The present invention relates to powdered hard surface cleaning compositions.

More particularly the present invention relates to powdered hard surface cleaning compositions which, when mixed or added to water or are otherwise wetted readily effervesce to form a foam. Hard surface cleaning compositions which directed to be used in the cleaning of lavatory appliance, particularly toilets, bidets and the like are well known to the art. A large number of cleaning compositions in the form of liquid compositions which are applied directly to the interior of a toilet bowl are well know and most of these are known art compositions which are typically acidic, largely aqueous in compositions and frequently are thickened either with the use of a thickener constituent or by selection of specific surfactants which result in a viscous liquid composition. Such are widely used and many enjoy a great degree of commercial success.

Also known are a large number of cleaning compositions which are in the form of a table or block with are typically provided as monolithic block structures which are provided either to the interior of a toilet tank, frequently referred to as an in the cistern ("ITC") block, or alternately are provided with a hook, or other holder often referred to as a 'cage' which acts to suspend such a block within the toilet bowl itself, frequently at a point beneath the upper rim of the toilet bowl. Such blocks are frequently referred to as in the bowl ("ITB") blocks. Both such types of ITC and ITB blocks, and many compositions for making the same are well known to the relevant art.

Notwithstanding their widespread use, such liquid compositions and block compositions frequently fail to provide a significant degree of foaming during the cleaning of the toilet bowl, which is detrimental from a consumer standpoint. While good cleaning of surfaces, including hard surfaces may be obtained with little or no foam visible to a consumer with certain surfactants, compositions which provide a significant

amount of visible foam during use of the product in the cleaning of a hard surface, viz., a toilet bowl is particularly advantageous as consumers frequently strongly associate cleaning efficacy with good foaming.

It is therefore amongst the objects of the invention to provide a hard surface cleaning composition which provides good foaming when used to clean such surfaces, especially where such surfaces are toilets or other lavatory appliances.

It is a further object of the invention to provide methods for the cleaning of hard surfaces, particularly lavatory appliances.

These and other objects of the invention will become apparent from a reading of the following specification and consideration of the examples.

In one aspect of the invention there is provided a pulverent hard surface cleaning composition which, when mixed or added to water or are otherwise wetted readily effervesces to form a foam.

In a further aspect of the invention there is provided a pulverent hard surface cleaning composition which, when mixed or added to water or are otherwise wetted readily effervesces to form a foam, and which further provides a degree of disinfecting or sanitizing to hard surfaces treated with aqueous compositions formed by mixing the pulverent hard surface cleaning composition with water. hi a further aspect of the invention there is provided an improved method for the cleaning of hard surfaces, particularly lavatory appliances and especially the bowls of toilets which method includes the step of: adding a quantity of the pulverent hard surface cleaning composition which, when mixed or added to water or are otherwise wetted readily effervesces to form a foam which contacts the hard surface.

The compositions of the invention necessarily include a gas generator system which provides an effervescent effect, namely the evolution of a gas from a liquid resulting from a chemical reaction. This reaction can be between, for example, an acid and an alkali metal carbonate, to produce carbon dioxide gas. Any gas generator system may be used in the compositions of the invention. Preferably the gas generator system comprises both an acid component which is an acid or acid source, which in the presence of water is capable of reacting with an alkali component which is an alkali or an alkali

source in order to produce a gas. Preferably the resultant gas is oxygen, nitrogen dioxide or carbon dioxide but any other gas may also be formed.

The acid component may be any organic, mineral or inorganic acid, or mixtures thereof. Preferably the acid source is an organic acid. The acid component is preferably substantially anhydrous or non-hygroscopic and the acid is preferably also water-soluble or water dispersible. Exemplary useful organic acids include citric acid, maleic acid, maleic acid, fumaric acid, aspartic acid, glutaric acid, tartaric acid, succinic acid, adipic acid, monosodium phosphate, boric acid, and mixture thereof. Preferred are citric acid, maleic acid, maleic acid, and mixtures, especially citric acid which is both effective and widely commercially available. Citric acid provided in a "coated" form, (e.g,

CITROCOAT, ex. Jungbunzlauer, Basel, CH) may also be advantageously used in the acid source.

The alkali component may be any suitable alkali or alkali source which has the capacity to react with the acid component when contacted with water to produce a gas. Exemplary alkali components include alkali metal carbonates, e.g, sodium carbonate, potassium carbonate, bicarbonate, sesquicarbonate, as well as perborates and percarbonates, as well as thereof.

The relative amounts of the acid components to the alkali component may vary widely, however preferably the respective molar ratios of the acid component to the alkali component be within the range of 1-5:1-5, preferably in respective molar ratios of 1-2.5:1-2.5, more preferably in the range of the former to the latter of 1-2:1-2. Most preferably the acid component to alkali component be present in approximately equal molar ratios to ensure the evolution of the gas. In certain further particularly preferred embodiments the acid component, especially where the acid component is citric acid, is present in a molar excess such at that the respective molar ratio of the acid component to the alkali component is at least 1-2:1, preferably at 1-3:1. An excess of the acid component provides for the delivery of the excess acid component not consumed in the gas formation reaction to the hard surface being cleaned, or to the water within which the acid component and the alkali component are contacted. The delivery of an excess acid component may advantageously decrease the pH of the water, or aid in the dissolution certain forms of hard surface stains including limescale and soap scum stains, or both.

