MXPA99007528A - Alkaline liquid hard-surface cleaning compositions comprising n-vinylpyrrolidone copolymer - Google Patents

Abstract

Liquid hard-surfaces cleaning compositions are disclosed which have a pH above 9 and comprise a copolymer of N-vinylpyrrolidone and an alkylenically unsaturated monomer or a mixture thereof, preferably a quaternized or unquaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymer. These compositions provide excellent first time and next time cleaning performance on hard-surfaces soiled by various soils especially grease while exhibiting excellent stability against bacterial contamination.

Description

LIQUID ALKALINE COMPOSITIONS FOR CLEANING HARD SURFACES COMPRISING A N-VINYL PYROLROLONE COPOLYMER TECHNICAL FIELD The present invention relates to liquid compositions for cleaning hard surfaces, especially those soiled with greasy stains and / or burned / sticky food residues typically found in kitchens.

BACKGROUND OF THE INVENTION Liquid compositions for cleaning hard surfaces have been described in the art. Most of the attention that has been put into such compositions has been in providing remarkable cleanliness over a variety of soils. In fact, it is known to include certain polymers in compositions for cleaning generally hard surfaces to obtain a primary cleaning benefit when the compositions are first used on a hard surface treated therewith a secondary cleaning benefit by modifying the Hard surface to minimize or even prevent the redeposition of dirt or otherwise facilitate repeated cleaning. However, such compositions are not entirely satisfactory because consumers look for hard surface cleaning compositions that are efficient in cleaning performance both on the first and subsequent (subsequent) times provided on a hard surface treated therewith, especially the grease cleaning performance. In this way, the object of the present invention is to formulate a liquid composition for cleaning hard surfaces that provides an excellent cleaning benefit both the first time and the following on various soils, especially greasy soils and / or burned food residues. sticky ones typically found in kitchens. In addition, a disadvantage associated with liquid compositions for cleaning conventional hard surfaces is that their stability against bacterial contamination is not satisfactory from the point of view of a formulator. In fact, bacterial instability can cause notable disadvantages for the consumer such as color instability and / or odor instability of the compositions. The conventional answer to this problem may be to add a bactericidal agent such as glutaraldehyde. However, said agents have the disadvantages that they can impart an unfavorable odor to the compositions and increase the final cost of the composition. The formulators then look for alternative solutions. It is then another object of the present invention to formulate a liquid composition for cleaning hard surfaces that provides an excellent cleaning benefit both in the first and in the following on various soils, exhibiting at the same time improved stability against bacterial contamination. It has now been found that these objects can be satisfied by formulating a liquid composition having a pH of more than 9, and comprising a particular anti-cracking ingredient, namely a copolymer of vinylpyrrolidone with an alkylenically unsaturated monomer or mixtures thereof and preferably a copolymer of vinylpyrrolidone / dialkylaminoalkylacrylate or meta-platelet. In fact, it has surprisingly been discovered that the use of said copolymer of vinylpyrrolidone with an alkyl unsaturated monomer as defined herein, and especially of a quaternized or non-quaternized vinylpyrrolidone / dialkylaminoalkylacrylate or methacrylate copolymer, in a liquid composition having a pH of more than 9, provides improved cleaning performance both first-time and subsequent times on the surface treated therewith at a low total level of anti-fouling ingredients. Furthermore, it has been found that improved stability against bacterial contamination is obtained by formulating a liquid composition comprising a copolymer as defined herein, at a pH of more than 9. An advantage of the present invention is that the cleaning performance of the first and subsequent times is obtained with the compositions according to the present invention on various types of soils / stains, providing the same time an appearance of adequate surface on said surfaces. Another advantage of the present invention is that the liquid compositions of the present invention can be used to clean hard surfaces made from a variety of materials such as glazed or unglazed ceramic tiles, vinyl, non-wax vinyl, linoleum, melamine, glass, wood plasticized, both with concentrated and diluted conditions, for example, up to a dilution level of 1: 200 (composition: water). The following patent applications are representative of the prior art. WO 94/26858 describes a liquid composition for cleaning hard surfaces (pH 2-8) with nonionic surfactants (1-30%) and anionic polymers having an average molecular weight of less than 1,000,000, said polymers being free of quaternary nitrogen groups. Said compositions provide a surprising benefit of initial cleaning, in addition to the anti-scrubbing benefit. In fact WO 94/26858 discloses that acrylic, methacrylic and maleic anhydride derivatives such as styrene-maleic copolymers produce a vein-free finish after drying. EP-A-374 471 discloses liquid compositions for cleaning hard surfaces, which are formulated to leave on the treated surface, a protective barrier layer that serves to protect it against a later deposition of dirt. These compositions comprise an alkylphenyl ether of polyethylene glycol, lecithin and a copolymer of aminofunctional polydimethylsiloxane as a protective barrier compound, and one or more glycols. Copolymers of vinylpyrrolidone with an alkylenically unsaturated monomer or mixtures thereof are not described. EP-A-635 567 describes liquid compositions for cleaning hard surfaces, comprising a cleaning agent capable of being deposited on the surface during cleaning and of forming a dry layer adhered to the surface, said layer having a resistance cohesive, so that at least the outermost surface portion of the layer is removable by subsequent washing. Polyvinylpyrrolidone is described. Copolymers of vinylpyrrolidone with an alkylenically unsaturated monomer or mixtures thereof are not described.

BRIEF DESCRIPTION OF THE INVENTION The present invention encompasses a liquid hard surface cleaning composition having a pH of greater than 9 and comprising a copolymer of vinylpyrrolidone with an alkylenically unsaturated monomer or mixtures thereof. The present invention also encompasses a method for cleaning hard surfaces in which a liquid composition as defined hereinbefore is contacted with said surfaces.

