WO2013160092A1

WO2013160092A1 - Hard surface treatment composition

Info

Publication number: WO2013160092A1
Application number: PCT/EP2013/057339
Authority: WO
Inventors: Somnath Das; Amitava Pramanik; Deboleena SARKAR
Original assignee: Unilever N.V.; Unilever Plc; Conopco, Inc., D/B/A Unilever
Priority date: 2012-04-24
Filing date: 2013-04-09
Publication date: 2013-10-31

Abstract

The present invention is in the field of hard surface treatment compositions. The invention particularly relates to hard surface treatment compositions that render a substrate hydrophobic and also repellent to aqueous stains and soils. It is an object of the present invention to provide a composition that is transparent, metal free, and upon use, renders a surface hydrophobic and repellant to stains and soils. It has been found that hydrophobicity and aqueous stain and soil repellence can be imparted to a surface by the deposition of polystyrene or a polystyrene copolymer onto the said surface.

Description

HARD SURFACE TREATMENT COMPOSITION

Field of the invention

The present invention is in the field of hard surface treatment compositions; and in particular relates to hard surface treatment compositions to render a substrate hydrophobic and also repellent to aqueous stains and soils. Background of the invention

Water droplets have a tendency to stick to surfaces. These water droplets are usually a mixture of water and fine particulate matter in the form of dust or dirt. The particulate matter is either present on the surface before being wetted or is already in a mixture with water when the droplets come in contact with the surface. When the water droplets settle on a surface and eventually dry up, they leave spots or streaks on the surface giving a stain-like appearance. Such an appearance on surfaces is not appreciated by present day consumers. Without wishing to be bound by a theory, it is believed that the behaviour of a liquid droplet on a surface depends on the adhesive forces between the surface and the liquid. If the adhesive forces are attractive, the liquid droplet is pulled towards the surface and remains on the surface. It is therefore thought that by making said surfaces hydrophobic, water droplets can be repelled by the surface, minimizing the contact of the water droplets with the surface and causing water droplets to bead and cover less of the surface when the surface is horizontal and even roll off inclined and vertical surfaces, and thus preventing surfaces from water damage and deposition of stains and soils. It is also thought that the consumers prefer transparent compositions for treating surfaces, especially when the surfaces to be treated are transparent or reflective surfaces such as glasses or mirrors which require a neat application. Transparent cleaning compositions give the impression of purity, whilst turbid or opaque compositions may give the consumer the impression that dirt may deposit from the cleaning composition or may even be abrasive and damage surfaces.

Metal soap based compositions have been proposed in the past for imparting hydrophobicity to surfaces. Our co-pending application IN-2963/MUM/201 1 describes hard surface cleaning compositions. It particularly relates to a method and composition for cleaning of a surface and imparting repellence of soils. It relates to the object of providing a stable surface cleaning composition which can make the surface hydrophobic and oleophobic as well as provide superior cleaning; and proposes a composition comprising fluoro silane with a solvent and a polyvalent metal salt was found to render both hydrophobicity and oleophobicity making the surface less susceptible to soiling, by both aqueous and oily stains and also provides better cleaning. However, the composition described therein is an opaque composition due to the presence of metal complexes, and the use of which is also less preferred as is it not perceived as being eco-friendly. Thus, there is an unfulfilled need for a hydrophobic composition which is transparent and devoid of metals.

Surface treatment compositions in the field of cleaning and preservation of hard surfaces are known. US 4,725,319 discloses a composition for cleaning and preserving hard surfaces comprising surfactants, non-metal-crosslinked polymers, an alkaline-reacting complexing agent, a water-soluble organic solvent and an alkalizing agent to maintain a pH between 8 to 10.5. However, the composition disclosed in this document does not provide satisfactory results on water and aqueous stain and soil repellence.

IN-1293/MUM/201 1 describes a hard surface cleaning composition comprising poly-aluminium-chloride (PAC), soap of C8-C18 fatty acid, a surfactant selected from non-ionic surfactants or quaternary ammonium cationic surfactants, poly vinyl alcohol(PVA) and a quaternary silicon oil. However, metal soaps formed therein contribute to the opaqueness of the composition, thereby leaving a need for transparent hydrophobic compositions.

It is therefore an object of the present invention to provide a composition for rendering a surface hydrophobic.

It is another object to provide a transparent, water-repellent composition for the treatment of surfaces.

It is another object to provide a metal free, water-repellent composition for the treatment of surfaces.

It is yet another object to provide a composition for protecting a surface from water damage and deposition of stains and soil. It is yet another object to provide a composition with superior cleaning benefits.

Surprisingly, it has been found that hydrophobicity and aqueous stain and soil repellence can be imparted to a surface by the deposition of polystyrene or a polystyrene copolymer onto the said surface.

Summary of the invention

Accordingly, in a first aspect, the present invention provides a hard surface treatment composition comprising a polymer composition selected from 0.001 - 0.15% by weight of the total composition of polystyrene and 0.005 - 10% by weight of the total composition of acetone, wherein the ratio of acetone to polystyrene is at least 5: 1 ; or 0.001 - 0.3% by weight of the total composition of a polystyrene copolymer; 0.015 - 8% by weight of the total composition of cationic hydrophilic silane and water, wherein the pH of the composition is between 2 and 6. In a second aspect, the invention provides a method for rendering a surface hydrophobic or stain-repellant comprising the steps in sequence of applying the composition as according to the invention onto a surface and; allowing it to dry. In a third aspect, the invention provides the use of the polymer composition for rendering a surface hydrophobic or stain-repellant.

