MXPA06010861A - Liquid acidic hard surface cleaning composition - Google Patents

Abstract

The present invention describes liquid aqueous acidic cleaning compositions suitable for removing limescale, comprising an acid system, wherein said acid system comprises formic acid and an acid forming slightly water soluble calcium salts. The compositions of the present invention deliver excellent limescale removal performance as well as outstanding greasy soap scum cleaning on hard-surfaces.

Description

CLEANING COMPOSITION LIQUID AC1D1CA FOR HARD SURFACES TECHNICAL FIELD The present invention relates to liquid compositions for cleaning hard surfaces. More specifically, the compositions of the present invention provide improved performance for removing settling stains that can be found on a variety of surfaces such as bathrooms, toilets and kitchen surfaces.

BACKGROUND OF THE INVENTION Liquid compositions for cleaning hard surfaces have been described in the industry. Much attention on such compositions has focused on providing superior cleaning for a variety of soils and surfaces. Clearly, the tap water contains a certain amount of solubilized ions that after the evaporation of water eventually deposit as salts, such as calcium carbonate, on the hard surfaces that are often in contact with water, resulting in an anesthetic aspect of the surfaces. The formation of sedimentation and the deposition phenomenon is even more serious in places where the water is especially hard.

It is well known in the industry that sedimentation deposits can be chemically removed with acidic solutions. However, it has been found that the compositions provided in the industry are not completely satisfactory from the point of view of the consumer, especially regarding the scale release properties achieved when applying the cleaning composition on the surface to be treated, it allows to act on said surface without any other mechanical cleaning and / or stirring action and then it is eliminated by rinsing. Therefore, the object of the present invention is to provide a composition suitable for removing tartar from hard surfaces or from an object, exhibiting a superior scale cleaning performance, especially when the cleaning composition is applied on a hard surface or object. , it is allowed to act on said hard surface or object and then it is eliminated by rinsing (that is, under soaking conditions). It has been found that the above objective is met by formulating an aqueous acidic liquid composition suitable for removing scale, comprising an acid system, wherein said acidic system comprises formic acid and an acid forming calcium salts slightly soluble in water. In addition, the compositions according to the present invention are advantageously less complex than tartar cleaning compositions described in the industry and therefore practically more economical in their formulation while providing superior performance for removing tartar.

It is another advantage of the present invention to provide acidic cleaning compositions which are safe for consumers and do not damage the treated surface, especially delicate surfaces such as linoleum, glass, plastic, laminated wood, metal or varnished surfaces. More advantages and more specific properties of the compositions of the present invention will become apparent after reading the following description of the invention. U.S. Pat. no. No. 4,587,030 discloses an acidic cleaning composition comprising a mixture of weak inorganic acid (eg, phosphoric or sulfamic acid) and a weak organic acid, a surfactant system comprising a major proportion of a cationic amine oxide surfactant and a cosolvent. U.S. Pat. no. 6,121, 219 describes a cleaning composition suitable for removing carbohydrate and protein soils, the composition comprising phosphoric acid, an organic carboxylic acid, a specific solvent, a phosphonate sequestering agent and a quaternary amine composition. U.S. Pat. no. No. 5,935,921 discloses a scale cleaning composition comprising phosphoric acid, a trialkyl amine phosphonic acid, an amine oxide, a cationic surfactant and an alkanol.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to an aqueous acidic liquid composition for removing scale, comprising an acid system, wherein the acid system comprises formic acid and an acid forming calcium salts slightly soluble in water. The present invention also includes a process for removing scale from hard surfaces or objects, comprising the step of applying a composition as described above on the hard surface or object, allowing the composition to act on the hard surface or object, optionally passing a Wipe over the hard surface or object and then rinse the composition. In another aspect, the present invention relates to the use, in a composition suitable for removing tartar from a hard surface or an object, from a combination of formic acid and an acid forming calcium salts slightly soluble in water, to improve the scale cleaning performance of said composition.

