AU669151B2 - A cleaning formulation - Google Patents

Description

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AUSTRALIA

PATENTS ACT 1990 66 3 1 COMPLETE SPECIRCATION FOR A STANDARD PATENT

ORIGINAL

I I I Name and Address of Applicant: Actual Inventor(s): Address for Service: Invention Title: So-Safe Speciality Products Pty. Ltd.

Chard Road Brookvale New South Wales 2100

AUSTRALIA

Michael Jeffrey Hunter Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia A Cleaning Formulation

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ASSOCIATED PROVISIONAL APPLICATION DETAILS [31] Application No(s) [33] Country PL1024 AU [32] Application Date 21 February 1992 The following statement is a full description of this invention, including the best method of performing it known to me/us:- 5815/3 i_ i 1 TECHNICAL FIELD This invention relates to cleaning formulations, processes for their preparation and methods for cleaning glassware and a beer line.

BACKGROUND ART The formulations used for cleaning an apparatus such as a beer line or an apparatus made of glass, contain compounds which are scheduled as poisons. Products sold in the market for an apparatus made of glass, which rely simply on surfactants, are ineffective at removing lipstick and create corrosion problems and are unlikely to be compatible in hard water.

In an apparatus such as a beer line, an alkali/peroxide solution has been used in the past to clean beer lines. The alkali usually acts as a detergent in the lines, while the peroxide bleaches the lines so that they appear clean, by removing any discolouration from the interior surface of the lines. The alkali is commonly sodium or potassium hydroxide the peroxide is commonly hydrogen peroxide. Beer is often served as draught beer from kegs. Beer lines connect the kegs to the bar area. On a regular basis, generally once a week, the beer lines must be cleaned, in order that the quality and taste of the beer is not adversely affected. Also, the lines must be kept clean for general health reasons. The lines will normally extend from the keg to the beer tap at the bar. The lines are generally constructed from flexible plastic for much of their length, but various fittings such as the tap, and the valve which taps the keg are constructed from other materials such as brass, stainless steel and so forth.

s In general, beer line cleaning formulations should have no organic odour and ,should not decompose, become rancid or lose efficiency before at least 12 months when stored at ambient temperatures. The cleaning formulation should be stable to oxidation.

S 25 The detergent should not contain hypochlorite or available chlorine in any form other than trace amounts, or any other halogen compounds. The cleaning formulation should prevent the formation of scale build-up in beer drawing equipment. The cleaning solution should be safe in case of accidental ingestion, and for example should be safe as a one in *ten solution in beer, as a quantitative determination of health hazard or accidental 30 ingestion. The cleaning formulation should also have no harmful effects on the beer drawing equipment, and should not be appreciably corrosive to metal or plastic parts, and should also not cause staining, discolouration, pitting, and so forth. The cleaning *composition should be free from abrasives, which in quantitative terms means insoluble matter at the recommended concentrations should not exceed 0.05% w/v.

For use in cleaning beer lines, the known cleaning formulations had an initial pH of between 8 and 13. The pH was important because to purge the detergent from the beer lines, carbon dioxide was generally used, which affects the pH value, and the pH of the cleaning solution was not to fall below 6.

i (V 2 In the past, the known beer line cleaning formulations were found to have a corrosive effect on the beer lines after continuous use for a long period. The corrosion occurs particularly on metal fittings, and especially on brass and copper fittings.

There is a need for a cleaning formulation which is a safer alternative to the currently marketed products and which does not create corrosion problems and is likely to be compatible in hard water.

OBJECTS OF INVENTION It is an object of this invention to provide a formulation for cleaning an apparatus such as a beer line or an apparatus made of glass which will not be classified as a dangerous good.

Another object is to provide a formulation for cleaning an apparatus such as a beer line or an apparatus made of glass which does not create corrosion problems and which will be compatible in hard water.

A further object is to provide a process for preparing the formulations.

Another object is to provide a method of cleaning glassware and another object is to provide a method of cleaning a beer line using the formulations.

DISCLOSURE OF INVENTION As used throughout the specification and claims the term "apparatus" refers to any apparatus made of glass or metal or plastic.

The present inventor has unexpectedly found a formulation for cleaning an apparatus which is not classified as a dangerous good and is a safer alternative to the currently marketed products. The inventor has also found that the formulation is effective for glass cleaning or beer line cleaning.

