ES2253873T3 - ACID WATER CLEANING COMPOSITIONS. - Google Patents

Abstract

Compositions described herein are aqueous detergent compositions, preferably hard surface cleaning compositions, which contain alkyl aryl sulfonate surfactant, selected hydrophobic cleaning solvent, polycarboxylic acid, and aqueous solvent system in solution and/or a micellar phase, the pH being from about 2 to about 4. These have excellent soap scum removal and hard water deposit removal properties and are easy to rinse. Such compositions optionally contain additional anionic sulfate surfactant, cationic surfactant, peroxide and/or hydrophilic polymer for additional benefits.

Description

Acidic aqueous cleaning compositions.

Field of the Invention

The present invention relates to compositions liquid detergents for use in surface cleaning hard, especially bathroom surfaces. These compositions typically contain detergent surfactants, solvents, detergency builders, etc.

Background of the invention

The use of detergents and surfactants Synthetic organic water soluble to clean hard surfaces is well known. The known liquid detergent compositions comprise organic cleaning solvents, surfactants detergents and detergent builders and / or abrasives optional

In the document WO-A-9715649, for example, is describes an aqueous cleaning composition for hard surfaces comprising an acid chelating component, a mixture of hydrophobic and hydrophilic solvents and a surfactant component and / or hydrotrope

Liquid cleaning compositions have the great advantage that they can be applied to hard shaped surfaces pure or concentrated to directly supply dirt a relatively high level of, p. e.g., surfactant material and / or organic solvent Therefore, the cleaning compositions liquids can provide greater foam removal than soap, grease and oily dirt that wash solutions diluted, e.g. eg, those prepared from compositions powder cleaners.

The present invention provides compositions aqueous acidic hard surface cleaners suitable for remove dirt that is usually found in the room bath, said compositions having specific mixtures of surfactants, solvents and organic acids. These compositions Acid hard surface cleaners remove foam from Soap and hard water marks. The compositions may have disinfectant properties achieved by choosing certain active substances, including citric acid and cationic surfactants, and can be used with or without additives such as hydrogen peroxide to get advantages additional inhibition of mold or stain formation humidity. In addition, the compositions may incorporate advantageous one or more hydrophilic polymers to achieve better  surface wetting properties and formation of movies / streaks

Summary of the invention

The detergent cleaning compositions of hard surfaces of the present invention comprise:

to.

 from 0.5% to 5% of alkylbenzene detergent surfactant sulfonate;

b.

 from 1% to 8% hydrophobic cleaning solvent selected from the group that consists of: di-propylene glycol mono-butyl ether; tri-propylene glycol mono-butyl ether; ethylene glycol mono-hexyl ether and mixtures thereof;

C.

 from 2% to 8% water-soluble polycarboxylic acid;

d.

 he remainder an aqueous solvent system, and

where the compositions cleaners are predominantly in the micellar phase with a pH of the 2 a composition Four.

It is believed that cleaning improvement is a function direct from surfactants, solvents and polycarboxylic acids specific selected.

Detailed description of the invention

The compositions of the invention are especially useful for cleaning stains that are found usually in the bathrooms. These spots include dust particles, hard water marks, fatty acids, triglycerides, lipids, insoluble fatty acid soaps, and Similar. Detergent compositions can be used in many different types of surfaces such as ceramic, fiber glass, polyurethane and plastic surfaces.

to. Alkylbenzene sulfonate

The alkylbenzene sulfonates are a component essential of the invention. Because of their abundance, these Surfactants have considerable cost advantages with compared to other anionic surfactants. Alkylbenzene Suitable sulfonates can be neutralized with any metal alkaline such as lithium, sodium, potassium and the like, or they can alternatively neutralized with an ammonium derivative or C 1 -C 9 ammonium salt such as mono-ethanol amine, diethylamine and tri-isopropanol amine. They can be obtained by any suitable process that results in the formation of derivatives of "2-phenyl of low molecular weight" or "2-phenyl of high molecular weight", although derivatives of "2-phenyl of low molecular weight". These Surfactants are marketed by different suppliers to global level, including Witco Corporation (One American Lane, Greenwich, Connecticut 06831), Stepan Company (Edens & Witnetka Rd, Northfield, Illinois 60093) and BASF Aktiengesellschaft (ESA / 1550, D-67056 Ludwigshafen, Germany).

