WO2009112794A1

WO2009112794A1 - Thickened hard surface cleaning compositions comprising fatty amine alkoxylate

Info

Publication number: WO2009112794A1
Application number: PCT/GB2009/000314
Authority: WO
Inventors: Farid Ahmad Nekmard
Original assignee: Reckitt Benckiser Inc.; Reckitt Benckiser (Uk) Limited
Priority date: 2008-03-14
Filing date: 2009-02-06
Publication date: 2009-09-17
Also published as: GB0804727D0

Abstract

Thickened aqueous acidic hard surface treatment composition having a pH of 3 or less which comprise: 0.001 - 10%wt of one or more fatty amine alkoxylate compounds; 0.001 - 5 %wt. of a hydrotrope compound or salt thereof; up to 20%wt. an acid constituent; and, at least 75%wt. water; wherein the one or more fatty amine alkoxylate compounds and the a hydrotrope compound or salt thereof are present in respective weight ratios of from 1:0.1 to 1:1, and that when the compositions comprise oxalic acid, the compositions exclude a source of metal ions.

Description

THICKENED HARD SURFACE CLEANING COMPOSITIONS

COMPRISING FATTY AMINE ALKOXYLATE COMPOUNDS

The present invention relates to thickened acidic hard surface cleaning compositions containing fatty amine alkoxylate compounds, e.g., tallowamine, soyamine ethoxylate compounds. More particularly the present invention relates to thickened acidic hard surface treatment compositions which necessarily include one or more fatty amine alkoxylate compounds, preferably one or more fatty amine ethoxylate compounds, particularly tallowamines and soyamine ethoxylate compounds, further with a hydrotrope constituent, especially wherein said hydro trope constituent is a xylene sulfonate compound or salt thereof.

Hard surface cleaning compositions are commercially important products and enjoy a wide field of use, and are known in assisting in the removal of dirt and grime from surfaces, especially those characterized as useful for cleaning "hard surfaces". Hard surfaces include those which are frequently encountered in lavatories, for example lavatory fixtures such as toilets, shower stalls, bathtubs, bidets, sinks, etc., as well as countertops, walls, floors, etc. In such lavatory environments two types of commonly encountered stains in lavatories include "hard water" stains, "soap scum" stains as well as "rust stains". Such hard surfaces, and such stains, may also be found in different environments as well, including kitchens, hospitals, etc. Hard water stains are mineral stains caused by the deposition of salts, such as calcium or magnesium salts which are frequently present in hard water which is commonly encountered. Soap scum stains are residues of fatty acid soaps, such as soaps which are based on alkaline salts of low fatty acids. These fatty acids are known to precipitate in hard water due to the presence of metal salts therein leaving an undesirable residue upon such surfaces. Still further stains, typically referred to as greasy stains, are surface residues which generally comprise hydrophobic materials often with further materials which leave unsightly residues on surfaces. Rust stains are typically formed by the presence of undesired amounts of iron oxides in water which may form unsightly deposits on hard surfaces. Advantageously, a successful cleaning product exhibits a number of technical features, e.g., good cleaning efficacy in the treatment of one or more of the foregoing stains, good storage stability and preferably also capable of providing a useful degree of disinfection or sanitization of surfaces treated with the compositions. Although the art is replete with a large number of cleaning compositions useful for the cleaning of hard surfaces there nonetheless remains a real and continuing need in the art for further improved cleaning compositions useful in the cleaning of hard surfaces, particularly those exhibiting one or more of the foregoing technical features.

According to a first aspect of the invention there is provided thickened aqueous acidic hard surface treatment compositions which necessarily include one or more fatty amine alkoxylate compounds, preferably one or more fatty amine ethoxlate compounds, particularly tallowamine and soyamaine ethoxylate compounds, further with a hydrotrope compound or salt thereof, and an acid constituent which includes one or more acids which may be organic or inorganic acids, which compositions form stable single phase compositions. Wherein the compositions include oxalic acid, the compositions preferably exclude a source of metal ions, e.g., metal salts, however the compositions may include a source of metal ions wherein oxalic acid is absent or excluded from the compositions.

According to a second aspect of the invention there is provided a thickened aqueous acidic hard surface treatment composition according to the first aspect of the invention which necessarily includes an acid constituent which comprises one or more organic acids but excludes phosphoric acid.

According to a third aspect of the invention there is provided a thickened aqueous acidic hard surface treatment composition according to the first aspect of the invention which necessarily includes an acid constituent which comprises one or more organic acids which may include phosphoric acid According to a fourth aspect of the invention there is provided a thickened aqueous acidic hard surface treatment composition according to the first, or second aspects of the invention which necessarily includes an acid constituent which comprises one or more organic acids preferably one or more organic acids selected from formic acid, sulfamic acid and oxalic acid, but which composition necessarily excludes phosphoric acid.

According to a fifth aspect of the invention there is provided a thickened aqueous acidic hard surface treatment composition according to the first, or third aspects of the invention which necessarily includes an acid constituent which comprises one or more organic acids preferably one or more organic acids selected from formic acid, sulfamic acid and oxalic acid, but which composition may further include phosphoric acid.

According to a sixth aspect of the invention there is provided a thickened aqueous acidic hard surface treatment composition according to any of the foregoing aspects of the invention which necessarily includes both a fatty amine alkoxylate compound and a hydrotrope compound, especially preferably a fatty amine ethoxylate and sodium xylene sulfonate, in which the respective compounds are preferably present in respective wt:wt ratios of 1 :0.1 to 1:1, preferably 1 :0.1 to 1 :0.75, yet more preferably 1 :0.2 to 1 :0.6, and still more preferably 1 :0.2 to 1 :0.35.

According to a seventh aspect of the invention there is provided a thickened aqueous acidic hard surface treatment composition according to any of the foregoing aspects of the invention, which exclude further one or more compounds which exhibit a hydrotropic functionality, e.g., sodium cumene sulfonate, with the exception of sodium xylene sulfontate which may be present.

According to a sixth aspect of the invention there is provided a method for the manufacture of thickened, single phase, aqueous acidic hard surface treatment compositions according to any of the foregoing aspects of the invention.

According to an eighth aspect of the invention there is provided a method for the treatment of hard surfaces in need of a cleaning and/or sanitizing and/or disinfecting treatment utilizing a thickened aqueous acidic hard surface treatment composition a described herein. These and other aspects of the invention will become more apparent from the following specification.

The compositions of the invention necessarily comprise one or more fatty amine alkoxylate compounds, e.g., tallowamine, soyamine ethoxylate compounds, and fatty alkyl amine ethoxylate compound. Exemplary useful fatty amine alkoxylate compounds include tertiary amine alkoxylates according to the formula:

wherein R is a C₈ -C₂₄ straight chained or branched alkyl group, preferably a C₈ - Ci₈ straight chained or branched alkyl group, and further wherein each of w, x, y, a, b, and c are identical or different and are a number from O to 100 with the proviso that w+χ+y+a+b+c is at least 2.