According to a first embodiment of this invention there is provided a cleaning formulation for cleaning an apparatus comprising: 0.5-98.98wt% "emianolamine, diethanolamine, triethanolamine or a mixture thereof; 0.01-15wt% water softener; and 0.01-10wt% corrosion inhibitor.

30 Typically a solvent is selected which is of low flammability and toxicity.

Examples of organic solvents include monoethanolamine, diethanolamine, triethanolamine, or other like solvents or mixtures thereof. Preferably monoethanolamine is used. Generally 5-75 wt% monoethanolamine is used in the formulations of the invention. Usually 6.36-i50wt% monoethanolamine is used in the formulation of the first 35 embodiment.

A salt solution may also be added to the formulations of the invention. Examples of salt solutions include solutions of lithium chloride, lithium bromide, lithium iodide, sodium chloride, potassium chloride or mixtures thereof.

SRA4 I |l I^^fj i 3 The water softener is generally selected from anionic surfactants, nonionic surfactants, cationic surfactants or amphoteric surfactants.

The anionic surfactants may be selected from sulphonates, alkylbenzenesulphonates, alcohol sulphates, ethoxylated alcohol sulphates, sulphated alkylphenol ethoxylates, sulphated natural oils and fats, or phosphate esters. Examples of alkylbenzenesulphonates include dodecylbenzenesulphonate, tridecylbenzenesulphonate, or nonylbenzenesulphonate. Examples of alcohol sulphates include sodium lauryl sulphate, sodium 2-ethylhexyl sulphate, sodium 2-decyl sulphate, ammoniun lauryl sulphate, potassium lauryl sulphate, diethanolammonium lauryl sulphate, triethanolammonium sulphate, sodium octyl sulphate, sodium decyl sulphate, magnesium lauryl sulphate, or sodium tridecyl sulphate. Examples of ethoxylated alcohol sulphates include ethoxylated alcohol sulphates from C 12 -C15. Examples of sulphated natural oils and fats include animal, vegetable or fish oils. Examples of phosphate esters include butyl phosphate, hexyl phosphate, octyl phosphate, decyl phosphate, hexyl polyphosphate, octyl polyphosphate, sodium polyphosphate, or other phosphated and polyphosphated alcohols.

The nonionic surfactants may be selected from polyoxyethylene surfactants, polyoxyethylene esters, anhydrosorbitol esters, or ethoxylated anhydrosorbitol esters.

The cationic surfactants may be selected from 2-alkyl-l-(2-hydroxyethyl)-2imidazolines or quaternary ammonium 7'lts.

Typically the amount of water softener used in the formulations of this invention is 2-7.5 wt%. Generally amorphous sodium polyphosphate (Calgon T) is used as 3.6 wt% in the formulation of the first embodiment.

Generally the corrosion inhibitor may be selected from inorganic inhibitors, organic inhibitors or v-pour-phase inhibitors. Inorganic inhibitors may be classified as functioning with or without oxygen. Examples of inhibitors functioning without oxygen include chromate and nitrate, examples of inhibitors requiring oxygen include sodium phosphates and borates. Examples of inorganic inhibitors include citric acid, sodium citrate, sodium nitrate, ammonia and the like. Examples of organic inhibitors include aniline, substituted anilines, pyridine, butylamine, benzoic acid, substituted benzoic acids, 30 benzenesulphonic acid, petroleum sulphonates, phosphate esters, glycerol esters, diethanolamine condensates, monoalkanolamine condensates, aliphatic mono-, di-, and polyamines derived from fatty and rosin acids, amine ethoxylates, 2-alkyl-l-(2- Shydroxyethyl)-2-imidazolinesamide amines, tolytriazole, nonamethyleneimine, quinoline, substituted quinolines, thiourea, dihexylamine, tolualdehyde, diphenylurea, carbon 35 di "phide, allylthiourea, octadecylamine, hexadecylamine. Vapour-phase inhibitors are usually volatile compounds containing one or more functional groups capable of inhibiting corrosion. Examples of these inhibitors include amine salts with nitrous or chromic acids; amine salts with carbonic, carbamic, acetic, or substituted or unsubstituted benzoic acids; organic esters of nitrous, phthalic, or carbonic acids; primary, secondary, or tertiary I m nn n_ in 1 11 4 aliphatic amines; cycloaliphatic and aromatic amines; polymethylene amines; mixtures of nitrites with urea, urotropine, and ethanolamine; nitrobenzene and 1-nitronaphthalene.