Detergent compositions according to the present invention are prepared with a relatively low level of substance active Typically, the compositions will comprise a level enough of surfactant and solvent, as discussed at then to be effective as surface cleaners hard but at the same time maintaining its economic cost; by Thus, they typically contain 0.5% to 5% surfactant of alkylbenzene sulfonate type, more preferably from 1% to 4% of alkylbenzene sulphonate surfactant, and even more preferably from 1.2% to 3% of alkylbenzene surfactant sulphonate It has been found that a low level of surfactant It can also be advantageous for the general cleaning capacity. Therefore, with alkylbenzene sulfonate levels greater than 5% a worse removal of hard watermarks is observed. Without pretend to impose any theory, it is believed that a high level of surfactant competes for surface sites with acid polycarboxylic acid necessary in the present invention, thus inhibiting the action of organic acid.

The alkylbenzene sulfonates included in the cleaning composition according to the invention has a length of average chain of 8 carbon atoms to 14 carbon atoms, plus preferably from 9 carbon atoms to 13 carbon atoms and with highest preference of 9 carbon atoms to 13 carbon atoms. The chain length distribution may vary from 8 atoms of carbon at 16 carbon atoms. Alkylbenzene mixtures Linear and / or branched sulphonates are suitable.

The ammonium and sodium salts of the C 11 to C 12 alkyl linear benzenesulfonates are most preferred in the context of the present invention. Examples of especially preferred commercial alkylbenzene sulphonates include Polystep A-13® marketed by Stepan, Calsoft L-40® slurry marketed by Pilot Chemical Company (11756 Burke Street, Santa Fe Springs, California) and Witconate P1059® marketed by Witco Corporation ( Greenwich, Connecticut). Alternatively, the desired alkylbenzene sulphonate surfactant can be produced in situ by neutralization of the corresponding alkylbenzene sulfonic acid. Examples of suitable alkylbenzene sulfonic acids include Biosoft® 100 marketed by Stepan Company, Calsoft LAS-99® marketed by Pilot Chemical and Lutensit A-LABS® marketed by BASF AG in Germany.

b. The hydrophobic cleaning solvent

The compositions may also contain one or more hydrophobic cleaning solvents at an effective level, so typical not less than 2%, and at least in ascending order of preference, 2% and 3%, and not exceeding, in ascending order of Preference, 8% and 6% by weight of the composition.

Good cleaning requires the use of solvent correct hydrophobic cleaner. The expression "cleaning solvent hydrophobic "means an agent that removes hydrophobic stains such as those usually found in the rooms of bathroom. The hydrophobic cleaning solvent can also help increase the viscosity, if necessary, and the stability of the composition. Such solvents typically have a C3-C6 hydrocarbon terminal attached to de one to three ethylene glycol or propylene glycol moieties to provide the adequate degree of hydrophobicity and preferably of tensioactivity Examples of hydrophobic cleaning solvents Commercial based on ethylene glycol chemistry include the mono-ethylene glycol n-hexyl ether (Hexyl Cellosolve® marketed by Union Carbide). Examples of hydrophobic cleaning solvents based on the chemistry of Commercial propylene glycol include derivatives of di-propylene glycol and tri-propylene glycol of the propyl alcohols and Butyl, which are marketed by Arco Chemical, 3801 West Chester Pike, Newtown Square, PA 19073) and Dow Chemicals (1691 N. Sweede Road, Midland, Michigan) under the trademarks Arcosolv® and Dowanol®. In the context of the present invention, the Preferred solvents are selected from the group consisting of ethylene glycol mono-hexyl ether, tri-propylene glycol butyl ether and di-propylene glycol butyl ether; ethylene glycol being mono-hexyl ether and the especially effective tri-propylene glycol butyl ether when used together with di-propylene glycol butyl ether The term "butyl" includes normal butyl groups, tertiary isobutyl and butyl. Di-propylene glycol Butyl ether is the most preferred cleaning solvent and is marketed under the trademarks Arcosolv DPnB® and Dowanol DPnB®. He di-propylene glycol t-butyl ether is marketed by Arco Chemical under the trade name Arcosolv PTB® The amount of hydrophobic cleaning solvent may vary. depending on the amount of other ingredients present in the composition, but should be present in a concentration of at less, in ascending order of preference, 2% and 3%, and less than, in ascending order of preference, 8, 6%, and 5% by weight of the total composition

The hydrophobic cleaning solvent is necessary to obtain acceptable cleaning. It is believed that the solvent acts by removing dirt that binds other dirt to the surface or releasing this dirt so it can be more easily reached and / or eliminated.

