MXPA01005559A - Enamel safe cleaning process - Google Patents

Abstract

The present invention describes a process of cleaning an enamel surface with a liquid acidic composition comprising an enamel safe acid wherein the pKa of said acid is 3.5 or higher;with the proviso that non mono-lower alkyl ethers or phenyl ethers or benzyl ethers of diethylene glycol, wherein the lower alkyl is of 2 to 6 carbon atoms, are present in said composition. The composition employed in said process is safe to enamel.

Description

CLEANING PROCEDURE THAT DOES NOT DAMAGE THE ENAMEL TECHNICAL FIELD The present invention relates to a method of cleaning enameled surfaces with a liquid acid composition.

BACKGROUND OF THE INVENTION Compositions for cleaning enameled surfaces are well known in the art. Liquid compositions having an acidic pH for cleaning enameled surfaces have been extensively described in the art, especially in hard surface cleaning application (eg, bath cleaner). In fact, it is known to use acid compositions to clean enameled surfaces since said formulations show good performance of soap cream removal and removal performance of limestone formations. Soap cream and limestone formations are soils that frequently occur on enameled surfaces, especially enameled surfaces located in bathrooms, kitchens and the like. However, there are some limitations regarding the convenience of acid compositions that are used as cleansing agents. enameled surfaces. In particular, it is known that enamel surfaces are sensitive to acids and can be severely damaged by acid compositions that are used to clean such surfaces. It is therefore an object of the present invention to provide a method of cleaning enameled surfaces with an acidic composition that does not damage the enamel surfaces while also exhibiting good cleaning performance over a variety of soils. It has now been discovered that the above object is satisfied by a method of cleaning an enamel surface with a liquid acid composition comprising an acid that does not damage the enamel. Advantageously, said method of cleaning enameled surfaces can be used on several enameled surfaces. Enameled surfaces can be found in several places, for example, in homes: in kitchens (sinks and the like); in bathrooms (tubs, sinks, shower tiles, enameled bathroom articles and the like); in washing machines; and dinnerware. An additional advantage of the process as described herein is that the compositions used to clean enamel surfaces show good stain / dirt removal performance. More particularly, the liquid acid compositions show good stain / dirt removal performance on various types of stains / soils, in particular: greasy soils, for example cream of greasy soap or greasy soils found in kitchens; limestone formations; mold; mildew; and other difficult stains that are on enameled surfaces.

TECHNICAL BACKGROUND The document E.U.A. 4,501, 680 discloses acidic liquid detergent compositions comprising mixtures of organic acids, a diethylene glycol ether and a surface active agent.

BRIEF DESCRIPTION OF THE INVENTION The present invention encompasses a process for cleaning an enameled surface with a liquid acid composition comprising an acid that does not damage the enamel in which the pKa of said acid is 3.5 or higher; provided that lower mono alkyl alkyls or phenyl ethers or benzene ethers of diethylene glycol are present in said composition, in which the lower alkyl is from 2 to 6 carbon atoms, in said composition. In another preferred embodiment said composition further comprises a surfactant. The present invention also encompasses the use of an acid that does not damage the enamel in a composition for cleaning an enameled surface in wherein the pKa of said acid is 3.5 or higher and said composition does not damage the enamel.

DETAILED DESCRIPTION OF THE INVENTION Process for treating a hard surface The present invention encompasses a process for treating an enamel surface with a composition liquid acid comprising an acid that does not damage the enamel as described herein. In a preferred embodiment said acid liquid composition is contacted with the enameled surface. By "enameled surface" means in the present any type of surface that is made of or coated with enamel. By "enamel" it means in the present white enamel of titanium or zirconium or white powder enamel of titanium or zirconium that is used as a coating for metallic surfaces (for example steel) preferably to avoid corrosion of said metallic surface. Enameled surfaces can typically be found in homes: for example, in bathrooms or kitchens: for example, tiles, sinks, showers, basins, toilets, tubs, sinks, equipment and similar accessories. Additionally, surfaces for kitchens, tableware and the like may have an enameled surface. Enameled surfaces can also be found in household appliances that may be coated with enamel on its interior and / or exterior surface including, but not limited to, water heaters, washing machines, automatic dryers, refrigerators, freezers, ovens, microwave ovens, dishwashers, etc. In addition, enameled surfaces can be found in industrial, architectural and similar applications. Examples of enamelled surfaces found in such applications include enamelled surfaces on or inside tanks, pipes, reaction vessels, pumps, chemical processing equipment, mechanical equipment, heat exchangers, hot water tanks, signs, silos or architectural panels . The process of the present invention provides that the liquid acid composition is applied to the surface to be treated. The composition may be in its pure form or in its diluted form. By "diluted form" means herein that said composition is typically diluted by the user with water. The composition is diluted before being used at a typical dilution level of 10 to 400 times its weight of water, preferably 10 to 200 and more preferably 10 to 100. A dilution level that is usually recommended is a dilution of 1.2% of the composition in water. By "in its pure form" it is to be understood that the liquid compositions are applied directly on the enameled surface which will be treated without suffering any dilution, ie the liquid compositions in The present are applied on the hard surface as described herein. A preferred method for cleaning an enameled surface according to the present invention is to apply the composition in diuretic form without rinsing the hard surface after application in order to obtain good dirt / stain removal performance. Another preferred method for treating an enameled surface is to apply the composition, which is described by the present invention, either in pure or diluted form, to leave it on the surface for a period of time to allow the composition to act, optionally carving said surface with a suitable instrument, for example, a sponge, and then rinse said surface preferably with water. The enameled surfaces to be treated can be soiled with a variety of soils, for example, greasy soils (eg, greasy soap, body fat, kitchen grease or burned / sticky food residues typically found in a kitchen and the like). ) or the so-called "spots containing limestone deposits". By "stains containing limestone deposition" means in the present any stain of pure limestone formation, that is, any stain composed essentially of mineral deposits, as well as stains containing limestone depositions, that is, stains that do not contain only mineral deposits such as calcium and / or carbonate magnesium but also soap cream (for example calcium stearate) and other fats (for example body fat).

Cleaning performance test method The diluted cleaning performance can be evaluated by the following test method: enameled tiles are prepared by applying an artificial dirt representative of grease / particles followed by maturation. The test compositions and the reference composition are diluted (eg, composition: water 1:50 or 1: 100), applied to a sponge, and used to clean the tiles with a Shenn carving tester. The number of carvings required to clean up to 100% clean is recorded. The result, that is, the number of carvings, of the test composition is compared against the result of the reference composition. The test method for evaluating pure cleaning performance is identical to the previous one except that the test and reference compositions are used undiluted and after cleaning a rinse cycle with clean water is performed.

Grease-soap cream cleaning performance test method In this test method glazed white tiles (typically 24 cm x 4 cm) are covered with typical greasy soap creams based mainly on calcium stearate and body dirt commercially available artificial inserts (eg, 0.3 grams with a sprinkler). The dirty tiles are then dried in an oven at a temperature of 140 ° C for 20 minutes and then ripen overnight at room temperature (approximately 20 ° C-25 ° C). The dirty tiles are then cleaned using 3 ml of the liquid composition of the present invention poured directly into a Spontex® sponge. The ability of the composition to remove cream of greasy soap is measured by the number of carvings needed to perfectly clean the surface. While the number of carvings is lower, the cleansing ability of the greasy soap of the composition is higher.

The Liquid Acid Composition The liquid acid compositions according to the present invention are preferably aqueous compositions. Therefore, they may comprise from 70% to 99%, preferably from 75% to 95% and more preferably from 85% to 95% by weight of the total water composition. The liquid compositions of the present invention are acidic and therefore preferably have a pH below 7, preferably from 1 to 6.5, more preferably from 1 to 5, even more preferably from 2 to 5 and most preferably from 2 to 4. The compositions according to the present invention are advantageously chemically stable, ie, there is virtually no chemical reaction between the different ingredients of the compositions, and are physically stable, that is, phase separation does not occur when stored in the rapid maturation test (RAT), that is, storage at 50 ° C for 10 days. A condition of the present invention is that the compositions do not contain a lower monoalkyl ether or phenyl ether or diethylene glycol benzyl ether, in which the lower alkyl is from 2 to 6 carbon atoms.

