MXPA00011442A - Acidic cleaning compositions with c10 - Google Patents

Abstract

Compositions described herein are aqueous detergent compositions, preferably hard surface cleaning compositions, which contain C10 alkyl sulfate detergent surfactant, optional hydrophobic cleaning solvent, optional, but preferred, mono- or poly-carboxylic acid, and optional, but preferred, aqueous solvent system, the pH being from about 2 to about 5. Such compositions optionally contain additional cosurfactant, preferably anionic surfactant, peroxide and/or hydrophilic polymer for additional benefits. Articles of manufacture comprising the composition and a sprayer and methods of use are also disclosed.

Description

ACID CLEANING COMPOSITIONS WITH TENSIOACTIVE AGENT DETERGENT OF ALQUILSULFATQ OF TEN ATOMS OF CARBON FIELD OF THE INVENTION The invention relates to liquid detergent compositions for use in cleaning hard surfaces, particularly bath surfaces. Said compositions typically comprise detergent surfactants, solvents, builders, etc.

BACKGROUND OF THE INVENTION The use of acidic detergent compositions comprising synthetic detergent surfactants, water soluble organic and cleaning solvents for cleaning hard surfaces in, for example, baths is well established. Liquid detergent compositions known for this purpose comprise organic cleaning solvents, detergent surfactants, and optional builders and / or abrasives. Liquid cleaning compositions are usually preferred, since they have the advantage that they can be applied to hard surfaces in pure or concentrated form whereby a relatively high level of, for example, surfactant material and / or organic solvent is supplied. ^^ * directly to the dirt. However, the solid compositions can also be used to form a cleaning solution when diluted with water. Concentrated liquid cleaning compositions have the potential to provide superior removal of soap, grease, and greasy dirt compared to diluted wash solutions, for example, those typically prepared from powder cleaning compositions. The present invention provides acid, preferably liquid, hard surface cleaning compositions suitable for removing the dirt commonly found in the bath, said compositions having specific surfactants, optional solvents, and, optionally, but preferred, organic acids. These acid hard surface cleaning compositions remove the soapy cream and the hard water marks. The compositions may have disinfectant properties achieved through the selection of antibacterial actives, including citric acid, and may be used with or without additives such as hydrogen peroxide for additional mold / moisture prevention benefits. In addition, advantageously, the compositions may incorporate one or more hydrophilic polymers for improved surface viscosity and / or wetting and / or film / marbling properties.

BRIEF DESCRIPTION OF THE INVENTION Acid detergent cleaning compositions for hard surfaces of the present comprise: a. from about 0.1% to about 10% of alkyl sulfate detergent surfactant, the alkyl group comprising about 10 carbon atoms on average, substantially all alkyl groups having between 2 carbon atoms and 10 carbon atoms average, and, preferably , most alkyl groups containing 10 carbon atoms; b. optionally, an effective amount, for example, from about 1% to about 8% of one or more organic cleaning solvents, preferably selected from the group consisting of: monopropylene glycol monopropylene glycol, monopropylene glycol monobutyl ether, monopropyl ether of dipropylene glycol, dipropylene glycol monobutyl ether; tripropylene glycol monobutyl ether; monobutyl ether of ethylene glycol; diethylene glycol monobutyl ether, ethylene glycol monohexyl ether and diethylene glycol monohexyl ether, and mixtures thereof; c. optionally, a minor amount that is preferably less than the amount of said alkyl sulfate detergent surfactant, for example, from about 0.25% to about 4%, surfactant coagent, preferably anionic and / or nonionic surfactant. , for example, selected from the group consisting of: linear or branched alkylbenzenesulfonates of C8- Cie; C 1 -C 8 alkylethylsulfates; and mixtures thereof; d. optionally, an effective amount, for example, of about 1% about 8% mono-or poly-carboxylic acid soluble in water; and. optionally, an effective amount, up to 5% hydrogen peroxide; F. optionally, an effective amount, up to about 1% of one or more, quaternary ammonium surfactants; g. optionally, from about 0.1% to about 1% of a thickening polymer selected from the group consisting of polyacrylates, gums and mixtures thereof, for example, xanthan gum; h. optionally, an effective amount, up to 0.5%, of different hydrophilic polymer than said thickener polymer, for example, polymer selected from the group consisting of: polystyrene sulfonate; polyvinyl pyrrolidone; Acrylic acid copolymer of polyvinyl pyrrolidone; polyvinylpyridine; polyvinylpyridine n-oxide; and mixtures thereof; i. optionally, an effective amount of perfume and additional adjuvants; and j. optionally, but preferably, the remainder being an aqueous solvent system, and wherein the cleaning compositions have a pH under conditions of use of about 2 to about 5. It is believed that the improved cleaning is the direct result of the selection of the C-io specific alkyl sulfate surfactant.

DETAILED DESCRIPTION OF THE INVENTION The compositions of the invention are especially useful for cleaning difficult to remove dirt commonly found in the bathroom. These include hard water spots, fatty acids, triglycerides, lipids, insoluble fatty acid soaps, and the like. The detergent compositions can be used on different types of surfaces, such as ceramics, fiberglass, polyurethane and plastic surfaces.