C. The anionic auxiliary surfactant

The detergent compositions herein invention optionally, but preferably, include a anionic auxiliary surfactant. These surfactants typically they comprise a hydrophobic chain containing from 8 to 18 atoms of carbon, preferably from 10 to 16 carbon atoms, and include a head group sulfate, sulphonate or hydrophilic carboxylate. Examples of preferred suitable anionic surfactants include linear or branched alkyl sulfate detergent surfactants (e.g., Stepanol AM® from Stepan), alkyl ethoxy sulfates (Witconate 7093® from Witco corporation, One American Lane, Greenwich, Connecticut). It has been found that in particular the C 8 -C 14 alkyl type surfactants linear and branched sulfates as they offer greater advantages of removal of hard watermarks and also cleaning the soap foam. In the context of thickened compositions, the alkyl sulfate type surfactant also helps provide Greater phase stability. Although the optional anionic surfactant can be used advantageously to improve the ability to removal of hard watermarks, is more expensive than LAS and It can induce the appearance of a higher level of soaps. In In general, the level of optional anionic surfactants in the compositions of the present invention is from 0.25% to 4%, more preferably from 0.5% to 3.5% and most preferably from 0.75% to 3%, by weight of the composition.

d. Nonionic alcohol or cationic surfactant

The detergent compositions herein invention may optionally comprise one or more alcohols not ionic and / or cationic surfactants. The combination of alkylaryl detergent surfactant with alcohol and / or cationic surfactant can provide higher viscosity, as described in provisional application codependent No. 60 / 066,563, filed on November 26, 1997, on behalf of Alan E. Sherry, Jeffrey L. Flora, Jason M. Knight and Zuchen Lin. The appliers claim the advantage of said filing date of the application. Cleaning compositions can be used that understand nonionic alcohol and cationic surfactant. In the present memory, "non-ionic alcohol" means a non-alcoholic linear or mono-branched ionic comprising a average of 8 carbon atoms to 16 carbon atoms, plus preferably from 9 carbon atoms to 14 carbon atoms and with highest preference of 10 carbon atoms to 13 carbon atoms. Examples of suitable non-ionic alcohols include the 2-butyl-1-octanol, he 2-methyl-1-undecanol and dodecanol. C10-13 non-ionic alcohols Linear are the most preferred. Examples of non-ionic alcohols Preferred commercials include Neodol 1® and Neodol 23® marketed by Shell Chemical (1 Shell Plaza, Houston, Texas 77252). It is believed that the best results are achieved when the Chain length of non-ionic alcohol matches the maximum of the alkylarylsulfonate type surfactant. For this reason, the non-ionic alcohols comprising less than 8 carbon atoms or have more than 16 carbon atoms are not preferred in this invention. If present, non-ionic alcohol has a effective concentration not exceeding 2%, more preferably a concentration of 1.5% or less and most preferably a concentration of 1.25% or less, by weight of the composition.

The detergent compositions herein invention that do not contain a non-ionic alcohol may contain one or more cationic surfactants. In this report, the cationic surfactants are those that at an acidic pH are They basically behave like cationic materials. The surfactant cationic creates viscosity through ion pairing with the alkylarylsulfonate type surfactant described above. Cationic surfactants can also provide properties. of disinfection and can be selected to improve this advantage. Preferred cationic materials are compounds of quaternary ammonium that have at least one hydrophobic chain with a length of 8 carbon atoms to 16 carbon atoms, more preferably from 10 carbon atoms to 16 carbon atoms and with highest preference of 12 carbon atoms to 14 carbon atoms. Suitable cationic surfactants include alkyl salts and quaternary alkylbenzyl ammonium (eg, Bardac® 208M from Lonza Inc., 1717 Route 208, Fairlawn, New Jersey 07410) and ammonium salts ethoxylated quaternary (e.g., Ethoquad® surfactants marketed by Akzo Nobel Chemicals, 300 South Riverside Plaza, Chicago, Illinois). Other cationic surfactants include ethoxylated amines (e.g., Ethomeen® surfactants marketed by Akzo Nobel Chemical), alkyldimethyl betaines (e.g. e.g., Rewoteric AM DML-35® from Witco Corporation), propyl betaine amido (e.g., Witco Rewoteric AMB 15U® Corporation) and amine oxides (eg Barlox 10S® from Lonza Inc.). The incorporation of quaternary ammonium surfactants is especially preferred in the compositions that must have antibacterial, fungistatic and fungicidal properties. The quaternary ammonium surfactants are known in the art and include alkyl tri-methyl derivatives C10-16 ammonium, di-alkyl dimethyl C8-14 ammonium and alkyl dimethylbenzyl C10-16 ammonium and mixtures thereof. The quaternary alkyl tri-methyl compounds C10-16 ammonium and di-alkyl dimethyl Suitable and commercial C8-C14 ammonium are marketed by Witco Corporation under the name Adogen®; the C10-16 alkyl dimethylbenzyl surfactants Suitable ammonium can be purchased from Lonza Inc. under the name Bardac® commercial. The counterion of ammonium surfactants Quaternary can be any of those known in the art such as bromide, chloride or methylsulfate. In the compositions that also contain hydrogen peroxide, the preferred counterion is Methylsulfate