DETAILED DESCRIPTION OF THE INVENTION Liquid compositions The compositions according to the present invention particularly suitable for cleaning a hard surface, are liquid compositions. The liquid compositions of the present invention are preferably, but not necessarily, formulated as aqueous compositions. The aqueous compositions typically comprise from 50% to 99% by weight of the total composition, of water, preferably from 60% to 95%, and more preferably from 80% to 95%. The liquid compositions herein are formulated at a pH of more than 9, preferably more than 10, most preferably 10.1 to 12 and more preferably 10.5 to 11. The pH of the compositions herein can be adjusted by any of the methods well known to those skilled in the art, such as alkalizing agents such as NaOH, KOH, K2CO3, Na2CO3 and the like. The compositions of the present invention comprise as an essential ingredient a copolymer of N-vinylpyrrolidone and an alkylenically unsaturated monomer or mixtures thereof. Typically, the compositions of the present invention comprise from 0.01% to 20% by weight of the total composition of a copolymer of N-vinylpyrrolidone and alkylenically unsaturated monomer or mixtures thereof, preferably from 0.01% to 10%, most preferably from 0.1% to 5% and more preferably from 0.2% to 2%. The N-vinylpyrrolidone of the suitable copolymers for use herein has the following repeating monomer: wherein n (degree of polymerization) is an integer of 10 to 1,000,000, preferably 20 to 100,000, and more preferably 20 to 10,000. The alkylenically unsaturated monomers of the copolymers suitable for use herein include unsaturated dicarboxylic acids such as maleic acid, chloromaleic acid, fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid, aconitic acid, acrylic acid and vinyl acetate. Any of the anhydrides of the unsaturated acids, for example, methacrylate, can be used. 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 vinipyrrolidone copolymer and the alkylenically unsaturated monomers or mixtures thereof is not especially critical, so long as the copolymer is water soluble, has some surface active activity and is adsorbed to the hard surface from the composition or liquid solution (that is, under dilute use conditions), comprising it in such a way as to increase the hydrophilic character of the surface. However, preferred copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers or mixtures thereof, 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 200,000. Said copolymers of N-vinylpyrrolidone and alkylenically unsaturated monomers such as the PVP / vinyl acetate copolymers are commercially available under the tradename Luviskol® series from BASF. The copolymers of vinyl pyrrolidone and alkylenically unsaturated monomers particularly preferred for use in the compositions of the present invention are copolymers of quartered or non-quaternized vinylpyrrolidone dialkylaminoalkylacrylate or methacrylate. The vinylpyrrolidone / dialkylaminoalkylacrylate or methacrylate copolymers (quartered or non-quartered) suitable for use in the compositions herein are in accordance with the following formula: wherein n is between 20 and 99, and preferably between 40 and 90% in moles, and m is between 1 and 80, and preferably between 5 and 40% in moles; RÍ represents H or CH 3; and denotes 0 or 1; R2 is -CH2-CHOH-CH2- or CxH2 ?, where 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 Polymers can be prepared by the process described in French patents Nos. 2,077,143 and 2,393,573 The copolymers of vinylpyrrolidone / dialkylaminoalkylacrylate or methacrylate quaternized or non-quaternized 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.The said vinylpyrrolidone / dialkylaminoalkylacrylate or methacrylate copolymers are commercially available under the name of copolymer 845®, Gafquat 734® or Gafquat 755® of ISP Corporation, New York, NY and Montreal, Canada, or of BASF under the tradename Luviquat® More preferred here are the quaternized copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate (polyquatemium-11), available from BASF The present invention is based on the discovery that the liquid compositions of the present invention having a pH of greater than 9 and comprising a copolymer of N-vinylpyrrolidone and an alkylenically unsaturated monomer as defined herein, and preferably a copolymer of vinylpyrrolidone / dialkylaminoalkylacrylate or methacrylate (quaternized or not quaternized), provide improved cleaning performance of both first and subsequent times when a hard surface is treated therewith, as compared to the cleaning performance of both first and subsequent times provided with the same compositions but comprising another polymer. anti-scrubbing for example poly (trimethylaminoethyl) methacrylate. In fact, it is particularly surprising to obtain this benefit, that is, not only improved cleaning performance of succeeding times but also improved cleaning performance for the first time, since the prior art compositions are not efficient in both primary and subsequent cleaning. . Likewise, this benefit is obtained at a lower total level of active anti-scrub ingredients compared, for example, with the use of other polymeric materials such as poly (trimethylaminoethyl) methacrylate. While not wishing to be bound by theory, the first-time cleaning benefit can be explained as the ability of the vinylpyrrolidone / alkylene-ionically initiated monomer copolymers to complex metals or other soils and thus facilitate their removal from the cleaned surfaces. While not wishing to be bound by theory, the cleaning benefit of following times can be explained as follows: it is speculated that the vinylpyrrolidone copolymer and the alkylenically-chained monomer as defined herein, especially vinylpyrrolidone / dialkylaminoalkylacrylate or methacrylate copolymer (quaternized or not quaternized), has the property of being adsorbed to a hard surface that is being treated first with it, in such a way that a hygroscopic layer is left. The resulting hygroscopic layer can attract and retain ambient atmospheric water vapor to more effectively reduce the adhesion of dirt once treated and / or facilitate the removal of subsequently deposited dirt thereon, ie, less work is required (e.g. , less carving and / or rubbing and / or less chemical action) to remove the dirt in the cleaning operation the next time, compared to a similar dirty hard surface that has been treated first with the same compositions without said vinylpyrrolidone copolymer and alkylenically unsaturated monomer or with other polymeric material, for example, poly (trimethylaminoethyl) methacrylate. An advantage of the present invention is that an effective cleaning performance of the first and subsequent times at a low total level of anti-scrubbing ingredients can be obtained. In a preferred embodiment, the compositions herein comprise from 0.2% to 2% by weight of the total composition of a copolymer of vinylpyrrolidone and alkylenically unsaturated monomer or mixtures thereof, preferably from 0.2% to 1.5% and most preferably from 0.3 % to 1%. Surprisingly, effective cleaning performance of the first and subsequent times is provided not only when a composition of the present invention is brought into contact with the hard surface to be cleaned in its concentrated form, but also when it comes into contact with the surface in its diluted form, for example up to a water dilution level: composition of 200: 1. By "cleaning performance" is meant herein the cleaning of various types of soils including greasy soils such as kitchen grease and / or burned / sticky food residues typically found in a kitchen (eg, burnt milk) and Similar. The initial cleaning performance of the composition in diluted form can be evaluated by the following test method: enamel, vinyl or ceramic tiles are prepared by applying an artificial dirt representative of grease / particulate, followed by aging. 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 Sheen friction tester. The number of passes required to obtain a 100% cleaning is recorded. A minimum of 6 replicas can be made, each result being generated in duplicate against the reference in each tile messed up. The subsequent cleaning performance of the composition in diluted form can be assessed by the following test method: after the detailed procedure for initial cleaning, the tiles used for this preliminary test are taken and re-soiled directly without first being washed or rinsed. The cleaning procedure is then repeated using the friction tester Sheen, taking care that the test compositions are used to clean the same part of the tile that was previously cleaned with them. The number of passes required to obtain a 100% cleaning is recorded. A minimum of 6 replicas can be made, each result being generated in duplicate against the reference in each tile messed up. This re-cleaning and cleaning procedure can be repeated up to 5 times. The test method that is used to evaluate the cleaning performance of the composition in pure form is identical to the previous one, except that the test compositions and references are used undiluted, and after cleaning, a cycle is carried out rinse with clean water. This rinse cycle can be repeated up to 5 times before the re-skimming step for the evaluation of subsequent cleaning. Yet another advantage of the present invention is that by formulating a liquid composition comprising a copolymer of vinylpyrrolidone and an alkylenically unsaturated monomer or mixtures thereof as defined hereinbefore, preferably vinylpyrrolidone / dialkylaminoalkylacrylate or methacrylate copolymer (quaternized or non-quaternized) a pH of more than 9, an improved stability against bacterial contamination is obtained. By "stability against bacterial contamination" is meant that the compositions of the present invention are less prone to contamination by bacteria or to support the growth of bacteria, compared to the same compositions formulated at a more neutral pH. Stability against bacterial contamination can be evaluated by culturing experiments with a set of standard strains of bacteria in a culture medium containing the composition to be tested.

Optional ingredients The liquid compositions according to the present invention can comprise several optional ingredients, depending on the technical benefit required and the treated surface.

