Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/046—Salts
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2068—Ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

• 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, as well as giving good cleaning on tough soils and stains.
• 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.
• 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.
• 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.
• hydrophobic composition which is transparent and devoid of metals.
• US 2004/0077517 and US 2004/0171515 disclose laundry (wash, rinse or care) composition comprising a cationically modified polymer and metal ions and cationic surfactants. They further disclose that the formulation may be applied onto both soft and hard surfaces. They further disclose the use of solvents including low molecular weight alcohols and glycols. What remains to be desired is a composition that imparts improved hydrophobicity to a surface.
• US 2004/0077517 and US 2004/0171515 do not disclose the use of glycol ethers in the compositions. The present inventors have shown that inclusion of glycol ethers enhance the repellence to water in addition to cleaning.
• 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.
• PAC poly- aluminium-chloride
• PVA poly vinyl alcohol
• metal soaps formed therein contribute to the opaqueness of the composition, thereby leaving a need for transparent hydrophobic compositions.
• Hard surface cleaning compositions comprising carboxylic polymers are disclosed in W097/24425 (The Procter & Gamble Company). These compositions provide improved cleaning and especially improved gloss on a surface, thought to be caused by the combination of a carboxylic polymer, surfactant and a divalent ion. However, improved results on the subsequent cleaning remain to be desired.
• compositions providing a next time cleaning benefit are not performing well on cleaning; they do not provide good stain removal, and leave water streaks and/or spots after wetting a treated surface upon drying. It is therefore an object of the present invention to provide easier cleaning upon the subsequent wash; also knows as a next time cleaning benefit.
• composition comprising a solvent, a carboxylic polymer, a metal ion and a cationic surfactant and having a pH of between 2 and 6, provides both stain repellence as well as good primary and secondary cleaning.
• the present invention provides a hard surface cleaning composition
• the invention further provides for a method for cleaning a hard surface comprising the steps in sequence of: (a) treating a surface with the composition according to anyone of the preceding claims; (b) leaving the surface for soils or stains to deposit; and (c) cleaning the surface with the compositions according to any one of the preceding claims.
• primary cleaning is meant that the composition itself, upon first use on a surface provides cleaning efficacy.
• secondary cleaning is meant that after first applying the composition to a surface, then leaving it to dry and leaving it for dirt to deposit, cleaning efficacy is obtained while applying the composition for a second or subsequent time.
• the invention provides a hard surface treatment composition
• sodium/potassium of the following acids: acrylic acid, C2-7 dicarboxylic acids; a water miscible glycol ether; a siloxane; a metal salt and a cationic surfactant, wherein the pH is from 2 to 6, preferably from 3 to 5.
• the composition leaves a deposition of a complex on the hard surface that is treated with the composition.
• the polymer-metal complex that forms in the current composition provides a more hydrophobic layer that is better and more homogeneously deposited onto the surface than the hydrophobic layers that have been disclosed in the art.
• the deposition is only achieved in the pH range of the invention. This imparts hydrophobicity to the surface and makes it water repellent. Hydrophobicity is measured by the contact angle of a water droplet on a treated surface. A contact angle above 90° is acceptable, above 100° is preferred.
• the polymer is typically a block or alternate copolymer having moieties A and B, wherein:
• A polystyrene, polyethylene, polypropylene, polyisobutylene, and
• B Water soluble alkali metal salt (sodium/ potassium) of the following acids: acrylic acid, C2-7 dicarboxylic acids;
• the copolymer may be a styrene/maleic copolymers, selected from block or alternate copolymer having, wherein A is selected from polystyrene; and B is maleic acid, forming the preferred polymers including
• Block copolymers consist of two or more block sequences, at least one of which is not a homopolymer or uniformly random copolymer sequence. In case of random copolymers the composition changes continuously along the polymer chain and with conversion, without giving rise to a detectable block structure (JOURNAL OF APPLIED POLYMER SCIENCE VOL. 1 1 , PP. 1581-1591 (1967))
• polystyrene-co-acrylic acid sodium salt
• polystyrene-block-poly (acrylic acid)sodium salt examples include poly(styrene-block-poly (acrylic acid)sodium salt.
• the most preferred copolymers of the present invention are poly(styrene-alt-maleic acid) and poly (styrene-alt-maleic anhydride).
• the polymer is present in the composition a concentration of from 0.2 to 6% by weight of the composition, preferably at least 0.3%, more preferably at least 0.5% by weight, but typically not more than 5%, more preferably not more than 3%, still more preferably not more than 2% by weight.
• the polymer composition concentrations beyond the scope of the invention deteriorate hydrophobicity.
• the composition comprises a water miscible glycol ether 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 wherein, is a substituted or unsubstituted C 2 - C 4 alkyl group, aryl group (preferably phenyl), or alkylaryl group; and R 2 is a substituted or unsubstituted C 2 - C 4 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, especially propylene glycol n-propyl ether.
