CN1771317A - 磨料硬表面清洁组合物 - Google Patents
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Abstract
本发明提供具有糊状稠度的水性酸性清洁组合物，其含有磨料、酸、能够和稀酸形成结构液体的阴离子表面活性剂和酸稳定的增稠剂。该组合物通过结合机械(研磨)作用和化学作用/溶解特别适合用于清洁多种油污和污物包括石灰垢和锈污物。
Description
技术领域
本发明涉及用于硬表面的含磨料清洁组合物。更加特别地，本发明涉及有效去除石灰垢(lime scale)和锈的硬表面清洁组合物。
背景技术和现有技术
本领域中磨料硬表面清洁组合物是公知的。然而很多年以前此种组合物只能以粉末形式得到，在过去的十年中液态组合物则更加流行。此类液态组合物是容易分散的膏状液体，从感觉和视觉观点来看对消费者具有更大的吸引力。但是，它们通常比粉末昂贵。
大部分这些组合物具有碱性pH因此对于去除大多数污物和油类污垢是非常有效的。但是，对于去除卫生间和浴室表面上的石灰垢和锈污物它们只是中等有效。为了这个目的研制了对去除石灰垢和锈污物更有效的酸性组合物。这些组合物可含有一种或多种不同的有机和/或无机酸。特别对于锈的去除通常包含草酸。
因此，US 5460742描述了酸性清洁组合物。所述组合物是包含5-50％磨料、两性和非离子表面活性剂和水合硅酸铝增稠剂(增稠粘土)的触变性液体。
US 3579456描述了包含至多60％磨料、至多10％多价有机酸如草酸、阴离子洗涤剂和铵基-两性离子洗涤剂的可倾倒酸性液体清洁剂。
US 3214380公开了包含草酸和作为磨料的石英粉的类似组合物。
US 4561993公开了包含至多20％无机酸、至多2.5％不是阴离子表面活性剂的表面活性剂、至多12％沉淀的二氧化硅悬浮剂和至多15％磨料的触变性液体磨料清洁剂。
US 5076955公开了包含阴离子表面活性剂、氧化铝和硅油的粘稠液体磨料清洁剂。所述清洁剂还含有制备工艺所需要的碱例如氢氧化钠和碳酸钠。
JP-A-53139606描述了包含无机或有机酸和增稠粘土的作为粘稠液体的酸性清洁剂。所述清洁剂还可以含有磨料。
WO 0127236公开了可以是酸性或中性并且可用于多种清洁用途包括机器清洗的清洁组合物，还公开了浴室和卫生间清洁剂。它们含有纳米微粒(1-200nm)无机化合物。此类化合物不适合用于并且不具有任何研磨作用。此外该组合物是触变性的，当放置时具有凝胶状稠度，通过摇动可被转变成可倾倒液体。
本领域已知很多其它酸性的锈去除组合物。一些是粉末并可含有磨料组分；其它是液体，其可被或可不被增稠以增加粘度，但是所述液体不合磨料因而只依靠溶解锈或石灰垢而去除它们。
需要一种锈和石灰垢去除产品，其具有液体磨料清洁剂的容易分散以及感觉和视觉外观的优点，但是其在使用中更加经济并且在被施用到尤其是倾斜或垂直表面上的污物上之后，可以和所述污物保持延长的接触，从而提供污物的化学去除或溶解。
发明简述
现在已经发现可以以糊状形式制备水性酸性磨料硬表面清洁组合物，该组合物通过机械(研磨)作用和化学作用/溶解的结合特别适合用于清洁多种油污和污物，包括石灰垢和锈污物。此类糊容易以所需要的量施用因而在使用中是经济的。
因此，本发明提供具有糊状稠度的水性酸性清洁组合物，其含有磨料、酸、能够和稀酸形成结构液体(structured liquid)的阴离子表面活性剂和任选的酸稳定的增稠剂。
此外，本发明提供用于从硬表面去除锈或石灰垢污物的方法，该方法包括将所述糊施用到污物上的步骤。
发明详述
本文中所提到的所有百分数都是“重量”，除非另有说明。
如上所述，本发明的酸性清洁组合物是糊。因而它们是非常粘稠、流动缓滞的液体。糊可以通过具有＞1000Pa.s，优选＞10000Pa.s的低剪切应力(＜10Pa)平台粘度(plateau viscosity)值和在1000Pa或更大，优选在200Pa和以上甚至更优选在100Pa或甚至50Pa和以上的剪切应力已经产生显著的剪切稀化进行表征。一种有用的糊在100Pa剪切应力具有至少0.1Pa.s，优选至少0.2Pa.s，更优选至少1Pa.s，甚至更优选至少2或甚至5Pa.s的粘度。
本发明的糊是酸性的，具有0-3的pH，优选2.5或更低，更加优选在或低于2或者1或更低。因此，它们以所需要的量含有无机和/或有机酸以给出期望的pH，以液体相计算通常的量为3-25％，优选至少5％(为本发明目的液体相定义为全部组合物减去磨料)。优选地它们至少含有无机酸(无机酸)并且无机酸的合适例子是盐酸，硫酸，氨基磺酸和磷酸，优选的量为液体相的5％或更多。硫酸和氨基磺酸是特别优选的。该组合物还可以另外地含有至多占液体相15％的有机酸，特别是二元-或多元-羧酸。草酸和柠檬酸是合适的例子。
本发明的糊含有固体微粒磨料，其量为全部组合物的20-75％，优选30-65％，更优选至少40％。适合的磨料具有7或更低但优选大于1的莫氏硬度。优选地，硬度至少为2。
