Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/75—Amino oxides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/88—Ampholytes; Electroneutral compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/90—Betaines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/92—Sulfobetaines ; Sulfitobetaines

Definitions

• the present invention relates generally to hard surface cleaners for use on ovens, sinks, toilets, bath tubs, shower stalls and the like. More specifically, the present invention comprises a rinsing solution for keeping these areas clean and free of mineral and other types of hard to remove deposits. BACKGROUND OF THE INVENTION
• the build-up of deposits in a shower can be cleaned with any one of a number of aggressive cleaners commercially available to the consumer.
• These cleaners which contain combinations of surfactants, builders, chelating agents, oxidizers, abrasives, and soluble salts, require repeated scrubbing or wiping with the cleaner, followed generally with a water rinse, to periodically remove the unsightly and unhealthy build-up in the shower.
• considerable labor is required to maintain a clean shower using these conventional cleaners.
• United States Patent No. 4,020,016 to Sokol discloses aqueous cleaning compositions for dissolving soap curds that require a non-ionic surfactant having an HLB (hydrophilic-lipophilic balance) number of at least 13.5.
• the composition also comprises ammonium, alkylamine or the hydroxy-alkylamine salt of nitrilotriacetic acid and an alkylene polyamine polycarboxylic acid as a chelating agent.
• the aqueous cleaning compositions are alleged to readily dissolve the soap curds with minimal manual effort. Soap curds form when the surfactants in the soap form complexes with metal ions and become insoluble.
• the composition is free of alkaline metal ions.
• U. S. Patent No. 5,536,452 to Black teaches an aqueous rinsing composition for removing deposits from the surfaces of showers and the like without the need for manual scrubbing or wiping.
• the composition is comprised of a nonionic surfactant which has a hydrophilic-lipophilic balance number (HLB) of 13 or less, in particular, ethoxylated alcohol and ethoxylated alkylphenols, a chelating agent, an alcohol, and optionally, ammonium hydroxide and/or morpholine and water.
• HLB hydrophilic-lipophilic balance number
• U. S. Patent No. 5,587,022 also to Black discloses the same nonionic compositions as the '452 patent and further claims a method for rinsing showers using them.
• nonionic surfactants disclosed in the prior art with an HLB of 13 or less have very low cloud points and tend to form complexes with calcium and magnesium ions that are naturally found in tap water. These nonionic-metal complexes are insoluble and hence form deposits on the very surfaces that the surfactant composition is supposed to clean. And to exacerbate the problem, these surfactants also have very poor lime soap dispersibility which is essential for the removal of the calcium and magnesium lauryls, palmitates, and stearates generally found in commercially available soaps that form a soapy scum or film on the kitchen and bathroom surfaces.
• nonionic surfactants used in the hard surface bathroom cleaners of the prior art are non-biodegradable, toxic and are irritating to the skin and eyes.
• surfactant's low solubility as indicated by their low cloud points excessive amounts of alcohol are required to formulate them into concentrated products.
• the present invention then is an improved liquid hard surface cleaner rinse in which the active surfactant is one or more amphoteric or zwitterionic surfactants which have been found to be far more compatible with all types of plastics resulting in no cracking or crazing even after repeated use.
• the active surfactant is one or more amphoteric or zwitterionic surfactants which have been found to be far more compatible with all types of plastics resulting in no cracking or crazing even after repeated use.
• These surfactants are also highly stable at all temperatures. They have extremely high cloud point values and therefore do not form calcium or magnesium ion complexes resulting in surface stains and deposits. They are biodegradable, non-toxic and hence more environmentally friendly in addition to being mild to the eyes and skin. They also have excellent lime soap dispersing power and improved surface cleaning capability so that no soapy scum residues are left after use. Moreover, they are much more soluble than the other surfactants requiring the addition of little to no alcohol in order to formulate the hard surface cleaner rinse composition
• the present invention is an improved liquid hard surface cleaner comprising any one or more of a number of amphoteric or zwitterionic compounds as the surface active agent that is particularly useful as a sink, bath or shower surface cleaner rinse.
• the composition may be comprised of the amphoteric surfactant(s) with water as the carrier solvent alone or preferably also include a chelating or sequestration agent, an acid or base solvent, other secondary surfactants, fragrances, and/or disinfectants.
• the compositions provide superior cleaning functions while at the same time are non-toxic, biodegradable and much more compatible with plastic surfaces so as to not only clean but protect the surfaces from other, less compatible compounds.