In the context of the present invention, the reference to "surface" typically means glass, ceramics, mirrors and vitreous or vitrified surfaces.

These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the present invention may be utilised in any other aspect of the invention. 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. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight/weight percentages unless otherwise indicated. Except in the operating and comparative 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 are to be understood as modified by the word "about". Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated.

Detailed description of the invention

In a first aspect, the invention relates to a composition for treating a surface comprising a polymer composition selected from polystyrene and acetone or a polystyrene copolymer, a cationic hydrophilic silane and water; and wherein the pH of the composition is between 2 and 6.

Polymer composition

The polymer composition of the present invention may either be polystyrene dissolved in acetone or a polystyrene copolymer. It is thought that a small amount of the polymer composition, when deposited onto a hard surface, reduces the surface energy of the surface and provides a hydrophobic layer on said surface, thereby preventing the water spilt on a surface to spread and result in stains.

Polystyrene [poly (1 -phenylethene-1 ,2-diyl)] is an aromatic polymer made from styrene monomer. The polystyrene used herein may be of any form. Non- limiting examples of the different forms of polystyrene that can used according to the present invention include sheet or molded polystyrene, polystyrene foam, expanded polystyrene, extruded polystyrene foam and oriented polystyrene or dispersed polystyrene particles. A dissolved form of polystyrene in a water- miscible solvent is preferred. Therefore, polystyrene is typically dissolved in acetone.

The weight average molecular weight of polystyrene is preferably between 1500 and 200,000 u, more preferably at least 10,000 u, still more preferably at least 20,000 u, even more preferably at least 50,000 u.

In the polymer composition, polystyrene may be present in a concentration of 0.001 - 0.15%. In order to get the best results on hydrophobicity, the

concentration is preferably not more than 0.1 %, more preferably not more than 0.09%, still more preferably not more than 0.05%, but preferably not less than 0.005% by weight of the total composition. In the polymer composition comprising polystyrene, acetone is present in a concentration of 0.005%- 10%, preferably at least 0.05%, more preferably at least 0.5%, but preferably not more than 5%. When present, acetone and polystyrene may be present in a ratio of at least 5: 1 , preferably at least 10: 1 , but preferably not more than 500: 1 , more preferably not more than 100: 1 , still more preferably not more than 20:1 .

More than 5% of acetone in the composition may be detrimental to acetone sensitive materials that may be present in the vicinity of the surfaces to be treated according to the invention. Therefore, it is preferable that not more than 5% of acetone is used.

Alternatively, a polystyrene copolymer may used in the polymer composition. The copolymer may be a styrene/maleic copolymers. The copolymers are selected from block or alternate copolymer having moieties A and B, wherein A is selected from polystyrene; and

B is selected from water soluble alkali metal salt (sodium/ potassium) of the following acids: acrylic acid, C2-7 dicarboxylic acids.

The preferred copolymers of the present invention are poly(styrene-a/f-maleic acid)sodium salt, poly(styrene-co-maleic acid) sodium salt, poly(styrene-co- acrylic acid) sodium salt, polystyrene-block-poly (acrylic acid)sodium salt and poly (styrene-a/f-maleic anhydride).

The most preferred copolymers of the present invention are poly(styrene-a/f- maleic acid) and poly (styrene-a/f-maleic anhydride).

The polymer composition comprising a polystyrene copolymer is present in a concentration of 0.001 - 0.3%, preferably not more than 0.1 %, more preferably not more than 0.09%, still more preferably not more than 0.05%, but preferably not less than 0.005% by weight of the total composition. The polymer composition concentrations beyond the scope of the invention deteriorate hydrophobicity.

Cationic hydrophilic silane

To further enhance the hydrophobicity or water repellency, the composition further comprises a cationic hydrophilic silane.

Cationic hydrophilic silanes are defined as an ionic salt having one or more silyl group attached to the quaternary nitrogen atom and at least one saturated hydrocarbon chain having at least 5 carbon atoms to the quaternary nitrogen.

The chemical structure may be written as follows: [(CH3(CH2)n)m(C_xH2x₊i)pN(CH₂)_qSi(0(C_xH2x₊i)3)]⁺ Y^", where Y= CI, F, Br, I, N03, N02; and

where, n,m,p,q are integers, 1 <x<10, m+p=3, 5<n<25, 1 <q<10. Cationic hydrophilic silanes bind to the negatively charged surfaces, with the hydrophobic chain exposed to the air- substrate interface. Such layers of silanes on smooth surfaces provide hydrophobicity.

The most preferred silanes are N, N-Didecyl-N-methyl (3-trimethoxysilylpropyl)- ammonium chloride and Dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride.