The level of cationic surfactant in the compositions of the present invention is preferably not greater than 2%, more preferably not greater than 1.5% and with maximum preference not exceeding 1.25%, by weight of the composition. The cationic surfactants can be used alone or together with non-ionic alcohols to improve viscosity.

If the cationic surfactant is present, the This level plus that of non-ionic alcohol will be at least 0.1%, more preferably at least 0.3%, most preferably at minus 0.5% and even more preferably from 0.5% to 2.0%, by weight of the composition.

and. Polycarboxylic acid

For the removal of hard watermarks, the compositions are acidic with a pH of 2 to about 4, plus preferably 3. The acidity is achieved, at least in part, by using one or more organic acids with a pKa lower than 5, preferably less than 4. These organic acids also they can contribute to form phase for thickening in case necessary, as well as to provide removal properties of hard water marks. It has been discovered that organic acids are very effective in achieving good elimination properties of hard water marks within the framework of the compositions herein invention. It has also been discovered that a lower pH and the use of one or more suitable acids is advantageous for the purpose of disinfection. Examples of suitable organic acids include acid citric, tartaric acid, succinic acid, glutaric acid, acid adipic, and mixtures thereof. These acids are found Easily available in the market. Examples of more acids Preferred include citric acid (marketed by Aldrich Corporation, 1001 West Saint Paul Avenue, Milwaukee, Wisconsin) and a mixture of succinic, glutaric and adipic acids marketed by DuPont (Wilmington, Delaware) as "AGS dibasic acids refined. "Citric acid is the most preferred. The amount of Organic acid in the compositions of the present invention may be from 1% to 10%, more preferably from 2% to 8% and with maximum preference of 3% to 6%, by weight of the composition.

F. Optional peroxide source

The compositions of the invention may contain peroxide, such as hydrogen peroxide, or a source of peroxide of hydrogen to achieve other disinfectant advantages, fungistatics and fungicides. Peroxide is believed to prolong the advantage due to its well-known residual properties and Slow decomposition to produce radical species. The components included in the cleaning composition herein  invention are basically compatible with the use of peroxides. The Preferred peroxides include benzoyl peroxide and peroxide. hydrogen. These may optionally be present in the compositions of the present invention at a level of 0.05% to 5%, more preferably from 0.1% to 3% and most preferably from 0.2% to 1.5%

If peroxide is present, it is desirable to include a stabilizing system Suitable stabilizer systems are known. A preferred stabilizing system consists of radical inactivators and / or metal chelators present at levels from 0.01% to 0.5%, more preferably from 0.01% to 0.25% and with highest preference of 0.01% to 0.10%, by weight of the composition. Examples of radical inactivators include such antioxidants. as propyl gallate, butyl hydroxytoluene (BHT) and butyl hydroxyanisole (BHA). Examples of suitable metal chelators include diethylene triamine pentaacetate, diethylene triamino pentamethylene phosphonate and hydroxyethyl diphosphonate.