适合的磨料在本发明组合物的酸性环境中是稳定的，并且可选自无机磨料例如二氧化硅，硅酸盐，硅铝酸盐，氧化铝，珍珠岩，浮石和石膏；有机聚合磨料例如聚乙烯，聚碳酸酯，聚氨酯，聚苯乙烯，聚丙烯，聚对苯二甲酸乙二醇酯，聚甲基丙烯酸甲酯和尼龙；和天然磨料例如碎坚果壳；和其混合物。一类特殊磨料是由微溶于水的无机盐形成并且以高于其饱和溶解度的量使用。该种类中合适的盐是三聚磷酸钠，四硼酸钠和硫酸钾。优选的磨料是：硅铝酸盐，氧化铝，水合氧化铝，长石和二氧化硅。特别优选的是长石和二氧化硅，和它们任何一种和石膏的混合物其中长石和/或二氧化硅占该磨料混合物的至少25％。
磨料的合适重均粒径在0.5-500μm范围。在该范围内可以取得良好清洁行为和低基底破坏之间的可接受的折中。5-100μm的重均粒径值是优选的并且10-50μm是特别优选的。
此外，本发明的糊包含适合于和酸性水相形成结构液体的阴离子表面活性剂。该结构液体能够提供液体中磨料的稳定悬浮。
适合种类的阴离子表面活性剂是在分子结构中具有含8-22个碳原子的支链或直链烷基或在烷基部分含6-20个碳原子的烷基芳基的有机硫酸单酯和磺酸。特别合适的是磺酸盐，更加特别的是：
-烷基苯磺酸盐，例如那些其中烷基含有6-20个碳原子并且优选是直链的烷基苯磺酸盐；
-烷烃磺酸盐，优选仲烷烃磺酸盐，更优选在烷基链中含10-18个碳原子的烷烃苯磺酸盐。
阴离子表面活性剂优选以液体相2-25％，更优选6-20％的量使用。
为了获得需要的糊粘度，本发明的组合物优选包含足够数量的酸稳定的增稠剂。增稠二氧化硅和增稠粘土在本领域中是公知的并且非常适合于此用途。适合的增稠粘土属于特别是膨润土或蒙脱土类粘土的绿土粘土矿物类。它们优选以液体相的1-25％，更优选至少2％或甚至5％的量进行使用。通常液体相的15％或甚至10％的最大水平就足以达到所需的糊状性能。具有低磨料水平的组合物优选含有足够的增稠二氧化硅或粘土以达到占全部组合物至少35％的不溶固体总水平。
本发明的组合物可以含有适当地加入到清洁组合物中的本领域公知的其它组分。因此，本发明的组合物可以包含其它的表面活性剂，特别是本领域已知的非离子或两性表面活性剂，只要这些表面活性剂不影响阴离子表面活性剂或所存在的表面活性剂的液体结构(structuring)性质。合适的表面活性剂描述于公知的教科书中：“Surface Active Agents”第1卷，Schwartz & Perry，Interscience1949；“Surface Active Agents”第2卷，Schwartz，Perry & Berch，Interscience 1958；Manufacturing Confectioners Company出版的现行版“McCutcheon’s Emulsifiers and Detergents”；“Tenside-Taschenbuch”，H.Stache，第2版.，Carl Hauser Verlag，1981。但是，通常非离子和/或两性表面活性剂的加入并不向本发明的组合物提供重大的额外益处，但却会增加成本。因此优选至多或者非离子或者两性表面活性剂存在，并最优选两者都不存在。
通常，两性离子或阳离子表面活性剂的存在根本不提供任何有用的用途，不含这些表面活性剂的组合物是本发明的优选实施方案。
本发明的组合物可含有有机溶剂以有助于该组合物的清洁性能。适合的溶剂是例如C1-C4脂族醇和单-或二-乙二醇或丙二醇或它们和C1-C6脂族醇的单醚。
其它可以存在的附加组分包括：香料，染料，荧光增白剂，抗菌剂/杀菌剂，漂白剂(尤其是过氧化物漂白剂)，等。优选不存在其它的在本发明组合物中并不提供任何有用用途的疏水添加剂例如矿物油，硅油或长链脂肪酸，特别优选不存在硅油。
本发明的组合物优选包装于例如桶或罐的容器中，从该容器中适当的量可以被取出并置于适当的敷涂器例如湿布或海绵上，或包装于例如管的容器中，从该容器中组合物可通过挤压而被分配。考虑到组合物的缓滞流动特性，组合物从其中只可以通过倾倒而被分配的容器并不合适。本发明的组合物提供了对多种油污和污物的优秀清洁性，特别是对在浴室和卫生间表面上普遍存在的污垢和污物例如皂垢、石灰垢和锈。它们在使用中用途更广泛并且比粉末产品容易定量。它们比液体磨料清洁剂对顽固的污垢给予更集中的清洁和过量的产品可被轻易地移走并通过将其放回管或罐包装中而被再次使用。此外，当施用于锈或石灰垢污物并放置一段时间以溶解这些污物时，它们相对于液体磨料清洁剂给出改进的清洁性，因为它们的粘着性更好从而具有延长的接触时间。
因此，本发明还提供了用于从硬表面去除锈和石灰垢污物的方法，包括如下步骤：将本发明的组合物施用到污物上，让组合物在污物上停留足够长的时间以通过溶解去除全部的或部分的污物，如果希望通过机械研磨作用去除剩余的污物，和通过擦拭和/或冲洗除去该组合物。
本发明的组合物可根据本领域公知的方法制造即通过以任何适当的顺序混合组分而制造。如果使用增稠二氧化硅或粘土，它们优选在加入磨料之前在搅拌下首先加入酸和水的混合物中并给予充分的时间进行水合。阴离子表面活性剂优选作为最后的组分加入。在阴离子表面活性剂加入之后糊结构出现并可能需要1-3天才能发展完全。
