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EP3418362A1 - Saurer reiniger mit kationischen quervernetzten verdickungsmitteln - Google Patents

Saurer reiniger mit kationischen quervernetzten verdickungsmitteln Download PDF

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Publication number
EP3418362A1
EP3418362A1 EP18153658.2A EP18153658A EP3418362A1 EP 3418362 A1 EP3418362 A1 EP 3418362A1 EP 18153658 A EP18153658 A EP 18153658A EP 3418362 A1 EP3418362 A1 EP 3418362A1
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EP
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Prior art keywords
acid
composition
hydrogen
composition according
alkyl
Prior art date
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EP18153658.2A
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English (en)
French (fr)
Inventor
Deepak Ahirwal
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of EP3418362A1 publication Critical patent/EP3418362A1/de
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    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • 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

Definitions

  • the present invention relates to acidic liquid compositions for cleaning a variety of hard surfaces such as hard surfaces found in around the house, such as bathrooms, toilets, garages, driveways, basements, gardens, kitchens, etc. More specifically, the thickened compositions of the present invention deliver good limescale removal performance (i.e., removal of pure limescale deposits and/or limescale-containing soils).
  • Acidic liquid compositions for cleaning limescale from hard-surfaces have been disclosed in the art.
  • Limescale deposits are formed due to the fact that tap water contains a certain amount of solubilised ions, which upon water evaporation eventually deposit as salts such as calcium carbonate on hard surfaces.
  • the visible limescale deposits result in an unaesthetic aspect of the surfaces.
  • the limescale formation and deposition phenomenon is even more acute in places where water is particularly hard.
  • limescale deposits are prone to combination with other types of soils, such as soap scum or grease, and can lead to the formation of limescale-soil mixture deposits (limescale-containing soils).
  • the removal of limescale deposits and limescale-containing soils is herein in general referred to as "limescale removal" or "removing limescale”.
  • a need remains for a thickened composition, which provides improved limescale removal efficacy, and improved limescale-soil deposit removal, for vertical and inclined surfaces, while also not inhibiting limescale removal for horizontal surfaces.
  • EP1509556 relates to thickened aqueous formulations containing cross-linked cationic polymers, novel homo- and copolymers their production and their use as thickeners for household formulations, especially for fabric softener applications.
  • EP0395282 relates to aqueous acidic solutions which are thickened by cationic polymer, the polymer being added to the solution in the form of particles below 10 micron in size.
  • WO2011/100405 relates to fabric and household hard surface treatment compositions comprising a mixture of cross-linked polyglycerol esters molecules each comprising at least two polyglycerol ester moieties, a non-crosslinker moiety; and a crosslinker moiety; and a carrier material.
  • WO 2013/0683 87 A1 relates to a thickener which can be obtained by inverse emulsion polymerization of at least one water-soluble ethylenically unsaturated monomer comprising at least one cationic monomer, at least one ethylenically unsaturated associative monomer, where the temperature is kept constant during the inverse emulsion polymerization and is at least 40°C, and the activator is added after the inverse emulsion polymerization in order to obtain the thickness.
  • WO2004/050815 A1 relates to aqueous compositions, preferably aqueous compositions comprising home- and/or copolymers.
  • WO99/06455 A1 relates to thickening agents for acidic aqueous compositions.
  • the present invention relates to a liquid acidic hard surface cleaning composition having a pH of from 0.1 to 6.5 and at least 0.5 wt% of organic acid, wherein the composition further comprises a thickener, the thickener comprising a cationic cross-linked thickening polymer, wherein the cationic cross-linked thickening polymer comprises monomers of: wherein: R 4 is hydrogen or methyl, preferably methyl; R 2 is hydrogen, or C 1 - C 4 alkyl, preferably hydrogen, R 3 is C 1 - C 4 alkyl, preferably C 2 alkyl; R 4 , R 5 , and R 6 are each independently chosen from hydrogen, or C 1 - C 4 alkyl, preferably C 1 - C 4 alkyl, more preferably methyl; X is chosen from -O-, or -NH-, preferably -O-; and Y is a halide, hydrogensulfate or methosulfate, preferably a halide, more preferably chloride;
  • compositions comprising the crosslinked thickening polymer, provide sufficient cling to deliver good limescale removal on vertical and inclined surfaces, while also providing improved limescale removal on horizontal surfaces.
