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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
• • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
  • C11D17/0013—Liquid compositions with insoluble particles in suspension
• • 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
  • C11D3/12—Water-insoluble compounds
  • C11D3/1233—Carbonates, e.g. calcite or dolomite
• • 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
  • C11D3/12—Water-insoluble compounds
  • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures

Definitions

• the present invention relates to scouring composition suitable for use in cleaning hard surfaces, especially rust stains from hard surfaces.
• Scouring compositions such as those particulate compositions or liquid, gel, paste-type compositions containing abrasive components are well known in the art. Such compositions are used for cleaning hard surfaces, especially those surfaces that tend to become soiled with mineral deposits for example kitchen and/or bathroom surfaces.
• Scouring compositions may also find use in removing metal stains from surfaces. More particularly, some scouring compositions are marketed as being capable of removing rust stains from surfaces. It has been noted by the Applicant, especially in less developed countries were poor water piping is still in existence, that metal oxidation products, for example, rust collects or deposits in the pipe and then flows with the water out of the water outlet pipe onto the surface in the home. The metal deposit collects on the surface leaving a sometimes coloured stain. Such metal-based stains are difficult to remove with general household hard surface cleaner and require specialist treatment with, for example a rust removing composition.
• compositions containing abrasives go some way in removing the metal-based stain, such compositions can scratch or otherwise harm the surface to which it is applied.
• compositions containing abrasives go some way in removing the metal-based stain, such compositions can scratch or otherwise harm the surface to which it is applied.
• compositions of the present invention also provide good cleaning performance. Moreover the compositions of the present invention also provide limescale and other mineral deposit removal.
• compositions of the present invention may be used on any hard surface.
• hard-surfaces it is meant herein any kind of surfaces typically found in houses like kitchens, bathrooms, or in car interiors or exteriors, e.g., floors, walls, tiles, windows, sinks, showers, shower plastified curtains, wash basins, WCs, dishes, fixtures and fittings and the like made of different materials like ceramic, vinyl, no-wax vinyl, linoleum, melamine, glass, any plastics, plastified wood, metal or any painted or varnished or sealed surface and the like.
• Hard-surfaces also include household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.
• the present invention relates to a scouring composition
• a scouring composition comprising a C1-6 carboxylic acid and an abrasive particulate component having hardness from 2 to 4 as measured according to the MOHS hardness scale.
• the present invention relates to a process for manufacturing a composition as described in the preceding sentence.
• the present invention relates to a process of treating a hard surface comprising the steps of contacting the hard surface with a scouring composition comprising a C1-6 carboxylic acid and an abrasive particulate component having hardness from 2 to 4 as measured according to the MOHS scale.
• the present invention relates to the use of a composition comprising oxalic acid and calcium carbonate to remove rust stains from a hard surface.
• the present invention relates to a scouring composition
• a scouring composition comprising a C1-6 carboxylic acid and an abrasive particulate component having hardness from 2 to 4 as measured according to the MOHS hardness scale.
• scouring composition it is meant a composition being in particulate, liquid or gel-type composition comprising an abrasive component. More preferably the composition is particulate.
• the level of water in the composition is limited to a level of less than 10%, more preferably less than 5%, most preferably less than 2% water in the composition.
• the pH of the composition on mixing with water is typically in the acidic range of pH less than 7, more preferably the pH is less than 4, even more preferably less than 2. According to the present invention pH is measured of a 25% dispersion of the composition in distilled water.
• compositions of the present invention comprises a C1-6 carboxylic acid, meaning a carboxylic acid comprising from 1 to 6 carbon atoms as an essential feature thereof.
• Suitable acids may preferably be mono, but are preferably dicarboxylic acids.
• Suitable acids are selected form the group consisting of formic acid, sulphamic acid, hydroxyacetic acid, citric acid, fumaric acid, maleic acid, glycolic acid, lactic acid, thioglycolic acid, thiomalic acid, oxalic acid and mixtures thereof.
• the most preferred acid is oxalic acid since it is capable of providing rust removal by not only reducing the pH of the composition in water to a level where solubilisation of rust stains is improved, but also acts as a chelating agent for Fe 3+ ions.