g. Optional hydrophilic polymer

In a preferred embodiment, the compositions of the present invention can advantageously incorporate low levels of hydrophilic polymer. It has been observed that these polymers improve surface water sagging and improve the removal of films and veins as described in the provisional application codependent No. 60 / 061,296, filed on 7 October 1997, on behalf of Nicola John Policicchio and Alan Edward Sherry Without pretending to impose any theory, it is believed that these polymers hydrophilically modify the ceramic surface thus reducing the surface tension of the water and inducing a better water sagging on said surface. This effect of sagging allows channeling dissolved dirt in the direction descending down the shower walls in the bathrooms, leaving less residual levels of dirt. It has also observed that hydrophilic polymers reduce the formation of surface stains caused by surfactants, especially in compositions that also include surfactants of the type quaternary ammonium The preferred hydrophilic polymers to be used in the compositions of the present invention include xanthan gum, polystyrene sulfonate, polyvinylpyrrolidone, polyvinylpyrrolidone / acrylate copolymer, polyvinyl pyridine and polyvinyl pyridine n-oxide. In the compositions that include Optional hydrogen peroxide, the most preferred polymers are the polyvinyl pyridine and polyvinyl pyridine n-oxide. Polymers preferred, if present, have an average molecular weight from 10,000 to 5,000,000, more preferably from 20,000 to 1,000,000 and most preferably from 30,000 to 500,000. Polymer level desired to achieve the desired advantages is from 0.001% to 0.10%, more preferably from 0.005% to 0.075% and most preferably 0.01% to 0.05%. The specific level of polymer depends on the objective of the formulator. Therefore, although better results are achieved Off-hook with a higher level of polymer, it has also discovered that this reduces the ability to remove marks of hard water.

Other optional surfactants and solvents:

In addition to the alkylarylsulfonates and the preferred optional anionic surfactants described previously, hydrophobic cleaning solvents, compositions of the present invention preferably comprise other additional anionic surfactants such as sulphonates of paraffin (Hostapur SAS® from Hoechst, Aktiengesellschaft, D-6230 Frankfurt, Germany) and surfactants alkylethoxy carboxylate detergents (Shell Neodex® Chemical Corporation).

Surfactants may also be present nonionic detergents. Nonionic Detergent Surfactants Suitable for use in the present invention are alkoxylated alcohols. which generally comprise 6 to 16 carbon atoms in the Hydrophobic alkyl alcohol chain. Alkoxylation groups Typical are ethoxy and / or propoxy groups. These compounds are marketed as the Neodol® series by Shell or the Lutensol® series  by BASF AG with a wide variety of chain lengths and degrees of alkoxylation. Nonionic Detergent Surfactants Preferred for use in the present invention are according to the formula R (X) n H, where R is an alkyl chain that it has 6 to 16 carbon atoms, preferably 6 to 10, X is an alkoxy group, preferably ethoxy, or a mixture of groups ethoxy and propoxy, n is an integer from 4 to 30, preferably of 5 to 8. Other non-ionic surfactants that can be used include those derived from natural sources such as sugars and include alkyl polyglucosides (eg, Simusol® surfactants from Seppic Corporation, 75 Quai d'Orsay, 75321 Paris, Cedex 7, France) and surfactants of the N-alkylglucosamide type. Nap present the non-ionic surfactant, its concentration is 0.1% at 3%, more preferably from 0.1% to 2%, by weight of the composition.

The compositions of the present invention they can also include hybrid ion surfactants such as sulfobetaines and hydroxy sulfobetains in an effective concentration which preferably does not exceed 2% by weight of the composition.

Other commercial sources of these surfactants can be found in McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition, 1997, McCutcheon Division, MC Publishing Company

h. The aqueous solvent system

The compositions are aqueous and comprise less 60% aqueous solvent by weight of the composition, more preferably from 60% to 90% by weight of the composition. The aqueous compositions are in micellar form and do not incorporate significant levels of water insoluble components that produce significant micellar swelling; The compositions they are also adjusted to a final pH of 2 to 4, preferably 3.

The aqueous solvent system can also comprise very water soluble solvents of low molecular weight typically present in detergent compositions, e.g. eg ethanol and isopropanol.

The compositions of the present invention they can also include other solvents and in particular paraffins and isoparaffins, which have been observed to basically reduce soaps created by the composition.

Components may also be present optional such as perfumes and other adjuvants conventional.

Optional perfume and additional adjuvants

An optional ingredient, but very preferred, is a perfume, usually a mixture of perfume ingredients. From In fact, it has been discovered that perfume ingredients, which are from typical form hydrophobic materials, contribute to create viscosity, maybe supporting the phase structure of the product, as well as to Improve overall product stability. At the moment memory, the perfume includes perfume components that are added mainly for his olfactory contribution.

Most hard surface cleaning products contain some perfume to provide an olfactory-looking advantage and mask any "chemical" smell the product may have. The main function of a small fraction of the highly volatile perfume components (with low boiling points) is to improve the fragrance of the product itself rather than to influence the subsequent odor of the surface to be cleaned. However, some of the less volatile and high-boiling perfume ingredients may provide an impression of freshness and cleanliness to the surfaces and it is sometimes desirable that these types of ingredients be deposited and kept on the dry surface. Preferred perfumes are the most water soluble and / or volatile to minimize the effects of staining and film formation. Perfumes useful in the present invention are described in more detail in US 5,108,660, issued to Michael on April 28, 1992, in col. 8, lines 48 to 68, et al. 9, lines 1 to 68, et al. 10, lines 1 to 24, of said patent and especially in said portion
specific.