In certain preferred embodiments w and b are each 0, and x+y+a+c is at least 2. In certain further preferred embodiments y and c are each 0, and w+x+a+b is at least 2.

In still further, and particularly preferred embodiments w, y, b and c are each 0, and x+a is at least 2.

Examples of certain preferred fatty alkyl amine ethoxylates include those from Akzo Nobel under the Ethomeen® tradename which may be represented by the formula:

(CH₂CH₂O)_mH

/

R-N

^N(CH₂CH₂O)_nH wherein: n and m, which may be the same or different, each independently have a value between 2 and 16, preferably a value between 2 to about 10, and wherein R represents a C₈ to C₂₄, preferably a Cio to Cj₈ linear, or branched alkyl chain. A preferred fatty alkyl amine compound is oleyl bis(2-hydroxyethylamine) which is also demonstrated in one or more of the examples. Of course mixtures of two or more fatty alkyl amine alkoxylates compounds may be present. The fatty alkyl amine alkoxylate compound or compounds, preferably fatty alkyl amine ethoxylate compounds, comprise between 0.001 - 10%wt, preferably between 0.01 - 7%wt, yet more preferably between 0.01 - 5%wt, and particularly preferably between 0.01 - 3.5%wt. based on the total weight of the compositions of which they form a part.

The inventive compositions necessarily include a hydrotrope constituent comprising one or more compounds which exhibit a hydrotropic functionality in the inventive compositions and preferably increase the viscosity of aqueous compositions which contain fatty alkyl amine alkoxylate compounds when added thereto. Exemplary hydro tropes include, inter alia, benzene sulfonates, naphthalene sulfonates, C₁-Cn alkyl benzene sulfonates, naphthalene sulfonates, Cs-Cn alkyl sulfonates, C₆-Cn alkyl sulfates, alkyl diphenyloxide disulfonates, and phosphate ester hydrotropes. The hydrotropic compounds of the invention are often provided in a salt form with a suitable counterion, such as one or more alkali, or alkali earth metals, such as sodium or potassium, especially sodium. However, other water soluble cations such as ammonium, mono-, di- and tri- lower alkyl, i.e., C_M alkanol ammonium groups can be used in the place of the alkali metal cations. Exemplary alkyl benzene sulfonates include, for example, isopropylbenzene sulfonates, xylene sulfonates, toluene sulfonates, cumene sulfonates, as well as mixtures thereof. Exemplary C5-C₁₁ alkyl sulfonates include hexyl sulfonates, octyl sulfonates, and hexyl/octyl sulfonates, and mixtures thereof. Particularly useful hydrotrope compounds xylene sulfonates, such as 2,4-xylene sulfonates, and 4,6-xylene sulfonates as well as salt forms thereof, e.g. sodium and potassium salt forms. When present the hydrotrope constituent may be present in any effective amounts, or they may be omitted. Advantageously, the hydrotrope constituent comprises 0.001 - 5 %wt., preferably 0.01 - 3.5 %wt, more preferably 0.01-1.75%wt. of the composition of which it forms a part.

The inventor has surprisingly discovered that the use of xylene sulfonates or salt forms thereof to the exclusion of other hydrotropes, and especially to the exclusion of cumene sulfonates or salts forms thereof provide thickened aqueous acidic hard surface treatment composition having excellent storage stability under adverse conditions, e.g., from temperatures as low as about -4°C, to as high as about 50 ⁰C for time periods of at least 1, preferably at least 2, more preferably at least 3 and especially preferably at least 4 weeks at temperatures within this range with only limited loss in viscosity. Advantageously, subsequent to storage at temperature of from about -4°C, to about 50 ⁰C when stored for at least 1 , preferably at least 2, more preferably at least 3 and especially preferably at least 4 weeks the viscosity of the compositions following storage deviated no more than 50%, preferably not more than 33%, yet more preferably not more than 25% from the initial viscosity of the compositions prior to subjecting the composition to such storage conditions.

Further surprisingly, preferred compositions of the invention achieved and retained such good viscosity characteristics even in the absence of metallic salts, particularly in the absence of sodium chloride. Such is advantageous as absence of metallic salts, especially preferably the absence of sodium chloride in the presence of oxalic acid eliminates the potential for reaction of these two constituents and the resultant formation of water insoluble oxalate salts which is desirably avoided. The presence of one or more metallic salts, e.g., sodium chloride has been known to the art as a source of metal ions necessary to thicken fatty alkyl amines, e.g., tallowamines ethoxylate in order to elevate the viscosity of compositions of which they form a part. Such metallic salts however are not needed in the compositions of the present invention.

According to certain specifically preferred embodiments the compositions provide a thickened aqueous acidic hard surface treatment composition which necessarily includes both a fatty amine alkoxylate compound and a hydrotrope compound, especially preferably a fatty amine ethoxylate and sodium xylene sulfonate, in which the respective compounds are preferably present in respective wt:wt ratios of 1 :0.1 to 1:1, preferably 1 :0.1 to 1 :0.75, yet more preferably 1 :0.15 to 1 :0.6, and still more preferably 1 :0.2 to 1 :0.35, and preferably in the absence of metallic salts, especially sodium chloride.

. The inventor has found that the retention of these constituents in such weight ratios provides for thickened aqueous acidic hard surface treatment compositions which exhibit excellent storage stability, good viscosity and good product performance even in the absence of metallic salts.