• Oxalic acid suitable for use herein can be in anhydrous form, dihydrate from, mixtures of the preceding forms and intermediate forms of the drying process from dihydrate to anhydrous (as described in Kirk-Othmer, 3 rd Edition Vol 16, page 618.) and are also preferably in particulate form.
• the anhydrous form of oxalic acid is the most preferred in terms of performance and stability, even more preferred is the Alfa crystalline structure over the Beta structure.
• oxalic acid dihydrate comprises less than 30% water, more preferably less than 15% water and even more preferably less than 10%water.
• the most preferred oxalic acid dihydrate for use herein comprises from 5-9% water.
• Oxalic acid dihydrate is available in particulate form from Allied Corporation, Rhone-Poulenc etc.
• the oxalic acid is preferably present in the composition at a level of from 5% to 50%, more preferably from 5% to 30% and most preferably from 8% to 16%.
• Abrasive components typically used in the past include silica, silicate, shale ash, perlite and quartz sand.
• abrasives as known and typically used in the art, when used to clean hard surfaces, leave visible scratch marks on the surface. Scratches on the surface, are visually and sensuously unpleasant, reduce shine and can weaken the surface, potentially leading to further damage.
• the composition of the present invention employs an abrasive component having hardness of 2 to 4 as measured according to MOHS hardness scale.
• the MOHS hardness scale is an internationally recognised scale for measuring the hardness of a compound versus a compound of known hardness, see Encyclopedia of Chemical Technology, Kirk-Othmer, 4 th Edition Vol 1, page18 or Lide, D.R (ed) CRC Handbook of Chemistry and Physics, 73 rd edition, Boca Raton, Fla.: The Rubber Company, 1992-1993 .
• the abrasive component is substantially insoluble or partially soluble in water. Most preferably the abrasive component is calcium carbonate.
• the abrasive component preferably has average particle size of less than 300 microns, more preferably less than 100 microns and most preferably from 5 to 100 microns.
• the abrasive component is preferably present in the composition in sufficient amount to provide an abrasive action. More Preferably the abrasive component in present at a level of from 50% to 99%, more preferably from 60% to 95% and most preferably from 75% to 90%.
• the preferred weight ratio of oxalic acid to carbonate is in the range of from 1:1 to 1:18, more preferably from 1:6 to 1:9 and most preferably from 1:7 to 1:8.
• Also claimed herein is a process of preparing the composition of the present invention.
• the process requires the steps of premixing the abrasive and any wet or water-containing ingredients; drying the premix formed in the preceding step to achieve a composition having a moisture content of less than 10%, preferably less than 5% water; and subsequently mixing the substantially dry premix with the carboxylic acid, preferably oxalic acid.
• these ingredients are preferably added in additional step preceding the step of mixing the abrasive with the wet or water-containing ingredients.
• a proportion of the abrasive is mixed with the perfume and pigment in order to achieve a homogenous distribution of perfume and/or pigment.
• a preferably 5% solution of pigment in water is mixed with the abrasive.
• the second step requires the drying of the premix. Drying can be achieved passively by allowing moisture to evaporate or actively using any suitable equipment and method.
• the premix is dried to a point whereby it contains less than 10% water, more preferably less than 5% water at this point the premix is said to be "substantially dry”.
• the substantially dry premix is then mixed with the oxalic acid.
• Additional optional ingredients dry or substantially dry ingredients, can be added before or after the drying step, but must not have the effect of increasing the water content of the composition to higher than 10% water.
• all additional ingredients namely wet, water-containing, dry or substantially dry ingredients are added to the composition prior to the drying step.
• compositions of the present invention may include one or more optional ingredients.
• optional ingredients may be selected from the group consisting of surfactants, inorganic acids, chelating agents, reducing agents, perfume and colouring agent
• compositions of the present invention optionally although preferably comprise a surfactant.
• surfactants provide additional cleaning performance benefits by removing a number of different types of soils for example greasy, oily soils. It has also been seen by the Applicants that due to the reaction of especially carbonate and oxalic acid, the evolution of gas, CO 2 , in combination with a surfactant results in the formation of foam. The presence of foam is aesthetically pleasing to consumers, which is then related to cleaning performance.
• Preferred surfactants are selected from the group consisting of nonionic, anionic, cationic, zwitterionic, amphoteric surfactants and mixtures thereof.