Optional ingredients suitable for use herein include surfactants, chelating agents, detergency builders, polymers, solvents, pH regulators, bactericides, hydrotropes, colorants, stabilizers, radical scavengers, bleaches, bleach activators, enzymes, suspending agents. soils, dye transfer agents, brighteners, foaming control agents, anti-dusting agents, dispersants, dye transfer inhibitors, pigments, dyes and / or perfumes. The liquid compositions of the present invention preferably comprise a surfactant, or mixtures thereof. Said surfactant may be present in the compositions according to the present invention in amounts of 0.1% to 50% by weight of the total composition, preferably from 0.1% to 20%, and more preferably from 1% to 10%. Surfactants are desired herein, since they further contribute to the cleaning performance and / or gloss benefit of the compositions of the present invention. The surfactants which are used herein include nonionic, anionic, cationic, amphoteric, zwitterionic surfactants, and mixtures thereof. Particularly preferred surfactants are the nonionic surfactants. Suitable nonionic surfactants for use herein include a group 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 aliphatic branched or linear (for example, secondary or Guerbet alcohols) or alkyl of aromatic nature. The length of the hydrophilic or polyoxyalkylene radical that is fused with any particular hydrophobic group can be easily adjusted to produce a water-soluble compound having the desired degree of balance between the hydrophilic and hydrophobic elements. For example, a well-known group of synthetic non-ionic detergents can be obtained commercially under the trade name "Pluronic". These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, in fact, exhibits insolubility in water, has a molecular weight of about 1500 to 1800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the solubility of the molecule in water as a whole, and the liquid character of the products is retained to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product. Other suitable non-ionic synthetic detergents include: (i) polyethylene oxide condensates of alkyl phenols, for example, the condensation products of alkyl phenols having an alkyl group containing about 6 to 12 carbon atoms in a chain configuration straight or branched chain, with ethylene oxide, said ethylene oxide being present in amounts equal to 10 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in said compounds can be derived from polymerized propylene, diisobutylene, octane and nonane; (ii) derivatives of the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine products which can vary in composition, depending on the balance desired between the hydrophobic and hydrophilic elements. Examples are compounds containing from about 40% to about 80% polyoxyethylene by weight, and having a molecular weight of from about 5,000 to about 11,000, resulting from the reaction of ethylene oxide groups with a hydrophobic base formed from the product of ethylene diamine reaction and excess propylene oxide, said base having a molecular weight of the order of 2500 to 3000; (iii) the condensation product of aliphatic alcohols having 8 to 18 carbon atoms, in straight chain or branched chain configuration, with ethylene oxide, for example, a condensate of ethylene oxide of coconut alcohol having 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having 10 to 14 carbon atoms; (iv) trialkyl sheet oxides and trialkyl phosphine oxides, wherein one alkyl group varies from 10 to 18 carbon atoms, and two alkyl groups vary from 1 to 3 carbon atoms; the alkyl groups may contain hydroxy substituent; Specific examples are dodecyl di (2-hydroxyethyl) amine oxide and tetradecyldimethylphosphine oxides. Also useful as the nonionic surfactant are the alkylpolysaccharides described in the US patent. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and polysaccharide, eg, a hydrophilic group of polyglucoside containing from about 1.3 to about 10, preferably from about 1.3 to about 3, more preferably from about 1.3 to about 2.7 units of saccharide. Any reducing saccharide containing 5 to 6 carbon atoms can be used, for example, portions of glucose, galactose and galactosyl can be replaced by the glucosyl portions (optionally, the hydrophobic group is attached in the 2-, 3-, positions, 4-, etc., thus giving a glucose or galactose as opposed to a glycoside or galactoside). The intersaccharide bonds can be, for example, between position 1 of the additional saccharide units and positions 2-, 3-, 4-, and / or 6 of the above saccharide units. Optionally, and less conveniently, there can 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, saturated or unsaturated, branched or unbranched, containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms. Preferably, the alkyl group can contain up to about three hydroxy groups and / or the polyalkylene oxide chain can contain up to about 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 glactoses . Suitable mixtures include coconut alkyl, di-, tetra- and pentaglucosides and tallow alkyl tetra-, penta- and hexaglucosides. Preferred alkyl polyglucosides have the formula: R2O (CnH2nO) t (glucosium)? wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms. carbon; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, more preferably from about 1.3 to about 2.7. The glucosyl 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 thereof, to form the glucoside (linkage at position 1). The additional glucosyl units can then be linked between their position 1 and the 2-, 3-, 4- and / or 6- position of the above glucosyl units, preferably predominantly the 2-position. Although not preferred, the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol, are also suitable for use herein. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800, and will exhibit insolubility in water. The addition of polyoxyethylene portions to this hydrophobic portion tends to increase the solubility of the molecule as a whole in water, and the liquid character is retained to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product , which corresponds to the condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include some of the commercially available Pluronic ™ surfactants, marketed by BASF. Also not preferred, although suitable for use as nonionic surfactants herein, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene, and has a molecular weight of from about 5000 to about 11,000. Examples of this type of nonionic surfactant, include some of the commercially available Tetronic ™ compounds, marketed by BASF. Other nonionic surfactants suitable for use herein include polyhydroxy fatty acid amides of the structural formula: O R 1 (O 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 C1 or C2 alkyl, and most preferably alkyl of d (is say, methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C7-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C11-C17 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to the chain, or an alkoxylated derivative (preferably ethoxylated or propolyxylated) thereof. Z will preferably 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 a raw material, high dextrose corn syrup can be used, as well as the individual sugars noted above. These corn syrups can produce a mixture of sugar component for Z. It should be understood that in no way is it intended to exclude other suitable raw materials. Z will preferably be selected from the group consisting of -CH2- (CHOH) n -CH2? H, -CH (CH2OHHCHOH) n -? - CH2OH, -CH2- (CHOH) 2 (CHOR ') (CHOH) -CH2OH, in where n is an integer from 3 to 5, inclusive, and R 'is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. More preferred are glycityls, where n is 4, particularly -CH 2 - (CHOH) 4-CH 2 OH. In the formula (I), R 1 may be, for example, N-methyl, N-ethyl, N-prolyium, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl. R2-CO-N < it can be, for example, cocoamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, seboamide, etc. Z can be 1-deoxyglucityl, 2-deoxyfuctilityl, 1-deoxymaltytyl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxyanityl, 1-deoxy-thiotriotityl, etc. In one embodiment of the present invention, suitable nonionic surfactants to be used are condensates of polyethylene oxide of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkyl polysaccharides, and mixtures thereof. More preferred are alkyl phenol ethoxylates having from 3 to 15 ethoxy groups, and C 1 -Cis alcohol ethoxylates (preferably C 1 on average) having from 2 to 10 ethoxy groups, and mixtures thereof. Particularly preferred surfactants also include the anionic surfactants. Suitable anionic surfactants for use herein include alkali metal fatty acids (eg, sodium or potassium), or soaps thereof, containing from about 8 to about 24, preferably from about 10 to about 20 carbon atoms. carbon. Fatty acids, including those used to make soaps, can be obtained from natural sources such as, for example, glycerides derived from plants or animals (for example, palm oil, coconut oil, babassu oil, soybean oil, oil of castor oil, tallow, whale oil, fish oil, fat, lard, and mixtures thereof). The fatty acids can also be prepared synthetically (for example, by oxidation of oil supply materials, or by the Fischer-Tropsch process). Alkali metal soaps can be obtained by direct saponification of fats and oils, or by neutralization of the free fatty acids that are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, that is to say, coconut and sodium and potassium tallow soaps.