A. Cm Alaminosulfate The alkyl sulfate is an essential component of the invention. Such surfactants provide considerable performance and / or cost advantages compared to other anionic surfactants. Suitable alkyl sulphates can be neutralized with an alkali metal base, preferably lithium, sodium and / or potassium hydroxides, or alternatively can be neutralized with an ammonium salt derivative of C1-C9 or ammonium such as monoethanolamine, diethanolamine and / or triethanolamine, diethylamine , triisopropanolamine etc. wherein the nitrogen atom has one to three substituents selected from alkyl and hydroxyalkyl groups containing from one to four carbon atoms. The alkyl sulfates can be produced by any suitable method. Such surfactants are commercially available from various suppliers globally, including Witco Corporation (One American Lane, Greenwich, Connecticut 06831), Stepan Company (Edens &Witnetka Rd, Northfield, Illinois 60093) and Imperial Chemical Industries (Concord Plaza, 3411 Silverside Rd, PO Box 15391, Wilmington, DE 19850-5391). Detergent compositions according to the present invention are prepared with relatively low levels of active. Typically, the compositions comprise sufficient surfactant and solvent, as described below, to be effective as hard surface cleaners and at the same time economical; they also typically contain about 0.5% about 5% C02 alkyl sulfate surfactant, most preferably from about 1% to about 4% C02 alkyl sulfate surfactant and still most preferably from about 1.2% to about 3% of C? 0 alkyl sulfate surfactant. It has been found that low levels of C 1 0 alkyl sulfate surfactant can be advantageous for the general cleaning performance. In the context of thickened compositions the alkyl sulfate surfactant also helps to provide improved phase stability. The alkyl sulfates of the invention have an average chain length of about 10 carbon atoms. The chain length distribution can vary from about 8 carbon atoms to about 12 carbons. However, the preferred alkyl sulfates are those containing C 1 0 alkyl sulfate. The ammonium and sodium salts of alkyl sulphates from Cío are more preferred in the context of the present invention. Examples of commercially available, particularly preferred C 1 S sodium alkyl sulfates include Polystep B25 from Stepan and Empicol 0137 from ICI. Alternatively, the desired C-10 alkyl sulfate surfactant can be produced in situ by neutralization of the C ylsulfuric acid. b. Optional organic cleaning solvent The compositions, optionally, may also comprise one or more organic cleaning solvents at effective levels, typically not less than 0.5%, and at least about, in increasing order of preference, 1% and about 2%, and no more than about, in increasing order of preference, 8% and about 6% by weight of the composition. The essential C-in alkyl sulfate surfactant provides exceptional cleaning even when a hydrophobic cleaning solvent is not present. However, good cleaning can be further improved by the use of the appropriate organic cleaning solvent. Organic cleaning solvent, refers to an agent that helps the surfactant to remove dirt such as is commonly found in bathrooms. The organic cleaning solvent may also participate in the formation of viscosity, if necessary, and increase the stability of the composition. Compositions containing C-io alkyl sulfate also have low foaming characteristics when the solvent is present. Therefore, the foam profile can largely be controlled simply controlling the level of hydrophobic organic cleaning solvent in the formulation. Additionally, it has been found that organic solvents facilitate rinsing of compositions comprising C10AS. It is believed that the rinsing benefits are obtained from a lower foam level and that the organic solvents suppress the foam analogously to silicone oils, occupying sites at the air-water interface at the same time that they are not active at the same time. the surface. Therefore, more hydrophobic solvents such as dipropylene glycol butyl ether are stronger foam suppressors than less hydrophobic solvents such as propylene glycol butyl ether. Such solvents typically have a terminal C3-C6 hydrocarbon attached from one to three portions of ethylene glycol or propylene glycol to provide the appropriate degree of hydrophobic capacity and, preferably, surface activity. Examples of commercially available hydrophobic cleaning solvents based on ethylene glycol chemistry include monoethylene glycol n-hexyl ether (Hexyl Cellosolve® available from Union Carbide). Examples of commercially available hydrophobic cleaning solvents based on propylene glycol chemistry include the di-, and tri-propylene glycol derivatives of propyl and butyl alcohol, which are available from Arco Chemical, 3801 West Chester Pike, Newton Square, PA 19073) and Dow Chemical (1691 N. Swede Road, Midland, Michigan) under the trade names Arcosoly® and Dowanol®. In the context of the present invention, the preferred solvents are selected from the group consisting of monopropyl ether of monopropylene glycol, monobutyl ether of monopropylene glycol, monopropyl ether of dipropylene glycol, monobutyl ether of dipropylene glycol; tripropylene glycol monobutyl ether; monobutyl ether of ethylene glycol; diethylene glycol monobutyl ether, ethylene glycol monohexyl ether and diethylene glycol monohexyl ether, and mixtures thereof. "Butyl" includes both normal butyl groups, such as isobutyl and tertiary butyl groups. Dipropylene glycol monobutyl ether is the most preferred cleaning solvent and is available under the trade names Arcosolv DPnB® and Dowanol DPnB®. The propylene glycol mono-t-butyl ether is commercially available from Arco Chemical under the trade name Arcosolv PTB®. The amount of organic cleaning solvent may vary depending on the amount of other ingredients present in the composition. The hydrophobic cleaning solvent is usually useful to provide good cleaning. c. Additional surfactant coagent The detergent compositions of the present invention may optionally include a small amount of anionic and / or nonionic detergent surfactant, preferably, co-surfactant anionic surfactant. Such anionic surfactants typically comprise a hydrophobic n containing from about 8 carbon atoms to about 18, preferably from about 10 to about 16 carbon atoms, and typically include a higher sulfonate or carboxylate hydrophilic group. Examples of suitable anionic surfactant coagents include linear or branched alkyl sulfate detergent surfactant (e.g., Stepan AM® from Stepan), alkylcytoxy sulfates (Witconate® 7093 from Witco Corporation), One American Lane, Greenwich, Connecticut). In general, the level of optional anionic surfactants in the compositions herein is from about 0.25% to about 4%, preferably from about 0.5% to about 3.5%, most preferably from about 0.75% to about 3% in weight of the composition. Other anionic surfactants include paraffinsulfonates (Hostapur SAS® from Hoechst, Aktiengesellst, D-6230 Frankfurt, Germany) and alkyleptocarboxylate detergent surfactant (Neodex® from Shell Chemical Corporation). Nonionic detergent surfactants may also be present. Suitable nonionic surfactant detergents for use herein are alkoxylated alcohols which generally comprise from about 6 to about 16 carbon atoms in the hydrophobic alkyl n of the alcohol. Typical alkoxylation groups are ethoxy and / or propoxy groups. Such compounds are commercially available under the Neodol® series from Shell, or Lutensol® from BASF AG with a wide variety of n lengths and degrees of alkoxylation. The preferred nonionic surfactants for use in the present are according to the formula R (X) nH, wherein R is an alkyl n having from about 6 to about 16 carbon atoms, preferably from about 6 to about 10, X is an alkoxy group, preferably ethoxy , or a mixture of ethoxy and propoxy groups, n is an integer from about 4 to about 30, preferably from about 5 to about 8. Other nonionic surfactants that can be used include those derived from natural sources such as sugars and include alkyl polyglucosides (for example, Simusol® surfactants from Seppic Corporation, 75 Quai d'Orsay, 75321 Paris, Cedex 7, France) and C-Ci6 N-alkyl glucosamide surfactants. If present, the concentration of nonionic surfactant is from about 0.1% to about 3%, most preferably from about 0.1% to about 2%, by weight of the composition. d. Monocarboxylic or polycarboxylic acid For the purposes of