DETAILED DESCRIPTION OF THE INVENTION Liquid Cleaning Composition for Hard Surfaces The compositions in accordance with the present invention are designed as hard surface cleaners; the preferred hard surfaces treated with them are those located in bathrooms and kitchens. The liquid compositions according to the present invention are aqueous compositions. Therefore, in general they comprise 70% to 99% by weight of the total water composition, preferably from 75% to 95% and more preferably from 80% to 95%. Acid The compositions of the present invention are acidic. Therefore, in general they have a pH below 7, preferably from 0 to 6, more preferably from 0.1 to 5, with a greater preference from 0.5 to 4.5. The compositions according to the present invention comprise an acid system, wherein the acid system comprises formic acid and an acid which forms calcium salts slightly soluble in water. By "calcium salts slightly soluble in water", it is to be understood herein any calcium sai having a solubility in water of 2.5% w / w and lower, in distilled water at 20 ° C. In a preferred embodiment, the compositions of the present invention comprise an acid that forms calcium salts practically insoluble in water, more preferably an acid that forms water-insoluble calcium salts. By "calcium salts practically insoluble in water", it should be understood herein any calcium salt having a solubility in water of 0.5% w / w and lower, in distilled water at 20 ° C. By "water-insoluble calcium salts", it is to be understood herein as any calcium salt having a solubility in water of 0.001% w / w and lower, in distilled water at 20 ° C. In the context of the present invention, the compositions comprise an acid which forms calcium salts which, in general, can have a solubility in water of up to 2.5% w / w, preferably up to 0.5% w / w, more preferably up to 0.001% w / w, in distilled water at 20 ° C. In general, the acid forming calcium salts slightly soluble in water to be used herein may be an inorganic acid, or an organic acid or a mixture thereof. Preferably, the inorganic acids for use herein have the first pK less than 3. Inorganic acids suitable for use herein are those selected from phosphoric acid, sulfuric acid and mixtures thereof. In a preferred embodiment of the present invention, phosphoric acid is selected as the acid that forms water-soluble calcium salts. Preferably, the organic acids for use herein have a pKa not exceeding 5. A typical organic acid that can be used herein is oxalic acid.

Therefore, typical examples of slightly water soluble calcium salts that can be formed in the context of the present invention are calcium monobasic orthophosphate Ca (H2PO4) 2 (solubility of about 1.8% w / w in distilled water at 30 ° C. ), calcium dibasic orthophosphate CaHP04 (solubility of approximately 0.0316% w / w in distilled water at 38 ° C), tribasic calcium orthophosphate Ca3 (P04) 2 (solubility approximately 0.002% w / w in distilled water at 20 ° C) , CaS04 calcium sulfate (approximate solubility of 0.209% w / w in distilled water at 30 ° C), calcium sulfate hydrate medium CaS04. H20 (approximate solubility of 0.3% w / w in distilled water at 20 ° C), calcium sulfate dihydrate CaSO4.2H2O (approximate solubility of 0.241% w / w in distilled water at 20 ° C), and calcium oxalate CaC2O4 (approximate solubility of 0.0067% w / w in distilled water at 13 ° C). However, for the purpose of the present invention, it is sufficient that at least one of the calcium salts mentioned above be formed. In a highly preferred embodiment of the present invention, the acid system comprises a combination of phosphoric acid and formic acid. The phosphoric acid can be purchased from J.T. Baker, while formic acid is commercially available from Fluka. The amount of acid herein may vary depending on the amount of other ingredients; however, suitable amounts of the acid system in the compositions of the present invention are generally comprised between 1.1% to 25.1% by weight of the total composition, preferably from 8% to 20% and more preferably from 10% to 17% . The compositions of the present invention may comprise from 0.1% to 3% by weight of the total formic acid composition, preferably from 0.5% to 2%, more preferably from 1% to 2%, with a greater preference of 1.5% to 2%. In addition, the compositions of the present invention may comprise from 1% to 25% by weight of the total composition of an acid forming calcium salts slightly soluble in water, or mixtures thereof, preferably from 5% to 20%, with more preference of 10% to 17%, with a greater preference of 10% to 15%. It has been unexpectedly discovered that aqueous acidic liquid compositions comprising an acid system, wherein said acidic system comprises formic acid and an acid that forms calcium salts slightly soluble in water, provide a better scale cleaning performance, compared to the yield of cleaning obtained with the same compositions but without formic acid. This better unexpected cleaning performance is especially superior under the so-called soaking conditions, that is, when no more mechanical actions are carried out to pass a rag and / or agitation. Without wishing to be bound by theory, it is believed that formic acid participates in the reduction of the precipitation of the slightly soluble calcium salts that can be formed as a result of the interaction between the calcium carbonate containing material and a cleaning composition containing acid. In the case of a cleaning composition comprising an acid system wherein the acid forming the slightly soluble calcium salts is phosphoric acid, it is likely that the CaHP04 salt forms. It has now been discovered that the formation of CaHP04 or other calcium salts slightly soluble in water is especially improved when the cleaning composition is used under soaking conditions. Under these conditions, the slightly soluble calcium salts mentioned above can even be added and form a crystalline shield on the tartar stain and then prevent the phosphoric acid from proceeding with its acidic action. It has been unexpectedly discovered that the presence of formic acid helps to reduce the formation of the CaHP04 salt through the action of protonation and through the purification of the free Ca2 calcium cation. An advantage more associated with the use of formic arises from its high effectiveness in weight due to its low molecular weight. However, due to environmental and / or consumer safety laws in some countries, the use of large amounts of formic acid, such as more than 3%, in cleaning products for hard surfaces would not be acceptable. Therefore, the use of formic acid as the only acid is not feasible since the required levels of formic acid needed to achieve a good scale removal performance would not be tolerated by the aforementioned laws.