  • essentially free of' a component means that no amount of that component is deliberately incorporated into the composition.
  • essentially free of' a component means that no amount of that component is present in the composition.
  • stable means that no visible phase separation is observed for a premix kept at 25°C for a period of at least two weeks, or at least four weeks, or greater than a month or greater than four months, as measured using the Floc Formation Test, described in USPA 2008/0263780 A1 .
  • component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.
  • the liquid acidic hard surface cleaning composition is the liquid acidic hard surface cleaning composition
  • compositions according to the present invention are designed as hard surfaces cleaners.
  • the compositions according to the present invention are liquid compositions (including gels) as opposed to a solid or a gas.
  • the liquid acidic hard surface cleaning compositions according to the present invention are preferably aqueous compositions. Therefore, they may comprise from 70% to 99% by weight of the total composition of water, preferably from 75% to 95% and more preferably from 80% to 95%.
  • the liquid compositions of the present invention are acidic. Therefore, they have a pH of less than 6.5.
  • the composition has a pH of from 1 to 6, more preferably from 2.0 to 2.5, still more preferably from 2.1 to 2.5, and most preferably from 2.1 to 2.4.
  • the pH of the cleaning compositions is measured at 25°C.
  • the compositions comprise an acid system.
  • the acid system may comprise any organic or inorganic acid well-known to those skilled in the art, or a mixture thereof.
  • the acid system comprises acids selected from the group consisting of: citric acid, formic acid, acetic acid, maleic acid, lactic acid, glycolic acid, succinic acid, glutaric acid, adipic acid, sulphamic acid, sulphuric acid, hydrochloric acid, phosphoric acid, nitric acid, methane sulphonic acid, oxalic acid and mixtures thereof, preferably acids selected from the group consisting of: citric acid, formic acid, acetic acid, lactic acid, phosphoric acid, oxalic acid and mixtures thereof.
  • the composition comprises an organic acid system, more preferably selected from the group consisting of: citric acid, formic acid, acetic acid, maleic acid, lactic acid, glycolic acid, succinic acid, glutaric acid, adipic acid, methane sulphonic acid, oxalic acid and mixtures thereof. More preferably, the organic acid system is selected from the group consisting of: citric acid, formic acid, oxalic acid, lactic acid and mixtures thereof.
  • the composition preferably comprises the organic acid system at a level of from 0.5 % to 15%, preferably from 0.5% to 10%, more preferably from 2% to 8%, most preferably from 4% to 7.5% by weight of the total composition.
  • the composition preferably comprises formic acid as part of the acid system.
  • the compositions of the present invention may comprise from 0.01% to 15%, preferably from 0.5% to 10%, more preferably from 1% to 8%, even more preferably from 1% to 6%, still more preferably 1% to 4%, yet more preferably 1% to 3%, yet still more preferably 2% to 3% by weight of the total composition of formic acid.
  • Lactic acid can be used as part of the acid system, especially where antimicrobial or disinfecting benefits are desired.
  • Such compositions may comprise up to 10% by weight of the total composition of lactic acid, preferably from 0.1% to 6%, more preferably from 0.2% to 4%, even more preferably from 0.2% to 3%, and most preferably from 0.5% to 2%.
  • compositions of the present invention may comprise from 0.1 to 30%, preferably from 2% to 20%, more preferably from 3% to 15%, most preferably from 3% to 10% by weight of the total composition of acetic acid.
  • compositions of the present invention may comprise from 0.1 to 5%, preferably from 0.1% to 3%, more preferably from 0.1% to 2%, most preferably from 0.5% to 2% by weight of the total composition of acetic acid.
  • compositions of the present invention may comprise from 0.1 to 30%, preferably from 1% to 20%, more preferably from 1.5% to 15%, most preferably from 2% to 10% by weight of the total composition of citric acid.