removing soap and hard water, the compositions are acidic with a pH of about 2 to about 5, most preferably about 3. The acidity is achieved, at least in part, by through the use of one or more organic acids having a pKa of less than about 5, preferably less than about 4. Such organic acids aid in the formation of phase for thickening, if necessary, as well as provide stain removal properties of hard water. It has been found that acids organic are very efficient to promote good hard water removal properties within the framework of the compositions of the present invention. A lower pH and the use of one or more suitable acids also proves to be advantageous for disinfection benefits. Examples of suitable monocarboxylic acids include acetic acid, glycolic acid or β-hydroxypropionic acid and the like. Examples of suitable polycarboxylic acids include citric acid, tartaric acid, succinic acid, glutaric acid, adipic acid and mixtures thereof. Said acids are commercially available in the market. Examples of more preferred polycarboxylic acids include citric acid (available from Aldrich Corporation, 1001 West St. Paul Avenue, Milwaukee, Wisconsin) and a mixture of succinic, glutaric and adipic acids available from DuPont (Wilmington, Delaware) sold as "di-basic acids". AGS refined ". Citric acid is the most preferred, particularly for cleaning soapy cream. Glycolic acid and the mixture of adipic, glutaric and succinic acids provide greater benefits for removal of hard water spots. The amount of organic acid in the compositions herein can be from about 1% to about 10%, most preferably from about 2% to about 8%, still most preferably from about 3% to about 6% by weight of the composition. and. Optional peroxide source The compositions of the invention may comprise peroxide such as hydrogen peroxide, or a source of hydrogen peroxide, for disinfectant, fungistatic and additional fungicide benefits. It is believed that peroxide increases the longevity of the benefit by its known residual capacity and slow decomposition to produce radical species. The components of the present composition are substantially compatible with the use of peroxides. Preferred peroxides include benzoyl peroxide and hydrogen peroxide. These may optionally be presented in the compositions herein at levels of from about 0.05% to about 5%, most preferably from about 0.1% to about 3%, still most preferably from about 0.2% to about 1.5%. When peroxide is present, it is desirable to provide a stabilizing system. Suitable stabilizing systems are known. A preferred stabilizer system consists of radical scavengers and / or metal chelators present at levels of from about 0.01% to about 0.5%, most preferably from about 0.01% to about 0.25%, still most preferably from about 0.01% to about 0.10%, by weight of the composition. Examples of radical scavengers include antioxidants such as propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA) and the like. Examples of suitable metal chelants include diethytriamine pentaacetate, diethytriamine pentamethyphosphonate, hydroxyethyldiphosphonate, and the like. f. Optional Quaternary Surfactant The incorporation of quaternary ammonium surfactants is particularly preferred for compositions designed to provide antibacterial, fungistatic and fungicidal properties. Quaternary ammonium surfactants are known in the art and include derivatives of C 10-16 alkytrimethylammonium, dialkyl dimethyl ammonium of Cg-u and C 10-16 alkyldimethylbenzylammonium and mixtures thereof. C10-16 alkyltrimethylammonium and commercially available quaternary Cg.14 quaternary dyalkyldimethylammonium are available from Witco Corporation under the trade name Adogen®; Suitable C10-16 alkyldimethylbenzylammonium surfactants can be purchased from Lonza incorporated under the trade name Bardac®. The quaternary ammonium surfactants are preferably present in no more than about 2%, most preferably no more than about 1.5%, most preferably no more than about 1% by weight of the composition. g. Optional thickener polymer They can also be used under polymer levels to thicken the compositions of the present invention. Cleaning compositions for thick baths are desired in areas where the use of sprinklers is not common. In general, a Brookfield viscosity (spindle # 2, 60 rpm) of about 80 cP to about 1,000 cP is convenient. Polymers such as high molecular weight acrylates or gums are particularly suitable for this purpose. Xanthan gum is a particularly preferred thickening agent. The polymeric thickening agent is present at a level of from about 0.10% to about 1.0%, most preferably from about 0.12% to about 0.75%, still most preferably from about 0.15% to about 0.5% by weight of the composition. For markets where spray products are common, vertical adhesion of the product sprayed on surfaces is desirable. It has been observed that the compositions of the present invention exhibit excel vertical adhesion properties, even in the absence of high molecular weight polymers. In addition, vertical adhesion can be improved through the use of very low levels of such polymers. Additional benefits obtained through polymeric rubbers include improved foam stability and a reduction in irritation of the product when sprayed. In the context of spray applications, the use of up to about 0.10% polymeric rubber, such as xanthan gum or guar gum, has been found to be extremely beneficial. The use of very low polymer levels limits the potential rinse negatives that can be observed at higher polymer levels. h. Optional hydrophilic polymer In a preferred embodiment, the compositions of the present invention can advantageously incorporate low levels of hydrophilic polymer. These polymers increase the formation of water film on surfaces and improve the formation of veining. It is believed that such polymers hydrophilically modify the ceramic surface thereby reducing the surface tension of water and inducing the improved removal of water film formation on said surfaces. This effect of removal of film formation allows the channeling of dissolved soils on shower walls in bathrooms, which leads to lower levels of residual dirt. Hydrophilic polymers have also been shown to mitigate the formation of surface spots caused by surfactants, especially for compositions that additionally include quaternary ammonium surfactant. Preferred hydrophilic polymers for use in conjunction with the compositions of the present invention include: polystyrene sulfonate, polyvinylpyrrolidone, polyvinylpyrrolidone / acrylate copolymer, polyvinylpyridine and polyvinylpyridine n-oxide. For compositions that include optional hydrogen peroxide, the most preferred polymers are polyvinylpyridine and polyvinylpyridine n-oxide. Preferred polymers, if present, have an average molecular weight of from about 10,000 to about 5,000,000, most preferably from about 20,000 to about 1,000,000, still most preferably from about 30,000 to about 500,000. The level of polymers suitable for achieving the desired benefits is from about 0.001% to about 0.10%, most preferably from about 0.005% to about 0.075%, still most preferably from about 0.01% to about 0.05%. The specific level of polymer depends on the objective of the formulator. Therefore, although it results in the removal of film formation from an increased level of polymer, it has been found that the hard water removal performance deteriorates. i. Optional Aqueous Solvent System The compositions that are aqueous, comprise at least 60% aqueous solvent by weight of the composition, most preferably from about 60% to about 90% by weight of the composition. Aqueous compositions typically contain the detergent surfactants in micellar form, and do not incorporate substantial levels of water insoluble components that induce significant micellar swelling; the compositions are preferably adjusted to a final pH of from about 2 to about 5, most preferably about 3. The aqueous solvent system can comprise highly water soluble solvents of low molecular weight, typically found in detergent compositions such as ethanol, isopropanol, etc. The compositions of the present invention may also include other solvents, and in particular paraffins and isoparaffins, which substantially reduce the foam created by the composition. j. Optional perfume and additional auxiliaries Optional components, such as perfumes and other conventional auxiliaries may also be present.

