Field of the invention

The present invention relates to a hard surface treatment composition. In particular, the composition comprises particle having average diameter of no greater than 3 microns; non-volatile silicone; and at least 30% of water by weight of the composition, wherein the weight ratio of the particle to the non-volatile silicone is at least 3:1. This invention also relates to a method and use for providing shine, smoothness, repair and/or less damage to a hard surface.

Background of the invention

New appliances in home and office are always shining and appealing. To maintain the surface cleanliness, hard surface treatment compositions have been widely employed for a long time. When cleaning the hard surface, rubbing may be needed to help remove tougher soils. In addition, daily use of the appliances may also affect the glossiness, smoothness, and shining of the hard surface.

Therefore, even if the hard surfaces are cleaned regularly, scratches on hard surface may be formed along with time because of wear for daily use and/or abrasion during the cleaning process. Thus the glossiness of the hard surface will be decreased, perceivable marks may be found, and the hard surface is not as shining and appealing as it was new. Sometime, the abrasive in the composition may help to improve the gloss of damaged hard surface, however, it may also bring damage to new/ smooth hard surface. The present inventors have recognized the needs to develop a hard surface treatment composition which can deliver the benefits of surface repair, surface shining, and/or surface smoothness while having less damage to the new/smooth hard surface. A composition comprising particle having average diameter of no greater than 3 microns; non-volatile silicone; and at least 30% of water by weight of the composition, wherein the weight ratio of the particle to the non-volatile silicone is at least 3:1 , was therefore developed. It was surprisingly found that such composition improved the surface gloss of the damaged hard surface, and generally didn't reduce the surface gloss of new/smooth hard surface. Summary of the invention

In a first aspect, the present invention provides a composition comprising particle having average diameter of no greater than 3 microns; non-volatile silicone; and at least 30% of water by weight of the composition, wherein the weight ratio of the particle to the nonvolatile silicone is at least 3:1 .

In a second aspect, the present invention provides a method for providing shine, smoothness, repair and/or less damage to a hard surface comprising a step of contacting the surface with a composition comprising particles having average diameter of no greater than 3 microns, and non-volatile silicones.

In a third aspect, the present invention provides use of a composition comprising particles having average diameter of no greater than 3 microns, and non-volatile silicones for surface shine, surface smoothness, surface repair, less damage, or a combination thereof.

All other aspects of the present invention will more readily become apparent upon considering the detailed description and examples which follow.

Detailed description of the invention

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 total 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.

"Hard surface" of present invention generally refers to any surface in household including the window, kitchen, bathroom, toilet, furniture, or floor 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.

"Particle size" as used herein refers to particle diameter in non-aggregated state unless otherwise stated. For polydisperse samples having particulate with diameter no greater than 1 μηη, diameter means the z-average particle size measured, for example, using dynamic light scattering (see international standard ISO 13321 ) with an instrument such as a Zetasizer Nano™ (Malvern Instruments Ltd, UK). For polydisperse samples having particulate with diameter greater than 1 μηη, diameter means the apparent volume median diameter (D50, also known as x50 or sometimes d(0.5)) of the particles measurable for example, by laser diffraction using a system (such as a Mastersizer™ 2000 available from Malvern Instruments Ltd) meeting the requirements set out in ISO 13320. "Non-volatile" as used herein means having vapor pressure from 0 to 0.1 mm Hg (13.3 Pa), preferably from 0 to 0.05 mm Hg, more preferably from 0 to 0.01 mm Hg at 25 °C. "Viscosity" as used herein means kinematic viscosity at 25°C and is reported as centiStokes (1 cSt = 1 rumV). Viscosity of fluids such as silicone can be determined, for example, by the relevant international standard, such as ISO 3104. Typically, the particle comprises polymer, inorganic material, or a combination thereof but preferably, the particle comprise inorganic material and even more preferably the particle is inorganic particle. Preferably, the particle comprises silica, titania, zirconia, alumina, calcium carbonate, silicate clay, or a mixture thereof. More preferably, the particle comprises silica, alumina, calcium carbonate, calcite, kaolin, zirconia, talc, or a mixture thereof. Even more preferably the particle comprises silica, alumina, zirconia, or a mixture thereof and most preferably the particle is alumina coated silica.