  • compositions herein can comprise an alkaline material.
  • the alkaline material may be present to trim the pH and/or maintain the pH of the compositions according to the present invention.
  • alkaline material are sodium hydroxide, potassium hydroxide and/or lithium hydroxide, and/or the alkali metal oxides such, as sodium and/or potassium oxide or mixtures thereof and/or monoethanolamine and/or triethanolamine.
  • suitable bases include ammonia, ammonium carbonate, choline base, etc.
  • source of alkalinity is sodium hydroxide or potassium hydroxide, preferably sodium hydroxide.
  • the amount of alkaline material is of from 0.001 % to 20 % by weight, preferably from 0.01 % to 10 % and more preferably from 0.05 % to 3 % by weight of the composition.
  • compositions herein would remain acidic compositions.
  • the liquid acidic hard surface cleaning compositions herein preferably have a viscosity of from 5 cps to 1000 cps at 10 s -1 , more preferably from 20 cps to 750 cps.
  • the viscosity is preferably from 50 cps to 500 cps and most preferably from 100 cps to 350 cps at 10 s -1 and 20°C.
  • the viscosity is preferably from 5 cps to 100 cps at 10 s -1 and 20°C. The viscosity is measured with a Rheometer, model AR 1000 (Supplied by TA Instruments) with a 4 cm conic spindle in stainless steal, 2° angle (linear increment from 0.1 to 100 sec -1 in max. 8 minutes).
  • the acidic cleaning composition comprises a thickener, wherein the thickener comprises a cationic cross-linked thickening polymer.
  • the cationic cross-linked thickening polymers comprises monomers of: wherein:
  • Cross-linking can be achieved using any suitable cross-linking agent, such as N,N'-methylenebis(acrylamide) (MBA), tetraallylammonium chloride (TAAC), pentaerythritol triacrylate (PETIA), and mixtures thereof. Tetraallylammonium chloride (TAAC), N,N'-methylenebis(acrylamide) (MBA), and combinations oftetraallylammonium chloride (TAAC) with N,N'-methylenebis(acrylamide) (MBA) are preferred.
  • the cross-linking agent is typically added at a level of from 50ppm to 1000 ppm, preferably from 300 ppm to 900 ppm.
  • the cationic cross-linked thickening polymer preferably has a molecular weight of at least 500,000 Daltons, preferably at least 1,000,000 Daltons, more preferably at least 2,000,000 Daltons.
  • the cationic cross-linked thickening polymer typically has a broad polydispersity which makes the upper limit to the molecular weight less relevant for the performance of the polymer.
  • Chain transfer agents can be used to increase the molecular weight of the cross-linked thickening polymer. Suitable chain transfer agents include mercaptanes, malic acid, lactic acid, formic add, isopropanol and hypophosphites, and mixtures thereof. Formic acid is preferred.
  • the chain transfer agent can be added at a level of from 100 ppm to 5,000 ppm, preferably from 2,000 ppm to 2,500 ppm.
  • the cationic cross-linked thickening polymer can comprise at least 30 mol%, preferably at least 60 mol%, more preferably at least 85 mol% of monomers according to formula I.
  • the resultant cationic cross-linked thickening polymer is a copolymer.
  • the cationic cross-linked thickening polymer is a copolymer where combinations of monomers of formula I and formula II are used, in addition to the cross-linking agent and chain transfer agent.
  • the monomers can be used in any suitable ratio.
  • the copolymer comprises combinations of monomers of formula I and formula II, the monomers are preferably present in a ratio of from 95:5 to 30:80, preferably from 90:10 to 60:40 of monomers of formula I to formula II.
  • the monomer of formula I is ethanaminium, N,N,N-trimethyl-2-((2-methyl-1-oxo-2-propenyl)oxy)-, chloride (CAS 26161-33-1), and the monomer of formula II is acrylamide (CAS 79-06-01) or methacrylamide (CAS 79-39-0).
  • Suitable cationic cross-linked thickening copolymers include Flosoft® FS222, supplied by SNF Floerger.
  • the cationic cross-linked thickening polymer can comprise exclusively monomers of formula I and formula II.