Perfume An optional, but highly preferred ingredient is a perfume, usually a mixture of perfume ingredients. In fact, the perfume ingredients, which are typically hydrophobic materials, have been shown to contribute to the formation of viscosity, perhaps through the support of the phase structure of the product, as well as to improve the overall stability of the product. As used herein, perfume includes constituents of a perfume that are added primarily for its olfactory contribution. Most hard surface cleaning products comprise a certain amount of perfume to provide an olfactory aesthetic benefit and to cover any "chemical" odor that the product may have. The main function of a small fraction of highly volatile perfume components, low boiling (which have low boiling points), in these perfumes is to improve the odor of the fragrance of the product itself, instead of impacting on the subsequent odor of the surface that has been cleaned. However, some of the less volatile, high-boiling perfume ingredients can provide a fresh and clean impression to surfaces, and it is sometimes desirable that these ingredients deposit and present on the dry surface. The perfumes are preferably those which are more soluble in water and / or volatile to minimize the formation of spots and films. The perfumes useful herein are described in greater detail in the U.S. patent. No. 5,108,660, Mchael, issued April 28, 1992, in columns 8, lines 48 to 68, and column 9 lines 1 to 68, and column 10 lines 1 to 24, said patent, and especially said specific portion, incorporated herein as a reference. The perfume components can be natural products such as essential oils, absolutes, resinoids, resins, concretes, etc., and / or synthetic perfume components such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, acetals, ketals, nitriles. , etc., including saturated and unsaturated compounds, aliphatic, carbocyclic and heterocyclic compounds. Examples of said perfume components are: geraniol, geranyl acetate, linalool, linaloyl acetate, tetrahydrolinalool, citronellol, citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate, tepineol, terpinyl acetate, acetate, 2-phenylethanol, 2-acetate phenylethyl, benzyl alcohol, benzyl acetate, benzyl salicylate, benzyl benzoate, styrallyl acetate, amyl salicylate, dimethylbenzylcarbinol, trichloromethylphenylcarbinyl acetate, p-tert.butyl-cyclohexyl acetate, sononyl acetate, alpha-n-aldehyde -aminocinnamic, alpha-hexyl cinnamic aldehyde, 2-methyl-3- (p-tert-butylphenyl) -propanal, 2-methyl-3- (p-isopropylphenyl) -propanal, 3- (p-tert-butylphenyl) - propanal, tricyclodecenyl acetate, tricyclodecenyl propionate, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexencarbaldehyde, 4- (4-methyl-3-pentenyl) -3-cyclohexencarbaldehyde, 4-acetoxy-3-pentyl tetrahydropyran, methyl dihydrojasmonate, 2-n- heptyl-cyclopentanone, 3-met? l-2-pent? l-cyclopentanone, n-decanal, n-dodecanal, 9-decenol-1, phenoxyethyl isobutyrate, phenylacetaldehyde dimethylacetal, phenylacetaldehyde diethyl acetal, geranonitrile, citranelonitrile, cedrite acetate , 3-isocanfil-cyclohexanol, cedrylic ether, isolongifolanone, aubepin nitrile, aubepin, heliotropin, coumarin, eugenol, vanillin, diphenyl oxide, hydroxycitronol, yonones, methylonones, sometilononones, ironones, cis-3-hexenol and esters of the same, indane musk fragrances, tetralin musk fragrances, isocroman musk fragrances, macrocyclic ketones, musk fragrances of macrolactone, ethylene brasilate, fragrance of aromatic nitro musk. The compositions herein typically comprise from about 0.1% to 2% by weight of the total composition of a perfume ingredient, or mixtures thereof, preferably from about 0.1% to 1.0%. In the case of the preferred peroxide-containing embodiment, the perfumes should be selected to be compatible with the oxidant. In a preferred embodiment, the perfume ingredients are hydrophobic and highly volatile, for example, ingredients having a boiling point of less than 260 ° C, preferably less than 255 ° C; and most preferably less than 250 ° C, and a ClogP of at least 3, preferably more than about 3.1, and still most preferably more than about 3.2.