不同于一些现有技术，本发明不需要首先制造磨料和表面活性剂在必须通过单独加入碱而变成碱性的介质中的预混物。现有技术的缺点是需要额外的酸以使pH降低到所需要的3或更低、优选2.5或更低、更优选2.0或更低的水平。虽然本发明组合物的一些组分，特别是阴离子表面活性剂盐，本身可能具有轻微的碱性，但是本发明组合物优选并不含有任何可感知数量的单独加入的碱，优选少于2％，更优选少于1％，甚至更优选少于0.5％或甚至根本没有。这并不排除中和阴离子表面活性剂酸所需要的碱的加入。
实施例
根据下述组成制备酸性磨料清洁糊(所有的百分数都基于全部组合物)
| 组分 | 实施例1 | 实施例2 | 实施例3 |
| 磨料：Feldspar FK45 | 60％ | 60％ | 60％ |
| 增稠粘土：MPV200 | 3％ | 4％ | 3％ |
| 阴离子表面活性剂LAS* | 4％ | 7.4％ | - |
| 阴离子表面活性剂SAS** | - | - | 8％ |
| 硫酸 | 2.5％ | 3％ | 2.5％ |
| 香料 | 0.2％ | 0.2％ | 0.2％ |
| 水 | ......至100％...... | ||
*)Isorchem 113TM
**)Hostapur SAS 60TM
图1给出了上述每个实施例的粘度对剪切应力关系的图。
Claims (9)
1.含有酸、磨料和阴离子表面活性剂的水性酸性清洁组合物，其特征在于：
-所述阴离子表面活性剂能够与稀酸形成结构液体；
-该组合物具有0-3的pH；
-和该组合物是在低于10Pa剪切应力下具有大于1000Pa.s平台粘度的糊并且在100Pa剪切应力下具有至少0.1Pa.s的粘度。
2.权利要求1的组合物，其特征在于它含有无机酸。
3.权利要求2的组合物，其特征在于所述无机酸选自硫酸和氨基磺酸。
4.权利要求1-3的组合物，其特征在于它额外含有二元-或多元羧酸。
5.权利要求1-4的组合物，其特征在于它含有20-75％的莫氏硬度在1-7之间、重均粒径在0.5-500μm之间的矿物磨料。
6.权利要求1-5的组合物，其特征在于所述阴离子表面活性剂选自烷基苯磺酸盐和仲烷烃磺酸盐并且存在的量是液体相的2-25％。
7.权利要求1-6的组合物，其特征在于该组合物包含酸稳定的增稠剂。
8.权利要求7的组合物，其特征在于所述酸稳定的增稠剂选自增稠二氧化硅和增稠粘土并且用量为液体相的1-25％。
9.从硬表面去除锈和石灰垢污物的方法，包括如下步骤：将本发明的组合物施用到污物上，让组合物在污物上停留足够长的时间以通过溶解去除全部的或部分的污物，如果希望通过机械研磨作用去除剩余的污物，和通过擦拭和/或冲洗除去该组合物。
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| EP03251668A EP1460125A1 (en) | 2003-03-18 | 2003-03-18 | Abrasive hard surface cleaning compositions |
| EP03251668.4 | 2003-03-18 |
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| CN (1) | CN1771317A (zh) |
| AR (1) | AR043739A1 (zh) |
| BR (1) | BRPI0407927A (zh) |
| HU (1) | HUP0500857A2 (zh) |
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| PL (1) | PL377722A1 (zh) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109536306A (zh) * | 2018-12-29 | 2019-03-29 | 河南绿澳化工科技有限公司 | 一种厕所清洗剂及其制作方法 |
| CN111699238A (zh) * | 2018-02-05 | 2020-09-22 | 日本曹达株式会社 | 尿石除去和防止用药剂 |
| CN116024051A (zh) * | 2022-12-30 | 2023-04-28 | 广东红日星实业有限公司 | 一种灌浆清洗剂及其制备方法与应用 |
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|---|---|---|---|---|
| NZ597055A (en) * | 2006-12-15 | 2012-12-21 | Colgate Palmolive Co | Liquid hand dish detergent having suspended particulate material |