Optional ingredients The compositions according to the present invention may comprise a variety of optional ingredients depending on the desired technical benefit and the treated surface. Optional ingredients suitable for use herein include chelating agents, non-ionic surfactants, vinylpyrrolidone homopolymer or copolymer, polysaccharide polymer, radical scavenger, perfumes, solvents, other surfactants, additives, buffers, bactericides, hydrotropes, dyes, stabilizers, bleaches, bleach activators, foam controlling agents such as fatty acids, enzymes, dirt suspending agents, dye transfer agents, brighteners, anti-soil agents, dispersants, dye transfer inhibitors, pigments, caustics, dyes. Chelating agent The compositions of the present invention may further comprise a chelating agent or mixtures thereof, as a highly preferred optional ingredient. The chelating agents can be incorporated into the composition herein in amounts ranging from 0% to 10% by weight of the total composition, preferably from 0.01% to 5.0%, more preferably from 0.05% to 1%. Phosphonate chelating agents suitable for use herein may include ethane alkali metal 1-hydroxydiphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as aminophosphonate compounds including amino aminotri (methylene phosphonic acid) (ATMP) , nitrile trimethylenephosphonates (NTP), ethylenediamine tetramethylene phosphonates and diethylenetriamine pentamethylene phosphonates (DTPMP). The phosphonate compounds may be present, either in their acid form or as salts of different cations, in some or all of their acid functional groups. Preferred chelating agents to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP). In a particularly preferred embodiment of the present invention, the selected chelating agent is ethane 1-hydroxyl diphosphonate (HEDP). These phosphonate chelating agents are commercially available from Monsanto under the trade designation DEQUEST®. In the compositions herein also aromatic chelating agents with polyfunctional substitutions may be useful. See US Pat. no. 3,812,044 issued to Connor et al. on May 21, 1974. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelating agent to be used herein is ethylene diamine-N'-disuccinic acid or the alkali metal, alkaline earth, ammonium salts or salts of ammonium substitutes thereof or mixtures thereof. Ethylenediamine-N, N'-disuccinic acids, especially the (S, S) isomer, have been extensively described in U.S. Pat. no. 4,704,233 by Hartman and Perkins of November 3, 1987. Ethylenediamine-N, N'-disuccinic acid is, for example, commercially available under the tradename ssEDDSO from Palmer Research Laboratories.

Suitable aminocarboxylates for use herein include ethylenediamine tetraacetates, diethylenetriamine pentaacetates, diethylenetriamine pentaacetate (DTPA), N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetraaminehexaacetates, ethanoldiglicines, propylenediaminetetraacetic acid (PDTA), and methylglycine acid. diacetic (MGDA), both in their acid form or in the form of alkali metal, ammonium and substituted ammonium salts. Particularly suitable aminocarboxylates for use herein are diethylenetriaminepentaacetic acid, propylenediaminetetraacetic acid (PDTA) which, for example, is commercially available from BASF under the trade name Trilon FS® and methylyglycinateacetic acid (MGDA). Some additional carboxylate chelating agents to be used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures of these. It has been unexpectedly discovered that the addition of a chelating agent such as HEDP to the composition of the present invention provides an unexpected improvement in terms of scale removal. In the context of the present invention, it has been discovered that the HEDP further reduces the precipitation of the slightly soluble calcium salts, by debugging the Ca2 + calcium cation. In that sense, HEDP and formic acid work in a similar way when it comes to improving the performance of scale removal. As a consequence, acidic compositions with lower formic acid content can be advantageously formulated when HEDP is included in the corresponding compositions. Without wishing to be bound by theory, it is further believed that a high synergistic effect is achieved in terms of scale removal performance, when a chelating agent such as those described above is combined with an acid which forms slightly soluble calcium salts, especially the phosphoric acid. Nonionic Surfactant The compositions of the present invention may preferably comprise a nonionic surfactant or a mixture thereof. Such a class of surfactants may be desirable as they contribute to the cleaning performance of the hard surface cleaning compositions herein. It has been found in particular that non-ionic surfactants contribute greatly to achieving a better grease soap foam removal performance. The compositions according to the present invention can comprise up to 15% by weight of the total composition of a nonionic surfactant or a mixture thereof, preferably from 0.1% to 15%, more preferably from 1% to 10%, even more preferably from 1% to 5% and with a greater preference from 1% to 3%. Nonionic surfactants suitable for use herein are non-ionic alkoxylated alcohol surfactants which can be readily made by condensation processes that are well known in the industry. However, a wide variety of said alkoxylated alcohols, especially ethoxylated and / or propoxylated alcohols are also conveniently available commercially. Surfactant catalogs are available that list a number of surfactants, including nonionics. Accordingly, the preferred alkoxylated alcohols for the present invention are the nonionic surfactants according to the formula RO (E) and (P) pH wherein R is a hydrocarbon chain of 2 to 24 carbon atoms, E is ethylene oxide and P is propylene oxide and yeyp, which represent the average degree of ethoxylation and propoxylation respectively, are from 0 to 24. The hydrophobic region of the nonionic compound can be a primary or secondary, linear or branched alcohol of 8 to 24 carbon atoms. Preferred nonionic surfactants for use in the compositions according to the invention are the condensation products of ethylene oxide with alcohols having a right alkyl chain, having from 6 to 22 carbon atoms, wherein the degree of ethoxylation is Suitable from 1 to 15, preferably from 5 to 12. Suitable nonionic surfactants are commercially available from Shell, for example under the tradename Dobanol® or from BASF under the tradename Lutensol®. Vinylpyrrolidone Homopolymer or Copolymer The compositions of the present invention may, optionally, comprise a vinylpyrrolidone homopolymer or copolymer, or a mixture thereof. In general, 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 with a greater preference from 0.05% to 1%. The vinylpyrrolidone homopolymers suitable for use herein are N-vinylpyrrolidone homopolymers having the following repeating monomer: wherein n (degree of polymerization) is an integer from 10 to 1,000,000, preferably from 20 to 100,000 and more preferably from 20 to 10,000. Accordingly, the vinylpyrrolidone homopolymers ("PVP") suitable for use herein have an average molecular weight of from 1,000 to 100,000,000, preferably from 2,000 to 10,000,000, more preferably from 5,000 to 1,000,000, and with greater preference 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 10,000), PVP K-30® (molecular weight) average of 40,000), PVP K-60® (average molecular weight of 160,000), and PVP K-90® (average molecular weight of 360,000). Other suitable vinylpyrrolidone homopolymers that 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 with experience in the field of detergents (see for example EP-A-262,897 and EP-A-256,696). Vinylpyrrolidone copolymers suitable for use herein include copolymers of N-vinyl pyrrolidone and unsaturated monomers of alkano-nials or mixtures thereof. The unsaturated alkylene 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 can be used, for example acrylate, methacrylate. Aromatic monomers such as styrene, sulfonated styrene, alpha methylstyrene, vinyltoluene, t-butyl styrene and well-known monomers can be used. For example, polymers of N-vinylimidazole N-vinylpyrrolidone especially suitable for use herein have an average molecular weight in the range of 5,000 to 1,000,000, preferably 5,000 to 500,000 and more preferably 10,000 to 200,000. The range of the average molecular weight was determined by light scattering as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113, "Modern Methods of Polymer Characterization".