  • the cationic cross-linked thickening polymer may be prepared as water in oil emulsions, wherein the cross-linked polymers are dispersed in the oil, preferably a mineral oil.
  • the cationic cross-linked thickening polymer can be present at a level of from 0.01% to 5.0% by weight of the total composition of the cationic cross-linked thickener, preferably from 0.1% to 2.5%, more preferably from 0.2% to 1.5% and most preferably from 0.3% to 0.75%.
  • Comparative cationic cross-linked thickening polymers include a homopolymer where exclusively monomers of formula I are used, in addition to the cross-linking agent and chain transfer agent.
  • Such cationic cross-linked thickening homopolymers are derived from monomers of ethanaminium, N,N,N-trimethyl-2-((2-methyl-1-oxo-2-propenyl)oxy)-, chloride (CAS 26161-33-1).
  • Such comparative cationic cross-linked thickening homopolymers include Rheovis CDE, supplied by BASF.
  • compositions according to the present invention may comprise a variety of optional ingredients depending on the technical benefit aimed for and the surface treated.
  • Suitable optional ingredients for use herein include other acids, preferably acetic acid and/or lactic acid and/or citric acid, chelating agents, nonionic surfactants, vinylpyrrolidone homopolymer or copolymer, polysaccharide polymer, radical scavengers, perfumes, solvents, other surfactants, builders, buffers, bactericides, hydrotropes, colorants, stabilizers, bleaches, bleach activators, suds controlling agents like fatty acids, enzymes, soil suspenders, brighteners, anti dusting agents, dispersants, pigments, and dyes.
  • acids preferably acetic acid and/or lactic acid and/or citric acid
  • chelating agents nonionic surfactants, vinylpyrrolidone homopolymer or copolymer, polysaccharide polymer, radical scavengers, perfumes, solvents, other surfactants, builders, buffers, bactericides, hydrotropes, colorants, stabilizers, bleaches
  • compositions of the present invention preferably comprise a nonionic surfactant, or a mixture thereof.
  • This class of surfactants may be desired as it further contributes to cleaning performance of the hard surface cleaning compositions herein. It has been found in particular that nonionic surfactants strongly contribute in achieving highly improved performance on greasy soap scum removal.
  • compositions according to the present invention may comprise up to 15% by weight of the total composition of a nonionic surfactant or a mixture thereof, preferably from 0.1% to 10%, more preferably from 0.5% to 5%, even more preferably from 1.0% to 3% by weight of the total composition.
  • Suitable nonionic surfactants for use herein are alkoxylated alcohol nonionic surfactants, which can be readily made by condensation processes which are well-known in the art. However, a great variety of such alkoxylated alcohols, especially ethoxylated and/or propoxylated alcohols, is conveniently commercially available. Surfactants catalogs are available which list a number of surfactants, including nonionics.
  • preferred alkoxylated alcohols for use herein are nonionic surfactants according to the formula RO(E)e(P)pH where R is a hydrocarbon chain of from 2 to 24 carbon atoms, E is ethylene oxide and P is propylene oxide, and e and p which represent the average degree of, respectively ethoxylation and propoxylation, are of from 0 to 24 (with the sum of e + p being at least 1).
  • the hydrophobic moiety of the nonionic compound can be a primary or secondary, straight or branched alcohol having from 8 to 24 carbon atoms.
  • Preferred nonionic surfactants for use in the compositions according to the invention are the condensation product of ethylene and/or propylene oxide with an alcohol having a straight alkyl chain comprising from 6 to 22 carbon atoms, wherein the degree of ethoxylation/propoxylation is from 1 to 15, preferably from 5 to 12 or mixtures thereof.
  • Such suitable nonionic surfactants are commercially available from Shell, for instance, under the trade name Neodol® or from BASF under the trade name Lutensol®.
  • the compositions of the present invention may comprise a vinylpyrrolidone homopolymer or copolymer, or a mixture thereof.
  • the compositions of the present invention may comprise from 0.01% to 5% by weight of the total composition of a vinylpyrrolidone homopolymer or copolymer, or a mixture thereof, more preferably from 0.05% to 3% and most preferably from 0.05% to 1%.