The compositions of the invention necessarily comprise an acid constituent, which includes one or more acids which are present in a sufficient amount in order to impart an acid pH to the compositions. The acids useful in the acid constituent may be one or more water soluble inorganic acids, mineral acids, or water soluble organic acids, with virtually all such known materials contemplated as being useful in the present inventive compositions. Exemplary inorganic acids include, e.g., phosphoric acid, potassium dihydrogenphosphate, sodium dihydrogenphosphate, sodium sulfite, potassium sulfite, sodium pyrosulfite (sodium metabisulfite), potassium pyrosulfite (potassium metabisulfite), acid sodium hexametaphosphate, acid potassium hexametaphosphate, acid sodium pyrophosphate, acid potassium pyrophosphate and sulfamic acid. Alkyl sulfonic acids, e.g., methane sulfonic acid may also be used as a co-acid component of the acid system. Strong inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid may also be used, however are less preferred due to their strong acidic character; if present are present in only minor amounts. However, the use of water soluble acids as are preferred, including water soluble salts of organic acids. Exemplary organic acids are those which generally include at least one carbon atom, and include at least one carboxyl group (--COOH) in its structure. Exemplary and referred examples of the organic acid to be used in the present invention include linear aliphatic acids such as formic acid, acetic acid, propionic acid, butyric acid and valeric acid; dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid and maleic acid; acidic amino acids such as glutamic acid and aspartic acid; and hydroxy acids such as glycolic acid, lactic acid, hydroxyacrylic acid, alpha-hydroxybutyric acid, glyceric acid, tartronic acid, malic acid, tartaric acid and citric acid, as well as acid salts of these organic acids. Preferred useful organic acids include citric acid, cresylic acid, dodecylbenzene sulfonic acid, phosphoric acid, salicylic acid, sorbic acid, sulfamic acid, acetic acid, benzoic acid, boric acid, capric acid, caproic acid, cyanuric acid, dihydroacetic acid, dimethylsulfamic acid, polyacrylic acid, 2-ethyl-hexanoic acid, fumaric acid, I-glutamic acid, isopropyl sulfamic acid, naphthenic acid, oxalic acid, phosphorous acid, valeric acid, maleic acid, acetic acid, adipic acid, formic acid, lactic acid, butyric acid, gluconic acid, malic acid, tartaric acid, as well as glycolic acid. The use of water soluble acids are preferred, including water soluble salts of organic acids.

The acid constituent may be present in any amount effective in imparting an acidic pH to the inventive compositions. The acid constituent may be present in any effective amount, but desirably is present in amounts totaling not more than about 20%wt., preferably between 0.1 - 10%wt. based on the total weight of the compositions of which they form a part.

According to certain and preferred embodiments the acid constituent comprises one or more organic acids but excludes inorganic acids.

According to certain and preferred embodiments of the invention, phosphoric acid is necessarily excluded from the inventive compositions.

According to further preferred embodiments the acid constituent is comprised of (preferably consists of) one or more acids selected from the group consisting of: formic acid, sulfamic acid and oxalic acid.

Preferred acids and acid constituents, including respective relative weight ratios of two or more acids forming an acid constituent are further described with reference to one or more of the examples.

The acid constituent may be present in any effective amount, but desirably is not present in amounts totaling more than about 20% wt. based on the total weight of the compositions. It is to be understood that the nature of the acid or acids selected to form the acid constituent will influence the amount of acid required to obtain a desired final pH or pH range, and the precise amount of acid required for a specific composition can be readily obtained by a skilled artisan utilizing conventional techniques. Further, the amount of acid present in the composition, keeping in mind any optional ingredients that may be present, should be in an amount such that the pH of the composition is about 3 or less, and especially within the preferred pH ranges indicated previously. Generally however, the inclusion of the acid constituent in an amount of from about 0.1 to 15%wt., more preferably from about 5 to 10%wt. has yielded good results. It is to be understood that the nature of the acid or acids selected to form the acid constituent will influence the amount of acid required to obtain a desired final pH or pH range, and the precise amount of acid required for a specific composition can be readily obtained by a skilled artisan utilizing conventional techniques. Preferably the pH of the inventive compositions is between 0.001 - 3.5, more preferably is between 0.1 - 2.5, yet more preferably is between 0.5 - 2, and still more preferably is between 0.5 - 1.5, and especially preferably is between 0.5 - 1. Certain specific and preferred pHs are demonstrated with reference to one or more of the Examples described hereinafter.

The compositions of the invention may optionally include one or more further surfactants based on nonionic, anionic, cationic, amphoteric or zwitterionic surfactants.

Exemplary anionic surfactants alcohol sulfates and sulfonates, alcohol phosphates and phosphonates, alkyl ester sulfates, alkyl diphenyl ether sulfonates, alkyl sulfates, alkyl ether sulfates, sulfate esters of an alkylphenoxy polyoxyethylene ethanol, alkyl monoglyceride sulfates, alkyl sulfonates, alkyl ether sulfates, alpha-olefin sulfonates, beta-alkoxy alkane sulfonates, alkyl ether sulfonates, ethoxylated alkyl sulfonates, alkylaryl sulfonates, alkylaryl sulfates, alkyl monoglyceride sulfonates, alkyl carboxylates, alkyl ether carboxylates, alkyl alkoxy carboxylates having 1 to 5 moles of ethylene oxide, alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide), sulfosuccinates, octoxynol or nonoxynol phosphates, taurates, fatty taurides, fatty acid amide polyoxyethylene sulfates, acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, alkylpolysaccharide sulfates, alkylpolyglucoside sulfates, alkyl polyethoxy carboxylates, and sarcosinates or mixtures thereof. These anionic surfactants may be provided as salts with one or more organic counterions, e.g, ammonium, or inorganic counteraions, especially as salts of one or more alkaline earth or alkaline earth metals, e.g, sodium.

Further examples of anionic surfactants include water soluble salts or acids of the formula (ROSO₃)_XM or (RSO₃)_XM wherein R is preferably a C₆-C₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Ci₀-C₂O alkyl component, more preferably a Ci₂-Ci₈ alkyl or hydroxyalkyl, and M is H or a mono-, di- or tri-valent cation, e. g., an alkali metal cation (e. g., sodium, potassium, lithium), or ammonium or substituted ammonium (e. g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like) and x is an integer, preferably 1 to 3, most preferably 1. Materials sold under the Hostapur and Biosoft trademarks are examples of such anionic surfactants.

Still further examples of anionic surfactants include alkyl-diphenyl- ethersulphonates and alkyl-carboxylates. Also useful as anionic surfactants are diphenyl disulfonates, and salt forms thereof, such as a sodium salt of diphenyl disulfonate commercially available as Dowfax® 3B2. Such diphenyl disulfonates are included in certain preferred embodiments of the invention in that they provide not only a useful cleaning benefit but concurrently also provide a useful degree of hydro tropic functionality. Other anionic surfactants can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of soap, C₆-C_2O linear alkylbenzenesulfonates, C₆-C₂₂ primary or secondary alkanesulfonates, C₆-C₂₄ olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, C₆-C₂₄ alkylpolyglycolethersulfates, alkyl ester sulfates such as Ci_4-I6 methyl ester sulfates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated Ci₂-Ci₈ monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C₆-Ci₄ diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside, branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH₂CH₂COkCH₂COCTM⁺ wherein R is a C₈-C₂₂ alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Examples of the foregoing anionic surfactants are available under the following tradenames: Rhodapon®, Stepanol®, Hostapur®, Surfϊne®, Sandopan®, Neodox®, Biosoft®, and Avanel®.

