CN1257534A - Akaline 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

Alkaline liquid hard surface cleaning compositions comprising N-vinylpyrrolidone copolymers

Technical Field

The present invention relates to liquid compositions for cleaning hard surfaces, especially those contaminated with oily stains and/or burnt/sticky food residues commonly found in kitchens.

Background

Liquid compositions for cleaning hard surfaces have been disclosed in the prior art. Much of the focus of such compositions has been on providing significant cleaning action on a variety of soils. In fact, it is known to include certain polymers in typical hard surface cleaning compositions in order to obtain a primary cleaning effect when the composition is first applied to a treated hard surface or a secondary cleaning effect due to an improved hard surface, in order to reduce or even prevent soil redeposition or otherwise facilitate repeated cleaning. However, such compositions are not entirely satisfactory as consumers desire hard surface cleaning compositions which are effective in providing both the first and next (subsequent) cleaning performance, particularly grease cleaning performance, to the treated hard surface.

It is therefore an object of the present invention to formulate liquid hard surface cleaning compositions which provide excellent first and next time cleaning performance on a variety of soils, especially greasy soils and/or burnt/sticky food residues commonly found in kitchens.

In addition, a disadvantage associated with conventional liquid hard surface cleaning compositions is their unsatisfactory stability against bacterial contamination from the point of view of the formulator. Indeed, bacterial instability can lead to consumer noticeable drawbacks such as color instability and/or odor instability of the composition. The conventional answer to this problem is to add a bactericide such as glutaraldehyde. However, such agents have the disadvantage that they can impart an unpleasant odour to the composition and increase the cost of the final composition. Accordingly, formulators are looking for additional solutions.

It is therefore another object of the present invention to formulate liquid hard surface cleaning compositions which provide excellent first and next time cleaning performance on a variety of soils while exhibiting improved stability against bacterial contamination.

It has now been found that these objects can be met by formulating liquid compositions having a pH above 9 and comprising specific anti-redeposition components, i.e. copolymers of vinylpyrrolidone and ethylenically unsaturated monomers or mixtures thereof, preferably quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers. In fact, it has surprisingly been found that the use of such copolymers of vinylpyrrolidone with ethylenically unsaturated monomers, in particular quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers, as defined above, in liquid compositions having a pH above 9, provides improved first and next time cleaning performance of the treated surface at a low total amount of the anti-redeposition component. In addition, it was found that improved stability against bacterial contamination is obtained by formulating liquid compositions comprising a copolymer as defined above with a pH above 9.

An advantage of the present invention is that the composition according to the invention gives first and next cleaning performance on various types of stains/soils while providing a good surface appearance to the surface.

Another advantage of the present invention is that the liquid compositions of the invention can be used to clean hard surfaces made of various materials, such as glazed and unglazed tiles, vinyl, non-waxy vinyl, linoleum, melamine, glass, plastic, plasticized wood, in neat and diluted conditions, for example, to a dilution level of 1: 200 (composition: water).

The following patent applications are examples of prior art.

WO94/26858 discloses liquid hard surface compositions (pH2-8) containing nonionic surfactants (1-30%) and anionic polymers having an average molecular weight of less than 1000,000, said polymers being free of quaternary nitrogen groups. The compositions have a surprising initial cleaning effect in addition to an anti-redeposition effect. In fact, WO94/26858 discloses that copolymers of acrylic acid, methacrylic acid and maleic anhydride derivatives, such as styrene and maleic acid, produce a streak-free modification after drying.

EP- ｃA-374471 discloses liquid hard surface cleaning compositions formulated to leave ｃA protective barrier on the treated surface, which protective barrier acts to protect the surface against redeposition of additional soil. These compositions comprise a polyethylene glycol alkylphenyl ether, lecithin and an amino-functional polydimethylsiloxane copolymer as a protective barrier compound and one or more glycols. Copolymers of vinylpyrrolidone and ethylenically unsaturated monomers or mixtures thereof are not disclosed.

EP- ｃA-635567 discloses ｃA liquid composition for cleaning solid surfaces comprising ｃA cleaning agent which is capable of depositing on the surface during the cleaning process and forming ｃA dry layer adhered to the surface, the dry layer having ｃA cohesive strength such that at least the outermost surface layer of the layer is removable by further washing. Polyvinylpyrrolidone is disclosed. Copolymers of vinylpyrrolidone and ethylenically unsaturated monomers or mixtures thereof are not disclosed.

Summary of The Invention

The present invention includes liquid hard surface cleaning compositions having a pH above 9 and comprising a copolymer of vinylpyrrolidone and an ethylenically unsaturated monomer, or mixtures thereof.

The present invention also includes a method of cleaning a hard surface wherein a liquid composition as defined herein above is contacted with said surface.

Detailed description of the invention liquid compositions

The compositions according to the invention which are particularly suitable for cleaning hard surfaces are liquid compositions. The liquid compositions of the present invention are preferably, but not necessarily, formulated as aqueous compositions. Aqueous compositions generally comprise from 50% to 99%, preferably from 60% to 95%, more preferably from 80% to 95% by weight of the total composition of water.

The liquid compositions of the present invention are formulated at a pH above 9, preferably a pH above 10, more preferably a pH of 10.1-12, most preferably a pH of 10.5-11. The pH of the compositions of the invention can be adjusted by any method known to those skilled in the art, for example, alkaline agents such as NaOH, KOH, K₂CO₃、Na₂CO₃And the like.

The compositions of the present invention comprise as an essential component a copolymer of N-vinylpyrrolidone and an ethylenically unsaturated monomer, or mixtures thereof. The compositions of the present invention generally comprise from 0.01% to 20% by weight of the total composition of a copolymer of N-vinylpyrrolidone and ethylenically unsaturated monomer or mixtures thereof, preferably from 0.01% to 10%, more preferably from 0.1% to 5%, most preferably from 0.2% to 2%.

N-vinyl pyrrolidone copolymers suitable for use in the present invention have the following repeating monomers:

wherein n (degree of polymerization) is an integer of 10 to 1000000, preferably 20 to 100000, more preferably 20 to 10000.

Ethylenically unsaturated monomers suitable for use in the copolymers of the present invention 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.

The molecular weight of the copolymer of vinylpyrrolidone and ethylenically unsaturated monomer or mixture thereof is not particularly critical as long as the copolymer is water-soluble, has some surface activity and can adsorb onto a hard surface from a liquid composition or solution containing it (i.e. under dilute use conditions), in such a way as to increase the hydrophilicity of the surface. However, preferred copolymers of N-vinylpyrrolidone and ethylenically unsaturated monomers or mixtures thereof have a molecular weight of 1000-000, preferably between 10000-500000, more preferably between 10000-200000.

Copolymers of N-vinylpyrrolidone with ethylenically unsaturated monomers, such as PVP/vinyl acetate copolymers, are commercially available from BASF under the trade name Luviskol @.

Particularly preferred copolymers of vinylpyrrolidone with ethylenically unsaturated monomers for use in the compositions of the present invention are quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers.

Vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers (quaternized or non-quaternized) suitable for use in the compositions of the present invention are according to the formula:wherein n is 20 to 99, preferably 40 to 90 mole%, and m is 1 to 80, preferably 5 to 40 mole%; r₁Represents H or CH₃(ii) a y is 0 or 1; r₂is-CH₂-CHOH-CH₂-or C_xH_2xWherein x is 2-18; r₃Represents lower alkyl of 1 to 4 carbon atoms, preferably methyl or ethyl, or

R₄Represents lower alkyl of 1 to 4 carbon atoms, preferably methyl or ethyl; x^-Selected from Cl, Br, I, 1/2SO₄、HSO₄And CH₃SO₃. The polymers can be prepared by the methods described in French patents 2077143 and 2393573.

The preferred quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers for use in the present invention have a molecular weight of 1000-1000000, preferably 10000-500000, more preferably 10000-100000.

The vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymer is commercially available under the name copolymer 845, Gafquat 734 or Gafquat 755 from ISP (New York, NY and Montreal, Canada) or from BASF under the name Luviquat.

Most preferred for the present invention is a quaternized copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate (polyquaternium-11) available from BASF.

The present invention is based on the discovery that liquid compositions of the invention having a pH above 9 and comprising a copolymer of N-vinylpyrrolidone with an ethylenically unsaturated monomer, preferably a vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymer (quaternized or non-quaternized), as defined herein, provide improved first and next time cleaning performance when treating hard surfaces compared to the first and next time cleaning performance provided by the same composition but comprising another anti-redeposition polymer, for example poly (trimethylaminoethyl) methacrylate. In fact, it is particularly surprising that this broad effect is obtained, i.e. not only the next wash performance is improved, but also the first wash performance, since the compositions of the prior art are not effective for both the initial and the subsequent wash. In addition, this effect is obtained at lower levels of total active anti-redeposition components than, for example, when using other polymeric substances such as poly (trimethylaminoethyl) methacrylate.

Although not wishing to be bound by theory, the first cleaning effect may be explained by the ability of the vinylpyrrolidone/ethylenically unsaturated monomer copolymer to chelate metal or other soil, thereby facilitating their removal from the surface being cleaned.

Although, without wishing to be bound by theory, the next cleaning effect may be explained as: it is speculated that copolymers of vinylpyrrolidone with ethylenically unsaturated monomers, as defined herein, in particular vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers (quaternized or non-quaternized) have the property of adsorbing to hard surfaces which have been treated for the first time in such a way that a lower hygroscopic layer remains thereafter. Once treated, the resulting hygroscopic layer can attract and retain atmospheric water vapor from the environment to more effectively reduce the adhesion of soils and/or facilitate the removal of soils subsequently deposited thereon, i.e., less work (e.g., less scrubbing and/or wiping and/or less chemical action) is required to remove soils in the next cleaning operation than in a similarly soiled hard surface treated for the first time with the same composition without the copolymer of vinylpyrrolidone and ethylenically unsaturated monomer or containing another polymeric species, such as poly (trimethylaminoethyl) methacrylate.

The advantage of the present invention is that effective first and next cleaning performance can be obtained with a total low amount of anti-redeposition components. In a preferred embodiment, the composition of the present invention comprises, based on the total weight of the composition, from 0.2% to 2% of a copolymer of vinylpyrrolidone and ethylenically unsaturated monomer or a mixture thereof, preferably from 0.2% to 1.5%, more preferably from 0.3% to 1%. Surprisingly not only when the composition of the invention is contacted in neat form with a hard surface to be cleaned, but also when the composition is contacted in diluted form, such as water: the highest dilution of the composition provides effective first and next time cleaning performance at 200: 1 contact surface.

By "cleaning performance" is meant herein the cleaning of various types of soils including grease, such as kitchen grease or burnt/sticky food residues (e.g. burnt milk) and the like commonly found in kitchens.

First dilution cleaning performance can be evaluated by the following test method: representative oily/granular artificial stains are applied thereto and then aged to prepare tiles of enamel, vinyl or ceramic. The test and reference compositions were diluted (e.g., 1: 50 or 1: 100 composition: water), applied to the sponge, and used together with a Sheen scrub tester to clean the tile. The number of cycles required to rinse to 100% clean is recorded. A minimum of 6 replicates were run for each contaminated tile, each time yielding two results relative to the reference composition.

The next dilution cleaning performance can be evaluated by the following test method: after the detailed procedure of the first cleaning, the tile used in the previous test was taken and directly re-contaminated without first being subjected to further washing or rinsing. The cleaning procedure was then repeated using a Sheen scrub tester, carefully allowing the test composition to be used to clean the same area of tile previously cleaned by them. The number of cycles required to rinse to 100% clean is recorded. A minimum of 6 replicates were run for each contaminated tile, each time yielding two results relative to the reference composition. This recontamination and washing step can be repeated up to 5 times.

The test method for evaluating the cleaning performance of the pure compositions was the same as the above method except that the test compositions and the reference compositions were used without dilution and rinsed with purified water after cleaning. This rinsing process can be repeated up to 5 times before the re-contamination step of the next cleaning evaluation.

A further advantage of the present invention is that improved stability against bacterial contamination is obtained by formulating liquid compositions having a pH above 9 and comprising a copolymer of vinylpyrrolidone and an ethylenically unsaturated monomer or a mixture thereof, preferably a vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymer (quaternized or non-quaternized).

By "stability against bacterial contamination" is meant that the compositions of the present invention have a lower tendency to contaminate or support the growth of bacteria than the same compositions formulated to a more neutral pH.

Stability against bacterial contamination can be assessed by culturing a test article with a standard series of strains of bacteria in a growth medium containing the composition being tested. Optional Components

The liquid composition of the present invention may comprise various optional components depending on the technical effect required and the surface to be treated.

Suitable optional ingredients for use in the present invention include surfactants, builders, chelating agents, polymers, solvents, buffers, bactericides, hydrotropes, colorants, stabilizers, radical scavengers, bleaches, bleach activators, foam control agents such as fatty acids, enzymes, soil suspending agents, dye transfer agents, brighteners, anti-dusting agents, dispersants, dye transfer inhibitors, pigments, dyes and/or perfumes.

The liquid composition of the present invention preferably comprises a surfactant or a mixture thereof. The surfactant may be present in the compositions of the present invention at a level of from 0.1% to 50%, preferably from 0.1% to 20%, more preferably from 1% to 10% by weight of the total composition.

Surfactants are desirable in the present invention because they also contribute to the cleaning performance and/or shine benefits of the compositions of the present invention. Surfactants useful herein include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.

Particularly preferred surfactants are nonionic surfactants. Suitable nonionic surfactants for use in the present invention include a class of compounds which can be broadly defined as those resulting from the condensation of an alkylene oxide group (hydrophilic) with an organic hydrophobic compound which may be branched or straight chain aliphatic (e.g., Guerbet or secondary alcohol) or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene group condensed with any particular hydrophobic group can be readily adjusted to give a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic moieties.

For example, a well-known class of nonionic synthetic detergents is commercially available under the trade name "Pluronic". These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide and propylene glycol. The hydrophobic portion of the molecule, of course, is rendered water insoluble and has a molecular weight of about 1500-1800. The addition of polyoxyethylene moieties to the hydrophobic portion tends to increase the water solubility of the overall molecule and the liquid character of the product is maintained to the point that the polyoxyethylene content is about 50% of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

(i) polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group of from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide present in an amount of from 10 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituents in such compounds may be derived from polypropylene, diisobutylene, octane, and nonane;

(ii) those compounds resulting from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine, wherein the amount of ethylene oxide and the product resulting from the reaction of propylene oxide and ethylenediamine in the composition may vary depending on the desired balance between hydrophobic and hydrophilic moieties. Examples are compounds containing from about 40% to about 80% by weight of polyoxyethylene and having a molecular weight of about 5000-;

(iii) condensation products of aliphatic alcohols having 8 to 18 carbon atoms in a linear or branched configuration with ethylene oxide, such as cocoalcohol ethylene oxide condensates wherein the cocoalcohol moiety has 10 to 30 moles of ethylene oxide per mole of cocoalcohol and 10 to 14 carbon atoms;

(iv) trialkyl amine oxides and trialkyl phosphine oxides, wherein one alkyl group has from 10 to 18 carbon atoms and the other two alkyl groups have from 1 to 3 carbon atoms; the alkyl group may contain a hydroxyl substituent; specific examples are dodecylbis (2-hydroxyethyl) amine oxide and tetradecyldimethylphosphine oxide.