• surfactants may be present in the composition according to the present invention in amounts of from 0.1% to 50%, preferably of from 0.1% to 20% and more preferably of from 1% to 10% by weight of the total composition.
• Suitable anionic surfactants for use in the compositions herein include water-soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
• Suitable anionic surfactants for use herein are water-soluble salts or acids of the formula RO(A) m SO 3 M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
• R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C
• Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
• Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
• Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 E(1.0)M), C 12 -C 18 alkyl polyethoxylate (2.25) sulfate, C 12 -C 18 E(2.25)M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate C 12 -C 18 E(3.0), and C 12 -C 18 alkyl polyethoxylate (4.0) sulfate C 12 -C 18 E(4.0)M), wherein M is conveniently selected from sodium and potassium.
• alkyl sulphonates including water-soluble salts or acids of the formula RSO 3 M wherein R is a C 6 -C 22 linear or branched, saturated or unsaturated alkyl group, preferably a C 12 -C 18 alkyl group and more preferably a C 14 -C 16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
• R is a C 6 -C 22 linear or branched, saturated
• Suitable alkyl aryl sulphonates for use herein include water- soluble salts or acids of the formula RSO 3 M wherein R is an aryl, preferably a benzyl, substituted by a C 6 -C 22 linear or branched saturated or unsaturated alkyl group, preferably a C 12 -C 18 alkyl group and more preferably a C 12 -C 16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium etc) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethy
• the most preferred surfactant in terms of performance is an anionic surfactant according to the above formula wherein R is benzyl substituted with a C12 alkyl group and M is Hydrogen i.e. linear C12 alkyl benzene sulphonate (HLAS).
• alkylsulfonates and alkyl aryl sulphonates for use herein include primary and secondary alkylsulfonates and primary and secondary alkyl aryl sulphonates.
• secondary C6-C22 alkyl or C6-C22 alkyl aryl sulphonates it is meant herein that in the formula as defined above, the SO3M or aryl-SO3M group is linked to a carbon atom of the alkyl chain being placed between two other carbons of the said alkyl chain (secondary carbon atom).
• anionic surfactants useful for detersive purposes can also be used herein. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 8 -C 24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
• alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C 14-16 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolysaccharides such as
• Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975, to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
• alkyl carboxylates and alkyl alkoxycarboxylates having from 4 to 24 carbon atoms in the alkyl chain, preferably from 8 to 18 and more preferably from 8 to 16, wherein the alkoxy is propoxy and/or ethoxy and preferably is ethoxy at an alkoxylation degree of from 0.5 to 20, preferably from 5 to 15.
• Suitable amphoteric surfactants for use herein include amine oxides having the following formula R 1 R 2 R 3 NO wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched hydrocarbon chain of from 1 to 30 carbon atoms.
• Preferred amine oxide surfactants to be used according to the present invention are amine oxides having the following formula R 1 R 2 R 3 NO wherein R1 is an hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from 6 to 20, more preferably from 8 to 16, most preferably from 8 to 12, and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched hydrocarbon chains comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups.
• R1 may be a saturated, substituted or unsubstituted linear or branched hydrocarbon chain.
• Suitable amine oxides for use herein are for instance natural blend C8-C10 amine oxides as well as C12-C16 amine oxides commercially available from Hoechst.
• Suitable zwitterionic surfactants for use herein contain both a cationic hydrophilic group, i.e., a quaternary ammonium group, and anionic hydrophilic group on the same molecule at a relatively wide range of pH's.
• the typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates, and the like can be used.
• R 1 is a hydrophobic group
• R 2 is hydrogen, C 1 -C 6 alkyl, hydroxy alkyl or other substituted C 1 -C 6 alkyl group
• R 3 is C 1 -C 6 alkyl, hydroxy alkyl or other substituted C 1 -C 6 alkyl group which can also be joined to R 2 to form ring structures with the N, or a C 1 -C 6 carboxylic acid group or a C 1 -C 6 sulfonate group
• R 4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms
• X is the hydrophilic group which is a carboxylate or sulfonate group.
• R 1 are aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chains that can contain linking groups such as amido groups, ester groups. More preferred R 1 is an alkyl group containing from 1 to 24 carbon atoms, preferably from 8 to 18, and more preferably from 10 to 16. These simple alkyl groups are preferred for cost and stability reasons.