The term "sebum" is used herein in connection with mixtures of fatty acids which typically have a carbon chain length distribution of approximately 2.5% C14, 29% C16, 23% C18, 2% acid palmitoleic, 41.5% oleic acid and 3% linoleic acid (the first three fatty acids named are saturated). Other mixtures with similar distribution, such as fatty acids derived from tallow and butter from several animals, are also included within the term tallow. The tallow may also be hardened (i.e., hydrogenated) to convert all unsaturated fatty acid portions or part thereof into saturated fatty acid portions. When the term "coco" is used herein, it refers to mixtures of fatty acids which typically have a carbon chain length distribution of about 8% C8, 7% C10, 48% C12, 17% of C 4, 9% of C16, 2% of C18, 7% of oleic acid and 2% of linoleic acid (the first six fatty acids named being saturated). Other sources having a similar carbon chain length distribution, such as palm kernel oil and babassu oil, are included within the term coconut oil. Other anionic surfactants suitable for use herein include water-soluble salts, particularly the alkali metal salts, of organic sulfuric reaction products having in the molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms, and a radical selected from the group consisting of ester radicals of sulfuric acid and sulfonic acid. Important examples of these synthetic detergents are sodium, ammonium and potassium alkyl sulphates, especially those obtained by sulfating the higher alcohols produced by reduction of tallow glycerides or coconut oil; Sodium or potassium alkylbenzenesulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, especially those of the types described in the U.S. Patents. Nos. 2,220,099 and 2,477,383, incorporated herein by reference; sodium alkyl glyceryl ether sulfonates, especially the ethers of the higher alcohols derived from tallow and coconut oil; monoglyceride sulfates and fatty acid sulfonates of sodium coconut oil; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (for example, coconut oil or tallow alcohols) and about three moles of ethylene oxide; sodium or potassium salts of ethylene oxide ether sulfates of alkylphenol with about four ethylene oxide units per molecule, and in which the alkyl radicals contain about 9 carbon atoms; the reaction product of fatty acids esterified with isothionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyl taurine in which the fatty acids, for example, are derived from coconut oil; and others known in the art, a number being specifically described in the US patents. Nos. 2,486,921, 2,486,922 and 2,396,278, incorporated herein by reference. Suitable zwitterionic detergents for use herein include betaine and betaine-like detergents, wherein the molecule contains basic groups and acids that form an inner salt, giving the molecule cationic and anionic hydrophilic groups on a broad scale of pH. Some common examples of these detergents are described in the US patents. Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference. The preferred zwitterionic detergent compounds have the formula: wherein R1 is an alkyl radical containing from 8 to 22 carbon atoms, R2 and R3 contain from 1 to 3 carbon atoms, R4 is an alkylene chain containing from 1 to 3 carbon atoms, X is selected from the group consisting of hydrogen and a hydroxyl radical, and Y is selected from the group consisting of of carboxyl and sulfonyl radicals, and wherein the sum of radicals R1, R2 and R3 is from 14 to 24 carbon atoms. 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 or N-alkyltaurines, such as those prepared by reacting dodecylamine with sodium isethionate in accordance with the teachings of the EU patent No. 2,658,072, N-higher alkylaspartic acids such as those produced in accordance with the teachings of the U.S. patent. No. 2,438,091, and the products marketed under the trade name "Miranoi" and described in the U.S. patent. No. 2,528,378, said patents being incorporated herein by reference. Other synthetic detergents, and listings of their commercial sources, can be found in McCutcheon's Detergents and Emulsifiers, North American edition of 1980, incorporated herein by reference. Suitable amphoteric surfactants include the amine oxides corresponding to the formula: RR 'R "N- * O wherein R is a primary alkyl group containing 6 to 24 carbons, preferably 10 to 18 carbons, and wherein 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 major part - of the molecules, generally at least 70%, preferably at least 90% of the molecules, and the oxides of amine which are especially preferred are those in which R contains 10 to 18 carbons, and R 'and R "are methyl Examples of the preferred amine oxides are N-hexyl dimethylamine oxide, N-octyldimethylamine oxide, N-deciidimethylamine, N-dodecyldimethylamine oxide, N-tetradecyldimethylamine oxide, N-hexadecyldimethylamine oxide, N-octadecyldimethylamine oxide, N-eicosiidimethylamine oxide, N-docosyldimethylamine oxide, N-tetracosyldimethylamine oxide, amine oxides corresponding in which both methyl groups or one of them are replaced with ethyl or 2-hydroxyethyl groups, and mixtures thereof A highly preferred amine oxide to be used herein is of N-decyldimethylamine. Other amphoteric surfactants suitable for the purpose of the invention are 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 to 24 carbons, preferably 10 to 18 carbons, and wherein 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. 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: [R2 (OR3) and] [R4 (OR3) and] 2R5N +? - wherein R2 is a group alkyl or alkylbenzyl 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 of them; 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 the joining of two groups R 4, -CH 2 CHOH-CHOHCOR 6 CHOHCH 2 OH, wherein R 6 is any hexose or hexose polymer having a molecular weight of less than about 1000, and hydrogen when and not being 0; R5 is equal to R4, or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not greater than 18; each y is from 0 to about 10, and the sum of the values of y is from 0 to about 15; and X is any compatible anion. Other cationic surfactants useful herein are also disclosed in the U.S. patent. 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference. The compositions of the present invention may comprise another anti-rutting ingredient above the N-vinyl pyrrolidone copolymer and the alkylenically unsaturated monomer or mixtures thereof. Anti-rutting ingredients suitable for use herein include those selected from the group consisting of polyalkoxylene glycol, single and double block polyalkoxylene glycol and a mixture thereof, as defined herein below. The compositions of the present invention can comprise up to 20% by weight of the total composition of said antirecuring ingredient or a mixture thereof, preferably from 0.01% to 10%, most preferably from 0.1% to 5% and more preferably from 0.2% to 2%. The polyalkoxylene glycols suitable for use herein are in accordance with the formula H-O- (CH2-CHR2?) N-H. The individual block polyalkoxy-glycols suitable for use herein are in accordance with the formula R1-O- (CH2-CHR2O) n-H. The double block polyalkoxylene glycols suitable for use herein are in accordance with the formula R? - O- (CH2-CHR2O) n-R3. In these formulas, the substituents Ri and R3 are each independently substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chains having from 1 to 30 carbon atoms, or linear or branched, substituted or unsubstituted hydrocarbon chains. amino carriers having from 1 to 30 carbon atoms, R 2 is hydrogen or a straight or branched hydrocarbon chain having from 1 to 30 carbon atoms, and n is an integer of more than 0. Preferably, R 1 and R 3 are each one independently alkyl groups, alkenyl groups or substituted or unsubstituted, saturated or unsaturated, linear or branched aryl groups, having from 1 to 30 carbon atoms, preferably from 1 to 16, more preferably from 1 to 8, and most preferably from 1 to 4 carbon atoms, or alkyl groups, alkenyl groups or linear or branched, substituted or unsubstituted aryl groups possessing amino and having from 1 to 30 carbon atoms, s preferably from 1 to 16, still more preferably from 1 to 8, and most preferably from 1 to 4 carbon atoms. Preferably, R2 is hydrogen or an alkyl group, alkenyl group or straight or branched aryl group having from 1 to 30 carbon atoms, more preferably from 1 to 16, more preferably from 1 to 8 carbon atoms, and most preferably is methyl or hydrogen. Preferably, n is an integer from 5 to 1000, most preferably from 10 to 100, even more preferably from 20 to 60 and more preferably from 30 to 50. Preferred polyalkoxylene glycols, monoblocked and diblocked polyalkoxylene glycols to be used herein have a weight molecular weight of at least 200, most preferably from 400 to 5000 and most preferably even from 800 to 3000. Individual block polyalkoxylene glycols suitable for use herein include 2-aminopropylpolyethylene glycol (PM 2000), methylpolyethylene glycol (MW 1800) and the like. Said single block polyalkoxylene glycols may be commercially available from Hoechst under the polyglycol or Hunstman series under the trademark XTJ®. Suitable polyalkoxylene glycols for use herein are polyethylene glycols such as polyethylene glycol (MW 2000).

Preferred double block polyalkoxylene glycols for use in accordance with the present invention include O, O'-bis (2-aminopropyl) polyethylene glycol (MW 2000), O, O, -bis (2-aminopropyl) polyethylene glycol (MW 400), OR .O'-dimethyl polyethylene glycol (MW 2000), dimethyl polyethylene glycol (MW 2000), or mixtures thereof. A double block polyalkoxyglycol which is preferred to be used herein is dimethylpolyethylene glycol (MW 2000). For example, dimethylpolyethylene glycol may be commercially available from Hoechst as the polyglycol series, for example PEG DME-2000®, or from Huntsman under the name of Jeffamine® and XTJ®. These polyalkoxylene glycols, single or double block polyalkoxylene glycols contribute to the benefit of the compositions of the present invention, that is, they help to further improve the cleaning performance of subsequent times. Other polymers suitable for use in the compositions of the present invention as preferred optional ingredients are vinylpyrrolidone homopolymers. Typically, the compositions of the present invention may comprise up to 20% by weight of the total composition, of a vinylpyrrolidone homopolymer, preferably from 0.01% to 10%, most preferably from 0.1% to 5% and more preferably from 0.2% to 2%. %. The vinylpyrrolidone homopolymers suitable for use herein, is a homopolymer 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 more preferably from 20 to 10,000. Accordingly, the vinylpyrrolidone homopolymers ("PVP") suitable for use herein have an average molecular weight of 1,000 to 100,000,000, preferably 2,000 to 10,000,000, more preferably 5,000 to 1,000,000, and most preferably 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 (average molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000) and PVP K-90 (average molecular weight of 360,000). Other suitable vinylpyrrolidone homopolymers which are commercially available from BASF Cooperation, include Sokalan HP 165 and Sokalan HP 12, vinylpyrrolidone homopolymers known to those skilled in the detergent field (see, for example, EP-A-262, 897 and EP-A-256, 696).