Acid that does not harm enamel As an essential ingredient, the compositions that are used in a process according to the present invention comprise an acid that does not damage enamel as defined herein. Said acid that does not damage the enamel has a pka of 3.5 or higher. Preferably the pka of said acid that does not damage the enamel is higher than 4.0. More preferably the pka of said acid that does not damage the enamel is higher than 4.5. Typically, the compositions of the present invention may comprise from 0.1% to 10%, preferably from 0.1% to 8% and more preferably from 0.1% to 6% by weight of the total composition of said acid which does not damage to! enamel. Suitable non-enamel-damaging acids having a pka of 3.5 or higher are organic or inorganic acids having a pka of 3.5 or higher or mixtures thereof.

Suitable organic acids having a pka of 3.5 or higher are aromatic or aliphatic organic acids having a pka of 3.5 or higher or mixtures thereof. Examples of suitable non-damaging organic aliphatic acids are selected from the group consisting of: acetic acid; acetoacetic acid; acrylic acid; anisic acid; ascorbic acid; formic acid, glutaric acid; Glycolic Acid; adipic acid; adipic acid; anisylpropionic acid; Aspartic acid; barbituric acid; butyric acid; caproic acid; ß-chlorobutyric acid; ? -chlorobutyric acid; chlorocinnamic acid; cinnamic acid; crotonic acid; Gallic acid; glutamic acid; heptanoic acid; hexanoic acid; hippuric acid; hydroxybutyric acid; β-hydroxypropionic acid; Itaconic acid; mesitylenic acid; methycinnamic acid; methylglutaric acid; Methylsuccinic acid; octanoic acid; phenytoic acid; propionic acid; suberic acid, succinic acid; uric acid; and valeric acid; and mixtures thereof. Examples of suitable non-aromatic organic enamel acids are selected from the group consisting of: o-aminobenzoic acid; m-aminobenzoic acid; p-aminobenzoic acid; benzoic acid; m-bromobenzoic acid; m-chlorobenzoic acid; p-chlorobenzoic acid; o-chlorophenylacetic acid; m-chlorophenylacetic acid; p-chlorophenylacetic acid; β- (o-chlorophenyl) propionic acid; β- (m-chlorophenyl) propionic acid; β- (p-chlorophenyl) propionic acid; 3,4-dihydroxybenzoic acid; 3,5-dihydroxybenzoic acid; 2,4-dinitrophenol; 3,6- dinitrophenol; diphenylacetic acid; ethylphenylacetic acid; hexahydrobenzoic acid; m-hydroxybenzoic acid; p-hydroxybenzoic acid; a-naphthoic acid; ß-naphthoic acid; nitrobenzene; o-nitrophenol; m-nitrophenol; p-nitrophenol; o-nitrophenylacetic acid; m-nitrophenylacetic acid; p-nitrophenylacetic acid; o-β-nitrophenylpropionic acid; p-β-nitrophenylpropionic acid; phenylacetic acid; α-phenylbutyric acid; a-phenylpropionic acid; β-phenylpropionic acid; m-phthalic acid; p-phthalic acid; o-toluic acid; m-toluic acid; and p-toiuic acid; and mixtures thereof. Examples of suitable inorganic acids that do not damage enamel are selected from the group consisting of: o-boric acid; carbonic acid; Germanic acid; hydrocyanic acid; hydrogen sulfide; m-silicic acid; o-silicic acid; telluric acid; and tetraboric acid; and mixtures thereof. Preferably said acids that do not damage the enamel having a pKa of 3.5 or higher are organic or inorganic acids having a pKa of 3.5 or higher or mixtures thereof. More preferably, said enamel-free acids having a pKa of 3.5 or higher are: aromatic or aliphatic organic acids having a pKa of 3.5 or higher; or inorganic acids having a pKa of 3.5 or higher; and mixtures thereof. The preferred aliphatic organic enamel-free acids are selected from the group consisting of: acetic acid; acetoacetic acid; acrylic acid; anicic acid; ascorbic acid; formic acid; glutaric acid; Glycolic Acid; succinic acid; and adipic acid; and mixtures thereof. Preferred non-aromatic organic enamel acids are selected from the group consisting of: benzoic acid; o-aminobenzoic acid; m-aminobenzoic acid; p-aminobenzoic acid; 3,4-dihydroxybenzoic acid; 3,5-dihydroxybenzoic acid; phenyl acetic acid; and mixtures thereof. Preferred inorganic enamel-free acids are selected from the group consisting of: telluric acid; carbonic acid; and hypochloric acid; and mixtures thereof. Acids that do not harm! Even more preferred enamel having a pKa of 3.5 or higher are selected from the group consisting of: acetic acid; acetoacetic acid; glutaric acid; adipic acid; succinic acid; and benzoic acid; and mixtures thereof. The most preferred enamel-damaging acids having a pKa of 3.5 or higher are selected from the group consisting of: acetic acid; glutaric acid; adipic acid; and succinic acid; and mixtures thereof. Suitable acids are commercially available from Aldrich, ICI and BASF. The present invention is based on the discovery that a process for cleaning enamel with a liquid acid composition comprising an acid that does not damage the enamel as described herein does not damage enameled surfaces.

In a preferred embodiment according to the present invention the compositions that are used in a process for cleaning enameled surfaces do not comprise any acid having a pKa of minus 3.5, more preferably less than 4.0. Another aspect of the present invention is the use of an acid that does not damage the enamel in a composition for cleaning an enameled surface in which the pKa of said acid is 3.5 or higher; whereby said composition does not damage the enamel. By "does not damage enameled surfaces" it means herein that the acid compositions as described herein avoid or at least reduce the damage to enameled surfaces treated therewith as compared to other acidic compositions. It is believed that the damage to enameled surfaces that can be caused by cations, more likely small cations, ie, cations having an ionic radius of 115 μm or less, present in an acidic composition that is used to treat said enameled surface. Such cations may be present in acidic compositions for example where a pH regulating ingredient or a pH regulating system is used to adjust the pH of said composition. It is believed that the cations penetrate and disperse through the surface layers of the crystalline enamel lattice. Said cations may eventually replace the cations that are originally present in said surface layers of the enamel crystal lattice and / or otherwise modify the layers surface of the enamel crystal lattice. The result of said replacement is that the enamel surface eventually loses its uniformity and consequently its brightness, that is, glare. The loss of brightness is perceived by consumers as damage to an enameled surface. While not wishing to be bound by theory, it is believed that by using an acid having a pKa of 3.5 or higher in an enamel cleaning composition, the pH of said composition is at an optimum scale to achieve good cleaning performance while which does not damage the treated enameled surface, ie, the composition is acidic, preferably the pH is below 7, more preferably the pH is from 1 to 6.5, even more preferably the pH is from 1 to 5, even more preferably the pH is from 2 to 5 and more preferably the pH is from 2 to 4, and therefore, the pH does not need further adjustment. In this way, there is no need to use a pH regulating ingredient or a pH regulator system other than acid that does not damage the enamel itself. In this way, it is believed that fewer cations that damage enamel are present in the enamel cleaning composition. In this way, the compositions that are used in a method for cleaning an enameled surface as described herein do not damage said enameled surfaces. The degree of enamel damage can be determined by the following enamel damage test method.

Enamel damage test method A few drops of the composition according to the present invention in its pure or diluted form are placed on an enameled surface (eg, an enameled tile) after which the surface is covered with a observation glass. After 15 minutes, the observation glass is removed, the enameled surface is rinsed with water (either demineralized or tap) and then dried. The visual examination (visual gradation) or surface gloss measurements allow to verify if the product does not damage (no difference in brightness against the untreated enameled surface) or if it damages (difference in brightness against the untreated enameled surface) enamel.