Also useful as nonionic surfactants are the alkyl polysaccharides disclosed in U.S. Pat. No. 4,565,647 issued to Llenado on 21.1.1986, having a hydrophobic group of from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide hydrophilic group, such as polyglycosides, containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing sugar containing 5 or 6 carbon atoms may be used, for example glucose, galactose, and the glycosyl moiety may be substituted with a galactosyl moiety (the hydrophobic group is optionally attached at the 2-, 3-, 4-, etc. position, thereby giving a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide linkage may, for example, be between the 2-, 3-, 4-and/or 6-position of the preceding saccharide unit and a position of another saccharide unit.

Optionally, but less preferably, polyoxyalkylene chains may be present linking the hydrophobic moiety and the polysaccharide moiety. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include saturated or unsaturated, branched or unbranched alkyl groups 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 3 hydroxyl groups and/or the polyoxyalkylene chain can contain up to about 10, preferably less than 5, oxyalkylene moieties. Suitable alkylpolysaccharides are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta-and hexaglucoside, galactoside, lactoside, glucose, fructoside, fructose and/or galactose. Suitable mixtures include cocoalkyl, di, tri, tetra and pentaglucosides and tallow alkyl tetra, penta and hexaglucosides.

Preferred alkylpolyglycosides have the formula:

R²O(C_nH_2nO)_t(sugar base)_xWherein R is²Selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl group contains from about 10 to about 18 carbon atoms, preferably from about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is 0 to about 10, preferably 0; x is from about 1.3 to about 10, preferably from about 1.3 to about 3, and most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is first prepared and then reacted with glucose or a source of glucose to form the glucoside (attachment at the 1 position). The additional glycosyl units can then be linked between their 1-position and the 2-, 3-, 4-and/or 6-position of the preceding glycosyl unit, preferably predominantly between the 2-positions.

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 in the present invention, although not preferred. The hydrophobic portion of these compounds preferably has a molecular weight of about 1500 to about 1800 and exhibits water insolubility. The addition of polyoxyethylene moieties to the hydrophobic portion tends to increase the water solubility of the overall molecule and the liquid character of the product is maintained to the point that the polyoxyethylene content is about 50% of the total weight of the condensation product, which is equivalent to condensation with up to about 40 moles of ethylene oxide. Examples of this type of compound include some commercially available pluronics^TMSurfactant, sold by BASF.

Not preferred, but also suitable for use as the nonionic surfactant of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of these products is made up of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of about2500 to about 3000 molecular weight. The hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight polyoxyethylene and has a molecular weight of from about 5000 to about 11000. Examples of this type of nonionic surfactant include some of the commercially available Tetronic surfactants^TMCompound, sold by BASF.

Other suitable nonionic surfactants for use in the present invention include the following structuresPolyhydroxy fatty acid amides of formula (la):

wherein: r¹Is hydrogen, C₁-C₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or mixtures thereof, preferably C₁-C₄Alkyl, more preferably C₁Or C₂Alkyl, most preferably C₁Alkyl (i.e., methyl); r²Is C₅-C₃₁Hydrocarbyl, preferably straight chain C₇-C₁₉Alkyl or alkenyl, more preferably straight-chain C₉-C₁₇Alkyl or alkenyl, most preferably straight chain C₁₁-C₁₇Alkyl or alkenyl groups or mixtures thereof; z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly attached, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycosyl group. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As a raw material, high glucose corn syrup can be used as well as the individual sugars listed above. These corn syrups may result in a mixture of sugar components as Z. It should be clear that no other suitable starting materials are intended to be excluded here. Z is preferably selected from-CH₂(CHOH)_n-CH₂OH，-CH(CH₂OH)(CHOH)_n-1-CH₂OH，-CH₂-(CHOH)₂(CHOR′)(CHOH)-CH₂OH, wherein n is an integer from 3 to 5, including 3 and 5, R' is H or a cyclic or aliphatic monosaccharide group, and alkoxylated derivatives thereof. Most preferred are glycosyl groups wherein n is 4, in particular-CH₂-(CHOH)₄-CH₂OH。

In the formula (I), R¹It may be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R²-CO-N < can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capramide, palmitamide, tallowamide, and the like.

Z may be 1-deoxyglucityl, 2-deoxyfructosyl, 1-deoxymaltosyl, 1-deoxylactosyl, 1-deoxygalactosyl, 1-deoxymannose, 1-deoxymaltotriosyl or the like.

In one embodiment of the present invention, suitable nonionic surfactants for use are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C's having 3 to 15 ethoxy groups₈-C₁₄Alkylphenol ethoxylates and C having 2 to 10 ethoxy groups₈-C₁₈Alcohol ethoxylate (preferably C)₁₀Average), and mixtures thereof.

Particularly preferred surfactants also include anionic surfactants. Suitable anionic surfactants for use in the present invention include alkali metal salts (e.g., sodium or potassium) of fatty acids containing from about 8 to about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms, or soaps.

Fatty acids, including those used in the preparation of soaps, can be derived from natural sources such as glycerides derived from plants or animals (e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale oil, fish oil, tallow, grease, lard, and mixtures thereof). Fatty acids may also be prepared synthetically (for example by oxidation of petroleum feedstocks or by the Fischer-Tropsch process).

Alkali metal soaps can be prepared by direct saponification of fats and oils or by neutralization of free fatty acids prepared by another production method. Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from coconut oil and tallow, i.e., tallow and coconut oil sodium and potassium soaps.

The term "tallow" as used herein relates to mixed fatty acids having generally the following approximate carbon chain length distribution: 2.5% C14 acid, 29% C16 acid, 23% C18 acid, 2% palmitoleic acid, 41.5% oleic acid, and 3% linoleic acid (the first 3 listed are saturated fatty acids). Other mixtures having similar distributions, such as fatty acids from various animal fats and oils and lard, are also included within the term tallow. Tallow can also be hardened (i.e., hydrogenated), converting some or all of the unsaturated fatty acid moieties to saturated fatty acid moieties.

The term "coconut oil" as used herein refers to mixed fatty acids generally having a carbon chain length distribution as follows: about 8% C8 acid, 7% C10 acid, 48% C12 acid, 17% C14 acid, 9% C16 acid, 2% C18 acid, 7% oleic acid and 2% linoleic acid (the first 6 listed are saturated fatty acids). Other sources of fatty acids having similar carbon chain length distributions, such as fatty acids from palm kernel oil and babassu oil, are also included in the term coconut oil.

Other suitable anionic surfactants for use herein include the water-soluble salts, particularly the alkali metal salts, of organic sulfuric acid reaction products having in their molecular structure an alkyl group containing from about 8 to about 22 carbon atoms and a group selected from sulfonic acid and sulfate ester groups. Important examples of these synthetic detergents are sodium, ammonium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols produced from the glycerides of reduced tallow or coconut oil; sodium or potassium alkyl benzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, particularly those of the type described in U.S. Pat. Nos. 2220099 and 2477383 (which are incorporated herein by reference); sodium alkyl glyceryl ether sulfonates, particularly those ethers of the higher alcohols derived from tallow and coconut oil; sodium mono-coconut oil fatty acid glyceride sulfate and sodium sulfonate; sodium or potassium salts of sulfuric acid esters of the reaction product of 1 mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohol) and about 3 moles of ethylene oxide; sodium or potassium alkyl phenol ethylene oxide ether sulfate having about 4 units of ethylene oxide per molecule, wherein the alkyl group contains about 9 carbon atoms; reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, where the fatty acids are derived, for example, from coconut oil; sodium or potassium salts of fatty acid amides of methyl tauride, wherein the fatty acids are derived, for example, from coconut oil; and other compounds known in the art, some of which are specifically listed in US2486921, US2486922 and US2396278 (which are incorporated herein by reference).