The cationic hydrophilic silane is present in the composition in a concentration of 0.015 - 8%, preferably not less than 0.02%, more preferably not less than 0.075%, but preferably not more than 7.5% by weight of the total composition. At siliane concentrations of above 8%, the composition phase separates. Water

The composition of the present invention is an aqueous composition comprising water. The composition is preferably made upto 100 percent by adding water.

Water miscible glycol ether

A water miscible glycol ether may be included in the composition of the present invention as an optional ingredient to improve the hydrophobicity or water repellency imparted by the composition, and to also enhance the cleaning properties of the composition. It is thought that these properties are imparted to the composition due to the HLB of the glycol ether.

Water miscible glycol ethers used in the present invention are of the formula R₁ - O - R₂OH

wherein, Ri is a substituted or unsubstituted C₂ - C₄ alkyl group or a substituted or unsubstituted aryl group, preferably phenyl; and R₂ is a substituted or unsubstituted C₂- C₄ alkylene group. Non-limiting examples of the water miscible glycol ethers include ethylene glycol monophenyl ether (2- phenoxyethanol), ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, propylene glycol propyl ether. The most preferred water miscible glycol ethers are ethylene glycol monophenyl ether (2- phenoxyethanol) and propylene glycol propyl ether.

When added to the composition, water miscible glycol ether may be present in the composition in a concentration of 0.003 - 5%, preferably between 0.005% - 4%, more preferably at least 0.5 %, but preferably not more than 2% by weight of the total composition. By water miscible, it is meant that at least 5% of the glycol ether is soluble in or miscible with water.

Siloxane

Siloxane may be added to the present composition as an optional ingredient to achieve a further increase in hydrophobicity or water repellency. Siloxanes that may be used according to the present invention are preferably of the following classes: a) siloxanes with reactive hydrogen b) non reactive siloxanes of high molecular weight and c) non reactive siloxanes of low molecular weight. a) Siloxanes with reactive hydrogen

Non-limiting examples of siloxanes with reactive hydrogen preferably include poly(methylhydrosiloxane), poly(ethylhydrosiloxane), poly(propylhydrosiloxane) or hexyldihydrosiloxane.

The most preferred siloxane in this class is poly(methylhydrosiloxane) (PMHS) b) Non reactive siloxanes of high molecular weight

Non-limiting examples of non reactive siloxanes of high molecular weight preferably include polydimethyl siloxane having a molecular mass of between 800 and 14000 u. Above 14000 u, the kinematic viscosity becomes too high (typically more than 3.5 St (St, or Stokes, being cm²/s), while it becomes too low below 800 u, typically less than 0.05 St.

The most preferred siloxane in this class is polydimethyl siloxane having an approximate molecular weight of between 6000 u and 13650 u. c) Non reactive siloxanes of low molecular weight

Non-limiting examples of non reactive siloxanes of low molecular weight preferably include low viscosity cyclomethicones, including hexamethylcyclotrisiloxanes, octamethylcyclotetrasiloxanes or decamethylcyclopentasiloxanes.

The most preferred siloxane in this class is cyclopentasiloxane.

When siloxane is present in the composition, it may be present in the composition in a concentration of 0.001 - 0.5%, preferably not less than 0.005%, more preferably not less than 0.05%, but preferably not more than 0.2% by weight of the total composition.

Surfactants

To achieve superior cleaning benefits along with good hydrophobicity or water repellency, surfactants may be added to the present composition. Cationic, non ionic (including pluronics) and zwitterionic surfactants are found to significantly improve the cleaning ability of the composition when delivered through the composition of the present invention without compromising on hydrophobicity.

Examples of surfactants that are compatible with the present composition are, but not limited to the following: a) Cationic surfactants: Di (hydrogenated tallow) dimethylammonium chloride, Dimethyldioctadecylammonium chloride, mixture of homologs commonly called Arquad, quarternary ammonium containing surfactants. b) Non ionic surfactants: Ethoxylated alcohols of general formula Cn(EO)m, where n=6 to 30 and m=8 to 30, alkoxylated ethers, surfactants with HLB between 6 to 30 including pluronics such as Ethylene oxide/Propylene oxide block co-polymers(diblock or triblock polymers), alkyl polyglucosides (Alkyl polyglycosides (ZCARE APGs) are a class of non-ionic surfactants derived from sugars and fatty alcohols. They are typically complex mixtures of compounds with different sugars comprising the hydrophilic end and C8-C40 alkyl groups comprising the hydrophobic end. Examples are Glucopon 425, Glucopon 215). c) Zwitterionic surfactants such as betaines, sultaines (eg. Cocamidopropyl hydroxysultaine).

When added to the composition, surfactants may be present in the composition in a concentration of 0.05 - 1 1 %, preferably between 0.05 % - 8 %, more preferably at least 0.25 %, but preferably not more than 5% by weight of the total composition.

Anionic surfactants are found to have an adverse effect on hydrophobicity even though the cleaning performance is good. This is possibly due to charge neutralization.

