GB2429015A - An aqueous hard-surface cleaning composition - Google Patents

Abstract

Hard surface cleaning compositions having an acidic pH which feature good cleaning properties and particularly effective removal of soap scum stains, while featuring low potential levels of irritability to the user. Said compositions comprise about 0.1-10 %wt. of an acid sequestrant constituent; about 0.1 -10 %wt. of an organic solvent constituent consisting solely of one or more hydrophobic solvents; about 0.001-1 %wt. of a single constituent which exhibits both anionic surfactant and hydrotrope properties; a metal cleaning effective amount of an inorganic chloride salt; and, about 0-20%wt. of one or more optional constituents; the balance to 100 % by weight of water, wherein said compositions are acidic in nature, and desirably exhibit a pH of about 5 or less. Said compositions desirably also provide disinfecting effects. Processes for the production of the said compositions, as well as methods for their use are also described.

Description

IMPROVEMENTS IN OR RELATED TO ORGANIC COMPOSITIONS

The present invention relates to improved cleaning compositions which find particular use in hard surface cleaning applications.

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 and "soap scum" 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.

Various formulations in compositions of cleaning agents have been produced, and it is generally known to the art which cleaning agents are generally suited for one type of stain but not necessarily for both classes of stains. For example, it is known to the art that highly acidic cleaning agents comprising strong acids, such as hydrochloric acids, are useful in the removal of hard water stains. However, the presence of strong acids is known to be an irritant to the skin and further has the potential of toxicological danger.

Other classes of cleaning compositions and formulations are known to be useful upon soap scum stains. However, generally such compositions comprise an organic and/or inorganic acid, one or more synthetic detergents from commonly recognized classes such as those described in U. S. Pat. No. 5,061,393; U.S. Pat. No. 5,008,030; U.S. Pat. No. 4,759,867; U.s. Pat. No. 5,192,460; U.S. Pat. No. 5,039,441. Generally, the compositions described in these patents are claimed to be effective in the removal of soap scum stains from such hard surfaces and may find further limited use in other classes of stains.

However, the formulations of most of the compositions within the aforementioned patents generally have relatively high amounts of acids (organic andlor inorganic), which raises toxicological concerns, and further none of the above patents provides any disinfecting properties.

Compositions are known to the art which do provide disinfection and sanitization through the use of certain classes of anionic surfactants coupled with an acidic component, such as that described in U.S. Pat. No. 5143720. However, the compositions in this U.S. patent would not be expected nor are believed to provide any significant cleaning benefit.

US Patent 6221823 describes compositions which comprise 0.1-10% by weight of an acid sequestrant constituent; 0.1-10% by weight of a mixture of hydrophobic and hydrophilic solvents; 1-8% by weight of a surfactant andlor hydrotrope constituent; 0- 20% by weight of one or more optional constituents; the balance to 100% by weight, water wherein the aqueous hard surface cleaning composition exhibits a pH of 7.0 or less, especially a pH of 5.0 and less. Although acidic, the improved hard surface cleaning compositions feature low irritability to the eyes and skin of consumers. The compositions also provide disinfecting effects. However these compositions are silent as to their cleaning efficacy of metal and metallic surfaces.

Published US Patent Application 2002/018791 8A 1 describes compositions having an acidic pH, providing good removal of soap scum stains, and further feature low levels of irritability to the user. The compositions comprise about 0. 1-10 % by weight of an acid sequestrant constituent; about 0.1 -10 % by weight of a mixture of hydrophobic and hydrophilic solvents; about 0.00 1-1 % by weight of a single constituent which exhibits both anionic surfactant and hydrotrope properties; about 0-20 % by weight of one or more optional constituents; the balance to 100 % by weight of water, wherein the aqueous hard surface cleaning composition exhibits a pH of 7 or less, especially a pH of about 5 or less. Although acidic, the improved hard surface cleaning compositions feature low irritability to the eyes and skin of consumers. The compositions also provide disinfecting effects. However these compositions are silent as to their cleaning efficacy of metal and metallic surfaces.

While these and other prior art compositions do provide one or more benefits, there is nonetheless a real and continuing need in the art to provide still further improved compositions which provide an improved cleaning, and desirably also a simultaneous sanitizing or disinfecting benefit to treated hard surfaces.

Accordingly, it is among the objects of the invention to provide improved cleaning compositions which provide the benefits of good cleaning to a treated hard surface, and especially to provide improved cleaning compositions which provide good removal of stains from hard surfaces, particularly good cleaning of metal or metallic surfaces. In certain preferred embodiments the inventive compositions may also provide a useful sanitizing or disinfecting benefit to treated surfaces A yet further object of the invention is to provide a readily pourable and readily pumpable cleaning composition which features the benefits described above.

It is also among the objects of the invention to provide a process for the cleaning of hard surfaces, particularly metal or metallic hard surfaces, which process comprises the step of: providing an improved cleaning composition as outlined above, and applying an effective amount to a hard surface requiring such treatment in order to provide an effective cleaning bbenefit.

These and other objects of the invention shall be more apparent from a reading of

the following specification and of the claims.

According to a first aspect of the invention there is provided an aqueous acidic hard surface cleaning composition which comprises the following essential constituents: Constituent (A): an acid sequestrant comprising citric acid together with another acid; Constituent (B): an organic solvent constituent consisting solely of one or more hydrophobic solvents; Constituent (C): a material having both surfactant and hydrotrope properties; and, Constituent (D): an inorganic chloride salt.

The aqueous acid hard surface cleaning compositions of the invention may also include one or more further optional constituents such as known art additives. By way of non-limiting example, said constituents may include: further surfactants, particularly surfactants which are useful for the removal of greasy soils, foaming agents and foam stabilizers, coloring agents, including dyes and pigment compositions, fragrances (whether natural or synthetically produced), fragrance adjuvants andlor fragrance solubilizers, viscosity modifying agents including thickeners or gelling agents, pH- adjusting agents, pH buffers, antioxidants, water softening agents, further solubilizing agents which might be useful in the solubilization of one or more of the constituents in water, preservative compositions, as well as other known art additives not particularly elucidated here. Such constituents as described above include known art compositions, including those described in McCutcheon's Detergents and Emulsifiers, North American Edition, 1998; Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., Vol. 23, pp. 478-54 1, the contents of which are herein incorporated by reference.

The compositions according to the invention are preferably acidic in character, exhibiting a pH of less than 7. Desirably, the pH is in the range of about I to about 5, yet more desirably is a pH in the range of about 1 to about 4, and most desirably is a pH of about 1 to about 3.

In a further aspect of the invention, there is also provided an improved process for cleaning of surfaces, especially hard surfaces, which includes the step of applying an effective amount of a the aforementioned aqueous acid hard surface cleaning composition to a hard surface in need of a cleaning treatment, particularly in the locus of stains on said surface.

According to a still further aspect of the invention there is provides an improved process for the cleaning of metal and metallic surfaces, which process includes the step of applying a cleaning effective amount of the aforementioned aqueous acidic hard surface cleaning composition to a metal or metallic surface in need of a cleaning treatment, particularly in the locus of stains on such surfaces, including tarnished surfaces.