In order to better improve the gloss of the hard surface, the particle preferably has a Mohs hardness of at least 3.5, more preferably at least 4.5, even more preferably from 5.5 to 10 and most preferably from 6.5 to 9. Mohs values are based on the hardness of the coated particles. The Mohs scale of mineral hardness is known to the skilled person and characterizes the scratch resistance of various minerals through the ability of a harder material to scratch a softer material. The particles suitable for use in this invention preferably comprise at least 25% by weight silicon dioxide (i.e., silica), and more preferably, at least 50% by weight silicon dioxide, and most preferably, at least 75% to 100% by weight silicon dioxide, based on total weight of particle and including all ranges subsumed therein. To obtain optimal shining, smoothing effect and/or less damage to the smooth surface, the particle preferably has an particle size of from 1 nm to 2 μηη, more preferably from 5 nm to 1 μηη, even more preferably from 15 nm to 500 nm, and most preferably from 30 to 200 nm. To bring less damage and/or improve gloss, the particle preferably has an average roundness (ratio of axes) of at least 0.3:1 , more preferably at least 0.5:1 and even more preferably at least 0.7:1 and most preferably at least 0.85:1. The roundness (ratio of axes) is a measurement of the length/width relationship with value in the range of 0 to 1. The length is the longest axis and the width is the shortest axis. A perfect circle has a roundness value of 1.0 and a thin rectangle value is approaching 0. To calculate the average roundness, image of particles should be taken, preferably with scanning electron microscopy (SEM), for example using Hitachi S4800. The average roundness is calculated by at least 20 particles in the image.

Suitable silica includes commercially available products from suppliers for example AkzoNobel under the names Bindizl™ CC301 , CC302, CC401 , 20/40, 50/80, 40/170, 30/360, and Levasil™ CAT80, 300/30. 200/40, 200/30, 100/45, 50/50, 30/50.

Typically, the particle is present in the composition in amount of from 0.01 to 40%, more preferably from 0.1 to 30%, even more preferably from 0.3 to 18%, still even more preferably from 1 to 12%, and most preferably from 3 to 8% by weight of the composition. For sake of clarity, it should be noted that the particle is different from the non-volatile silicone.

Preferably, the non-volatile silicone is emulsified droplets of silicone. The emulsified nonvolatile silicone suitable for use in the compositions of the invention preferably has a D¾2 average particle diameter (Sauter mean diameter) in the composition of from 10 nm to 20 microns, preferably from 20 nm to 5 microns, more preferably from 30 to 2 microns, even more preferably from 40 nm to 800 nm, and most preferably from 50 to 200 nm.

Preferably, the non-volatile silicone is present in the composition in amount from 0.005 to 10% by weight of the composition, more preferably from 0.01 to 5%, even more preferably from 0.02 to 3%, still even more preferably from 0.05 to 0.9 %, most preferably from 0.08 to 0.8% by weight of the total composition.

The viscosity of the non-volatile silicone itself (not the emulsion or the final hard surface treatment composition) is typically from 20 to 2,000,000 cSt (centi-Stokes) at 25 °C, more preferably from 100 cSt to 800,000 cSt, even more preferably from 800 to 400,000 cSt, still even more preferably from 4,000 to 30,000 cSt, and most preferably from 8,000 to 15,000 cSt. The weight-average molecular weight of the non-volatile silicone is preferably from 2,000 to 2,000,000, more preferably from 8,000 to 800,000, even more preferably from 20,000 to 400,000, and most preferably from 50,000 to 150,000 Daltons. The weight-average molecular weight may be measured by following the standard of ASTM D4001 -2013.