The logP of many ingredients has been registered; for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California, contains many, along with quotes from the original literature. However, the logP values are conveniently calculated by the "CLOGP" program, also available from Daylight CIS. This program also lists experimental logP values when they are available in the Pomona92 database. The "calculated logP" (ClogP) is determined by the fragment approach of Hansch and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sammens, J.B.

Taylor and C. A. Ramsden, Eds., P. 295, Pergamon Press, 1990, incorporated herein by reference). The fragment approach is based on the chemical structure of each ingredient and takes into account the numbers and types of atoms, the connection capacity of the atom, and the chemical bond. The ClogP values that are the most reliable and widely used calculations For this physicochemical property, they are preferably used in place of the experimental logP values in the selection of the main solvent ingredients that are useful in the present invention. Other methods that can be used to compute ClogP include, for example, the Crippen fragmentation method as described in J. Chem. Inf. Comput. Sci., 27, 21 (1987); the method of Viswanadhan fragmentation as described in J. Chem, Inf. Comput. Sci., 29, 163 (1989); and the Broto method as described in Eur. J. Med. Chem. - Chím. Theor., 19, 71 (1984). The compositions herein may comprise a variety of other optional ingredients, including additional assets and builders, as well as aesthetic ingredients. In particular, the rheology of the compositions herein will be suitable for suspending particles in the composition, for example abrasive particles. Efficiency builders that are efficient for hard surface cleaners and that have reduced film / streaking characteristics at critical levels are other optional ingredients. Preferred builders are the carboxylic acid builders described above as part of the description of the polycarboxylic acid, including citric and tartaric acids. Tartaric acid improves cleaning and can minimize the problem of film / streaking that normally occurs when builders are added to hard surface cleaners. The detergency builder is presented at levels that provide improved detergency, and, if not part of the acid pH adjustment described above, typically occur at a level of from about 0.1% to about 0.3%, most preferably about 0.1% to about 0.3%. 0.2 to about 2%, and still most preferably from about 0.5 to about 1%. The compositions herein may also comprise other adjunct agents that are known in the art for detergent compositions. Preferably they are not used at levels that can cause unacceptable film / grain formation. Non-limiting examples of other auxiliaries are: enzymes such as proteases, hydrotropes such as sodium toluenesulfonate, sodium cumensulfonate and potassium xylene sulfonate; thickeners other than hydrophilic polymers at a level of from about 0.01% to about 0.5%, preferably from about 0.05% to about 0.4%; and aesthetic enhancement ingredients such as colorants, with the proviso that they do not affect the formation of film / grain. Antibacterial agents may be present, but preferably only at levels lower than 0.5%, preferably less than 0.4%, to avoid problems of film / veining formation. The more hydrophobic antibacterial / germicidal agents, such as orthobenzyl para-chlorophenol, are avoided. If presented, said materials should be maintained at levels of less than 0.1%.

Processing Methods The compositions herein can be made by mixing all the ingredients. In general, a preferred order of addition is first to incorporate water, C-io alkyl sulfate surfactant and organic acid, followed by any hydrophobic cleaning solvent. Once the solvent is added, the pH is adjusted to optimum as desired by the formulator. Then optional peroxide, perfume, polymer and colorant can be added.