• the hydrophobic group R 1 can also be an amido radical of the formula R a -C(O)-NH-(C(R b ) 2 ) m , wherein R a is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, preferably an alkyl group containing from 8 up to 20 carbon atoms, preferably up to 18, more preferably up to 16, R b is selected from the group consisting of hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3, more preferably 3, with no more than one hydroxy group in any (C(R b ) 2 ) moiety.
• Preferred R 2 is hydrogen, or a C 1 -C 3 alkyl and more preferably methyl.
• Preferred R 3 is a C 1 -C 4 carboxylic acid group or C1-C4 sulfonate group, or a C 1 -C 3 alkyl and more preferably methyl.
• Preferred R 4 is (CH2) n wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is from 1 to 3.
• Suitable cationic surfactants for use herein include derivatives of quaternary ammonium, phosphonium, imidazolium and sulfonium compounds.
• Preferred cationic surfactants for use herein are quaternary ammonium compounds wherein one or two of the hydrocarbon groups linked to nitrogen are a saturated, linear or branched alkyl group of 6 to 30 carbon atoms, preferably of 10 to 25 carbon atoms, and more preferably of 12 to 20 carbon atoms, and wherein the other hydrocarbon groups (i.e.
• quaternary ammonium compounds suitable for use herein are non-chloride/non halogen quaternary ammonium compounds.
• the counterion used in said quaternary ammonium compounds are compatible with any peracid and are selected from the group of methyl sulfate, or methylsulfonate, and the like.
• compositions of the present invention are trimethyl quaternary ammonium compounds like myristyl trimethylsulfate, cetyl trimethylsulfate and/or tallow trimethylsulfate.
• trimethyl quaternary ammonium compounds are commercially available from Hoechst, or from Albright & Wilson under the trade name EMPIGEN CM®.
• alkoxylated nonionic surfactants are suitable for use herein.
• Suitable alkoxylated nonionic surfactants are capped alkoxylated nonionic surfactants, especially capped ethoxylated nonionic surfactants, and non-capped alkoxylated nonionic surfactants, especially non-capped ethoxylated nonionic surfactants, or mixtures thereof
• Suitable capped alkoxylated nonionic surfactants for use herein are according to the formula: R 1 (O-CH 2 -CH 2 ) n -(OR 2 ) m -O-R 3 wherein R 1 is a C 8 -C 24 linear or branched alkyl or alkenyl group, aryl group, alkaryl group, preferably R 1 is a C 8 -C 18 alkyl or alkenyl group, more preferably a C 10 -C 15 alkyl or alkenyl group, even more preferably a C 10 -C 15 alkyl group; wherein R 2 is a C 1 -C 10 linear or branched alkyl group, preferably a C 2 -C 10 linear or branched alkyl group; wherein R 3 is a C 1 -C 10 alkyl or alkenyl group, preferably a C 1 -C 5 alkyl group, more preferably methyl; and wherein n and m are integers independently
• Suitable non-capped alkoxylated nonionic surfactants are according to the formula RO-(A) n -H, wherein : R is a C 8 to C 24 , preferably a C 8 to C 18 , more preferably a C 10 to C 16 , even more preferably a C 13 to C 16 , alkyl or alkenyl chain; A is an ethoxy or propoxy or butoxy unit; and wherein n is from 1 to 20, preferably from 1 to 15 and, more preferably from 2 to 15, even more preferably from 2 to 12 and most preferably 7; or mixtures thereof.
• Preferred R chains for use herein are the C 13 to C 16 alkyl chains.
• Non-capped ethoxy/butoxylated, ethoxy/propoxylated, butoxy/propoxylated and ethoxy/butoxy/propoxylated nonionic surfactants may also be used herein.
• Preferred non-capped alkoxylated nonionic surfactants are non-capped ethoxylated nonionic surfactants.
• the surfactant herein when present, is a mixture of nonionic surfactants.
• said surfactant is a mixture of alkoxylated nonionic surfactants, more preferably a mixture of non-capped ethoxylated nonionic surfactants, even more preferably a mixture of a C 14-16 EO7 non-capped ethoxylated nonionic surfactant and a C 13-15 EO7 non-capped ethoxylated nonionic surfactant
• compositions of the present invention is an inorganic acid or generator thereof.