Further optional ingredients

Common cleaner and aesthetic additives such as perfumery molecules including encapsulates, fluorescers and optical brighteners, antimicrobial actives such as essential oils and cationic amino surfactants, anti insect actives such as DEET and picaridin, fluoropolymers/ flurosurfactants, viscosity modifiers such as gum resins, polysaccharides, fatty alcohols, polyols (such as polyvinyl alcohol, glycerol), ingredients that give a delayed release of perfumes, room freshening agents and anti stick agents, viscosifying agents such as gums (Xanthum, guar, kelzan), polymers (carbopol, starch or its derivatives, polysaccharides), stabilizers such as polyols (polyvinyl alcohol, polyethylene glycols or copolymers), fluorosilanes, flouro surfactants, flouro siloxanes or fluoro polymers for anti oil sticking, oil repellence and easy oil removal properties, chelating agents such as hydroxamate, EDTA, NTA, DTPA type metal chelators, citrate and organic crystal habit modifying agents, surface care actives such as silicone emulsion, silicone resins, surface curing agents and silicone elastomers. The pH of the composition is between pH 2 and 6, preferably at least pH 3, more preferably not more than pH 5.

Method for rendering a surface hydrophobic

In a second aspect, the invention relates to a method for rendering a surface hydrophobic or stain-repellant comprising the steps in sequence of applying the composition according to the invention onto a surface and allowing the surface to dry.

It is preferred that the surface is wiped after the application of the composition and before it is allowed to dry. The composition may be applied by any known ways such as by using a mop, wipes, spray, including spray guns, atomizers, or other direct application. The applied composition may be optionally wiped using a mop, wipes, paper, cloth etc. It is preferred that the surface is not rinsed after the application of the

composition and before drying.

Use of the composition In a third aspect, the invention relates to the use of the polymer composition for rendering a surface hydrophobic or stain-repellant.

Product format The composition may be packaged in the form of any commercially available bottle for storing the liquid or in the form of a kit comprising the concentrated liquid along with instructions for it use. The bottle containing the liquid can be of different sizes and shapes to accommodate different volumes of the liquid; preferably between 0.25 and 2 L, more preferably between 0.25 and 1 .5 L or even between 0.25 and 1 L. The bottle is preferably provided with a dispenser, which enables the consumer an easier mode of dispersion of the liquid. Spray or pump-dispensers may be used. However, a trigger spray dispenser is the most preferred.

A kit comprising the concentrated liquid that may be diluted with water as per the instructions provided for achieving the desired concentrations is also included in the scope of this invention. The liquid is typically concentrated by reducing the amount of water in the composition. A concentrated composition is preferably concentrated to a factor between 1 .5 and 25, more preferably between 1 .5 and 10, still more preferably between 1.5 and 5.

The kit comprising the concentrated liquid may also be used to refill the commercially available bottle.

The invention will now be illustrated by means of the following non limiting examples.

Examples

Materials

Polystyrene in Acetone: Prepared by dissolving Styrofoam™ in acetone by placing 0.05 g of Styrofoam(trade-mark) in 0.5 g acetone( A. R )( ex Merck) and left to soak

overnight. The soft mass disintegrated with time and dissolved in acetone. A small residue of cross linked Styrofoam™ remaining in the solvent was discarded.

Polystyrene copolymer : Poly(styrene-a/f-maleic acid) sodium salt solution

13 wt. % in H₂0 (ex Sigma Aldrich) N, N-Didecyl-N-methyl (3-trimethoxysilylpropyl)- ammonium chloride (ex Gelest, SID3392.0)

Dimethyloctadecyl[3-(trimethoxysilyl)propyl] ammonium chloride solution 42 wt. % in methanol (ex Sigma Aldrich)

Water miscible glycol Propylene glycol propyl ether -Dowanol PnP (trade ether mark) (ex Sigma Aldrich)

2-phenoxyethanol (ex Sigma Aldrich)

Siloxanes PMHS : Poly(methylhydrosiloxane)-average M_n

1 ,700-3,200 (ex Sigma Aldrich) cyclopentasiloxane :(ex Dow Corning, DC 245 fluid)

PDMS-350 cSt : Polydimethyl siloxane polymer fluid with viscosity 350 cSt (ex Dow Corning, DC 200)

Surfactants: Cationic : Cetylpyridinium chloride (CPC), Benzalkonium chloride (BAC), Cetyl trimethyl ammonium chloride (CTAB) (ex Sigma Aldrich) , Arquad (ex Akzo Nobel)

Anionic : Sodium dodecyl benzene sulphonate (SDBS) commonly referred to as l_AS(linear alkyl sulphonate), sodium dodecyl sulfate (SDS) commonly referred to as PAS (primary alkyl sulphate) (ex Sigma Aldrich) Non ionic : C12E03 and C12E07 ethoxylated alcohol (ex

BASF), Glucopon 425, Glucopon 215 (ex Cognis), F77 (ex BASF) Treatment procedure

0.25 ml of the treatment solution was spread uniformly on a 2.5 cm by 12 cm clean glass microscopic slide. The solution was left on the glass substrate for 1 minute and wiped with a tissue paper till completely dry. The dried treated slide was used for testing water repellency.

Test for water repellence (Hydrophobicity):

Contact angle in accordance with the present invention is the angle at which the liquid interface meets a solid surface. The contact angle determines the hydrophobicity imparted to a surface. Contact angles above 80° are considered to be good.