Preferred corrosion inhibitors include nitrilotris phosphate (Dequest 2000), sodium gluconate, benzotriazole, or mixtures thereof. Typically a mixture of corrosive inhibitors is used. Typically the amount of corrosion inhibitor used in the formulations of the invention is 0.1-8 wt%. Usually the formulation of the first embodiment comprises 0.68- 3.42 wt% nitrilotris phosphate (Dequest 2000), 0.68-3.34 wt% sodium gluconate and 0.22-0.8 wt% benzotriazole.

The surfactant may be selected from anionic, cationic, amphoteric or nonionic surfactants having good emulsifying, cleaning, dispeising and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants. The surfactants may be combined but anionic and cationic surfactants are generally not used together because one precipitates the other. Either cationic or anionic may be used with nonionic and amphoteric. The surfactant may be a domestic or industrial detergent.

Suitable anionic surfactants can be both so-called water-soluble soaps and watersoluble synthetic surface-active compounds. Suitable soaps are the alkali metal salts, alkaline earth metal salts, salts of higher saturated and unsaturated C 8

-C

2 4 fatty acids or unsubstituted or substituted ammonium salts of higher fatty acids (C 10

-C

2 2 e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyllaurin salts.

More frequently, however, so-called synthetic surfactants are used, especially fatty alcohol sulphonates, fatty alcohol sulphates, sulphonated benzimidazole derivatives, alkyl sulphates or alkylsulphonates. The fatty alcohol sulphonates or sulphates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C 8

-C

24 alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulphonic acid, of dodecylsulphate or of a mixture of fatty alcohol sulphates obtained from natural fatty acids. These compounds also comprise the salts of sulphated and sulphonated fatty 30 alcohol/ethylene oxide adducts. Examples include ammonium lauryl sulphate, triethanolamine lauryl sulphate, alkylarene sulphonates, sodium lauryl sulphate and i sodium alkylsulphate. The sulphonated benzimidazole derivatives preferably contain 2 sulphonic acid groups and one fatty acid radical containing 8 to 24 carbon atoms.

Examples of alkylaryl-sulphonates are the sodium, calcium or triethanolamine salts of 35 dodecylbenzenesulphonic acid, dibutylnaphthalenesulphonic acid, or of a condensate of naphthalenesulphonic acid and formaldehyde. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide. The ammonium and potassium salts of these acids are IL I I I I I IIII I II

I

I I A o powerful anionic surfactants. The longer chain acids, especially C 8 and higher have unique surface-active properties.

Further examples of anionic surfactants are sodium alkyl glyceryl ether sulphonates; alkyl ether sulphates of the formula RO(C2H40)nSO3M wherein R is alkyl or alkenyl having from about 10 to about 20 carbon atoms, n is 1 to 30 and M is a watersoluble cation, alkali metal and ammonium; alkali metal salts of alkylbenzene and alkyl toluene sulphonic acids where alkyl has from about 9 to about 15 carbon atoms; and alkali metal and amine salts of alkyl alkoxy carboxylic acids of the general formula: R-O(CnH2nO)m-R1COOM where R is a straight or branched alkyl having from 8 to 18 carbon atoms, n is 2 to 4, m is 1 to 100, Rlis CH 2

CH

2

CH

2 or CH 2

CH

2

CH

2 and M is a sodium, potassium, lithium, ammonium, diethylammonium or triethylammonium cation or other cation, including multivalent cations.

Nonionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable nonionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Nonionic surfactants may include polyethyleneoxy ethers of alkylphenols, alkanols, esters and polyethyleneoxy compounds with amide links. Nonionic surfactants may also include alcohol ethoxylates. Generally the ethoxylates are of octyl-, nonyl- and dodecyl phenol, natural and synthetic alcohols, saturated and unsaturated fatty acids and both block and random copolymers. Alcohol ethoxylates such as those of the Teric series are preferred. Especially preferred nonionic surfactants are Teric 305, which is poly(oxy- 30 1,2-ethanediyl), alpha-dodecyl-omega-hydroxy-phosphate, Teric 16A22, or a mixture of these surfactants.