Suitable non-volatile silicones include polydiorganosiloxane, in particular polydimethylsiloxane which have the CTFA designation dimethicone. Also suitable for use in compositions of the invention are polydimethyl siloxanes having hydroxyl end groups, which have the CTFA designation dimethiconol. Also suitable for use in compositions of the invention are silicone gums having a slight degree of cross-linking, as are described for example in WO 96/31 188. A further preferred class of silicones is aminosilicone. Preferably, the non-volatile silicone comprises dimethicone, dimethiconol, aminosilicone, ether-modified silicone or a combination thereof. More preferably, the non-volatile silicone comprises ether-modified silicone, aminosilicone or a mixture thereof. Even more preferably, the non-volatile silicone comprises aminosilicone. By "aminosilicone" is meant a silicone containing at least one primary, secondary or tertiary amine group, or a quaternary ammonium group. Preferably, the aminosilicone is silicone containing at least one primary, secondary, or tertiary amine group. Preferably, the primary, secondary tertiary amine group, and/or quaternary ammonium group is carried by side or pendant group carried by the polymeric backbone. Suitable aminosilicone is described in EP 455,185 (Helene Curtis). The aminosilicone is preferably emulsified with non ionic and/or cationic surfactant.

Preferably, the non-volatile silicone comprises at least 25% of aminosilicone by weight of the total non-volatile silicone, more preferably at least 50% of aminosilicone, and even more preferably at least 75% of aminosilicone by weight of the total non-volatile silicone. Most preferable non-volatile silicone is aminosilicone.

The aminosilicone suitable for use in the present invention may be represented by the formula of: R ¹ aR ₃ -aSi-(0-Si R ₂ )m-(0-Si RbR ¹ 2-b)n-0-SiR ¹ aR ₃ -a (I )

each R is independently hydrogen, phenyl, OH or a C1-C10 alkyi group, preferably R is OH or a C1-C6 alkyi group and more preferably a C1-C6 alkyi group, and most preferably a CH3 group;

each a is independently an integer from 0 to 3, preferably each a is 0;

each b is an integer from 0 to 1 , b may be 2 when a is not 0, preferably b is 0 or

1 and most preferably b is 1 ;

m and n are integers whereby the sum of n+m ranges from 1 to 3,500, preferably from 10 to 2000 and more preferably from 100 to 1200;

each R ¹ is independently a monovalent radical of formula -(CR ² 2) _X L,

where:

each R ² is independently H , OH , OCH3 or C1-4 alkyi, preferably each R ² is independently H , or C1-4 alkyi;

x is integer from 1 to 10, preferably from 2 to 6;

and L is an amine or a quaternized amine represented by one of the following groups:

-NR ³ -(CR ² ₂ )y-N(R ³ ) ₂ (1 )

-N(R ³ ) ₂ (2)

-[N(R ³ )-(CR ² ₂ )y]z -N(R ³ ) ₂ , (3)

-N ⁺ (R ³ ) ₃ A- (4)

-N(R ³ )-(CR ² ₂ )y -N ⁺ (R ³ ) ₃ A-, (5)

-[N(R ³ )-(CR ² ₂ ) _y ]z -N ⁺ (R ³ ) ₃ A-, (6)

-[N ⁺ (R ³ ) ₂ -(CR ² ₂ )y]z -N (R ³ ) ₂ (A-) ^Z , (7)

-[N ⁺ (R ³ )-(CR ² ₂ )y]z -N ⁺ (R ³ ) ₃ (A-) ^Z+1 , (8) where:

each R ² is independently H , OH , OCH ₃ or C1-4 alkyi;

each R ³ is independently hydrogen, phenyl, benzyl or a Ci to Ci ₂ alkyi; each y is independently an integer from 1 to 4;

each z is independently an integer from 1 to 5; and each A ^" is independently anion, preferably fluoride, chloride, bromide or iodide anion.