An anionic surfactant compound which may be particularly useful in the inventive compositions when the compositions are at a pH of 2 or less are one or more anionic surfactants based on alphasulphoesters including one or more salts thereof. Such particularly preferred anionic surfactants may be represented by the following general structures:

wherein, in each of the foregoing:

R¹ represents a C₆ - C₂₂ alkyl or alkenyl group; each of R² is either hydrogen, or if not hydrogen is a SO₃ ^" having associated with it a cation, X⁺, which renders the compound water soluble or water dispersible, with X preferably being an alkali metal or alkaline earth metal especially sodium or potassium, especially sodium, with the proviso that at least one R², preferably at least two R² is a

(SO₃ ^") having an associated cation X⁺, and, R represents a Ci-C₆, preferably C 1-C4 lower alkyl or alkenyl group, especially methyl. Notwithstanding the above, in certain preferred embodiments optional surfactants based on anionic surfactants are necessarily absent from the compositions.

One class of exemplary, albeit optionally, useful nonionic surfactants are polyethylene oxide condensates of alkyl phenols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to

12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, the ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene and the like. Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol and diisooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.

Further optionally useful nonionic surfactants include the condensation products of aliphatic alcohols with from about 1 to about 60 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol and the condensation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from about 10 to 14 carbon atoms). Other examples are those C₆ -Ci i straight-chain alcohols which are ethoxylated with from about 3 to about 6 moles of ethylene oxide. Their derivation is well known in the art. Examples include Alfonic® 810-4.5 (also available as Teric G9A5), which is described in product literature from Sasol as a C_8-io having an average molecular weight of 356, an ethylene oxide content of about 4.85 moles (about 60 wt.%), and an HLB of about 12; Alfonic® 810-2, which is described in product literature from Sasol as a C_8- io having an average molecular weight of 242, an ethylene oxide content of about 2.1 moles (about 40 wt.%), and an HLB of about 12; and Alfonic® 610-3.5, which is described in product literature from Sasol as having an average molecular weight of 276, an ethylene oxide content of about 3.1 moles (about 50 wt.%), and an HLB of 10. Product literature from Sasol also identifies that the numbers in the alcohol ethoxylate name designate the carbon chain length (numbers before the hyphen) and the average moles of ethylene oxide (numbers after the hyphen) in the product. Further exemplary useful nonionic surfactants include alcohol ethoxylates which are described as C₉-C1₁ ethoxylated alcohols and marketed under the Neodol® tradename. The Neodol® 91 series non- ionic surfactants of interest include Neodol 91- 2.5, Neodol 91-6, and Neodol 91-8. Neodol 91-2.5 has been described as having about 2.5 ethoxy groups per molecule; Neodol 91-6 has been described as having about 6 ethoxy groups per molecule; and Neodol 91-8 has been described as having about 8 ethoxy groups per molecule. Still further examples of ethoxylated alcohols include the Rhodasurf® DA series non-ionic surfactants available from Rhodia which are described to be branched isodecyl alcohol ethoxylates. Rhodasurf D A-530 has been described as having 4 moles of ethoxylation and an HLB of 10.5; Rhodasurf DA-630 has been described as having 6 moles of ethoxylation with an HLB of 12.5; and Rhodasurf DA- 639 is a 90% solution of DA-630.

Further examples of useful nonionic surfactants include alcohol ethoxylates including ClO oxo -alcohol ethoxylates available from BASF under the Lutensol ON tradename. They are available in grades containing from about 3 to about 11 moles of ethylene oxide (available under the names Lutensol ON 30; Lutensol ON 50; Lutensol ON 60; Lutensol ON 65; Lutensol ON 66; Lutensol ON 70; Lutensol ON 80; and Lutensol ON 110).

Yet further examples of ethoxylated alcohols include those from Tomah Products (Milton, WI) under the Tomadol tradename with the formula RO(CH₂CH₂O)_nH where R is the primary linear alcohol and n is the total number of moles of ethylene oxide. The ethoxylated alcohol series from Tomah include 91-2.5; 91-6; 91-8 - where R is linear C9/C10/C11 and n is 2.5, 6, or 8; 1-3; 1-5; 1-7; 1-73B; 1-9; - where R is linear CI l and n is 3, 5, 7 or 9; 23-1; 23-3; 23-5; 23-6.5 - where R is linear C12/C13 and n is 1, 3, 5, or 6.5; 25-3; 25-7; 25-9; 25-12 - where R is linear C12/C13 C14/ C15 and n is 3, 7, 9, or 12; and 45-7; 45-13 - where R is linear C14/ C15 and n is 7 or 13.

Other examples of potentially useful nonionic surfactants include those having a formula RO(CH₂CH₂O)_nH wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from Ci₂H₂₅ to Ci₆H₃₃ and n represents the number of repeating units and is a number of from about 1 to about 12. Surfactants of this formula are presently marketed under the Genapol® tradename. available from Clariant, Charlotte, N.C., include the 26-L series of the general formula RO(CH₂CH₂O)_nH wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from Ci₂H₂₅ to Ci₆H₃₃ and n represents the number of repeating units and is a number of from 1 to about 12, such as 26-L-l, 26-L-1.6, 26-L-2, 26-L-3, 26-L-5, 26-L-45, 26-L-50, 26-L-60, 26-L- 6ON, 26-L-75, 26-L-80, 26-L-98N, and the 24-L series, derived from synthetic sources and typically contain about 55% Ci₂ and 45% C]₄ alcohols, such as 24-L-3, 24-L-45, 24- L-50, 24-L-60, 24-L-60N, 24-L-75, 24-L-92, and 24-L-98N. From product literature, the single number following the "L" corresponds to the average degree of ethoxylation (numbers between 1 and 5) and the two digit number following the letter "L" corresponds to the cloud point in °C of a 1.0 wt.% solution in water.

A specific class of potentially useful, albeit optional, nonionic surfactants include are monobranched alkoxylated ClO-fatty alcohols and/or Cl 1-fatty alcohols; these are jointly referred to as CIO/CI 1-fatty alcohols. These materials are nonionic surfactants are monobranched and may have various degrees of alkoxylation, and are typically ethoxylated with between about 3 and 14 moles of ethylene oxide, typically 4, 5, 6, 7, 8, 9, 10 or 14 moles ethylene oxide. Such nonionic surfactants are presently commercially available under the Lutensol® (ex. BASF AG) and are available in a variety of grades e.g., Lutensol® XL 40 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 4 moles of ethoxylation, Lutensol® XL 50 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 5 moles of ethoxylation, Lutensol® XL 60 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 6 moles of ethoxylation, Lutensol® XL 70 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 7 moles of ethoxylation, Lutensol® XL 40 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 4 moles of ethoxylation, Lutensol® XL 79 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 7 moles of ethoxylation, Lutensol® XL 80 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 8 moles of ethoxylation, Lutensol® XL 89 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 8 moles of ethoxylation, Lutensol® XL 90 recited by its supplier to be a C 10-Guerbet alcohol which is approximately 9 moles of ethoxylation, Lutensol® XL 99 recited by its supplier to be a ClO-Guerbet alcohol which is approximately 9 moles of ethoxylation, Lutensol® XL 100 recited by its supplier to be a ClO-Guerbet alcohol which is approximately 10 moles of ethoxylation, Lutensol® XL 140 recited by its supplier to be a ClO-Guerbet alcohol which is approximately 14 moles of ethoxylation, all available from BASF AG. Alternately or additionally, nonionic surfactant based on monobranched alkoxylated ClO-fatty alcohols marketed under the Lutensol® XP series of surfactants, also ex. BASF AG, may also be used. While the foregoing materials are ethoxylated, it is to be understood that other alkoxylated, e.g., propoxylated, butoxylated, as well as mixed ethoxylated and propoxylated branched nonionic alkyl polyethylene glycol ether may also be used.