In a yet further aspect of the invention there is provided a process for the manufacture of an aqueous acid hard surface cleaning composition as described hererin.

Constituent A. The constituents which comprise Constituent A is a combination of citric acid together with another acid which in combination is found to be effective in the removal of hard water stains from hard surfaces, particularly lavatory surfaces as denoted above. The acids which are useful in Constituent A may include any inorganic acid, or may include any organic acid, and may also include mixtures of two or more acids which or soluble or dispersible in water.

Exemplary useful in inorganic acids include: sulfuric acid, hydrochloric acid, phosphoric acid, as well as other water dispersible or water soluble inorganic or mineral acids not specifically eludicated herein but which nonetheless may be found effective in the inventive compositions.

Exemplary useful organic acids include any known art organic acid which may be found effective in the inventive compositions. Generally useful organic acids are those which include at least one carbon atom, and include at least one carboxyl group (--COOH) in its structure. Preferred are water soluble organic acids which contain from 1 to about 6 carbon atoms, and at least one carboxyl group as noted.and exemplary 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, propionic acid, polyacrylic acid, 2-ethyl-hexanoic acid, formic acid, fumaric acid, 1-glutamic acid, isopropyl sulfamic acid, naphthenic acid, oxalic acid, phosphorous acid, valerie acid, benzene sulfonic acid, xylene sulfonic acid, as well as any acid listed as a registered pesticide active ingredient with the United States Environmental Protection Agency.

Further useful acids include: sulfonic acids, maleic acid, acetic acid, adipic acid, lactic acid, butyric acid, gluconic acid, malic acid, tartaric acid, as well as glycolic acid.

Desirably glycolic acid and citric acid are used, as they are effective, in plentiful supply, and may be advantageously used.

These acid sequestrants provide free acidity within the cleaning composition. The free acid reacts with fatty acid metal salts within soap scum stains, releasing the metal ions and freeing the fatty acid, which facilitates the removal of these undesired stains from hard surfaces. These acid sequestrants also sequester the resulting free metal ions which are released from the soap scum stains. Also, where the acid sequestrants are selected to feature disinfecting properties, they concomitantly provide requisite anti- microbial activity necessary to disinfect the cleaned surface.

Constituent A necessarily comprises a first acid sequestrant which comprises citric acid and a second acid sequestrant which is at least one further acid described above, as it has been observed by the inventor that citric acid provides good disinfecting action in the compositions of the invention, but in certain formulations may be insufficiently acidic in order to effectively remove certain stains. The addition of at least one further acid provides additional cleaning effect which was not observed in certain formulations with citric acid alone. Preferably, the further acid is selected from the group consisting of lactic acid, tartaric acid, and glycolic acid.

As the inventive compositions are necessarily acidic in nature (jH < 7.0) there should be sufficient acid present in the composition such that the pH of the composition is desirably less than 6, preferably from about 5.0 to about 1.0, more preferably from about 4.0 to about 1.0.

Constituent A is desirably present in the formulations in ranges of about 0.1 to about l0%wt., preferably about l%wt. to about 8%wt., and more preferably about 5%wt.

to about 6%wt., based on the total weight of a composition. In preferred embodiments however, citric acid comprises at least about l%wt. of the total weight of the acid sequestrants of Constituent A, more preferably citric acid comprises at least about 25%wt., yet more preferably at least about 40%wt., and most preferably citric acid comprises at least about 50%wt.of the total weight of Constituent A. Constituent B. Constituent B is an organic solvent constituent consisting solely of one or more hydrophobic solvents. Constituent B acts to assist in the dissolution of the fatty acids from a hard surface being treated with the inventive compositions. Certain fatty acids present in the soap scum residues are solubilized and/or rendered at least partially miscible in water due to the presence of Constituent B, which facilitates the removal of the stain from the surface. The one or more hydrophobic solvents of Constituent B are also useful in penetrating the stain and act as a carrier for the further constituents of the invention, especially the constituents comprising Constituent A, thus bringing them through the layer of the stain to the surface upon which the stain is present, and thereby aiding in the effective dissolution of the stain and its removal.

The hydrophobic solvents forming Constituent B should demonstrate solubilization of the aliphatic portions of the fatty acids within the soap scum stains.

Exemplary useful hydrophobic solvents include mineral spirits, tripropylene glycol n- butyl ether, propylene glycol phenyl ether, dipropylene glycol n-propyl ether, ethylene glycol phenyl ether, and particularly propylene glycol n- butyl ether and dipropylene glycol n-butyl ether; Constituent B may be one such solvent or a mixture of two or more hydrophobic solvents. The one or more hydrophobic solvents of Constituent B exhibit a solubility in water of about 0 mI/I 00 ml water to about 20 ml/I 00 ml water, but desirably the one or more hydrophilic solvents of Constituent B exhibit an aqueous solubility in water of not more than 30 nil/l00 ml water.

With regard to the effective amounts of Constituent B, Constituent B is desirably present in amounts of about 0.1 %wt. to about 1 0%wt. based on the total weight of the inventive composition, preferably about I %wt. to about 5%wt., and more preferably about 1.5%wt. to about 4% by weight.

In particularly preferred embodiments of the present invention the sole organic solvents present are hydrophobic solvents, which are present to the exclusion of hydrophilic solvents. Preferred as the sole organic solvents are those which exhibit an aqueous solubility in water of not more than about 20 ml/100 ml water.

Constituent C. The constituents comprising Constituent C provide for the reduction of the interfacial tension between the soil and the compositions of the invention which facilitates the wetting of the stain as well as providing a hydrotropic functionality.

Such a hydrotropic functionality aids in the solubilization of greater amounts of fatty acids in a stain and in the removal of the stain from a surface.

Exemplary materials useful as Constituent C include one or more compounds such as: alkyl phenoxy benzene disulfonates (also known as alkyl diphenyl oxide disulfonates), linear alkyl benzene sulfonates and alkylnaphthalene sulfonates and salts thereof. Such compositions are known to the art, and available as anionic surfactants.

These also include but are not limited to: alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or the magnesium salts of one or more of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkyl amide sulfonates, alkylarylsulfonates, olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl sarcosinates, acyl isethionates, and N-acyl taurates.

Generally, the alkyl or acyl radical in these various compounds comprise a carbon chain containing 12 to 20 carbon atoms.

Exemplary alkyl phenoxy benzene disulfonates (also known as alkyl diphenyl oxide disulfonates) include metal salts and organic salts of alkylphenoxy benzene disulfonates, such as sodium dodecyl diphenyloxide disulfonate, sodium hexyl diphenyloxide disulfonate, sodium n-decyl diphenyloxide disulfonate, as well as sodium n-hexadecyl diphenyloxide disulfonate. Other metal counterions or organic counterions may be substituted in the place of the sodium noted in the recited alkyl phenoxy benzene disulfonates noted above, as well as mixtures of two or more alkyl phenoxy benzene disulfonates. Many of these materials are available under the Dowfax (Dow Chemical, Midland, Mich.) or Calfax (Pilot Chemical, Santa Fe Springs, Calif.) trademarks.