Preferably, in formula (I), each R is independently OH, or C1-C4 alkyl group; each a is 0; b is 1 or 2; m and n are integers wherein the sum of n+m ranges from 30 to 2,000; each R ¹ is independently a monovalent radical of formula -(CR ² 2) _X L, where each R ² is independently H, or C1-4 alkyl, x is integer from 1 to 4, and L is an amine or a quaternized amine represented by -NR ³ -(CR ² ₂ ) _y -N(R ³ ) ₂ or N(R ³ )-(CR ² ₂ ) _y -N ⁺ (R ³ ) ₃ A-, where each R ² is independently H, or C1-4 alkyl; each R ³ is independently hydrogen, or a Ci to C ₄ alkyl; each y is independently an integer from 1 to 4; and each A ^" is fluoride, chloride, bromide or iodide anion.

More preferably, in formula (I), each R is methyl; each a is 0; b is 1 ; m and n are integers wherein the sum of n+m ranges from 50 to 1 ,500; each R ¹ is independently a monovalent radical of formula -(CH2)xL, wherein x is integer from 1 to 4, and L is an amine or a quaternized amine represented by -NR ³ -(CH2)y-N(R ³ )2 or -N(R ³ )-(CH2)y-N ⁺ (R ³ ) ₃ A-, where each R ³ is independently hydrogen, or a Ci to C ₄ alkyl; each y is independently an integer from 1 to 4; and each A ^" is fluoride, chloride, bromide or iodide anion. Most preferably, in formula (I), each R is methyl; each a is 0; b is 1 ; m and n are integers wherein the sum of n+m ranges from 80 to 1 ,000; each R ¹ is independently a monovalent radical of formula -(Chb^L, wherein L is an amine or a quaternized amine represented by -NR ³ -(CH ₂ ) ₂ -N(R ³ ) ₂ or -N(R ³ )-(CH ₂ ) ₂ -N ⁺ (R ³ ) ₃ A-, where each R ³ is independently hydrogen, or methyl; and A ^" is chloride anion.

The mole % amine functionality of the aminosilicone is preferably in the range of from 0.1 to 8%, more preferably from 0.3 to 6% and most preferably from 0.5 to 4%,

Preferably, the aminosilicone is amino functional polysiloxanes having the CTFA designation "amodimethicone".

To have a better surface gloss, appearance and/or hydrophobicity, the weight ratio of the particle to the non-volatile silicone is preferably from 4:1 to 100:1 , more preferably from 5:1 to 40:1 , even more preferably from 7:1 to 20:1 , and most preferably from 8:1 to 15:1.

The hard surface treatment composition of the present invention comprises at least 30% of water by weight of the composition. Preferably, the composition comprises at least 50%, more preferably from 70 to 99%, even more preferably from 77 to 97% and most preferably from 84 and 93% of water by weight of the composition.

Surfactants can for instance advantageously contribute to the cleaning efficacy, the formulation stability, and/or surface gloss of the hard surface treatment composition according to the present invention. Therefore, the hard surface treatment composition may comprise 0.1 to 20 %, more preferably from 0.6 to 12%, even more preferably from 2 to 8%, and still even more preferably from 4 to 6% of one or more surfactants by weight of the total composition.

Any type of surfactant, i.e. anionic, cationic, nonionic, zwitterionic or amphoteric can be used. However, to provide better glossiness to the hard surface, it is preferable that the composition comprise non-ionic, anionic or a mixture thereof. More preferably the composition comprises non-ionic surfactant and most preferably the surfactant in the composition is non-ionic surfactant.

It is preferred that at least 25%, more preferably at least 50%, even more preferably at least 75% and still more preferably at least 90% by weight of the surfactants are nonionic surfactant. Thus, it is preferred that the hard surface treatment composition comprises from 0.1 to 15% preferably from 0.3 to 9%, more preferably from 0.5 to 8 %, and even more preferably from 2 to 6 % of one or more non-ionic surfactants.