  • Suitable vinylpyrrolidone homopolymers for use herein are homopolymers of N-vinylpyrrolidone having the following repeating monomer: wherein n (degree of polymerisation) is an integer of from 10 to 1,000,000, preferably from 20 to 100,000, and more preferably from 20 to 10,000.
  • suitable vinylpyrrolidone homopolymers for use herein have an average molecular weight of from 1,000 to 10,000,000, preferably from 5,000 to 1,000,000, and more preferably from 50,000 to 500,000.
  • Suitable vinylpyrrolidone homopolymers are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15® (viscosity molecular weight of 10,000), PVP K-30® (average molecular weight of 40,000), PVP K-60® (average molecular weight of 160,000), and PVP K-90® (average molecular weight of 360,000).
  • vinylpyrrolidone homopolymers which are commercially available from BASF Cooperation include Sokalan HP 165®, Sokalan HP 12®, Luviskol K30®, Luviskol K60®, Luviskol K80®, Luviskol K90®; vinylpyrrolidone homopolymers known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-256,696 ).
  • Suitable copolymers of vinylpyrrolidone for use herein include copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers or mixtures thereof.
  • the alkylenically unsaturated monomers of the copolymers herein include unsaturated dicarboxylic acids such as maleic acid, chloromaleic acid, fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid, aconitic acid, acrylic acid, N-vinylimidazole and vinyl acetate. Any of the anhydrides of the unsaturated acids may be employed, for example acrylate, methacrylate. Aromatic monomers like styrene, sulphonated styrene, alpha-methyl styrene, vinyl toluene, t-butyl styrene and similar well known monomers may be used.
  • N-vinylimidazole N-vinylpyrrolidone polymers for use herein have an average molecular weight range from 5,000 to 1,000,000, preferably from 5,000 to 500,000, and more preferably from 10,000 to 200,000.
  • the average molecular weight range was determined by light scattering as described in Barth H. G. and Mays J. W. Chemical Analysis Vol 113,"Modern Methods of Polymer Characterization ".
  • Such copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers like PVP/vinyl acetate copolymers are commercially available under the trade name Luviskol® series from BASF.
  • vinylpyrrolidone homopolymers are advantageously selected.
  • compositions of the present invention may comprise a chelating agent or mixtures thereof, as a preferred optional ingredient.
  • Chelating agents can be incorporated in the compositions herein in amounts ranging from 0% to 10% by weight of the total composition, preferably 0.01% to 5.0%, more preferably 0.05% to 1%.
  • Suitable phosphonate chelating agents to be used herein may include 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 chelating agents to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP).
  • DTPMP diethylene triamine penta methylene phosphonate
  • HEDP ethane 1-hydroxy diphosphonate
  • the chelating agent is selected to be ethane 1-hydroxy diphosphonate (HEDP).
  • HEDP ethane 1-hydroxy diphosphonate
  • 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 to be used herein include tetra sodium glutamate diacetate (GLDA), ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA), N- hydroxyethylethylenediamine triacetates, 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.
  • GLDA tetra sodium glutamate diacetate
  • DTPA diethylene triamine pentaacetate
  • N- hydroxyethylethylenediamine triacetates nitrilotri-acetates
  • 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® methyl glycine di-acetic acid (MGDA), tetra sodium glutamate diacetate (GLDA) which is, for instance, commercially available from AkzoNobel under the trade name Dissolvine® GL.
  • PDTA diethylene triamine penta acetic acid
  • MGDA Trilon FS® methyl glycine di-acetic acid
  • GLDA tetra sodium glutamate diacetate
  • carboxylate chelating agents to be used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.
  • a chelating agent preferably HEDP
  • compositions of the present invention may further comprise a solvent or a mixture thereof, as an optional ingredient.
  • Solvents to be used herein include all those known to those skilled in the art of hard-surfaces cleaner compositions.
  • the compositions herein comprise an alkoxylated glycol ether (such as n-Butoxy Propoxy Propanol (n-BPP)) or a mixture thereof.