Examples of nonionic surfactants are the polyethylene oxide condensates of alkyl and dialkyl phenols, having a straight or branched alkyl of from about 6 to about 12 carbon atoms, with ethylene oxide wherein the amount of ethylene oxide present is from about 3 to about 25 moles per mole of alkyl and dialkyl phenol; and the benzyl ether of such alkyl phenols; the condensation products of aliphatic alcohols with ethylene oxide of the formula RO(C2H40)nH wherein R is straight or branched alkyl having from about 8 to 22 carbon atoms and n is 3 to 40; and the primary, monoethanoland diethanolamides of I i- i

C.

6 saturated and unsaturated fatty acids having an alkyl moiety of from about 8 to 22 carbon atoms.

Representative examples of nonionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/ polyethylene oxide adducts, tributylphenoxypolyethylene ethanol, polyethylene glycol, octylphenoxypolyethoxyethanol, oleic acid, lanolin alcohols, propylene glycol, propylene glycol monostearate, propylene glycol monolaurate, glycerol monooleate, sorbitan monopalmitate and sorbitan monoiaurate. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable nonionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. One example is diisobutylcresoxy ethoxyethyl dimethylbenzyl ammonium chloride monohydrate. The salts are preferably in the form of halides, methylsulphates or ethylsulphates, e.g.

stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)-ethylammonium bromide.

Typical examples of cationic surfactants also include high molecular weight fatty amine blend, high molecular weight amine blend, tertiary amines:polyoxyethylene fatty amines, polyoxy-ethylene (20) tallow amine, N-cetyl-N-ethyl morpholinium ethyl sulphate or other like cationic surfactants.

Examples of amphoteric surfactants are the aminocarboxylic and aminosulphonic acids and salts thereof such as alkali metal 3-(dodecylamino)propionate and alkali metal 3- (dodecylamino)propane-l-sulphonate; and alkyl and alkylamido betaines such as cocamidopropyl betaine.

Typically two surfactants are used in the formulation of the invention. Typically the amount of surfactant is 1-10 wt%. Preferably 1.2 wt% Teric 305 is used together with 0.9 wt% Teric 16A22.

The peroxide/oxygen releasing substance may be selected from hydrogen peroxide, zinc peroxide, benzoyl peroxide or other like peroxides or oxygen releasing substances. Preferably the formulation of the first embodiment is in two parts, one part comprising the peroxide and some of the corrosive inhibitor, and the other part comprising the remaining ingredients. The two parts are mixed together to form a single solution when required. Peroxide requires storage in the absence of light, and special care due to its reactive nature. Generally the amount of peroxide/oxygen releasing substance is 6-9 wt%. Typically the peroxide is hydrogen peroxide and 7.9 wt% is used in the formulation of the first embodiment.

According to a second embodiment of this invention there is provided a process of preparing a cleaning formulation comprising mixing 0.5-98.98wt% tethanolamine, diethanolamine, triethanolamine or a mixture thereof; 0.01-15wt% water softener; and 0.01-10wt% corrosion inhibitor.

7 According to a third embodiment of this invention there is provided a method of cleaning glassware, comprising washing the glassware with an effective amount of the formulation of the first embodiment.

According to a fourth embodiment of this invention there is provided a method of cleaning a beer line, comprising flushing said beer line with an effective amount of the formulation of the first embodiment.