Optional Surfactant The liquid compositions of the present invention may preferably comprise a surfactant. Surfactants may be desired herein since they contribute in addition to the cleaning performance of the compositions of the present invention. The surfactants to be used herein include nonionic surfactants, cationic surfactants, anionic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Accordingly, the compositions according to the present invention may comprise up to 15%, more preferably from 0. 5% to 8%, even more preferably from 0.5% to 8% and more preferably 0.5% to 8% by weight of the total composition of a surfactant. Suitable nonionic surfactants for use herein include a class of compounds, which can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be branched or linear aliphatic (for example, Guerbet or secondary alcohol) or aromatic alkyl in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with a particular hydrophobic group can be easily adjusted to provide a water-soluble compound having the desired degree of equilibrium between hydrophilic and hydrophobic elements. According to this, suitable non-ionic synthetic detergents include: (i) The polyethylene oxide condensates of alkylphenols, for example, the condensation products of alkylphenols having an alkyl group containing from about 6 to 20 carbon atoms in a straight chain or branched chain configuration, preferably 8 to 14, and more preferably from 8 to 12 carbon atoms, with ethylene oxide. Ethylene oxide is typically present in equal amounts of 3 to 25, preferably 10 to 25 moles of ethylene oxide per mole of alkylphenol. The alkyl substituent in such compounds can be derived from polymerized propylene, diisobutylene, octane and nonane; the examples of this kind of nonionic surfactants include Triton N-57®, an ethoxylated nonylphenol (5EO) from Rohm & Hass and Imbentin O200® an ethoxylated octyl phenol (20EO) from KOLB. (ii) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine products which may vary in composition depending on the balance between the hydrophobic and hydrophilic elements that are desired. Examples are compounds containing from about 40% to 80% polyoxyethylene by weight and having a molecular weight of from 5,000 to 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base consisting of the ethylene diamine reaction product and excess of propylene oxide, said base has a molecular weight of the order of 2500 to 300. Examples of this type of nonionic surfactants include certain commercially available Tetronic ™ compounds, marketed by BASF. (iii) The condensation product of aliphatic alcohols having from 2 to 24 carbon atoms, in straight chain or branched chain configuration, preferably from 6 to 22, more preferably from 6 to 28, and even more preferably from 8 to 18 carbon atoms, with from 2 to 35, preferably from 4 to 25, more preferably from 5 to 18, and even more preferably from 3 to 15 moles of ethylene oxide. Examples of this type of material are a condensate of ethylene oxide of coconut alcohol having from 5 to 18 moles of ethylene oxide per mole of coconut alcohol, the fraction of coconut alcohol has from 9 to 14 carbon atoms. Other examples of this type of nonionic surfactants include certain of the commercially available Dobanol®, Neodol®, available from Shell or Lutesol® from BASF. For example Dobanol® 91.5 (C9-C11 EO5), Dobanol® 91.8 (C9-C11 E08) and Lutesol® AO30 (C12-C14 EO30). (iv) trialkylamine oxides and trialkyl phosphine oxides in which an alkyl group is on the scale of 10 to 18 carbon atoms and two alkyl groups are on the scale of 1 to 3 carbon atoms; the alkyl groups may contain hydroxy substituents; Specific examples are dodecyl di (2-hydroxyethyl) amine oxide and tetradecydimethylphosphine oxide. (v) The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol; the hydrophobic portion of these compounds will preferably have a molecular weight of 1500 to 1800 and will exhibit insolubility in water. The addition of polyoxyethylene portions to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained to the point where the polyoxyethylene content is 50% of the total weight of the product of condensation, which corresponds to condensation with up to 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available Pluronic ™ surfactants, marketed by BASF. Also useful as a nonionic surfactant are the alkyl polysaccharides described in U.S. Patent 4,565,647, Filling, published January 21, 1986, which have a hydrophobic group that it contains from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms and polysaccharide, for example a polyglycoside, hydrophilic group containing from 1.3 to 10, preferably from 1.3 to 3, more preferably from 1.3 to 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, for example glucose, galactose and galactosyl portions can be substituted for the glucosyl portions. (Optionally, the hydrophobic group is attached at positions 2-, 3-, 4-, etc. therefore it provides a glucose or galactose as opposed to a glycoside or galactoside). The intersaccharide linkages can be, for example, between position one of the additional saccharide units and positions 2-, 3-, 4- and / or 6- of the preceding saccharide units. Optionally, and less desirably, there may be a polyalkylene oxide chain linking the hydrophobic portion and the polysaccharide portion. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, whether saturated or unsaturated, branched or unbranched containing from 8 to 18, preferably from 10 to 16 carbon atoms. Preferably, the alkyl group may contain up to 3 hydroxy groups and / or the polyalkylene oxide chain may contain up to 10, preferably less than 5, alkylene oxide portions. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta- and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructose and / or Galactoses Suitable mixtures include cocoalkyl di-, tri-, tetra- and pentaglucosides and tallowalkyl tetra-, penta- and hexaglucosides. Preferred alkyl polyglycosides have the formula: R20 (CnH2nO) t (glycosyl)? wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, and much more preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is first formed and then reacted with glucose, or a source of glucose, to form the glucoside (linkage at position 1). The additional glycosyl units can then be linked between their position 1 and the above glycosyl units in the 2-, 3-, 4- and / or 6 position, preferably predominantly in the 2-position. Other suitable non-ionic surfactants to be used herein include polyhydroxy fatty acid amides of the structural formula: O R1 (0 R ^ - C- N- Z wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C1-C4 alkyl, more preferably preferably Ci or C2 alkyl, and more preferably C1 alkyl (ie, methyl): and R2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably alkyl or alkenyl C9-C17 straight chain, and more preferably straight chain C11-C17 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a straight hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Preferably, Z will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw materials, corn syrup with high concentration of dextrose can be used as well as the individual sugars listed above. These corn syrups can provide a mixture of sugar components for Z. It should be understood that in no way is it intended to exclude other suitable raw materials. Preferably, Z will be selected from the group consisting of -CH2- (CHOH) n-CH2? H, -CH (CH2OHHCHOH) n -? - CH2OH, -CH2- (CHOH) 2 (CHOR ') (CHOH) -CH2OH, wherein n is an integer from 3 to 5, inclusive, and R 'is H or a cyclic or aiiphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls in which n is 4, particularly -CH2- (CHOH) 4-CH2OH. In the formula (I), R 1 can be, for example, N-methyl, N-ethyl, N-propyium, N-isopropyl, N-butyium, N-2-hydroxyethyl or N-2-hydroxypropyl.

R2-CO-N < it can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, seboamide, etc. Z may be 1-deoxyiglucityl, 2-deoxyfructityl, 1-deoxymaltitiio, 1-deoxy-acetyl, 1-deoxygalactityl, 1-deoxyanityl, 1-deoxymalototriotityl, etc. Other suitable nonionic surfactants for use herein include the amine oxides corresponding to the formula: RR 'R "N? O in which R is a primary alkyl group containing from 6 to 24 carbon atoms, preferably from 10 to 18 carbon atoms, and in which R' and R" are each, independently, an alkyl group containing from 1 to 6 carbon atoms. The arrow in the formula is a conventional representation of a semipolar link. Preferred amine oxides are those in which the primary alkyl group has a straight chain in at least the majority of the molecules, generally at least 70%, preferably at least 90% of the molecules, and the amine oxides which are especially preferred are those in which R contains from 10 to 18 carbon atoms and R 'and R "are both methyl Illustrative of the preferred amine oxides are N-hexyl dimethylamine oxide, N-octyldimethylamine oxide, N-decyldimethylamine oxide, N-dodecyldimethylamine oxide, N-tetradecyldimethylamine oxide, N-hexadecyldimethylamine oxide, N-octadecyldimethylamine oxide, N-eicloidimethylamine oxide, N-dococyldimethiamine oxide, N-oxide tetracocyldimethylamine, the corresponding amine oxides in which one or both of the methyl groups are replaced with ethyl or 2-hydroxyethyl groups and mixtures thereof. A more preferred amine oxide to be used herein is N-decyldimethylamine oxide. Other nonionic surfactants suitable for the purpose of the invention are the phosphine or sulfoxide surfactants of the formula: RR 'R "A? O wherein A is a phosphorus or sulfur atom, R is a primary alkyl group containing 6-24 carbon atoms, preferably 10-18 carbon atoms, and in which R 'and R "are each independently selected from methyl, ethyl and 2-hydroxyethyl. The arrow in the formula is a conventional representation of a semipolar link. In a preferred embodiment, the nonionic surfactants suitable for use are condensates of polyethylene oxide of alkylphenols, condensates of polyethylene oxide of alkyl alcohols, alkylpolysaccharides, or mixtures thereof. The most preferred are C6-C2o alkylphenol ethoxylates, preferably Cd-C12 alkyl, having from 3 to 25, preferably from 10 to 25 ethoxy and ethoxylated groups of C2-C24 alcohol, preferably Cß-Cis having 2 to 35, preferably from 4 to 25, more preferably from 5 to 18 and more preferably from 3 to 15 ethylene oxide units, and mixtures thereof.