  • compositions of the present invention may comprise from 0.1% to 5% by weight of the total composition of a solvent or mixtures thereof, preferably from 0.5% to 5% by weight of the total composition and more preferably from 1% to 3% by weight of the total composition.
  • compositions of the present invention may comprise an additional surfactant, or mixtures thereof, on top of the nonionic surfactant already described herein. Additional surfactants may be desired herein as they further contribute to the cleaning performance and/or shine benefit of the compositions of the present invention.
  • Surfactants to be used herein include anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. Accordingly, the compositions according to the present invention may comprise up to 15% by weight of the total composition of another surfactant or a mixture thereof, on top of the nonionic surfactant already described herein, more preferably from 0.5% to 5%, even more preferably from 0.5% to 3%, and most preferably from 0.5% to 2%.
  • Different surfactants may be used in the present invention including anionic, cationic, zwitterionic or amphoteric surfactants. It is also possible to use mixtures of such surfactants without departing from the spirit of the present invention.
  • Preferred surfactants for use herein are anionic and zwitterionic surfactants since they provide excellent grease soap scum cleaning ability to the compositions of the present invention.
  • Anionic surfactants may be included herein as they contribute to the cleaning benefits of the hard-surface cleaning compositions of the present invention. Indeed, the presence of an anionic surfactant contributes to the greasy soap scum cleaning of the compositions herein. More generally, the presence of an anionic surfactant in the liquid acidic compositions according to the present invention allows to lower the surface tension and to improve the wettability of the surfaces being treated with the liquid acidic compositions of the present invention. Furthermore, the anionic surfactant, or a mixture thereof, helps to solubilize the soils in the compositions of the present invention.
  • anionic surfactants for use herein are all those commonly known by those skilled in the art.
  • the anionic surfactants for use herein include alkyl sulphonates, alkyl aryl sulphonates, or mixtures thereof.
  • linear alkyl sulphonates include C8 sulphonate like Witconate® NAS 8 commercially available from Witco.
  • anionic surfactants useful herein include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, alkyl sulphates, alkyl aryl sulphates alkyl alkoxylated sulphates, C8-C24 olefinsulfonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkyl ester sulfonates such as C14-16 methyl ester sulfonates; acyl glycerol sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates, acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), alkyl polyethoxy carboxylates such as those of the formula RO(CH2CH2O)kCH2COO-M+ wherein R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation.
  • alkyl ester sulfonates such as C14-16 methyl ester sulfonates
  • 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.
  • Suitable zwitterionic surfactants for use herein contain both basic and acidic groups which form an inner salt giving both cationic and anionic hydrophilic groups on the same molecule at a relatively wide range of pH's.
  • the typical cationic group is a quaternary ammonium group, although other positively charged groups like phosphonium, imidazolium and sulfonium groups can be used.
  • the typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates, and the like can be used.
  • zwitterionic surfactants i.e. betaine/sulphobetaine
  • betaine/sulphobetaine Some common examples of zwitterionic surfactants (i.e. betaine/sulphobetaine) are described in U.S. Pat. Nos. 2,082,275 , 2,702,279 and 2,255,082 .
  • coconut dimethyl betaine is commercially available from Seppic under the trade name of Amonyl 265®.
  • Lauryl betaine is commercially available from Albright & Wilson under the trade name Empigen BB/L®.
  • a further example of betaine is Lauryl-immino-dipropionate commercially available from Rhodia under the trade name Mirataine H2C-HA®.
  • Particularly preferred zwitterionic surfactants for use in the compositions of the present invention are the sulfobetaine surfactants as they deliver optimum soap scum cleaning benefits.
  • sulfobetaine surfactants include tallow bis(hydroxyethyl) sulphobetaine, cocoamido propyl hydroxy sulphobetaines which are commercially available from Rhodia and Witco, under the trade name of Mirataine CBS® and Rewoteric AM CAS 15® respectively.