The formulations of the inventior may further comprise a solvent. The solvent may be various organic solvents, including, for example: aliphatic hydrocarbons such as gasoline, petroleum, benzine, mineral spirits, petroleum, naphtha, V.M. P. naphtha, decalin, tetralin, p-cymene, cyclohexane, paraffin, hydrocarbons having from 5 to 19 carbon atoms, pentane, hexane, decane, tetradecane and nonadecane and the like; aromatic hydrocarbons such as benzene, toluene, xylene, and the like; aromatic naphtha aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate, dioctyl phthalate and the like; halogenated hydrocarbons such as trichloroethylene, perchloroethylene, chloroform, carbon tetrachloride, ethylene trichloride, benzene monobromide, benzene monochloride, benzene dichloride and the like; alcohols such as amyl alcohol, ethyl alcohol, isopropyl alcohol, hexanol, 2ethylbutyl alcohol, 2-ethylhexyl alcohol, cyclohexanol, methyl alcohol, methylamyl alcohol, benzyl alcohol, butyl alcohol, ethylene glycol, ethylene glycol monomethyl, and the like; ketones such as acetone, acetonylacetone, diisobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, methyl butyl ketone, methylcyclohexanone, cyclohexanone, methyldipropyl ketone, methyl ethyl ketone, methyl n-hexyl ketone, methyl isobutyl ketone, methyl propyl ketone, mesityl oxide, and the like; esters such as acetates, butyrates, propionates, formates and the like; alcohol esters such as butyl lactate, isopropyl lactate, ethyl lactate, ethyl oxypropionate, diethyl maleate and the like; ketone esters such as ethyl acetoacetate, ethyl pyruvate and the like; ethers such as isopropyl ether, ethyl ether, diethyl carbitol, diethyl cellosolve, butyl ether, monomethyl ether, dipropylene glycol methyl ether and the like; ketone alcohols such as acetonylmethanol, diacetone alcohol, dihydroxyl acetone, pyruvyl alcohol and the like; ether alcohols such as isopropyl cellosolve, carbitol, glycidol, cellosolve, glycol ether, benzyl cellosolve, butyl carbitol, butyl cellosolve, methyl carbitol, methyl cellosolve, triethyleneglycol monoethyl ether and the like; 8 glycols and glycol ethers such as propylene glycol monomethyl ether, 2methoxyethanol, 2-butoxyethanol, 5-ethoxy-l-pentanol and the like; ketone ethers such as acetal ethyl ether, acetonyl-methanol ethyl ether, methyl ethoxyethyl ether, and the like; ester ethers such as butylcarbitol acetate, butyl cellosolve acetate, carbitol acetate, crllosolve acetate, 3-methoxybutyl acetate, methylcarbitol acetate, methyl cellosolve acetate, and the like.

Other organic solvents may be used in the formulations for example, methylene chloride, strongly polar solvents such as N-methyl-2-pyrrolidinone, dimethyl sulphoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil, amines such as triethylalomine and triethylamine.

Preferably the solvent is miscible with water. Usually the amount of solvent is between wt%, preferably 1.81 wt% N-methyl-2-pyrrolidinone is used in the formulation of the first embodiment.

The formulations of the invention may further comprise a disinfectant and/or a sanitizer. Examples of disinfectants and/or sanitizers include aliphatic alcohols such as ethyl alcohol, hypochlorites such as sodium or calcium hypochlorite, N-chloramines such as sodium N-chloro-p-toluenesulfonamide, N,N-dichloro-p-toluenesulfonamide, N,Ndichloro-p-carboxybenzenesulfonamide, iodine and organic iodine compounds, and other like disinfectants and/or sanitizers. The preferred disinfectant is amphoteric alkylaminomethyl glycine (Tego 51 and usually the amount used in the formulation of the first embodiment is 1-5 wt%, preferably 1.81 wt% is used in the formulation of the first embodiment.

The water softener may be a sequestering agent or chelating agent. Examples of sequestering agents or chelating agents include polyphosphates such as sodium tripolyphosphate or sodium hexametaphosphate; aminocarboxylic acids such as ethylenediaminetetraacetic acid; 1,3-diketones such as acetylacetone; hydroxycarboxylic acids such as citric acid, tartaric acid or gluconic acid; nolyamines such as ethylenediamine; amino alcohols such as triethanolamine; aromatic heterocyclic bases such as dipyridyl; phenols such as salicylaldehyde; aminophenols such as oxinesulphonic acid; oximes such as dimethylglyoxime; Schiff bases such as disalicylaldehyde 1,2propylenediimine; tetrapyrroles such as tetraphenylporphin; sulphur compounds such as dimercaptopropanol; synthetic macrocyclic compounds; polymeric compounds or phosphonic acids such as nitrilotrimethylenephosphonic acid. Preferably 3.6 wt% EDTA is used in the formulation of the first embodiment.

The formulations of the invention may further comprise an emulsifier/stabilizer.

Emulsifiers/stabilizers generally have anionic, cationic, amphoteric or nonionic properties. Examples of emulsifiers/stabilizers may be found amongst the surfactants discussed earlier.