Said copolymers of N-vinyl pyrrolidone and unsaturated alkylene monomers such as PVP / vinylacetate copolymers are commercially available under the tradename of BASF's Luviskol® series. In accordance with a highly preferred embodiment of the present invention, the vinylpyrrolidone homopolymers are advantageously selected. Polysaccharide Polymer The compositions of the present invention may, optionally, comprise a polysaccharide polymer or a mixture thereof. In general, the compositions of the present invention may comprise from 0.01% to 5% by weight of the total composition of a polysaccharide polymer or a mixture thereof, more preferably from 0.05% to 3% and most preferably 0.05. % to 1%. Polysaccharide polymers suitable for use herein include substituted cellulose materials such as carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, succinoglycan and polymers of natural polysaccharides such as xanthan gum, guar gum, locust bean gum, tragacanth gum or derivatives thereof, or mixtures of these. Especially polysaccharide polymers for use herein are xanthan gum and derivatives thereof. Xanthan gum and its derivatives may be commercially available, for example, by Kelco under the tradename Keltrol RD®, Kelzan S® or Kelzan T®. Another suitable xanthan gum is commercially available from Rhone-Poulenc under the tradename Rhodopol T® and Rhodigel X747®. The succinoglycan gum to be used herein is commercially available from Rhone-Poulenc under the trade name Rheozan®. Without intending to be limited by theoryit has been demonstrated that the homopolymers or copolymers of vinylpyrrolidone, preferably the homopolymer of vinylpyrrolidone and the polymers of polysaccharides, preferably the xanthan gum or derivatives thereof, described herein, when added to an aqueous acidic composition provide a better shine to the treated surface, as well as a better benefit for the next cleaning of said surface, while providing a good cleaning performance for the first time on hard surfaces and a good performance of scale removal. In addition, the formation of water marks and / or tartar deposits when it dries is reduced or even eliminated. Moreover, vinylpyrrolidone homopolymers or copolymers and polysaccharide polymers provide long-lasting protection against the formation of watermarks and / or tartar sediment deposits, thus achieving long-lasting gloss surfaces. An additional advantage related to the use of vinylpyrrolidone homopolymers or copolymers and polysaccharide polymers, in the acidic compositions herein, is that by adhering to the hard surface it makes it more hydrophilic, the surfaces themselves become softer (this it can be perceived touching those surfaces) and this contributes to providing a perception of a surface perfectly without scale.

