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HUE026232T2 - Method and composition for cleaning hard surfaces - Google Patents

Method and composition for cleaning hard surfaces Download PDF

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Publication number
HUE026232T2
HUE026232T2 HUE12756756A HUE12756756A HUE026232T2 HU E026232 T2 HUE026232 T2 HU E026232T2 HU E12756756 A HUE12756756 A HU E12756756A HU E12756756 A HUE12756756 A HU E12756756A HU E026232 T2 HUE026232 T2 HU E026232T2
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HU
Hungary
Prior art keywords
composition
quaternary
cleaning
hard surface
water
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HUE12756756A
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Hungarian (hu)
Inventor
Wuye Ouyang
Qingsheng Tao
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Unilever Nv
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Publication of HUE026232T2 publication Critical patent/HUE026232T2/en

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0036Soil deposition preventing compositions; Antiredeposition agents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/162Organic compounds containing Si

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Disclosed is a method and composition for cleaning hard surfaces and process for making the composition. The method comprises treating the surface with a composition comprising 0.001 to 10 wt. % of a hydrolyzed quaternary silane having three hydroxy ligands and one hydrophilic ligand, and/or its oligomer, an anionic surfactant, and water, wherein the hydrophilic ligand is selected from -OH, -SH, -NH2, or group having a molar ratio of C: Q less than 3:1, wherein Q is selected from O, S, N, or combination thereof. After treating the hard surface with the method, the hard surface has robust water sheeting ability and therefore proving long lasting effect for cleaning.

Description

Description
FIELD OF THE INVENTION
[0001] The present invention relates to a method and a composition for cleaning hard surfaces, to obtain a protective layer for robust water sheeting effect and/or a long lasting effect for cleaning. Moreover, the invention relates to a process for making the hard surface cleaning composition.
BACKGROUND OF THE INVENTION
[0002] With the global urbanization and improvement of living conditions, especially in developing countries, more and more people move to cities with more spaces to live, and thus more household surface to clean. Also, people would like relief from housework and have more time for other activities. Therefore, the requirement of consumerfor household cleaning product is continually increasing. Other than the basic cleaning function, the benefits including less effort, less time to clean, a better cleaning result are desired.
[0003] Forming a water sheeting layer during cleaning and after cleaning may deliver such benefits. The hard surface will dry easily due to the water spreading area being larger upon sheeting. Also drying will be more uniform such that unappealing water mark will not be formed onto the hard surfaces, giving the consumer an appealing appearance, even when the hardness of water is high. The end cleaning result will be better. Moreover, for subsequent cleaning, the soil particulates will be distributed uniformly on the hard surface instead of aggregated within the water marks, due to the uniform water film. Therefore, another benefit is that the hard surface has visually cleaner appearance. Thus the period between cleaning can be prolonged, and so save effort and time for consumers.
[0004] Efforts have been made to provide hard surface cleaning composition for water spreading benefit. US patent published as US7699941 (The Clorox Company) discloses cleaning composition comprising a water-soluble or water-dispersible copolymer. The cleaning compositions are said to enhance hard surfaces to exhibit excellent water spreading and oil-repellency and therefore provide a next time easier cleaning consumer benefit.
[0005] US patent published as US7745383 (Henkel AG & Co. KGaA) discloses cleaner for hard surfaces, especially glass. Application of the cleaner containing a colloidal silica sol results in a modification of the steaming potential of the surface by -5 to -50 mV. The cleaner is said to be used to hydrophilize and clean hard surfaces.
[0006] International patent application published as WO 2009/121682 (Unilever) discloses use of citric acid and/or a salt of citric acid in cleaning composition for cleaning hard surfaces. The use of citric acid and/or a salt of citric acid will facilitate the removal of soil and obtain a next time cleaning benefit.
[0007] However, the robustness of the water spreading layer is not always good. Often after rinsing, the layer may deteriorate and the water sheeting effect disappears. We have recognized a need to develop a method and composition for hard surface cleaning which can deposit a robust water sheeting layer during the operation of cleaning and that remains after cleaning. The present invention, therefore, is directed to a method and composition for cleaning a hard surface and process for making the composition. More particularly, the invention involves methods using compositions comprising quaternary hydrolyzed silane, and anionic surfactant, to treat hard surface. The treated hard surface surprisingly has good water sheeting effect and long lasting effect for cleaning.
DEFINITIONS
Hard surface [0008] "Hard surface" for the purposes of the present invention means any surface comprising a hard material such as glass, glazed ceramics, metal, stone, plastics, lacquer, wood, or combination thereof. Typically, the hard surface is in a household including window, kitchen, bathroom, toilet, furniture, floor, or the like.
Hydrophilic [0009] "Hydrophilic" for the purposes of the present invention is used to describe a molecule or portion of a molecule that is attracted to, and tends to be dissolved by water, ora surface that has a contact angle of water less than 90 ° at 25 °C.
Oligomer [0010] "Oligomer" for the purposes of the present invention means a molecule that consists of several monomer units, for example, from 2 to 100, more preferably, from 2 to 60 monomer units.
Hydro Ivzation [0011] "Hydrolyzation" for the purposes of the present invention refers to a reaction with water. "Hydrolyzable" herein means the compound may react with water. "Hydrolyzed" means the compound is the reaction product of another compound with water.
Miscellaneous [0012] Except in the examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use may optionally be understood as modified by the word "about".
[0013] All amounts are by weight of the final composition, unless otherwise specified.
[0014] It should be noted that in specifying any range of values, any particular upper value can be associated with any particular lower value.
[0015] For the avoidance of doubt, the word "comprising" is intended to mean "including" but not necessarily "consisting of or "composed of. In other words, the listed steps or options need not be exhaustive.
[0016] The disclosure of the invention as found herein is to be considered to cover all embodiments as found in the claims as being multiply dependent upon each other irrespective of the fact that claims may be found without multiple dependency or redundancy.
[0017] Where a feature is disclosed with respect to a particular aspect of the invention (for example a composition of the invention), such disclosure is also to be considered to apply to any other aspect of the invention (for example a method of the invention) mutatis mutandis.
SUMMARY OF THE INVENTION
[0018] In a first aspect; the present invention provides a method for cleaning a hard surface comprising: treating the surface with a composition comprising: (a) 0.001 to 10 wt. % of a hydrolyzed quaternary silane having three hydroxy ligands and one hydrophilic ligand, and/or its oligomer; (b) an anionic surfactant; and (c) water; wherein the hydrophilic ligand is selected from -OH, -SH, -NH2, or group having a molar ratio of C: Q less than 3:1, wherein Q is selected from O, S, N, or combination thereof.
[0019] In a second aspect, the present invention provides a hard surface cleaning composition comprising: (a) 0.001 to 10 wt. % of a hydrolyzed quaternary silane having three hydroxy ligands and one hydrophilic ligand, and/or its oligomer; (b) 0.001 to 3.9 wt. % of an anionic surfactant; and (c) water; wherein the hydrophilic ligand is selected from -OH, -SH, -NH2, group having a molar ratio of C: Q less than 3:1, wherein Q is selected from O, S, N, or combination thereof.
[0020] In a third aspect, the present invention provides a process for the preparation of a hard surface cleaning composition comprising the steps of: (a) forming a reaction mixture comprising water and from 0.001 to 10 wt. % of a quaternary silane precursor; and (b) hydrolyzing the quaternary silane precursor in the mixture to provide a hydrolyzed quaternary silane having three hydroxy ligands and one hydrophilic ligand, and/or its oligomer; and (c) combining the mixture with from 0.001 to 3.9 wt. % of an anionic surfactant; and (d) recovering the hard surface cleaning composition; wherein the hydrophilic ligand is selected from -OH, -SH, -NH2, group having a molar ratio of C: Q less than 3:1, wherein Q is selected from O, S, N, or combination thereof.