.I:

9 In some cases it may be necessary to add a thickener to increase the viscosity, in order to provide a more stable emulsion. Typical thickeners or gelling agents include soap gels, gums, such as Xanthan gum or Guar gum, starches such as furcellaran, hypnean, dextran, or tamarind, proteins, alginates, pectic gels such as sodium pectate, alkylceilulose hydrophilic colloids, for example, hydroxypropylmethyl cellulose, sodium carboxymethyl cellulose, hydroxymethylcellulose, ethyl succinylated Cellulose, succinylated zein, or carboxymethylcellulose, polymers such as sodium poly (styrene sulfonate) with poly (vinyl methyl pyridinium) chloride, sodium poly (styrene sulfonate) with poly (vinyl benzyl trimethyl ammonium) chloride, strongly acidic polyanion with strongly basic polycation, vinyl acetate homopolymer, polyvinyl alcohol resin, or carboxypolymethylene (a carboxyvinyl polymer or a polyacrylic acid polymer), bentonite and mixtures thereof or other like thickeners. Other thickeners or gelling agents include aluminium mono-, di-, and tristearates, aluminium palmitate, aluminium octanoate, magnesium aluminium silicate, and sodium fluorosilicate. It may, in some instances, be desirable to use various thickeners or gelling agents in combination, either as a mixture or in layers. Thickeners or gelling agents which have been found to be useful for such purposes include sodium alginate, potassium alginate, polygalacturonic acid and a mixture of gelatin and sodium alginate. Other suitable thickeners or gelling agents include, but are not limited to, alginate with gelatin.

Once the thickener or gelling agent has been chosen, there a;re numerous parameters which influence the character of the gel matrix. A sodium alginate solution, for example, will form a gel when a complexing agent is added. Calcium chloride (CaC12) is typically used as the complexing agent. However, other calcium salts such as calcium nitrate and calcium hydroxide are useful complexing agents. Copper salts (particularly copper sulfate), chitosan (a deacylated chitin), potassium chloride, ammonium chloride, lanthanum chloride, ferric chloride, cobaltous chloride, sodium tetraborate, and other compounds generally with multivalent cations.

Usually 0.1-1 wt% is used in the formulation of the first embodiment, preferably 0.22 wt% alkyl acrylate crosspolymer (TR1 C10-C30) may be used in the formulation of the first embodiment.

The formulations of the invention may further comprise a preservative such as formaldehyde (formalin), methyland ethyl paraben, 1,2-benzoisothiazol-3-(2H)-ones, and the like.

The formulations of the invention may be dispensed for use as lquids using conventional dispensing devices such as squeeze bottles fitted with a suitable dispensing nozzle or containers fitted with trigger spray pumps; or as an aerosol from conventional aerosol containers fitted with a suitable dispensing valve and button.

In the case of an aerosol container, the container will contain an aerosol propellant or nixture of propellants sufficient to provide adequate pressure to dispense the i formulations on each actuation of the aerosol valve until substantially all of the formulation is eventually exhausted. Propellants and propellant systems which may be employed are well known in the art. Examples of propellants include low boiling chloro and fluoro substituted alkanes and low boiling aliphatic hydrocarbons such as propane/isobutane mixtures.

The pH of the formulations of the invention should be in the range of from about to 13.0. It is preferable that the pH range does not fall below 6.0. Typically the best results are obtained in the pH rang- of from about 9.5 to 13.0. This pH range is also preferred when the formulation is to be dispensed from an aerosol container of the type having tin-containing metallic components which will be exposed to the formulation, e.g., tin-containing metallic inner walls, since an acid pH can have deleterious effects on such metallic components. However, compositions having a pH in the acidic range can be dispensed from aerosol containers having substantially no exposed inner metallic components such as those having metallic inner walls which are coated with plastic material.

If required a buffering agent is added to the formulation in order to achieve the desired pH in the above-disclosed pH range, for example, citric acid, ammonia, Na4EDTA and the like. The choice of a particular buffering agent is well within the skill of the art.

An advantage of the formulations of the invention is that they represent a considerably safer alternative to the currently marketed products.

BEST MODE AND OTHER MODES FOR CARRYING OUT THE

INVENTION

A typical formulation for cleaning glassware is made by mixing 6.36 wt% monoethanolamine, 3.63 wt% amorphous sodium polyphosphate, 0.68 wt% nitrilotris phosphate (Dequest 2000), 0.68 wt% sodium gluconate, 1.81 wt N-methyl pyrrolidone, 1.2 wt% Teric 305, 0.9 wt% Teric 16A22, 1.81 wt% amphoteric alkylaminoethyl glycine (Tego 51 0.22 wt% benzotriazole, 0.22 wt% alkyl acrylate crosspolymer (TR1 C10-C30) and 82.49 wt% water.