It is contemplated by the inventors that similar nonionic surfactants based on monobranched alkoxylated Cl 1 -fatty alcohols may be used to substitute part of, or all of the nonionic surfactant based on monobranched alkoxylated ClO-fatty alcohols. These include for example, the Genapol® UD series described as tradenames Genapol® UD 030, Cπ-oxo-alcohol polyglycol ether with 3 EO; Genapol® UD, 050 Cn-oxo-alcohol polyglycol ether with 5 EO; Genapol® UD 070, Cn-oxo-alcohol polyglycol ether with 7 EO; Genapol® UD 080, Cn-oxo-alcohol polyglycol ether with 8 EO; Genapol® UD 088, Cn-oxo-alcohol polyglycol ether with 8 EO; and Genapol® UD 110, Cn-oxo-alcohol polyglycol ether with 11 EO (ex. Clariant). A further class of nonionic surfactants which are contemplated to be useful include those based on alkoxy block copolymers, and in particular, compounds based on ethoxy/propoxy block copolymers. Polymeric alkylene oxide block copolymers include nonionic surfactants in which the major portion of the molecule is made up of block polymeric C₂-C₄ alkylene oxides. Such nonionic surfactants, while preferably built up from an alkylene oxide chain starting group, and can have as a starting nucleus almost any active hydrogen containing group including, without limitation, amides, phenols, thiols and secondary alcohols.

A further group of such useful nonionic surfactants containing the characteristic alkylene oxide blocks are those which may be generally represented by the formula (A): HO-(EO)_x(PO)_y(EO)z-H (A)

where EO represents ethylene oxide,

PO represents propylene oxide, y equals at least 15,

(EO)_x+y equals 20 to 50% of the total weight of said compounds, and, the total molecular weight is preferably in the range of about 2000 to 15,000. These surfactants are available under the PLURONIC tradename from BASF or Emulgen from Kao. Another group of nonionic surfactants appropriate for use in the new compositions can be represented by the formula (B):

R-(EO,PO)_a(EO,PO)_b-H (B)

wherein R is an alkyl, aryl or aralkyl group, where the R group contains 1 to 20 carbon atoms, the weight percent of EO is within the range of 0 to 45% in one of the blocks a, b, and within the range of 60 to 100% in the other of the blocks a, b, and the total number of moles of combined EO and PO is in the range of 6 to 125 moles, with 1 to 50 moles in the PO rich block and 5 to 100 moles in the EO rich block. Further nonionic surfactants which in general are encompassed by Formula B include butoxy derivatives of propylene oxide/ethylene oxide block polymers having molecular weights within the range of about 2000-5000.

Still further useful nonionic surfactants containing polymeric butoxy (BO) groups can be represented by formula (C) as follows:

RO-(BO)_n(EO)^H (C)

wherein R is an alkyl group containing I to 20 carbon atoms, n is about 5-15 and x is about 5-15. Also useful as the nonionic block copolymer surfactants, which also include polymeric butoxy groups, are those which may be represented by the following formula (D):

HO-(EO)_x(BO)_n(EO)_y-H (D)

wherein n is about 5-15, preferably about 15, x is about 5-15, preferably about 15, and y is about 5-15, preferably about 15. Surfactants based on amine oxides are also contemplated to be possibly useful in the present inventive compositions as optional nonionic surfactants. Exemplary amine oxides include: alkyl di(Ci-C₇) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples of such compounds include lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, and those in which the alkyl group is a mixture of different amine oxide, dimethyl cocoamine oxide, dimethyl (hydrogenated tallow) amine oxide, and myristyl/palmityl dimethyl amine oxide; alkyl di(hydroxy C₁-C₇) amine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples of such compounds include bis(2-hydroxyethyl) cocoamine oxide, bis(2-hydroxyethyl) tallowamine oxide; and bis(2-hydroxyethyl) stearylamine oxide; alkylamidopropyl di(Ci-C₇) amine oxides in which the alkyl group has about 10- 20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Examples of such compounds include cocoamidopropyl dimethyl amine oxide and tallowamidopropyl dimethyl amine oxide; and alkylmorpholine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or unsaturated. Notwithstanding the foregoing, in certain preferred embodiments optional surfactants based on nonionic surfactants are necessarily absent from the compositions.

Exemplary cationic surfactant compositions include those which provide a germicidal effect to the compositions, and especially preferred are quaternary ammonium compounds and salts thereof, which may be characterized by the general structural formula:

where at least one of Ri, R₂, R₃ and R₄ is a alkyl, aryl or alkylaryl substituent of from 6 to 26 carbon atoms, and the entire cation portion of the molecule has a molecular weight of at least 165. The alkyl substituents may be long-chain alkyl, long-chain alkoxyaryl, long- chain alkylaryl, halogen-substituted long-chain alkylaryl, long-chain alkylphenoxyalkyl, arylalkyl, etc. The remaining substituents on the nitrogen atoms other than the abovementioned alkyl substituents are hydrocarbons usually containing no more than 12 carbon atoms. The substituents Ri, R₂, R₃ and R₄ may be straight-chained or may be branched, but are preferably straight-chained, and may include one or more amide, ether or ester linkages. The counterion X may be any salt-forming anion which permits water solubility of the quaternary ammonium complex.

Further exemplary quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like. Other suitable types of quaternary ammonium salts include those in which the molecule contains either amide, ether or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, N-(laurylcocoaminoformylmethyl)-pyridinium chloride, and the like. Other very effective types of quaternary ammonium compounds which are useful as germicides include those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenzyltrimethyl ammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like.