Advantageously, these benefits are obtained at low levels of vinylpyrrolidone homopolymers or copolymers and polysaccharide polymers, preferably xanthan gum or derivatives thereof, described herein, therefore it is another advantage of the present invention to provide the benefits desired at a low cost. Radical scavenger The compositions of the present invention may also comprise a radical scavenger or a mixture thereof. Radical scavengers suitable for use herein include the well-known mono-substituted dihydroxybenzenes and their analogs, the alkyl and aryl carboxyiates, and mixtures thereof. Preferred radical scavengers for use herein include di-tert-butyl hydroxytoluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone, tert-butyl-hydroxyanisole, benzoic acid, toluic acid, catechol, t-butyl catechol, benzylamine, 1, 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl gallate or mixtures thereof and highly preferred is di-tert-butyl hydroxytoluene. These radical scavengers such as N-propyl gallate can be commercially available from Ñipa Laboratories under the trade name Nipanox S1®. When radical scavengers are used, in general they may be present in amounts up to 10% by weight of the total composition and preferably from 0.001% to 0.5% by weight. The presence of radical scavengers can contribute to the chemical stability of the compositions of the present invention. Perfume The perfume compositions and compositions suitable for use herein are, for example, those described in EP-A-0957156 in the paragraph entitled "Perfume" on page 13. In a highly preferred embodiment of the present invention, the The compositions comprise a perfume composition advantageously selected from the group comprising floral acetate, eucalyptol and mixtures thereof. The compositions herein may comprise a perfume ingredient, or mixtures thereof, in amounts of up to 5.0% by weight of the total composition, preferably in amounts of 0.1% to 1.5%. Solvent The compositions of the present invention may further comprise a solvent or a mixture thereof, as an optional ingredient. The solvents to be used herein include all those known to those with knowledge in the hard surface cleaning compositions industry. In general, the 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.

Additional Surfactant The compositions of the present invention may comprise an additional surfactant, or mixtures thereof, in addition to the nonionic surfactant already described herein. Additional surfactants may be desired herein since they further contribute to the cleaning performance and / or gloss benefit of the compositions of the present invention. The 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 can comprise up to 15% by weight of the total composition of another surfactant or a mixture thereof, in addition to the anionic surfactant already described herein, more preferably from 0.5% to 5% , even more preferably from 0.5% to 3% and with a greater preference 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 these surfactants without departing from the spirit of the present invention. Preferred surfactants for use herein are anionic and zwitterionic surfactants, since they provide a cleaning capacity of fatty soap scum to the compositions of the present invention. Anionic surfactants may be included herein since they contribute to the cleaning benefits of the hard surface cleaning compositions of the present invention. Clearly, the presence of an anionic surfactant contributes to the cleansing of fatty soap scum of the compositions herein. More generally, the presence of an anionic surfactant in the liquid acidic compositions according to the present invention allows to decrease the surface tension and improve the wettability of the surfaces treated with the acidic liquid compositions of the present invention. In addition, the anionic surfactant, or a mixture thereof, helps to solubilize the dirt in the compositions of the present invention. The anionic surfactants suitable for use herein are all commonly known to those of ordinary skill in the industry. Preferably, the anionic surfactants for use herein include alkylsulfonates, alkylarylsulfonates, or mixtures thereof. Particularly suitable linear alkylsulfonates include C12-C16 paraffin sulphonates such as Hostapur ® SAS commercially available from Hoechst. Other anionic surfactants useful in the present include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C8-C24 sulfonates of olefin, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of citrates of alkaline earth metal, p. eg, as described in British patent specification no. 1, 082, 179; alkyl ester sulfonates such as C14_16 methyl ester sulfonates; acyl glycerol sulfonates, alkyl phosphates, isethionates such as acyl isethionate, N-acyl taurate, alkyl succinamates, acyl sarcosinates, alkyl polysaccharide sulfates such as alkyl polyglucoside (the non-sulfonated nonionic compounds described below), alkyl polyethoxy carboxylates such as those with the formula RO (CH2CH20) 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. Also suitable are resin acids and hydrogenated resin acids such as turpentine, hydrogenated turpentine and resin acids and hydrogenated resin acids present in or derived from the resin oil. Other examples are described in Surface Active Agents and Detergents (Vol. I and II of Schwartz, Perry and Berch). A variety of these surfactants is also described in general terms in U.S. Pat. no. 3,929,678, issued to Laughiin et al. on December 30, 1975, from column 23, line 58 to column 29, line 23. Zwitterionic surfactants suitable for use herein contain basic and acidic groups that form an internal salt that yields both cationic and anionic hydrophilic groups in the same molecule with a relatively broad pH range. The typical cationic group is a quaternary ammonium group, although other positively charged groups such as the phosphonium, imidazolium and sulfonium groups can be used. Typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups such as sulfates, phosphonates and the like can be used. Some common examples of zwitterionic surfactants (ie, betaine / sulfobetaine) are described in U.S. Pat. num. 2,082,275; 2,702,279; and 2,255,082 which are incorporated by reference herein.

