The present invention is related to hard surface cleaning compositions, particularly hard surface cleaning compositions which are effective in the cleaning of soap scum stains from hard surfaces.

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. 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.

While the prior art provides a number of compositions which provide effective cleaning of one or more, typically all of the foregoing classes of stains, there is still a real and continuing need in the art to provide improved hard surface cleaning compositions which are effective in the treatment of many types of stains typically encountered on hard surfaces, particularly in a home or commercial environment, especially in or around

kitchens, bathrooms where cleanliness is of especial importance. It is to such needs that the compositions of the present invention are particularly directed.

Broadly, the present invention relates to liquid acidic hard surface cleaning compositions which are effective against common stains encountered on hard surfaces particularly "soap scum" stains, as well as methods for their use.

According to one aspect of the present invention there are provided hard surface cleaning compositions which comprise (and in certain preferred embodiments, consist essentially of):

0.25 - 15%wt. of an acid system which necessarily comprises formic acid and at least one further acid selected from inorganic and organic acids;

0.01 — 3.5%wt. of at least one nonionic surfactant based on monobranched alkoxylated C 10/Cl 1 -fatty alcohols; optionally but in some cases desirably at least one cosurfactant constituent including one or more anionic, nonionic, cationic, amphoteric or zwitterionic surfactants; optionally one or more organic solvents; optionally one or more further constituents selected 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, opacifying agents, hydrotropes, abrasives, and preservatives, as well as other optional constituents known to the art; and the balance, water, wherein water comprises at least 80%wt. of the composition, but not more than 90%wt. of the composition.

In certain preferred embodiments the nonionic surfactant based on monobranched alkoxylated C 10/Cl 1 -fatty alcohols is the sole surfactant constituent present in the compositions, to the exclusion of further anionic, nonionic, cationic, amphoteric or zwitterionic surfactants.

In a still further preferred embodiment, the nonionic surfactant based on monobranched alkoxylated C 10/Cl 1 -fatty alcohols is present in conjunction with an alkylpolyglucoside surfactant to the exclusion of further anionic, nonionic, cationic, amphoteric or zwitterionic surfactants.

In yet further preferred embodiments the compositions exclude the one or more organic solvents.

In further preferred embodiments there are provided carrier substrates, e.g., wipes, sponges, and the like comprising a highly aqueous liquid acidic hard surface cleaning composition as described herein.

The present invention also provides for methods for the treatment of stained hard surfaces in need of cleaning which comprises the step of applying a cleaning effective amount of the hard surface cleaning composition as described herein to a hard surface in need of a cleaning treatment. The present invention also provides hard surface treatment compositions, e.g, hard surface cleaning and/or disinfecting compositions which exhibit reduced stress cracking of polymeric surfaces, which compositions include one or more water soluble zinc compounds which have been observed by the present inventors to reduce stress cracking of acrylic based polymers, e.g., polymethylmethacrylate. The present invention also provides for a method for reducing stress cracking of polymers and polymeric surfaces which method contemplates the inclusion of effective amounts of one or more water soluble zinc compounds in hard surface cleaning and/or disinfecting compositions.

The present invention also provides for compositions which exhibit good cleaning properties against dirt and stains commonly found in household, commercial and residential settings, particularly in lavatory settings wherein soap scum stains are frequently encountered.

It is contemplated that due to the highly acidic pH of the inventive compositions, in addition to good cleaning of certain stains commonly encountered on hard surfaces, the inventive compositions may also provide a disinfecting or sanitizing benefit of hard surfaces wherein the presence of undesired microorganisms are suspected such as gram positive or gram negative bacteria.

These and further aspects of the invention including especially preferred aspects will become more apparent from the following specification.

The hard surface cleaning compositions of the invention necessarily includes an acid system which comprises formic acid and at least one further acid selected from organic and inorganic acids.

Formic acid is an essential constituent of the acid system of the hard surface cleaning compositions taught herein. The formic acid is present in an amount of up to 15%wt, more preferably is present in an amount of at least about 0.25 — 15%wt, yet more preferably in an amount of about 0.5 — 12%wt, still more preferably in an amount of about 1 - 7.5%wt. based on the total weight of the hard surface cleaning composition of which it forms a part. Most desirably formic acid comprises at least about 2%wt, more preferably at least about 2.25%wt. of the hard surface cleaning composition of which it forms a part.

As noted the acid system necessarily includes at least one further acid, which may be selected from organic and inorganic acids, which are to be understood to include acid salts of organic acids as well. Exemplary organic acids which may be used include linear aliphatic acids such as 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, α-hydroxybutyric acid, glyceric acid, tartronic acid, malic acid, tartaric acid and citric acid, as well as acid salts of these organic acids as noted. Exemplary inorganic acids for use in the present invention include 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 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 acid character; if present are present in only minor amounts in the acid system. The use of water soluble acids are preferred, including water soluble salts of organic acids. In addition to the formic acid which forms

an essential constituent of the acid system, one or more of these acids may also be included.