Exemplary linear alkyl benzene sulfonates include metal salts and organic salts of linear alkyl benzene sulfonates, such as sodium dodecylbenzene sulfonate, sodium nonylbenzene sulfonate, isopropylamine salts of linear alkyl benzene sulfonic acid, triethanolamine dodecylbenzene sulfonate, diethanolamine dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, sodium tridecylbenzene sulfonate, as well as mixtures of sodium dodecylbenzenesulfonate with sodium toluene sulfonate, sodium cumene sulfonate andlor with sodium xylene sulfonate. Other metal counterions or organic counterions may be substituted in the place of the counterions noted in the recited linear alkyl benzene sulfonates noted above, as well as mixtures of two or more linear alkyl benzene sulfonates.

Exemplary alkylnaphthalene sulfonates include metal salts and organic salts of alkylnaphthalene sulfonates such as sodium diisopropylnaphthalene sulfonate, butylnaphthalene sodium sulfonate, nonylnaphthalene sodium sulfonate, sodium dibutylnaphthalene sulfonate and sodium dimethylnaphthalene sulfonate. Other metal counterions or organic counterions may be substituted in the place of the counterions noted in the recited alkylnaphthalene sulfonates noted above, as well as mixtures of two or more alkylnaphthalene sulfonates.

Further useful as constituents used in Constituent C include sodium xylene sulfonate, sodium cumene sulfonate, and naphthalene sulfonates, as well as mixtures of two or more of the above.

Constituent C is a single constituent which exhibits both anionic surfactant and hydrotrope properties. With regard to the effective amounts of Constituent C, Constituent C is present in amounts of about 0. 001%wt. to about l0%wt. based on the total cleaning composition weight, preferably is present in amounts of about 1 %wt. to about 5%wt., and more preferably about I.5%wt. to about 2.5%wt.

Constituent D: A further essential constituent of the invention is at least one inorganic chloride salt. The inorganic chloride salt is desirably present in an amount effective to provide improved cleaning of metal surfaces, particularly copper surfaces which are immersed or contacted with the inventive compositions. The inorganic chloride salt(s) used in the compositions of the present invention can be any watersoluble inorganic chloride salt or mixtures of such salts. For purposes of the present invention, "water-soluble" means having a solubility in water of at least 10 grams per hundred grams of water at 20 C. Examples of suitable salts include various alkali metal and/or alkaline earth metal chlorides including sodium chloride, calcium chloride, magnesium chloride and zinc chloride. Particularly preferred are sodium chloride and calcium chloride which have been surprisingly observed to provide excellent metal cleaning efficacy particularly of aged copper surfaces. The inorganic chloride salt(s) is present in the compositions of the present invention in an amount which will provide an improved cleaning of metal surfaces, particularly copper surfaces, compared to an identical composition which excludes the inorganic chloride salts(s). Preferably the inorganic chloride salt(s) are present in amounts of from about 0. 0000 1 to about 10% by weight, desirably from about 0.00001 to about 10% by weight, more desirably from about 0.001 to about 2.5% by weight, yet more desirably from about 0.01 to about 1.5% by weight and most desirably from about 0.2 to about 1. 5%weight. Particularly preferred inorganic chloride salt(s) and weight percentages thereof are described with reference to one or more of the Examples.

The inventors have unexpectedly discovered that sulfate salts do not provide improved cleaning of metal surfaces this function, and the inventors do not expect that other non-chloride alkali metal andlor alkaline earth metal salts, e.g. those based on borates, bromides, fluorides, phosphates, carbonates, bicarbonates, citrates, acetates, lactates, provide such an improved metal cleaning function. In certain preferred embodiments the sole inorganic salts present are one or more inorganic chloride salts.

As is noted above, the compositions according to the invention are aqueous in nature. Water is added to Constituents A, B, C and D in order to provide 100% by weight of the composition. The water may be tap water, but is preferably distilled and is most preferably deionized 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 interfere with the operation of Constituents A, B, C, as well as any other optional components which may be included in the inventive compositions.

The compositions according to the invention may comprise one or more of the following optional components, the total weight of such optional constituents preferably not exceeding about 20%wt. of the total weight of the composition, more preferably not exceeding about lO%wt., and most preferably less than 10%wt. based on the total weight of the composition according to the invention.

Non-ionic surfactants of the conventionally known and used variety in this class of cleaning agents may be added in effective amounts, i.e., amounts which are shown to be effective in the cleaning compositions in facilitating the removal of greasy soils. Such greasy soils are to be differentiated from the hard water stains and the soap scum stains described earlier in this specification. However, it is also to be appreciated that the non- ionic surfactants of this optional constituent also may be at least partially effective in the solubilization and removal of soap scum stains. Exemplary nonionic surfactants include known nonionic surfactants which generally consist of a hydrophobic moiety, such as C6- C20 primary or secondary, branched or straight chain monoalcohols, C8-C18 mono- or dialkyphenols, C6-C20 fatty acid amides, and a hydrophilic moiety which consists of alkylene oxide units. These nonionic surfactants are, for instance, alkoxylation products of the above hydrophobic moieties, containing from 2 to 30 moles of alkylene oxide. As alkylene oxides, ethylene-, propylene- and butylene oxides and mixtures thereof are used. - 10-

Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with an alkylene oxide, especially ethylene oxide or with the polyhydration product thereof, a polyalkylene glycol, especially polyethylene glycol, to form a water soluble or water dispersible nonionic surfactant compound. By way of non-limiting example, particularly examples of suitable nonionic surfactants which may be used in the present invention include the following: One class of useful nonionic surfactants include polyalkylene 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 an alkylene oxide, especially an 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.

A further class of useful nonionic surfactants include the condensation products of aliphatic alcohols with from about 1 to about 60 moles of an alkylene oxide, especially an 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 -C11 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, which is described in product literature from Sasol as a C8-lO having an average molecular weight of 356, an ethylene oxide content of -11 - about 4.85 moles (about 60 wt.%), and an HLB of about 12; Alfonic 8 10-2, which is described in product literature as a C8-C 10 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 6 10-3.5, which is described in product literature 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. Other examples of alcohol ethoxylates are 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). Other examples of ethoxylated alcohols include the Neodol 91 series non-ionic surfactants available from Shell Chemical Company which are described as C9-C11 ethoxylated alcohols. 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. Further examples of ethoxylated alcohols include the Rhodasurf DA series non- ionic surfactants available fromRhodia which are described to be branched isodecyl alcohol ethoxylates. Rhodasurf DA-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 ethoxylated alcohols include those from Tomah Products (Milton, WI) under the Tomadol tradename with the formula RO(CH2CH2O)H 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 C11 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 andnis7orl3. - 12-

A further class of useful nonionic surfactants include primary and secondary linear and branched alcohol ethoxylates, such as those based on C6-C18 alcohols which further include an average of from 2 to 80 moles of ethoxylation per mol of alcohol.

