   The composition according to claim 1, further comprising a thickener selected from synthetic smectite-type clays, natural rubbers and mixtures thereof.   The composition according to claim 1, further comprising a salt having a divalent cation, in particular magnesium.   The composition according to claim 1, further comprising a fragrance or a fragrance base for solvent odor masking. 6. A composition according to claim 5 , wherein the perfume or perfume base contains ionone or a mixture of ionones.   The composition according to claim 1, further comprising a cyclodextrin malodor control agent. Cookware and cooking soils from tableware, a method for removing sticking dirt or scorching dirt, cookware / table with hard surface cleaning composition according to any one of claims 1-7 Said method comprising treating an edible utensil. 9. The method of claim 8 , comprising pretreating the cookware / tableware with a hard surface cleaning composition prior to manually or automatically washing the dishes. Before washing dishes manually or automatically, pre-treat cookware / tableware with a hard surface cleansing composition and crawl the prepared cookware / tableware until the soil is fully swollen The method of claim 8 including the step of covering with a cling film.