The components of the acid system should be present in sufficient amounts such that the pH of the compositions is 2.5 or less, preferably a pH in of at least 0.1 and not in excess of 2.5, more preferably are at a pH of 0.1 - 2.5, yet more preferably are at a pH of 0.2 - 2, and most preferably is at a pH of 0.25 - 1.5. The acid system is present in amounts of from 0.25 - 15%wt., preferably from 8 - 15%wt., most preferably from 9- 1 l%wt. based on the total weight of the hard surface cleaning composition of which it forms a part. Citric acid is preferably included in the inventive compositions as part of the acid system. When present, the citric acid is present in an amount of up to 15%wt, more preferably is present in an amount of at least about 0.25 - 15%wt, yet more preferably in an amount of about 0.5 - 12%wt, still more preferably in an amount of about 1 - 7.5%wt. based on the total weight of the hard surface cleaning composition of which it forms a part. According to certain particularly preferred embodiments citric acid is necessarily present, desirably in an amount of at least about 2%wt, as it has been observed by the present inventors that the inclusion of citric acid improves the hard surface cleaning performance over longer contact times with such stained surfaces, and/or for the removal of difficult to clean stains. Phosphoric acid may be preferably included in the inventive compositions as part of the acid system. When present, the phosphoric acid is present in an amount of up to 15%wt, more preferably is present in an amount of at least about 0.25 - 15%wt, yet more preferably in an amount of about 0.5 - 12%wt, still more preferably in an amount of about 1 - 7.5%wt. based on the total weight of the hard surface cleaning composition of which it forms a part. According to certain particularly preferred embodiments phosphoric acid is necessarily present, desirably in an amount of at least about 1.25%wt, as it has been observed by the present inventors that the inclusion of phosphoric acid improves the efficacy of hard surface cleaning performance.

Maleic acid may be preferably included in the inventive compositions as part of the acid system. When present, the maleic acid is present in an amount of up to 15%wt, more preferably is present in an amount of at least about 0.25 - 15%wt, yet more

preferably in an amount of about 0.5 - 12%wt, still more preferably in an amount of about 0.5 - 7.5%wt. based on the total weight of the hard surface cleaning composition of which it forms a part. According to certain particularly preferred embodiments maleic acid is necessarily present, desirably in an amount of at least about 0.75%wt. in order to improve the efficacy of hard surface cleaning performance.

According to certain preferred embodiments, the acid system comprises, preferably consists essentially of formic acid and citric wherein the weight ratios of the formic acid to the citric acid is at least about 1:1, preferably are in the range of about 1: 1- 2.2 such that the amount of citric acid present is equal to or up to about 2.2 times the amount of the formic acid present in the hard surface cleaning composition. According to further particularly preferred embodiments, the acid system consists essentially of formic acid and citric acid in the respective weight ratios included above, to the exclusion of other organic and inorganic acids.

According to other preferred embodiments, the acid system comprises, preferably consists essentially of formic acid, citric and phosphoric acid wherein the weight ratios of the formic acid to the citric acid is at least about 1:1, preferably are in the range of about 1 : 1-2.2 such that the amount of citric acid present is equal to or up to about 2.2 times the amount of the formic acid present in the hard surface cleaning composition, and wherein phosphoric acid is present in an amount which is not in excess of the amount of formic acid present, and preferably is present within the weight ratio of formic acid to phosphoric acid of 1:0.01-0.36, preferably 1:0.15-0.36, and most preferably is present in the weight ratio of 1:0.30 - 0.36, such that both the amount of citric acid present is equal to or up to about 2.2 times the amount of the formic acid present in the hard surface cleaning composition, and concurrently phosphoric acid is also present in an amount of up to about one-third of the amount of the formic acid present. According to further particularly preferred embodiments, the acid system consists essentially of formic acid, citric acid and phosphoric acid in the respective weight ratios included above, to the exclusion of other organic and inorganic acids.

The present inventors have surprisingly found excellent cleaning performance particularly rapid cleaning performance of soap scum stains with the use of the preferred, and particularly the especially preferred acid systems taught herein. This performance is

surprising and technically significant in that rapid and early effective removal of soap scum stains (e.g., soils, deposits) from hard surfaces, (e.g., lavatory tiles, sinks as well as plumbing fixtures and lavatory appliances, as well as mirrors and glass surfaces) are now made possible per the present inventive compositions. While the present inventors have cited that formic acid is an essential constituent of the present inventive compositions, it is contemplated that part of, or all of the formic acid may be substituted by sulfamic acid as it is expected that sulfamic acid may provide similarly good cleaning of soap scum from hard surfaces when included in the acid system of the present invention, including preferred embodiments of the invention as described herein. The use of formic acid, to the exclusion of sulfamic acid remains highly preferred as it is believed that sulfamic acid is more prone to cause damage to hard surfaces treated with the hard surface cleaning compositions within which they are present partly in place of, and especially wholly in place of the formic acid. In certain particularly preferred embodiments, sulfamic acid is absent from the inventive compositions.

While the present inventors have cited that formic acid is an essential constituent of the present inventive compositions, it is contemplated that the formic acid may be omitted. In certain particularly preferred embodiments, while formic acid acid is absent from the inventive compositions, the inventive compositions include at least one of the acids discussed above.