These examples include the Genapol UD (ex. Clariant, Muttenz, Switzerland) described under the tradenames Genapol UD 030, Ci i-oxoalcohol polyglycol ether with 3 EU; Genapol UD, 050 C11-oxo-alcohol polyglycol ether with 5 EU; Genapol UD 070, C11- oxo-alcohol polyglycol ether with 7 EU; Genapol UD 080, Cii-oxo-alcohol polyglycol ether with 8 EU; Genapol UD 088, C1 i-oxo-alcohol polyglycol ether with 8 EU; and Genapol UD 110, C1 -oxo-alcohol polyglycol ether with 11 EU.

A further class of useful nonionic surfactants include those surfactants having a formula RU(CH2CH2U)H wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C12H25 to C16H33 and n represents the number of repeating units and is a number of from about Ito about 12. Surfactants of this formula are presently marketed under the Genapol tradename (ex. Clariant), which surfactants include the "26- L" series of the general formula RO(CH2CFI2O)H wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C12H25 to C16H33 and n represents the number of repeating units and is a number of from 1 to about 12, such as 26-L-1, 26-L-1.6, 26-L-2, 26-L-3, 26-L-5, 26-L-45, 26-L-50, 26-L-60, 26-L- 60N, 26-L-75, 26-L-80, 26-L-98N, and the 24-L series, derived from synthetic sources and typically contain about 55% C12 and 45% C14 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, all sold under the Genapol tradename.

A further class of useful nonionic surfactants include 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.

One group of such useful nonionic surfactants containing the characteristic alkylene oxide blocks are those which may be generally represented by the formula (A): - 13- H0-(E0)(P0)(EO)-J-J (A) where EU represents ethylene oxide, P0 represents propylene oxide, y equals at least 15, (E0)+ 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 (ex. BASF) or Emulgen (ex. Kao.) A further group of such useful nonionic surfactants containing the characteristic alkylene oxide blocks are those can be represented by the formula (B): R(E0,P0)a(E0,P0)bH (B) wherein R is an alky], aryl or aralkyl group, where the R group contains 1 to 20 carbon atoms, the weight percent of EU 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 EU and PU is in the range of 6 to 125 moles, with ito 50 moles in the PU rich block and 5 to 100 moles in the EU rich block. Specific 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 examples of useful nonionic surfactants include those which can be represented by formula (C) as follows: RU-(BU)(EU)-H (C) wherein EU represents ethylene oxide, BO represents butylene oxide, R is an alkyl group containing Ito 20 carbon atoms, n is about 5-15 and xis about 5-15.

- 14 - Yet further useful nonionic surfactants include those which may be represented by the following formula (D): H0-(E0)(BO)(Eo)-H (D) wherein E0 represents ethylene oxide, BO represents butylene oxide, 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.

Still further exemplary useful nonionic block copolymer surfactants include ethoxylated derivatives of propoxylated ethylene diamine, which may be represented by the following formula: H(E0)Y(P0)X\ ____ / (P0)(Eo) H N CH2CH2NN (E) H(EO)(P0) / N(P0)(EO)H where (E0) represents ethoxy, (P0) represents propoxy, the amount of (P0) is such as to provide a molecular weight prior to ethoxylation of about 300 to 7500, and the amount of(E0) is such as to provide about 20% to 90% of the total weight of said compound.

Further useful non-ionic surfactants which may be used in the inventive compositions include those presently marketed under the trade name Pluronics (ex.

BASF). The compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4,000 and preferably 200 to 2,500. The addition of polyoxyethylene radicals of the hydrophobic portion tends to increase the solubility of the molecule as a whole so as to make the surfactant water-soluble. The molecular weight of the block polymers varies - 15- from 1,000 to 15,000 and the polyethylene oxide content may comprise 20% to 80% by weight. Preferably, these surfactants are in liquid form and particularly satisfactory surfactants are available as those marketed as Pluronics L62 and Pluronjcs L64.

Alkylmonoglyocosides and alkylpolyglycosides which find use in the present inventive compositions include known nonionic surfactants which are alkaline and electrolyte stable. Alkylmonoglycosides and alkylpolyglycosides are prepared generally by reacting a monosaccharide, or a compound hydrolyzable to a monosaccharide with an alcohol such as a fatty alcohol in an acid medium. Various glycoside and polyglycoside compounds including alkoxylated glycosides and processes for making them are disclosed in U.S. Pat. Nos. 2,974,134; 3,219,656; 3,598,865; 3,640, 998; 3,707,535, 3,772,269; 3,839,318; 3,974,138; 4,223,129 and 4,528,106 the contents of which are incorporated by reference.

One exemplary group of such useful alkylpolyglycosides include those according to the formula: R20(CnH2nO)r(Z)x wherein: R2 is a hydrophobic group selected from alkyl groups, alkylphenyl groups, hydroxyalkylphenyl groups as well as mixtures thereof, wherein the alkyl groups may be straight chained or branched, and which contain from about 8 to about 18 carbon atoms, n has a value of 2 - 8, especially a value of 2 or 3; r is an integer from 0 to 10, but is preferably 0, Z is derived from glucose; and, x is a value from about I to 8, preferably from about 1.5 to 5.

Preferably the alkylpolyglycosides are nonionic fatty alkylpolyglucosides which contain a straight chain or branched chain C8 -C15 alkyl group, and have an average of from about 1 to 5 glucose units per fatty alkylpolyglucoside molecule. More preferably, the nonionic fatty alkylpolyglucosides which contain straight chain or branched C8 -C15 alkyl group, and have an average of from about 1 to about 2 glucose units per fatty alkylpolyglucoside molecule.

A further exemplary group of alkyl glycoside surfactants suitable for use in the practice of this invention may be presented by the following formula (A): - 16- RO-(R1 O)y-(G)X-Zb (A) wherein: R is a monovalent organic radical containing from about 6 to about 30, preferably from about 8 to 18 carbon atoms, R1 is a divalent hydrocarbon radical containing from about 2 to about 4 carbon atoms, y is a number which has an average value from about 0 to about I and is preferably 0, G is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms; and, x is a number having an average value from about 1 to 5 (preferably from 1.1 to 2); Z is 02M1, -O- C-R2, O(CH), CO2M', OSO3M', or 0(CH2)SO3M'; R2 is (CH2)C02 M' or CHCHCO2M' ; (with the proviso that Z can be 02M' only if Z is in place of a primary hydroxyl group in which the primary hydroxyl-beanng carbon -OM1 atom, -CH2OH, is oxidized to form a group) b is a number of from 0 to 3x +1 preferably an average of from 0.5 to 2 per glycosal group; p isitolO, M' is H or an organic or inorganic counterion, particularly cations such as, for example, an alkali metal cation, ammonium cation, monoethanolamine cation or calcium cation.

As defined in Formula (A) above, R is generally the residue of a fatty alcohol having from about 8 to 30 and preferably 8 to 18 carbon atoms. Examples of such alkyiglycosides as described above include, for example APG 325 CS Glycoside which is described as being a 50% C9 -C11 alkyl polyglycoside, also commonly referred to as D- glucopyranoside, (commercially available from Henkel KGaA) and Glucopon 625 CS which is described as being a 50% C10 -C16 alkyl polyglycoside, also commonly referred to as a D-glucopyranoside, (ex. Henkel).