Some examples of suitable alkyldimethyl betaines include coco-dimethyl betaine, lauryldimethyl betaine, decyl dimethyl betaine, 2- (N-decyl-N, N-dimethyl-ammonia) acetate, 2- (N-coco N, N-) acetate. dimethylammonium), myristyldimethyl betaine, palmityldimethyl betaine, cetyldimethyl betaine and stearyldimethyl betaine. For example, coconut dimethyl betaine is available in the market by Seppic with the commercial name of Amonyl 265®. Laurylbetaine is available in the market by Albright & Wilson with the commercial name of Empigen BB / L®. Another example of betaine is lauryliminopropionate available commercially by Rhone Poulenc under the trade name Mirataine H2C-HA®. Especially preferred zwitterionic surfactants for use in the compositions of the present invention are the unique sulfobeta surfactants as they provide an optimum soap scum cleaning benefit. Examples of suitable sulfobetaine surfactants include tallow bis (hydroxyethyl) sulfobetaine, cocoamidopropyl hydroxy sulfobetaines which are commercially available from Rhone Poulenc and Witco, under the tradename Mirataine CBS® and Rewoteric AM CAS 15® respectively. Suitable amines for use herein are for example C12 dimethylamine, coconut dimethylamine, C12-C16 dimethylamine. Said amines may be commercially available by Hoechst under the trade name of Genamin®, AKZO under the trade name of Aromox® or Fina under the trade name of Radiamine®.

Suitable quaternary ammonium surfactants for use herein according to the formula R1R2R3R4N + X ", wherein X is a counter-ion such as a halogen, methyl sulfate, methyl sulfonate, or hydroxide, R1 is a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group containing from 1 to 30 carbon atoms, preferably from 12 to 20, more preferably from 8 at 20 and R2, R3 and R4 are independently hydrogen, or saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl groups containing from 1 to 4 carbon atoms, preferably from 1 to 3 and more preferably methyl. In highly preferred quaternary ammonium surfactants in this disclosure, R1 is a C10-C18 hydrocarbon chain, with a higher preference C12, C14, or C16, and R2, R3, and R4 are three methyl, and X is a halogen, preferably bromide or chloride, with a greater preference bromide. Amphoteric and ampholytic detergents, which may be cationic or anionic depending on the pH of the systems, are represented by detergents such as dodecylbeta-alanine, N-alkyltaurines such as that which is prepared by reacting dodecylamine with sodium isethionate in accordance with what teaches the US patent no. 2,658,072; the higher N-alkylaspartic acids, produced in accordance with the teachings 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, patents that are incorporated herein by reference. Additional synthetic detergents and the list of their commercial sources can be found in McCutcheon's Detergents and Emulsifiers, North American Ed. 1980, incorporated herein by reference. Suitable amphoteric surfactants include amine oxides. Examples of amine oxides for use herein are, therefore, coconut dimethylamine oxides, C12-C16 dimethylamine oxides. Said amine oxides may be available commercially by Hoechst, Stephan, AKZO (under the trade name of Aromox®) or FINA (under the trade name of Radiamox®). Other amphoteric surfactants suitable for the purpose of the invention are phosphine or sulfoxide surfactants. Suitable cationic surfactants for use in the compositions of the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants such as alkyldimethylammonium halogenides. Other cationic surfactants useful herein are also described in U.S. Pat. no. 4,228,044 to Cambre, issued October 14, 1980, incorporated herein by reference. Colorant The liquid compositions according to the present invention can be colored. Accordingly, they may comprise a dye or a mixture thereof. The dyes suitable for use herein are acid stable dyes. By "acid-stable", it is to be understood a compound that is chemically and physically stable in the acidic environment of the compositions herein.

Caustic Product In order to maintain the pH of the composition described herein, the composition may also comprise a caustic product or a mixture thereof, as an optional ingredient. The caustic product to be used herein includes all those known to those having knowledge in the industry of hard surface cleaning compositions, such as metal hydroxides, ammonia, and the like. A preferred caustic product is NaOH. The process of removing scale from a hard surface or an object The present invention also includes a process for removing scale from a hard surface or an object comprising a step of applying a composition as described above on the hard surface or object. By "hard surface", it should be understood in the present any type of surface that is generally found in houses such as bathrooms, kitchens, or inside or outside of the cars, p. eg, floors, walls, tiles, windows, sinks, showers, plasticized curtains for showers, toilets, toilets, crockery, accessories and the like made of different materials such as ceramics, vinyl, vinyl without wax, linoleum, melamine, glass, any plastic, laminated wood, metal or any painted surface, varnished or sealed and the like. The term "surfaces" as used herein also includes appliances that include, but are not limited to, washing machines, automatic dryers, refrigerators, freezers, ovens, microwave ovens, dishwashers, etc. The objects of the present are objects that are subject to tartar formation on them. These objects can be water taps or parts of them, water valves, cutlery and the like. Although the compositions of the present invention may comprise inorganic acids such as phosphoric acid, it has been unexpectedly discovered that a wide range of surfaces or objects, including surfaces or metal objects, such as aluminum, chrome steel or stainless steel, can be treated with the compositions mentioned above without damaging or corroding said surfaces. Preferred processes for removing tartar from a hard surface or from an object comprises the step of applying a composition according to the present invention on said hard surface or object, allowing said composition to act on said hard surface or object, preferably by a effective amount of time, more preferably for a period between 1 and 10 minutes, with a greater preference for a period between 2 and 4 minutes; optionally passing a cloth over said hard surface or object with an appropriate instrument, e.g. ex. a sponge; and then preferably rinsing said surface with water. Unexpectedly, the process of the present invention allows to achieve a better scale removal performance without any mechanical cleaning action and / or additional agitation. This particular convenience will obviously be much appreciated by consumers as it provides a great time saving for the user.