As the formation of a substantial amount of gas from the gas generator system is preferred according to certain preferred embodiments of the invention, it is preferred that the gas generator system comprise at least 70 %wt., preferably at least 75%wt, more preferably at least 80% wt., yet more preferably at least 85%wt. of the total weight of the pulverent compositions of which they form a part.

It is to be understood that any effective amount of the gas generator system may be present however, although it should be realized that decreasing amounts of the gas generator system within the pulverent compositions taught herein concomitantly reduces the foam height formed. The inventive compositions also includes a surfactant constituent which includes one surfactants which may be used to provide a cleaning benefit to hard surfaces being treated with the inventive compositions. Such may be one or more anionic, nonionic, cationic, amphoteric or zwitterionic surfactants as well as mixtures thereof. Known art surfactants may be used in the pulverent compositions taught herein. Exemplary useful anionic surfactants 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.

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 C ₁₀ -C ₂₀ alkyl component, more preferably a

C ₁₂ -C ₁₈ 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. Further examples anionic surfactants include alkyl- diphenyl-ethersulphonates and alkyl-carboxylates. 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 ₂ O linear alkylbenzenesulfonates, C ₆ -C ₂₂ primary or secondary alkanesulfoiiates, 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 (containing up to 10 moles of ethylene oxide); alkyl ester sulfates such as C _14-16 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 C ₁₂ -C ₁₈ monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C ₆ -C ₁₄ diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formula RO(CH ₂ CH ₂ O) _IC CH ₂ COO-M ⁺ wherein R is a C ₈ -C ₂₂ alkyl, k is an integer from 0 to 25, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Other anionic surfactants, although not particularly elucidated herein may also be considered for use in the present inventive compositions.

Exemplary nonionic surfactants which may find use in the present invention include known art nonionic surfactant compounds. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration

product thereof, polyethylene glycol, to form a water soluble nonionic surfactant compound. Further, the length of the polyethylenoxy hydrophobic and hydrophilic elements may various. Exemplary nonionic compounds include the polyoxyethylene ethers of alkyl aromatic hydroxy compounds, e.g., alkylated polyoxyethylene phenols, polyoxyethylene ethers of long chain aliphatic alcohols, the polyoxyethylene ethers of hydrophobic propylene oxide polymers, and the higher alkyl amine oxides.

Illustrative examples of suitable nonionic surfactants include, inter alia, condensation products of alkylene oxide groups with an organic hydrophobic compound, such as an aliphatic compound or with an alkyl aromatic compound. The nonionic synthetic organic detergents generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water soluble nonionic detergent. Further, the length of the polyethenoxy hydrophobic and hydrophilic elements may be varied to adjust these properties. Illustrative examples of such a nonionic surfactants include the condensation product of one mole of an alkyl phenol having an alkyl group containing from 6 to 12 carbon atoms with from about 5 to 25 moles of an alkylene oxide. Another example of such a nonionic surfactant is the condensation product of one mole of an aliphatic alcohol which may be a primary, secondary or tertiary alcohol having from 6 to 18 carbon atoms with from 1 to about 10 moles of alkylene oxide. Preferred alkylene oxides are ethylene oxides or propylene oxides which may be present singly, or may be both present.

Still further illustrative examples of nonionic surfactants include primary and secondary linear and branched alcohol ethoxylates, such as those based on C ₆ -Ci _S alcohols which further include an average of from 2 to 80 moles of ethoxylation per mol of alcohol. Examples include the Genapol® series of linear alcohol ethoxylates from Clariant Corp., Charlotte, NC. Further examples of useful nonionic surfactants include secondary C ₁₂ -Cj ₅ alcohol ethoxylates, including those which have from about 3 to about 10 moles of ethoxylation. Such are available in the Tergitol® series of nonionic surfactants (Dow Chemical, Midland, MI), particularly those in the Tergitol® "15-S-"

series. Further exemplary nonionic surfactants include linear primary Ci ₁ -C ₁₅ alcohol ethoxylates, including those which have from about 3 to about 10 moles of ethoxylation. Such are available in the Tomadol® (ex. Tomah Inc.) series of nonionic surfactants. Yet further examples of useful nonionic surfactants include C ₆ -Ci ₅ straight chain alcohols ethoxylated with about 1 to 13 moles of ethylene oxide, particularly those which include about 3 to about 6 moles of ethylene oxide. Examples of such nonionic surfactants include Alfonic® 810-4.5, which is described as having an average molecular weight of 356, an ethylene oxide content of about 4.85 moles and an HLB of about 12; Alfonic® 810-2, which is described as having an average molecular weight of 242, an ethylene oxide content of about 2.1 moles and an HLB of about 12; and Alfonic® 610-3.5, which is described as having an average molecular weight of 276, an ethylene oxide content of about 3.1 moles, and an HLB of 10.