• water miscible glycol 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 0.2 %, but preferably not more than 2% by weight of the total composition. The best cleaning results are obtained at a concentration of between 0.2 and 5% by weight.
• water miscible it is meant that at least 5% of the glycol ether is soluble in or miscible with water.
• the composition further comprises a metal ion. It is thought that the metal ion of the salt aids in the deposition of a complex on the surface and imparts additional hydrophobicity. This is thought to be due to the metal polymer complex formation, which deposits on the surface of the substrate. It also aids the deposition of the optional siloxane onto the surface. It is further thought that a higher positive charge on the metal ion also helps in deposition on negatively charged surfaces like glass or ceramics.
• the metal ion is selected from water soluble trivalent and tetravalent metal ions; and/or bi valent transition metal ions. Any combination of two or more of the metal or transition metal ions is also included in the purview of the present invention.
• the metal ions include: bivalent Zn(ll), trivalent Al(lll), Ti(lll), Fe(lll), Tetravalent Ti(IV).
• the most preferred metal ions are aluminium (Al 3+ ) and Zinc (Zn 2+ ), of which aluminium (Al 3+ ) is the most preferred.
• the metal ion is typically added to the composition in the form of a salt; preferred salts are halides, nitrate, sulphate and acetate for the metal ions indicated.
• the preferred salts are Aluminum chloride, polyaluminum chloride, aluminium nitrate, zinc nitrate, zinc chloride, zinc sulphate and zinc acetate.
• the metal ion is present in the composition in a concentration of between 0.01 and 0.5% by weight.
• the metal ion is preferably present in a concentration of at least 0.02% or even at least 0.05% by weight of the composition, but typically not more than 0.45% or even not more than 0.4% by weight of the composition.
• the best hydrophobicity results are obtained at a concentration of between 0.05 and 0.25% by weight.
• the composition comprises a cationic surfactant.
• the most preferred cationic surfactants are quaternary ammonium cationic surfactants.
• the quaternary ammonium surfactants are preferably halides of Benzalkonium, Cetyl- trimethyl-ammonium, Tetradecyl-trimethyl-ammonium, Dodecyl-trimethyl-ammonium, Stearyl-trimethyl-ammonium, Octadecyl-trimethyl-ammonium, Dodecylpyridinium, Cetylpyridinium, Tetrabutyl-ammonium, Tetraheptyl-ammonium, 1 ,3-Decyl-2-methyl- imidazolium, 1 -Hexadecyl-3-methyl-imidazolium, Didecyl-dimethyl-ammonium, Didecyl- dimethyl-ammonium.
• the most preferred cationic surfactant are Cetyl-trimethyl- ammonium halides.
• chlorides and iodides are the most preferred, bromide and fluorides are equally contemplated in the context of the invention.
• the cationic surfactant is present in the composition in a concentration of between 0.002 and 0.07% by weight.
• the cationic surfactant is preferably present in a concentration of at least 0.01 % or even at least 0.02% by weight of the composition, but typically not more than 0.06% by weight of the composition. The best
• hydrophobicity results are obtained at a concentration of between 0.02 and 0.06% by weight
• siloxane When the siloxane is present in the composition a further increase in hydrophobicity or water repellency is achieved.
• Siloxanes that are preferred in 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. These siloxanes preferably have a molecular mass of between 1700 and 3200 u. The most preferred siloxane in this class is
• 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 4000 cSt (centistokes; Stokes (St) being cm 2 /s), while it becomes too low below 800 u, typically less than 50 cSt.
• the most preferred siloxane in this class is polydimethyl siloxane, preferably having an approximate molecular weight of between 6000 u and 13650 u.
• 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.
• siloxanes are polymethylhydrosiloxane (PMHS),
• PDMS polydimethylsiloxane
• cyclopentasiloxane and mixtures thereof.
• siloxane When siloxane is present in the composition, it may be present in the composition in a concentration of between 0.1 and 10% by weight, preferably not less than 0.5% by weight, but preferably not more than 8% or even not more than 5% by weight of the total composition. The best hydrophobicity results are obtained at a concentration of between 0.5 and 5% by weight.
• Optional ingredients When siloxane is present in the composition, it may be present in the composition in a concentration of between 0.1 and 10% by weight, preferably not less than 0.5% by weight, but preferably not more than 8% or even not more than 5% by weight of the total composition. The best hydrophobicity results are obtained at a concentration of between 0.5 and 5% by weight.
• the composition according to the invention further comprises an acid stabile abrasive material; both natural acid stabile abrasives and synthetic materials are considered in the purview of the present invention.
• an acid stabile abrasive material both natural acid stabile abrasives and synthetic materials are considered in the purview of the present invention.