• Inorganic acids are preferred components as they are believed to provide a source of hydrogen ions and thus further reduce the pH of the composition in aqueous environment, for example when the particulate composition is in contact with water.
• Reducing the pH of the composition in use in the presence of water aids the removal of metal stains, especially rust stains.
• metal stains especially rust stains.
• iron oxide rust
• Reducing the pH of the composition in use in the presence of water aids the removal of metal stains, especially rust stains.
• Suitable inorganic acids include all those capable of providing a pH as stated above. More preferred inorganic acids are selected from the group consisting of phosphoric acid, hydrochloric acid, ammonium bifluride and further acids generated therefrom in situ and sulfuric acid.
• Another class of optional compounds for use herein include chelating agents or mixtures thereof.
• Chelating agents can be incorporated in the compositions herein in amounts ranging from 0.0% to 10.0% by weight of the total composition, preferably 0.1% to 5.0%.
• Chelating agents can be beneficial in the composition herein as a means of complexing metal ions from the metal ion stain. Suitable complexing agents include any having an affinity for stain-causing metal ions, for example Fe 3+ .
• Suitable chelating agents for use herein include the phosphonate chelating agents.
• Phosphonate chelating agents are those selected from the group consisting of alkali metal ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP).
• the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
• Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®.
• Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al.
• Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.
• a preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
• Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins.
• Ethylenediamine N,N'- disuccinic acids is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
• Suitable amino carboxylates for use herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA), N-hydroxyethylethylenediamine triacetates, N-hydroxyethylethylenediamine triacetic acid (HEDTA), nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
• DTPA diethylene triamine pentaacetate
• HEDTA N-hydroxyethylethylenediamine triacetic acid
• HEDTA N-hydroxyethylethylenediamine triacetic acid
• Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS® and methyl glycine di-acetic acid (MGDA).
• PDTA propylene diamine tetracetic acid
• MGDA methyl glycine di-acetic acid
• carboxylate chelating agents for use herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.
• compositions as described herein are a reducing agent.
• a further aid for removing metal ion-based stains may be to reduce the metal ion to a more oxidised state.
• a composition comprising a reducing agent will reduce Fe 3+ to Fe 2+ which is more water soluble than the Fe 3+ ion.
• Any reducing agent known in the art capable of reducing a metal ion and being compatible with at least the essential ingredients of the present compositions are preferred herein.
• the most preferred reducing agent are ascorbic acid, bisulfite, thiourea and mixtures thereof.
• compositions of the present invention may also, preferably comprise a moisture trap as an optional ingredient.
• moisture trap it is meant, a hygroscopic compound that readily absorbs moisture/water from it's surroundings.
• Suitable moisture traps may be any of those commonly known in the art and compatible with the essential ingredients herein.
• Preferred examples of moisture traps include silicagel, sodium acetate and mixtures thereof.
• Suitable perfumes for use herein include materials which provide an olfactory aesthetic benefit and/or cover any "chemical" odour that the product may have.
• the main function of a small fraction of the highly volatile, low boiling (having low boiling points), perfume components in these perfumes is to improve the fragrance odor of the product itself, rather than impacting on the subsequent odor of the surface being cleaned.
• perfume components in these perfumes provide a fresh and clean impression to the surfaces, and it is desirable that these ingredients be deposited and present on the dry surface.
• Perfume ingredients can be readily solubilized in the compositions, for instance by the amphoteric surfactant.
• the perfume ingredients and compositions suitable to be used herein are the conventional ones known in the art.
• compositions herein may comprise a perfume ingredient, or mixtures thereof, in amounts up to 5.0%, more preferably in amounts of 0.1% to 1.5% by weight of the total composition.
• the liquid compositions of the present invention may also comprises a builder or a mixture thereof, as an optional ingredient.
• Suitable builders for use herein include polycarboxylates and polyphosphates, and salts thereof.
• the compositions of the present invention comprise up to 20.0 % by weight of the total composition of a builder or mixtures thereof, preferably from 0.1% to 10.0% , and more preferably from 0.5% to 5.0%.