Further nonionic surfactants which may be included in the inventive compositions include alkoxylated alkanolarnides, preferably C8-C24 alkyl di(C2-C3 alkanol amides), as represented by the following formula: - 17R5-CO-NH-R6-OH wherein R5 is a branched or straight chain C8-C24 alkyl radical, preferably a Cio-C16 alkyl radical and more preferably a C12-C14 alkyl radical, and R6 is a C1-C4 alkyl radical, preferably an ethyl radical.

The inventive compositions may also include a nonionic amine oxide constituent.

Exemplary amine oxides include: (A) Alkyl di (lower alkyl) 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. The lower alkyl groups include between 1 and 7 carbon atoms.

Examples 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; (B) Alkyl di (hydroxy lower alkyl) 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 are bis(2-hydroxyethyl) cocoamine oxide, bis(2- hydroxyethyl) tallowamine oxide; and bis(2-hydroxyethyl) stearylamine oxide; (C) Alkylamidopropyl di(lower alkyl) 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 are cocoamidopropyl dimethyl amine oxide and tallowamidopropyl dimethyl amine oxide; and (D) 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.

Preferably the amine oxide constituent is an alkyl di (lower alkyl) amine oxide as denoted above and which may be represented by the following structure: R1 R2-N O R1 wherein each: R1 is a straight chained C 1-C4 alkyl group, preferably both R1 are methyl groups; and, R2 is a straight chained C8-C18 alkyl group, preferably is C10-C4 alkyl group, most preferably is a C12 alkyl group.

Each of the alkyl groups may be linear or branched, but most preferably are linear. Most preferably the amine oxide constituent is lauryl dimethyl amine oxide. Technical grade mixtures of two or more amine oxides may be used, wherein amine oxides of varying chains of the R2 group are present. Preferably, the amine oxides used in the present invention include R2 groups which comprise at least 50%wt., preferably at least 60%wt.

of C12 alkyl groups and at least 25%wt. of C14 alkyl groups, with not more than 15%wt.

of C16, C18 or higher alkyl groups as the R2 group.

Of course the nonionic surfactant constituent, when present, my comprise two or more nonionic surfactants.

Such nonionic surfactants are per Se, known to the art, and are more particularly described in McCutcheon S Detergents and Emulsifiers, noted above.

Foaming agents, and foam stabilizing agents may be provided, including alkyl sulfates, alkyl sulfonates, amine oxides, as well as alkanolamides. Such may be especially desirable where the composition is packaged in a pressurized device, i.e., an aerosol canister or in a hand-held pumpable container (such as a hand held trigger-spraying vessel).

Further optional, but desirable constituents, include fragrances, natural or synthetically produced. Such fragrances may be added in any conventional manner, adniixing to a composition or blending with other constituents used to form a composition, in amounts which are found to be useful to enhance or impart the desired scent characteristic to the composition, and/or to cleaning compositions formed therefrom. Fragrances refer to and to include any non-water soluble fragrance substance or mixture of such substances including those which are naturally derived (i. e., obtained by extraction of flower, herb, blossom or plant), those which are artificially derived or produced (i.e., mixture of natural oils and/or oil constituents), and those which are synthetically produced substances (odiferous substances). Generally perfumes are complex mixtures or blends various organic compounds including, but not limited to, certain alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils such as from about 0 to about 85% by weight, usually from about 10 to about 70% by weight, the essential oils themselves being volatile odiferous compounds and also functioning to aid in the dissolution of the other components of the perfume. In the present invention, the precise composition of the perfume is of no particular consequence to cleaning performance so long as it may be effectively included as a constituent of the compositions, and have a pleasing fragrance. For those compositions which are intended to be used in a domestic environment, the perfume, as well as the other ingredients used in making up compositions of the invention should be cosmetically acceptable, i.e., feature low toxicity or no toxicity, hypoallergenic character, etc. In compositions which include a fragrance, it is frequently desirable to include a fragrance solubilizer which assists in the dispersion, solution or mixing of the fragrance constituent in an aqueous base. These include known art compounds, including condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-C10-C20 15.alkanoic acid esters having a HLB of 8 to 17 are also known as nonionic surfactants.

Further examples of such suitable surfactants include water soluble nonionic surfactants of which many are commercially known and, by way of non-limiting example, include the primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxide-propylene oxide condensates of primary alkanols, and condensates of ethylene oxide with sorbitan fatty acid esters. This fragrance solubilizer component is added in minor amounts, preferably in an amount effective in aiding in the solubilization of the fragrance component, but not in any significantly greater proportion, such that it would be considered as a detergent constituent. Such minor amounts recited herein are generally up to about 0.5% by weight of the total composition, but more generally present an amount of about 0. 1% by weight and less, and preferably present in amounts of about 0.05% by weight and less.

Further optional, but advantageously included constituents are one or more coloring agents which find use in modifying the appearance of the compositions and enhance their appearance from the perspective of a consumer or other end user. Known coloring agents may be incorporated in the compositions in any effective amount to improve or impart to compositions a desired appearance or color. Such a coloring agent - 20 or coloring agents may be added in a conventional fashion, i.e., admixing to a composition or blending with other constituents used to form a composition.

The use of one or more pH buffering compositions so as to maintain the pH of the inventive compositions may also be added. While the compositions of the invention generally does not require a pH buffering composition, the use of such a pH buffering composition may provide the benefit of hard water ion sequestration. Examples of such useful pH buffer compounds and/or pH buffering systems or compositions are 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, citrates, and their alkali metal salts. Such buffers keep the pH ranges of the compositions of the present invention within acceptable limits.

Others, not particularly elucidated here may also be used. Preferably, citric acid, such as is available in an anhydrous salt form of an alkali metal citric acid is added as it is readily commercially available, and effective. The addition of such a buffering agent is desirable in certain cases wherein long term, i.e., prolonged storage, is to be anticipated for a composition, as well as insuring the safe handling of said aqueous composition.

Preservatives which do not include a disinfectant component may also be added in minor amounts in the formulations according to the invention. Compositions known in the art may be used. Examples of such preservatives compounds include those which are presently commercially available under the trademarks Kathono CG/ICP (Rohm & Haas, Philadelphia Pa.), Suttocide A (Sutton Labs, Chatham N.J.) as well as Midtect TFP (Tn-K Co. , Emerson, N.J.). Such preservatives are generally added in only minor amounts, i.e., amounts of about 0.5% by weight of the total composition, more generally an amount of about 0.1% by weight and less, and preferably present in amounts of about 0.05% by weight and less. Typically such preservative constituents are not necessary in the inventive compositions.

Thickening and/or gelling agents may be added to the hard surface cleaning compositions according to the present invention in order to modify the viscous and/or - 21 - thixatropic properties thereof. For example, in certain applications it is contemplated that it may be desirable to provide a more viscous, viz., higher viscosity than that of water, whether for aesthetic or functional reasons.

For example, the addition of a suitable amount of a gelling agent may be desired not only for aesthetic reasons but also to limit the spreading of the composition as it is applied to a surface. This function is desirable in providing a means to apply the composition over a limited area, such as directly onto a stain, without applying an excess onto the surrounding area of a surface. This function also aids in the surface retention time on non-horizontal surfaces, ensuring that the cleaning composition is in contact with a stained surface without flowing off too rapidly. Similarly, thixotropic properties may also be desired under certain circumstances. In order to provide such functional features to the composition, known thickening and gelling agents including, but not limited to, cellulose compounds, xanthan gums, polymers and/or clays may be added. For xanthan gums, those available under the Kelco or Keltrol trademarks are useful.

