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WO2013045277A1 - Method and composition for cleaning hard surfaces - Google Patents

Method and composition for cleaning hard surfaces

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Publication number
WO2013045277A1
WO2013045277A1 PCT/EP2012/067918 EP2012067918W WO2013045277A1 WO 2013045277 A1 WO2013045277 A1 WO 2013045277A1 EP 2012067918 W EP2012067918 W EP 2012067918W WO 2013045277 A1 WO2013045277 A1 WO 2013045277A1
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WO
Grant status
Application
Patent type
Prior art keywords
surface
hard
water
composition
cleaning
Prior art date
Application number
PCT/EP2012/067918
Other languages
French (fr)
Inventor
Wuye OUYANG
Qingsheng Tao
Original Assignee
Unilever N.V.
Unilever Plc
Hindustan Unilever Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND 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, glass beads
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND 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 AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND 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 AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND 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

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

METHOD AND COMPOSITION FOR CLONING HARD SURFACES

FIELD OF THE INVENTION

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

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 consumer for 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.

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.

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.

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.

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.

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

"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. Hvdrophilic

"Hydnophilic" 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, or a surface that has a contact angle of water less than 900 at 25 °C.

Oligomer

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.

Hvdrolvzation

"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

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".

All amounts are by weight of the final composition, unless otherwise specified.

It should be noted that in specifying any range of values, any particular upper value can be associated with any particular lower value.

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. 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.

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

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.

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. 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 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

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 hydrophilicity 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.

Typically, the hydrolyzed quaternary silane may be hydrolyzed from quaternary silane precursor having a formula; (R1)sSi - 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.

The quaternary silane precursor employed in this invention preferably comprises tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetrapropyl orthosilicate (TPOS), tetrabutyl orthosilicate (TBOS), aminomethyltriethoxysilane, 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. 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).

The amount of the hydrolyzed quaternary silane and/or its oligomer, employed in the hard surface cleaning formulation will be from 0.001 to 10% by weight of the composition, more preferably from 0.01 to 4%, and most preferably from 0.05 to 2%. 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.

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.

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.

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.

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.

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%. 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.

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. 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.

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.

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.

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. 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. 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. 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/or scratch resistance. Further aspects of the 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.

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.

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.

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.

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.

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 fomnation 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.

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.

When recovering the hard surface cleaning composition, any other necessary or optional components may be combined with the mixture.

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

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 cleaner. 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. 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) (AEO7) 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

When the composition containing quaternary silane precursor (TEOS, TBOS, GLU-S or mixtures thereof), surfactant (SLES, CTAB, or AEO7) 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 under such 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

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 water droplets 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

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

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

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 850 to the horizontal surface. After a certain period of time, optical image was recorded to compare the hydrophilicity and cleanness.

Example 1

This example demonstrates the effect of surfactants on water sheeting effect of cleaning compositions. 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

Figure imgf000017_0001

* Herein the hydrolyzed TEOS means the product of hydrolyzation of TEOS. The content of hydrolyzed TEOS is calculated by dividing the weight concentration of TEOS by molecular weight of TEOS and multiplying the molecular weight of tetrahydroxysilane.

** The mirror was treated by formulation D before there was precipitation visible by naked eye.

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, AEO7 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

This example demonstrates the increase of durability of hydrophilicity by combination of hydrolyzed quaternary silane with anionic surfactant.

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

Figure imgf000018_0001
* Calculated as in Example 1 .

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 This example demonstrates the water sheeting effects of formulations with different weight ratio of hydrolyzed quaternary silane with anionic surfactant.

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

Figure imgf000019_0001
* Calculated as in Example 1 .

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

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.

Formulations in Table 4 were prepared (according to section of Preparation of the composition). Hydnophilicity tests were conducted (according to the method in section of Test). The results are shown in Table 4. Table 4

Figure imgf000020_0001

* Calculated as in Example 1 .

** Herein the hydrolyzed GLU-S means the product of hydrolyzation of GLU-S. The content of hydrolyzed GLU-S is calculated by dividing the weight

concentration of GLU-S by molecular weight of GLU-S and multiplying the molecular weight of N-(3- trihydroxysilylpropyl)gluconamide.

*** Herein the hydrolyzed TEOS means the product of hydrolyzation of TBOS. The content of hydrolyzed TBOS is calculated by dividing the weight concentration of TEOS by molecular weight of TBOS and multiplying the molecular weight of tetrahydroxysilane.

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

This example demonstrates the immediate cleaning performance of the formulation L (see Table 3) by comparing it with a polymer-based hard surface formulation.

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

This example demonstrates the long lasting effect of the formulation L (see Table 3) by comparing it with the polymer-based hard surface formulation.

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.

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 clear. 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.

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

This example demonstrates the applicability of formulation L (see Table 3) to different hard surfaces: steel and plastic coated panel.

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. 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 -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.
2. The method according to claim 1 wherein the hydrolyzed quaternary silane is hydrolyzable from a quaternary silane precursor having the formula; (R1)3 Si - 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-triethoxysilylpropyl)gluconamide, tetrachlorosilane, or a mixture thereof.
4. The method according to any one 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 carboxylates, or a mixture thereof.
5. The method according to claim 4 wherein the anionic surfactant comprises sodium lauryl ether sulphate, linear alkyl benzenesulphonate sodium, or a 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 any one 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, or a 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 ether sulphate, 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 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.
20. The process according to claim 19 wherein the quaternary silane precursor has the formula; (R1)sSi - R2 wherein
R1 is selected from alkoxy, or halogen; and
R2 is selected from hydroxy, hydroxyalkyl, aminoalkyl, alkoxy, halogen, or its ester or amide.
PCT/EP2012/067918 2011-09-30 2012-09-13 Method and composition for cleaning hard surfaces WO2013045277A1 (en)

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