The contact angle of the sessile droplet was measured using a Kruss

goniometer by placing a 10 microlitre of distilled water droplet on the glass slide. The angle was analyzed by the image J software using the Drop snake plug-in.

Test for cleaning:

Cleaning performance of the present invention was measured by using Gloss-o- meter (Trimicrogloss apparatus UK) by placing the cleaned slide on a black background (RGB=0,0,0) and measuring the gloss at 60 degree angle. Higher the value of gloss, better is the cleaning. A gloss value in parity with the control or above the control is considered to be good.

Example 1 : Effect of concentration of polystyrene on water repellency or hydrophobicity:

In this example, different concentrations of polystyrene are compared. Ex1 to Ex5 are example compositions according to the present invention which are compared to Comp A to D (Comparative examples) comprising polystyrene in a concentration outside the scope of the present invention.

Variation in the concentrations of polystyrene shows that good water repellency or hydrophobicity is obtained at a polystyrene concentration according to the invention.

Example 2: Effect of concentration of polystyrene on water repellency or hydrophobicity with a decreased concentration of water miscible glycol ether (Dowanol PnP): In this example, different concentrations of polystyrene are compared with a lesser concentration of propylene glycol propyl ether (Dowanol PnP) than used in Example 1 . In this set of examples and comparative examples, Dowanol PnP is used in a concentration of 1 % by weight of the total composition. Set Polystyrene Acetone Dowanol Silane PH contact wt% wt% PnP wt% wt% angle on

glass (°)

Ex6 0.005 0.045 0.05 5 87

Ex7 0.009 0.091 ¹ 0.05 5 88

Ex8 0.023 0.227 ¹ 0.05 5 89

Ex9 0.045 0.455 ¹ 0.05 5 89

Ex10 0.091 0.909 ¹ 0.05 5 86

Comp A1 0.182 1.818 ¹ 0.05 5 77

Comp B1 0.364 3.636 ¹ 0.05 5 76

Comp C1 0.455 4.545 0.05 5 77

Comp D1 0.909 9.091 ¹ 0.05 5 74

Reduction in the concentration of Dowanol PnP shows that good water repellency or hydrophobicity is still obtained at a polystyrene concentration according to the invention. However, the contact angle is observed to slightly vary.

Example 3: Effect of concentration of polystyrene copolymer on water repellency or hydrophobicity:

In this example, different concentrations of polystyrene copolymer are

compared

with comparative compositions having polystyrene copolymer in a concentration beyond the claimed range. Experiments were conducted with two water miscible glycol ethers.

Table 1 illustrates the effect of different concentrations of polystyrene copolymer when the water miscible glycol ether used is 2-phenoxyethanol. Table 1

Poly(styrene-a/f-maleic acid) sodium salt solution

Table 2 illustrates the effect of different concentrations of polystyrene copolymer when the water miscible glycol ether used is propylene glycol propyl ether (Dowanol PnP).

Table 2

Set ¹ Polystyrene Dowanol Silane PH contact angle on copolymer wt% PnP wt% wt% glass (°)

Ex18 0.001 ¹ 0.05 5 82

Ex19 0.005 ¹ 0.05 5 82

Ex20 0.01 ¹ 0.05 5 86

Ex21 0.02 ¹ 0.05 5 88

Ex22 0.05 ¹ 0.05 5 88

Ex23 0.1 ¹ 0.05 5 89

Ex24 0.2 ¹ 0.05 5 88

Comp E1 0.5 ¹ 0.05 5 84 (solution turbid)

Comp F1 1 ¹ 0.05 5 81 (solution turbid)

Comp G1 2 ¹ 0.05 5 82 (solution turbid) ¹ Poly(styrene-a/f-maleic acid) sodium salt solution

It is inferred from the results of the above tables that good water repellency or hydrophobicity is obtained at a polystyrene copolymer concentration according to the invention irrespective of the glycol ether used.

Example 4: Effect of concentration of silane on water repellency or

hydrophobicity: This example demonstrates the effect of concentration of silane on water repellency. The example compositions Ex 25 to Ex33 are compared with comparative examples H to K comprising different amounts of silane which are beyond the claimed range.

Set Polystyrene Acetone Dowanol Silane PH contact wt% wt% PnP wt % wt% angle on glass (°)

Comp H 0.05 0.5 ¹ 0.005 5 72

Comp I 0.05 0.5 ¹ 0.01 5 74

Ex25 0.05 0.5 ¹ 0.02 5 88

Ex26 0.05 0.5 ¹ 0.04 5 89

Ex27 0.05 0.5 ¹ 0.05 5 89

Ex28 0.05 0.5 ¹ 0.075 5 90

Ex29 0.05 0.5 ¹ 0.1 5 90

Ex30 0.05 0.5 ¹ 0.5 5 92

Ex31 0.05 0.5 ¹ 2 5 92

Ex32 0.05 0.5 ¹ 5 5 90

Ex33 0.05 0.5 ¹ 7.5 5 90

87 (phase

Comp J 0.05 0.5 1 9 5 separation)

84 (phase

Comp K 0.05 0.5 1 10 5 separation) The table above shows that best results for water repellency or hydrophobicity are obtained at a silane concentration within the scope of the present invention. The table also shows that at higher silane concentrations, the compositions phase separate.