In another embodiment of the present invention there is provided a process for removing scale from an object comprising a step of immersing said object in a bath comprising a composition in accordance with the present invention, leaving said object in said bath for the purpose of composition act, preferably for an effective amount of time, more preferably for a period comprised between 1 and 10 minutes, with a greater preference for a period comprised between 2 and 4 minutes; and then preferably rinsing said object with water. In another aspect, the present invention relates to the use, in a composition suitable for removing tartar from a hard surface or an object, from a combination of formic acid and an acid forming calcium salts slightly soluble in water, for improve the scale cleaning performance of said composition. In another preferred modality, the present invention is directed to the use described above, where the improvement of the cleaning performance of tartar is achieved when said composition is applied on said hard surface or object, said composition is allowed to act on said hard surface or object and then said surface hard or object is rinsed. According to yet another embodiment, the present invention relates to the use, in a composition suitable for removing tartar from a hard surface or an object, of a combination of formic acid and an acid forming calcium salts slightly soluble in water. water, to reduce the formation of said slightly soluble calcium salts on said hard surface or object.

The compositions of the present invention can be brought into contact with the surface or object to be treated in its pure form or its diluted form. Preferably, the composition is applied in its pure form. By "diluted form", it is to be understood herein that the user dilutes said composition, generally with water. The composition is diluted before use at a general dilution level of 10 to 400 times its weight of water, preferably 10 to 200 and more preferably 10 to 100. The usual recommended dilution level is a dilution of 1.2. % of the composition in water. The compositions according to the present invention are especially suitable for treating hard surfaces located in bathrooms or kitchens and preferably in bathrooms. However, it is commonly known that bath surfaces may be soiled with so-called "tartar-containing spots". "Stain containing tartar" is understood herein as any stain of pure scale, that is, any stain composed practically of mineral deposits, as well as other stains that contain not only mineral deposits such as calcium carbonate and / or magnesium, but also soap scum (eg, calcium stearate) and other fat (eg body fat). Accordingly, it has been unexpectedly discovered that when the compositions of the present invention also comprise a surfactant, preferably a nonionic surfactant, those compositions allow to achieve a superior cleaning performance on different tartar containing spots comprising not only pure scale deposits. , but also at least 10% by weight of the total stain of organic deposits such as soap and grease foam, preferably more than 30%. Tartar removal performance test method: The ability to remove tartar from the composition according to the present invention can be evaluated by dipping a block of marble (the marble blocks are, chemically speaking, very similar to tartar, i.e. they are practically formed by calcium carbonate) in 20 g of this composition. The marble is weighed before and after the experiment and the yield is expressed in the grams of the marble block dissolved in time. Consequently, the tartar removal performance can also be evaluated by detecting the release of C02. Fatty soap cleaning performance test method: In this test method, white enamel tiles (generally 24 cm x 4 cm) are covered with fatty soap scum dirt, mainly based on calcium stearate and artificial body dirt available on the market (eg 0.3 grams with a sprayer). The dirty tiles are dried in an oven at a temperature of 140 ° C for 20 minutes and then aged overnight at room temperature (between 20 ° C-25 ° C). Then the dirty tiles are cleaned using 3 mL of the composition of the present invention placed directly on a Spontex® sponge. The ability of the composition to remove fatty soap scum is measured by the amount of passes necessary to perfectly clean the surface. The lower the amount of passes, the greater the cleaning capacity of the soapy foam of the composition.

EXAMPLES The following compositions were made comprising the ingredients listed in the proportions mentioned (weight%). The examples herein are used to exemplify the present invention, but are not used to limit or otherwise define the scope of the present invention. Compositions I and VI are compositions in accordance with the present invention, while Composition VII is a comparative example.