The zwitterionic surfactants suitable for use herein contain basic groups and acids which form an inner salt which gives cationic and hydrophilic anionic groups on the same molecule in a relatively broad range of pHs. The typical cationic group is a quaternary ammonium group, although other positively charged groups such as phosphonium, imidazolium and sulfonium may be used. Typical anionic hydrophilic groups are carboxylates and sulfonates although other groups such as sulfates, phosphonates and the like can be used. A generic formula for preferred zwitterionic surfactants for use herein (ie betaine and / or sulfobetaine) is: wherein R is a hydrophobic group; R2 is hydrogen, d-Cß alkyl, hydroxyalkyl or another substituted CrC 6 alkyl group; R3 is C Cß alkyl, hydroxyalkyl or another substituted C?-C6 alkyl group which may also be attached to R 2 to form ring structures with N, or a C de-C6 carboxylic acid group or a C su-C su su su su su su su su su su su su subunion group; Cß; R4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxyalkylene, or polyalkoxy group containing from 1 to 10 carbon atoms; and X is the hydrophilic group which is a carboxylate or sulfonate group, preferably a sulfonate group. Preferred hydrophobic R1 groups are aliphatic or aromatic chains, saturated or unsaturated, of hydrocarbons substituted or not substituted which may contain linking groups such as amido groups, ester groups. The most preferred Ri is an alkyl group containing from 1 to 24, preferably from 8 to 18, and more preferably from 10 to 16 carbon atoms. These simple alkyl groups are preferred for reasons of cost and stability. However, the hydrophobic group Ri can also be an amido radical of the formula Ra-C (O) -NRb- (C (Rc) 2) m, in which Ra is an aiiphatic or aromatic hydrocarbon chain, saturated or not saturated, substituted or unsubstituted containing from 8 to 20 carbon atoms, preferably an alkyl group containing from 8 to 20, preferably up to 18, more preferably up to 16 carbon atoms, Rb is a hydrogen or short alkyl or alkyl chain substituted containing from 1 to 4 carbon atoms, preferably a group selected from the group consisting of methyl, ethyl, propyl, ethyl or propyl substituted by hydroxy and mixtures thereof, more preferably methyl or hydrogen, Rc is selected from the group consisting of hydrogen and hydroxy groups, and m is from 1 to 4, preferably 2 to 3, more preferably 3, with no more than one hydroxy group in any portion (C (Rc) 2). The preferred R 2 is hydrogen, or an alkyl or substituted alkyl containing from 1 to 4 carbon atoms, preferably a group selected from the group consisting of methyl, ethyl, propyl, ethyl or propyl substituted by hydroxy and mixtures thereof, more preferably methyl. The preferred R3 is a C1-C4 carboxylic acid group, a C1-C4 sulfonate group, or an alkyl or substituted alkyl containing 1 to 4 carbon atoms, preferably a group selected from the group consisting of methyl, ethyl, propyl, ethyl or propyl substituted by hydroxy and mixtures thereof, more preferably methyl. The preferred R 4 is (CH 2) n in which n is an integer from 1 to 10, preferably from 1 to 6, more preferably from 1 to 3. Some common examples of betaine / sulfobetaine are described in the U.S. patent. Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated by reference herein. Examples of suitable alkyldimethylbetaines in particular include coco-dimethylbetaine, lauryldimethylbetaine, decyl dimethylbetaine, 2- (N-decyl-N, N-dimethyl-ammonia) acetate, 2- (N-coconut, N, N-dimethylammonium) myristyldimethylbetaine acetate, palmityldimethylbetaine, cetyl dimethylbetaine, stearyl dimethylbetaine. For example, cocodimethylbetaine is commercially available from Seppic under the trade name of Amonyl 265®. Laurylbetaine is commercially available from Albright & Wilson under the trade name Empigen BB / L®. A further example of betaine is lauryl imino dipropionate commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA®. The zwitterionic surfactants that are particularly preferred for use in the compositions of the present invention are the sulfobetaine surfactants since they provide optimal fat cleansing benefits.

Examples of suitable sulfobetaine surfactants in particular include bait bis (hydroxyethyl) sulphobetaine, cocoamidopropylhydroxy sulphobetaines which are commercially available from Rhone Poulenc and Witco, under the trade name Mirataine CBS® and Rewoteric AM CAS 15® respectively. Additional examples of amidobetaines / amidosulfobetaines include cocoamidoethylbetaine, cocoamidopropylbetaine or acylamidopropylene (hydropropylene) sulfobetaine Cio-C fat. For example, Cι-Cu fatty acid (hydropropyl) sulfobetaine acylamidopropylene is commercially available from the Sherex Company under the tradename "Varion CAS® sulphobetaine". Suitable amines for use herein are according to the following formula RR'R "N in which R is saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl groups containing from 1 to 30 carbon atoms, and preferably from 1 to 20 carbon atoms, and in which R 'and R "are independently saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl groups containing from 1 to 30 carbon atoms or hydrogen. Particularly preferred amines to be used according to the present invention are amines having the following formula RR'R "N in which R is a saturated or unsaturated, straight or branched alkyl group containing from 1 to 30 carbon atoms. carbon, preferably from 8 to 20, more preferably from 6 to 16, more preferably from 8 to 14 carbon atoms and wherein R 'and R "are independently substituted or unsubstituted, linear or branched alkyl groups containing from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups, or mixtures of The amines suitable for use herein are for example C2 dimethylamine, cocodimethylamine, C12-C16 dimethylamine Said amines may be commercially available from Hoechst under the tradename Genamin®, AKZO under the trade name Aromox ® or Fina under the trade name Radiamine®.

Suitable quaternary ammonium surfactants for use herein are according to the formula R? R2R3R N + X ", wherein X is a counterion such as halogen, methyl sulfate, methyl sulfonate, or hydroxide, R1 is a saturated or unsaturated, substituted or unsubstituted, linear or branched group containing from 1 to 30 carbon atoms, preferably from 12 to 20, more preferably from 8 to 20 carbon atoms 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 the present R1 is a C10-C18 hydrocarbon chain, more preferably C12, Cu, or Cie, and R2, R3 and R4 are all three methyl, and X is halogen, preferably bromide or chloride, more preferably bromide.

Examples of quaternary ammonium surfactants are myristyltrimethylammonium methylsulfate, cetyltrimethylammonium methylsulfate, lauryltrimethylammonium bromide, stearyl trimethylammonium bromide, (S ), cetyltrimethylammonium bromide (C ) and myristyltrimethylammonium bromide (M ). Most highly preferred herein are the lauryltrimethylammonium salts. Said trimethylammonium trisodium surfactants may be commercially available from Hoechst, or from Albright & Wilson under the Empigen CM® trade name.

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 halides, and those surfactants having the formula: [R¿ (OR-3) and] [R4 (OR) and] 2R 55MN ++ XV wherein R2 is an alkyl or alkylbenzyl group having 8 to 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH (CH3) -, -CH2CH (CH2OH) -, -CH2CH2CH2-, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by joining the two groups R 4, -CH 2 CHOH-CHOHCOR 6 CHOHCH 2 OH wherein R 6 is any hexose or hexose polymer having a weight molecular of less than 1000, and hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chain in which the total number of carbon atoms of R2 plus R5 is not more than 18; each y is from 0 to 10 and the sum of the values of y is from 0 to 15; and X is any compatible anion.