• Such suitable and preferred polycarboxylates include citrate and complexes of the formula: CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B) wherein A is H or OH; B is H or -O-CH(COOX)-CH 2 (COOX); and X is H or a salt-forming cation.
• a and B are both H, then the compound is oxydissuccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts.
• TDS tartrate disuccinic acid
• Still other ether polycarboxylates suitable for use herein include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulfonic acid.
• ether hydroxypolycarboxylate builders include the ether hydroxypolycarboxylates represented by the structure : HO-[C(R)(COOM)-C(R)(COOM)-O] n -H wherein M is hydrogen or a cation wherein the resultant salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or different and selected from hydrogen, C 1-4 alkyl or C 1-4 substituted alkyl (preferably R is hydrogen).
• Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903, all of which are incorporated herein by reference.
• Preferred amongst those cyclic compounds are dipicolinic acid and chelidanic acid.
• polycarboxylates for use herein are mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, benezene pentacarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.
• carboxylate builders herein include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973, incorporated herein by reference.
• carboxylates for use herein, but which are less preferred because they do not meet the above criteria are alkali metal, ammonium and substituted ammonium salts of polyacetic acids.
• polyacetic acid builder salts are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine, tetraacetic acid and nitrilotriacetic acid.
• polycarboxylates are those also known as alkyliminoacetic builders such as methyl imino diacetic acid, alanine diacetic acid, methyl glycine diacetic acid, hydroxy propylene imino diacetic acid and other alkyl imino acetic acid builders.
• compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanediotes and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986, incorporated herein by reference.
• Useful succinic acid builders include the C5-C20 alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid.
• Alkyl succinic acids typically are of the general formula R-CH(COOH)CH 2 (COOH) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., C 10 -C 20 alkyl or alkenyl, preferably C 12 -C 16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
• R is hydrocarbon, e.g., C 10 -C 20 alkyl or alkenyl, preferably C 12 -C 16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
• the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.
• succinate builders include : laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0 200 263, published November 5, 1986.
• useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
• polyacetal carboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979, incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, an ester of glyoxylic acid and a polyerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
• Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
• Suitable polyphosphonates for use herein are the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates.
• the most preferred builder for use herein is citrate.
• compositions of the present invention may further comprise a solvent or a mixtures thereof where the composition is in liquid, gel or paste-type form.
• Solvents for use herein include all those known to the those skilled in the art of hard-surfaces cleaner compositions. Suitable solvents for use herein include ethers and diethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms, glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, C6-C16 glycol ethers and mixtures thereof.
• Suitable glycols to be used herein are according to the formula HO-CR1R2-OH wherein R1 and R2 are independently H or a C2-C10 saturated or unsaturated aliphatic hydrocarbon chain and/or cyclic. Suitable glycols to be used herein are dodecaneglycol and/or propanediol.
• Suitable alkoxylated glycols to be used herein are according to the formula R-(A)n-R1-OH wherein R is H, OH, a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein R1 is H or a linear saturated or unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, and A is an alkoxy group preferably ethoxy, methoxy, and/or propoxy and n is from 1 to 5, preferably 1 to 2.
• Suitable alkoxylated glycols to be used herein are methoxy octadecanol and/or ethoxyethoxyethanol.
• Suitable alkoxylated aromatic alcohols to be used herein are according to the formula R (A) n -OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 2 to 10, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
• Suitable alkoxylated aromatic alcohols are benzoxyethanol and/or benzoxypropanol.
• Suitable aromatic alcohols to be used herein are according to the formula R-OH wherein R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
• R is an alkyl substituted or non-alkyl substituted aryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 and more preferably from 1 to 10.
• a suitable aromatic alcohol to be used herein is benzyl alcohol.
• Suitable aliphatic branched alcohols to be used herein are according to the formula R-OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12.
• Particularly suitable aliphatic branched alcohols to be used herein include 2-ethylbutanol and/or 2-methylbutanol.
• Suitable alkoxylated aliphatic branched alcohols to be used herein are according to the formula R (A) n -OH wherein R is a branched saturated or unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from 2 to 15 and more preferably from 5 to 12, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
• Suitable alkoxylated aliphatic branched alcohols include 1-methylpropoxyethanol and/or 2-methylbutoxyethanol.