Further examples of suitable nonionic surfactants 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., glycosides or polyglycosides. 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. Commercially available examples of these surfactants include decyl polyglucoside (available as APG 325 CS from Henkel) and lauryl polyglucoside (available as APG 600 CS and 625 CS from Henkel). Further useful nonionic surfactants aree ethoxylated octyl and nonyl phenols. Particularly suitable non-ionic ethoxylated octyl and nonyl phenols include those having from about 7 to about 13 ethoxy groups. Such compounds are commercially available under the trade name Triton® X (Dow Chemical, Midland, MI), as well as under the tradename Igepal® (Rhodia, Princeton, NJ). One exemplary and particularly preferred nonylphenol ethoxylate is Igepal® CO-630. Still further examples of suitable nonionic surfactants are 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.

Further nonionic surfactants, although not particularly elucidated herein may also be considered for use in the present inventive compositions.

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

where at least one OfR ₁ , R ₂ , R ₃ and R ₄ is a alkyl, aryl or alkylaryl substituent of from 6 to 26 carbon atoms, and the entire cation portion of the molecule has a molecular weight of at least 165. The alkyl substituents may be long-chain alkyl, long-chain alkoxyaryl, long- chain alkylaryl, halogen-substituted long-chain alkylaryl, long-chain alkylphenoxyalkyl, arylalkyl, etc. The remaining substituents on the nitrogen atoms other than the abovementioned alkyl substituents are hydrocarbons usually containing no more than 12 carbon atoms. The substituents Ri, R ₂ , R ₃ and R ₄ may be straight-chained or may be branched, but are preferably straight-chained, and may include one or more amide, ether or ester linkages. The counterion X may be any salt-forming anion which permits water solubility of the quaternary ammonium complex.

Exemplary quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like. Other suitable types of quaternary ammonium salts include those in which the molecule contains either amide, ether or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl

ammonium chloride, N-(laιιrylcocoaminofomiylmethyl)-pyridinium chloride, and the like. Other very effective types of quaternary ammonium compounds which are useful as germicides include those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenzyltrimethyl ammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like.

Preferred quaternary ammonium compounds which act as germicides and which are be found useful in the practice of the present invention include those which have the structural formula:

wherein R ₂ and R ₃ are the same or different C ₈ -C ₁₂ alkyl, or R ₂ is C _12- i ₆ alkyl, Cg- ₁₈ alkylethoxy, C _8-18 alkylphenolethoxy and R ₃ is benzyl, and X is a halide, for example chloride, bromide or iodide, or is a methosulfate anion. The alkyl groups recited in R ₂ and R ₃ may be straight-chained or branched, but are preferably substantially linear.

Particularly useful quaternary germicides include compositions which include a single quaternary compound, as well as mixtures of two or more different quaternary compounds. Such useful quaternary compounds are available under the BARD AC®, B ARQUAT®, HYAMINE®, LONZABAC®, and ONYXIDE® trademarks, which are more fully described in, for example, McCutcheon's Functional Materials (Vol. 2), North American Edition, 1998, as well as the respective product literature from the suppliers identified below. For example, BARD AC® 205M is described to be a liquid containing alkyl dimethyl benzyl ammonium chloride, octyl decyl dimethyl ammonium chloride; didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (also available as 80% active (BARDAC® 208M)); described generally in McCutcheon's as a combination of alkyl dimethyl benzyl ammonium chloride and dialkyl dimethyl ammonium chloride); BARDAC® 2050 is described to be a combination of

octyl decyl dimethyl ammonium chloride/didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (also available as 80% active (BARD AC® 2080)); BARDAC ® 2250 is described to be didecyl dimethyl ammonium chloride (50% active); BARDAC® LF (or BARDAC® LF-80), described as being based on dioctyl dimethyl ammonium chloride (BARQUAT® MB-50, MX-50, OJ-50 (each 50% liquid) and MB-80 or MX-80 (each 80% liquid) are each described as an alkyl dimethyl benzyl ammonium chloride; BARDAC® 4250 and BARQUAT® 4250Z (each 50% active) or BARQUAT® 4280 and BARQUAT 4280Z (each 80% active) are each described as alkyl dimethyl benzyl ammonium chloride/alkyl dimethyl ethyl benzyl ammonium chloride. Also, HY AMINE® 1622, described as diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride (50% solution); HYAMINE® 3500 (50% actives), described as alkyl dimethyl benzyl ammonium chloride (also available as 80% active (HYAMINE® 3500-80)); and HYMAINE® 2389 described as being based on methyldodecylbenzyl ammonium chloride and/or methyldodecylxylene-bis-trimethyl ammonium chloride. (BARDAC®, BARQUAT® and HYAMINE® are presently commercially available from Lonza, Inc., Fairlawn, New Jersey). BTC® 50 NF (or BTC® 65 NF) is described to be alkyl dimethyl benzyl ammonium chloride (50% active); BTC® 99 is described as didecyl dimethyl ammonium chloride (50% acive); BTC® 776 is described to be myrisalkonium chloride (50% active); BTC® 818 is described as being octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (available also as 80% active (BTC® 818-80%)); BTC® 824 and BTC® 835 are each described as being of alkyl dimethyl benzyl ammonium chloride (each 50% active); BTC® 885 is described as a combination of BTC® 835 and BTC® 818 (50% active) (available also as 80% active (BTC® 888)); BTC® 1010 is described as didecyl dimethyl ammonium chloride (50% active) (also available as 80% active (BTC® 1010-80)); BTC® 2125 (or BTC® 2125 M) is described as alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl ethylbenzyl ammonium chloride (each 50% active) (also available as 80% active (BTC® 2125 80 or BTC® 2125 M)); BTC® 2565 is described as alkyl dimethyl benzyl ammonium chlorides (50% active) (also available as 80% active (BTC® 2568)); BTC® 8248 (or BTC® 8358) is described as alkyl dimethyl benzyl ammonium chloride