Example 5: Effect of concentration of the water miscible glycol ether on water repellency or hydrophobicity:

In this example, different concentrations of water miscible glycol ether according to the invention in combination with polystyrene are compared with

compositions having water miscible glycol ether in a concentration outside the scope of the present invention. The comparative study was conducted with two water miscible glycol ethers, the results of which are tabulated separately in table 3 and table 4.

Table 3 demonstrates the effect of different concentrations of propylene glycol propyl ether (Dowanol PnP)

Table 3

Set Polystyrene Acetone Dowanol Silane PH contact wt% wt% PnP wt% wt% angle on glass (°)

Ex34 0.05 0.5 0.005 0.05 5 81

Ex35 0.05 0.5 0.1 0.05 5 84

Ex36 0.05 0.5 0.5 0.05 5 89

Ex37 0.05 0.5 1 0.05 5 90

Ex38 0.05 0.5 2 0.05 5 89

Ex39 0.05 0.5 3 0.05 5 88

Ex40 0.05 0.5 4 0.05 5 81

Comp L 0.05 0.5 5 0.05 5 79

Comp M 0.05 0.5 7 0.05 5 79 Comp N 0.05 0.5 10 0.05 5 78

Comp 0 0.05 0.5 12 0.05 5 75

Table 4 demonstrates the effect of different concentrations of 2-phenoxy ethanol.

Table 4

The results indicate that the concentration of the water miscible glycol ether should not be more than 5% by weight of the total composition.

Example 6: Effect of concentration of the water miscible glycol ether (propylene glycol propyl ether-Dowanol PnP) on water repellency or hydrophobicity in combination with a polystyrene copolymer: In this example, different concentrations of propylene glycol propyl ether according to the invention in combination with polystyrene copolymer (Ex 49 to Ex 56) are compared with compositions having propylene glycol propyl ether in a concentration outside the scope of the present invention (Comp P to S).

The results indicate that best results for water repellency or hydrophobicity are obtained at a propylene glycol propyl ether (Dowanol PnP) concentration within the scope of the present invention. It is also inferred that polystyrene copolymer has almost the same enhanced hydrophobicity as polystyrene when used in the composition along with Dowanol PnP.

Example 7: Effect of pH of the treatment composition on water repellency or hydrophobicity: The table below shows compositions within the pH range according to the invention (Ex 57 to Ex 60) which are compared to compositions of comparative examples T, U, V and W, which are outside the claimed pH range. Set Polystyrene Acetone Dowanol Silane PH contact wt% wt% PnP wt% wt% angle on glass (°)

Ex57 0.05 0.5 0.05 3 89

Ex58 0.05 0.5 ¹ 0.05 4 87

Ex59 0.05 0.5 ¹ 0.05 5 91

Ex60 0.05 0.5 ¹ 0.05 6 81

Comp T 0.05 0.5 ¹ 0.05 7 75

Comp U 0.05 0.5 ¹ 0.05 8 69

Comp V 0.05 0.5 ¹ 0.05 9 54

Comp

W 0.05 0.5 1 0.05 10 57

Water repellency or hydrophobicity decreases at high pH. Acceptable contact angles are obtained within the pH range of the invention. The best results are obtained at pH 3 to 5.

Example 8: Effect of each component of the composition on water repellency or hydrophobicity: In this example, the water repellency or hydrophobicity imparted by the composition according to the invention (Ex61 ) is compared to different combinations of the components in comparative examples Y1 to Y7, where the comparative example compositions are comprised of at least one component of the composition.

Set Poly- Acetone Dowanol Silane PH contact

sty ren wt% PnP wt% wt% angle on

wt% glass (°)

Ex61 a 0.05 0.5 1 0.05 5 90

Ex61 b 0.05 0.5 - 0.05 5 80

Comp Y1 - - 1 - 5 42 Comp Y2 - - - 0.05 5 74

Comp Y3 - 0.5 - - 5 25

Comp Y4 0.05 - - - 5 unstable

Comp Y5 0.05 0.5 - - 5 51

Comp Y6 0.05 0.5 1 - 5 62

The table shows that the composition according to the invention performs better than any of the combinations with one of the components missing. Although good hydrophobicity is achieved in the combination devoid of the optional water miscible glycol ether (Ex61 b), better results are obtained when water miscible glycol ether is present amongst the other components of the composition (Ex61 a).

Example 9: Additional effect of Siloxane on water repellency or hydrophobicity:

In this example is illustrated the additional effect of siloxane in the composition of the present invention and also the performance of different siloxanes.