Notwithstanding the foregoing, in certain preferred embodiments optional surfactants based on cationic surfactants are necessarily absent from the compositions. Exemplary amphoteric surfactants which are contemplated to be useliil in the cosurfactant constituent include one or more water-soluble betaine surfactants which may be represented by the general formula:

wherein Ri is an alkyl group containing from 8 to 18 carbon atoms, or the amido radical which may be represented by the following general formula:

O H Il I R-C-N- (CH₂)_a-R2 wherein R is an alkyl group having from 8 to 18 carbon atoms, a is an integer having a value of from 1 to 4 inclusive, and R₂ is a C₁-C₄ alkylene group. Examples of such water-soluble betaine surfactants include dodecyl dimethyl betaine, as well as cocoamidopropylbetaine.

Notwithstanding the above, in certain preferred embodiments optional surfactants based on amphoteric surfactants are necessarily absent from the compositions.

Notwithstanding the foregoing, in certain preferred embodiments optional surfactants based on zwitterionic surfactants are necessarily absent from the compositions.

When present these one or more further optional surfactants based on nonionic, anionic, cationic, amphoteric or zwitterionic surfactants may be present singly or in mixtures. When present they may be included in any amount which is effective to provide improved cleaning performance to the compositions, but also not deleteriously affect the thickening system of the compositions. Advantageously, when present the total amount of the further optional surfactants does not exceed 25%wt., preferably does not exceed 15%wt. and yet more preferably does not exceed 10%wt. of the total weight of the composition.

Water is the primary constituent of the inventive compositions as the compositions are largely aqueous in nature, and comprise at least 75%wt., preferably at least about 80%wt. water, more preferably at least about 82%wt. water, still preferably at least about 85%wt., and in certain preferred embodiments comprise at least about 87%wt. water. The amount of water is added to order to provide to 100% by weight of the compositions of the invention. The water may be tap water, but is preferably distilled water, and is most preferably deionized water or soft water. If the water is tap water, it is preferably substantially free of any undesirable impurities such as organics or inorganics, especially minerals salts which are present in hard water which may thus undesirably interfere with the operation of the constituents present in the aqueous compositions according to the invention.

The compositions of the present invention can also optionally comprise one or more further constituents which are directed to improving the aesthetic or functional features of the inventive compositions. Such conventional additives known to the art include but not expressly enumerated here may also be included in the compositions according to the invention. By way of non-limiting example these may include: coloring agents, fragrances and fragrance solubilizers, viscosity modifying agents including one or more thickeners, pH adjusting agents and pH buffers including organic and inorganic salts, optical brighteners, organic solvents, opacifying agents, abrasives, and preservatives, as well as other optional constituents known to the art. Many of these materials are known to the art, per se, and are described in McCutcheon 's Detergents and Emulsifiers, North American Edition, 1998; Kirk-Othmer, Encyclopedia of Chemical Technology, 4th Ed., Vol. 23, pp. 478-541 (1997). Such optional, i.e., non-essential constituents should be selected so to have little or no detrimental effect upon the desirable characteristics of the present invention. When present the total amount of such further constituents is not more than about 20%wt, preferably not more than about 15%wt., based on the total weight of the composition of which it forms a part. Byway of non-limiting example pH adjusting agents include phosphorus containing compounds, monovalent and polyvalent salts such as of silicates, carbonates, and borates, certain acids and bases, tartrates and certain acetates. Byway of further non-limiting example pH buffering compositions include the alkali metal phosphates, polyphosphates, pyrophosphates, triphosphates, tetraphosphates, silicates, metasilicates, polysilicates, carbonates, hydroxides, and mixtures of the same. Certain salts, such as the alkaline earth phosphates, carbonates, hydroxides, can also function as buffers. It may also be suitable to use as buffers such materials as aluminosilicates (zeolites), borates, aluminates and certain organic materials such as gluconates, succinates, maleates, and their alkali metal salts. When present, the pH adjusting agent, especially the pH buffers are present in an amount effective in order to maintain the pH of the inventive composition within a target pH range.

The inventive compositions may include one or more coloring agents which may be included to impart a desired color or tint to the compositions. The compositions of the invention optionally but in certain cases desirably include a fragrance constituent. Fragrance raw materials may be divided into three main groups: (1) the essential oils and products isolated from these oils; (2) products of animal origin; and (3) synthetic chemicals.

The essential oils consist of complex mixtures of volatile liquid and solid chemicals found in various parts of plants. Mention may be made of oils found in flowers, e.g., jasmine, rose, mimosa, and orange blossom; flowers and leaves, e.g., lavender and rosemary; leaves and stems, e.g., geranium, patchouli, and petitgrain; barks, e.g., cinnamon; woods, e.g., sandalwood and rosewood; roots, e.g., angelica; rhizomes, e.g., ginger; fruits, e.g., orange, lemon, and bergamot; seeds, e.g., aniseed and nutmeg; and resinous exudations, e.g., myrrh. These essential oils consist of a complex mixture of chemicals, the major portion thereof being terpenes, including hydrocarbons of the formula (C5H8)n and their oxygenated derivatives. Hydrocarbons such as these give rise to a large number of oxygenated derivatives, e.g., alcohols and their esters, aldehydes and ketones. Some of the more important of these are geraniol, citronellol and terpineol, citral and citronellal, and camphor. Other constituents include aliphatic aldehydes and also aromatic compounds including phenols such as eugenol. In some instances, specific compounds may be isolated from the essential oils, usually by distillation in a commercially pure state, for example, geraniol and citronellal from citronella oil; citral from lemon-grass oil; eugenol from clove oil; linalool from rosewood oil; and safrole from sassafras oil. The natural isolates may also be chemically modified as in the case of citronellal to hydroxy citronellal, citral to ionone, eugenol to vanillin, linalool to linalyl acetate, and safrol to heliotropin.

Animal products used in perfumes include musk, ambergris, civet and castoreum, and are generally provided as alcoholic tinctures. The synthetic chemicals include not only the synthetically made, also naturally occurring isolates mentioned above, but also include their derivatives and compounds unknown in nature, e.g., isoamylsalicylate, amylcinnamic aldehyde, cyclamen aldehyde, heliotropin, ionone, phenylethyl alcohol, terpineol, undecalactone, and gamma nonyl lactone. Fragrance compositions as received from a supplier may be provided as an aqueous or organically solvated composition, and may include as a surface-active agent, typically a surfactant, in minor amount. Such fragrance compositions are quite usually proprietary blends of many different specific fragrance compounds. However, one of ordinary skill in the art, by routine experimentation, may easily determine whether such a proprietary fragrance composition is compatible in the compositions of the present invention.

One or more coloring agents may also be used in the inventive compositions in order to impart a desired colored appearance or colored tint to the compositions. Known art water soluble or water dispersible pigments and dyes may be added in effective amounts.