These vinylpyrrolidone homopolymers contribute to the benefit of the compositions of the present invention, that is, they help to further improve the cleaning performance of the first and subsequent times. The compositions herein may further comprise other polymeric compounds, up to a level of 20% by weight of the total composition, preferably from 0.01% to 5%, such as a polymer containing carboxylate, or mixtures thereof. By "carboxylate-containing polymer" is meant herein a polymer or copolymer comprising at least one monomer unit, containing at least one carboxylate functionality. Any polymer containing carboxylate known to those skilled in the art can be used in accordance with the present invention, such as homo- or co-polymeric polycarboxylic acids or their salts including polyacrylates, and polymers or copolymers of maleic anhydride and / or acrylic acid and the like, or mixtures thereof. In addition, said carboxylate-containing polymers can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence is adequate, in the polymeric polycarboxylates of the present, of monomeric segments which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Said polymers based on acrylic acid, which are useful herein, are the water-soluble salts of polymerized acrylic acid. The average molecular weight of said polymers in the acid form preferably ranges from about 2,000 to 1,000,000, more preferably from about 10,000 to 150,000 and most preferably from about 20,000 to 100,000. The water-soluble salts of said acrylic acid polymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl, U.S. Pat. 3,308,067, issued March 7, 1967. Copolymers based on acrylic acid / maleic acid can also be used as a preferred carboxylate-containing polymer. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of said copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, and most preferably from about 7,000 to 65,000. The ratio of acrylate: maleate segments in said copolymers will generally range from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. The water-soluble salts of said acrylic acid / maleic acid copolymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. The snowflake! Soluble acrylate / maleate dimers of this type are known materials which are described in European Patent Application No. 66915, published on December 15, 1982. Particularly preferred is an acrylic acid / maleic acid copolymer with an average molecular weight of approximately 70,000. Said copolymers are commercially available from BASF under the tradename SOKALAN CP5. Other carboxylate-containing polymers suitable for use herein include cellulose derivatives such as carboxymethylcellulose. For example, carboxymethylcellulose can be used as a salt with conventional cations such as sodium, potassium, amines or substituted amines. The compositions according to the present invention may further comprise a divalent counterion, or mixtures thereof. All divalent ions known to those skilled in the art may be used herein. Preferred divalent ions which will be used herein are calcium, zinc, cadmium, nickel, copper, cobalt, zirconium, chromium and / or magnesium, and more preferred are calcium, zinc and / or magnesium. Said divalent units can be added in the form of salts, for example, as chloride, acetate, sulfate, formate and / or nitrate, or as a complex metal salt. For example, calcium may be added in the form of calcium chloride, magnesium such as magnesium acetate or magnesium sulfate, and zinc as zinc chloride. In one embodiment of the present invention, said carboxylate-containing polymer and said divalent counterion can be added as an ingredient, provided that the molar ratio of said carboxylate-containing polymer: said divalent counterion / salt is from 12: 1 to 1: 32. . In the embodiment herein, wherein said carboxylate-containing polymer and said divalent counterion are present in the compositions herein, they are preferably present at a molar ratio of said polymer: said divalent counterion of 12: 1 to 1: 32, more preferably from 8: 1 to 1: 16, and most preferably from 4: 1 to 1: 6. Preferred molar ratios of said polymer: said divalent counter ion, are those where excellent shine is obtained in the most economical way. The liquid compositions of the present invention may further comprise a builder or a mixture thereof, as an optional ingredient. Suitable detergency builders for use herein include polycarboxylates and polyphosphates, and salts thereof. Typically, the compositions of the present invention comprise up to 20% by weight of the total composition, of a builder or mixtures thereof, preferably from 0.1% to 10%, and more preferably from 0.5% to 5%.

Suitable and preferred polycarboxylates for use herein are organic polycarboxylates wherein the highest LogKa, measured at 25 ° C / ion resistance at 0.1M, is between 3 and 8, where the sum of LogKCa + LogKMg, measured at 25 ° C / ionic resistance at 0.1M, is greater than 4, and where LogKCa = LogKMg ± 2 units, measured at 25 ° C / ionic resistance at 0.1M. Said suitable and preferred polycarboxylates include citrate and complexes of the formula: CH (A) (COOX) -CH (COOX) -O-CH (COOX) -CH (COOX) (B) wherein A is H or OH; B is H u -O-CH (COOX) -CH 2 (COOX); and X is H or a salt forming cation. For example, if in the above general formula A and B are H, then the compound is oxydisuccinic acid and its water-soluble salts. If A is OH and B is H, then the compound is monosuccinic tartrate acid (TMS) and its water-soluble salts. If A is H and B is -O- CH (COOX) -CH2 (COOX), then the compound is disuccinic tartrate acid (TDS) and its water-soluble salts. Mixtures of these detergency builders are especially preferred for use herein. Particularly from TMS to TDS, these builders are described in the U.S. patent. No. 4,663,071, issued to Bush et al., May 5, 1987. Other polycarboxylate ether suitable for use herein include copolymers of maleic anhydride with ethylene or methyl vinyl ether, 1,3-trihydroxybenzene 2,4,6- trisulphonic and carboxymethyloxysuccinic acid.