• Suitable alkoxylated linear C1-C5 alcohols to be used herein are according to the formula R (A) n -OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4, wherein A is an alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1 to 5, preferably 1 to 2.
• Suitable alkoxylated aliphatic linear C1-C5 alcohols are butoxy propoxy propanol (n-BPP), butoxyethanol, butoxypropanol, ethoxyethanol or mixtures thereof. Butoxy propoxy propanol is commercially available under the trade name n-BPP® from Dow chemical.
• Suitable linear C1-C5 alcohols to be used herein are according to the formula R-OH wherein R is a linear saturated or unsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2 to 4.
• Suitable linear C1-C5 alcohols are methanol, ethanol, propanol or mixtures thereof.
• Suitable solvents include butyl diglycol ether (BDGE), butyltriglycol ether, ter amilic alcohol and the like. Particularly preferred solvents to be used herein are butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.
• BDGE butyl diglycol ether
• ter amilic alcohol ter amilic alcohol
• Particularly preferred solvents to be used herein are butoxy propoxy propanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.
• compositions of the present invention comprise up to 20% by weight of the total composition of a solvent or mixtures thereof, preferably from 0.5% to 10% by weight and more preferably from 1% to 8%.
• compositions herein may also comprise a bleaching component.
• Suitable bleaching agents comprise any of those commonly referred to as peroxygen bleaches.
• Suitable peroxygen bleaches for use herein include hydrogen peroxide or sources thereof.
• a source of hydrogen peroxide refers to any compound which produces active oxygen when said compound is in contact with water.
• Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates, preformed percarboxylic acids, persilicates, persulphates, perborates, organic and inorganic peroxides and/or hydroperoxides.
• the present invention also encompasses a process of treating a hard-surface wherein the surface is contacted with a composition comprising a C1-6 carboxylic acid and an abrasive particulate component.
• Hard-surfaces any kind of surfaces typically found in houses like kitchens, bathrooms, or in car interiors or exteriors, e.g., floors, walls, tiles, windows, sinks, showers, shower plastified curtains, wash basins, WCs, dishes, fixtures and fittings and the like made of different materials like ceramic, vinyl, no-wax vinyl, linoleum, melamine, glass, any plastics, plastified wood, metal or any painted or varnished or sealed surface and the like.
• Hard-surfaces also include household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.
• the composition of the present invention is applied to the surface, preferably by either (i) applying the composition directly to the surface and then contacting the surface and composition with a cloth or sponge or other suitable application device or (ii) applying the composition to the cloth, sponge or other suitable application device and then contacting the surface with the application device and composition.
• the composition In order to activate the rust removal performance, the composition must also come into contact with water, this can be achieved either by application of water to the surface or to the application device.
• the composition is applied to a damp cloth, sponge or other suitable application device which is then used to treat the surface
• compositions of the present invention are exemplified by the present examples, which are not meant to be limiting. All amounts are represented as weight % of the total composition.
• Example 1 HLAS (100% pure) 1.20% Perfume 0.15% Pigment 0.015% moisture 0.285% oxalic acid anhydrous 12.00% Calcium carbonate 86.35%
• Example 2 HLAS 1.20% Perfume 0.15% Pigment 0.015% moisture 0.285% oxalic acid dihydrate 16.7% silicagel 5% calcium carbonate 76.65%
• compositions above are typically prepared by mixing the calcium carbonate and all other ingredients with the exception of any acids to form a premix, allowing the premix to dry or actively drying the premix if necessary, to achieve a composition which contains less than 5% moisture.
• the substantially dry premix is then mixed with the oxalic acid to form a homogeneous composition.
• pigment forms a component of the composition
• a 5% solution of pigment in water is prepared and then mixed with a small proportion (approximately 10%) of the calcium carbonate.
• perfume is present in the composition it is also added to a small proportion of carbonate prior to mixing with the remaining ingredients.
• ⁇ 10% of the CaCO3 (calcium carbonate) is mixed with the HLAS until the surfactant and the carbonate are homogeneously mixed.

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• 2000
  • 2000-04-27 EP EP00870087A patent/EP1111038A1/de not_active Withdrawn
  • 2000-12-20 AU AU25887/01A patent/AU2588701A/en not_active Abandoned
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