The compositions of the invention necessarily comprise a nonionic surfactant which are monobranched alkoxylated ClO-fatty alcohols and/or Cl 1-fatty alcohols; these are jointly referred to as C 10/Cl 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 ClO-Guerbet alcohol which is approximately 4 moles of ethoxylation, Lutensol® XL 50 recited by its supplier to be a C10-Guerbet alcohol which is approximately 5 moles of ethoxylation, Lutensol® XL 60 recited by its supplier to be a C10-Guerbet alcohol which is

approximately 6 moles of ethoxylation, Lutensol® XL 70 recited by its supplier to be a ClO-Guerbet alcohol which is approximately 7 moles of ethoxylation, Lutensol® XL 40 recited by its supplier to be a ClO-Guerbet alcohol which is approximately 4 moles of ethoxylation, Lutensol® XL 79 recited by its supplier to be a ClO-Guerbet alcohol which is approximately 7 moles of ethoxylation, Lutensol® XL 80 recited by its supplier to be a ClO-Guerbet alcohol which is approximately 8 moles of ethoxylation, Lutensol® XL 89 recited by its supplier to be a ClO-Guerbet alcohol which is approximately 8 moles of ethoxylation, Lutensol® XL 90 recited by its supplier to be a ClO-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 aso 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, Cii-oxo-alcohol polyglycol ether with 3 EO; Genapol® UD, 050 Cπ-oxo-alcohol polyglycol ether with 5 EO; Genapol® UD 070, Cπ-oxo-alcohol polyglycol ether with 7 EO; Genapol® UD 080, Cu-oxo-alcohol polyglycol ether with 8 EO; Genapol® UD 088, Cπ-oxo-alcohol polyglycol ether with 8 EO; and Genapol® UD 110, Cπ-oxo-alcohol polyglycol ether with 11 EO (ex. Clariant).

The nonionic surfactant based on monobranched alkoxylated C 10/Cl 1 -fatty alcohols (and/or Cl 1 -fatty alcohols) is necessarily present in the hard surface cleaning compositions in amount of from 0.01 - 3.5%wt, preferably in amount of from 1 - 3%wt,

yet more preferably from 1.5 - 2.25%wt. based on the total weight of the hard surface cleaning composition of which it forms a part.

The hard surface cleaning compositions of the invention optionally but in some cases desirably comprise at least one co-surfacant constituent. Such a co-surfactant may be one or more surfactants selected from one or more further anionic, nonionic, cationic, amphoteric or zwitterionic surfactants;

Exemplary of anionic surfactants which may be present include 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 (ROSO ₃ ) _X M or (RSO ₃ ) _X M wherein R is preferably a C ₆ -C ₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Ci ₀ -C ₂₀ alkyl component, more preferably a Ci ₂ -Ci ₈ 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 hydrotropic 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, C ₆ -C ₂₀ linear alkylbenzenesulfonates, C ₆ -C ₂₂ primary or secondary alkanesulfonates, C ₆ -C ₂₄ olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, C ₆ -C ₂₄ alkylpolyglycolethersulfates, alkyl ester sulfates such as Ci _4- I ₆ 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 Ci ₂ -Ci ₈ monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C ₆ -Ci ₄ 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(CH ₂ CH ₂ O) _k CH ₂ COO ^~~ M ⁺ wherein R is a C ₈ -C ₂₂ 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®, Surfine®, 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:

R ¹ represents a C ₆ — C ₂₂ alkyl or alkenyl group; each of R ² is either hydrogen, or if not hydrogen is a SO ₃ ^" 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 R ² , preferably at least two R ² is a (SO ₃ ^" ) having an associated cation X ⁺ , and,

R ³ represents a C ₁ -C ₆ , preferably Ci-C ₄ lower alkyl or alkenyl group, especially methyl. According to certain preferred embodiments, anionic surfactants are however expressly excluded from the compositions of the present invention.

One class of exemplary 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 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 C ₆ -Cn 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-I0 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- I ₀ 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 ethoxylated available from Shell Chemical Company which are described as Cg-C ₁₁ 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 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 D A-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(CH ₂ CH ₂ O) _n 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 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 useful nonionic surfactants include those having a formula RO(CH ₂ CH ₂ O) _n H wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C ₁₂ H ₂₅ to C ₁₆ H ₃₃ 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(CH ₂ CH ₂ O) _n H wherein R is a mixture of linear, even carbon-number hydrocarbon chains ranging from C ₁₂ H ₂₅ to C ₁₆ H ₃₃ 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-60N, 26-L- 75, 26-L-80, 26-L-98N, and the 24-L series, derived from synthetic sources and typically contain about 55% C ₁₂ and 45% C ₁₄ 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 ⁰ C of a 1.0 wt.% solution in water.

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 C ₂ -C ₄ 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):

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) _x -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)χ(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. Still further useful nonionic block copolymer surfactants include ethoxylated derivatives of propoxylated ethylene diamine, which may be represented by the following formula:

where (EO) represents ethoxy,

(PO) represents propoxy, the amount of (PO) _x is such as to provide a molecular weight prior to ethoxylation of about 300 to 7500, and the amount of (EO) _y is such as to provide about 20% to 90% of the total weight of said compound. Surfactants based on amine oxides are also contemplated to be useful in the cosurfactant constituent in the present inventive compositions. Exemplary amine oxides include:

alkyl di(Ci-C ₇ ) 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 Ci-C ₇ ) 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-C ₇ ) 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.