| WO2010039574A1 (en) | 2008-09-30 | 2010-04-08 | The Procter & Gamble Company | Liquid hard surface cleaning composition |
| WO2010039571A1 (en) | 2008-09-30 | 2010-04-08 | The Procter & Gamble Company | Liquid hard surface cleaning composition |
| WO2010039572A1 (en) | 2008-09-30 | 2010-04-08 | The Procter & Gamble Company | Liquid hard surface cleaning composition |
| WO2011087736A1 (en) * | 2009-12-22 | 2011-07-21 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
| JP5559893B2 (ja) | 2009-12-22 | 2014-07-23 | ザ プロクター アンド ギャンブル カンパニー | 液体クリーニング及び／又はクレンジング組成物 |
| CN102869758B (zh) | 2010-04-21 | 2014-11-19 | 宝洁公司 | 液体清洁和/或净化组合物 |
| US9353337B2 (en) | 2010-09-21 | 2016-05-31 | The Procter & Gamble Company | Liquid cleaning composition |
| EP2431453B1 (en) | 2010-09-21 | 2019-06-19 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
| EP2431451A1 (en) | 2010-09-21 | 2012-03-21 | The Procter & Gamble Company | Liquid detergent composition with abrasive particles |
| CA2839966C (en) | 2011-06-20 | 2016-08-23 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
| EP2537917A1 (en) | 2011-06-20 | 2012-12-26 | The Procter & Gamble Company | Liquid detergent composition with abrasive particles |
| US8703685B2 (en) | 2011-06-20 | 2014-04-22 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition comprising polylactic acid abrasives |
| US8852643B2 (en) | 2011-06-20 | 2014-10-07 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
| ES2577147T3 (es) | 2012-10-15 | 2016-07-13 | The Procter & Gamble Company | Composición detergente líquida con partículas abrasivas |
| US20140352721A1 (en) * | 2013-05-29 | 2014-12-04 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
| EP2808379A1 (en) * | 2013-05-29 | 2014-12-03 | The Procter & Gamble Company | Liquid cleaning and/or cleansing composition |
| EA031894B1 (ru) * | 2014-09-11 | 2019-03-29 | Юнилевер Н.В. | Композиция пасты для чистки твердых поверхностей |
| RU2601305C1 (ru) * | 2015-08-25 | 2016-11-10 | федеральное государственное бюджетное образовательное учреждение высшего образования "Пермский национальный исследовательский политехнический университет" | Чистящая паста |