• Common cleaner and aesthetic additives such as perfumes, fluorescers and optical brighteners, antimicrobial agents (antibacterial agents such as essential oils, eugenol, cationic amino surfactants), fluoropolymers and/or fluorosurfacatnts, viscosity modifiers such as gum resins, polysaccharides, fatty alcohols, polyols (such as polyvinyl alcohol, glycerol) essential oils etc may also be included.
• the invention further provides for a method for cleaning a hard surface comprising the steps in sequence of: (a) treating a surface with the composition according to anyone of the preceding claims; (b) leaving the surface for soils or stains to deposit; and (c) cleaning the surface with the compositions according to any one of the preceding claims.
• 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.
• PMHS Poly(methylhydrosiloxane)-average M n 1 ,700-3,200 (ex Sigma
• PDMS-cyclopentasiloxane Polydimethyl siloxane - cyclopentasiloxane (ex Dow Corning, DC 245 fluid)
• PDMS-350 cSt Polydimethyl siloxane polymer fluid with viscosity 350 cSt (ex Dow Corning, DC 200)
• Metal salt Polyaluminum chloride (Arya PAC ex Grasim)
• Non-ionic C 12 EO ⁇ 7> (ex BASF)
• 0.25 ml of the treatment solution was spread uniformly on a 2.5 cm X 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 checking water repellency.
• Farrell extra virgin olive oil, commercially available ex: Jindal; Batch No. L1 1370263
• 0.1 ml of olive oil was smeared uniformly on a 2.5 cm x 12 cm clean glass microscopic slide.
• the stained glass slide was heated in an air oven at 95°C for 48 hours.
• the aged glass surface was treated with treatment formulation (treatment procedure discussed above).
• a good glossy surface typically has a gloss value of 1 10 or above by this measurement protocol.
• measurement value is an indication of higher cleaning.
• a good glossy surface typically has a gloss value of 1 10 or above by this measurement protocol.
• 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. Higher contact angle is an indication of higher hydrophobicity imparted by a treatment formulation on a substrate. A contact angle of 93° and above is considered hydrophobic by this measurement protocol.
• the present invention gives the benefit of rendering a hard surface (like glass) to provide both superior primary and secondary cleaning (as reflected by gloss values of 1 10 and above at 60° angle) and is also hydrophobic (water contact angle of 93° and above) when treated with the composition mentioned in the claim.
• Example 1 a Effect of ingredients:
• Example compositions 1 and 2 are compared with compositions lacking one or more of the essential components (Comparative example compositions A-l).
• Dowanol PnP is propylene glycol n-propyl ether
• hydrophobicity contact angle, CA
• primary as well as secondary cleaning are given in the table below.
• compositions with all individual components of the invention in a higher concentration are compared with compositions lacking one or more of the essential components (Comparative example compositions AA-I I).
• Dowanol PnP is propylene glycol n-propyl ether
• Example 3 comprises cationic surfactant, while comparative examples J and K comprise anionic surfactant and nonionic surfactant respectively. All compositions had a pH of 4.
• hydrophobicity is provided when the formulation includes cationic surfactants, whereas anionic and non ionic surfactants do not provide adequate hydrophobicity.
• Example 3 Effect of different metal ions.
• the pH in all compositions was 4 and the surfactant was CTAB.
• Trivalent metal ions (Al) and bivalent transition metal ion (Zn)-containing formulations provide hydrophobic effect on substrate while those containing non transitional bivalent metal ions do not provide hydrophobicity.
• Examples 7-10 are within the claimed range, while examples N and O are outside. All compositions had a pH of 4, and the metal ion was Al 3+ and the surfactant was CTAB.
• Examples 7-10 are within the claimed range, while examples N and O are outside. All compositions had a pH of 4, and the metal ion was Al 3+ and the surfactant was CTAB at a concentration of 0.02%w. polymer siloxane dowanol PnP metal ion CA
• the base composition was as given in the table below. All compositions had a pH of 4, and the metal ion was Al 3+ at a concentration of 0.1 %w, the polymer was present in a concentration of 1 .5%w and the surfactant was CTAB at a concentration of 0.02%w. The solvent percentage is varied.
• the metal ion was Al 3+ at a concentration of 0.1 % by weight and the surfactant was CTAB at a concentration of 0.02% by weight, and the pH was 4.
• Example 8 Effect of the metal ion concentration.
• compositions had a pH of 4, and the metal ion was Al 3+ and the surfactant was CTAB at a concentration of 0.02%w.
• the metal ion was Al 3+ at a concentration of 0.1 % by weight and the surfactant was CTAB at a concentration of 0.02% by weight.
• V 1 .5 2 2 8 77 The table above shows that the formulation according to the invention imparts hydrophobicity onto a surface in a pH range of 2-6.

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• 2013
  • 2013-09-02 WO PCT/EP2013/068047 patent/WO2014040869A1/en active Application Filing
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  • 2013-09-02 EP EP13759688.8A patent/EP2895587A1/de not_active Withdrawn
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