By way of non-limiting example exemplary amphoteric surfactants which are contemplated to be useful 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:

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 R ₂ is a Ci-C ₄ alkylene group. Examples of such

water-soluble betaine surfactants include dodecyl dimethyl betaine, as well as cocoamidopropylbetaine.

A cosurfactant which is desirably present according to certain preferred embodiments of the invention is an alkylpolyglucoside which is to be understood as including alkylmonoglucosides and alkylpolyglucosides surfactant based on a polysaccharide, which are preferably one or more alkyl polyglucosides. These materials may also be referred to as alkyl monoglucosides and alkylpolyglucosides. Suitable alkyl polyglucosides are known nonionic surfactants which are alkaline and electrolyte stable.

Such include alkyl glucosides, alkyl polyglucosides and mixtures thereof. Alkyl glucosides and alkyl polyglucosides can be broadly defined as condensation articles of long chain alcohols, e.g., C ₈ -C ₃₀ alcohols, with sugars or starches or sugar or starch polymers i.e., glucosides or polyglucosides. These compounds can be represented by the formula (S) _n — O — R wherein S is a sugar moiety such as glucose, fructose, mannose, and galactose; n is an integer of from about 1 to about 1000, and R is a C _8-30 alkyl group. Examples of long chain alcohols from which the alkyl group can be derived include decyl alcohol, cetyl alcohol, stearyl alcohol, lauryl alcohol, myristyl alcohol, oleyl alcohol and the like.

Alkyl mono- and polyglucosides 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 glucoside and polyglucoside compounds including alkoxylated glucosides and processes for making them are disclosed in U.S.

Patent No. 2,974,134; U.S. Patent No.3,219,656; U.S. Patent No. 3,598,865; U.S. Patent

No. 3,640,998; U.S. Patent No. 3,707,535; U.S. Patent No. 3,772,269; U.S. Patent No.

3,839,318; U.S. PatentNo. 3,974,138; U.S. Patent No. 4,223,129; and U.S. Patent No. 4,528,106.

Exemplary useful alkyl glucoside surfactants suitable for use in the practice of this invention may be represented by formula I below:

wherein:

R is a monovalent organic radical containing from about 6 to about 30, preferably from about 8 to about 18 carbon atoms; R ₁ is a divalent hydrocarbon radical containing from about 2 to about 4 carbon atoms; O is an oxygen atom; y is a number which has an average value from about 0 to about 1 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 O ₂ M ¹ ,

O

Il

— 0-C-R ₂

0(CH ₂ ), CO ₂ M ¹ , OSO ₃ M ¹ , or 0(CH ₂ )SO ₃ M ¹ ; R ₂ is (CH ₂ )CO ₂ M ¹ or CH=CHCO ₂ M ¹ ; (with the proviso that Z can be O ₂ M ¹ only if Z is in place of a primary hydroxyl group in which the primary hydroxyl-bearing carbon atom, — CH ₂ OH, is oxidized to form a

group); b is a number of from O to 3x+l preferably an average of from 0.5 to 2 per glycosal group; p is 1 to 10,

M ¹ is H ⁺ or an organic or inorganic cation, such as, for example, an alkali metal, ammonium, monoethanolamine, or calcium.

As defined in Formula I above, R is generally the residue of a fatty alcohol having from about 8 to 30 and preferably 8 to 18 carbon atoms.

Further exemplary useful alkylpolyglucosides include those according to the formula II:

R ₂ O-(C _n H _2n O) _r -(Z) _x II wherein: R ₂ 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 1 to 8, preferably from about 1.5 to 5. Preferably the alkylpolyglucosides are nonionic fatty alkylpolyglucosides which contain a straight chain or branched chain Cg -Ci ₅ 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 C ₈ -Ci ₅ alkyl group, and have an average of from about 1 to about 2 glucose units per fatty alkylpolyglucoside molecule.

Examples of such alkylpolyglucosides as described above include, for example, APG™ 325 which is described as being a Cp-C ₁₁ alkyl polyglucoside, also commonly referred to as D-glucopyranoside, (ex. Cognis). Further exemplary alkylpolyglucosides include Glucopon® 625 CS which is described as being a Ci ₀ -Ci ₆ alkyl polyglucoside, also commonly referred to as a D-glucopyranoside, (ex. Cognis), lauryl polyglucoside available as APG™ 600 CS and 625 CS (ex. Cognis) as well as other materials sold under the Glucopon® tradename, e.g., Glucopon® 215, Glucopon® 225, Glucopon® 425, especially one or more of the alkyl polyglucosides demonstrated in one or more of the examples. It is believed that the alkylpolyglucoside surfactants sold under the Glucopon® tradename are synthezied at least in part on synthetically produced starting constituents and are colorless or only slightly colored, while those sold under the APG™ are synthesized at least in part on naturally occurring or sourced starting constituents and are more colored in appearance.