BRIEF DESCRIPTION OF THE FIGURES
[0021]
Figure 1 is an optical image of mirror plate after deposition of particulate soils and then cleaning by a formulation according to the invention (a) and a comparative formulation (b);
Figure 2 is an optical image of mirror plate, with left half treated by a formulation according to the invention and right half treated by a comparative formulation, placed at outdoors balcony for two weeks during the raining season;
Figure 3 is an optical image of mirror plate, with left half treated by a formulation according to the invention and right half treated by a comparative formulation, placed at outdoors balcony for two months;
Figure 4 is an optical image of water droplet on plastic coated panel, with only right half treated by a formulation according to the invention; and
Figure 5 is an optical image of water droplet on steel, with only right half treated by a formulation according to the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0022] The hydrolyzed quaternary silane in this invention is a silane with four ligands wherein three ligands are hydroxy ligands and other ligand is hydrophilic group. In order to achieve a good water sheeting effect, the hydrophilic group may be selected from -OH, -SH, -NH2. Additionally or alternatively, the hydrophilic group comprises group having a molar ratio of C:Q less than 3:1, preferably from 1:2 to 2:1, wherein Q is selected from O, S, N, or combination thereof. Too high ratio of C:Q will destroy the hyd rophilicity of the group. It is also possible that two or more silanol of the hydrolyzed quaternary silane condensate together to form oligomers. However, this condensation should not lead to excessive polymerization, otherwise, the silane may not be well dispersed and may even precipitate.
[0023] Typically, the hydrolyzed quaternary silane may be hydrolyzed from quaternary silane precursor having a formula; (R1)3Si - R2. R1 represents the hydrolysable ligands which could be hydrolyzed to be hydroxyl group. R1 may be selected from alkoxy, halogen, or the like. The requirement for R2 is to be hydrophilic itself if it is not hydrolysable, or could become hydrophilic group after hydrolysis if it is hydrolysable. Thus, R2 comprises hydroxy, alkoxy, alkylhydroxy, alkylamine, alkyloic acid, or its ether, ester or amide. Additionally or alternatively, R2 comprises halogen.
[0024] The quaternary silane precursor employed in this invention preferably comprises tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetrapropyl orthosilicate (TPOS), tetrabutyl orthosilicate (TBOS), aminomethyltriethox-ysilane, aminomethyltrimethoxysilane, sulfanylmethyltriethoxysilane, N-(3-triethoxysilylpropyl)gluconamide (GLU-S), tetrabromosilane, tetrachlorosilane. In the more preferred embodiment, the quaternary silane precursor comprises TEOS, TMOS, TPOS, TBOS, N-(3-triethoxysilylpropyl)gluconamide, tetrachlorosilane, or a mixture thereof. Even more preferably, the quaternary silane precursor is selected from TEOS, TBOS, N-(3-triethoxysilylpropyl)gluconamide or a mixture thereof.
[0025] For example, the quaternary silane precursors suitable for use in this invention include TEOS from Shanghai Chemical Reagent Co. Ltd (China); TBOS from Sigma-Aldrich (Germany); and/or GLU-S) from Gelest Inc. (USA).
[0026] The amount of the hydrolyzed quaternary silane and/or its oligomer, employed in the hard surface cleaning formulation will beírom 0.001 to 10% by weight of the composition, more preferably from 0.01 to 4%, and most preferably from 0.05 to 2%.
[0027] When combining a hydrolyzed quaternary silane with surfactant, it is unexpectedly found that different types of surfactant behave differently. Neither cationic nor non-ionic surfactant is as compatible with the hydrolyzed quaternary silane as anionic surfactant. It is surprisingly found that the combination of anionic surfactant and the hydrolyzed quaternary silane provides not only a stable formulation but also a better water sheeting effect to the hard surface.
[0028] Thus, the surfactant suitable for this invention at least comprises anionic surfactant. The anionic surfactant preferably comprises alkyl benzene sulphonate, secondary alkane sulphonate, primary alkyl sulphate, alkyl ether sulphate, alpha olefin sulphonate, alkyl carboxylates, or a mixture thereof.
[0029] Examples of such anionic surfactants are salts of
Alkyl benzene sulphonate, such as those in which the alkyl group contains of 6 to 20 carbon atoms, typically 10 to 20 carbon atoms;
Secondary alkane sulphonate, especially those in which the alkane group have 15 to 17 carbon atoms;
Primary alkyl sulphate, especially those wherein the alkyl contains 12 to 14 carbon atoms;
Alkyl ether sulphate having 12 to 15 carbon atoms and with 1 to 3 ethoxy groups;
Alpha olefin sulphonate wherein the alpha olefin contains 14 to 16 carbon atoms;
Alkyl carboxylates wherein the alkyl group contain 10 to 18 carbon atoms; or a mixture thereof.
[0030] The preferred anionic surfactants are the alkali metal (such as sodium and potassium) and/or alkaline earth metal (such as calcium and magnesium) salt of alkyl ether sulphate having 10 to 20 carbon atoms and 1 to 5 ethoxy groups, and/or alkyl benzene sulphonate wherein the alkyl contains 10 to 14 carbon atoms. More preferably, the anionic surfactants comprise sodium lauryl ether sulphate, linear alkyl benzene sulphonate sodium, mixtures thereof, or the like.
[0031] Typically, the hard surface cleaning composition comprises anionic surfactant in an amount of 0.01 to 50 % by weight, preferably 0.01 to 10% by weight. More preferably, the hard surface cleaning composition comprises anionic surfactant in an amount of 0.01 to 3.9% by weight, and most preferably, from 0.05 to 2% by weight.
[0032] Other surfactant may be present. But preferably at least 50% by total weight of surfactant is anionic surfactant, more preferably, at least 75% by weight, most preferably from 80 to 100%.
[0033] When the hydrolyzed quaternary silane, and/or its oligomer, is combined with anionic surfactant, the weight ratio of hydrolyzed quaternary silane, and/or its oligomer to anionic surfactant (silane: surfactant) is preferably in the range of 20:1 to 1:20. More preferably, the weight ratio of silane: surfactant is in the range of the 10:1 to 1:5. In the most preferred embodiment, the weight ratio of silane: surfactant is in the range of 4:1 to 1:2.
[0034] The hard surface cleaning composition preferably comprises water in the range of 0.01 to 99.9 % by weight of the composition, more preferably 5% to 99% by weight. Even more preferably, the hard surface cleaning composition comprises water in an amount of 25 to 95% by weight.
[0035] The composition may further comprise a component to improve water sheeting effect and/or increase the robustness of water sheeting effect. Such component may comprise a component having a carboxylic acid group. The component may be polymer and/or organic compound. Exemplary acids include, without limitation, acrylic acid, citric acid, polyacrylic acid, glycolic acid, lactic acid, acetic acid, gluconic acid. Preferably, the component comprises acrylic acid, citric acid, polyacrylic acid, or a mixture thereof. The preferred amount is in the range of 0.1 % to 10% by weight of the composition.
[0036] The composition may also comprise colourants, whiteners, optical brightness, soil suspending agents, detersive enzymes, bleaching agent, gel-control agents, freeze-thaw stabilisers, bactericides, abrasives, preservatives, and/or perfumes.
[0037] When treating a hard surface by the composition, any general way for cleaning a hard surface is acceptable. Typically, the way for treating a hard surface by the composition is spraying the composition onto the hard surface, or wiping the hard surface by wipe impregnated with the composition, or dripping the composition onto the hard surface, or combination thereof. Preferably, the way for treating a hard surface is spraying the composition onto a hard surface, and/or wiping a hard surface by wipe impregnated with the composition. When the spraying is employed for treating a hard surface, there is no limitation how the composition is sprayed. Typically, a spraying bottle for hard surface cleaning product is favourable. When wiping is employed for treating a hard surface, wipe including woven or nonwoven cloth, natural or synthetic sponges or spongy sheets, "squeegee" materials, paper towel, or the like is suitable. The wipe may be impregnated dry, or more preferably in wet form.