Suitable zwitterionic detergents for use in the present invention include betaines and betaine-like detergents in which the molecule contains both basic and acidic groups that form internal salts, which impart to the molecule a broad pH rangeCationic and anionic hydrophilic groups. Some common examples of such detergents are described in US2,082,275, US2,702,279 and US2,255,082, which are incorporated herein by reference. Preferred zwitterionic detergent compounds have the formula:

wherein R is¹Is an alkyl radical having from 8 to 22 carbon atoms, R²And R³Containing 1 to 3 carbon atoms, R⁴Is an alkylene chain containing 1 to 3 carbon atoms, X is selected from hydrogen and hydroxy, Y is selected from carboxy and sulfo, and wherein R is¹、R²And R³The sum of the carbon atoms of the radicals is 14 to 24.

Representative of amphoteric and amphoteric detergents which may be cationic or anionic depending on the pH of the system are, for example, dodecyl β -alanine, N-alkyltaurines such as those prepared by reacting dodecylamine with sodium isethionate according to the teaching of U.S. Pat. No. 3,2658072, N-higher alkyl aspartates such as those prepared according to the teaching of U.S. Pat. No. 3,38091, and the products sold under the trade name "Miranol" and described in U.S. Pat. No. 4,8378, which patents are incorporated herein by reference.

Further synthetic detergents and their commercial sources are listed in McCutcheon's detergents and emulsifiers, north american editors, 1980, which are incorporated herein by reference.

Suitable amphoteric surfactants include amine oxides of the formula:

wherein R is a primary alkyl group having 6 to 24 carbon atoms, preferably 10 to 18 carbon atoms, and R' are each independently an alkyl group having 1 to 6 carbon atoms. The arrow in the formula is a normal representation of a semipolar bond. Preferred amine oxides are those in which at least the majority of the molecules, generally at least 70%, preferably at least 90%, of the primary alkyl groups in the molecules are linear, particularly preferred amine oxides are those in which R contains from 10 to 18 carbon atoms and R' and R "are both methyl. Examples of preferred amine oxides are N-hexyldimethylamine oxide, N-octyldimethylamine oxide, N-decyldimethylamine oxide, N-dodecyldimethylamine oxideAmines, N-tetradecyldimethylamine oxide, N-hexadecyldimethylammonium oxide, N-octadecyldimethylamine oxide, N-eicosyldimethylamine oxide, N-docosyldimethylamine oxide, N-tetracosyldimethylamine oxide, the corresponding amines in which one or two methyl groups are substituted with ethyl or 2-hydroxyethyl groups, and mixtures thereof. The most preferred amine oxide for use in the present invention is N-decyldimethylamine oxide.

Other suitable amphoteric surfactants for the purposes of the present invention are phosphine or sulfoxide surfactants of the formula:

wherein A is a phosphorus or sulfur atom, R is a primary alkyl group having from 6 to 24 carbon atoms, preferably from 10 to 18 carbon atoms, wherein R 'and R' are each independently selected from the group consisting of methyl, ethyl and 2-hydroxyethyl. The arrow in the formula is a normal representation of a semipolar bond.

Cationic surfactants suitable for use in the compositions of the present invention are those having one long chain hydrocarbon group. Examples of such cationic surfactants include ammonium salt surfactants such as alkyl dimethyl ammonium halides, and those having the formula:

[R²(OR³)_y][R⁴(OR³)_y]₂R⁵N⁺X^-wherein R is²Is alkyl or alkylbenzyl having 8 to 18 carbon atoms in the alkyl chain, each R³Is selected from-CH₂CH₂-、-CH₂CH(CH₃)-、-CH₂CH(CH₂OH)-、-CH₂CH₂CH₂-and mixtures thereof; each R⁴Is selected from C₁-C₄Alkyl radical, C₁-C₄Hydroxyalkyl radical, by linking two R⁴Benzyl ring structure formed by the radicals, -CH₂CHOH-CHOHCOR⁶CHOHCH₂OH, wherein R⁶Is any hexose or hexose polymer group having a molecular weight of less than about 1000, and hydrogen (when y is other than 0); r⁵Is as in R⁴The same group, or an alkyl chain, wherein R²Adding R⁵No more than about 18 total carbon atoms; each y is 0 to about 10 and the sum of the values of y is 0 to about 15; x is any compatible anion.

Other cationic surfactants useful in the present invention are also described in Cambre, U.S. patent 4,228,044, issued 10/14/1980, which is incorporated herein by reference.

The compositions of the present invention may contain, in addition to the copolymer of N-vinylpyrrolidone and ethylenically unsaturated monomer or mixture thereof, another anti-redeposition component. Suitable anti-redeposition components for use in the present invention include those selected from the group consisting of polyalkyleneoxy glycols, mono-and di-capped polyalkyleneoxy glycols, and mixtures thereof, as defined below. The compositions of the present invention may contain up to 20% by weight of the total composition of said antiresoiling ingredient or a mixture thereof, preferably from 0.01% to 10%, more preferably from 0.1% to 5%, most preferably from 0.2% to 2%.

Suitable polyalkyleneoxy glycols for use in the present invention are according to the formula H-O- (CH)₂-CHR₂O)_n-H。

Suitable mono-capped polyalkyleneoxy glycols for use in the present invention are according to formula R₁-O-(CH₂-CHR₂O)_n-H。

Suitable di-capped polyalkoxylene glycols for use in the present invention are according to formula R₁-O-(CH₂-CHR₂O)_n-R₃。

In these formulae, the substituent R₁And R₃Each independently is a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain having 1 to 30 carbon atoms, or a linear or branched, substituted or unsubstituted hydrocarbon chain having 1 to 30 carbon atoms with an amino group, R₂Is hydrogen or a straight or branched hydrocarbon chain having 1 to 30 carbon atoms, and n is an integer greater than 0.

Preferably R₁And R₃Each independently of the others, is a substituted or unsubstituted, saturated or unsaturated, straight-chain or branched alkyl, alkenyl or aryl radical having 1 to 30 carbon atoms, preferably 1 to 16 carbon atoms, more preferably 1 to 8 carbon atoms, most preferably 1 to 4 carbon atoms, or an amino-bearing alkyl radical having 1 to 30 carbon atomsA linear or branched, substituted or unsubstituted alkyl, alkenyl or aryl group of carbon atoms, preferably 1 to 16 carbon atoms, more preferably 1 to 8 carbon atoms, most preferably 1 to 4 carbon atoms. Preferably R₂Is hydrogen or a linear or branched alkyl, alkenyl or aryl group having 1 to 30 carbon atoms, preferably 1 to 16 carbon atoms, more preferably 1 to 8 carbon atoms, most preferably R₂Is methyl or hydrogen. Preferably n is an integer from 5 to 1000, more preferably from 10 to 100, even more preferably from 20 to 60, most preferably from 30 to 50.

Preferred polyalkyleneoxy glycols, mono-and di-capped polyalkyleneoxy glycols used in the present invention have a molecular weight of at least 200, more preferably 400-.

Suitable mono-capped polyalkyleneoxy glycols for use in the present invention include 2-aminopropyl polyethylene glycol (MW2000), methyl polyethylene glycol (MW1800) and the like. Such mono-capped polyalkyleneoxy glycols are commercially available from Hoescht in the polyethylene glycol series or from Hunstman under the trade name XTJ @. Suitable polyalkyleneoxy glycols for use in the present invention are polyethylene glycols, such as polyethylene glycol (MW 2000).

Suitable di-capped polyalkyleneoxy glycols for use in the present invention include O, O ' -bis (2-aminopropyl) polyethylene glycol (MW2000), O, O ' -bis (2-aminopropyl) polyethylene glycol (MW400), O, O ' -dimethyl polyethylene glycol (MW2000), dimethyl polyethylene glycol (MW2000) or mixtures thereof. The preferred di-capped polyalkoxylene glycol for use in the present invention is dimethyl polyethylene glycol (MW 2000). For example, dimethyl polyethylene glycol is commercially available from Hoescht in the polyethylene glycol series, e.g., PEG DME-2000, or from Huntsman under the name Jeffamine^®And XTJ^®And (4) carrying out commercial purchase.