(80% active) (also available as 90% active (BTC® 8249)); ONYXIDE® 3300 is described as n-alkyl dimethyl benzyl ammonium saccliarinate (95% active). (BTC® and ONYXIDE® are presently commercially available from Stepan Company, Northfield, Illinois.) Polymeric quaternary ammonium salts based on these monomelic structures are also considered desirable for the present invention. One example is POLYQUAT®, described as being a 2-butenyldimethyl ammonium chloride polymer.

Preferred cationic surfactants which are particularly suited for use in the pulverent compositions are and B ARQU AT® MS-100 described as being alkyl dimethyl benzyl ammonium chloride, as well as HYAMINE® 1622, described as diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, both of which are availablein a solid, or powdered form containing 100% actives of the specific cationic surfactant.

Further cationic surfactants, although not particularly elucidated herein may also be considered for use in the present inventive compositions.

Non-limiting examples of exemplary useful amphoteric surfactants include alkylbetaines, particularly those which may be represented by the following structural formula:

RN(CHa) ₂ CH ₂ COO ^" wherein R is a straight or branched hydrocarbon chain which may include an aryl moiety, but is preferably a straight hydrocarbon chain containing from about 6 to 30 carbon atoms. Further exemplary useful amphoteric surfactants include amidoalkylbetaines, such as amidopropylbetaines which may be represented by the following structural formula:

RCONHCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ COO- wherein R is a straight or branched hydrocarbon chain which may include an aryl moiety, but is preferably a straight hydrocarbon chain containing from about 6 to 30 carbon atoms. Exemplary betaines include dodecyl dimethyl betaine, cetyl dimethyl betaine, dodecyl amidopropyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine, and dodecyldimethylammonium hexanoate.

Further amphoteric and zwitterionic surfactants, although not particularly elucidated herein may also be considered for use in the present inventive compositions.

Preferably the surfactant constituent is provided as an essentially anhydrous or non-hydroscopic composition which is readily dispersible in water, particularly in combination with the gas generator system when these are combined and contacted with water. Preferred surfactants which may be used in the inventive compositions are sarcosinate surfactants which are alkali metal salts of N-alkyl-N-acyl amino acids. These are salts derived from the reaction of (1) N-alkyl substituted amino acids of the formula:

R ₁ -NH-CH ₂ -COOH where R ₁ is a linear or branched chain lower alkyl of from 1 to 4 carbon atoms, especially a methyl, for example, aminoacetic acids such as N-methylaminoacetic acid (i.e. N- methyl glycine or sarcosine), N-ethyl-aminoacetic acid, N-butylaminoacetic acid, etc., with (2) saturated natural or synthetic fatty acids having from 8 to 18 carbon atoms, especially from 10 to 14 carbon atoms, e.g. lauric acid, and the like.

The resultant reaction products are salts which may have the formula:

where M is an alkali metal ion such as sodium, potassium or lithium; R ₁ is as defined above; and wherein R ₂ represents a hydrocarbon chain, preferably a saturated hydrocarbon chain, having from 7 to 17 carbon atoms, especially 9 to 13 carbon atoms of

O

the fatty acyl group ² Exemplary useful sarcosinate surfactants include cocoyl sarcosinate, lauroyl sarcosinate, myristoyl sarcosinate, palmitoyl sarcosinate, stearoyl sarcosinate and oleoyl sarcosinate, and tallow sarcosinate. Such materials are also referred to as N-acyl sarcosinates.

A preferred surfactant for use in the surfactant constiuent is an anhydrous sarcosinate which is commercially available as Crodasinic® LF95, which is described by it supplier to be sodium lauryl sarcosinate.

Preferred for use herein are alkali metal or ammonium salts of sarcosinate surfactants.