[0038] Whilst not being bound by any particular theory or explanation, we believe that the composition exerts it effect by depositing hydrolyzed quaternary silane and/or its oligomer, and anionic surfactant onto a hard surface, forming a layer attached to the hard surface. The layer could enhance water spreading behaviour. Water will be easily spread along the hard surface, resulting in a better visual appearance.
[0039] After treating the surface with the composition, the method for cleaning hard surface may optionally further comprises the steps of allowing soil and/or stains to deposit. Thus, the soil or stains will be easily removed when the hard surface is subsequently cleaned according to the method of this invention. Meanwhile, the hydrolyzed quaternary silane and/or its oligomer and anionic surfactant are also preferably applied to the hard surface during the subsequent cleaning. Optionally, treating of a hard surface with the composition may be followed by a rinsing step, preferably with water.
[0040] A preferred method for cleaning a hard surface comprises the steps in sequence of: (i) treating a hard surface with composition according to the invention; (ii) allowing the soil or stains to deposit on the surface; and (iii) cleaning the surface to remove the soil or stains.
[0041] The present invention may also deliver other benefits such as long last cleaning, less effort for cleaning, less surface corrosion, less noise during cleaning, and/orscratch resistance. Further aspects ofthe present invention comprise methods for obtaining one or more these other benefits in a hard surface cleaning operation and/or use the composition in the methods in the manufacture of products for delivering any one more such benefits mentioned in this invention.
[0042] The soils and stains of present invention may comprise all kinds of soils and stains generally encountered in the household, either of organic or inorganic origin, whether visible or invisible to the naked eye, including soiling solid debris and/or with bacteria or other pathogens. Specifically the method and compositions according to the invention may be used to treat surface susceptible to fatty or greasy soil and stains.
[0043] The hard surface of present invention generally refers to any surface in household including the window, kitchen, bathroom, toilet, furniture, floor, or the like or any surface in car, ship, and airplane including windows, mirrors, sinks, basins, toilet bowls, baths/shower trays, wall tiles, floor tiles, cooker tops, oven interiors, cookware, washing machine drums, cooker hoods, extractor fans. These surfaces, for example, may be made of glass, glazed ceramics, metal, stone, plastics, lacquer, wood, or combination thereof. Especially, the method and composition according to the invention is used to treat the hard surface of window, kitchen, bathroom, and toilet. Preferably, the method and composition in this invention is used to treat glass.
[0044] There is no limitation as to how the hard surface cleaning composition may be made. However, in a preferred aspect, the process for the preparation of a hard surface cleaning composition comprises the steps of: (a) forming a reaction mixture comprising water and from 0.001 to 10 wt. % of a quaternary silane precursor; and (b) hydrolyzing the quaternary silane precursor in the mixture to provide a hydrolyzed quaternary silane having three hydroxy ligands and one hydrophilic ligand., and/or its oligomer; and (c) combining the mixture with from 0.001 to 3.9 wt. % of an anionic surfactant; and (d) recovering the hard surface cleaning composition; wherein the hydrophilic ligand is selected from -OH, -SH, -NH2, or group having a molar ratio of C: Q less than 3:1, wherein Q is selected from O, S, N, or combination thereof.
[0045] When forming a reaction mixture comprising water and from 0.001 to 10 wt. % quaternary silane precursor, there is no limitation in respects to the sequence of mixing water and quaternary silane precursor. Either water is added into quaternary silane precursor, or quaternary silane precursor is added into water. Generally, stirring is used for making water and quaternary silane precursor well mixed.
[0046] The hydrolyzation of quaternary silane precursor could be carried out when the mixture is either acidic or alkali. To avoid easily excessive polymerization, the mixture is preferably acidic. More preferably, the pH value of the mixture is in the range of 2 to 7. The lower the pH of the mixture is, the faster the hydrolyzation of quaternary silane precursor will be conducted when the mixture is acid. There is no limitation for the acid used to tune the pH of the mixture, for example, hydrochloric acid, sulphuric acid, or citric acid. It is noted that another requirement for the hydrolyzation of quaternary silane precursor is that the quaternary silane precursor has an amount of less than 10% by weight of the mixture, preferably, less than 4% by weight of the mixture. After hydrolyzation, a hydrolyzed quaternary silane having three hydroxy ligands and one hydrophilic ligand, and/or its oligomer is provided. The hydrophilic ligand is selected from -OH, -SH, -NH2, group having a molar ratio of C: Q less than 3:1, wherein Q is selected from O, S, N, or combination thereof. Without wishing to be bound to any theory, it is believed that the formation of oligomer will depend on the concentration of quaternary silane precursor. The higher concentration the mixture has, oligomer with larger molecular weight will be yielded.
[0047] When combining the mixture with an anionic surfactant, the amount of anionic surfactant is from 0.01 to 3.9% by weight of the composition. Preferably, there is not limitation to the sequence and way for mixing only that the mixture and anionic surfactant is mixed uniformly.
[0048] When recovering the hard surface cleaning composition, any other necessary or optional components may be combined with the mixture.
[0049] The composition could be packed in any form of conventional hard surface cleaning product. The preferred packaging is spray applicators. Pump dispersers (weather spray or non-spray pumps) and pouring applications (bottles etc) are also possible. It is also possible to impregnate a wipe with the composition.
EXAMPLES
Materials [0050] The test surfaces in the examples included standard mirror (glass), plastic coated panel, or steel. These surfaces were cleaned prior to the use by commercial hard surface deaner. The artificial soil used in the examples has the formulation: 0.51 wt. % of tripalmitin, 0.26 wt. % of glyceryl trioleate, 0.1 wt. % of paraffin, 0.05 wt. % of palmitic acid, 3.6 wt. % of kaolin, 0.02 wt. % of carbon black and 95.48 wt. % of ethanol.
[0051] The chemicals involved in the examples include:
Tetraethyl orthosilicate (TEOS) from Shanghai Chemical Reagent Co. Ltd (China);
Teteabutyl orthosilicate (TBOS) from Sigma Aldrich (Germany); N-(3-triethoxysilylpropyl)gluconamide (GLU-S) from Gelest Inc. (USA);
Sodium lauryl ether sulphate (1 EO) (SLES) from Cognis (Germany);
Cetyltrimethylammonium chloride (CTAC) from Cognis (Germany);
Lauryl/tetradecyl Alcohol Ethoxylate Ether (7EO) (AE07) from UNIQEMA (UK);
Hydrochloric acid (HCI, 36 wt%) from Shanghai Chemical Reagent Co. Ltd (China);
Deionized water is produced by Milli-Q system (Millipore, USA).
Preparation of the formulation [0052] When the composition containing quaternary silane precursor (TEOS, TBOS, GLU-S or mixtures thereof), surfactant (SLES, CTAB, or AE07) and water was prepared, they were weighed separately according to content and volume of composition. Then, the quaternary silane precursor, surfactant, and deionized water were mixed under stirring of 400 rpm by stirrer (IKA, RT 15 power, Germany) at ambient condition. After stirring for one hour, HCI was added to the mixture to adjust the pH of the mixture to 3. The quaternary silane precursor will be hydrolyzed undersuch condition. The hydrolysis speed will depend on the acidity of the mixture. Higher the acidity is, faster the hydrolyzation is. After stirring for another three hours, the composition was ready for treating a hard surface. When the composition containing only quaternary silane precursor and water was prepared, all the steps were same except that no surfactant was mixed. When the composition of surfactant and water were prepared, only the weighing and mixing steps were needed. The composition was packaged into conventional container for household care product including spray applicator and bottle for further use.
Test
Hard surface cleaning method [0053] The compositions are used for cleaning a hard surface. One ordinary way to cleaning a hard surface is spray and wipe or drip and wipe. Firstly, 0.1 to 0.2 g of the composition is sprayed by a spray applicator or placed by a pipette onto a hard surface (mirror/glass, steel, plastic coated panel). Subsequently, the hard surface is wiped by wipe from J-Cloth (UK) for one minute. Then, the hard surface is air dried for 10 minutes.