Other cationic surfactants useful herein are also disclosed in the US patent. 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference. Amphoteric and ampholytic detergents which may be cationic or anionic depending on the pH of the system are represented by detergents such as dodecylbeta-alanine, N-alkyltaurines such as those prepared by reacting dodecylamine with sodium isethionate according to the teachings of the US patent. No. 2,658,072, N-higher alkylapartic acids such as those produced in accordance with the teachings of the U.S.A. No. 2,438,091, and the products sold under the trade name "Miranol", and which are described in the US patent. No. 2,528,378, said patents being incorporated herein by reference. Additional synthetic detergents and listings of their commercial sources can be found in McCutcheon's Detergents and Emulsifiers, North American Ed. 1980, incorporated herein by reference. Suitable anionic surfactants for use herein are those commonly known to those skilled in the art. Preferably, the anionic surfactants for used herein include alkyl sulfonates, alkyl arylsulfonates, alkyl sulfates, alkoxylated alkyl sulfates, linear or branched C6-C20 alkyl-alkoxylated diphenyl oxide disulfonates, or mixtures thereof. Suitable alkyl sulfonates for use herein include water-soluble salts or acids of the formula RSO3M in which R is a C6-C2o straight or branched alkyl group, saturated or unsaturated, preferably a Cs-Cis alkyl group and more preferably a C10-C16 alkyl group, and M is H or a cation, for example, an alkali metal cation (for example sodium, potassium, lithium), or ammonium or substituted ammonium (for example methyl, dimethyl, and trimethylammonium cations and quaternary ammonium cations, such as tetramethyl ammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like). Suitable alkyl aryl sulfonates for use herein include water-soluble salts or acids of the formula RSO3M in which R is an aryl group, preferably a benzyl, substituted by a saturated or unsaturated saturated or unsaturated C -C2o alkyl group, preferably an alkyl group of Cs-Ci8 and more preferably a C10-C16 alkyl group, and M is H or a cation, for example , an alkali metal cation (for example sodium, potassium, lithium, calcium, magnesium and the like) or ammonium or substituted ammonium (for example methyl, dimethyl, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl ammonium cations and dimethyl piperidinium and cations of quaternary ammonium derivatives of alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). An example of a C-C6 alkyl sulfonate is Hostapur® SAS available from Hoechst. An example of commercially available alkyl aryl sulfonate is lauryl aryl sulfonate from Su.Ma. Particularly preferred alkyl aryl sulfonates are alkyl benzene sulphonates commercially available under the tradename Nansa® available from Albright & Wiíson. The alkyl sulfate surfactants suitable for use herein are according to the formula R 1 SO 4 M wherein R 1 represents a hydrocarbon group selected from the group consisting of straight or branched alkyl radicals containing from 6 to 20 carbon atoms and alkyl phenyl radicals containing from 6 to 18 carbon atoms in the alkyl group. M is H or a cation, for example, an alkali metal cation (for example sodium, potassium, lithium, calcium, magnesium and the like) or ammonium or substituted ammonium (for example methyl, dimethyl, and trimethyl ammonium cations and ammonium cations) quaternary, such as tetramethyl ammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). The branched alkyl sulphates which are particularly preferred for use herein are those containing from 10 to 14 total carbon atoms such as Isalchem 123 AS®. Isalchem 123 AS® available commercially from Enichem is a C12-13 surfactant which is 94% branched. This material can be described as CH3- (CH2) -CH (CH2OS? 3Na) - (CH2) n-CH3 where n + m = 8-9. The alkyl sulfates which are also preferred are the alkyl sulfates wherein the alkyl chain comprises a tota! of 12 carbon atoms, that is, sodium 2-butyl octyl sulfate. Said allchyl sulfate is commercially available from Condea under the trade name Isofol® 12S. Suitable linear alkyl sulfonates in particular include C12-C16 paraffinsulfonate such as Hostapur® SAS commercially available from Hoechst. Suitable alkyl sulphate akoxylated surfactants for use herein are according to the formula RO (A) mS? 3M wherein R is an unsubstituted C6-C20 alkyl or hydroxyalkyl group having an alkyl component of Ce- C2o, preferably a C2-C2o alkyl or hydroxyalkyl, more preferably C2-C2 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is larger than 0, typically between 0.5 and 6, more preferably between 0.5 and 3, and M is H or a cation which may be, for example, a metal cation (for example sodium, potassium, lithium, calcium, magnesium, etc.), ammonium cation or substituted ammonium cation. The ethoxylated alkyl sulphates as well as any propoxylated alkyl sulphates are contemplated herein. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethyl ammonium and quaternary ammonium cations, such as tetramethyl ammonium, dimethyl piperidinium and cations derived from arallamine such as ethylamine, diethylamine, triethylamine, mixtures thereof, and Similar. Illustrative surfactants are polyethoxylated alkyl sulfate of C12-C18 (1.0) (C2-C18E (1.0) SM), polyethoxylated alkyl sulfate of C-12-C18 (2.25) (Ci2-C18E (2.25) SM), polyethoxylated alkyl sulfate of C12 C18 (3.0) (C? 2-C? 8E (3.0) SM), and C12-C18 polyethoxylated alkyl sulfate (4.0) (C? 2-C? 8E (4.0) SM), in which M is selected from convenient way of sodium and potassium. The linear or branched C6-C20 alkoxylated alkyl diphenyl oxide disulfonate surfactants suitable for use herein are according to the following formula: wherein R is a linear or branched, saturated or unsaturated C6-C2o alkyl group, preferably a C12-C18 alkyl group and more preferably a C4-C6 alkyl group, and X + is H or a cation, for example, an alkali metal cation (eg, sodium, potassium, lithium, calcium, magnesium and the like). The linear or branched Cd-C2o alkoxylated alkyl diphenyl oxide disulfonate surfactants particularly suitable for use herein are branched C12 diphenium oxide diphenyl acid and linear diphenyl oxide sodium disulfonate salt of C16 respectively available commercially by DOW under the tradename Dowfax 2A1® and Dowfax 8390®. Other anionic surfactants useful herein include salts (including, for example, sodium, potassium, ammonium salts, and substituted ammonium such as mono, di- and triethanolamine salts) of soap. C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, for example, as described in British Patent Specification No. 1, 082,179, C8-C24 alkyl polyglycol ether sulfates (containing up to 10 moles) ethylene oxide); alkyl ester sulfonates such as Cu-iß methyl ester sulfonates; acyl glycerol sulfonates, olei glycerol fatty sulfates, alkyl phenol ethylene oxide sulfates ethylene, alkyl phosphates, isethionates such as the isethionates, N-acyl taurates, alkyl succinamates and sulfosucinates, sulfosuccinate mono esters (especially C12-C18 mono esters) saturated and unsaturated), sulfosucinate diesters (especially saturated and unsaturated C-C diesters), acyl sarcosinates, alkylpolysaccharide sulfates such as alkylpoiiglucoside sulfates (the non-sulfated nonionic compounds being described below), alkyl polyethoxy carboxylates such as of the formula RO (CH2CH2O)? CH2COO-M + in which R is a C8-C22 alkyl is an integer from 0 to 10, and M is a soluble cation of salt formation. Resin acids and hydrogenated resin are also suitable, such as rosin, hydrogenated rosin, and rosin and hydrogenated rosin acids present in or derived from wood oil. Additional 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 described in the US patent. No. 3,929,678 issued December 30, 1975 to Laughlin, et al., in column 23, row 58 to column 29, row 23. Preferably the surfactants that will be used herein as optional ingredients are selected from the group consisting of surfactants nonionics, cationic surfactants, anionic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. More preferably, said surfactant is a nonionic surfactant or an anionic surfactant or a mixture thereof.

Other Optional Ingredients The compositions herein may further comprise conventional enamel cleaning ingredients. Preferably, the liquid compositions according to the present invention may comprise a variety of optional ingredients depending on the technical benefit sought and the treated surface. Optional ingredients suitable for use herein include a solvent, a builder, a chelator, a bactericide, a hydrotrope, a dye, a stabilizer, a radical scavenger, a vinylpyrrolidone homopolymer or copolymer, a polysaccharide polymer, a bleach, a bleach activator, a preservative, an agent for control of foams such as a fatty acid, an enzyme, a dirt remover, a dye transfer agent, a brightener, an anti-dusting agent, a dispersant, a dye transfer inhibitor, a pigment, a dye and / or a perfum.

Solvent The compositions of the present invention may further comprise a solvent, as a highly preferred optional ingredient. Solvents are desired herein because they contribute to the cleaning performance of greasy soils of the present composition. Suitable solvents for use herein include glycols or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, branched aliphatic alcohols, alkoxylated aliphatic branched alcohols, linear C 1 -C 5 alkoxylated alcohols, linear C 5 Cr alcohols, alkyl and cycloalkyl hydrocarbons of C8-Cu and halohydrocarbons and mixtures thereof with the proviso that said solvent is not a lower mono alkyl ether or phenyl ether or diethylene glycol benzyl ether, wherein the lower alkyl is from 2 to 6 carbon atoms. The glycoids suitable for use herein are according to the formula HO-CR1R2-OH in which R and R2 are independently H or an aliphatic and / or cyclic saturated or unsaturated C2-C10 hydrocarbon chain. Suitable glycols for use herein are dodecanglicoi and / or propanediol.