• the liquid hard surface cleaner rinse compositions of the present invention consist of an amphoteric surface active agent, water and a number of other optional ingredients which can vary as desired by the formulator depending on the particular application, strength necessary, etc.
• the amphoteric surfactants are generally classified as betaines, sultaines, amphopropionates, amine oxides and carboxylates.
• the surfactants which have been found to provide the benefits of the invention can be represented by the formulae:
• R is selected from the group of alkyl, alkylarylalkyl, arylalkyl, alkylaminoalkyl and sulfonated derivatives thereof, alkylamidoalkyl, or alkoxylalkyl, and the hydroxy-substituted derivatives thereof wherein the alkyl group contains from about 1 to about 16 carbon atoms, the aryl group is up to and including two fused rings and the alkoxy group contains from 4 to 18, preferably 4 to 10, carbon atoms wherein the total carbon atom content of the R group is no more than about 18 carbon atoms.
• R can be butyl, hexyl, 2- ethyihexyl, octyl, capryl, caprylyl, coco, lauryl, palmitic and the like. Substituents from natural sources contain mixed carbon chain lengths or can be purified to reduce the number of chain lengths in the alkyl groups.
• R can also be alkylamidoalkyl, such as butylamidoethyl or caprylamidopropyl, cocoamidopropyl and alkoxyalkyl such as cocooxypropyl, decyloxypropyl, hexyloxymethyl or hexyloxy -2- hydroxy- propyl.
• R can also be
• R 1 and R 2 independently represent alkyl chains of from about 1 to about 6 carbon atoms, preferably methyl, and the hydroxy-substituted derivatives thereof or hydroxy polyoxyethylene, polyoxypropylene or mixed polyether polymers of EO and PO having no more than 20 ether linkages; or R ⁇ and R 2 may jointly be -CH 2 CH 2 OCH 2 CH 2 - or -CH 2 CH 2 SCH 2 CH 2 - so as to form together with the nitrogen atom a morpholine or thiomorpholine ring.
• R 3 represents an alkyl or hydroxy- substituted alkyl group of from 1 to about 4 carbon atoms
• R 4 represents R 6 OH, R 5 YM, preferably R 5 COOM, or hydrogen where R 6 is a lower alkyl of from 1 to about 4, preferably 2, carbon atoms and the hydroxy- substituted derivatives thereof
• R 5 represents alkyl or hydroxy-substituted alkyl of from 1 to about 4, preferably 1 or 2 carbon atoms
• Y represents COO " or S0 3 "
• M represents hydrogen and or an alkali metal such as sodium or potassium and x equals 1 or 2.
• the surfactants are low to moderate foaming or non- foaming as foaming creates difficulties when used as a cleansing rinse, i.e. foams will not readily flow as a rinse off the surface to be cleaned thereby leaving residue.
• the compounds of Formula I generally defined as betaines and sultaines are well known compounds and can be made by well known methods. Betaine is trimethyl glycine. Replacing one of the methyl groups provides a betaine derivative, commonly an alkyl betaine. Betaines are zwittenonic and internally compensated salts. The remaining two methyl groups can be replaced such as with hydroxyethyl groups to form dihydroxyethyl alkyl glycinate.
• R is C 4 to C 16 alkyl, alkylamidoalkyl or alkoxyalkyl.
• the alkyl group or portion of the group is preferably about C 4 to about C 10 .
• R ⁇ and R 2 are preferably methyl. When R ⁇ and R 2 are not methyl, they can optionally be substituted with an electron withdrawing group such as OH,
• sultaines Materials which employ a sulfonate or hydroxy alkyl sulfonate in place of the carboxyl group, by analogy, are described as sultaines. These are well known compositions.
• R 7 is selected from alkyl, aryl, or alkylaryl groups of from about 4 to about 16 carbon atoms or alkoxymethylene wherein the alkoxy group contains from about 4 to about 8 carbon atoms;
• R ⁇ and R 2 are as defined hereinbefore with the proviso that when the alkyl group is an alkyl of from about 2 to about 6 carbon atoms, the alkyl group is substituted by an electron-donating group on the beta carbon atom thereof.
• R 3 represents an alkyl or hydroxy-substituted alkyl group of from 1 to 4 carbon atoms.
• Q is a covalent bond or:
• R 7 group contains from about 4 to about 14, commonly from about 4 to about 8 carbon atoms.
• R 7 is alkoxymethyl containing from about 4 to about 8 carbon atoms in the alkoxy group such as butoxymethyl, hexyloxymethyl, 2- ethylhexyloxymethyl and the like.