Hydrophilicity test
The hydrophilicity of hard surface after treating by each composition was measured by using a water drop test. This test is used to measure how well the water spreads on the hard surface after treating by each composition. First, a mirror plate (with area of 7 cm by 7 cm) is cleaned in acetone ultrasonically and a paper towel. Next, the mirror is cleaned by the composition according to the hard surface cleaning method. Then, one 50 μι water droplet at room temperature was placed and allowed spread on the mirror. After five minutes, the diameter of the water droplet was measured. Because of the possible unevenness and inhomogeneity, the shape of the spread waterdroplets was not always round, will be approximately elliptic. The length of long axis and short axis of the elliptic water droplet will be measured. The "diameter" of such water droplet is calculated to be the square root of product of the lengths of short axis and long axis. The measurement was conducted at least three times to calculate the average diameter and its standard deviation. The higher value of the water droplet diameter means better water sheeting effect.
Durability test of the hydrophilicity [0054] This method is designed to test the robustness of the protective layer. A mirror plate was cleaned by a composition according to the hard surface cleaning method. Then, the hydrophilicity test was conducted on the mirror plate. After air drying for 1 hour, the mirror plate was flushed by tap water for 10 seconds. The hydrophilicity test was conducted again after air drying for 1 hour. The difference of results for these two hydrophilicity test demonstrate the robustness of protective layer. The smaller the difference is, the better the robustness is. immediate cleaning test [0055] The cleaning test is used to measure how the composition will influence the subsequent cleaning steps. First, a mirror plate (with area of 42 cm by 15 cm) was cleaned by ordinary household product in market. Then, the artificial soil (6.8 g) is sprayed onto the mirror plate and aged overnight for 12 to 20 hours. 4 g of composition is placed on the onto the mirror plate by spraying or dripping, followed by a cleaning process by mop for 1 minutes. Then, the residue is measured by optical image.
Long last cleaning test [0056] A mirror plate (48 cm by 33 cm) was cleaned according to the hard surface cleaning method, left half by the composition according to the invention, right half is cleaned by a comparative cleaning comprising a commercial polymeric agent (PolyQuart Ampho 149, from Cognis, Germany) claimed to assistant hard surface cleaning. The mirror plate was placed almost vertically on a balcony with a tilt angle of about 85 ° to the horizontal surface. After a certain period of time, optical image was recorded to compare the hydrophilicity and cleanness.
Example 1 [0057] This example demonstrates the effect of surfactants on water sheeting effect of cleaning compositions.
[0058] Formulations A, B, C, and D in Table 1 were prepared (according to section of Preparation of the composition). It is noted that composition D was not stable. There was white precipitate in the composition D after storage over one night. Then, these formulations were used to clean the mirror plates and the hydrophilicity test was conducted onto the mirror plates (according to section of Test). The result of hydrophilicity test is shown in the right hand column of Table 1.
Table 1
[0059] As shown in Table 1, when combining TEOS with cationic surfactant, CTAC induced the deterioration of water sheeting effect. Although the water sheeting effect by combining TEOS with non-ionic surfactant, AE07 is on par with TEOS only, the formulation is not stable. Surprisingly, only combing TEOS and anionic surfactant, SLES can result in a stable formulation and better water sheeting effect of the treated hard surface.
Example 2 [0060] This example demonstrates the increase of durability of hydrophilicity by combination of hydrolyzed quaternary silane with anionic surfactant.
[0061] Formulation E and F in Table 2 were prepared (according to section of Preparation of the composition). These formulations were used to conduct hydrophilicity test and robustness test of hydrophilicity (according to the method in section of Test). The result is shown in Table 2.
Table 2
[0062] Before rinsing with tap water, the water sheeting effects of these two formulations are almost the same as shown in Table 2. However, after the mirror plates were flushed by tap water, the water sheeting effect decreases much more rapidly without the addition of TEOS. This result indicated that combining TEOS and SLES will increase the durability of water sheeting effect.
Example 3 [0063] This example demonstrates the water sheeting effects of formulations with different weight ratio of hydrolyzed quaternary silane with anionic surfactant.
[0064] Formulations in Table 3 were prepared (according to section of Preparation of the composition). Hydrophilicity tests were conducted (according to the method in section of Test. The results are shown in Table 3.
Table 3
[0065] As can be seen, the formulations impart better water sheeting effect to the mirror plates when the weight ratio of hydrolyzed TEOS to SLES is in the range of 9:1 to 1:13. The best water sheeting effect in Table 3 is achieved when the weight ratio of hydrolyzed TEOS to SLES is 3:5.
Example 4 [0066] This example demonstrates the water sheeting effects of formulations prepared from various quaternary silane precursors including GLU-S and TBOS, or their combination with TEOS, and SLES.
[0067] Formulations in Table 4 were prepared (according to section of Preparation of the composition). Hydrophilicity tests were conducted (according to the method in section of Test. The results are shown in Table 4.
Table 4
[0068] When comparing formulations P and Q, it is manifested that combining GLU-S and SLES can also result in excellent water sheeting effect beside TEOS. Formulation R and S indicates the combination of GLU-S, TEOS, and SLES also results in the excellent water sheeting effect. Similar effects can be achieved by combining TBOS and SLES (see formulation T). These results demonstrate both GLU-S and TBOS can combine with SLES to cooperatively induce water sheeting effect.
Example 5 [0069] This exam pie demonstrates the immediate cleaning performance of the formulation L (see Table 3) by comparing it with a polymer-based hard surface formulation.
[0070] Immediate cleaning test was conducted (according to the method described in section of Test) by using formulation L and the comparative formulation comprising polymer of PolyQuart Ampho 149 (Cognis, Germany). Figure 1 shows the cleaning results of the formulations against high particulate soil. The end result after cleaning by these two formulations is almost the same as shown in the picture. It is manifested that the immediate cleaning performance of formulation L is on par with the comparative formulation.
Example 6 [0071] This example demonstrates the long lasting effect of the formulation L (see Table 3) by comparing it with the polymer-based hard surface formulation.
[0072] Long last cleaning test was conducted (according to the method described in section of Test) by using formulation L and the comparative formulation in example 5. After two weeks during the raining season, the optical image was recorded as shown in figure 2. After two months, another optical image was recorded as shown in figure 3.
[0073] In figure 2, it is clear that there are few water droplets on the left side of the picture, while there are lots of water droplets on the right side. Even the border between these two halves is quite dear. This indicates the water sheeting effect on mirror plate treated by formulation L remains effective. In contrast, the water sheet effect on mirror plates treated by the comparative formulation has decreased a lot after two weeks. This result demonstrates the long last water sheeting effect of formulation L.
[0074] Figure 3 show the cleaning effect for longer time. Clearly apparent is that the right half of the mirror plate is covered by a layer of white dust which results in decreased transparency. The left half is clearer with less soil deposited. These results demonstrate the long last cleaning effect of formulation L, resisting the deposition of soils even over two months.
Example 7 [0075] This example demonstrates the applicability of formulation L (see Table 3) to different hard surfaces: steel and plastic coated panel.
[0076] Formulation L was used to treat steel and plastic coated panel (according to the cleaning method in the section of Test). On each plate, only the right half was treated by formulation L. Figure 4 shows the result on plastic coated panel. As can be seen, the diameter of water droplet on the right half is much bigger than that of the left one, indicating much better water sheeting effect of right half than left half. Figure 5 is the result on the steel surface. It is also demonstrated that the water sheeting becomes better after treatment by formulation L. This example demonstrates formulation L is suitable to be employed to a range of hard surfaces including steel and plastic coated panel.