Spraying Dispenser The article of manufacture herein comprises the composition in a sprayer dispenser. The acid cleaning composition is placed in a spray dispenser to be distributed on the surface to be cleaned. Said spray dispenser may be any of the manually activated means, known in the art, to produce a spray of liquid droplets as is known in the art, for example, of the trigger type., of the pump type, non-aerosol spray media, self-pressurized, and aerosol type. The sprayer dispenser of the present does not normally include those which substantially increase foam in the acid cleaning composition. The yield is increased by providing droplets of smaller particles. Conveniently, the average particle diameter is from about 10 μm to about 120 μm, most preferably from about 20 μm to about 100 μm. A degree of foam and / or drainage resistance, as discussed hereinabove, can provide improved acceptance. The sprayer dispenser can be an aerosol dispenser. However, the aerosol dispenser must comprise a container that can withstand acidic conditions. The dispenser must be able to withstand an internal pressure in the approximate scale of 1.40 kg / cm2 gauge to 7.733 kg / cm2 gauge; more preferably, approximately 1.40 kg / cm 2 gauge at 4,921 kg / cm 2 gauge. The aerosol dispenser uses a sealed container, a pressure, from which the acid cleaning composition is dispensed, through a special actuator / valve assembly, under pressure. The aerosol dispenser is pressurized by incorporating a gaseous component, generally known as a propellant. Common aerosol propellants, for example, gaseous hydrocarbons, such as isobutane and mixed halogenated hydrocarbons, are not preferred. Halogenated hydrocarbon propellants, such as chlorofluorohydrocarbons, have been said to contribute to environmental problems. The hydrocarbon propellants can ignite. The preferred propellants are air, nitrogen, inert gases, carbon dioxide, etc. A more complete description of commercially available aerosol dispensers appears in U.S. Patent Nos. 3,436,772, Stebbins, issued April 8, 1969; and No. 3,600,325, Kaufman et al, issued August 17, 1971; both incorporated here as a reference. The sprayer dispenser can be a non-aerosol, self-pressurized container having a rolled liner and an elastomeric sleeve. The selfprespressed dispenser comprises a liner / sleeve assembly containing a thin, flexible, radially expandable, rolled plastic liner, from about 0.254 to about 0.508 mm thick, within an elastomeric, essentially cylindrical sleeve. The liner / sleeve assembly is capable of containing a substantial amount of odor-absorbing fluid product, and of causing the product to be dispensed. A more complete description of the spray dispensers self-pressurized can be found in U.S. Patent Nos. 5,111,971, Winer, issued May 12, 1992, and No. 5,232,126, Winer, issued August 3, 1993; both incorporated here as a reference. Another type of aerosol spray dispenser is one in which a barrier separates the acid cleaning composition from the propellant (preferably compressed air or nitrogen), as described in U.S. Patent No. 4,260,110, issued April 7, 1981. and incorporated here as a reference. Said dispenser can be obtained from EP Spray Systems, East Hanover, New Jersey. Most preferably, the spray dispenser is a spray dispenser with pump, not spray, manually activated. Said pump spray dispenser comprises a container and a pump mechanism that is firmly screwed or secured onto the container. The container comprises a reservoir for containing the acid cleaning composition to be supplied. The pump mechanism comprises a pumping chamber, of substantially fixed volume, having an opening at its inner end. A pump rod having a piston at one of its ends arranged to move reciprocally in the pumping chamber is located within the pump chamber. The pump rod has a passage through it, with a dispensing outlet at the outer end of the passage, and an axial entry port, located inwardly thereof. The container and the pump mechanism can be constructed of any conventional material used in the manufacture of pump spray dispensers, including, but not limited to: polyethylene, polypropylene, polyethylene terephthalate; mixtures of polyethylene, vinyl acetate and elastomeric rubber. A preferred container is made of clear polyethylene terephthalate. Other materials may include stainless steel that is resistant to acid and / or glass. A more complete description of dispensing devices that are commercially available appears in U.S. Patent Nos. 4,895,279, Schultz, issued January 23, 1990; 4,735,347, Schultz et al., Issued April 5, 1988; and 4,274,560, Carter, issued June 23, 1981, all of which are hereby incorporated by reference. It is highly preferable that the sprayer dispenser be a trigger spray dispenser, activated manually. Said trigger sprinkler dispenser comprises a container and a trigger, both of which may be constructed of any conventional material used in the manufacture of the trigger sprinkler dispensers, including, but not limited to: polyethylene, polypropylene, polyacetal, polycarbonate, terephthalate polyethylene, polyvinyl chloride, polystyrene, polyethylene blends, vinyl acetate and elastomeric rubber. Other materials may include stainless steel that is resistant to acid and / or glass. The spray dispenser with trigger does not incorporate a propellant gas in the acid cleaning composition. The trigger sprinkler dispenser of the present typically is one that acts on a discrete amount of the composition itself. acid cleaning, typically by means of a piston or a collapsible bellows, which moves the composition through a nozzle to create a thin liquid spray. Said trigger sprinkler dispenser typically comprises a pump chamber having a piston or a bellows which is movable in a limited stroke, in response to the trigger, to vary the volume of the pump chamber. This pumping chamber or bellows chamber collects and contains the product to be dispensed. The trigger sprinkler dispenser typically has an outlet check valve to block communication and fluid flow through the nozzle, and which responds to pressure within the chamber. For trigger sprinklers, of the piston type, when the trigger is compressed, it acts on the fluid in the chamber and the spring, increasing the pressure on the fluid. For the bellows sprinkler dispenser, when the bellows is compressed the pressure on the fluid increases. The increase in fluid pressure in any of the trigger sprinkler dispensers, acts to open the outlet check valve, from the top. The upper valve allows the product to be forced through the whirl chamber and out through the nozzle to form a discharge pattern. An adjustable nozzle cap can be used to vary the pattern of the dispensed fluid. For the piston spray dispenser, when the trigger is released, the spring acts on the piston to return it to its original position. For the bellows sprinkler dispenser, the bellows acts as a spring to return it to its original position. This action causes a vacuum in the camera. s? The fluid that responds acts to close the outlet valve, at the same time that it opens the inlet valve, which carries product upwards, to the chamber, from the reservoir. A more complete description of the dispensing devices available in commerce appears in U.S. Patent Nos. 4,082,223, Nozawa, issued April 4, 1978; 4,161, 288, McKinney, issued July 17, 1985; 4,434,917, Saito et al., Issued March 6, 1984; 4,819,835, Tasaki, issued April 11, 1989; 5,303,867, Peterson, issued April 19, 1994; all of these are incorporated herein by reference. A wide variety of trigger or spray sprinklers with a finger operated pump is suitable for use with the compositions of this invention. They are readily available from suppliers such as Calmar, Inc., City of Industry, California, E. U. A .; C.S. I. (Continental Sprayers, Inc.), St. Peters, Missouri; Berry Plastics Corp., Evansville, Indiana, E. U. A., a distributor of Guala® sprinklers; or Seaquest Dispensing, Cary, Illinois.