A suitable class of nonionic surfactants can be broadly described as compounds produced by the condensation of simple alkylene oxides, which are hydrophilic in nature, with an aliphatic or alkyl-aromatic hydrophobic compound having a reactive hydrogen atom. The length of the hydrophilic or polyoxyalkylene chain which is attached to any particular hydrophobic group can be readily adjusted to yield a compound having the desired balance between hydrophilic and hydrophobic elements. This enables the choice of nonionic surfactants with the right HLB.

Particular examples include:

• the condensation products of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut alcohol/ethylene oxide condensates having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol;

• condensates of alkylphenols having C6-C15 alkyl groups with 5 to 25 moles of ethylene oxide per mole of alkylphenol;

· polyoxyethylene sorbitan fatty acid esters, for example polyoxyethylene sorbitan Ce-24 fatty acid esters;

• alkyl polyglucosides (APG), for example Cs-Ci6 alkyl polyglycoside, including those from the Glucopon ^® range, e.g. Glucopon ^® 425. It is preferred that the non-ionic surfactants are selected from ethoxylated alkyl alcohols and alkyl polyglucosides. More preferably the surfactants are ethoxylated alkyl alcohols and even more preferably ethoxylated C8-C12 alkyl alcohols, whereby yet more preferably the average degree of ethoxylation is between 5 and 8. An example of particularly effective (and therefore preferred) surfactants are ethoxylated C9-C11 alkyl alcohols with an average degree of ethoxylation of 8, including for instance the commercially surfactant Neodol 91 -8.

The weight ratio of the particle to the non-ionic surfactant is preferably in the range of 1 :10 to 15:1 , more preferably from 1 :5 to 8:1 , even more preferably from 0.4:1 to 3:1.

The composition preferably comprises organic solvents selected from C1-8 alcohol, ether having 2 to 16 carbon atoms, ester of C2-24 organic acid; Ce-18 cyclic terpene, and a mixture thereof. More preferably the composition comprises ethanol, isopropyl alcohol, n-butanol, iso-butanol, n-butoxypropanol, dipropylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, methyl ester of caprylic acid, methyl ester of heptylic acid, dimethyl-2-methyl glutarate, esters of polyglycerol, soybean oil methyl ester, limonene or a mixture thereof. Even more preferably the composition comprises ethanol, isopropyl alcohol, dipropylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, methyl ester of caprylic acid, methyl ester of heptylic acid, dimethyl-2-methyl glutarate, esters of polyglycerol, soybean oil methyl ester, limonene or a mixture thereof. Most preferably the composition comprises isopropyl alcohol, dipropylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monopropyl ether, or a mixture thereof. The organic solvent may be present in the composition in a concentration of 0 to 20%, preferably 0.5-15% by weight of the composition.

The composition may comprise from 0.2 to 1.2% of thickener by weight of the composition. This provides the optimum rheological properties of the composition. Suitable thickeners include the modified celluloses for example hydroxyethyl cellulose. The hard surface cleaning composition according to the invention may further comprise dyes, perfume, and/or preservatives. If present, the amount may be from 0.001 to 5% by weight of the composition.

The composition preferably has a pH of between 1 and 14, more preferably 3 to12. The pH values referred to herein are measured at a temperature of 25 °C.

In general, the hard surface treatment composition of the invention may have any appearance, ranging from opaque to fully transparent. However, the composition is preferably at least partially transparent or translucent, more preferably transparent. By at least partially transparent or translucent is meant that a 1 cm thick sample of the composition transmits at least 20%, preferably at least 50%, of light having wavelength of 460 nm. By transparent is meant that a 1 cm thick sample of the composition transmits at least 70%, preferably at least 90%, of light having wavelength of 460 nm. The composition may be packed in any form, but preferably is packaged as a conventional hard surface treatment or cleaning product. The preferred packaging is a spray applicator. Pump dispersers (whether spray or non-spray pumps) and pouring applications (bottles etc) are also possible. It is also possible to impregnate a wipe with the composition.