[0077] These results demonstrate that the methods and/or compositions according to the present invention surprising yield superior cleaning effect including good water sheeting effect and long lasting cleansing.
Claims 1. A method for cleaning a hard surface comprising: treating the surface with a composition comprising: (a) 0.001 to 10 wt. % of a hydrolyzed quaternary silane having three hydroxy ligands and one hydrophilic ligand, and/or its oligomer; (b) an anionic surfactant; and (c) water; wherein the hydrophilic ligand is selected from -OFI, -SH, -NH2, or group having a molar ratio of C: Q less than 3:1, wherein Q is selected from O, S, N, or combination thereof. 2. The method according to claim 1 wherein the hydrolyzed quaternary silane is hydrolyzable from a quaternary silane precursor having the formula; (R1)3Si-R2 wherein R1 is selected from alkoxy, or halogen; and R2 is selected from hydroxy, hydroxyalkyl, aminoalkyl, alkoxy, or its ester, or amide, or halogen. 3. The method according to claim 2 wherein the quaternary silane precursor comprises tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetrapropyl orthosilicate (TPOS), tetrabutyl orthosilicate (TBOS), N-(3-triethoxys-ilylpropyl)glucnamide, tetrachlorosilane, or a mixture thereof. 4. The method according to anyone of claims 1 to 3 wherein the anionic surfactant comprises alkyl benzene sulphonate, secondary alkane sulphonate, primary alkyl sulphate, alkyl ether sulphate, alpha olefin sulphonate, alkyl carboxy-lates, or a mixture thereof. 5. The method according to claim 4 wherein the anionic surfactant comprises sodium lauryl ether sulphate, linear alkyl benzenesulphonate sodium, ora mixture thereof. 6. The method according to any one of the preceding claims wherein the composition comprises the anionic surfactant in an amount in the range of 0.01 to 10 % by weight. 7. The method according to claim 6 wherein the composition comprises the anionic surfactant in an amount in the range of 0.01 to 3.9 % by weight. 8. The method according to any one of the preceding claims wherein the composition comprises the hydrolyzed quaternary silane and/or its oligomer in the range of 0.01 to 4% by weight. 9. The method according to any one of the preceding claims wherein the composition comprises the hydrolyzed quaternary silane and/or its oligomer and an anionic surfactant in a weight ratio between 1:20 to 20:1. 10. The method according to any one of the preceding claims wherein the composition comprises a component having carboxylic acid group. 11. The method according to claim 10 wherein the component comprises acrylic acid, citric acid, polyacrylic acid, or a mixture thereof. 12. The method according to anyone of the preceding claims wherein the hard surface comprises glass, metal, wood, plastics, vitreous enamel, stone, ceramic, or combinations thereof. 13. The method according to any one of the preceding claims wherein the method further comprises the step of allowing soil or stains to deposit on the surface after treating the surface with the composition. 14. The method according to claim 13 wherein the soil or stain is a fatty soil or stain. 15. A hard surface cleaning composition comprising: (a) 0.001 to 10 wt. % of a hydrolyzed quaternary silane having three hydroxy ligands and one hydrophilic ligand, and/or its oligomer; (b) 0.001 to 3.9 wt. % of an anionic surfactant; and (c) water; wherein the hydrophilic ligand is selected from -OH, -SH, -NH2, or group having a molar ratio of C: Q less than 3:1, wherein Q is selected from O, S, N, or combination thereof. 16. The cleaning composition according to claim 15 wherein the hydrolyzed quaternary silane is hydrolyzable from a quaternary silane precursor comprising tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetrapropyl orthosilicate (TPOS), tetrabutyl orthosilicate (TBOS), N-(3-triethoxysilylpropyl)gluconamide, tetrachlorosilane, ora mixture thereof. 17. The cleaning composition according to claims 15 or 16 wherein the anionic surfactant comprises alkyl benzene sulphonate, secondary alkane sulphonate, primary alkyl sulphate, alkyl ethersulphate, alpha olefin sulphonate, alkyl carboxylates, or a mixture thereof. 18. The cleaning composition according to any one of claims 15 to 17 wherein the composition comprises hydrolyzed quaternary silane and/or its oligomer and an anionic surfactant in a weight ratio between 1:10 to 10:1. 19. A process for the preparation of a hard surface cleaning composition comprising the steps of: (a) forming a reaction mixture comprising water and from 0.001 to 10wt. % of a quaternary silane precursor; and (b) hydrolyzing the quaternary silane precursor in the mixture to provide a hydrolyzed quaternary silane having three hydroxy ligands and one hydrophilic ligand., and/or its oligomer; and (c) combining the mixture with from 0.001 to 3.9 wt. % of an anionic surfactant; and (d) recovering the hard surface cleaning composition; wherein the hydrophilic ligand is selected from -OH, -SH, -NH2, or group having a molar ratio of C: Q less than 3:1, wherein Q is selected from O, S, N, or combination thereof. 20. The process according to claim 19 wherein the quaternary silane precursor has the formula; (R1)3Si-R2 wherein R1 is selected from alkoxy, or halogen; and R2 is selected from hydroxy, hydroxyalkyl, aminoalkyl, alkoxy, halogen, or its ester or amide.
Patentansprüche 1. Verfahren zur Reinigung einer harten Oberfläche, umfassend: das Behandeln der Oberfläche mit einer Zusammensetzung, die umfasst: (a) 0,001 bis 10 Gew.-% eines hydrolysierten quaternären Silans mit drei Hydroxyliganden und einem hydrophilen Liganden und/oder eines Oligomers davon; (b) ein anionisches Tensid; und (c) Wasser; wobei der hydrophile Ligand ausgewählt ist aus -OH, -SH, -NH2 oder einer Gruppe mit einem Molverhältnis von C:Q von weniger als 3:1, wobei Q ausgewählt ist aus O, S, N oder Kombinationen davon. 2. Verfahren nach Anspruch 1, wobei das hydrolysierte quaternäre Silan aus einem quaternären Silan-Vorläufer der Formel (R1)3Si-R2 hydrolysierbar ist, wobei R1 ausgewählt ist aus Alkoxy oder Halogen; und R2 ausgewählt ist aus Hydroxy, Hydroxyalkyl, Aminoalkyl, Alkylcarbonsäure oder deren Ester oder Amid oder Halogen. 3. Verfahren nach Anspruch 2, wobei der quaternäre Silan-Vorläufer Tetraethylorthosilicat (TEOS), Tetramethylortho-silicat (TMOS), Tetrapropylorthosilicat (TPOS), Tetrabutylorthosilicat (TBOS), N-(3-Triethoxysilylpropyl)-glucona-mid, Tetrachlorsilan oder ein Gemisch davon umfasst. 4. Verfahren nach einem der Ansprüche 1 bis 3, wobei das anionische Tensid Alkylbenzolsulfonat, sekundäres Alkan-sulfonat, primäres Alkylsulfat, Alkylethersulfat, alpha-Olefinsulfonat, Alkylcarboxylate oder ein Gemisch davon umfasst. 5. Verfahren nach Anspruch 4, wobei das anionische Tensid, Natriumlaurylethersulfat, lineares Alkylbenzolsulfonat-natrium oder ein Gemisch davon umfasst. 