The benefits of the compositions described in this specification include particularly: disinfection, good removal of hard water stains, good removal of soap scum stains, relatively low toxicity, as well as ease in handling of the composition due to its readily pourable or pumpable characteristic. Further, when one or more of the optional constituents are added, i.e., fragrance, foaming agents, coloring agents, the aesthetic and consumer appeal of the product is favorably improved.

The inventive compositions provide certain technical benefits when used on hard surfaces, particularly: satisfactory removal of hard water stains, satisfactory removal of soap scum stains, and optionally but desirably in preferred embodiments also provide satisfactory disinfection or sanitization of hard surfaces. In preferred embodiments, the compositions are readily pourable and are desirably provided as a ready to use pourable product in a manually squeezable (manually deformable) bottle. In use, the consumer generally applies an effective amount of the composition and within a few moments thereafter, wipes off the treated area with a rag, towel, brush or sponge, usually a disposable paper towel or sponge. In certain applications, however, especially where undesirable stain deposits are heavy, the composition according to the invention may be left on the stained area until it has effectively loosened the stain deposits after which it - 22 - may then be wiped off, rinsed off, or otherwise removed. For particularly heavy deposits of such undesired stains, multiple applications may also be used.

The inventive compositions are desirably provided as a ready to use product which may be directly applied to a hard surface. By way of example, hard surfaces suitable for coating with the polymer 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 , Conan 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, Formica , Conan and stone. Still further hard surfaces include those associated with medical facilities, e. g., hospitals, clinics as well as laboratories, e.g., medical testing laboratories.

As noted previously the composition is particularly effective in the cleaning of metal and metallic surfaces. Such surfaces are commonly encountered in lavatory environments, e.g., lavatory fixtures, as well as kitchen environments, e.g, cookware, utensils, dishware and the like. The compositions also find use in the cleaning of metal surfaces upon or within the interior of kitchen and lavatory appliances, e.g. in the cleaning of metal surfaces on kitchen appliances, including but not limited to polished, chromed, burnished or so called brushed" or matte metal surfaces such as on kitchen countertops, appliance housings, appliance surfaces including exterior surfaces such as doors, as well as interior surfaces such as the interior spaces of dishwashers, ovens, kitchen ranges and the like. In preferred embodiments the inventive compositions provide excellent cleaning benefits and also surprisingly provide improved cleaning and reduction of stains, tarnish or other metal discoloration, e.g., as may be caused by the buildup of dirt, grease, and the like or metal oxidation of treated metal surfaces. This effect is most pronounced on copper surfaces, however it is to be understood that the 23 - inventive compositions find use in the cleaning treatment of all metal surfaces as may be encountered in such environments. By way of nonlimiting example such metals include aluminum, copper, steel, stainless steel, brass, metal alloys which may include one or more of the former metals, as well as chromed metal and non-metal substrates which have a metal or metallized surface.

The hard surface cleaner composition provided according to the invention can be desirably provided as a ready to use product in a manually operated spray-dispensing container. Such a typical container is generally made of synthetic polymer plastic material, such as polyethylene, polypropylene, polyvinyl chloride or the like, and includes a spray nozzle, a dip tube and associated pump dispensing parts, and is thus ideally suited for use in a consumer "spray and wip&' application. In such an application, the consumer generally applies an effective amount of the cleaning composition using the pump and within a few moments thereafter, wipes off the treated area with a rag, towel, or sponge, usually a disposable paper towel or sponge. In certain applications, however, especially where undesirable stain deposits are heavy, the cleaning composition according to the invention may be left on the stained area until it has effectively loosened the stain deposits, after which it may then be wiped off, rinsed off, or otherwise removed.

For particularly heavy deposits of such undesired stains, multiple applications may also be used.

In a yet a further embodiment, the compositions according to the invention may be formulated so that they may be useful in conjunction with an "aerosol" type product wherein they are discharged from a pressurized aerosol container. If the inventive compositions are used in an aerosol type product, it is preferred that corrosion resistant aerosol containers, such as coated or lined aerosol containers be used. Such are preferred as they are known to be resistant to the effects of acidic formulations. Known art propellants, such as liquid propellants as well as propellants of the non-liquid form, i.e., pressurized gases, including carbon dioxide, air, nitrogen, hydrocarbons as well as others may be used.

Whereas the present invention is intended to be used in the types of liquid forms described, nothing in this specification shall be understood as to limit the use of the composition according to the invention with a further amount of water to form a cleaning - 24 - solution therefrom. In such a proposed diluted cleaning solution, the greater the proportion of water added to form said cleaning solution, the greater may be the reduction of the rate andlor efficacy of the thus formed cleaning solution in the cleaning of a hard surface, as well as a reduction in disinfectant efficacy.

Accordingly, longer residence times upon the stain to effect their loosening andlor the usage of greater amounts may be necessitated. Conversely, nothing in the specification shall be also understood to limit the forming of a "super-concentrated" cleaning composition based upon the composition described above. Such a super- concentrated composition is essentially the same as the compositions described above except in that they include a lesser amount of water.

While the cleaning compositions are most beneficial for use in undiluted form, viz., their form as described above, they may also be diluted toform a cleaning composition therefrom. Such cleaning compositions may be easily prepared by diluting measured amounts of the compositions in further amounts of water by the consumer or other end user in certain weight ratios of composition to water, and optionally, agitating the same to ensure even distribution of the composition in the water. The aqueous compositions according to the invention may be used without further dilution, but may also be used with a further aqueous dilution, i.e., in composition to water concentrations of about 1:0 to extremely dilute dilutions such as about 1:10,000, but preferably would be used in a weight or volume ratio proportion of about 1:10 to about 1:100. Generally better results and faster removal are to be expected at lower relative dilutions of the composition and the water.

The compositions according to the invention are easily produced by any of a number of known art teclmiques. Conveniently, a part of the water is supplied to a suitable mixing vessel further provided with a stirrer or agitator, and while stirring, the remaining constituents are added to the mixing vessel, including any final amount of water needed to provide to 1 00%wt. of the inventive composition.

The following examples below illustrate exemplary formulations and preferred formulations of the composition according to the instant invention. It is to be understood that these examples are presented by means of illustration only and that further useful formulations falling within the scope of this invention and the claims may be readily - 25 produced by one skilled in the art and not deviate from the scope and spirit of the invention. Throughout this specification and in the accompanying claims, weight percents of any constituent are to be understood as the weight percent of the active portion of the referenced constituent, unless otherwise indicated.

Examples

Preparation of Example Formulations: Exemplary formulations illustrating certain preferred embodiments of the inventive compositions and described in more detail in Table I below were formulated generally in accordance with the following protocol.

Into a suitably sized vessel, a measured amount of water was provided after which the constituents were added in the following sequence: thickening agents, surfactant, acid and then the remaining constituents. Mixing, which generally lasted from 5 minutes to 60 minutes was maintained until the particular formulation appeared to be homogeneous.