The preferred trigger sprinklers are the Guala® sprayer inserted in blue, available from Berry Plastics Corp., or the Calmar TS800-IA®, TS1300®, and TD-800-2®, available from Calmar, Inc. for the characteristics of fine and uniform spray, spray volume and pattern size. More preferred are sprinklers with precompression and finer spray characteristics and even distribution, such as Japan's Yoshino sprinklers. Any suitable bottle or container can be used with the trigger sprinkler; being preferred a bottle of around 500 ml, good ergonomic qualities, and similar to the Cinch® bottle. It can be made of any material, such as high density polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyethylene terephthalate, glass or any other material that forms bottles. It is preferred to make it of high density polyethylene or transparent polyethylene terephthalate. For smaller fluid sizes, (such as from 29.57 to 236.56 milliliters), a finger operated pump with a corked or cylindrical bottle may be used. The preferred pump for this application is the cylindrical Euromist II®, from Seaquest Dispensing. Most preferred are those having precompression characteristics. As used herein, all numerical values are approximations based on normal variations; all parts, percentages and ratios are by weight unless otherwise specified, and all patents and other publications are incorporated herein by reference.

Soapy Smelt Cleaning: Standard soiled dishes that are used to provide a reproducible standard soiled surface are treated with each product and the surface is cleaned with a sponge using a Gardner Straight line Washability Machine. The number of passes required to complete the cleanup is measured and recorded. Compositions that do not clean dirty dishes in 50 passes are assigned a pass count of 50+.

Hard water cleaning: Four pieces of marble for each tested product of approximate dimensions 3 / "x 3" x U "are weighed to four decimal places using an analytical balance The pieces are placed in 100 ml beakers containing 20 ml. grams of the product for a total of 10 minutes Marble pieces are removed, rinsed and left to dry, then reweighed and weight loss recorded, using averages of four tests for each product, the removal rate of hard water is recorded as follows: (average weight loss of the marble pieces immersed in the control product / average weight loss of the marble pieces immersed in the experimental compositions) * 100. The subsequent compositions were tested in comparison with Dow Bath Room aerosol®, the leading bath cleaner in the US The tests included a performance evaluation of hard water and soapy cream. rosol Dow Bath Room removed the soapy cream in 30 passes and also removed 10 mg of CaCO3 using the chunk test.

Rinse test facility This test measures the ease with which cleaning compositions are rinsed. Five ml of product are placed evenly in a washbasin and the cleaning is simulated by rubbing the product on the surface with a sponge at a constant pressure. The resulting foam is washed using 7 grains per gallon of water, and the amount of water needed to completely rinse the product in the sink is obtained by collecting the water under the sink in a larger beaker and measuring the volume. The collection of the product under the sink also allows to quantify the foam level by measuring the height of the foam on the collected solution.

EXAMPLES The present invention is further illustrated by the following examples and comparative examples. The following compositions are made by mixing the ingredients listed in the proportions listed in the listing order of addition.

COMPOSITION Effect of the type of anionic surfactant The type effect of anionic surfactant was evaluated in the context of formulations comprising: 2.0% anionic surfactant 3.0% citric acid 0.16% ammonium hydroxide 0.2% perfume. following surfactants do not completely remove the soapy cream from the test dishes even after cleaning for 50 passes: Diphenyl ether disulfonate of C12 Alkylbenzene sulfonate -. C10 diphenyl ether disulfonate C14.17 paraffin sulphonate or C12 diphenyl ether disulfonate C10 ethoxylated sulfate C10 sulphonyl ether diphenyl ethoxylate sulphonate (2) C12 olefin sulphonate sulphide C14.16 C12 ethoxylated sulphate (C12) 0 The above data suggested a poor cleaning performance for ethoxylated sulfates, paraffinsulfonates and benzenesulfonates. The cleaning results are in contrast to those obtained for C10 alkyl sulphates shown below.

Chain length effect of alkyl sulfate The data suggest that cleaning performance of soapy cream is very sensitive to the chain length of alkyl sulfate, with better results obtained at AS of C10. Excellent cleansing can also be achieved by using combinations of alkyl sulfate surfactant including C 10 AS or by combinations of alkyl sulfates that do not include C 10 AS, but have an average of around 10 carbon atoms. Combinations of surfactants with Cio AS also provide excellent calcium carbonate removal as measured by the calcium chip test.

Effect of solvent in cleaning soapy soap with AS The data shows that organic solvents improve cleaning and that at a given level of solvent, the best cleaning performance is achieved with AS de Cío. In general, the higher the level of solvent, the better the cleaning performance of soapy cream will be. The efficiency of AS of Cio means that lower levels of solvent can be used while still improving the cleaning of improved soapy cream than for other lengths of AS chains at higher solvent levels. The data also indicate that the solvent can be used to adjust the amount of water needed to rinse the composition. Low chain alkyl sulphates generate low levels of foam but are easy to rinse. Compositions with AS de Cío generate a higher level of foam but they are not so easy to rinse. The AS-based compositions of C12 generate excessive foam and are more difficult to rinse; or, in other words, a higher level of solvent is required for compositions based on AS of C12 in order to improve rinsing.

Effect of solvent type on cleaning performance and foam control The incorporation of organic solvent in the formulations comprising AS of C10 generally improves the cleaning of soapy cream. Additionally, the solvent induces a significant reduction in the level of foam that generally results in an improved rinse. Note that the foam level can be adjusted simply through the selection of the type and level of organic cleaning solvent.