6. Verfahren nach einem der vorstehenden Ansprüche, wobei die Zusammensetzung das anionische Tensid in einer Menge im Bereich von 0,01 bis 10 Gew.-% umfasst. 7. Verfahren nach Anspruch 6, wobei die Zusammensetzung das anionische Tensid in einer Menge im Bereich von 0,01 bis 3,9 Gew.-% umfasst. 8. Verfahren nach einem der vorstehenden Ansprüche, wobei die Zusammensetzung das hydrolysierte quaternäre Silan und/oder das Oligomer davon in einer Menge im Bereich von 0,01 bis 4 Gew.-% umfasst. 9. Verfahren nach einem der vorstehenden Ansprüche, wobei die Zusammensetzung das hydrolysierte quaternäre Silan und/oder das Oligomer davon und ein anionisches Tensid in einem Gewichtsverhältnis von 1:20 bis 20:1 umfasst. 10. Verfahren nach einem der vorstehenden Ansprüche, wobei die Zusammensetzung eine Komponente mit einer Carbonsäuregruppe umfasst. 11. Verfahren nach Anspruch 10, wobei die Zusammensetzung Acrylsäure, Citronensäure, Polyacryl säure oder ein Gemisch davon umfasst. 12. Verfahren nach einem der vorstehenden Ansprüche, wobei die harte Oberfläche Glas, Metall, Holz, Kunststoffe, glasartiges Email, Stein, Keramik oder Kombinationen davon umfasst. 13. Verfahren nach einem der vorstehenden Ansprüche, wobei das Verfahren nach der Behandlung der Oberfläche mit der Zusammensetzung ferner die Stufe umfasst, bei der man die Abscheidung von Schmutz oder Flecken auf der Oberfläche zulässt. 14. Verfahren nach Anspruch 13, wobei es sich beim Schmutz oder Flecken um einen fettigen Schmutz oder Flecken handelt. 15. Reinigungszusammensetzung für harte Oberflächen, umfassend: (a) 0,001 bis 10 Gew.-% eines hydrolysierten quaternären Silans mit drei Hydroxyliganden und einem hydrophilen Liganden und/oder eines Oligomers davon; (b) 0,001 bis 3,9 Gew.-% eines anionisches Tensids; und (c) Wasser; wobei der hydrophile Ligand ausgewählt ist aus -OH, -SH, -NH2 oder einer Gruppe mit einem Molverhältnis von C:Q von weniger als 3:1, wobei Q ausgewählt ist aus O, S, N oder Kombinationen davon. 16. Reinigungszusammensetzung nach Anspruch 15, wobei das hydrolysierte, quaternäre Silan aus einem quaternären Silan-Vorläufer hydrolysierbar ist, der Tetraethylorthosilicat (TEOS), Tetramethylorthosilicat (TMOS), Tetrapropy-lorthosilicat (TPOS), Tetrabutylorthosilicat (TBOS), N-(3-Triethoxysilylpropyl)-gluconamid, Tetrachlorsilan oder ein Gemisch davon umfasst. 17. Reinigungszusammensetzung nach Anspruch 15 oder 16, wobei das anionische Tensid Alkylbenzolsulfonat, sekundäres Alkansulfonat, primäres Alkylsulfat, Alkylethersulfat, alpha-Olefinsulfonat, Alkylcarboxylate oder ein Gemisch davon umfasst. 18. Reinigungszusammensetzung nach einem der Ansprüche 15 bis 17, wobei die Zusammensetzung hydrolysiertes quaternäres Silan und/oderein Oligomer davon und ein anionisches Tensid in einem Gewichtsverhältnis von 1:10 bis 10:1 umfasst. 19. Verfahren zur Herstettrxng einer Reinigungszusammensetzung für harte Oberflächen, umfassend die folgenden Stufen: (a) das Bilden eines Reaktionsgemisches, das Wasser und 0,001 bis 10 Gew.-% eines quaternären Silan-Vorläufers umfasst; und (b) das Hydrolysieren des quaternären Silan-Vorläufers im Gemisch zur Bereitstellung eines hydrolysierten quaternären Silans mit drei Hydroxyliganden und einem hydrophilen Liganden und/oderdes Oligomers davon; und (c) das Vereinigen des Gemisches mit 0,001 bis 3,9 Gew.-% eines anionischen Tensids; und (d) das Gewinnen der Reinigungszusammensetzung für harte Oberflächen; wobei der hydrophile Ligand ausgewählt ist aus -OH, -SH, -NH2 oder einer Gruppe mit einem Molverhältnis von C:Q von weniger als 3:1, wobei Q ausgewählt ist aus O, S, N oder Kombinationen davon. 20. Verfahren nach Anspruch 19, wobei der quaternäre Silan-Vorläufer die Formel (R1)3Si-R2 aufweist, wobei R1 ausgewählt ist aus Alkoxy oder Halogen; und R2 ausgewählt ist aus Hydroxy, Hydroxyalkyl, Aminoalkyl, Alkoxy, Halogen oder dessen Ester oder Amid. Revendications 1. Procédé pour un nettoyage d’une surface dure comprenant : le traitement de la surface avec une composition comprenant : (a) de 0,001 à 10 % en poids d’un silane quaternaire hydrolysé présentant trois ligands hydroxy et un ligand hydrophile, et/ou son oligomère ; (b) un tensioactif anionique ; et (c) de l’eau ; dans lequel le ligand hydrophile est choisi parmi -OH, -SH, -NH2, ou un groupe présentant un rapport molaire de C:Q inférieur à 3:1, où Q est choisi parmi O, S, N, ou une combinaison de ceux-ci. 2. Procédé selon la revendication 1, dans lequel le silane quaternaire hydrolysé est hydrolysable à partird’un précurseur de silane quaternaire présentant la formule ; (R1)3Si-R2 dans laquelle R1 est choisi parmi un groupe alcoxy, ou un halogène ; et R2 est choisi parmi un groupe hydroxy, hydroxyalkyle, aminoalkyle, alcoxy, ou son ester, ou un amide, ou un halogène. 3. Procédé selon la revendication 2, dans lequel le précurseur de silane quaternaire comprend de l’orthosilicate de tétraéthyle (TEOS), de l’orthosilicate de tétraméthyle (TMOS), de l’orthosilicate de tétrapropyle (TPOS), de l’orthosilicate de tétrabutyle (TBOS), du N-(3-triéthoxysilylpropyl)gluconamide, du tétrachlorosilane, ou un mélange de ceux-ci. 4. Procédé selon l’une quelconque des revendications 1 à 3, dans lequel le tensioactif anionique comprend un ben-zènesulfonate d’alkyle, un sulfonate d’alcane secondaire, un sulfate d’alkyle primaire, un sulfate d’alkyléther, un sulfonate d’oléfine-alpha, des carboxylates d’alkyle, ou un mélange de ceux-ci. 5. Procédé selon la revendication 4, dans lequel le tensioactif anionique comprend du lauryléthersulfate de sodium, un benzènesulfonate de sodium d’alkyle linéaire, ou un mélange de ceux-ci. 6. Procédé selon l’une quelconque des revendications précédentes, dans lequel la composition comprend le tensioactif anionique dans une quantité dans l’intervalle de 0,01 à 10 % en poids. 7. Procédé selon la revendication 6, dans lequel la composition comprend le tensioactif anionique dans une quantité dans l’intervalle de 0,01 à 3,9 % en poids. 8. Procédé selon l’une quelconque des revendications précédentes, dans lequel la composition comprend le silane quaternaire hydrolysé et/ou son oligomère dans l’intervalle de 0,01 à 4 % en poids. 9. Procédé selon l’une quelconque des revendications précédentes, dans lequel la composition comprend le silane quaternaire hydrolysé et/ou son oligomère et un tensioactif anionique dans un rapport massique entre 1:20 et 20:1. 10. Procédé selon l’une quelconque des revendications précédentes, dans lequel la composition comprend un constituant présentant un groupe acide carboxylique. 