The surfactant constituent may be present in any effective amount, however it is preferred that the total amount of any surfactants present be in the range of from about 0.01 - 10%wt, preferably from about 0.01 - 5%wt, and most preferably from about 0.5 - 3%wt. based on the total weight of the pulverent compositions of which they form a part. With respect to the surfactants which find use in the inventive compositions, it is to be realized that while any surfactant is contemplated to be useful, conveniently surfactants which are substantially anhydrous are most conveniently used as they can be readily used in a dry blending or dry mixing operation. However, surfactants which are supplied in a liquid carrier or medium may also be used, particularly if they are first applied to some of the components used to produce the pulvurent compositions, conveniently as a premixture which is formed prior to the final mixing operation or step(s) used to form the inventive compositions. For example, such surfactants supplied in a liquid carrier medium may be first mixed, or sprayed onto the alkali constituent, e.g., sodium bicarbonate, and optionally further on any anti-caking materials, e.g., sodium sulfate which may be used. Such will permit the surfactant to be absorbed or adsorbed onto such materials. Preferably thereafter this premixture is allowed to dry prior to addition to the remaining constituents used to form the pulvurent compositions. Of course such surfactants may be applied to other of the constituents of the pulvurent compositions it only being required that the surfactant is substantially non-reactive with such constituent or constituents used for form the premixture. When the formation of a premixture is necessary or convenient, the use of surfactants having lower proportion of liquid carriers to the surfactant are preferred, as less water or other liquid carrier need be absorbed or adsorbed.

In accordance with certain preferred embodiments, pulvurent compositions of the invention include one more sarcosinates in the surfactant constituent, optionally with one or more further surfactants described herein, hi accordance with certain particularly preferred embodiments of the pulvurent compositions of the invention, the sole surfactants of the surfactant constituents are one or more sarcosinates.

The compositions of the present invention can also optionally comprise one or more further constituents which are directed to improving the aesthetic or technical features of the inventive compositions. Such conventional additives known to the art include but not expressly enumerated here may also be included in the compositions according to the invention. By way of non-limiting example without limitation these may include : anti-caking constituents, colorants, fragrances, fillers, dilutents as well as one or more further materials not noted previously. Many of these materials are known to the art, per se, and are described in McCutcheon 's Detergents and Emulsifiers, North American Edition, 1998; Kirk-Othmer, Encyclopedia of Chemical Technology, 4th Ed., Vol. 23, pp. 478-541 (1997. Such optional, i.e., non-essential constituents should be selected so to have little or no detrimental effect upon the desirable characteristics of the present invention. When present, the one or more optional constituents present in the inventive compositions do not exceed about 20%wt, preferably do not exceed 15%wt., of the pulverent composition of which they form a part. Preferred compositions of the invention are pulverent compositions which are generally dry free flowing powders with minimal or no tendency to agglomerate or clump. Any such clumps which may form are generally readily broken up by manually lightly striking such a clump. Preferred compositions of the invention are pulverent compositions bulk density 1 - 1.4, more preferably exhibit a bulk density of 1 - 1.2. The addition of one or more anti-caking constituents may improve the dry flow characteristics of the pulverent compositions being taught herein. In certain compositions, such anti-caking constituents are optional constituents, in other and in certain preferred embodiments one or more anti-caking constituents are essential constituents. In order to adjust the bulk density of the pulverent compositions it is frequently advantageous to add one or more anti-caking constituents which may be based on water insoluble particulate materials, or which may be water soluble materials in powder or particulate form. The addition of such anti-caking constituents may, depending upon their size, shape and density may be used to adjust the bulk density and the flow properties of the pulverent to specific value or to a specific range of values. The addition of one or

more such anti-caking constituents frequently is advantageous in improving the dry flow characteristics of the pulverent compositions.

By way of non-limiting example, useful anti-caking constituents include water insoluble solid particulate materials. Exemplary water insoluble solid particulate materials include inorganic solid particles such as silica particles including colloidal silicas, fumed silicas, precipitated silicas and silica gels. Non-limiting examples of colloidal silicas include Snowtex C, Snowtex O, Snowtex 50, Snowtex OL, Snowtex ZL available from Nissan Chemical America Corporation and colloidal silicas sold under the tradename Ludox available from W.R. Grace & Co. Non-limiting examples of fumed silicas include hydrophilic and hydrophobic forms available as Aerosil 130, Aerosil 200, Aerosil 300, Aerosil R972 and Aerosil R812 available from Degussa Corp. and those available from Cabot Corp. under the trade name Cab-O-Sil including Cab-O-Sil M-5, HS-5, TS-530, TS-610, and TS-720. Non-limiting examples of precipitated silicas include those available in both hydrophilic and hydrophobic versions from Degussa Corp. under the trade name Sipenat including Sipernat 350, 360, 22LS, 22S, 320, 5OS, DlO,

DIl, D17, and C630; those sold by W.R. Grace & Co. under the trade name Syloid, those sold by the J.M. Huber Corp. under the tradename Zeothix and Zeodent, and those available from Rhodia under the trade name Tixosil. Also useful in the present invention are spherical silica solid particles available in various particle sizes and porosities. Non limiting examples of spherical silica solid particles include MSS-500/H, MSS-500/3H, MSS-500, MSS-500/3, MSS-500/N and MSS-500/3N available from KOBO Products Inc.; those available from Presperse Inc. under the trade name Spheron including Spheron P-1500 and L-1500, and those available from Sunjin Chemical Co. under the trade name Sunsil including Sunsil 20, 2OL, 2OH, 5OL, 50, 5OH, 130L, 130 and 130H. Calcium carbonate may also be used, as well as any other water insoluble carbonates or borates which are available as water insoluble solid particulate materials.