Other useful polycarboxylate builders include the hydroxypolycarboxylate ether represented by the structure: HO- [C (R) (COOM) -C (R) (COOM) -O] nH wherein M is hydrogen or a cation wherein the salt The resultant is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably, n is from about 2 to about 10, more preferably n averages from about 2 to about 4), and each R is the same or different and selected from hydrogen, C 1-4 alkyl or C? -4 substituted alkyl (preferably, R is hydrogen). Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in the U.S. Patents. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903, each of which is incorporated herein by reference. Preferred among said cyclic compounds are dipicolinic acid and chelidanic acid. Polycarboxylates also suitable for use herein are melific acid, succinic acid, polymaieic acid, benzene 1, 3,5-tricarboxylic acid, benzenecarboxylic acid and carboxymethyloxysuccinic acid, and soluble salts thereof. Other carboxylate builder builders suitable herein include the carboxylated carbohydrates described in the U.S. patent. 3,723,322, Diehl, issued March 28, 1973, incorporated herein by reference. Other carboxylates suitable for use herein, but which are less preferred because they do not meet the above criteria, are the alkali metal, ammonium and substituted ammonium salts of polyacetic acids. Examples of polyacetic acid builder salts are sodium, potassium, lithium, ammonium and substituted ammonium salts, of ethylenediaminetetraacetic acid and nitrilotriacetic acid. Other suitable but less preferred polycarboxylates are those known as alkyliminoacetic builders, such as methyliminodiacetic acid, alanin diacetic acid, methyl glycine diacetic acid, hydroxypropylene iminodiacetic acid and other builders of alkyliminoacetic acid. Also suitable in the compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds described in the U.S. patent. 4,566,984, Bush, issued January 28, 1986, incorporated herein by reference. Useful succinic acid builders include C5-C20 alkylsuccinic acids, and you come out of them. A particularly preferred compound of this type is dodecenylsuccinic acid. The alkylsuccinic acids are typically of the general formula R-CH (COOH) CH2 (COOH), ie, succinic acid derivatives, wherein R is hydrocarbon, for example, C10-C20 alkyl or alkenyl, preferably C 2- C16, or wherein R can be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the aforementioned patents. The succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group, and are described in European patent application 86200690.5 / 0200263, published November 5, 1986. Examples of useful builders include also carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexane-hexacarboxylate and sodium and potassium cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates and copolymers of maleic anhydride with methyl vinyl ether or ethylene. Other suitable polycarboxylates are the polyacetal carboxylates described in the U.S. patent. 4,144,226, Crutchfield et al., Issued March 13, 1979, incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, a glyoxylic acid ester and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate upon rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant. Polycarboxylate builders are also described in the U.S. patent. 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid. Polyphosphonates suitable for use herein are the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by tripolyphosphates, pyrophosphates and vitreous polymeric metaphosphates), and phosphonates. The most preferred builder for use herein is citrate. Suitable perfumes to be used herein include materials that provide an olfactory aesthetic benefit and / or encompass any "chemical" flavor that the product may have. The main function of a small fraction of the highly volatile and low-boiling perfume components (having low boiling points) in these perfumes is to improve the fragrance of the product itself, rather than having an impact on the subsequent aroma of the product. surface that is being cleaned. However, some of the less volatile and high-boiling perfume ingredients give a fresh and clean impression to the surfaces, and it is convenient 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 the nonionic detergent surfactants. The ingredients and perfume compositions suitable for use herein are those conventional in the art. The selection of any perfume component, or amount of perfume, is based solely on aesthetic considerations. Suitable perfume compositions and compositions can be found in the art, including US patents. Nos. 4,145,184, Brain 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 being incorporated herein by reference. In general, the degree of substantivity of a perfume is almost proportional to the percentages of the substantive perfume material used. Relatively substantive perfumes contain at least about 1%, preferably at least about 10%, of substantive perfume materials. Substantive perfume materials are those aromatic compounds that are deposited on surfaces by the cleaning process, and are detectable by people with normal olfactory acuity. Such materials typically have vapor pressures lower than those of the perfume material on average. Likewise, they typically have molecular weights of about 200 and more, and are detectable at levels lower than those of the perfume material on average. The perfume ingredients useful herein, together with their aromatic character 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 the highly volatile and low boiling perfume ingredients are: anethole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, isobornyl acetate, camphene, ciscitral (neral), citronellal, citronellol, citronellyl acetate, para-cymene, decanal, dihydrolinalool, dihydromyrcenol, dimethyl phenyl carbinol, eucalyptol, geranial, geraniol, geranyl acetate, geranyl nitrile, cis-3-hexeniio acetate, hydroxycitronellal, d-limonene, linalool, linalool oxide, linalyl acetate, linalyl propionate, methyl anthranilate, alpha-methyl ionone, methyl nonyl acetaldehyde, methyl fenii carbinyl acetate, laevo acetate -mentyl, menthone, iso-menthone, myrcene, mycorrhil acetate, mircenol, nerol, neryl acetate, nonyl acetate, phenyl ethyl alcohol, alpha-pinene, beta-pinene, gamma-terpinene, alpha-terpineol, bet a-terpineol, terpinyl acetate and vertenex (para-tertiary butyl cyclohexyl 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. Lemon oil and orange terpenes contain approximately 95% d-limonene. Examples of moderately volatile perfume ingredients are: amyl cinnamic aldehyde, iso-amyl salicylate, beta-caryophyllene, cedrene, cinnamic alcohol, coumarin, dimethyl benzyl carbinyl acetate, ethyl vanillin, eugenol, iso-eugenol, flower acetate, heliotropin , 3-cis-hexenyl salicylate, hexyl salicylate, lilial (para-tertiary butyl-alpha-methyl-hydrocinnamic aldehyde), gamma-methyl ionone, nerolidol, patchouli alcohol, phenyl hexanol, beta-selinose, trichloromethyl phenyl carbinyl acetate, triethyl citrate, vanillin and veratraldehyde. The cedar wood terpenes are formed mainly of alpha-cedrene, beta-cedrene and other sesquiterpenes of C15H24. Examples of the less volatile and high boiling perfume ingredients are: benzophenone, benzyl salicylate, ethylene brasylate, galaxolide (1, 3,4,6,7, 8-hexahydro-4,6,6,7, 8,8-hexamethyl-cyclopenta-gamma-2-benzopyran), hexyl cinnamic aldehyde, lyral (4- (4-hydroxy-4-methyl pentyl) -3-cyclohexene-10-carboxyaldehyde), methyl cedrone, methyl dihydrojasmonate , methyl-beta-naphthyl ketone, musk ndanone, musk ketone, musk *** and phenyl ethyl phenyl acetate. The selection of a particular perfume ingredient is determined primarily by aesthetic considerations. The liquid compositions herein may further comprise a perfume ingredient, or mixtures thereof, in amounts up to 5.0% by weight of the total composition, preferably in amounts of 0.1% to 1.5%. Another class of optional compounds that will be used herein, includes chelating agents, or mixtures thereof. Chelating agents can be incorporated into the compositions herein in amounts ranging from 0.0% to 10.0% by weight of the total composition, preferably from 0.1% to 5.0%. Phosphonate chelating agents suitable for use herein may include alkali metal 1 -hydroxydiphosphonates (HEDP), alkylene poly (alkylene phosphonates), as well as aminophosphonate compounds, including amino aminotri (methylene phosphonic acid) (ATMP), nitrilotriemethylene phosphonates (NTP), ethylenediaminetetramethylenephosphonates and diethylenetriaminepentamethylenephosphonates (DTPMP). The phosphonate compounds can be present in their acid form or as salts of different cations in all their acid functionalities, or some of them. Preferred phosphonate chelating agents to be used herein are diethylenetriam and nopentamethylphosphonate (DTPMP) and ethane-1-hydroxy diphosphonate (HEDP). Said 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 the US patent. 3,812,044, issued May 21, 1974 to Connor and others. Preferred compounds of this type in their acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelating agent for use herein is ethylenediamine-N, N'-disuccinic acid, or alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. Ethylenediamine-N, N'-disuccinic acids, especially the (S, S) isomer, have been extensively described in the US patent. 4,704,233, from November 3, 1987 to Hartman and Perkins. Such acids, for example, are commercially available under the tradename ssEDDS®, from Palmer Research Laboratories. Suitable aminocarboxylates for use herein include ethylenediaminetetraacetates, diethylenetriaminepentaacetates, diethylenetriaminepentaacetates (DTPA), N-hydroxyethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates., triethyltraminehexalacetates, ethanol diglycine, propylenediaminetetraacetic acid (PDTA) and methyl diamine glycolic acid (MGDA), in their acid form, or in their alkali metal, ammonium and substituted ammonium salt forms. Particularly suitable aminocarboxylates for use herein are diethylenetriaminepentaacetic acid, propylene diamine tetraacetic acid (PDTA) which, for example, is commercially available from BASF under the tradename Trilon FS®, and diacetic methyl glycine acid (MGDA).