A typical formulation for cleaning beer lines is a two part formulation. Part A is made by mixing 50 wt% monoethanolamine, 2.67 wt% nitrilotris phosphaste (Dequest 2000), 3.34 wt% sodium gluconate, 0.8 wt% benzotriazole, 3.6 wt% EDTA and 39.59 wt% water. Part B is made by mixing 7.9 wt% hydrogen peroxide, 0.75 wt% nitrilotris phosphaste (Dequest 2000), and 91.35 wt% water.

Part A may be stored and sold in convenient quantities, :3gether with part B.

Due to the low level of hydrogen peroxide, namely 7.9 wt%, the formulation may be stored and transported without being classified as a dangerous good. Part A and part B are mixed together in a ratio about 3:1 to 5:1, part A:part B. Usually part A and part B are mixed in the ratio 4:1. The mixture of part A and part B may be used to clean the p.

~I

b; beer lines without further dilution. Generally the mixture is further diluted to a ratio of about 1:200 to 1:100, mixture: water. Usually the mixture is diluted 1:160.

Normally, the beer line cleaning formulation is made up in a beer keg, which is commonly an 18 gallon keg. The beer line cleaning formulation is then forced through the beer lines, and the cleaning formulation is allowed to remain in the lines for some period of time, for example, overnight. The formulation is then forced out of the lines, by purging with carbon dioxide gas, and the lines are then washed with plain water for some time. Once the lines no longer contain any trace of the cleaning formulation, beer may be reintroduced into the lines.

The formulations of this invention were tested for their effectiveness as cleaning solutions by standard testing methods applicable to cleaning solutions. The formulations of the invention were found to be relatively free of chlorine and relatively stable when tested at 50 0 C for one week (concentrated formulation and diluted to 4 parts with water) and 80°C for five minutes (diluted to 4 parts with water). Furthermore no visible residue was detected when the formulations of this invention were used to remove lipstick and standard dirt, even when the formulations were used undiluted, stored for one week at 500 C or when the formulation was diluted to 4 parts water and stored for one week at 50 0

C.

The formulations of this invention were also found to be compatible with hard water, for example, when diluted to 4 parts with water, the formulations were compatible with 200 ppm and 400 ppm hardness. The formulations were relatively noncorrosive to stainless S steel 304, copper, brass and polythene. The formulations of this invention had an alkaline SpH and the matter insoluble with water was found not to exceed 0.05% EXAMPLE 1 A formulation comprising: 6.36 wt% monoethanolamine; S3.63 wt% amorphous sodium polyphosphate; 0.68 wt% nitrilotris phosphaste (Dequest 2000); 0.68 wt% sodium gluconate; 1.81 wt% N-methyl pyrrolidone; 1.2 wt% Teric 305; S 0.9 wt% Teric 16A22; S..1.81 wt% amphoteric alkylaminoethyl glycine (Tego 51 0.22 wt% benzotriazole; 0.22 wt% alkyl acrylate crosspolymer (TR1 C10-C30); and 82.49 wt% water was found to be effective as a glassware cleaner.

EXAMPLE 2 A two-part formulation, wherein part A comprises: wt% monoethanolamine; 1 12 2.67 wt% nitrilotris phosphaste (Dequest 2000); 3.34 wt% sodium gluconate; 0.8 wt% benzotriazole; 3.6 wt% EDTA; and 39.59 wt% water; and part B comprises: 7.9 wt% hydrogen peroxide; 0.75 wt% nitrilotris phosphaste (Dequest 2000); and 91.35 wt% water; was found to be effective as a beer line cleaner.

INDUSTRIAL APPLICABILITY The formulations of the invention can be readily utilized in the cleaning industry to produce clean glassware and clean beer lines.

i

Claims (5)

1. A cleaning formulation for cleaning an apparatus, comprising:

5-75wt% monoethanolamine, diethanolamine, triethanolamine or mixtures thereof; 2-7.5wt% water softener; 0.1-8wt% corrosion inhibitor; solvent; 1-10wt% surfactant additional to any surfactant comprising the corrosion inhibitor; 1-5wt% disinfectant; 0.1-lwt% thickener; and