The anti-caking constituents may also be one or more water soluble materials in powder or particulate form. Exemplary materials of this type include any soluble inorganic alkali, alkaline earth metal salt or hydrate thereof which however is not used in the gas generator system, including, e.g. chlorides such as sodium chloride, magnesium chloride and the like, sulfates such as magnesium sulfate, copper sulfate, sodium sulfate,

zinc sulfate and the like, borax, borates such as sodium borate and the like, as well as others similar materials known to the art but not particularly recited herein. Sodium sulfate is particularly preferred for use as water soluble anti-caking material as it readily dissolves and has little effect on the pH of the water containing the pulvurent composition when it is dissolved. When present the anti-caking constituent is present in an amount of from about 0.001 - 25%wt, preferably from 0.01 - 15%wt., based on the total weight of the pulverent composition of which it forms a part. When included, one or more such water insoluble solid particulates may be present in any effective amount in order to adjust the bulk density and or the dry flow characteristics of the pulverent compositions of which they form a part.

The inventors have found that advantageously the acid constituent of the gas generator system may be formed into a premixture or preblend with a hydrophilic water insoluble solid particulate materials, e.g, a silica based water insoluble solid particulate material which has observed to provide a degree of occlusion or coating to the acid constituent. Such may be advantageous especially with the use of a hygroscopic acid constituent, e.g., citric acid, as the hydrophilic water insoluble solid particulate material will absorb water such as water in humid air to a great degree thus improving the overall storage stability of the pulverent compositions. The inventors have additionally found that the inclusion of even a minor amount of hydrophobic water insoluble solid particulate materials is also advantageously present, particularly when both hydrophilic water insoluble solid particulate materials are also present as the hydrophobic water insoluble solid particulate materials, even in minor amounts, helps to reduce clumping or caking of the pulverent compositions. Thus, advantageously both a hydrophobic precipitated silica and a hydrophilic precipitated silica are included in accordance with preferred embodiments of the pulverent compositions, particularly when the former is present with respect to the latter in %wt:%wt. ratios of 1:1-10, preferably 1:3-10, more preferably 1:5-10.

The pulverent compositions of the invention optionally but in certain cases desirably includes 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 maybe 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 Hs) _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 determine whether such a proprietary fragrance composition is compatible in the pulverent compositions of the present invention.

Advantageously when a fragrance composition is incorporated into the pulverent compositions it is either supplied in a powdered form, e.g., FIRCRYST (ex. Firmenich) which includes solid phase fragrance compositions, or may be supplied as a liquid composition. Advantageously when supplied as a liquid composition the fragrance composition is either first adsorbed or absorbed , e.g, by spraying onto a pulverent carrier material such as a silica, fumed silica, or zeolite and thereafter supplied as a component to the pulverent compositions of the invention. Alternately and similarly advantageously when the fragrance composition is supplied as a liquid composition it is adsorbed or absorbed onto one of the other constituents used to form the inventive compositions, either during or preferably prior to mixing of the constituents together to form the inventive compositions.

When included, the fragrance composition may be present in any effective amount. Advantageously the fragrance composition comprises up to 3%wt., more preferably from 0.001 - 2%wt. based on the total weight of the pulverent compositions of which they form a part.

Optionally but in some cases advantageously the pulverent compositions of the invention include a colorant, which may be one or more dyes adsorbed or absorbed onto a pulvurent carrier material such as described above with reference to the fragrance composition, or which may be one or various organic and inorganic pigments. The organic pigments are generally various aromatic types including azo, indigoid, triphenylmethane, anthraquinone, and xanthine dyes which are designated as D&C and FD&C blues, browns, greens, oranges, reds, yellows, etc. Exemplary organic pigments generally consist of insoluble metallic salts of certified color additives formed from dyestuff "lakes" Exemplary inorganic pigments include iron oxides, ultramarine and chromium or chromium hydroxide colors, and mixtures thereof.

When included, the colorant may be present in any effective amount. Advantageously the colorant comprises up to 3%wt, more preferably from 0.001 — 2%wt. based on the total weight of the pulverent compositions of which they form a part.

The pulverent compositions may be formed by dry blending of the constituent using conventional apparatus in order to provide a homogenous physical blend of the constituents. Optionally, when a fragrance constituent is used it is first adsorbed or absorbed onto a pulverent carrier material in a separate premix or preblend, and subsequently added to the remaining constituents used to form the pulverent compositions.

The pulverent compositions are conveniently packaged into recloseable containers which permit for the convenient removal of measured quantities of the compositions just prior to their use. A resealable tub or jar with a sealable lid is one form of a recloseable container useful with the pulverent compositions. Preferably the recloseable container can be sufficiently sealed to provide a vapor barrier between the contents of the container and the ambient environment so to minimize the exposure of the pulverent compositions to humid ambient air.