Other carboxylate chelating agents that will be used herein include salicylic acids, aspartic acid, glutamic acid, glycine, malonic acid, or mixtures thereof. The compositions according to the present invention may further comprise an agent for the control of foams, such as 2-alkylalcanol, or mixtures thereof, as a preferred optional ingredient. Particularly suitable for use in the present invention are 2-alkyl alkanols having an alkyl chain comprising from 6 to 16 carbon atoms, preferably from 8 to 12 carbon atoms, and a terminal hydroxy group, said chain of alkyl being substituted in the alpha position by an alkyl chain comprising from 1 to 10 carbon atoms, preferably from 2 to 8, and more preferably from 3 to 6 carbon atoms. Such suitable compounds are commercially available, for example, in the Isofol® series, such as Isofol® 12 (2-butyl octanol) or Isofol® 16 (2-hexyl decanol). Typically, the compositions herein may comprise up to 2% by weight of the total composition of a 2-alkyl alkanol, or mixtures thereof, preferably from 0.1% to 1.5%, and more preferably from 0.1% to 0.8%. The compositions of the present invention may further comprise a solvent or a mixture thereof. The solvents that will be used herein include all those known to those skilled in the art of hard surface cleaning compositions. Suitable solvents for use herein include ethers and diethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms, glycols or alkoxylated glycols, alkoxylated aromatic alcohols , aromatic alcohols, branched aliphatic alcohols, branched alkoxylated aliphatic alcohols, linear alkoxylated C1-C5 alcohols, linear C1-C5 alcohols, hydrocarbons and halohydrocarbons of C8-C14 alkyl and cycloalkyl, C6-C16 glycol ethers, and mixtures of the same. Suitable glycols to be used herein are in accordance with the formula HO-CR1 R2-OH, wherein R1 and R2 are independently H or a C2-C10 saturated or unsaturated aliphatic hydrocarbon chain, and / or a chain of cyclic hydrocarbon. Suitable glycoids to be used herein are dodecane glycol and / or propanediol. Suitable alkoxylated glycols to be used herein are in accordance with the formula R- (A) n-R 1 -OH, wherein R is H, OH, a saturated or unsaturated linear alkyl of 1 to 20 carbon atoms, preferably from 2 to 15, and more preferably from 2 to 10 carbon atoms, wherein R 1 is H or a linear saturated or unsaturated alkyl of 1 to 20 carbon atoms, preferably 2 to 15, and more preferably 2 to carbon atoms, and A is an alkoxy group, preferably ethoxy, methoxy and / or propoxy, and n is from 1 to 5, preferably from 1 to 2. Suitable alkoxylated glycols to be used herein are methoxyoctadecanol and / or ethoxyethoxyethanol .

Suitable alkoxylated aromatic alcohols to be used herein are in accordance with the formula R (A) n-OH, wherein R is an aryl group substituted by alkyl or unsubstituted by alkyl of 1 to 20 carbon atoms, preferably 2 to 15, and more preferably 2 to 10 carbon atoms, wherein A is an alkoxy, preferably butoxy, propoxy and / or ethoxy group, and n is an integer from 1 to 5, preferably from 1 to 2. The aromatic alcohols Suitable alkoxylates are benzoxyethanol and / or benzoxypropanol. Suitable aromatic alcohols which will be used herein are in accordance with the formula R-OH, wherein R is an aryl group substituted by alkyl or unsubstituted by alkyl of 1 to 20 carbon atoms, preferably 1 to 15, and more preferably from 1 to 10 carbon atoms. For example, a suitable aromatic alcohol to be used herein is benzyl alcohol. Suitable aliphatic branched alcohols which will be used herein are in accordance with the formula R-OH, wherein 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. Particularly suitable aliphatic branched alcohols which will be used herein include 2-ethylbutanol and / or 2-methyIbutanol. Suitable alkoxylated aliphatic branched alcohols to be used herein are in accordance with the formula R (A) n-OH, wherein 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, preferably butoxy, propoxy and / or ethoxy group, and n is an integer from 1 to 5, preferably from 1 to 2. Suitable alkoxylated aliphatic branched alcohols they include 1-methylpropoxyethanol and / or 2-methylbutoxyethanol. Suitable linear akoxylated C1-C5 alcohols to be used herein are in accordance with the formula R (A) n-OH, wherein R is a saturated or unsaturated linear alkyl group of 1 to 5 carbon atoms, preferably 2 to 4, wherein A is an alkoxy, preferably butoxy, propoxy and / or ethoxy group, and n is an integer from 1 to 5, preferably from 1 to 2. Suitable linear alkoxylated aliphatic C1-C5 alcohols are butoxypropoxypropanol (n) -BPP), butoxyethanol, butoxypropanol, ethoxyethanol, or mixtures thereof. Butoxipropoxypropanol is commercially available under the tradename n-BPP® from Dow Chemical. Suitable linear C 1 -C 5 alcohols to be used herein are in accordance with the formula R-OH, wherein R is a saturated or unsaturated linear alkyl group of 1 to 5 carbon atoms, preferably 2 to 4. Suitable linear C1-C5 alcohols are methanol, ethanol, propanol, or mixtures thereof. Other suitable solvents include butyl diglycol ether (BDGE), butyltriglycol ether, ter-amyl ether, and the like. Particularly preferred solvents which will be used herein are butoxy propoxy propanol, butyldiglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol, and mixtures thereof. Typically, the compositions of the present invention comprise up to 20% by weight of the total composition, of a solvent or mixtures thereof, preferably from 0.5% to 10% by weight, and more preferably from 1% to 8%. The liquid compositions herein may also comprise a chlorine releasing component. The compositions according to the present invention typically comprise up to 20% by weight of the total composition of a chlorine-releasing component, preferably from 0.1% to 15%, most preferably from 1% to 10% by weight. The chlorine release component suitable for use herein is an alkali metal hypochlorite. Advantageously, the composition of the invention is stable in the presence of this bleaching component. Although alkali metal hypochlorites are preferred, other hypochlorite compounds may also be used herein, and may be selected from calcium and magnesium hypochlorite. A preferred alkali metal hypochlorite to be used herein is sodium hypochlorite.

Packaging Form of the Compositions The compositions herein can be packaged in various suitable detergent packaging forms 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 operated spray supply containers, 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 disperser, preferably in a spray spray dispenser or pump spray dispenser. In addition, said spray type dispersers allow uniformly applying to a relatively large area of a hard surface to be cleaned, liquid cleaning compositions suitable for use in accordance with the present invention. Such spray type dispensers are particularly suitable for cleaning vertical surfaces. Suitable spray type dispensers to be used in accordance with the present invention include manually operated foam tripping type dispensers marketed, for example, by Specialty Packaging Products, Inc. or Continental Sprayers, Inc. These types of dispensers are describe, for example, in documents US-4,701, 311 to Dunnining and others, and US-4,646,973 and US-4,538,745 to Focarracci. Particularly preferred to be used herein are spray type dispensers such as T 8500®, commercially available from Continental Spray International, or T 8100®, commercially available from Canyon Northern Ireland. In said dispenser, the liquid composition is divided into liquid fine droplets which result in a spray that is directed onto the surface to be treated. Furthermore, in said spray type dispenser, the composition contained in the body of said dispenser is directed through the head of said dispenser by energy communicated to a pumping mechanism by the user as said user operates said pumping mechanism. More particularly, in said head of the spray type dispenser, the composition is forced against an obstacle, for example, a grid or a cone or the like, thus providing shocks to help atomize the liquid composition, i.e., to facilitate the formation of liquid drops.

Process for Cleaning a Hard Surface The present invention also encompasses a method for cleaning a hard surface, wherein a liquid composition having a pH of more than 9 and comprising a copolymer of N-vinylpyrrolidone and a liquid is contacted with said surface. alkylenically unsaturated monomer or mixtures thereof as defined herein, preferably a quaternized or non-quaternized vinylpyrrolidone / dialkylaminoalkylacrylate or methacrylate copolymer.

The characteristics of the compositions used in the process for cleaning a hard surface (optional ingredients, levels, etc.) are as defined hereinabove. By "hard surfaces" is meant herein any type of surface typically found in houses, such as kitchens, bathrooms, interiors or exteriors of automobiles, floors, walls, tiles, windows, sinks, showers, plasticized shower curtains, washbasins, WCs, plates, articles and accessories and the like, made of different materials such as ceramics, vinyl, non-waxy vinyl, linoleum, melamine, glass, any type of plastic, laminated wood, metal or any painted or varnished or sealed surface, and the like . Hard surfaces also include household appliances that include, but are not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers, etc. The liquid compositions of the present invention can be contacted with the surface to be cleaned, in its pure form or in its diluted form. By "dilute form" it is meant herein that said liquid composition is typically diluted by the user with water. The composition is diluted before use to a typical dilution level of 10 to 200 times its weight of water, preferably 10 to 100. The usual recommended dilution level is a 1.2% dilution of the composition in water.

In the preferred method for cleaning hard surfaces according to the present invention, wherein said composition is used in diluted form, there is no need to rinse the surface after the application of the composition to obtain an initial and subsequent cleaning performance, as well as well as a good surface appearance. The present invention will be better illustrated by the following examples.