When present, any cosurfactant(s) may be present in any cleaning effective amounts up to about 3%wt, preferably are present in amounts of from about 0.01 - 2.5%wt, yet more preferably from about 0.01 - 2%wt, based on the total weight of the composition of which it forms a part. Desirably the one or more of the cosurfacants which are included in the hard surface cleaning compositions are selected to exhibit a surface tension at a 1% concentration in water of less than about 30 dynes/cm measured using a ring tensionometer according to accepted laboratory practices. It has been surprisingly found that in the hard surface cleaning compositions of the invention, that excellent cleaning was achieved even at minimal cosurfactant concentrations when the cosurfactant(s) exhibited such a low surface tension.

In certain preferred embodiments the nonionic surfactant based on monobranched alkoxylated C 10/Cl 1 -fatty alcohols is the sole surfactant constituent present in the compositions, to the exclusion of further anionic, nonionic, cationic, amphoteric or zwitterionic surfactants.

In a still further preferred embodiment, the nonionic surfactant based on monobranched alkoxylated C 10/Cl 1 -fatty alcohols is present in conjunction with an alkylpolyglucoside surfactant to the exclusion on further anionic, nonionic, cationic, amphoteric or zwitterionic surfactants. The inventive compositions may optionally one or more organic solvents.

Exemplary useful organic solvents which may be present in the inventive compositions include those which are at least partially water-miscible such as alcohols (e.g., low molecular weight alcohols, such as, for example, ethanol, propanol, isopropanol, and the like), glycols (such as, for example, ethylene glycol, propylene glycol, hexylene glycol, and the like), water-miscible ethers (e.g. diethylene glycol diethylether, diethylene glycol dimethylether, propylene glycol dimethylether), water-miscible glycol ether (e.g. propylene glycol monomethylether, propylene glycol mono ethylether, propylene glycol monopropylether, propylene glycol monobutylether, ethylene glycol monobutylether, dipropylene glycol monomethylether, diethyleneglycol monobutylether), lower esters of monoalkylethers of ethylene glycol or propylene glycol (e.g. propylene glycol monomethyl ether acetate), and mixtures thereof. Glycol ethers having the general

structure Ra-Rb-OH, wherein Ra is an alkoxy of 1 to 20 carbon atoms, or aryloxy of at least 6 carbon atoms, and Rb is an ether condensate of propylene glycol and/or ethylene glycol having from one to ten glycol monomer units. Mixtures of two or more specific organic solvents may be used, or alternately a single organic solvent may be provided as the organic solvent constituent. When present, of the foregoing classes of organic solvents, one or more glycol ethers or monohydric alcohols, especially Ci-C ₄ alcohols are preferably used. When present such organic solvent(s) may be present in amounts of up to about 2%wt, preferably are present in amounts of from about 0.01 - 1.2%wt. As stated previously however, in certain particularly preferred embodiments, organic solvents are excluded from the inventive compositions.

The inventive compositions may optionally include one or more one or more further constituents useful in improving one or more aesthetic characteristics or the compositions or in improving one or more technical characteristics of the compositions. Exemplary further optional constituents 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, opacifying agents, hydrotropes, abrasives, and preservatives, as well as other optional constituents providing improved technical or aesthetic characteristics known to the relevant art. When present, the total amount of such one or more optional constituents present in the inventive compositions do not exceed about 10%wt, preferably do not exceed 2.5%wt, and most preferably do not exceed 1.2%wt.

By way 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. Further exemplary pH adjusting agents include mineral acids, basic compositions, and organic acids, which are typically required in only minor amounts. By way 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 (C ₅ H ₈ ) _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 hydrotrope or emulsifier 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 detennine 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.

The inventive compositions may include a hydrotrope constituent comprising one or more compounds which exhibit a hydrotropic functionality in the inventive compositions. Exemplary hydrotropes include, inter alia, benzene sulfonates, naphthalene sulfonates, Ci-Cπ alkyl benzene sulfonates, naphthalene sulfonates, C ₅ -Cn alkyl sulfonates, C ₆ -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., Ci _-4 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 C ₅ -Cn alkyl sulfonates include hexyl sulfonates, octyl sulfonates, and hexyl/octyl sulfonates, and mixtures thereof. Particularly useful hydrotrope compounds include benzene sulfonates, o-toluene sulfonates, m-toluene sulfonates, and p-toluene sulfonates; 2,3-xylene sulfonates, 2,4-

xylene sulfonates, and 4,6-xylene sulfonates; cumene sulfonates, wherein such exemplary hydrotropes are generally in a salt form thereof, including sodium and potassium salt forms. When present the hydrotrope constituent may be present in any effective amounts, or they may be omitted. Advantageously, when present the hydrotrope constituent comprises 0.001 - 1.5%wt. of the composition of which it forms a part.