The pulverent compositions are particularly useful in the cleaning of hard surfaces. 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 pulverent compositions are particularly useful in the treatment of toilets, particularly toilet bowls. In use, a quantity of the pulverent composition is supplied to the water at the bottom of the toilet bowl, and almost immediately the gas generator system contacting the water initiates a rapid and pronounce effervescence causing the formation of a volume of foam which rises upward from the surface of the water in the bottom of the toilet bowl. According to preferred embodiments this rising foam is quickly generated and fills a substantial volume of the headspace within the toilet bowl above the level of the water. According to preferred embodiments the foam height above

water level of the bowl is at least 5 cm above the level of water in the toilet bowl in 30 seconds subsequent to the addition of at least 120 grams of the pulverent composition to the toilet bowl water. Of course, depending upon the geometry and configuration of the toilet bowl and the amount of the pulvurent composition dosed, the foam height may be lesser or greater than the above.

Additionally it is contemplated that the pulvurent composition may be supplied to the upper supply tank or cistern of the toilet, wherein it is permitted to react with the water contained therein.

It is also contemplated that the pulvurent compositions may also be compacted into monolithic shapes, e.g, tablets, bars, etc., by conventional means, e.g, tabletting presses, and the like. Such monolithic shaped forms of the pulvurent composition provide for more controlled dosing and easier handling by the use of the compositions.

The rapid foaming effect is particularly attractive from a consumer standpoint in that the rapid rate of foam generation and volume of foam generated with the headspace provides an indicia of good product performance. Additionally the rapid rate of foam generation and volume of foam generated with the headspace ensures that the foam also functions as a delivery carrier medium for the surfactant constituent ensuring that the interior surfaces of the bowl contacted by the foam are also concurrently contacted by the surfactant constituent comprised in the pulverent compostion. Even when the composition is provided to the toilet supply tank or cistern, the durability of the foam formed is often sufficient such that visible foam is perceived following several flushes, particularly wherein the contents of the toilet supply tank or cistern are not substantially emptied, e.g. "low volume" toilets which normally used only several liters, e.g., about 6 liters or less per flush cycle. This permits for part of the dissolved pulvurent composition to be retained in the toilet supply tank or cistern between flushes.

The pulverent compositions may also be supplied to other vessels other than toilets, e.g., basins, bowls, buckets, mop buckets and the like containing a quantity of water. In such other vessels, a similar effervescent effect and product performance is also expected. hi order to further illustrate the present invention, various examples including preferred embodiments of the invention are described amongst the examples, rn these

examples, as well as throughout the balance of this specification and claims, all parts and percentages are by weight unless otherwise indicated.

Examples: Exemplary pulverent compositions according to the invention were produced by dry blending measured amounts of specific constituents by use of a conventional laboratory tumble blender for dry powdered materials. Where necessary one more surfactants may be preblended with part or all of the alkali constituent, e.g., sodium bicarbonate and then allowed to dry. In certain examples a fragrance constituent, supplied as a liquid composition may have been absorbed or adsorbed onto a pulverent carrier material prior to addition to the constituents. Although the order of addition is usually not critical, in the formation of the examples of Table 1, the acid constituent, sodium sulfate and any hydrophilic materials were first supplied to the blender and allowed to mix about 15 minutes until the blend was homogenous in appearance. Next, the remaining constituents were added, and dry blending was resumed a further 15 minutes until the final pulverent power composition was homogenous in appearance. Typically the total blending time will vary upon the size and type of the mixing equipment used, and the quantity of the materials to be mixed or blended. It is only required that the blending until a pulverent composition having a well mixed, generally homogenous appearance is produced.

Exemplary pulverent compositions are described on the following Table 1; the amounts of each constituent in each formulation is reported in weight percent and as all constituents were provided in anhydrous form, or in the case of certain fragrance constituents which were rendered into a powered form, each of the constituents are presumed to be 99%-100%wt. actives. The total amount of each formulation formed was 100%wt.

M M

The identity of the constituents used to form the compositions of Table 1 are identified more specifically on the following Table 2.

The compositions were tested for cleaning as well as for antimicrobial efficacy.

Antimicrobial Efficacy:

Samples of the pulverent compositions described on Table 1 were evaluated for antimicrobial efficacy against several challenge organisms according to the protocols outlined in British Standard EN 13697:2001 for Chemical disinfectants and antiseptics - Quantitative non-porous surface test for the evaluation of bactericidal and/or fungicidal activity of chemical disinfectants used in food, industrial, domestic and institutional areas - Test method and requirements without mechanical action (phase2/step 2).

This test method utilizes 4 bacteria {Staphylococcus aureus, ATCC 6538; Escherichia coli, ATCC 10536; Enterococcus hirae, ATCC 10541, and Ps eudomonas

aeruginosa, ATCC 15542) to demonstrate bactericidal activity on a test hard surface (i.e. 2cm diameter stainless steel discs).