The exemplary compositions were readily pourable, and retained well mixed characteristics (i.e., stable mixtures) upon standing. The constituents may be added in any order.

Examples of inventive formulations, "El" through "E8" including certain particularly preferred formulations are shown in Table 1 below. The constituents were used "as supplied" from their respective supplier and unless otherwise stated, the percent actives in each of the as supplied constituents are considered to be 100% active. To each of the compositions was added deionized water or tap water in "quantum sufficient" (q.s.) in order to provide 100 parts by weight of the specific composition.

- 26 - Table I ______ ______ ______ ______ ___________________________ El E2 E3 E4 E5 Plurafac SL-62 0.9 0.9 0.9 0.9 0.9 Stepanol WAC (29%) 2.1 2.1 2.1 2.1 2.1 Dowfax3B2 2.1 2.1 2.1 2.1 2.1 Dowanol DPnB 2.73 2.73 2.73 2.73 2.73 Dowanol PnP 0.89 0.89 0.89 0.89 0. 89 citric acid (50%) 5.0 5.0 5.0 5.0 5.0 hydroxyacetic acid (70%) 2.8 2.8 2.8 2.8 2.8 sodium chloride 1.0 2.0 3.0 5.0 2.0 fragrance (proprietary composition) 0.2 0.2 0.2 0.2 0.2 colorant (proprietary composition) -- -- -- -- 0.5 tap water -- -- -- -g.s.

deionized water g.s. g.s. g.s g.s -- Table_I ______ ______ ______ ____________________________ E6 E7 E8 PlurafacSL-62 0.9 0.9 0.9 Stepanol WAC (29%) 2.1 2.1 2.1 Dowfax3B2 2.1 2.1 2.1 Dowanol DPnB 2.73 2.73 2.73 Dowanol PnP 0.89 0.89 0.89 citric acid (50%) 5.0 5.0 5.0 hydroxyacetic acid (70%) 2.8 2.8 2.8 calcium chloride 2.0 -- -- magnesium chloride (6 H20) -- 4.28 -- zinc chloride -- -- 2.0 fragrance (proprietary composition) 0.2 0.2 0.2 colorant (proprietary composition) -- -- -- tap water g.s. g.s. g.s In addition to the above exemplary formulations, two comparative compositions were also produced as indicated below on Table 2. As before, the constituents were used "as supplied" from their respective supplier and unless otherwise stated, the percent actives in each of the as supplied constituents are considered to be 100% active. To each of the compositions was added deionized water or tap water in "quantum sufficient" (q.s.) in order to provide 100 parts by weight of the specific composition. The first of these comparative compositions, Cl included no inorganic salts. The second of these comparative compositions, C2, included sodium sulfate as an inorganic salt.

- 27 -

Table 2 _____ _____

_________________________ Cl C2 PlurafacSL-62 0.9 0.9 Stepanol WAC (29%) 2.1 2.1 Dowfax 3B2 2.1 2.1 Dowanol DPnB 2.73 2.73 Dowanol PnP 0.89 0.89 citric acid (50%) 5.0 5.0 hydroxyacetic acid (70%) 2.8 2.8 sodium sulfate -- 2.0 fragrance (proprietary composition) 0.2 0.2 colorant (proprietary composition) -- 0.5 deionized water q.s. q.s.

The identity of the constituents used to form the Example and Comparative formulations are identified on the following Table 3.

Table 3

constituent Identity Plurafac SL-62 EOIPO block copolymer, nonionic ________________________________ surfactant, I 00%wt. active Stepanol WAC (29%) sodium lauryl sulfate, 29%wt.active Dowfax 3B2 diphenyl oxide disulfonate, 45%wt.

_________________________________ active Dowanol DPnB dipropylene glycol n-butyl ether, _____________________________ 100%wt. active Dowanol PnP propylene glycol n-propyl ether, _____________________________ 100%wt. active citric acid (50%) aqueous citric acid, 50%wt. actives hydroxyacetic acid (70%) aqueous hydroxyacetic acid, 70%wt.

_________________________________ actives sodium chloride sodium chloride, anhydrous ______________________________ laboratory grade, 98-100%wt. active calcium chloride calcium chloride, anhydrous ________________________________ laboratory grade, 98-1 00%wt. active magnesium chloride (6 H20) magnesium chloride (6 H20), anhydrous laboratory grade, 98- ________________________________ 1 00%wt. active zinc chloride zinc chloride, anhydrous laboratory ______________________________ grade, 98-1 00%wt. active sodium sulfate sodium sulfate, anhydrous ______________________________ laboratory grade, 98-100%wt. active fragrance (proprietary composition) fragrance (proprietary corn position) - 28 - colorant (proprietary composition) colorant (proprietary composition) tap water water from municipal water supply deionized water deionized water The compositions of Table 1 were subjected to several tests to evaluate the ability of the compositions to clean soiled copper metal surfaces.

To the test was performed utilizing a number of equally soiled, weathered U.S. coins (pennies) which would initially visually observed and judged to be unifoi-mly soiled. These coins include a copper surface.

The cleaning efficacy of the compositions according to El, E2, E3 and E4 were evaluated by partially immersing a penny into a volume of each of the aforesaid compositions and thereafter rinsing with distilled or tap water and allowing to dry. No surface agitation or stirring of the test composition was performed. Also the pennies were approximately 50% immersed so that the resultant "cleaned" and "uncleaned" sides could be visually evaluated on a side-by-side basis. A composition according to comparative Cl was similarly tested as well. The degree of cleaning efficacy was judged on a scale of"0" to "5", with no visually observed cleaning of the penny to the judged as a "0" score, and within the maximum cleaning to a shiny brightness being a established as the highest end of the scale and being rated a "5". The results of the cleaning test are disclosed on the following Table 4A.

Table 4A

El E2 E3 E4 Cl Rated cleaning result Immersion Time: 15 seconds 1 2 I 3 I 5 I 0 As is evident from the foregoing, fast acting cleaning of the penny's copper surface was attained in a short time with improved cleaning results observed with increasing amounts of the sodium chloride salt. Conversely the penny cleaned with the comparative Cl formulation evidenced no visible cleaning.

The cleaning efficacy of the compositions according to ES, E6, E7 and E8 were similarly evaluated as well, but over several time intervals. A composition according to comparative C2 was similarly tested as well. Each of the pennies were immersed for intervals of 15, 30, or 60 seconds in each of the compositions described on foregoing - 29 - tables at the end of their immersion were quickly removed and dried. No mechanical abrasion or scrubbing the was applied to the metal surface before, during, or after the immersion tests. Afterwards, the degree of cleaning efficacy was judged on a scale of"0" to "5", with no visually observed cleaning of the penny to the judged as a "0" score, and within the maximum cleaning to a shiny brightness being a established as the highest end of the scale and being rated a "5". The results of the cleaning test are disclosed on the

following Table 4B.