| WO2023112046A1 (en) * | 2021-12-17 | 2023-06-22 | Saint-Gobain Glass France | A descaling composition for glass substrates |
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| JPS5951599B2 (ja) * | 1977-05-12 | 1984-12-14 | 武田薬品工業株式会社 | 洗浄剤 |
| JPS57100197A (en) * | 1980-12-13 | 1982-06-22 | Taisho Pharmaceutical Co Ltd | Detergent |
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| SU1209711A1 (ru) * | 1984-09-24 | 1986-02-07 | Уральский филиал Всесоюзного научно-исследовательского и проектного института химической промышленности | Средство дл чистки твердой поверхности |
| GB2168377A (en) * | 1984-12-17 | 1986-06-18 | Procter & Gamble | Stable liquid dishwashing detergent containing abrasive, clay and low density particles |
| GB8522526D0 (en) * | 1985-09-11 | 1985-10-16 | Unilever Plc | Liquid abrasive cleaner compositions |
| JPS6317999A (ja) * | 1986-07-09 | 1988-01-25 | 花王株式会社 | 研磨剤含有洗浄剤組成物 |
| DE3908971A1 (de) * | 1989-03-18 | 1990-09-20 | Benckiser Gmbh Joh A | Scheuernd wirkendes reinigungsmittel |
| US5460742A (en) * | 1993-05-18 | 1995-10-24 | Reckitt & Colman Inc. | Aqueous acidic hard surface cleaner with abrasive |
| JPH08176592A (ja) * | 1994-12-26 | 1996-07-09 | Central Glass Co Ltd | ガラス板用洗浄剤 |
| US5679877A (en) * | 1996-06-14 | 1997-10-21 | Colgate-Palmolive Co. | Thickened liquid cleaning composition containing an abrasive |
| DE19948859A1 (de) * | 1999-10-08 | 2001-11-08 | Henkel Kgaa | Thixotropes wäßriges Reinigungsmittel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111699238A (zh) * | 2018-02-05 | 2020-09-22 | 日本曹达株式会社 | 尿石除去和防止用药剂 |
| CN109536306A (zh) * | 2018-12-29 | 2019-03-29 | 河南绿澳化工科技有限公司 | 一种厕所清洗剂及其制作方法 |
| CN116024051A (zh) * | 2022-12-30 | 2023-04-28 | 广东红日星实业有限公司 | 一种灌浆清洗剂及其制备方法与应用 |
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| PL377722A1 (pl) | 2006-02-06 |
| EP1460125A1 (en) | 2004-09-22 |
| AR043739A1 (es) | 2005-08-10 |
| MXPA05009368A (es) | 2005-11-04 |
| HUP0500857A2 (en) | 2007-08-28 |
| BRPI0407927A (pt) | 2006-02-21 |
| RU2005132177A (ru) | 2006-02-27 |
| WO2004083353A1 (en) | 2004-09-30 |
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