• R ⁇ and R 2 are each preferably methyl, hydroxyethyl, 2-hydroxypropyl, or a morpholine ring.
• X is preferably hydrogen and n is preferably 1.
• Q is preferably a covalent bond.
• a particularly preferred group of compounds can be described as alkylether hydroxypropyl sultaines.
• This group of surfactants can typically be incorporated in aqueous solutions that can have high acid or alkaline content, particularly having a relatively high alkali content, for example, within the range of from 5 to about 50%, and preferably from about 25 to about 50% sodium or potassium hydroxide or equivalent such as strong sodium carbonate, silicate and phosphate solutions.
• R represents the residue of glycidyl ether of a lauryl myristyl alcohol mixture.
• compositions that can be defined as imidazoline derivatives, preferably where R is alkylamidoalkyl, which are well known and can be made by well known methods. These are true amphoteric surfactants as they are anionic above the isoelectric point, cationic below the isoelectric point and zwitterionic in the isoelectric range. These compounds have at least two sites capable of ionization or protonization, i.e., a tertiary amine, carboxylate or sulfonate group with electronegative charge.
• alkylamphoacetate or propionate as used in the invention such as capryl, coco or tallow, at alkaline pH is an anionic surfactant as represented below:
• the compounds of Formula III likewise are capable of different ionic forms depending on pH as illustrated by the following preferred compounds:
• Alkyloamphodicarboxylates e.g., diacetates and dipropionates
• Formula II and III includes the sulfonated derivatives as well as the carboxylated derivatives.
• Formula II of the invention are the amino and imino carboxylates which are well known and also vary ionic form depending on pH.
• the above compounds differ from the imidazoline-derived materials since they have no amide group and differ from the betaines since the nitrogen is not quatemized. These ionic variations are intended to be included within the formula defining the compounds useful in this invention.
• liquid hard surface cleaner rinse solutions utilized in accordance with the invention can contain the amphoteric surfactants in amounts ranging from 0.1 to 5.0%, and preferably from about 0.1 to 3.0%, active percent by weight of the solution. Concentrated solutions, generally designed for dilution can contain higher percentages, such as up to about 40% active weight percent of the surfactants. As discussed supra, these can be comprised solely of surfactant and water but preferably will also comprise additional components.
• amphoteric surfactant component of the hard surface cleaner rinse compositions of the present invention other additional components are preferably added for best results.
• these comprise a sequesterant or chelating agent, a hydrophilic solvent and an acid or a base which is added in order to increase or decrease the pH of the liquid cleaner composition as required by local environmental conditions.
• Optional ingredients such as buffers, fragrances, disinfectants, colorants for visual aesthetics and other secondary surfactants for increased surface active cleaning power may also be included.
• the chelating or sequestration agent is ethylene diamine tetraacetate (EDTA) or one of its salts such as diammonium EDTA, a commercially available 44% solution that is easy to mix, economical in cost, and has low toxicity.
• EDTA ethylene diamine tetraacetate
• chelating agents that may be used are, for example but not limited to, hydroxyethyl ethylene diaminetriacetic acid (HEEDTA), propanolamine, polyamino-carboxylic acid, diethylenetriamine pentacetic acid (DTPA) and nitrolotriacetic acid (NTA) can be substituted for EDTA or diammonium EDTA on an equivalent chelating strength basis.
• HEEDTA hydroxyethyl ethylene diaminetriacetic acid
• DTPA diethylenetriamine pentacetic acid
• NTA nitrolotriacetic acid
• the chelating or sequestering agent is preferably mixed in the liquid hard surface cleaner in an amount of about 0.01 wt. % to 5.0 wt. % based on the total weight of the liquid cleaner rinse.
• the other chelating agents mentioned above, as well as a solution of diammonium EDTA of different concentration can be mixed in the liquid hard surface cleaner rinse composition in an amount of about 0.1 wt. % to 3.0 wt. %.
• a base or acid may be incorporated in the composition to increase or decrease the pH of liquid hard surface cleaner rinse depending on the acidity or alkalinity required for the cleaning conditions; i.e. water hardness, etc.
• the pH of the aqueous shower rinsing solution is preferably in the pH range of about 3 to 10, more preferably in the pH range of from about 5.0 to 9.0.
• a hydrophilic solvent which increases the solvent properties and improves the sheeting action of the rinse by keeping the viscosity low in order to minimize any residual film on both sink and shower surfaces, can optionally be added to the liquid hard surface cleaner rinse in the range of about 0.5 wt. % to about 5.0 wt. % of the total weight of the cleaner rinse.