  • Amphoteric and ampholytic detergents which can be either cationic or anionic depending upon the pH of the system are represented by detergents such as dodecylbeta-alanine, N-alkyltaurines such as the one prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 2,658,072 , N-higher alkylaspartic acids such as those produced according to the teaching of U.S. Pat. No. 2,438,091 , and the products sold under the trade name "Miranol", and described in U.S. Pat. No. 2,528,378 . Additional synthetic detergents and listings of their commercial sources can be found in McCutcheon's Detergents and Emulsifiers, North American Ed. 1980.
  • Suitable amphoteric surfactants include the amine oxides.
  • amine oxides for use herein are for instance coconut dimethyl amine oxides, C12-C16 dimethyl amine oxides. Said amine oxides may be commercially available from Clariant, Stepan, and AKZO (under the trade name Aromox®).
  • Other suitable amphoteric surfactants for the purpose of the invention are the phosphine or sulfoxide surfactants.
  • Cationic surfactants suitable for use in compositions of the present invention are those having a long-chain hydrocarbyl group.
  • cationic surfactants include the quaternary ammonium surfactants such as alkyldimethylammonium halogenides.
  • Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044 , Cambre, issued October 14, 1980.
  • cross-linked thickening polymers described herein are particularly useful in acidic cleaning compositions for processes for providing improved limescale removal, and improved limescale-soil deposit removal, especially on horizontal surfaces.
  • Such processes can comprise the steps of: applying the liquid acidic hard surface cleaning composition onto said hard-surface or said object; leaving said composition on said hard-surface or said object to act; optionally wiping said hard-surface or object and/or providing mechanical agitation, and then rinsing said hard-surface or said object.
  • compositions according to the present invention are particularly suitable for treating hard-surfaces located in and around the house, such as in bathrooms, toilets, garages, on driveways, basements, gardens, kitchens, etc., and preferably in bathrooms. It is however known that such surfaces (especially bathroom surfaces) may be soiled by the so-called "limescale-containing soils".
  • limescale-containing soils it is meant herein any soil which contains not only limescale mineral deposits, such as calcium and/or magnesium carbonate, but also soap scum (e.g., calcium stearate) and other grease (e.g. body grease).
  • limescale deposits it is mean herein any pure limescale soil, i.e., any soil or stains composed essentially of mineral deposits, such as calcium and/or magnesium carbonate.
  • hard-surface any kind of surfaces typically found in and around houses like bathrooms, kitchens, basements and garages, 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, enamel, painted and un-painted concrete, plaster, bricks, vinyl, no-wax vinyl, linoleum, melamine, Formica®, glass, any plastics, metals, chromed surface and the like.
  • surfaces as used herein also include household appliances including, but not limited to, washing machines, automatic dryers, refrigerators, freezers, ovens, microwave ovens, dishwashers and so on.
  • Preferred hard surfaces cleaned with the liquid aqueous acidic hard surface cleaning composition herein are those located in a bathroom, in a toilet or in a kitchen, basements, garages as well as outdoor such as garden furniture, gardening equipments, driveways etc.
  • the objects herein are objects that are subjected to limescale formation thereon.
  • Such objects may be water-taps or parts thereof, water-valves, metal objects, objects made of stainless-steel, cutlery and the like.
  • the preferred process of cleaning a hard-surface or an object comprises the step of applying a composition according to the present invention onto said hard-surface or object, leaving said composition on said hard-surface or object to act, preferably for an effective amount of time, more preferably for a period comprised between 10 seconds and 10 minutes, most preferably for a period comprised between 15 seconds and 4 minutes; optionally wiping said hard-surface or object with an appropriate instrument, e.g. a sponge; and then preferably rinsing said surface with water.
  • a composition according to the present invention onto said hard-surface or object, leaving said composition on said hard-surface or object to act, preferably for an effective amount of time, more preferably for a period comprised between 10 seconds and 10 minutes, most preferably for a period comprised between 15 seconds and 4 minutes; optionally wiping said hard-surface or object with an appropriate instrument, e.g. a sponge; and then preferably rinsing said surface with water.
  • the processes described herein allow good removal of limescale- soap mixture depositions (such as greasy soap scum) with only moderate mechanical wiping and/or agitation action.