Bacterial cultures were grown on agar medium and harvested after the appropriate incubation and transfer series. The initial inoculum was adjusted to the required levels (1.5 - 5.0 x 10 ⁸ organisms / mL for bacteria, 1.5 - 5.0 x 10 ⁷ organisms / mL for fungi). Testing was performed at a temperature of 20°C ± I ⁰ C . At least 2 minutes before the start of the test, 1 mL of each adjusted test culture was added to 1 mL of interfering substance (i.e. 0.06% Bovine Albumin for "clean" conditions; 0.6% Bovine Albumin for "dirty" conditions). For each test organism, two test surfaces (replicates, or "Rep" in the following tables) were inoculated with 0.05 mL (50 μL) of the test organism / bovine albumin mixture. The challenge microorganism was spread over the surface of the disc, and allowed to dry for up to one hour at 37 ⁰ C. After drying, 0.ImL of the test substance was placed onto the test surface, ensuring that the dried inoculum was totally covered by the test substance. After a contact time of 5 minutes, the treated disc was subcultured into a test tube containing 10 mL of neutralization media and 5 grams of sterile glass beads. The disc was agitated (shaker or vortex) to remove any surviving organism with the glass beads. Serial dilutions were performed, and the appropriate dilutions were plated. The above procedure was also performed for a control substance, namely sterile hard water. The test materials were incubated at 37 ⁰ C for over two nights. The agar plates were counted, and the number of organisms surviving on each disc was calculated. Log ₁₀ values of these recoveries were determined. A neutralization assay was also performed for each test organism to demonstrate the neutralization of the active ingredient at the contact time. A reduction in viability was calculated for each test substance replicate by subtracting the Logio recovery value of the test substance from the Log ₁₀ recovery value of the control substance replicate for each challenge microorganism. In order to be assigned a "PASS" score per this test, a > 4 log reduction must be achieved for each of the 4 bacteria to demonstrate bactericidal activity on surfaces.

Several example formulations from Table 1 were tested at a 1:15 (vol/vol) dilution formed by combining 1 part (volume) to 14 parts (volume) deionized water and allowing the pulvurent composition to form a foam then subside prior to antimicrobial testing. The resulting pH's of the tested compositions was approximately 5. The testing

was performed at 2O ⁰ C (±1°C), for 5 minute contact times against the four test bacteria according to EN 13697:2001 under "clean conditions" as denoted above; plural replicates were tested. The results are reported on following Tables A - D.

As may be seen from the results indicated above, the inventive composition exhibits good antimicrobial efficacy against several known microorganisms commonly found in lavatory, kitchen and other environments, albeit in certain instances at levels which were effective although unsatisfactory to meet the high standards of the British Standard EN 13697:2001 scoring protocol. However, hi each test the compositions of the invention consistently demonstrated a > 2 log reduction against all tested bacteria.

Surprisingly the composition of E3 which included a quaternary ammonium surfactant having germicidal properties scored poorly or worse than comparable compositions which included only the sodium lauryl sarcosinate surfactant.

Cleaning:

A sample according to E4 of Table 1 was tested for its cleaning efficacy of against a prior art liquid toilet bowl cleaning composition, HARPIC Active Cleaning Gel (ex. Reckitt Benckiser pic, UK) and Kaboom "Bowl Blaster", a powdered toilet bowl cleaner (ex. Orange GIo International Inc.).

First a series of 11 standard white test toilet bowls were carefully cleaned using a highly acidic toilet bowl cleaning composition using a brush, and thereafter flushed sufficient times to remove any visual residues on the interior bowl surfaces. A wet vacuum or pump was then used to withdrawl all water remaining at the bottom of each toilet bowl. Next, a 10 grams of a sample standardized fecal soil, "Feclone 14-Brown") was painted onto the interior surfaces of all but one of the toilet bowls in a uniform

thickness and in a uniform pattern of coverage for each of the toilet bowls, and thereafter allowed to dry. Subsequently the water at the bottom of each toilet was replenished by flushing each toilet once. The one toilet which was untreated with the sample standardized fecal soil was used as a "clean control" toilet bowl.

Thereafter three 120 grams samples of each test product were prepared for use, providing nine total samples to be used for cleaning 9 toilets. One of the toilets treated with the sample standardized fecal soil was not treated further and was used as a "dirty control" toilet bowl. The remaining 9 toilets were used in the test.

Subsequently the samples of each of test products were supplied to different toilet bowl. The two powdered compositions, E4 and Bowl Blaster were poured directly to the water in the toilet bowl. The 120 gram sample of the HARPIC liquid composition was approximately equally evenly distributed beneath the rim of the toilet bowl and allowed to run down the inclined interior sidewall of the toilet bowl. The products were allowed to act undisturbed for 60 seconds following application. Thereafter a nylon bristled toilet cleaning brush was then manually applied in a circular motion around the inclined interior sidewall of the toilet bowl using constant pressure for 15 seconds, and then the toilet was flushed once. This was repeated for each of the 9 toilets.

Subsequently 20 test subjects were asked to rate the degree of cleanliness of each of the toilets on a scale of 1 to 9, with the "clean control" toilet bowl being established as a scale score of "9", and with the "dirty control" toilet bowl being established as a scale score of "1". The recorded scoring results of the 20 test subject was tallied and statistically evaluated at an at least 95% confidence level. The results of the test were as follows:

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