Suitable alkoxylated glycols for use herein are according to the formula R- (A) nR? -OH in which R is H, OH, a saturated or unsaturated linear alkyl of 1 to 20 carbon atoms, preferably 2 to 15 and more preferably 2 to 10 carbon atoms, in which Ri is a saturated or unsaturated linear alkyl of 3 to 20 carbon atoms, preferably 3 to 15 and more preferably 3 to 10 carbon atoms, and A is an alkoxy, preferably ethoxy, methoxy and / or propoxy group and n is from 1 to 5, preferably 1 to 2. The alkoxylated glycols suitable for use herein are methoxyoctadecanol and / or ethoxyethoxyethanol. The alkoxylated aromatic alcohols suitable for use herein are according to the formula R (A) n-OH in which R is a substituted alkyl group or a substituted non-alkyl aryl group of 1 to 20 carbon atoms, preferably 2 to 15 and more preferably 2 to 10 carbon atoms, wherein A is an alkoxy group preferably butoxy, propoxy and / or ethoxy, and n is an integer from 1 to 5, preferably 1 to 2, with the proviso that n is not an integer of 2 if A is an ethoxy group: Suitable alkoxylated aromatic alcohols are benzoxyethanol and / or benzoxypropanol. Aromatic alcohols suitable for use herein are according to the formula R-OH in which R is a substituted alkyl group or substituted non-alkyl aryl of 1 to 20 carbon atoms, preferably 1 to 15 and more preferably from 1 to 10 atoms of carbon. For example, an aromatic alcohol suitable for use herein is benzyl alcohol. Branched aiiphatic alcohols suitable for use herein are according to the formula R-OH in which R is a saturated or unsaturated branched alkyl group of 1 to 20 carbon atoms, preferably 2 to 15 and more preferably 5 to 12 carbon atoms. Branched aliphatic alcohols particularly suitable for use herein include 2-ethylbutanoi and / or 2-methylbutanol. The alkoxylated branched aliphatic alcohols suitable for use herein are according to the formula R (A) n-OH in which R is a saturated or unsaturated branched alkyl group of 1 to 20 carbon atoms, preferably 2 to 15 and more preferably from 5 to 12 carbon atoms, wherein A is an alkoxy group preferably butoxy, propoxy and / or ethoxy, and n is an integer from 1 to 5, preferably 1 to 2 with the proviso that n is not an integer of 2 if A is an ethoxy group. Suitable alkoxylated aliphatic branched alcohols include 1-methypropoxyethanol and / or 2-methylbutoxyethanol. The linear alkoxylated C1-C5 alcohols suitable for use herein are according to the formula R (A) n-OH in which R is a saturated or unsaturated linear alkyl group of 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms, in which A is an alkoxy group preferably butoxy, propoxy and / or ethoxy, and n is an integer from 1 to 5, preferably 1 to 2 with the proviso that n is not an integer of 2 if A is an ethoxy group. Suitable alkoxylated aliphatic linear C1-C5 alcohols are butoxypropoxypropanol (n-BPP), butoxyethanol, butoxypropanol, ethoxyethanol or mixtures thereof. Butoxipropoxypropanol is commercially available under the trade name n-BPP® from Dow Chemical. The linear C1-C5 alcohols suitable for use herein are according to the formula R-OH in which R is a saturated or unsaturated linear alkyl group of 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms. carbon. Suitable linear C1-C5 alcohols are methanol, ethanol, propanol or mixtures thereof. Other suitable solvents include butyltriglycol ether, teramyl alcohol, and the like. Particularly preferred solvents for use herein are butoxipropoxypropane, benzyl alcohol, butoxypropanol, ethanoi, methanol, isopropanol and mixtures thereof. The preferred solvent for use herein is butoxypropoxypropanol (n-BPP). Typically the compositions of the present invention can comprise from 0.1% to 8%, preferably from 0.5% to 5% and more preferably from 1% to 3% by weight of the total composition of a solvent.

Vinylpyrrolidone Homopolymer or Copolymer The compositions of the present invention may comprise a vinylpyrrolidone homopolymer or copolymer.

Typically, the compositions of the present invention may comprise from 0.01% to 5%, more preferred from 0.05% to 3% and more preferred still from 0.05% to 1% by weight of the total composition of a vinylpyrrolidone homopolymer or copolymer. The vinylpyrrolidone homopolymers suitable for use herein are homopolymers of N-vinylpyrrolidone having the following repeating monomer: wherein n (degree of polymerization) is an integer of 10 to 1,000,000, preferably 20 to 100,000 and most preferably 20 to 10,000. Accordingly, the vinylpyrrolidone homopoimers ("PVP") suitable for use in the present invention have an average molecular weight of from about 1,000 to 100,000,000, preferably from 2,000 to 10,000,000, most preferably from 5,000 to 1,000,000, and very much the same. 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® (molecular weight at viscosity 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). Other suitable vinylpyrrolidone homopolymers that are commercially available from BASF Corporation include Sokalan HP 165® and Sokalan HP 12®; Luviskol K30®, Luviskol K60®, Luviskol K80®, Luviskol K90®, and other vinylpyrrolidone homopolymers known to those skilled in the detergent field (see for example EP-A-262,897 and EP-A-256,696). Vinylpyrrolidone copolymers suitable for use in the present invention 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, taconic 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-methyl-styrene, vinyl toluene, t-butyl styrene and similar well-known monomers can be used. The molecular weight of the vinyl pyrrolidone copolymer is not especially important as long as the copolymer is water-soluble, has some surface activity and is adsorbed on the hard surface from the liquid compositions or solutions (i.e. under conditions of use). diluted) that comprise it in such a way as to increase the hydrophilic character of the surface. However, the copolymers of N-vinylpyrrolidone and preferred unsaturated alkylenically unsaturated monomers or mixtures thereof, have a molecular weight between 1,000,000 and 1,000,000, preferably between 10,000 and 500,000 and most preferably between 10,000 and 200,000. For example particularly suitable polymers of N-vinylimidazoi N-vinylpyrrolidone 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 most preferably 10,000 to 200,000. The average molecular weight scale was determined by light screening as described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113, "Modern Methods of Polimer Characterization". Such copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers, such as the PVP / vinyl acetate copolymers are available under the tradename Luviskoi® series from BASF. The vinylpyrrolidone copolymers suitable for use in the compositions of the present invention also include quaternized or non-quaternized vinylpyrrolidone copolymers / dialkylaminoalkyl methacrylate or acrylate. The vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers (quaternized or non-quatemized) suitable to be used in the compositions of the present invention are in accordance with the following formula: wherein n is between 20 and 99 and preferably between 40 and 90 mol% and m is between 1 and 80, and preferably between 5 and 40 mol%, Ri represents H or CH3; and denotes 0 or 1; R2 is -CH2-CHOH-CH2- or CxH ^, wherein x = 2 to 18; R3 represents a lower alkyl group of 1 to 4 carbon atoms, preferably methyl or ethyl, or R4 denotes a lower alkyl group of 1 to 4 carbon atoms, preferably methyl or ethyl; X "is selected from the group consisting of Cl, Br, I, I / 2SO4, HSO4 and CH3SO3. The polymers can be prepared by the process described in French Patent Nos. 2,077,143 and 2,393,573.

The copolymers of quaternized or non-quaternized vinylpyrrolidone / diarykylaminoalkyl methacrylate or methacrylate preferred for use herein have a molecular weight of between 1,000 and 1,000,000, preferably between 10,000 and 500,000 and more preferably between 10,000 and 100,000. Such vinylpyrrolidone / dialkylaminoalkyl acrylate or methacrylate copolymers are commercially available under the name of copolymer 845MR, Gafquat 734MR or Gafquat 755MR from ISP Corporation, New York, NY and Montreal, Canada or from BASF under the tradename Luviquaí R). The vinylpyrrolidone homopolymers or copolymers which are preferred to be used herein are vinylpyrrolidone homopolymers.