These polyalkyleneoxy glycols, mono-or di-capped polyalkyleneoxy glycols contribute to the effectiveness of the compositions of the present invention, i.e., they also help to improve next time cleaning performance.

Other suitable polymers as preferred optional components for use in the compositions of the present invention are homopolymers of vinylpyrrolidone. The compositions of the present invention may generally comprise up to 20% by weight of the total composition of a homopolymer of vinylpyrrolidone, preferably from 0.01% to 10%, more preferably from 0.1% to 5%, most preferably from 0.2% to 2%.

Suitable vinylpyrrolidone homopolymers for use in the present invention are N-vinylpyrrolidone homopolymers having the following recurring monomers:wherein n (degree of polymerization) is an integer of 10 to 1000000, preferably 20 to 100000, more preferably 20 to 10000.

Thus, suitable vinylpyrrolidone homopolymers ("PVP") for use in the present invention have an average molecular weight of 1000-.

Suitable homopolymers of vinylpyrrolidone are commercially available from ISP company, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight 10000), PVP K-30 (average molecular weight 40000), PVP K-60 (average molecular weight 160000) and PVP K-90 (average molecular weight 360000). Other suitable vinylpyrrolidone homopolymers commercially available from BASF include Sokalan HP 165 and Sokalan HP 12; homopolymers of vinylpyrrolidone are known to the person skilled in the art of detergents (see, for example, EP-A-262897 and EP-A-256696).

These vinylpyrrolidone homopolymers contribute to the effectiveness of the compositions of the present invention, i.e., they also help to improve first and next cleaning performance.

The compositions of the present invention may also contain other polymers, such as carboxylate-containing polymers, or mixtures thereof, typically in amounts up to 20%, preferably from 0.01% to 5%, by weight of the total composition.

By "carboxylate-containing polymer" is meant herein a polymer or copolymer comprising at least one monomeric unit containing at least one carboxylate functionality. Any carboxylate-containing polymer known to those skilled in the art may be used in accordance with the present invention, such as homo-or co-polymeric polycarboxylic acids or salts thereof, including polyacrylates, and polymers and copolymers of maleic anhydride or/and acrylic acid, and the like, or mixtures thereof. In fact, such carboxylate-containing polymers may be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in the acid form. Unsaturated monomeric acids that 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 of monomer segments that do not contain carboxylate groups, such as vinyl methyl ether, styrene, ethylene, and the like, in the polymeric polycarboxylates of the present invention is also suitable.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers useful in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form is preferably about 2000-1000000, more preferably about 10000-150000, most preferably about 20000-100000. Water-soluble salts of such acrylic polymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Such soluble polymers are known. The use of such polyacrylates in detergent compositions is disclosed in US3308067 to Diehl, granted 3, 7, 1967.

Acrylic acid/maleic acid based copolymers may also be used as preferred carboxylate-containing polymers. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is preferably about 2000-100000, more preferably about 5000-75000, and most preferably about 7000-65000. The ratio of acrylic acid moieties to maleic acid moieties in such copolymers is generally from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. Water-soluble salts of such acrylic acid/maleic acid copolymers may include, for example, alkali metal salts, ammonium salts and substituted ammonium salts. Such soluble acrylic acid/maleic acid copolymers are known substances described in European patent application EP66915, published 12.15.1982. Particularly preferred are maleic/acrylic copolymers having an average molecular weight of about 70000. Such copolymers are commercially available from BASF under the trade name SOKALAN CP 5.

Other suitable carboxylate-containing polymers for use in the present invention include cellulose derivatives, such as carboxymethyl cellulose. For example, carboxymethyl cellulose may be used in the form of a salt with a conventional cation such as sodium, potassium, amine or substituted amine.

The compositions of the present invention may also comprise a divalent counterion or a mixture thereof. All divalent ions known to those skilled in the art can be used in the present invention. Preferred divalent ions for use in the present invention are calcium, zinc, cadmium, nickel, copper, cobalt, zirconium, chromium and/or magnesium, more preferably calcium, zinc and/or magnesium. The divalent ions may be added in the form of salts, for example as chlorides, acetates, sulfates, formates and/or nitrates or as chelated metal salts. For example, calcium may be added as calcium chloride, magnesium as magnesium acetate or magnesium sulfate, and zinc as zinc chloride.

In one embodiment of the invention, the carboxylate-containing polymer and the divalent counterion may be added as one component, provided that the molar ratio of the carboxylate-containing polymer to the divalent counterion/salt is from 12: 1 to 1: 32.

In an embodiment of the present invention wherein the carboxylate-containing polymer and the divalent counterion are present in the composition of the present invention, the molar ratio of the polymer to the divalent counterion is preferably in the range of from 12: 1 to 1: 32, more preferably in the range of from 8: 1 to 1: 16, most preferably in the range of from 4: 1 to 1: 6. Preferred molar ratios of the polymer to the divalent counterion are those values that give excellent gloss in the most economical manner.

The liquid compositions of the present invention may also comprise as optional components a builder or mixtures thereof. Suitable builders for use in the present invention include polycarboxylic and polyphosphoric acids, and salts thereof. Typically, the compositions of the present invention comprise up to 20% builder or mixtures thereof, preferably from 0.1% to 10%, more preferably from 0.5% to 5% by weight of the total composition.

Suitable and preferred polycarboxylates for the present invention are organic polycarboxylates having a maximum LogKa of between 3 and 8 as determined at 25 ℃/0.1M ionic strength; the sum LogKCa + LogKMg is higher than 4, measured at 25 ℃/0.1M ionic strength; measured at 25 ℃/0.1M ionic strength, where LogKCa ═ LogKMg ± 2 units.

Such suitable and preferred polycarboxylates include citrates and complexes of the formula:

CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B) Wherein A is H or OH; b is H or-O-CH (COOX) -CH₂(COOX); x is H or a salt-forming cation. For example, in the above formula, if both A and B are H, the compound is oxydisuccinic acid and its water soluble salts. If A is OH and B is H, the compound is tartaric acid monosuccinic acid (TMS) and its water-soluble salts. If A is H, B is-O-CH (COOX) -CH₂(COOX), the compound is tartaric acid disuccinic acid (TDS) and water-soluble salts thereof. Mixtures of these builders are particularly preferred for use herein. In particular TMS to TDS, disclosed in US4663071 issued to Bush et al 5.5.1987.

Other ether polycarboxylates suitable for use herein include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxybenzene-2, 4, 6-trisulfonic acid, and carboxymethoxysuccinic acid.

Other useful polycarboxylate builders include the ether hydroxypolycarboxylates represented by the following structural formula:

HO-[C(R)(COOM)-C(R)(COOM)-O]_n-H wherein M is hydrogen or a cation which renders the resulting salt 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 is on average from about 2 to about 4), each R is the same or different and is selected from hydrogen, C₁-C₄Alkyl or C₁-C₄Substituted alkyl (R is preferably hydrogen).

Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, as described, for example, in US patents 3923679; US 3835163; US 4158635; US4120874 and US4102903, all of which are incorporated herein by reference.

Preferred among those cyclic compounds are dipicolinic acid and chelidamic acid.

Also suitable polycarboxylates for the present invention are mellitic acid, succinic acid, polymaleic acid, benzene 1, 3, 5-tricarboxylic acid, benzene pentacarboxylic acid and carboxymethoxysuccinic acid and soluble salts thereof.

Carboxylate builders also suitable for use herein include carboxylated carbohydrates as in U.S. Pat. No. 3,32,22 to Diehl, 1973, 28, which is incorporated herein by reference.

Other suitable carboxylates for use in the present invention, but less preferred because they do not meet the above criteria, are the alkali metal, ammonium and substituted ammonium salts of polyacetic acid. Examples of polyacetate builder salts are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid.