  • compositions of the present invention may be contacted to the surface or the object to be treated in its neat form or in its diluted form.
  • the composition is applied in its neat form.
  • diluted form it is meant herein that said composition is diluted by the user, typically with water.
  • the composition is diluted prior use to a typical dilution level of 10 to 400 times its weight of water, preferably from 10 to 200 and more preferably from 10 to 100.
  • Usual recommended dilution level is a 1.2% dilution of the composition in water.
  • compositions herein may be packaged in any suitable container, such as bottles, preferably plastic bottles, optionally equipped with an electrical or manual trigger spray-head.
  • the pH is measured on the neat composition, at 25°C, using a Sartarius PT-10P pH meter with gel-filled probe (such as the Toledo probe, part number 52 000 100), calibrated according to the instructions manual.
  • Limescale removal is measured using a gravimetric method quantifying the weight loss of a marble chip (calcium carbonate, 2.0 cm x 2.0 cm x 0.5 cm blocks of Carrara, supplied by Crombé Haachtsesteenweg 1465, 1130 Brussel) after immersion in the product.
  • the marble chip is thoroughly cleaned with demineralised water and put in a pre-heated oven (105°C) (WTC Binder Type Series M240 or IP20, temperature range 20-250°C. Precision ⁇ 0.75%) for 15 minutes.
  • the marble chip is then taken out of the oven and left for 15 minutes in a constant humidity cabinet at 25°C, 70% RH (Climatic Control Cabinet from HERAEUS Belgium Type HC0033 (3302)).
  • each marble chip is weighed (initial weight) using an analytical balance (precision ⁇ 0.1mg).
  • a plastic cup (Ava papierwaren, model nr. 2 CR) is filled with 20 grams of test product.
  • the marble chip is immersed in the cup for 5 minutes.
  • the marble chip is then taken out of the cup and rinsed thoroughly with demineralised water.
  • the chip is then dried in the oven at 105°C for 15 minutes and then transferred to the humidity cabinet for 15 minutes (25°C, 70%RH).
  • the marble chip is weighed (final weight).
  • the weight lost (final weight - initial weight) represents the limescale removed in mg of Calcium carbonate.
  • the test is repeated a total of 5 times and the result averaged.
  • the results are presented as an index vs the reference (index 100).
  • Example 1 is a composition of the present invention, comprising Rheovis CDE as the thickening polymer, while examples A to C are comparative compositions which comprised either chitosan, a linear cationic thickener, or Xanthan gum, an anionic thickener.
  • Nonionic surfactant sourced as Neodol® 91-8 from Shell.
  • Cationic cross-linked thickener of use in the present invention supplied by SNF Floerger
  • Cationic cross-linked thickener of use in the present invention supplied by BASF 4
  • Cationic linear thickener supplied by i-chess chemicals Pvt Ltd under the tradename Cee'san TH®
  • Kelzan T® is a Xanthan gum supplied by Kelco.
  • Polyvinylpyrrolidone sourced as PVP K-60 from Ashland Inc.
  • compositions comprising the cationic cross-linked thickener provide improved lime-scale removal, at similar viscosities, when compared to either non-cross-linked cationic thickener (chitosan) or Xantham gum (comparative examples A and B).
  • inventive compositions provide improved limescale removal even when compared to compositions comprising lower levels of Xanthan gum, having a much lower viscosity (comparative example C).
  • Flosoft® FS222 is a cationic cross-linked thickening polymer comprising monomers of formula I and formula II, with at least 85 mol% of monomer of formula I.
  • Rheovis® CDE is a cationic cross-linked thickening polymer which is a homopolymer of monomers of formula I.
  • compositions comprising cationic cross-linked thickening polymers comprising both monomers of formula I and formula II provide further improved limescale removal, even at higher viscosities.
  • Examples 3 to 11 are further examples of compositions of the present invention.
  • Formic acid, lactic acid and acetic acid are commercially available from Aldrich.

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US20220364018A1 (en) * 2021-05-14 2022-11-17 Ecolab Usa Inc. Neutralizing instrument reprocessing

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