Polysaccharide polymer. The compositions of the present invention may comprise a polysaccharide polymer. Typically, the compositions of the present invention can comprise from 0.01% to 5%, more preferably from 0.05% to 3% and more preferably from 0.05% to 1% by weight of the total composition of a polysaccharide polymer. Polysaccharide polymers suitable for use in the present invention include substituted cellulose materials such as carboxymethylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, succinoglycan and polysaccharide polymers that are they naturally occur as xanthan gum, guar gum, locust bean gum, tragacanth gum or derivatives thereof, or mixtures thereof. Particularly preferred polysaccharide polymers for use herein are xanthan gum and derivatives thereof. Xanthan gum and its derivatives may be commercially available for example from Kelco under the tradename Keltrol RD® Kelzan S® or Kelzan T®. Another suitable Xanthan gum is commercially available from Rhone Poulenc under the trade name Rhodopol T® and Rhodigel X747®. The succinoglycan gum for use herein is commercially available from Rhone Poulenc under the trade name Rheozan ®.

Colorant Liquid compositions according to the present invention may be colored. According to this, they can comprise a colorant. The colorants suitable for use herein are stable colorants. By "stable" is meant herein a compound that is chemically and physically stable in the acidic environment of the compositions herein.

Conservative. The compositions according to the present invention may additionally comprise a preservative as an optional ingredient.

The preservatives for use herein include all those known to those skilled in the art of hard surface cleaning compositions. The preservatives are desired herein because they contribute to the stability of the present compositions. Suitable preservatives for use herein are diazolidinyl urea, triethyl citrate, propyl 4-hydroxybenzoate, sorbic acid, Na salt of p-hydroxybenzoate or glutaraldehyde or a mixture thereof.

Radical scavenger The compositions according to the present invention can comprise a radical scavenger. Radical scavengers suitable for use herein include the well known mono and dihydroxybenzenes and their analogues., alkyl and aryl carboxylates 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-hydroxy anisole, benzoic acid, toluic acid , catechoi, 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-buty-hydroxytoluene. Such radical scavengers, such as N-propyl-gallate, may be commercially available from Ñipa Laboratories under the trade name Nipanox S1 (R).

Radical scavengers, when used, are typically present herein in amounts of up to 10% and preferably 0.0017 or 0.5% by weight of the total composition. The presence of radical scavengers can contribute to the chemical stability of the compositions of the present invention.

Perfume The compositions according to the present invention may further comprise a perfume. Perfumes suitable for use in the present include materials that provide an olfactory aesthetic benefit and / or that cover any "chemical" odor that the product may have. The main function of a small fraction of highly volatile, low-boiling perfume components (which have low boiling points) in these perfumes is to improve the odor of the fragrance of the product itself, rather than to impact the odor subsequent surface that is going to be cleaned. However, some of the more volatile, high boiling perfume ingredients provide a fresh and clean impression to the surfaces, and it is desirable that these ingredients are deposited and are present on the dry surface. The perfume ingredients can be easily solubilized in the compositions, for example, by an anionic detergent surfactant, when present. The perfume ingredients and compositions suitable for use herein are ios conventional ones known in the art. The selection of any perfume component, or the amount of perfume, is based solely on aesthetic considerations. Suitable perfume compositions and compositions can be found in the art including U.S. Pat. Nos: 4,145,184, Brian and Cummins, issued March 20, 1979; 4,209,417, Whyte, issued June 24, 1980; 4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young, issued May 1, 1979, all of these patents are incorporated herein by reference. In general, the degree of substantivity of a perfume is generally proportional to the percentages of substantive perfume material used. Relatively substantive perfumes contain at least 1%, preferably at least 10%, of substantive perfume materials. Substantive perfume materials are those odorous compounds that are deposited on surfaces by means of the cleaning process and are detectable by persons with normal olfactory acuity. Such materials typically have lower vapor pressures than those of an average perfume material. In addition, they typically have molecular weights of about 200 and above, and are detectable at levels below those of an average perfume material. The perfume ingredients useful herein, along with their characteristic odor and their physical and chemical properties, such as boiling point and molecular weight, are given in "Perfume and Flavor Chemicals (Aroma) Chemicals), "Steffen Arctander, published by the author 1969, incorporated herein by reference Examples of low volatile, highly volatile perfume ingredients are: anethole, benzaldehyde, benzyl acetate, benzyl alcohol, formate benzyl, isobornyl acetate, camphene, ciscitrai (neral), citronellal, citronellol, citronellyl acetate, para-cymene, decanal, dihydrolinalool, dihydromyrcenol, dimethyphenylcarbinol, eucalyptol, geranial, geraniol, geranyl acetate, geranyl nitrile, cis acetate -3-hexenyl, hydroxycitronellal, d-limonene, linalool, linalool oxide, linalyl acetate, linalyl propionate, methyl anthranilate, alphamethyl ionone, methylnonyl acetaidehide, methylphenylcarbinyl acetate, iaevomenthium acetate, menthone, isomenthone, micron , myrcenyl acetate, mircenol, nerol, neryl acetate, nonyl acetate, phenylethyl alcohol, alphapinene, betapinene, gamatefinine, alphaterpineol, betaterpineol, acet Terpinyl and vertenex (para-tertiary-butylcyclohexyl acetate). Some natural oils also contain large percentages of highly volatile perfume ingredients. For example, bleach contains as main components: linalool; linalyl acetate; geraniol; and citronellol. The lemon oil and the orange terpenes contain, both, approximately 95% of d-limonene. Examples of moderately volatile perfume ingredients are: amylcinnamic aldehyde, isoamyl salicylate, betacarophyoiene, cedrene, cinnamic alcohol, coumarin, dimethylbenzylcarbinyl acetate, ethylvaniline, eugenol, isoeugenol, flower acetate, heliotropin, 3-cis-hexenyl salicylate, Hexyl salicylate, lilial (para-tertiary butyl-lalphamethylhydrocinnamic aldehyde), gamma-meti! ionone, nerolidoi, patchouli alcohol, phenylhexanol, betaselinene, trichloromethylphenylcarbinyl acetate, triethyl citrate, vanillin and veratraidehyde. Cedar wood terpenes are mainly composed of alpha-cedrene, beta-cedrene and other sesquiterpenes of C? SH24- Examples of high-boiling, less volatile perfume ingredients are: benzophenone, benzyl salicylate, brassylate ethylene, galaxolide (1, 3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyran), hexycinnamic aldehyde, lyral (4- (4 -hydroxy-4-methylypentyl) -3-cyclohexen-10-carboxaldehyde), methyl-cedrylon, methyldihydro-jasmonate, methyl-beta-naphthyl ketone, mustard indanone, muskyl ketone, musk tibetan and phenylethyl phenylacetate. The selection of any particular perfume ingredient is defined primarily by aesthetic considerations. The compositions herein may comprise a perfume ingredient, in amounts of up to 5.0%, preferably in amounts of 0.1% to 1.5% by weight of the total composition.

Chelating Agent Another class of optional compounds to be used herein include chelating agents.

The chelating agents can be incorporated into the compositions herein in amounts in the scale of up to 10.0%, preferably from 0.01% to 5.0% by weight of the total composition. Phosphonate chelating agents suitable for use herein may include alkali metal ethanyl hydroxydiphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino aminotri (methylene phosphonic acid) (ATMP), trimethylene phosphonates. of nitrile (NTP), etiiendiamintetramethylenephosphonates, and diethylenetriaminpentamethylenephosphonates (DTPMP). The phosphonate compounds may be present in their acid form or as salts of different cations in some or all of their acid functionalities. Preferred phosphonate chelating agents for use herein are diethylenetriaminpentamethylene phosphonate (DTPMP) and ethane 1-hydroxydiphosphonate (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 patent of E.U.A. 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-disuifobenzene. A preferred biodegradable chelating agent for use herein is ethylene diamine N, N'-disuccinic acid, or alkali metal, or metal alkaline earth, ammonium or substituted ammonium salts thereof or mixtures thereof. Ethylene diamine N, N'-disuccinic acids, especially the (S, S) isomer, have been extensively described in the US patent. 4,704,233, issued November 3, 1987, to Hartman and Perkins. Ethylene diamine N, N'-disuccinic acid is commercially available, for example, under the tradename ssEDDS® from Palmer Research Laboratories. Suitable aminocarboxylates for use herein include ethylenediamine tetraacetate, diethylenetriamine pentaacetate, diethylenetriamine pentaacetate (DTPA), N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetraminehexaacetates, ethanol diglycine, propylenediamine tetraacetic acid (PDTA) ) and methyl glycine diacetic acid (MGDA) in its acid form, or in its alkali metal, ammonium and substituted ammonium salt forms. Particularly suitable aminocarboxylates for use herein are diethylenetriamine pentaacetic acid, propylene diamine tetraacetic acid (PDTA), which is, for example, commercially available from BASF under the tradename Trilon FS® and diacytic acid methylglycine (MGDA). . Additional carboxylate chelating agents for use herein include salicylic acids, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.