11. Procédé selon la revendication 10, dans lequel le constituant comprend de l’acide acrylique, de l’acide citrique, du poly(acide acrylique), ou un mélange de ceux-ci. 12. Procédé selon l’une quelconque des revendications précédentes, dans lequel la surface dure comprend du verre, du métal, du bois, des matières plastiques, de l’émail vitreux, de la pierre, de la céramique, ou des combinaisons de ceux-ci. 13. Procédé selon l’une quelconque des revendications précédentes, dans lequel le procédé comprend de plus l’étape consistant à laisser de la salissure ou des taches se déposer sur la surface après le traitement de la surface avec la composition. 14. Procédé selon la revendication 13, dans lequel la saleté ou la tache est une saleté ou une tache grasse. 15. Composition de nettoyage de surface dure comprenant : (a) de 0,001 à 10 % en poids d’un silane quaternaire hydrolysé présentant trois ligands hydroxy et un ligand hydrophile, et/ou son oligomère ; (b) de 0,001 à 3,9 % en poids d’un tensioactif anionique ; et (c) de l’eau ; dans laquelle le ligand hydrophile est choisi parmi -OF, -SH, - NH2, ou un groupe présentant un rapport molaire de C:Q inférieur à 3:1, où Q est choisi parmi O, S, N, ou une combinaison de ceux-ci. 16. Composition de nettoyage selon la revendication 15, dans laquelle le silane quaternaire hydrolysé est hydrolysable à partir d’un précurseur de silane quaternaire comprenant de l’orthosilicate de tétraéthyle (TEOS), de l’orthosilicate de tétraméthyle (TMOS), de l’orthosilicate de tétrapropyle (TPOS), de l’orthosilicate de tétrabutyle (TBOS), du N-(3-triéthoxysilylpropyl)gluconamide, du tétrachlorosilane, ou un mélange de ceux-ci. 17. Composition de nettoyage selon les revendications 15 ou 16, dans laquelle le tensioactif anionique comprend un benzènesulfonate d’alkyle, un sulfonate d’alcane secondaire, un sulfate d’alkyle primaire, un sulfate d’alkyléther, un sulfonate d’oléfine-alpha, et des carboxylates d’alkyle, ou un mélange de ceux-ci. 18. Corn position de nettoyage selon l’une quelconque des revendications 15 à 17, dans laquelle la corn position comprend un silane quaternaire hydrolysé et/ou son oligomère et un tensioactif anionique dans un rapport massique entre 1:10 et 10:1. 19. Procédé pour la préparation d’une composition de nettoyage de surface dure comprenant les étapes consistant : (a) à former un mélange réactionnel comprenant de l’eau et de 0,001 à 10 % en poids d’un précurseur de silane quaternaire ; et (b) à hydrolyser le précurseur de silane quaternaire dans le mélange pourfournir un silane quaternaire hydrolysé présentant trois ligands hydroxy et un ligand hydrophile, et/ou son oligomère ; et (c) à combiner le mélange avec de 0,001 à 3,9 % en poids d’un tensioactif anionique ; et (d) à récupérer la composition de nettoyage de surface dure ; dans lequel le ligand hydrophile est choisi parmi -OH, -SH, -NH2, ou un groupe présentant un rapport molaire de C:Q inférieur à 3:1, où Q est choisi parmi 0, S, N, ou une combinaison de ceux-ci. 20. Procédé selon la revendication 19, dans lequel le précurseur de silane quaternaire présente la formule ; (R1)3Si-R2 dans laquelle R1 est choisi parmi un groupe alcoxy, ou un halogène ; et R2 est choisi parmi un groupe hydroxy, hydroxyalkyle, aminoalkyle, alcoxy, un halogène, ou son ester, ou un amide.

Claims (7)

Μ JÁRÁS ÉS KÉSZÍTMÉNY KÉMÉNT FELÖLITEK TISZTÍTÁSÁRA. Szabadalmi igénypontokΜ DRY AND PREPARATION TO CLEAN CLEAN UP. Claims 1. Eljásás^km&amp;y .fdülét tisztítására, amely magában foglalja a kővetkezőket; a felület kezelés«. a következőket tanalm&amp;zö keszítmét-ro-d; (a.) 9,001-10 tömegéé hifeàizâtt, kväfemer szilán, &amp;mdy három hidfoxíiígandot és egy iktámfd Kgandot tartalmaz, és/vagy ©higc-morjc, (b) aakmos fetüfeíaküv anyag és (c) via, ahol a biárofil ligand a következők .közül választott; -OH, SH, -NH> vagy csoport, amelyben, a C:Q molmátry kisebb, ásást 3: 1, ahol Q jelentése Ö, S, N Mlzil választott; s agy ezek kotnbsoácsös.1. Crashing ^ km for cleaning &amp; ydfd, which includes the following; surface treatment «. I teach the following things: (a.) 9.001-10% by weight, containing quaternary silane, &amp; mdy three hydoxydandandes and an αtamphd Kgand, and / or © higc-morjc, (b) acrylic fetal material and (c) wherein the pharophile ligand is the following: .selected by; -OH, SH, -NH> or a group in which the C: Q molar fraction is smaller, digging 3: 1, where Q is Ö, S, N is Mlzil; and they are the same thing. 2. Az 1, igénypont szerinti eljárás, ahol a hidrolizált, kvatemer sdlás t'ÍÉ t;Si-R.''' kéglstü. kvatemer szüánptekwrzottsOl .hklrolizálható, ahol .Rs jelentése alkosd vagy hidegén; és g? jelentése a következők közül választott: hidrád, iádroxialkíl, araíaaaHcil, alkod vagy észterei, vagy aröá vagy balogén, 3. A 2, igénypont igénypont szerkói eljárás, ahol a kvatsmsr szilánpreknrzor magában foglalja a következőket: fetraedl-orteszilik át (TEÖS), íetratnetfoerfosfeikái (TMOS), tsfcapmpii-ortoszilMi (TPOÉh tett»·· bsiii'-öztoszilikál (TBÖS), N-(3-footezlsatliipropl!)-glókoaei®ld, ídraklórszilán vagy ezek keveréke.The method of claim 1, wherein the hydrolysed, quaternary effluent is t'ÍÉ t; Si-R '' ''. a quaternary paraffin can be obtained by means of a cholesterol, wherein .Rs is alkoxy or cold; and g? is selected from the group consisting of: hydrate, iodoalkoxy, arylAcyl, alkyd or its esters, or aroma or balogen, 3. The method of claim 2, wherein the quatsmsil silane precursor comprises the following: fetraedl-orthosylate (TEÖS), tetratnetfoerphosphores ( TMOS), tsfcapmpii-orthosilMi (TPOÉh-made · · · · · · · * · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·ail '; 4. Az 1-3. igénypontok:'bármelyike szerinti eljárás, ahol az aniont® felületaktív anyag magában foglalja a következőket; alkil-benzoi-szráfonát, szeknndez nlkámsnlfonát, primer alkil-sxuliát, áikü-éser--szn!fát, &amp;lfa-olefitä-sznifoöat, alkil-katboxilátok vagy ezek keveréke. 5. A4. igénypont szerinti eljárás, ahol az antant® lehileiakitv anyag magában foglalja· a kővetkezőket: nlsrkiîï-hntril-szalfat, egyenes láncé alkiÉbeozolszttíLmát-sátdons vagy keverékük. é, Az e&amp;Ő igénypontok ifermelyike szerinti eljátás, ahol a készítmény az .anionok foluletsRiiv anyagot 0,01-10 lomeg% mennyiségben tartalmazza, 7. A 6, igénypont szerinö ellátás, ahol a készítmény az anion«® fehíistaktív anyagot 0,0! -3,9 tomegM mennyiségben tartalmazz;·. g. Az. előző igénypontok bármelyike szerinti eljárás, ahol a készítmény a hídroiizált kvatemer szifont éa’vagy ©íigometét 0,01 -4 töosegfo motmytségben lartalmazza,4. Referring to 1-3. The method of any one of claims 1 to 3, wherein the anionic surfactant comprises the following; alkylbenzenesulphonate, sequentially occurring sulfonate, primary alkylxylate, aliphatic ester, &amp; lfa olefinic siphole, alkyl catboxylates, or mixtures thereof. 