Table - Copoer Cleaning _____________________________________ __________________________ E5 E6 E7 E8 C2 _______________________________ Rated cleaning result Immersion Time: _____________________________________ l5seconds 3 3 3 3 Q seconds 3.5 3.5 3.5 3.5 0 seconds 4 4.5 4.5 4.5 1 As can be understood from a review of the results disclosed on the table, the compositions comprising inorganic chloride salts were observed to be better performing in this cleaning of the copper surface than other inorganic salts, namely the inorganic sulfate salts, as exemplified by the results of C2.

While not wishing to be bound by the following, it is hypothesized by the inventors that most metal oxides particularly copper oxide show some degree of solubility and an acidic medium and the presence of the preferred inorganic acid, citric acid, and the example formulations exhibit synergistically improved dissolution of any surface oxide layer on the coin after, or during the simultaneous cleaning of any inorganic soils or organic soils which were present on the surface of each of the coins prior to the initiation of the test. It is nonetheless surprising to see that the inclusion on the inorganic salts provided an approximate three-fold improvement in the metal cleaning performance as is evident from a comparison of the results disclosed for the example composition El and the very similar comparative composition Cl which however did not include any inorganic chloride salts. It is also concurrently surprising to note that the compositions provide good storage stability notwithstanding the amounts of the inorganic salts present in their formulation.

- 30 - Cleaning Efficacy: Formulations of the present invention are expected to have good cleaning efficacy of hard surfaces, including surfaces other than metal or metallic surfaces.

Antimicrobial Efficacy: It is expected that certain of the preferred inventive composition will also provide an effective sanitizing or disinfecting benefit against one or more of the following: Staphylococcus aureus (gram positive type pathogenic bacteria) (ATCC 6538), Salmonella choleraesuis (gram negative type pathogenic bacteria) (ATCC 10708), Escheria coli (gram negative type pathogenic bacteria) (ATCC 11229) and Pseudomonas aeruginosa (ATCC 15442).

It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.

- 31 -

Claims (16)

1. Claims: 1. An aqueous hard surface cleaning composition which comprises:

   A) an acid sequestrant constituent; B) a mixture of hydrophobic and hydrophilic solvents; C) a surfactant andlor hydrotrope constituent; D) an inorganic chloride salt constituent; io optionally one or more optional constituents; the balance to 100% by weight, water wherein the aqueous hard surface cleaning composition exhibits a pH of 7.0 or less.
2. 2. An aqueous hard surface cleaning composition according to claim lwhich comprises: 0.1 - 10% by weight of an acid sequestrant constituent; 0.1 10% by weight of a mixture of hydrophobic and hydrophilic solvents; I - 8% by weight of a surfactant andlor hydrotrope constituent; 0.00001-10% by weight of an inorganic chloride salt; 0 - 20% by weight of one or more optional constituents; the balance to 100% by weight, water wherein the aqueous hard surface cleaning composition exhibits a pH of 7.0 or less.
3. 3. The aqueous hard surface cleaning composition according to claim I wherein the acid sequestrant constituent is selected from: citric acid, cresylic acid, dodecylbenZefle 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, propionic acid, polyacrylic acid, 2-ethyl-hexanoic acid, formic acid, funiaric acid, 1-glutamic acid, isopropyl sulfamic acid, naphthenic acid, oxalic acid, phosphorus acid, valeric - 32 -

   F-

   acid, benzene sulfonic acid, xylene sulfonic acid, sulfonic acids, maleic acid, acetic acid, adipic acid, lactic acid, butyric acid, gluconic acid, malic acid, tartaric acid, and glycolic acid.
4. 4. The aqueous hard surface cleaning composition according to claim 1 wherein the acid sequestrant constituent comprises at least 25% by weight of citric acid.
5. 5. The aqueous hard surface cleaning composition according to claim 3 wherein the acid sequestrant constituent comprises at least 50% by weight of citric acid.
6. 6. The aqueous hard surface cleaning composition according to claim 1 wherein the mixture of hydrophobic and hydrophilic solvents includes a hydrophobic solvent which is an organic solvent which demonstrates solubilization of the aliphatic portions of the fatty acids comprised within the soap scum stains.
7. 7. The aqueous hard surface cleaning composition according to claim 1 wherein the mixture of hydrophobic and hydrophilic solvents includes a hydrophobic solvent which is an organic solvent selected from: mineral spirits, tripropylene glycol n- butyl ether, propylene glycol phenyl ether, dipropylene glycol n-propyl ether, ethylene glycol phenyl ether, propylene glycol n-butyl ether, and dipropylene glycol n-butyl ether.
8. 8. The aqueous hard surface cleaning composition according to claim 1 wherein the mixture of hydrophobic and hydrophilic solvents includes a hydrophilic solvent which is an organic solvent effective in solubilizing the hydrophobic solvent in water.
9. 9. The aqueous hard surface cleaning composition according to claim 1 wherein the mixture of hydrophobic and hydrophilic solvents includes a hydrophilic solvent which is selected from: glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-propyl ether, ethylene glycol - 33 - n-butyl ether, diethylene glycol n-butyl ether, diethylene glycol methyl ether, propylene glycol, ethylene glycol, isopropanol, ethanol, methanol, diethylene glycol monoethyl ether, ethylene glycol mono-butyl ether acetate, and diethylene glycol monoethyl ether acetate.
10. 10. The aqueous hard surface cleaning composition according to claim 1 wherein the surfactant and/or hydrotrope constituent includes one or more anionic surfactants.
11. 11. The aqueous hard surface cleaning composition according to claim 10 wherein the surfactant and/or hydrotrope constituent includes one or more anionic surfactants selected from: alkyl phenoxy benzene disulfonates, linear alkyl benzene sulfonates, alkylnaphtalene sulfonates and salts thereof.
12. 12. The aqueous hard surface cleaning composition according to claim 10 wherein the surfactant and/or hydrotrope constituent includes one or more anionic surfactants selected from alkali metal salts, ammonium salts, amine salts, aminoalcohol salts or the magnesium salts of alkyl sulfates, alkyl ether sulfates, alkylamidoether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, olefinsulfonates, paraffin sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfosuccinamate, alkyl sulfoacetates, alkyl phosphates, alkyl ether phosphates, acyl sarconsinates, acyl isethionates, or N-acyl taurates.
13. 13. The aqueous hard surface cleaning composition according to claim 10 wherein the surfactant and/or hydrotrope constituent is selected from: sodium xylene sulfonates, sodium cumene sulfonates and naphthalene sulfonates.
14. 14. The aqueous hard surface cleaning composition according to claim I which includes an optional constituent selected from: nonionic surfactants, foaming agents, foam stabilizers, coloring agents, fragrances (whether natural or - 34 - synthetically produced), fragrance adjuvants and/or fragrance solubilizers, viscosity modifying agents, thickeners, gelling agents, pH adjusting agents, pH buffers, antioxidants, water softening agents, further solubilizing agents useful in the solubilization of one or more of the constituents in water, and, preservative compositions.
15. 15. The aqueous hard surface cleaning composition according to claim 1 wherein the pH of the composition is from about 5.0 to about 1.0.
16. 16. A process for the removal of stains from hard surfaces which comprises the step of applying an effective amount of the composition according to claim Ito a hard surface needing such treatment.

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