Bleaching agents Liquid compositions herein may also comprise a bleaching component. Any bleach known to those skilled in the art may be suitable for use herein including any peroxygen bleach as well as any hypohaiite bleach. Peroxygen bleaches suitable for use herein include hydrogen peroxide or sources thereof. As used herein a "hydrogen peroxide" source refers to any compound that 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, persulfates, perborates, peroxides and / or organic and inorganic hydroperoxides. Suitable hypohalite bleaches for use herein include chlorine releasing components such as, for example, alkali metal hypochlorites. Advantageously, the compositions according to the present invention are stable in the presence of this bleaching component. Although alkali metal hypochlorites are preferred, other hypochlorite compounds may also be used herein and, for example, may be selected from calcium and magnesium hypochlorite. A preferred alkali metal hypochlorite for use herein is sodium hypochlorite.

Bleach activators In a preferred embodiment in which the compositions of the present invention comprise a peroxygen bleach, said compositions may further comprise a bleach activator. "Bleach activator" refers to a compound that reacts with peroxygen bleach such as hydrogen peroxide to form a peracid. The perished formed in this way constitutes the activated bleach. Bleach activators suitable for use herein include those belonging to the class of esters, amides, imides, or anhydrides. Examples of suitable compounds of this type are described in British patent GB 1 586 769 and GB 2 143 231 and a method for their formation in the form of pellets is described in published European patent application EP-A-62 523. Suitable examples of such compounds to be used herein are tetracetylethylenediamine (TAED), sodium 3,5,5 trimethylhexanoyloxybenzenesulfonate, diperoxydodecanoic acid as described for example in the USA No. 4,818,425 and peroxyadipic acid nonyl amide as described for example in E.U.A. No. 4 259 201 and n-nonanoyloxybenzenesulfonate (NOBS). Also suitable are the N-acylcaprolactams selected from the group consisting of substituted or unsubstituted benzoylcaprolactam, octanoylcaprolactam, nonanoylcaprolactam, hexanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, formylcaprolactam, acetylcaprolactam, propanoylcaprolactam, butanoylcaprolactam, pentanoylcaprolactam or mixtures thereof. A particular family of bleach activators of interest is described in EP 624 154 and particularly preferred in that family is acetyltriethyl citrate (ATC). Acetyltriethyl citrate has the advantage that it is not harmful to the environment and eventually degrades into citric acid and alcohol. Additionally, acetyltriethyl citrate has a good hydrolytic stability in the product with storage and is an efficient bleach activator. Finally, it provides good training capacity to the composition.

Packaging form of the compositions. The compositions herein can be packaged in a variety of suitable detergent packages known to those skilled in the art. The liquid compositions are preferably packaged in conventional plastic detergent bottles. In one embodiment the compositions herein can be packaged in manually or electrically operated spray jets, which are usually made of synthetic organic polymer plastic materials. Accordingly, the present invention also encompasses liquid cleaning compositions of the invention packaged in a spray jet, preferably in a trigger spray jet or in a pump spray jet.

In fact, said sprinkler-type jets allow to apply uniformly to a relatively large area of a surface to be cleaned, the liquid cleaning compositions suitable for use in accordance with the present invention. Such sprinkler type jets are particularly suitable for cleaning vertical surfaces. Sprinkler-type jets suitable for use in accordance with the present invention include hand-operated foam trigger dispensers sold for example with Specialty Packaging Products, Inc. or Continental Sprayers, Inc. These types of dispensers are described, for example, in E.U.A. 4,701, 311 to Dunnining et al, and E.U.A. 4,646,973 and E.U.A. 4,538,745 both to Focarracci. Particularly preferred to be used herein are sprinkler type sprays such as T 8500® commercially available from Continental Spray International or T 8100® commercially available from Canyon, Northern Ireland. In said spout the liquid composition is divided into fine liquid droplets resulting in a spray which is directed on the surface to be treated. In fact, in said sprayer-type spout the composition contained in the body of said spout is directed through the head of the sprayer-type spout through energy communicated to a pump mechanism by the user as said user activates the pumping mechanism. More particularly, in said sprayer-type spout head the composition is forced against an obstacle, for example a mesh or a cone or the like, thereby providing impulses. which help to atomize the liquid composition, that is, help the formation of liquid drops.

EXAMPLES These compositions comprising the ingredients listed in the listed proportions (weight percentage) were made.

Ingredients: I II III IV V VI Vil VIII IX X XI (% by weight) Dobanol® 91-8 1.3 1.5 - 3.5 - - - 2.5 - - Isalchem 123 - 1.5 - 3.5 - 1.4 5.0 - - 3.0 3.0 AS® Lutensol®AO30 - - - - - 1.5 - 2.0 - - - n-BPP 2.0 2.0 2.0 - 2.0 2.0 2.0 - 3.0 5.8 2.0 Benzoic acid 3.5 - - - - 1.5 5.5 - - - - Adipic acid - 2.0 1.0 - - 0.5 - 5.0 - - - Succinic acid - - 1.0 - 1.5 - - - 3.5 2.5 - Teluric acid - - - 1.5 - - - - - - 4.0 Luviskol K60® 0.1 - - 0.05 0.1 - 0.1 - - 0.1 0.1 Kelzan T® 0.3 0.6 - 0.3 - - - 0.3 - - 0.3 Water and Up to 100 children The pH of these examples is acidic. Isalchem 123 AS® is a branched alkyl sulfate commercially available from Enichem. Kelzan T® is a xanthan gum supplied by Kelco. Luviskoi K60® is a polyvinylpyrrolidone supplied by BASF. n-BPP is butoxypropoxypropanol available commercially from Dow Chemical.

Dobanol® 91-8 is an ethoxylated Cg-Cn alcohol commercially available from Shell. Lutensol® AO 30 is an alcohol ethoxylate of C? - Commercially available from BASF. All the above compositions do not damage the enamel when they are used to treat enameled surfaces.

Claims (11)

NOVELTY OF THE INVENTION CLAIMS

1. - A method for cleaning an enameled surface with a liquid acid composition comprising an acid that does not damage the enamel in which the pka of said acid is 3.5 or higher; with the proviso that no lower monoalkyl ethers or phenyl ethers or benzyl diethylene glycol ethers are present, in which the lower alkyl is from 2 to 6 carbon atoms, in said composition.

2. The process according to claim 1, further characterized in that the pka of said acid is higher than 4.O.-

3. The process according to any of the present claims, further characterized in that said acid does not Damage to enamel that has a pka of 3.5 or higher is an organic or inorganic acid that has a pka of 3.5 or higher or a mixture thereof.

4. The process according to any of the preceding claims, further characterized in that said composition comprises 0.1% to 10% by weight of the total composition of said acid that does not damage the enamel.

5. The process according to any of the preceding claims, further characterized in that said composition has a pH below 7.

6. - The method according to any of the preceding claims, further characterized in that said composition further comprises a surfactant.

7. The method according to claim 6, further characterized in that said composition comprises up to 15% by weight of the total composition of said surfactant.

8. The process according to any of the preceding claims, further characterized in that said composition further comprises a solvent.

9. The process according to claim 8, further characterized in that said composition comprises from 0.1% to 8% by weight of the total composition of said solvent.

10. The process according to any of the preceding claims, further characterized in that said composition does not comprise an acid having a pka of less than 3.5.

11. The use of an acid that does not damage the enamel in a composition for cleaning an enameled surface in which the pka of said acid is 3.5 or higher, whereby said composition does not damage the enamel.