A further optional constituent are one or more preservatives. 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-l,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 one or more abrasives may be included in the inventive compositions. Exemplary abrasives include: oxides, e.g., calcined aluminum oxides and the like, carbonates, e.g., calcium carbonate and the like, quartzes, siliceous chalk, diatomaceous earth, colloidal silicon dioxide, alkali metasilicates, e.g., sodium metasilicate and the like, perlite, pumice, feldspar, calcium phosphate, organic abrasive materials based on comminuted or particulate polymers especially one or more of polyolefins, polyethylenes,

polypropylenes, polyesters, polystyrenes, acetonitrile-butadiene-styrene resins, melamines, polycarbonates, phenolic resins, epoxies and polyurethanes, natural materials such as, for example, rice hulls, corn cobs, and the like, or talc and mixtures thereof. The particle size of the abrasive agent typically may 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 most hard 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 available at a generally low cost. A single type of abrasive, or a mixture of two or more differing abrasive materials may be used.

Optionally the compositions may include an effective amount of at least one inorganic chloride salt, which are believed to improve the metal cleaning characteristics of the inventive compositions. The inorganic chloride salt is desirably present in an amount effective to provide improved cleaning of metal 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 water-soluble 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 0.00001 to about 2.5% by weight, desirably in amounts of 0.001 to about 2% 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. In certain preferred embodiments the sole inorganic salts present are one or more inorganic chloride salts.

The inventive compositions may also include a quantity of one or more water soluble zinc compounds with anions such as nitrate, sulfate, halide (especially fluoride), phosphate (where soluble), carbonate and carboxylate (such as the anions from Ci-C ₁ O mono or multi carboxy function containing carboxylic acids, especially acetate and citrate). A particularly preferred water soluble zinc salt is zinc sulfate hexahydrate which has been observed by the present inventors to reduce stress cracking of acrylic based polymers, e.g., polymethylmethacrylate. Such water soluble zinc compound may be present in any effective amount, but typically not in excess of about 0.5%wt, but typically is present in an amount of from about 0.01 - 0.3%wt. Thus, the present invention contemplates a method for reducing stress cracking of polymers and polymeric surfaces which method contemplates the inclusion of effective amounts of one or more water soluble zinc compounds in hard surface cleaning and/or disinfecting compositions, as well as hard surface cleaning and/or disinfecting compositions which include effective amounts of one or more water soluble zinc compounds in order to reduce stress cracking of polymers and polymeric surfaces.

The inventive compositions may include a 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.

Examples of the cellulose derivatives include methyl cellulose ethyl cellulose, hydroxymethyl cellulose hydroxy ethyl cellulose, hydroxy propyl cellulose, carboxy methyl cellulose, carboxy methyl hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxy propyl methyl cellulose, ethylhydroxymethyl cellulose and ethyl hydroxy ethyl cellulose.

Exemplary polycarboxylate polymers thickeners have a molecular weight from about 500,000 to about 4,000,000, preferably from about 1,000,000 to about 4,000,000, with, preferably, from about 0.5% to about 4% crosslinking. Preferred polycarboxylate polymers include polyacrylate polymers including those sold under trade names Carbopol®, Acrysol® ICS-I and Sokalan®. The preferred polymers are polyacrylates. Other monomers besides acrylic acid can be used to form these polymers including such monomers as ethylene and propylene which act as diluents, and maleic anhydride which acts as a source of additional carboxylic groups.

Exemplary clay thickeners comprise, for example, colloid-forming clays, for example, such as smectite and attapulgite types of clay thickeners. The clay materials can be described as expandable layered clays, i.e., aluminosilicates and magnesium silicates. The term "expandable" as used to describe the instant clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water. The expandable clays used herein are those materials classified geologically as smectites (or montmorillonite) and attapulgites (or polygorskites).

Preferred thickeners are those which provide a useful viscosity increasing benefit at the ultimate pH of the compositions, particularly thickeners which are useful at pH's of about 3 or less. When a thickener constituent is present, the inventive compositions typically exhibit viscosities in excess of 50 cps at room temperature, and preferably exhibit a viscosity of at least 100 cps at room temperature, but preferably also does not exceed 20,000 cps at the same temperature.

As is noted above, the compositions according to the invention are largely aqueous in nature. 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 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 undesirably interfere with the operation of the constituents present in the aqueous compositions according to the invention. Preferably at least 80%wt, more preferably at least 85%wt of the compositions are water.

While in certain embodiments the compositions may comprise a thicker constituent, it is generally preferred the compositions exhibit viscosities similar to that of water. The compositions preferably have a viscosity of not more than about 50 cps at room temperature, more preferably have a viscosity of not more than about 30 cps at room temperature.

The compositions according to the invention are desirably provided as a ready to use product which may be directly applied to a hard surface. Hard surfaces which are to be particularly denoted are lavatory fixtures, lavatory appliances (toilets, bidets, shower stalls, bathtubs and bathing appliances), wall and flooring surfaces especially those which include refractory materials and the like. Further hard surfaces which are particularly denoted are those associated with dishwashers, kitchen environments and other environments associated with food preparation. Hard surfaces which are those associated with hospital environments, medical laboratories and medical treatment environments. Such hard surfaces described above are to be understood as being recited by way of illustration and not be way of limitation.