Other suitable, but less preferred polycarboxylates are those builders also known as alkyl iminodiacetic acids, such as methyl iminodiacetic acid, alanine diacetic acid, methyl glycine diacetic acid, hydroxy propylene iminodiacetic acid, and other alkyl iminodiacetic acid builders.

Also suitable for use in the compositions of the present invention are the 3, 3-dicarboxy-4-oxa-1, 6-hexanedioic acid salts and related compounds disclosed in U.S. patent number US4566984 to Bush, granted on 28.1.1986 (incorporated herein by reference). Useful succinic acid builders include C₅-C₂₀Alkyl succinic acids and salts thereof, a particularly preferred compound of this class is dodecenyl succinic acid. Alkyl succinic acids typically have the general formula: R-CH (COOH) CH₂(COOH), i.e. a derivative of succinic acid, wherein R is a hydrocarbon, e.g. C₁₀-C₂₀Alkyl or alkenyl, preferably C₁₂-C₁₆Or wherein R may be substituted with a hydroxy, sulfo, sulfoxyl or sulfone substituent, all as described in the above patents.

Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like. Lauryl succinate is a preferred builder in this group and is described in European patent application 86200690.5/0200263 published on 5.11.1986.

Examples of useful builders also include sodium and potassium carboxymethoxymalonate, sodium and potassium carboxymethoxysuccinate, sodium and potassium cis-cyclohexanehexacarboxylate, sodium and potassium cis-cyclopentanetetracarboxylate, water-soluble polyacrylates, and copolymers of maleic anhydride with vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylates disclosed in U.S. Pat. No. 4144226 to Crutchfield et al, issued on 3/13 1979, incorporated herein by reference. These polyacetal carboxylates can be prepared by reacting together, under polymerization conditions, a glyoxylic ester and a polymerization initiator. The resulting polyacetal carboxylate ester is then linked to chemically stable end groups to stabilize the polyacetal carboxylate, prevent rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.

Polycarboxylate builders are also disclosed in Diehl, U.S. patent 3308067 (incorporated herein by reference), issued 3, 7, 1967. Such materials include the water soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Suitable polyphosphates for use in the present invention are polyphosphoric acids (examples are tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), alkali metal, ammonium, and alkanolammonium salts of phosphonic acids. The most preferred builder for use in the present invention is citrate.

Suitable fragrances for use in the present invention include substances that provide an olfactory aesthetic effect and/or cover any "chemical" odor that the product may have. The primary function of a small fraction of the highly volatile, low boiling (with low boiling) perfume components in these perfumes is to improve the fragrance of the product itself, rather than to impart a subsequent fragrance to the surface being cleaned. Some low volatility, high boiling perfume components provide an impression of freshness and cleanliness to surfaces and it is desirable for these components to be deposited and present on dry surfaces. The perfume components are readily soluble in the composition, for example by use of nonionic detergent surfactants.

Perfume components and compositions suitable for use in the present invention are those conventionally known in the art. The selection of any perfume component or amount of perfume is based solely on aesthetic considerations.

Suitable fragrance compounds and compositions can be found in the prior art, including U.S. patent nos. 4145184 to Brain and Cummins, 3, 20, 1979; US patent US4209417 to whiyte, granted 24.6.1980; U.S. Pat. No. 5,000,15705 to Moeddel, 5/7/1985; U.S. patent No. US4152272 issued 5/1 1979 to Young, all of which are incorporated herein by reference.

Generally, the degree of perfume substantivity is roughly proportional to the percentage of substantive perfume used. The relative substantivity perfume contains at least about 1%, preferably at least about 10% substantivity perfume.

Substantive perfumes are those scented compounds that are deposited on a surface by a cleaning process and are detectable by a person with normal olfactory acuity. Typically, the vapor pressure of such materials is lower than the vapor pressure of the average fragrance. In addition, they typically have a molecular weight of about 200 and above 200 and are detectable at lower than average perfume usage.

The Perfume components useful in the present invention, together with their fragrance profile, their physical and chemical properties such as boiling point and molecular weight, are given in steffen arctander in 1969 as "fragrance and flavor Chemicals" (Aroma Chemicals) ", by the authors, which is incorporated herein by reference.

Examples of highly volatile, low boiling perfume components are anethole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate, isobornyl acetate, camphene, cis citral (neral), citronellal, citronellol, citronellyl acetate, p-cymene, decanal, dihydrolinalool, dihydromyrcenol, dimethylphenylcarbinol, eucalyptol, geranial, geraniol acetate, geranonitrile, cis-3-hexenyl acetate, hydroxycitronellal, d-limonene, linalool oxide, linalyl acetate, linalyl propionate, methyl anthranilate, α -methylionone, methylnonyl acetaldehyde, methylphenylmethylmethanol acetate, menthyl levulinate, menthone, isomenthone, myrcene acetate, myrcenol, linalool, nerol, neryl acetate, nonyl acetate, phenethyl alcohol, α -pinene, terpinene 32-pinene, γ -terpinene, terpinene-36-terpinene, 539-2-terpinyl acetate, and certain terpene containing as essential aromatic components, for example, limonene, linalool, and limonene, linalool, and limonene, linalool, a volatile perfume components, and a perfume containing as.

Examples of moderately volatile perfume components are amyl cinnamic aldehyde, isoamyl salicylate, β -caryophyllene, cedrene, cinnamyl alcohol, coumarin, dimethylbenzyl methyl acetate, ethyl vanillin, eugenol, isoeugenol, vanillyl acetate, heliotropin, 3-cis-hexenyl salicylate, hexyl salicylate, lilac aldehyde (p-tert-butyl- α -methylhydrocinnamaldehyde), gamma-methylionone, nerolidol, patchouli alcohol, phenyl hexanol, β -sirinene, trichloromethyl phenyl methyl carbinol acetate, triethyl citrate, vanillin, and veratraldehyde.

Examples of lower volatility high boiling perfume components are benzophenone, benzyl salicylate, vinyl brassylate, galaxolide (1, 3, 4, 6, 7, 8-hexahydro-4, 6, 6, 7, 8, 8-hexamethylcyclopent-gamma-2-benzopyran), hexyl cinnamaldehyde, neocarvyl aldehyde (4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-10-carbaldehyde), methyl cedryl ketone, methyl dihydrojasmonate, methyl- β -naphthalenone, musk indanone, musk ketone, saffron and phenethylphenyl acetate.

The choice of any particular perfume component is primarily made for aesthetic reasons.

The compositions of the present invention may comprise perfume components or mixtures thereof in an amount of up to 5.0%, preferably from 0.1% to 1.5% by weight of the total composition.

Another class of optional compounds for use in the present invention includes chelating agents or mixtures thereof.

The chelating agent may be incorporated in the compositions of the present invention in an amount of from 0 to 10.0%, preferably from 0.1% to 5.0% by weight of the total composition.

Suitable phosphonate chelants for use in the present invention may include ethane 1-hydroxy bisAlkali metal phosphonates (HEDP), alkylene poly (alkylene phosphonates), and amino phosphonate compounds including amino tris (methylene phosphonic Acid) (ATMP), Nitrilo Trimethylene Phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and Diethylene Triamine Penta Methylene Phosphonates (DTPMP). These phosphonate compounds may be present in their acid form or as salts with different cations on some or all of their acid functional groups. Preferred phosphonate chelants for use herein are diethylenetriamine pentamethylenephosphonate (DTPMP) and ethane 1-Hydroxydiphosphonate (HEDP). Such phosphonate chelants are available from Monsanto under the trade name DEQUEST^®And (4) obtaining the product.

Multifunctional substituted aromatic chelating agents may also be used in the compositions of the present invention. See Connor et al, US3812044, issued 5, 21, 1974. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1, 2-dihydroxy-3, 5-disulfobenzene.