Effect of organic acid v type The data show that cleaning is not obtained in the absence of organic acid, although there is presence of solvent. The organic acid also improves the removal of calcium carbonate in the test of pieces of calcium. Additionally, improved cleaning can be achieved using higher levels of C10 AS without the need for solvent (Comparison Composition No. 20 with compositions No. 10 and 11). Finally, the best cleaning results are achieved with citric acid although other acids such as glycolic acid or a mixture of adipic, succinic and glutaric acids also provide excellent results. In addition, the removal of improved hard water is obtained using the glycolic acid or admixture of adipic, glutaric and succinic acids as long as the compositions are at a pH of 3.

Effect of polymer thickener and hydrophilic polymer Excellent cleaning performance is achieved in the context of a liquid thickened with xanthan gum. Rinsing requires more water due to the thickener effect, but can be reduced by incorporating organic solvents into the composition.

The following low viscosity spray compositions were made according to the invention: The addition of low levels of gum to the compositions of the invention has a small negative effect on the test of pieces of calcium, but does not affect the cleaning of soapy cream. The polymeric rubbers can be used advantageously to increase the vertical adhesion of the product and improve the foam stability, as well as to reduce the irritation of the product when it is sprayed. * Polystep B29 from Stepan Corporation ** Polystep B25 from Stepan Corporation *** Sodium dodecyl sulphate from Aldrich Chemical **** Stepanol WA extra from Stepan Corporation 'PnB: Propylene glycol n-butyl ether (Dow Chemical) "DPnB: Dipropylene glycol n-butyl ether (Dow Chemical) m C4E02: Butylcarbitol ( Union Carbide) * 50.5% citric acid solution from Cargill Corporation ** 70% glycolic acid solution made by DuPont Corporation and sold by Aldrich Chemical *** 100% active refined dibasic acid (adipic, succinic and adipic) from Du Pont Corporation to xanthan gum sold under the name Keltrol RD, manufactured and sold by Kelco corporation p PVP-K60 manufactured and sold by BASF AG.

Claims (9)

NOVELTY OF THE INVENTION CLAIMS

1. - An acid cleaning composition for hard surfaces comprising: a. from about 0.1% to about 10% of alkyl sulfate detergent surfactant, the alkyl group comprising about 10 carbon atoms on average, substantially all alkyl groups having between two carbon atoms of the average 10 carbon atoms; b. optionally, an effective amount of organic cleaning solvent; c. optionally, a smaller amount, which is preferably less than the amount of a. of surfactant coagent; d. optionally, an effective amount of water soluble mono- or pol-carboxylic acid; and. optionally, an effective amount, up to 5% hydrogen peroxide; F. optionally, an effective amount, up to about 1% of one or more, quaternary ammonium surfactants; g. optionally, from about 0.1% to about 1% of a thickening polymer selected from the group consisting of polyacrylates, gums and mixtures thereof; h. optionally, an effective amount, up to 0.5%, of a hydrophilic polymer, and i. optionally, an effective amount of perfume and additional adjuvants; and j. the remainder being an aqueous solvent system, wherein the cleaning compositions have a pH under conditions of use of about 2 to about 5.

2. - A composition according to claim 1, further characterized in that it comprises: (A) a) from about 1% to about 4.5% by weight of the composition of said alkyl sulfate surfactant; b) from about 1% to about 6% by weight of the composition of one, or more, organic cleaning solvents; and d) from about 2% to about 6% by weight of the citric acid composition; and j) from about 60% to about 90% by weight of the composition of said aqueous solvent system, said composition having a pH of about 3; or (B) a) from about 1.2% to about 4% by weight of the composition of said alkyl sulfate surfactant; b) from about 3% to about 6% by weight of the composition of one, or more, organic cleaning solvents; d) from about 3% to about 5% by weight of the citric acid composition; and j) from about 60% to about 90% by weight of the composition of said aqueous solvent.

3. A composition according to claim 1 or 2, further characterized in that, in said alkyl sulfate detergent surfactant, said alkyl group comprises from about 8 to about 10 carbon atoms.

4. A composition according to claim 3, further characterized in that it additionally comprises: either c) from about 0.25% to about 4% by weight of the composition of an anionic surfactant coagent selected from the group consisting of: C 2 -C 8 paraffinsulfonates; C 8 -C 8 alkyletoxy sulfates; and mixtures thereof; or e) from about 0.05% to about 5% by weight of the hydrogen peroxide composition; or mixtures thereof.

5. A composition according to any of claims 1-4, further characterized in that it also comprises: h) from about 0.01% to about 0.2%, from about 0.001 to about 0.1%, or from about 0.01% to about 0.05% by weight of the composition of said hydrophilic polymer, said hydrophilic polymer selected from the group consisting of: polystyrene sulfonate; polyvinyl pyrrolidone; acrylic copolymer / polyvinylpyrrolidone; polyvinylpyridine; n-polyvinyl pyridine oxide; and mixtures thereof.

6. A composition according to any of claims 1-5, further characterized in that said organic cleaning solvent is dipropylene glycol n-butyl ether and / or contains polycarboxylic acid preferably selected from the group consisting of: citric acid and mixtures of succinic acids, glutaric and adipic, most preferably citric acid as a pH adjuster and preferably having a pH of about 3 or less.

7. An article of manufacture comprising the composition according to any of claims 1-6 in a spray disperser optionally comprising a trigger spray device and capable of providing droplets with an average weight diameter of about 10. at approximately 120 μm.

8. The method of cleaning a surface consisting of applying an effective amount of the composition according to any of claims 1-6 to said surface, optionally using a trigger spray device, and rinsing said surface.

9. The method according to claim 8, further characterized in that said surface is fouled with mold and said composition contains an effective amount of hydrogen peroxide and / or contains an effective amount of hydrophilic polymer.