The pH of these examples is below 7. The phosphoric acid is purchased from J. T. Baker. Formic acid is supplied by Fluka. HEDP is a chelating agent supplied by Monsanto. Dobanol 91-8 is a non-ionic ethoxylated alcohol surfactant supplied by Shell. Kelzan T® is a xanthan gum supplied by Kelco. Luviskol K60® is a polyvinylpyrrolidone supplied by BASF. The perfume ^ 'generally comprises a mixture of floral acetate and eucalyptol.

Compositions I to VI exhibit excellent scale removal performance under immersion conditions and provide superior cleaning performance in fatty soap scum as they comprise a nonionic surfactant. Comparative data A tartar removal performance experiment was conducted in accordance with the tartar removal performance test method as described above, using a 40 gram marble block erged in 20 grams of a scale removal composition. at room temperature for 10 minutes. The scale removal performance of a composition according to the present invention (Example I) was evaluated against a reference composition (Example VII) and expressed in the milligrams of the marble block that dissolved in 10 minutes.

The above results clearly show the best scale removal performance under immersion conditions with a composition according to the present invention (eg Composition I), ie compositions comprising formic acid in addition to an acid forming calcium salts slightly soluble, compared to a reference composition that does not comprise formic acid in addition to an acid that forms slightly soluble calcium salts.

Claims (15)

NOVELTY OF THE INVENTION CLAIMS

1. An acidic liquid composition suitable for removing tartar; the composition comprises an acid system, wherein the acid system comprises formic acid and an acid which forms calcium salts slightly soluble in water.

2. The composition according to claim 1, further characterized in that the acid forming the calcium salts slightly soluble in water is phosphoric acid.

3. The composition according to claims 1-2, further characterized in that the composition comprises from 1.1% to 25.1% by weight of the total composition, preferably from 8% to 20% by weight of the total composition, and with more 10% to 17% by weight preference of the total acid system composition.

4. The composition according to claims 1-3, further characterized in that it comprises from 1% to 25% by weight of the total composition, preferably from 5% to 20%, more preferably from 10% to 17%, with a greater preference of 10% to 15% of said acid forming calcium salts slightly soluble in water, preferably phosphoric acid, and from 0.1% to 3% by weight of the total formic acid composition, preferably 0.5% by weight 2%, more preferably from 1% to 2%, with a greater preference of 1.

5% to 2%. The composition according to any of the preceding claims, further characterized in that it additionally comprises a chelating agent, preferably a phosphonate chelating agent, more preferably a chelating agent selected from the group comprising alkali metal ethane 1-hydroxyl diphosphonates, polyalkylene (alkylene phosphonate), amino aminotri (methylene phosphonic acid), trimethylene phosphonate nitrile, ethylene diamine tetra methylene phosphonate and diethylenetriamine penta methylene phosphonate, and mixtures thereof, and most preferably alkali metal 1-hydroxyl diphosphonates.

6. The composition according to any of the preceding claims, further characterized in that it additionally comprises a nonionic surfactant, preferably a nonionic surfactant which is the condensation product of ethylene oxide with an alcohol having a right alkyl chain comprising from 6 to 22 carbon atoms, wherein the degree of ethoxylation is from 1 to 15, preferably from 5 to 12 or mixtures thereof.

The composition according to any of the preceding claims, further characterized in that the composition has a pH of less than 7, preferably from 0 to 6, preferably from 0.1 to 5, and with a greater preference from 0.5 to 4.5.

8. The composition according to any of the preceding claims, further characterized in that the composition further comprises one or more ingredients selected from a group of vinylpyrrolidone homo or copolymers, polysaccharide polymers, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, scrubbers of radicals, caustic products, perfumes and dyes, and mixtures of these.

9. A process to remove tartar from a hard surface or an object; the process comprises a step of applying the composition according to any of the preceding claims on the hard surface or object, allowing the composition to act on the hard surface or object, optionally wiping the hard surface or object with a cloth and then rinsing the surface hard or object.

10. A process to remove tartar from an object; the process comprises the step of immersing the object in a bath comprising a composition according to any of claims 1 to 9, leaving the object in the bath for the composition to act on, and then rinsing the object.

11. The process according to claims 9-10, further characterized in that the surface or object is located in a bathroom or in a kitchen, preferably in a bathroom.

12. The use, in a composition suitable for removing scale from a hard surface or an object, from a combination of formic acid and an acid forming calcium salts slightly soluble in water, to improve the cleaning performance of scale of the composition.

13. The use claimed in claim 12, wherein the improvement of scale cleaning performance is achieved when the composition is applied on the hard surface or object.; The composition is left to act on the hard surface or object and then the hard surface or object is rinsed.

14. The use, in a composition suitable for removing tartar from a hard surface or an object, from a combination of formic acid and an acid forming calcium salts slightly soluble in water, to reduce the formation of calcium salts slightly soluble on the hard surface or object.

15. The use claimed in claims 12-14, wherein the acid forming calcium salts slightly soluble in water is phosphoric acid.