Preferred biodegradable chelating agents for use in the present invention are ethylenediamine N, N' -disuccinic acid, or alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof. Ethylenediamine N, N' -disuccinic acid, particularly the (S, S) isomer, has been widely described in U.S. Pat. No. 4,4704233 to Hartman and Perkins, issued 11/3 1987. For example, ethylenediamine N, N' -disuccinic acid is available from palm Research Laboratories under the trade name ssedDS^®And (4) obtaining the product.

Suitable aminocarboxylates for use in the present invention include: ethylenediaminetetraacetate, Diethylenetriaminepentaacetate (DTPA), N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, hydroxyethyldiglycine, propylenediaminetetraacetic acid (PDTA) and methylglycinediacetic acid (MGDA), all in acid form or in the form of their alkali metal, ammonium and substituted ammonium salts. An aminocarboxylate particularly suitable for use in the present invention is diethylenetriaminepentaacetic acid, for example Trilon FS from BASF^®Commercially available propylenediaminetetraacetic acid (PDTA) and methylglycinediacetic acid (MGDA).

Other carboxylate chelating agents useful in the present invention include: salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid, or a mixture thereof.

Particularly suitable for use in the present invention are 2-alkyl alkanols having an alkyl chain containing from 6 to 16 carbon atoms, preferably from 8 to 12 carbon atoms, substituted at the α -position, and a terminal hydroxyl group, the alkyl chain containing from 1 to 10 carbon atoms, preferably from 2 to 8 carbon atoms, more preferably from 3 to 6 carbon atoms^®Series such as Isofol^®12 (2-butyloctanol) or Isofol^®16 (2-hexyldecanol) is commercially available. The compositions of the present invention generally 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%, most preferably from 0.1% to 0.8%.

The compositions of the present invention may also comprise a solvent or mixture thereof. Solvents useful in the present invention include all those solvents known to those skilled in the art of hard surface cleaner compositions. Suitable solvents for use in the present invention include ethers and diethers having 4 to 14 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 8 to 10 carbon atoms; diols or alkoxylated diols, alkoxylated aromatic alcohols, branched aliphatic alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, C8-C14 alkyl and cycloalkyl hydrocarbons and halogenated hydrocarbons, C6-C16 glycol ethers, and mixtures thereof.

Suitable diols for use in the present invention are according to the formula HO-CR1R2-OH, wherein R1 and R2 are independently H or a C2-C10 saturated or unsaturated aliphatic hydrocarbon chain and/or ring. Suitable diols for use in the present invention are dodecanediol and/or propylene glycol.

Suitable alkoxylated diols for use in the present invention are those according to the formula R- (A) n-R1-OH, wherein R is H; OH; linear saturated or unsaturated alkyl having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, wherein R1 is H or linear saturated or unsaturated alkyl having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, a is alkoxy, preferably ethoxy, methoxy and/or propoxy, and n is 1 to 5, preferably 1 to 2. Suitable alkoxylated diols for use in the present invention are methoxyoctadecanol and/or ethoxyethoxyethanol.

Suitable alkoxylated aromatic alcohols for use in the present invention are according to the formula R (A)_n-OH, wherein R is an alkyl-substituted or non-alkyl-substituted aryl group having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, 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. Suitable alkoxylated aromatic alcohols are benzoyloxyethanols and/or benzoyloxypropanols.

Suitable aromatic alcohols for use in the present invention are according to the formula R-OH, wherein R is an alkyl substituted or non-alkyl substituted aryl group having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms. For example, a suitable aromatic alcohol for use in the present invention is benzyl alcohol.

Suitable branched aliphatic alcohols for use in the present invention are according to the formula R-OH, wherein R is a branched saturated or unsaturated alkyl group having from 1 to 20 carbon atoms, preferably from 2 to 15 carbon atoms, more preferably from 5 to 12 carbon atoms. Branched aliphatic alcohols particularly suitable for use in the present invention include 2-ethylbutanol and/or 2-methylbutanol.

Suitable alkoxylated branched aliphatic alcohols for use in the present invention are according to the formula R (A)_n-OH, wherein R is a branched, saturated or unsaturated alkyl group having from 1 to 20 carbon atoms, preferably from 2 to 15 carbon atoms, 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 from 1 to 2. Suitable alkoxylated branched aliphatic alcohols include 1-methylpropoxyethanol and/or 2-methylbutoxyethanol.

Suitable alkoxylated linear C1-C5 alcohols for use in the present invention are according to the formula R (A)_n-OH, wherein R is a linear saturated or unsaturated chain having 1 to 5 carbon atoms, preferably 2 to 4 carbon atomsSaturated alkyl, wherein A is alkoxy, preferably butoxy, propoxy and/or ethoxy, and n is an integer from 1 to 5, preferably from 1 to 2. Suitable alkoxylated linear aliphatic C1-C5 alcohols are butoxypropoxypropanol (n-BPP), butoxyethanol, butoxypropanol, ethoxyethanol or mixtures thereof. T-shirtOxoxypropoxypropanol is available under the trade name n-BPP^®Commercially available from Dow chemical.

Suitable linear C1-C5 alcohols for use in the present invention are according to the formula R-OH, wherein R is a linear saturated or unsaturated alkyl group of 1 to 5 carbon atoms, preferably 2 to 4 carbon atoms. Suitable linear C1-C5 alcohols are methanol, ethanol, propanol or mixtures thereof.

Other suitable solvents include butyl diglycol ether (BDGE), butyl triglycol ether, tertiary amyl alcohol (ter amide alcohol) alcohol, and the like. Particularly preferred solvents for use in the present invention are butoxypropoxypropanol, butyl diglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol, isopropanol and mixtures thereof.

The compositions of the present invention generally comprise up to 20% by weight of solvent or mixture thereof, preferably from 0.5% to 10% by weight, more preferably from 1% to 8% by weight, based on the total weight of the composition.

The liquid composition of the present invention may also comprise a chlorine-releasing component. The composition according to the invention generally comprises up to 20% of chlorine-releasing components, preferably from 0.1% to 15%, more preferably from 1% to 10%, by weight of the total composition.

Suitable chlorine-releasing components for use in the present invention are alkali metal hypochlorites. Advantageously, the compositions of the present invention are stable in the presence of such bleach components. Although alkali metal hypochlorites are preferred, other hypochlorite compounds may be used in the present invention, and may be selected from calcium hypochlorite and magnesium hypochlorite. The preferred alkali metal hypochlorite for use in the present invention is sodium hypochlorite. Packaged form of composition

The compositions of the present invention may be packaged in a variety of suitable detergent packages known to those skilled in the art. The liquid compositions of the present invention are preferably packaged in conventional detergent plastic bottles.

In one embodiment, the compositions of the present invention may be packaged in a manually operated spray-type spray container, which is typically made from synthetic organic polymeric molding materials. Accordingly, the present invention also includes the liquid cleaning compositions of the present invention packaged in a spray-type sprayer, preferably a trigger spray-type sprayer or a pump spray-type sprayer.

In fact, the spray-type sprayer enables the liquid cleaning compositions suitable for use in the present invention to be applied uniformly over a relatively large area of hard surface to be cleaned. Such spray-type sprayers are particularly useful for cleaning vertical surfaces.

Suitable spray-type sprinklers for use in accordance with the present invention include manually operated foam trigger-type sprinklers such as those sold by specialty packaging Products, inc. These types of sprinklers are disclosed in, for example, US4701311 to dunning et al and US4646973 and US4538745 to focraracci. Particularly preferred for use in the present invention is, for example, T8500 commercially available from continuous SprayInternational^®Or T8100 commercially available from Canyon, Northern Ireland^®A spray type sprayer. With such sprayers, the liquid composition is divided into fine droplets, producing a mist of droplets that acts directly on the surface being treated. In fact, with this type of spray-type sprayer, when the user activates the suction device, the composition contained in said sprayer body passes directly through the head of the spray-type sprayer, by means of the energy transmitted by the user to the suction device. More specifically, in the spray head of said spray-type sprayer, the composition impacts an obstacle, such as a grid or cone, etc., thereby providing an impact that helps atomize the liquid composition, i.e., helps form droplets. Method for cleaning hard surfaces

The invention also comprises a method of cleaning a hard surface wherein a liquid composition having a pH above 9 and comprising a copolymer of N-vinylpyrrolidone and an ethylenically unsaturated monomer as defined herein or a mixture thereof, preferably a quaternized or non-quaternized vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymer, is contacted with said surface.