The present invention also provides a method for providing shining, smoothing, repair and/or less damage to a hard surface comprising a step of contacting the surface with a composition comprising particles having average diameter of no greater than 3 microns, and non-volatile silicones onto the surface. Preferably, the composition is the hard surface treatment composition of the present invention. The present invention also provides use of a composition comprising particles having average diameter of no greater than 3 microns, and non-volatile silicones for surface shining, surface smoothing, surface repair, or a combination thereof. Preferably, the composition is the hard surface treatment composition of the present invention. The present invention is illustrated by way of the following non-limiting examples.

Examples

Material

- Bindzil CC401 is an aqueous dispersion of colloidal silica supplied by AkzoNobel, having Z-average particle size of 13.1 nm.

Levasil 30/50 is an aqueous dispersion of colloidal silica supplied by AkzoNobel, having Z-average particle size of 1 10.7 nm.

Bindzil CAT80 is an aqueous dispersion of colloidal silica supplied by AkzoNobel, having Z-average particle size of 109.7 nm.

Dow Corning ^® 2-8168 emulsion is a microemulsion of amodimethicone supplied by Dow Corning, having Z-average particle size of 76.3 nm

SF-929A Finishing Agent is polyether-modified silicone supplied by Guangdong BioMax Si&F New Material Co., Ltd.

- Modisurf is block propoxylated and ethoxylated quaternised polyamine, supplied by Croda.

Sorbosil AC77 is abrasive silica supplied by PQ Corporation, having a weight mean particle size (dso) of 8.1 microns. Calcite, 800 grit is abrasive calcium carbonate supplied by Zhangjiajie Hengliang Mining Co. Ltd.

Example 1

This example demonstrates the gloss increase of damaged hard surface after treatment by composition containing different particles in different concentrations.

The hard surface treatment compositions were prepared following the formulation in Table 1 .

Table 1

Random scratches on new black poly(methyl methacrylate) (PMMA) tiles (10cmx10cm) were generated on its central 3.5cmx3.5cm area by employing a Martindale abrasion and pilling tester (M235, SDL Atlas, UK) under a load pressure of 10 KPa and abrasion speed of 71.3 rpm. The gloss of the damaged PMMA tiles was measured by a glossmeter (Multi gloss 268plus gloss meter, Konica Minolta Optics Inc., Japan).

The damaged PMMA tiles were treated by the sample in Table 1 respectively in same manner. Then, the glosses of the tiles were measured again. The gloss of the tiles before and after treatment was recorded in Table 2.

Table 2

As can be seen from Table 2, the compositions containing either colloidal particle or abrasives are capable of enhancing the surface gloss. In addition, it was found that Bindzil CAT80 can improve the gloss more than abrasives.

Example 2

This example demonstrates the gloss change of new/smooth hard surface after treatment by composition containing different particles.

The experiments were conducted in a similar manner as described in Example 1 except that new black poly(methyl methacrylate) tiles (10cmx10cm) were employed for test.

Table 3

Gloss

Samples

Before treatment After treatment Increase (AG)

3 86.00 85.93 -0.07

A 86.00 79.00 -7.00

B 86.00 76.87 -9.13 It was found from Table 3 that the abrasives decreased the gloss of new tiles, indicated that the tiles were damaged. In contrast, the gloss of new tiles remained almost same after treated by composition of the present invention, showing that the composition of the present invention generally did not bring damage to the new/smooth surface.

Example 3

This example demonstrates the gloss increase of hard surface after treatment by composition containing different polymers.

The experiments were conducted in a similar manner described in Example 1. The gloss increases were shown in last row of Table 4.

Table 4

This data shows that the gloss was increased much more by composition containing non-volatile silicone than by composition containing other polymers. In addition, composition containing aminosilicone enhanced the gloss more than composition containing other non-volatile silicone.

Example 4

This example demonstrates the effect of the weight ratio of silica to silicone on gloss increase. The experiments were conducted in a similar manner described in Example 1. The gloss increases were shown in last row of Table 5.

Table 5

The data shows that the gloss was increased much more when the weight ratio of the particle to the non-volatile silicone is at least 3:1 .