• Any short-chain alcohol such as ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, and isobutyl alcohol, can be used, although isopropyl alcohol is preferred.
• Ethylene glycol, propylene glycol, glycerol, the isopropyl ether of ethylene glycol or the ethyl ether of ethylene glycol can be used as possible substitutions for a short-chain alcohol.
• a builder is also optionally added as a buffer for the system according to the hardness of the tap water. These are selected from the group comprising silicates, citrates, phosphates, pyrophosphates and polyphosphates, borates, amines and mixtures thereof. The amount added may vary according to local conditions but generally ranges from about 0.01 wt. % to about 3.0 wt. %.
• the liquid hard surface cleaner rinse preferably contains one or more fragrances to provide a fresh and clean smell.
• fragrance is optional, it satisfies the expectation of consumers that a clean shower, bath, toilet or sink would smell "fresh and clean".
• a composition which lacks a fragrance additive still performs satisfactorily in cleaning the bath, sink, or shower surfaces.
• Pine scent is the preferred fragrance.
• any of a number of commercially available fragrances or color additives may be used to provide a fresh and clean smell and is well within the skill of those in the art.
• 0.005% to 0.008% of fragrance additive is mixed with the aqueous rinsing solution composition based on the initial concentration of the fragrance additive supplied by the manufacturer.
• the water used in this liquid hard surface cleaner rinse of the present invention should have negligible amounts of metal ions and be capable of not leaving any residue or deposit after evaporation from a shower surface. Distilled water or deionized water is preferred as the source of water for dilution of the individual components as well as for the water added as the balance of the composition for an aqueous shower rinsing solution.
• Local conditions such as the degree of water hardness, altitude above sea level, and the composition of the indigenous soils, should also be taken into consideration in formulating the liquid hard surface cleaner rinse composition.
• the amount of surfactant, sequestration or chelating agent, buffer, hydrophilic solvent and acid or base incorporated may be increased/decreased to account for greater/lesser water hardness and soils with higher/lower calcium and magnesium levels.
• alcohols having lower vapor pressure can be used.
• the liquid hard surface cleaner rinse is a dilute amphoteric surfactant solution containing additional additives and the bath, shower or sink is rinsed after use to prevent the build-up of deposits.
• the rinsing solution is best sprayed on the surfaces of shower stalls, bath tubs, sinks, and toilets with a pump or pressurized sprayer.
• the rinsing solution is applied to bath, shower or sink surfaces before the deposits dry and set. While the rinsing solution does soften and remove dried deposits, it works best in the removal of deposits that are still wet. The rinsing solution transports these undesirable deposits down wet surfaces by gravity and onto the bath, shower or sink drain.
• Previously accumulated build-up of undesirable deposits that have already dried and set can be softened and completely removed, albeit gradually, with continued application of the rinsing solution after each use of the respective bath, shower or sink. While no wiping or other mechanical action is required to remove such previously dried and set deposits, gentle wiping accelerates the removal of softened deposits that have accumulated over a period of time. Furthermore, in contrast to simply rinsing the shower surfaces with plain tap water or soapy water, both of which leave deposits, the present invention prevents streaking and air dries spot free.
• the aqueous hard surface cleaner rinsing solution provides a product for maintaining baths, sinks, and showers clean with the minimum of effort.
• Hard surface rinse cleaners of the present inventions were compared to those of the prior art in terms of the degree to which a particular cleaner caused cracking and/or crazing of the plastic surface and in terms of each formulation's ability to remove soap scum, dirt, greasy film etc.
• Each of the surfactants tested was formulated as a standard rinse solution consisting of the following components in their respective amounts. The solutions were then repeatedly applied to a number of plastic surfaces in a standard dishwasher at 80°C and observed at intermittent intervals of 1 hour for 24 cycles (24 hours).
• EDTA 1.5 wt. %
• amphoteric hard surface cleaner rinses of the present invention substantially outperformed those of the prior art (nos. 3-5) and Black '536 (no. 2).
• amphoteric surfactants are more compatible with the plastic surfaces resulting in less cracking and crazing, they were more effective in removing soap scum, films, and other visually discernible deposits.

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• 1999
  • 1999-05-19 AU AU40014/99A patent/AU4001499A/en not_active Abandoned
  • 1999-05-19 EP EP99923187A patent/EP1080173A1/de not_active Withdrawn
  • 1999-05-19 WO PCT/US1999/010943 patent/WO1999060085A1/en not_active Application Discontinuation

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