The characteristics (optional components, amounts, etc.) of the compositions used in the method of cleaning hard surfaces are as described herein above.

By "hard surface" is meant herein any surface commonly found in the home, such as a kitchen, bathroom, or any surface in the interior or exterior of a vehicle, for example, floors, walls, tiles, windows, sinks, showers, molded shower curtains, sinks, WCs, dishware, fixtures, and the like, made of different materials such as ceramics, vinyl, non-wax vinyl, paint cloth, melamine, glass, any plastic, plasticized wood, metal, or any painted or closed surface, and the like. Hard surfaces also include household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers, and the like.

The liquid compositions of the present invention may be contacted with the surface to be cleaned in neat or diluted form.

By "diluted form" is meant herein that the liquid composition is diluted by the user, typically with water. Before use, the composition is generally diluted with water to 10 to 200 times, preferably 10 to 100 times, its weight. It is generally recommended that the dilution of the composition in water be 1.2%.

In a preferred method of cleaning hard surfaces according to the invention, the composition is used in diluted form, and after application of the composition, rinsing of the surface is not required, in order to obtain excellent first and next cleaning performance with excellent surface appearance.

The invention is further illustrated by the following examples.

Examples

The following compositions were prepared by mixing the listed components in the proportions listed. All proportions are% by total weight of the composition.

These compositions are used in neat and diluted form to clean hard surfaces such as floors. Providing excellent first and next cleaning performance and surface appearance to the surface being cleaned. All of these compositions also provide excellent stability against bacterial contamination.

Composition (% by weight)

AB C D E F nonionic surfactant C9-11 EO 5- -2.52.41.92.5C 12, 14EO 5- -2.53.62.92.5C 7-9 EO 63.28- -Dobanol 23-31.33.2- -AO211.94.82.01.00.84.0 anionic surfactant NaPS-3.0- -NaLAS 0.9-0.8- -NaCS 1.23.01.51.52.6-C₈AS 0.82.0- -Isalchem AS 0.60.6-buffer Na₂CO₃1.02.00.20.60.60.6 citrate- -0.750.50.50.5 alkali- -0.50.30.330.3 foam control agent fatty acid 0.40.80.40.60.30.5 Isofol 12 ^ 0.3-0.30.30.3-Polymer Polyquat 11 ^ 0.51.00.50.31.00.6 ^ BLuviskol 73W capsules- -PEG DME-2000 capsules- -water and minor components … … … … to 100% … … … … … PH 10.7510.759.59.59.59.5

G H I J K nonionicSurfactant C9-11 EO 5-2.52.52.52.5C 12, 14 EO52.52.52.52.52.5C7-9 EO 6- - -Dobanol 23-3- - -AO 21-2.02.02.02.0 anionic surfactant NaPS- - -NaLAS 4.00.80.80.80.8 NaCS 2.31.51.51.51.5C₈AS Isalchem AS buffer Na₂CO₃1.00.21.00.20.2 citrate-0.75-0.750.75 base-0.50.30.50.5 foam control fatty acid 0.40.40.50.40.4 Isofol 12 0.30.30.30.30.3 polymer polyethylene quat 11 0.3-0.30.5-Luviskol 73W-0.5- -0.5 PEG DME-2000 polyethylene glycol terephthalate-0.50.5 water and subcomponent … … … -100% … … … pH 10.59.511.09.59.5 Polyquat 11 are quaternized vinyl pyrrolidone and methacrylic acid commercially available from BASFCopolymers of dimethylaminoethyl ester. Luviskol 73W polyethylene based commercially available from BASFA 7: 3 copolymer of pyrrolidone and vinyl acetate. PEG DME-2000 polyethylene glycol (MW2000) commercially available from Hoescht. Isofol 12 are 2-butyl octanol. Dobanol 23-3 are C12-C13 EO 3 nonionic surfactants commercially available from SHELL. C₈AS is octyl sulfate commercially available from Albright and Wilson under the trade name Empimin LV 33. Na PS is sodium paraffin sulfonate. NaLAS is sodium linear alkyl benzene sulfonate. NaCS is sodium cumene sulfonate. AO21 is a C12-14EO21 alcohol ethoxylate. Isalchem AS are alkyl sulfates/branched alcohols commercially available from Enichem.

Claims (13)

1. A liquid hard surface cleaning composition having a pH above 9 and comprising a copolymer of N-vinyl pyrrolidone and ethylenically unsaturated monomers or mixtures thereof.

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

3. A composition according to any preceding claim, wherein said N-vinylpyrrolidone in said copolymer has the following repeating monomer:

wherein n is an integer from 10 to 1000000, preferably from 20 to 100000, more preferably from 20 to 10000, wherein the ethylenically 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, α -methyl styrene, vinyl toluene, t-butyl styrene and mixtures thereof.

4. A composition according to any preceding claim in which the copolymer of N-vinylpyrrolidone and ethylenically unsaturated monomer is a quaternized or non-quaternized vinylpyrrole according to the formulaAlkanone/dialkylaminoalkyl acrylate or methacrylate copolymer:

wherein n is 20 to 99, preferably 40 to 90 mole%, and m is 1 to 80, preferably 5 to 40 mole%; r₁Represents H or CH₃(ii) a y is 0 or 1; r₂is-CH₂-CHOH-CH₂-or C_xH_2xWherein x is 2-18; r₃Represents lower alkyl of 1 to 4 carbon atoms, preferably methyl or ethyl, or

R₄Represents lower alkyl of 1 to 4 carbon atoms, preferably methyl or ethyl; x^-Selected from Cl, Br, I, 1/2SO₄、HSO₄And CH₃SO₃。

5. A composition according to claim 4, wherein the copolymer of N-vinylpyrrolidone with an ethylenically unsaturated monomer is a quaternized vinylpyrrolidone/dialkylaminoalkyl methacrylate copolymer.

6. A composition according to any preceding claim which is an aqueous liquid composition having a pH above 10, more preferably a pH of from 10.1 to 12, most preferably a pH of from 10.5 to 11.

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

8. A composition according to any preceding claim, further comprising an anti-recontamination component selected from:

a polyalkylene oxide glycol according to the formula:

H-O-(CH₂-CHR₂O)_n-H，

a mono-capped polyalkoxylene glycol of the formula:

R₁-O-(CH₂-CHR₂O)_n-H，

a di-capped polyalkoxylene glycol of the formula:

R₁-O-(CH₂-CHR₂O)_n-R₃，

and mixtures thereof, wherein the substituent R₁And R₃Each independently is a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain having 1 to 30 carbon atoms, or a linear or branched, substituted or unsubstituted hydrocarbon chain having 1 to 30 carbon atoms with an amino group, R₂Is hydrogen or a straight or branched hydrocarbon chain having 1 to 30 carbon atoms, and wherein n is an integer greater than 0.

9. A composition according to claim 8 comprising up to 20% by weight of the total composition of said antiresoiling ingredient and mixtures thereof, preferably from 0.01% to 10%, more preferably from 0.1% to 5%, most preferably from 0.2% to 2%.

10. A composition according to any preceding claim further comprising at least one optional ingredient selected from other polymers, perfumes, suds control agents, chelants, builders, solvents, buffers, 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, dyes and mixtures thereof.

11. A method of cleaning a hard surface wherein a liquid composition according to any preceding claim is contacted with the surface.

12. A method of cleaning a hard surface according to claim 11 wherein the composition is contacted with the surface after dilution with water.

13. The method of claim 12, wherein the surface is not rinsed after the composition is contacted with the surface.