The inventive compositions may be packaged in any suitable container particularly flasks or bottles, including squeeze-type bottles, as well as bottles provided with a spray apparatus which is used to dispense the composition by spraying. The inventive compositions are readily pourable and readily pumpable cleaning compositions which features the benefits described above. Accordingly the inventive compositions are desirably provided as a ready to use product in a manually operated spray dispensing container, or may be supplied in aerosolized product wherein it is discharged from a pressurized aerosol container. Propellants which may be used are well known and conventional in the art and include, for example, a hydrocarbon, of from 1 to 10 carbon atoms, such as n-propane, n-butane, isobutane, n-pentane, isopentane, and mixtures thereof; dimethyl ether and blends thereof as well as individual or mixtures of chloro-, chlorofluoro- and/or fluorohydrocarbons- and/or hydrochlorofluorocarbons (HCFCs). Useful commercially available compositions include A-70 (Aerosol compositions with a vapor pressure of 70 psig available from companies such as Diversified and Aeropress) and Dymel® 152a (1,1-difluoroethane from DuPont). Compressed gases such as carbon dioxide, compressed air, nitrogen, and possibly dense or supercritical fluids may also be

used. In such an application, the composition is dispensed by activating the release nozzle of said aerosol type container onto the area in need of treatment, and in accordance with a manner as above-described the area is treated (e.g., cleaned and/or sanitized and/or disinfected). If a propellant is used, it will generally be in an amount of from about 1% to about 50% of the aerosol formulation with preferred amounts being from about 2% to about 25%, more preferably from about 5% to about 15%. Generally speaking, the amount of a particular propellant employed should provide an internal pressure of from about 20 to about 150 psig at 70 ⁰ F.

The compositions according to the invention can also be suited for use in a consumer "spray and wipe" application as a cleaning composition. In such an application, the consumer generally applies an effective amount of the 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, e.g., soap scum deposits, the 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, particularly soap scum stains, multiple applications may also be used. Optionally but frequently desirably, after the composition has remained on the surface for a period of time, it could be rinsed or wiped from the surface.

It is contemplated that certain preferred embodiments of inventive formulations may also provide a disinfecting or sanitizing benefit to hard surfaces wherein the presence of undesired microorganisms are suspected such as gram positive or gram negative bacteria. This is due to the low pH of particularly preferred embodiments of the invention, particularly wherein the compositions are at a pH of 3 or less, preferably at a pH of 2 or less and most preferably at a pH of about 1.75 or less.

Also provided is a method for the treatment of hard surfaces wherein the presence of such undesired microorganisms are suspected which method includes the step of applying a disinfecting or sanitizing effective amount of a composition described herein. Whereas the compositions of the present invention are 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 solution therefrom. In such a proposed diluted cleaning solution, the greater the proportion of water added to form said cleaning dilution will, the greater may be the reduction of the rate and/or efficacy of the thus formed cleaning solution. Accordingly, longer residence times upon the stain to effect their loosening and/or the usage of greater amounts may be necessitated. Conversely, nothing in the specification shall be also understood to limit the forming of a "concentrated" cleaning composition based upon the composition described above. Such a concentrated ingredient composition is essentially the same as the cleaning compositions described above except in that they include a lesser amount of water.

The composition of the present invention, whether as described herein or in a concentrate or concentrate form, can also be applied to a hard surface by the use of a carrier substrate. One example of a useful carrier substrate is a wet wipe. The wipe can be of a woven or non- woven nature. Fabric substrates can include nonwoven or woven pouches, sponges including both closed cell and open celled sponges, including sponges formed from celluloses as well as other polymeric material, as well as 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. The carrier substrate useful with the present inventive compositions may also be a wipe which includes a film forming substrate 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 compositions of the present invention may be advantageously absorbed onto the carrier substrate, i.e., a 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. In use, a wipe is removed from the container and then wiped across an area in need of treatment; in case of difficult to treat stains the wipe may be re-wiped across the area in need of treatment, or a plurality of saturated wipes may also be used.

The following examples below illustrate exemplary formulations as well as preferred embodiments 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:

A number of formulations were produced by mixing the constituents outlined in Table 1-A 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 the formulation was homogenous in appearance. It is to be noted that the constituents might be added in any order, but it is preferred that a first premixture is made of any fragrance constituent with one or more surfactants used in the inventive compositions. Thereafter, a major amount of water is first provided to a suitable mixing vessel or apparatus as it is the major constituent and thereafter the further constituents are added thereto convenient. The order of addition is not critical, but good results are obtained where the surfactants (which may be also the premixture of the fragrance and surfactants) are added to the water prior to the remaining constituents. The exact compositions of the example formulations are listed on Tables 1-A, 1-B, below, and are identified by one or more digits preceded by the letter "E".

All of the formulations on the foregoing Table 1-A are indicated in weight percent, and each composition comprised 100%wt. The individual constituents on Table 1-A were used, "as-supplied" from their respective source and unless otherwise indicated, each of the constituents are to be understood as being "100%wt. actives". Deionized water was added in quantum sufficient, "q.s.", to provide the balance to 100%wt. of each

of the example compositions. The sources of the constituents used in the formulations of Tables 1 are described on the following Table 2.