EXAMPLES The following compositions were obtained by mixing the indicated ingredients in the indicated proportions. All proportions are in% by weight of the total composition. These compositions were used in their pure and diluted form to clean hard surfaces such as floors, and provided excellent subsequent cleaning performance, as well as good initial cleaning and good surface appearance to the cleaned surfaces.

Compositions (% by weight): AB Nonionic surfactants EO5 from C9-11 2.5 2.4 1.9 2.5 EO5 from C12-14 2.5 3.6 2.9 2.5 EO6 from C7-9 3.2 8 -Dobanol® 23-3 1 .3 3.2 -AO21 1.9 4.8 2.0 1.0 0.8 4.0 Anionic surfactants PS of Na 3.0 LAS of Na 0.9 - 0.8 - - CS of Na 1.2 3.0 1.5 1.5 2.6 AS of C8 0.8 2.0 - - -Isalchem® AS _ _ 0.6 0.5 0.6 PH regulator Na2CO3 1.0 2.0 0.2 0.6 0.6 0.6 Citrate 0.75 0.5 0.5 0.5 Caustic 0.5 0.3 0.33 0.3 Foam control Fatty acid 0.4 0.8 0.4 0.6 0.3 0.5 Isofol 12® 0.3 - 0.3 0.3 0.3 - Polyquat 11® Polymers 0.5 1.0 0.5 0.3 1.0 0.6 Luviskol 73W® PEG DME-2000® Water and minor ingredients Up to 100% Efct 10.75 10.75 9.5 9.5 9.5 9.5 H K Nonionic surfactants EO5 of C9-1 1 2.5 2.5 2.5 2.5 EO5 of C12-14 2.5 2.5 2.5 2.5 2.5 EO6 of C7-9 Dobanol® 23-3 AO21 2.0 2.0 2.0 2.0 Anionic surfactants PS of Na LAS of Na 4.0 0.8 0.8 0.8 0.8 CS of Na 2.3 1.5 1.5 1.5 1.5 AS of C8 Isalchem® AS PH regulator Na2CO3 1.0 0.2 1.0 0.2 0.2 Citrate 0.75 - 0.75 0.75 Caustic 0.5 0.3 0.5 0.5 Foam control Fatty acid 0.4 0.4 0.5 0.4 0.4 Isofol 12® 0.3 0.3 0.3 0.3 0.3 Polyquat 11® 0.3 0.3 0.3 Polymers Luviskol 73W® 0.5 0.5 PEG DME-2000® 0.5 0.5 Water and minor ingredients _ _ Up to 100% _ ßH 10.5 9.5 11.0 9.5 9.5 Polyquat 11 is a quaternized copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate commercially available from BASF. Luviskol 73W® is a copolymer of polyvinylpyrrolidone and vinyl acetate 7: 3 commercially available from BASF. PEG DME-2000® is dimethylpolyethylene glycol (PM 2000) commercially available from Hoechst. Isofol 12® is 2-butyl octanol. Dobanol® 23-3 is a C12-C3 EO 3 nonionic surfactant commercially available from SHELL. AS of C8 is octyl sulfate available from Albright and Wilson, under the tradename of Empimin® LV 33. PS of Na is sodium paraffinsulfonate. The Na is sodium linear alkylbenzenesulfonate CS Na is sodium cumenesulfonate AO21 is an ethoxylated alcohol of EO21 of C12-14. Isalchem® AS is a branched alcohol alkyl sulfate commercially available from Enichem.

Claims (13)

NOVELTY OF THE INVENTION CLAIMS

1. A liquid composition for cleaning hard surfaces having a pH of more than 9 and comprising a copolymer of N-vinylpyrrolidone and an alkylenically unsaturated monomer or mixtures thereof.

2. A composition according to claim 1, comprising 0.01% to 20% by weight of the total composition of a copolymer of N-vinylpyrrolidone and an alkylenically unsaturated monomer or mixtures thereof, preferably 0.01% a to 10 %, most preferably 0.1% to 5% and more preferably 0.2% to 2%.

3. A composition according to any of the preceding claims, further characterized in that in said copolymer said N-vinylpyrrolidone has the following repeating monomer: wherein n is an integer of 10 to 1,000,000, preferably 20 to 100,000, and more preferably 20 to 10,000, and wherein said alkylenically unsaturated monomer is typically selected from the group consisting of maleic acid, chloromaleic acid, fumaric acid , itaconic acid, citraconic acid, phenylmaleic acid, aconitic acid, acrylic acid, vinyl acetate and anhydrides thereof, styrene, sulfonated styrene, alpha-methyl styrene, vinyl toluene, t-butyl styrene, and mixtures thereof.

4. A composition according to any of the preceding claims, further characterized in that said copolymer of N-vinylpyrrolidone and alkylenically unsaturated monomer is a copolymer of quaternized or non-quaternized vinylpyrrolidone / dialkylaminoalkylacrylate or methacrylate in accordance with the following formula: wherein n is between 20 and 99 and preferably between 40 and 90 mole%, and m is between 1 and 80 and preferably between 5 and 40 mole%; Ri represents H or CH 3; and denotes 0 or 1; R2 is -CH2-CHOH-CH2- or C? H2x, wherein x = 2 to 18; Rs 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, 1 / 2SO4, HSO4 and CH3SO3

5. A composition according to claim 4, further characterized in that said copolymer of N-vinylpyrrolidone and alkylenically unsaturated monomer is a quaternized or non-quaternized vinylpyrrolidone / dialkylaminoalkylacrylate or methacrylate copolymer

6. A composition according to any of the foregoing claims, which is an aqueous liquid composition having a pH of more than 10, most preferably 10.1 to 12 and more preferably from 10.5 to 11.

7. A composition according to any of the preceding claims, which further comprises a surfactant selected from the group consisting of nonionic surfactants, anionic surfactants, zwitterionic surfactants, amphoteric surfactants, cationic surfactants and mixtures thereof, typically at a level from 0.1% to 50% by weight of the total composition, preferably from 0.1% to 20% and more preferably from 1% to 10%.

8. - A composition according to any of the preceding claims, which further comprises an anti-rutting ingredient selected from the group consisting of: a polyalkoxy-glycol according to the formula H-O- (CH2-CHR2O) n-H; an individual block polyalkoxyglycol of the formula R? -O- (CH2-CHR2O) n-H; a double block polyalkoylene glycol of the formula R? -O- (CH2-CHR2?) n -R3 and a mixture thereof, wherein the substituents Ri and R3 are each independently substituted or unsubstituted hydrocarbon chains, saturated or embedded, linear or branched having 1 to 30 carbon atoms, or linear or branched hydrocarbon chains, substituted or unsubstituted amino carriers having from 1 to 30 carbon atoms, R 2 is hydrogen or a linear hydrocarbon chain or branched having from 1 to 30 carbon atoms, and wherein n is an integer of more than 0.

9. A composition according to claim 8, which comprises up to 20% by weight of the total composition of said ingredient. antirrassuciamiento and mixtures thereof, preferably of

0. 01% to 10%, most preferably from 0.1% to 5% and more preferably from

0. 2% to 2%.

10. A composition according to any of the preceding claims, which further comprises at least one optional ingredient selected from the group consisting of other polymers, perfumes, foam control agents, chelating agents, builders, solvents, pH regulators, bactericides, hydrotropes, colorants, stabilizers, radical scavengers, bleaches, bleach activators, enzymes, soil suspending agents, dye transfer agents, brighteners, anti-dusting agents, dispersants, dye transfer inhibitors, pigments , colorants and mixtures thereof. 1.

A method for cleaning a hard surface, further characterized in that a liquid composition according to any of the preceding claims is contacted with said surface.

12. The process for cleaning a hard surface according to claim 1, further characterized in that said composition is contacted with said surface after having been diluted with water.

13. The method according to claim 12, further characterized in that said surface is not rinsed after said composition has been put in contact with it.