Set PolyAceDowanol Silane SiloType of P contact styrene tone PnP wt% wt% xane Siloxane H angle on wt% wt% wt% glass (°)

Ex 38 0.05 0.5 2 0.05 - - 5 89

Ex62 0.05 0.5 2 0.05 0.2 PMHS 5 97

Ex63 0.05 0.5 2 0.05 0.1 PMHS 5 97

Ex64 0.05 0.5 2 0.05 0.05 PMHS 5 94

Ex65 0.05 0.5 2 0.05 0.025 PMHS 5 89

Ex66 0.05 0.5 2 0.05 0.005 PMHS 5 88

Ex67 0.05 0.5 2 0.05 0.2 cyclopenta 5 95

siloxane

Ex68 0.05 0.5 2 0.05 0.1 cyclopenta 5 94 siloxane

Ex69 0.05 0.5 2 0.05 0.05 cyclopenta 5 94 siloxane

Ex70 0.05 0.5 2 0.05 0.025 cyclopenta 5 88 siloxane

Ex71 0.05 0.5 2 0.05 0.005 cyclopenta 5 88 siloxane

Ex72 0.05 0.5 2 0.05 0.2 PDMS - 5 97

350 cSt

Ex73 0.05 0.5 2 0.05 0.1 PDMS - 5 97

350 cSt

Ex74 0.05 0.5 2 0.05 0.05 PDMS - 5 95

350 cSt

Ex75 0.05 0.5 2 0.05 0.025 PDMS - 5 89

350 cSt

Ex76 0.05 0.5 2 0.05 0.005 PDMS - 5 89

350 cSt

The table above shows that better results for hydrophobicity are obtained when siloxane is added to the composition of the present invention (Ex62 to Ex76) when compared to the composition without siloxane (Ex 38). Different siloxanes compared are found to be equally beneficial in imparting additional hydrophobicity.

Example 10: Transparency of the composition:

In this example, the transparency of the composition of the present invention (Ex 77) is demonstrated in comparison to the present composition with siloxane (Ex 78) and the hard surface cleaning composition of 1293/MUM/201 1 (Comp Z1 ). Measurement of transmittance:

10 mL of the compositions were taken in a clear quartz cuvette of path length 1 cm and analyzed instantly by measuring the transmittance in the visible light in a spectrophotometer (PERKIN Elmer Lambda 900), between 400-700nm. A blank sample of deionised water was run for comparison. The transmittance of water was taken to be 100%. The transmittance of the samples was noted at 550 nm and 700 nm respectively. Higher the transmittance, greater is the transparency of the compostion.

The results are tabulated below.

Set Contact % Transmittance (nm)

angle on

glass (°) @ 550 nm @ 700 nm

Ex77 89 94 96

Comp Z1 82 27 56 Ex78 96 76 82

The results show that the best hydrophobicity is obtained for the composition comprising siloxane (Ex78) when compared to the composition of the present invention without siloxane (Ex77) and the composition of

1293/MUM/201 1 (Comp Z1 ). However, the composition (Ex77) shows the best results for transparency.

Example 11 : Effect of concentration and the type of surfactant on water repellency or hydrophobicity and cleaning performance:

In this example, different concentrations of surfactants according to the invention are compared with the control compositions having no surfactants, to study the cleaning performance. The comparative study was conducted with 4 types of surfactants, the results of which are tabulated in the below table. All of the example compositions below contained 0.05%w poly styrene, 0.5%w acetone, 2%w dowanol PnP, 0.05%w silane and 0.2%w siloxane

Set Type of Surfactant Surfactant PH contact cleaning

Siloxane wt% angle on (gloss glass (°) value)

Control PMHS - - 5 97 121

Control PDMS - 5 95 120

cyclopentas

iloxane

CompAA PMHS 0.05 SDS 5 68 121

Comp AB PMHS 0.1 (anionic) 5 69 120

Comp AC PMHS 0.25 5 69 125

Comp AD PMHS 0.5 5 69 131

Comp AE PMHS 2 5 64 135

Comp AF PDMS 5 5 60 135

cyclopentasil

oxane Comp AG PDMS 10 5 59 141 cyclopentasil

oxane

Ex79 PMHS 0.05 5 93 122

Ex80 PMHS 0.1 5 91 121

Ex81 PMHS 0.25 5 92 126

Ex82 PMHS 0.5 5 93 131

Ex83 PMHS 2 5 88 135

Ex84 PDMS 5 5 84 139 cyclopentasil CTAB

oxane (cationic)

Ex85 PDMS 10 5 76 139 cyclopentasil

oxane

Ex86 PMHS 0.05 5 93 125

Ex87 PMHS 0.1 5 91 127

Ex88 PMHS 0.25 5 92 131

Ex89 PMHS 0.5 5 92 136

Ex90 PMHS 2 5 86 137

Ex91 PDMS 5 5 81 139 cyclopenta

siloxane

Ex92 PDMS 10 C12E07 5 76 140 cyclopenta (nonionic)

siloxane

Ex93 PMHS 0.05 5 93 125

Ex94 PMHS 0.1 5 90 127 Ex95 PMHS 0.25 5 92 129

Ex96 PMHS 0.5 5 92 136

Glucopon

Ex97 PMHS 2 425 5 90 135

Ex98 PDMS 5 (nonionic) 5 89 134

cyclopentasil

oxane

Ex99 PDMS 10 5 84 136

cyclopentasil

oxane

The above example illustrates that anionic surfactants give a good cleaning performance but retards hydrophobicity of the composition, while cationic and non-ionic surfactants gives a cleaning performance without appreciable deterioration in hydrophobicity. Even though Ex85 and Ex92 shows a contact angle of less than 80, under the circumstance with a high surfactant concentration of 10 %w,the results are considered to be good.