5. A4. A method according to claim 1, wherein the antanthene lime-containing material comprises the following: nlsrkiîï-httril-scalate, straight chain alcohols or mixtures thereof. and, wherein the composition comprises the .anion foluletive material in an amount of 0.01 to 10% by weight, the composition of claim 6, wherein the composition is an anion ®? ! Contains 3.9 tomegM; g. The method according to any one of the preceding claims, wherein the composition comprises the hydrolyzed quaternary siphon and the graft © 9. Az előző igénypontok bármelyike szerinti eljárás, ahol a készítmény &amp; hidrolizált kvatemer szílánt és/vagy öligomefot és arnonos felületaktív anyagot 1:20 és 30:1 közötti tömegarányban halmaza». 1Ö. Az előző igénypontok Mrtady&amp;e .szerinti ef árás, aboi a Részferfooy karfepns3v--e$»p<ntöí tartalmazó összetevői tart&amp;lürtz, 11. A 10. igénypont szerinti eljárás, ahol az Összetevő akrílsttvat, cítronssavat,. poKakrilsavat tartalmaz vagy ezek keverékét íntsaitaazza. U. Az előző· igénypontok bármelyike szerinti eljárás, ahol a kemény felület nmgah&amp;n foglalja a követke-sőkes: üveg, fém, is, otóanyag, fe'agzomáae, kó vagy ezek kombinációiThe method of any one of the preceding claims, wherein the composition &amp;amp; hydrolysed quaternary strap and / or kigomome and arnon surfactant in a weight ratio of 1:20 to 30: 1. 1o. The prior art claims include the components of Mrtady &amp; e., Comprising the components of the subfferoy karfepns3v - e $ p < p &gt; &amp; lrtz, 11. The method of claim 10, wherein the Ingredient is acrylic, cytonic acid. contains poachacrylic acid or a mixture of these. A method according to any one of the preceding claims, wherein the hard surface comprises nmgah &amp;n; 13. Az eleső igénypontok bármelyike szclfeti eljárás, amely magában foglalja továbbá a .következő lé-pest: szennyeződés vagy felt lerakódásának lefestóvé tétek a felületen a felület készítménnyel történő .kezelése «társ, 14:. A13. Igénypont szerinti eljárás, aboi a szennyeződd vagy felt zsíros szennyeződés vagy felt.13. A method according to any one of the preceding claims, further comprising treating the contamination or deposition on the surface with the following composition. A13. The method according to claim, contaminant or fatty contamination or coating. 15. Kemény felszínt tisztító készitöfesty, sanely tartalmazza á -következőket: fa) 0,001-Ki tömeg% iódrobzált, kvatetner szilán, amely bérem Indroxiiigaodot Is egy Mdrefii ligandet tartalmaz, és/vagy ennék öligömetje, (lï) 0,001-3,9 iöoieg'/á anionos felületaktív aoyag é&amp; (<:} víz, ató a biâreii ligand a kővetkezők közli választolt: -OH, -SH, -Ml2 vagy csoport, mtmybm a C:Q mókráay kisebb, abat 3:1, aboi Q jisfemêse O, S, H közül választott; vagy ezek:kombinációi. .tá, A 13. igénypont szerinti tiszdtókészitmény, aboi s hrdmirzált, kvatemer szilán a következik bármelyikét magában foglaló kvsiemer szilánirreknízorbói Mdrolizálh&amp;tó:' retraetil-ortezíHkát (IROS), tetrametil-ortoszilikát fIMOS), tetmpropil-onosziKkáí (TROS), ieirabutil-ortöszüikái (TSOS), N-ß-trietoxiszüüpropil)-glSkonsmkl, tatmkSőrszilán vagy ezek keveréke 1?. A 15. vagy 16. igénypont szerinti tisztítókészüméay, ahol az -aniones felületaktív anyag magában foglalja a kővetkezőket: aSkil-leozol-sznlfeoáí, szekunder alkán-szalíenát, primer aikll-szslfát, ailcü-éier-szölfet, aife-plefin-sztófeoát, alM-kmboxiíátök vagy ezek keveréke; ág. A 15-17.. igénypontok hámmlyíks szerintii Sászíiíőkészksnérty, aboi a készítmény 1:1.0 és :18:1 közötti femegamisyban tartalmaz Inárolizáli kvaferner szilám és/vagy oligomerét és anionos felületaktív anyagot.15. Hard Surface Cleansing Paint, which contains the following: fa) 0.001 to 1 wt.% Iodinated, quaternary silane, which also contains Indroxyl ligate and an Mdref ligand, and / or a killer thereof, (lï) 0.001-3.9 iöoieg '. / a anionic surfactant aoyag &amp; (<:} water, atoms are the ligand of the following, selected from the following: -OH, -SH, -Ml2, or a group, mtmybm is less than C, Q is selected from the group consisting of abat 3: 1, aboi Q tafemêse O, S, H; or combinations thereof. Purification composition according to claim 13, quaternary quaternary silane quaternary silane regenerating agent comprising: Mdrolizal &amp; p: retraethyl orthohexylate (IROS), tetramethyl orthosilicate fIMOS, tetmpropyl-onosaccharide ( TROS), iirabutyl-orthopedic (TSOS), N-β-triethoxysilpropyl) -glSconsil, tatmkSurililane, or a mixture thereof 1 ?. Cleaning detergent according to claim 15 or 16, wherein the anionic surfactant comprises the following: aSkyl-leosol sulfate, secondary alkane-salenate, primary alkyl sulfate, allyl-ether vine, aife-plephon stoolate, alm. -coxoxylates or mixtures thereof; branch. Compositions according to claims 15-17, wherein the composition comprises from 1: 1.0 to: 18: 1 in Inolized Kvaferner Silage and / or Oligomer and Anionic Surfactant. 113, Eljárás kemény felület tisztítására szolgáló készítmény előállítására, amely magában foglalja a kővetkező lépéseket: f&amp;) makslókeverék képzése, amely vizet és 0,001 · 10 tötneg% kvatemer szíiáaprekmrzprt tartalmaz, :és (b) a kvaiemet szilánprekntzor hrárolízálása a keverékben,, ezáltal hidrolízált kvatemer sziláit oiztositssa, amely bárom hidroxiligaodo· és egy hidroűl íig&amp;ndoi tartalmaz és/vagy obgomesje blBtosítása, és (eá a keverek kombinálása 0,001 -3.0 tömeg% anionos faMkaaktiv anyaggal, és (à) a ketsény feilík'í tisztítására szolgáló készümány kinyerése. akcl a bidrofe ligand a következők köz®! választó»: -OH, -SH, vagy csoport, amelyben a C;Q mőlarány kisebb, mint 3:1, aboi Q jelemése O, S, N közül választóit; vagy ezek kombinációi. 20, A19:. igénypont szerinti eljárás, aboi a kvatomer smláoprekurzor képlete (R sböl g; jelentése alkoxi vagy halogén; és RJ jeienílse a kővetkezők közül választolt: liidroxi, bldroxialkik ammoalktl, alkom, balogén vagy észtereik, vagy amid.A method for the preparation of a hard surface cleaning composition comprising the steps of: f &amp;) forming a blend of water containing 0.001 · 10 wt.% Of quaternary chromate powder: and (b) chiralizing the quaternary silane precursor in the mixture, thereby hydrolyzing. quatemerian silicates oiztositssa, which contains a bar of hydroxylic acid and a hydroelectric &amp; ndoi and / or an obgomesje blB, and (a combination of mixtures with 0.001-3.0% by weight of anionic faMactivating agent, and (à) recovering a kit for cleansing the herd. the bidrofe ligand is selected from the group consisting of: -OH, -SH, or a group in which the ratio of C; Q is less than 3: 1, the Ab is Q is selected from O, S, N, or combinations thereof. The process of claim A19, wherein the quaternary odor trap precursor (from R is g; is alkoxy or halogen; and RJ is a radical). selected from the group consisting of liidoxyl, bldroxialk ammoalktl, alcohols, balogens or esters, or amides.
HUE12756756A 2011-09-30 2012-09-13 Method and composition for cleaning hard surfaces HUE026232T2 (en)

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