A further optional constituent are one or more preservatives, although due to the acid pH of the composition such preservatives are not typically required to be present. When included, such preservatives are primarily included to reduce the growth of undesired microorganisms within the composition during storage prior to use. Exemplary useful preservatives include compositions which include parabens, including methyl parabens and ethyl parabens, glutaraldehyde, formaldehyde, 2-bromo-2-nitropropoane- 1,3-diol, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazoline-3-one, and mixtures thereof. One exemplary composition is a combination 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one where the amount of either component may be present in the mixture anywhere from 0.001 to 99.99 weight percent, based on the total amount of the preservative. Further exemplary useful preservatives include those which are commercially including a mixture of 5-chloro-2-methyl-4- isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one marketed under the trademark KATHON® CG/ICP as a preservative composition presently commercially available from Rohm and Haas (Philadelphia, PA). Further useful and commercially available preservative compositions include KATHON® CG/ICP II, a further preservative composition presently commercially available from Rohm and Haas (Philadelphia, PA), PROXEL® which is presently commercially available from Zeneca Biocides (Wilmington, DE), SUTTOCIDE® A which is presently commercially available from Sutton Laboratories (Chatam, NJ) as well as TEXTAMER® 38AD which is presently commercially available from Calgon Corp. (Pittsburgh, PA).

Optionally the compositions of the invention may include an ancillary thickener constituent, which may be added in any effective amount in order to increase the viscosity of the compositions. Exemplary thickeners useful in the thickener constituent include one or more of polysaccharide polymers selected from cellulose, alkyl celluloses, alkoxy celluloses, hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, carboxy alkyl celluloses, carboxy alkyl hydroxy alkyl celluloses, naturally occurring polysaccharide polymers such as xanthan gum, guar gum, locust bean gum, tragacanth gum, or derivatives thereof, polycarboxylate polymers, polyacrylamides, clays, and mixtures thereof.

According to preferred embodiments, such ancillary thickener components are necessarily excluded from the present inventive compositions.

Another optional constituent of the present invention is at least one abrasive material. Examples of abrasive materials include oxides, carbonates, quartzes, siliceous chalk, diatomaceous earth, colloidal silicon dioxide, alkali metasilicates, organic abrasive materials selected from polyolefins, polyethylenes, polypropylenes, polyesters, polystyrenes, acetonitrile-butadiene-styrene resins, melamines, polycarbonates, phenolic resins, epoxies and polyurethanes, natural materials selected from rice hulls, corn cobs, and the like, nepheline syenite, or talc and mixtures thereof. The particle size of the abrasive agent can range from about 1 μm to about 1000 μm, preferably between about 10 μm to about 200 μm, and more preferably between about 10 μm and about 100 μm. It is preferred to us those abrasive agents that will not scratch glass or ceramic surfaces. Such abrasive agents include calcium carbonate, siliceous chalk, diatomaceous earth, colloidal silicon dioxide, sodium metasilicate, talc, and organic abrasive materials. Calcium carbonate is preferred as being effective and widely available.

According to preferred embodiments, such abrasive materials are necessarily excluded from the present inventive compositions.

One particularly preferred optional constituent is a film forming polymer based on quaternized copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate, of which such preferred polymers include those described in U.S. Patent No. 4,080,310, to Ng, the contents of which are herein incorporated by reference. Such quaternized copolymers include those according to the general formula:

O O cr

NH- C— (CHz)₄ - C— NH- CIH₂- CH₂- Nt- CH₂- CH₂

H₂C CH₂ CH

OH wherein "x" is about 40 to 60. Further exemplary useful copolymers include copolymers of vinylpyrrolidone and dimethylaminoethylmethacrylate quaternized with diethyl sulphate (available as Gafquat® 755 ex., ISP Corp., Wayne, NJ).

In certain particularly embodiments such film forming polymers based on quaternized copolymers of vinylpyrrolidone and dimethylaminoethyl methacrylate form an essential constituent of the invention. When present, they may be included in any effective amount, but advantageously are present in amounts of from 0.001 - 0.5%wt, more preferably in amounts of from 0.001 - 0.2%wt, and most preferably, when present, are present in amounts of from 0.01 - 0.12%wt. based on the total weight of the compositions of which they form a part.

The compositions of the inventions may be produced by simple mixing of the constituents in water, preferably at least a major proportion of the deionized water is provided at room temperature to which is added under constant stirring the surfactant constituent, followed by the organic solvent constituent, and finally any optional constituent which may be included. Mixing continues until a homogenous mixture of the constituents is formed, after which mixing may be stopped and the compositions are ready for use. These as mixed compositions are preferably used without further dilution prior to their use in the treatment of hard surfaces.

Hard surface cleaning composition according to the invention is desirably provided as a ready to use product which may be directly applied to a hard surface. By way of example, hard surfaces include surfaces composed of refractory materials such as: glazed and unglazed tile, brick, porcelain, ceramics as well as stone including marble, granite, and other stones surfaces; glass; metals; plastics e.g. polyester, vinyl; fiberglass, Formica®, Corian® and other hard surfaces known to the industry. Hard surfaces which are to be particularly denoted are lavatory fixtures such as shower stalls, bathtubs and bathing appliances (racks, curtains, shower doors, shower bars) toilets, bidets, wall and flooring surfaces especially those which include refractory materials and the like. Further hard surfaces which are to be denoted are those associated with kitchen environments and other environments associated with food preparation, including cabinets and countertop surfaces as well as walls and floor surfaces especially those which include refractory materials, plastics, and stone. Such hard surfaces described above are to be understood as being recited by way of illustration and not be way of limitation.

The compositions of the invention may be formulated so to be supplied in as non- pressurized containers such as rigid containers or flasks, as well as in deformable containers or flask from which the inventive compositions may be dispensed. The non- pressurized containers may be provided with a conventional trigger-pump spray apparatus which when actuated by a user, is used to withdraw a quantity of the composition from the container and expel it from the trigger-pump spray apparatus as a spray or stream which may be directed to a hard surface in need of treatment. Beneficially the compositions of the invention are provided in a bottle or flask which includes an openable neck through which the compositions may be poured out onto a surface. Advantageously such a bottle or flask may be supplied with a flow directing nozzle though which the compositions of the invention may be dispensed.

The composition of the present invention, can also be applied to a hard surface by using a wet wipe preimpreganted with a quantity of the inventive composition. The wipe can be of a woven or non-woven nature. Fabric substrates can include nonwoven or woven pouches, sponges, in the form of abrasive or non-abrasive cleaning pads. Such fabrics are known commercially in this field and are often referred to as wipes. Such substrates can be resin bonded, hydroentangled, thermally bonded, meltblown, needlepunched, or any combination of the former.