Example 12: Effect of increased concentrations of the components of the composition on water repellency or hydrophobicity and cleaning performance:

In this example, example compositions with increased concentrations of the components of the composition are compared with each other to study the cleaning performance and hydrophobicity. The comparative study was conducted with 3 types of surfactants, the results of which are tabulated in the below table. Each of the compositions below contained 0.05%w of polystyrene, and 0.5% of acetone. The pH of all compositions was pH=5. Set dowanol Silane Siloxane SurfacSurfaccontac cleanin PnPwt% wt% (PMHS) tant tant t angle g wt% wt% on (gloss glass @ 60 deg)

Ex100 2 0.05 0.2 0.5 93 131

E≡x101 4 0.1 0.4 1 CTAB 89 135

Ex102 8 0.2 0.8 2 (cationic) 88 136

Ex103 4 0.1 0.4 2 90 139

Ex104 2 0.05 0.2 0.5 92 131

Ex105 4 0.1 0.4 1 C12E07 90 136

Ex106 8 0.2 0.8 2 (non ionic) 88 135

Ex107 4 0.1 0.4 2 90 134

Ex108 2 0.05 0.2 0.5 90 125

Ex109 4 0.1 0.4 1 Glucopon 87 128

215(non

E≡x110 8 0.2 0.8 2 88 131 ionic)

Ex11 1 4 0.1 0.4 2 89 130

Ex112 2 0.05 0.2 0.5 92 136

Ex113 4 0.1 0.4 1 Glucopon 90 136

425(non

Ex114 8 0.2 0.8 2 89 139 ionic)

Ex115 4 0.1 0.4 2 90 139

The above table demonstrates that increase in the concentration of the components of the composition, retains good hydrophobicity and cleaning performance.

Claims

1 . A hard surface treatment composition comprising:

a. a polymer composition selected from

i. 0.001 - 0.15% by weight of the total composition of

polystyrene, and 0.005 - 10% by weight of the total composition of Acetone,

wherein the ratio of acetone to polystyrene is at least 5: 1 ; or

ii. 0.001 - 0.3% by weight of the total composition of a

polystyrene copolymer;

b. 0.015 - 8% by weight of the total composition of cationic hydrophilic silane

c. Water

wherein the pH of the composition is between 2 and 6.

2. A hard surface treatment composition as claimed in claim 1 , wherein the polymer composition comprises the copolymer, and the copolymer is selected from block or alternate copolymer having moieties A and B, wherein: A is selected from polystyrene; and B is selected from water soluble alkali metal salt (sodium/ potassium) of acrylic acid or C2-7 dicarboxylic acids.

3. A hard surface treatment composition as claimed in claim 2, wherein the copolymer is selected from poly(styrene-a/f-maleic acid)sodium salt, poly(styrene-co-maleic acid) sodium salt, poly(styrene-co-acrylic acid) sodium salt, polystyrene-block-poly (acrylic acid)sodium salt or poly (styrene-a/f-maleic anhydride).

4. A hard surface treatment composition as claimed in claim 2 to 3, wherein the copolymer is poly(styrene-a/f-maleic acid) or poly (styrene-a/f-maleic anhydride).

5. A hard surface treatment composition as claimed in claim 1 to 4, wherein the composition further comprises 0.003 - 5% by weight of the total composition of water miscible glycol ether of the formula

Ri - O - R₂OH

wherein, Ri is a substituted or unsubstituted C₂ - C₄ alkyl group or a substituted or unsubstituted aryl group, preferably phenyl; and R₂ is a substituted or unsubstituted C₂- C₄ alkylene group.

6. A hard surface treatment composition as claimed in claim 5, wherein the water miscible glycol ethers are ethylene glycol monophenyl ether (2- phenoxyethanol), ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether or propylene glycol propyl ether.

7. A hard surface treatment composition as claimed in claims 1 to 6,

wherein the composition further comprises siloxane in a concentration of 0.001 - 0.5% by weight of the total composition.

8. A hard surface treatment composition as claimed in claim 7, wherein the siloxane is selected from any of the following classes:

a) siloxanes with reactive hydrogen

b) non reactive siloxanes of high molecular weight and

c) non reactive siloxanes of low molecular weight.

9. A hard surface treatment composition as claimed in claims 1 to 8,

wherein the composition further comprises a surfactant other than anionic surfactant in a concentration of 0.05 - 1 1 % by weight of the total composition.

10. A hard surface treatment composition as claimed in claim 9, wherein the surfactant is selected from cationic, non-ionic including pluronics and zwitterionic surfactants.

1 1 . A method for rendering a surface hydrophobic comprising the steps in sequence of:

a. applying the composition as claimed in claims 1 to 10 onto a surface and;

b. allowing it to dry.

12. A method for rendering a surface stain-repellant comprising the steps in sequence of:

a. applying the composition as claimed in claims 1 to 10 onto a surface and;

b. allowing it to dry.

13. A method for cleaning a surface comprising the steps in sequence of:

a. applying the composition as claimed in claims 9 or 10 onto a surface and;

b. allowing it to dry.

14. Use of the polymer composition for rendering a surface hydrophobic or stain-repellant.