19.8-85wt% water. 2. The cleaning formulation of claim 1, further comprising 6-9wt% peroxide/oxygen releasing agent. 3. The cleaning formulation of claim 1, comprising: 6.36wt% monoethanolamine; 3.63wt% amorphous sodium polyphosphate; 0.68wt% nitrilotris phosphate; 0.68wt% sodium gluconate; 1.81wt% N-methylpyrrolidone; 2. wt% mixture of poly(oxy-l,2-ethanediyl), alpha-dodecyl-omega- hydroxy-phosphate; 1.81wt% amphoteric alkylaminoethyl glycine; 0.22wt% benzotriazole; 0.22wt% alkyl acrylate crosspolymer; and

82.49wt% water. 4. The cleaning formulation of claim 1 being a two-part formulation, the first part comprising A 50wt% monoethanolamine; 2.67wt% nitrilotris phosphate; 3.34wt% sodium gluconate; 0.8wt% benzotriazole; 3.6wt% EDTA; and 39.50wt% water; and the second part comprising: B 7.9wt% hydrogen peroxide; 0.75wt% nitrilotris phosphate; and

91.35% water. S[N:\ibaa]00428:AK l 1 [N:\libaa]00428:SAK (L I: i The cleaning formulation of claim 4, wherein the ratio of the volume of A:B is 4:1. 6. A method of cleaning glassware, comprising washing said glassware with an effective amount of the cleaning formulation of any one of claims 1 to 7. A method of cleaning a beer line, comprising flushing said beer line with an effective amount of the cleaning formulation of any one of claims 1 to 8. A method of cleaning a beer line, comprising flushing said beer line with a cleaning formulation comprising: 0.5-98.98wt% monoethanolamine, diethanolamine, triethanolamine or a mixture thereof; 0.01-15wt% water softener; and 0.01-10wt% corrosion inhibitor. 9. The method of claim 8, wherein said water softener is selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, sequestering agents and chelating agents. The method of claim 9, wherein said water softener is an anionic surfactant. 11. The method of claim 10, wherein said anionic surfactant is amorphous sodium polyphosphate. 12. The method of claim 9, wherein said water softener is a chelating agent. 13. The method of claim 12, wherein said chelating agent is EDTA. 14. The method of any one of claims 8 to 13, wherein the corrosion inhibitor is selected from the group consisting of inorganic inhibitors, organic inhibitors and vapour- -J phase inhibitors. 15. The method of claim 14, wherein said corrosion inhibitor is nitrilotris phosphate, sodium gluconate, benzotriazole or a mixture thereof. 16. The method of any one of claims 1 to 15, further comprising 5-10wt% peroxide/oxygen releasing substance. 17. The method of claim 16, wherein the peroxide/oxygen releasing substance is hydrogen peroxide, zinc peroxide or benzoyl peroxide. 18. The method of claim 17, wherein said peroxide/oxygen releasing substance is hydrogen peroxide. 19. The method of any one of claims 1 to 18, wherein said formulation comprises 1-10wt% further surfactant. 20. The method of claim 19, wherein said further surfactant is an anionic surfactant, a nonionic surfactant, a cationic surfactant or an amphoteric surfactant. 21. The method of claim 20, wherein said further surfactant is a nonionic surfactant. L2 V 5 s[N:\libaa]00428:SAK i 22. The method of claim 21, wherein said further surfactant is a mixture of poly(oxy-l,2-ethanediyl) and alpha-dodecyl-omega-hydroxy-phosphate. 23. The method of any one of claims 8 to 22, further comprising solvent. 24. The method of any one of claims 1 to 23, further comprising disinfectant and/or a sanitiser. The method of any one of claims 1 to 24, further comprising 0.1-lwt% thickener/gelling agent. 26. A method of cleaning glassware, comprising washing said glassware with an effective amount of a cleaning formulation substantially as herein described with reference to Example 1. 27. A method of cleaning a beer line, comprising flushing said beer line with an effective amount of a cleaning formulation substantially as herein described with reference to Example 2. Dated 3 April, 1996 So-Safe Speciality Products Pty. Ltd. Patent Attorneys for the Applicant/Nominated Person SPRUSON FERGUSON I./ [N:\libaa]00428:SAK A Cleaning Formulation Abstract The invention relates to a cleaning formulation, process for its preparation and methods for cleaning glassware and a beer line. A cleaning formulation for cleaning an apparatus comprising 0.5-98.98wt% methanolamine, diethanolamine, triethanolamine or a mixture thereof; 0.01-15wt% water softener; and 0.01-10wt% corrosion inhibitor. S, 1 9* iii