All of the formulations on the foregoing Table 1-B are indicated in weight percent, and each composition comprises 100%wt. The individual constituents on Table 1-B are used, "as-supplied" from their respective source and unless otherwise indicated, each of the constituents is to be understood as being "100%wt. actives". Deionized water is added in quantum sufficient, "q.s.", to provide the balance to 100%wt. of each of the example compositions. The sources of the constituents used in the formulations of Table 1-B are also described on the following Table 2.

The cleaning performance of a composition according to Ex.7 - Ex.12 described on Table 1-A, was evaluated against a presently commercially available product, "BREF 'Ultrastark' Power-Reiniger" (ex. Henkel KGAA, Germany) which was used as a reference for comparative purposes.

The test protocol used was that established by the German Cosmetic, Toiletry, Perfumery and Detergent Association (IKW, viz., the "Industrieverband Kόrperpflege- und Waschmittel e.V.") and published as "Recommendations for the Quality Assessment of Bathroom Cleaners" (version 2002), published in the SOFW-Journal, 129, Nov, 2003. The specific test of the published tests used based on that under "3.2 Determination of the

cleaner's ability to remove lime soaps", which was generally adhered to as indicated in the following.

For this test high-gloss white ceramic tiles (4 inch by 4 inch glazed glossy white ceramic bathroom tiles), were initially cleaned with a mild abrasive cleaner, rinsed with water and wiped with ethanol. Subsequently the tiles are dried for 1 hour at 180° C in a preheated drying cabinet and then weighed.

The test soil used was a calcium stearate suspension of the following composition:

85.0 % ethanol, 96 MEK (denatured) 5.0 % calcium stearate, fine

9.8 % water, demineralized 0.2% soot/special black 4

Ethanol was made ready and calcium stearate was stirred into it. Then water and soot were added. The suspension was placed in an ultrasonic bath for 10 minutes and subsequently homogenized over 3 minutes with a Turrax (approx. 5000/min).

The suspension was applied onto the tiles from a distance of approximately. 25 cm with an airbrush pistol, (e.g. Badger model 150 with jet L). As a consequence of adjusting the airbrush system some of the ethanol was blown out by the compressed air (recommended pressure 2 bar), therefore the quantity to be applied was determined in pretests.

The tiles were dried for 1 hour at room temperature and then stored for 1 hour in a horizontal position in a preheated circulating drying oven at 180° C in order to melt the calcium stearate. Cooling was allowed to take place for approx. 1 hour in the switched off and slightly opened drying oven. The effectively applied mass of calcium stearate ° was calculated by another weighing and by determining the difference in weight compared with the empty, dried tile. According to the mass of the 5% calcium stearate suspension was applied (=5 g), in the test only tiles are used onto which 0.1 Ig ± 0.01 g of calcium stearate had been melted. Before testing the tiles were stored for at least 24 hours at room temperature.

Testing was carried out in the form of a five fold determination. For this purpose 0.5 ml of undiluted cleaner was placed with a pipette on an area of 3 x 2 cm on the tile. The exposure time was preferably 2.5; 5; and 7.5 minutes. Subsequently the tile was

rinsed under running water, and the loosened calcium stearate was removed mechanically by wiping a moist, fine-pored viscose sponge (approx. 90 x 40 x 40mm) once across the surface of the tile without applying any pressure Then the tile was rinsed with fully demineralized water and dried at room temperature. The time that the test cleaner needs to achieve a cleaning performance of 90-

100% is recorded. After drying the cleaning performance was visually assessed by two observers for each measuring point, estimating the soil removal in percent. To reduce variations of assessments, the observers were trained using suitable evaluation samples. The cleaning performance for each of the five exposure times was arrived at from the mean value of the two observations per measuring point.

To evaluate the total cleaning performance achieved, the average percentage soil removal was plotted geographically against the cleaning time. A comparison of the cleaning performance against time provides evidence of the efficacy of the test cleaner. In the test, 2 replicates were used for each of the tested formulae, two panelists were used to visually observe the sample bathroom tiles cleaned utilizing either the

BREF product or a composition according to E7 - E12. Visual grading occurred after 2.5 minutes contact time, 5 minutes contact time and 7.5 minutes contact time of a tested composition with a tile coated with the standardized soil prepared and applied according to the standardized test protocol. The test results are reported in the following Table 3, as well as on accompanying

Figure 1 which graphically presents the results of Table 3.

As is evident from the foregoing results, each of the compositions according to the present invention showed moderate, but in most cases, surprising and very significant improvement over the initial cleaning performance of the comparative product, BREF, with the best performance. Such performance is of technical significance as it suggest that lesser quantities of products based on the inventive compositions may be used to obtain comparable or better cleaning results as those which are provided by the BREF product. Such performance also indicates that the rapid initial cleaning performance requires lesser contact time, and thus lesser exposure to a consumer of the product which has been applied to a surface in order to achieve cleaning similar to or superior to the commercial BREF product, thus permitting it to be wiped off or rinsed away much sooner than surfaces contacted with the BREF product.

While the invention is susceptible of various modifications and alternative forms, it is to be understood that specific embodiments thereof have been shown by way of example in the foregoing which are not intended to limit the invention to the particular forms disclosed; on the contrary the intention is to cover all modifications, equivalents and alternatives falling within the scope and spirit of the invention as expressed in the appended claims.