Such nonwoven fabrics may be a combination of wood pulp fibers and textile length synthetic fibers formed by well known dry-form or wet-lay processes. Synthetic fibers such as rayon, nylon, orlon and polyester as well as blends thereof can be employed. The wood pulp fibers should comprise about 30 to about 60 percent by weight of the nonwoven fabric, preferably about 55 to about 60 percent by weight, the remainder being synthetic fibers. The wood pulp fibers provide for absorbency, abrasion and soil retention whereas the synthetic fibers provide for substrate strength and resiliency. The substrate of the wipe may also be a film forming material such as a water soluble polymer. Such self-supporting film substrates may be sandwiched between layers of fabric substrates and heat sealed to form a useful substrate. The free standing films can be extruded utilizing standard equipment to devolatilize the blend. Casting technology can be used to form and dry films or a liquid blend can be saturated into a carrier and then dried in a variety of known methods.

The compositions of the present invention are absorbed onto the wipe to form a saturated wipe. The wipe can then be sealed individually in a pouch which can then be opened when needed or a multitude of wipes can be placed in a container for use on an as needed basis. The container, when closed, sufficiently sealed to prevent evaporation of any components from the compositions.

The compositions are readily used in the cleaning of hard surfaces by application a cleaning effective amount of a hard surface cleaning composition according to any of the prior recited inventive aspects to a hard surface in need of such treatment, and concurrently or subsequently, wiping the surface with a cloth, wipe or wiping article.

According to a further aspect of the invention, there is provided a method for the manufacture of said compositions as described herein.

The following examples exhibit exemplary and preferred formulations of the invention. It is to be understood that these examples are provided by way of illustration only and that further useful formulations falling within the scope of the present invention and the claims may be readily produced by one skilled in the art without deviating from the scope and spirit of the invention.

Examples

Formulations according to the invention were produced by mixing the constituents outlined in Table 1 by adding the individual constituents into a beaker of deionized water at room temperature which was stirred with a conventional magnetic stirring rod. Stirring continued until each of the formulations were homogenous in appearance. It is to be noted that the constituents might be added in any order, but it is preferred that a major proportion of water be the initial constituent provided to a mixing vessel or apparatus as it is the major constituent and addition of the further constituents thereto is convenient. After the addition of the final constituent, mixing continued for 5 - 60 minutes to ensure homogenous blending and that a clear solution was obtained. These compositions according to the examples are indicated by the letter "E" followed by a digit. OO

^• viscosity measured at 2O⁰C, using a Brookfield LVD viscometer, coated spindle #2, at 30 rpm

The constituents used to form the examples as well as the comparative examples are identified more fully on the following Table 2.

As is evident from the results reported on Table 1, the compositions of the invention achieved good thickening in the absence of metallic salts, particularly in the absence of sodium chloride.

The storage stability of the El composition disclosed on Table 1 was evaluated at various temperatures over several weeks to evaluate the performance characteristics of the compositions at different time intervals of storage. The results of these tests and test conditions are presented on Table 3.

The viscosity of the El composition was periodically tested at the indicated time intervals after the test sample was removed from the storage environment, and allowed to stabilize at room temperature (20⁰C). At such time the viscosity was determined using a Brookfϊeld LVD viscometer using a #2 spindle rotating at 60 rpm. The pH was evaluated using a laboratory pH meter. The color of the sample was based on a five-point scale, wherein a ranking of "5" indicated excellent physical appearance with no separation and no noticeable color change or fading; "4" indicated good physical appearance with no phase separation, no color change but slight fading; "3" indicated acceptable appearance with no phase separation but with slight color change and slight fading, while "2" indicated an unacceptable appearance, with significant color loss and noticeable color fading. A ranking of "1" indicated a product with phase separation and with significant color loss and noticeable color fading. As seen from Table 1 , the El composition exhibited excellent retention of viscosity and excellent retention of visual characteristics over the various storage conditions and time parameters of the test. Such storage stability, and retention of viscosity is both surprising and technically advantageous.

As is further evident from the results reported on Table 3, the compositions of the invention achieved and retained good thickening in the absence of metallic salts, particularly in the absence of sodium chloride, over the time period of the test and under varying storage conditions.

While described in terms of the presently preferred embodiments, it is to be understood that the present disclosure is to be interpreted as by way of illustration, and not by way of limitation, and that various modifications and alterations apparent to one skilled in the art may be made without departing from the scope and spirit of the present invention.

Claims

Claims:

1. Thickened aqueous acidic hand surface treatment composition having a pH of 3 or less which comprises: 0.001 - 10%wt of one or more fatty amine alkoxylate compounds;

0.001 - 5 %wt. of a hydrotrope compound or salt thereof; up to 20%wt. an acid constituent; and, at least 75%wt. water; wherein the one or more fatty amine alkoxylate compounds and the a hydrotrope compound or salt thereof are present in respective weight ratios of from 1 :0.1 to 1 :1 with the proviso that when the compositions comprise oxalic acid, the compositions exclude a source of metal ions.

2. The composition according to claim 1 wherein: the acid constituent comprises one or more organic acids selected from formic acid, sulfamic acid and oxalic acid, but which acid constituent excludes phosphoric acid.

3. The composition according to claim 1 or 2 wherein the hydrotope constituent is a xylene sulfonate or salt form thereof.

4. The composition according to any of claims 1 - 3, herein the hydrotope constituent is a xylene sulfonate or salt form thereof to the exclusion of other hydrotropes.

5. The composition according to any of claims 1-4 wherein: the hydrotrope constituent comprises 0.001 - 5 %wt. of the composition.

6. The composition according to any of claims 1-5 wherein: the one or more fatty amine alkoxylate compounds and the a hydrotrope compound or salt thereof are present in respective weight ratios of from 1 :0.1 to 1 :0.75.

7. The composition according to claim 6 wherein: the one or more fatty amine alkoxylate compounds and the a hydrotrope compound or salt thereof are present in respective weight ratios of from 1 :0.15 to 1 :0.6.

8. The composition according to any preceding claim wherein:

. one or more fatty amine alkoxylate compounds according to the formula:

wherein R is a C₈ -C₂₄ straight chained or branched alkyl group, preferably a C₈ - Ci₈ straight chained or branched alkyl group, and further wherein each of w, x, y, a, b, and c are identical or different and are a number from 0 to 100 with the proviso that w+x+y+a+b+c is at least 2.

9. The composition according to any preceding claim wherein: the compositions exhibited a deviation of not more than 50% of initial viscosity when stored at temperatures of from -4⁰C, to 50 ⁰C when stored at such temperatures for a time period of 1 week.

10. A method for cleaning hard surfaces which comprises the step of: applying a cleaning effective amount of a composition according to any preceding claim cleaning composition according to any of the prior recited inventive aspects to a hard surface in need of such treatment, and concurrently or subsequently, wiping the surface with a cloth, wipe or wiping article.