Perfume components can be products natural such as essential oils, absolute, resinoids, resins, concrete, etc., and / or synthetic perfume components such as hydrocarbons, alcohols, aldehydes, ketones, ethers, acids, acetals, ketals, nitriles, etc., including compounds saturated and unsaturated and aliphatic, carbocyclic and heterocyclic Examples of these perfume components are: geraniol, geranyl acetate, linalool, linalyl acetate, tetrahydrolinalol, citronellol, citronellyl acetate, di-hydromyrcenol, dihydromyrcenyl acetate, terpineol, terpinyl acetate, acetate, 2-phenylethanol acetate 2-phenylethyl, benzyl alcohol, benzyl acetate, benzyl salicylate, benzyl benzoate, stiralyl acetate, amyl salicylate, dimethylbenzylcarbinol, acetate trichloromethylphenicarbinyl acetate p-tert-butyl-cyclohexyl, isononyl acetate, aldehyde alpha-n-amylokine, aldehyde alpha-hexyl-cinnamic, 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-cyclohexenecarbaldehyde, 4- (4-methyl-3-pentenyl) -3cyclohexenecarbaldehyde, 4-acetoxy-3-pentyl-tetrahydropyran, methyl dihydrojasmonate, 2-n-heptyl-cyclopentanone, 3-methyl-2-pentyl-cyclopentanone, n-decanal, n-dodecanal, 9-Decenol-1, isobutyrate phenoxyethyl, dimethyl acetal phenylacetaldehyde, phenylacetaldehyde of dicetyl acetal, geranonitrile, citronellonitrile, acetate cedrile, 3-isocanfil-cyclohexanol, cedril ether, isolongifolanone, hawthorn nitrile, hawthorn albar, heliotropin, coumarin, eugenol, vanillin, oxide diphenyl, hydroxycitronellal, ionone, methyl ionone, isomethyl ionone, iron, cis-3-hexenol and esters of the same, indane musk, tetralin musk, musk isochroman, macrocyclic ketone, macrolactone musk, brasilate of ethylene, aromatic nitroalmizcle. The compositions of the present invention typically comprise from 0.1% to 2% by weight of the total composition of a perfume ingredient, or mixtures of same, preferably from 0.1% to 1.0%. In the case of realization preferred containing peroxide, perfumes should be chosen from so that they are compatible with the oxidant. In one embodiment preferred, the perfume ingredients are hydrophobic and very volatile, e.g. eg, ingredients that have a boiling point less than 260 ° C, preferably less than 255 ° C and more preferably below 250 ° C, and a ClogP of at least 3, preferably greater than 3.1 and even more preferably greater than 3.2.

The logP values of many have been described ingredients and, for example, the Pomona92 database, marketed by Daylight Chemical Information Systems, Inc. (Daylight CIS), Irvine, California, contains numerous logP values along with references to the original bibliography. However, the logP values are calculated more conveniently using the "ClogP" program, also marketed by Daylight CIS. This program also includes experimental logP values if they are available in the Pomona92 database. The "calculated logP" (ClogP) is determined by the Hansch fragment method and Leo (A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., P. 295, Pergamon Press, 1990). The fragment method is based on the chemical structure of each ingredient and takes into account the number and the type of atoms, the connectivity between atoms and the bond chemical. To select the main solvent ingredients useful in the present invention preferably the ClogP values, which are the most reliable and most used estimates disseminated for this physical-chemical property, in place of the experimental logP value. Other methods that can used to calculate the ClogP value include, e.g. eg, the method Crippen fragmentation, as described in J. Chem. Inf. Comput Sci., 27, 21 (1987); the fragmentation method of Viswanadhan, as described in J. Chem. Inf. Comput. Sci., 29, 163 (1989); and the Broto method, as described in Eur. J. Med. Chem. - Chim. Theor., 19, 71 (1984).

The compositions of the present invention may understand other optional ingredients, including other active substances and detergency builders, as well as purely aesthetic ingredients. In particular the rheology of the compositions of the present invention would be suitable for suspend particles in the composition, e.g. eg particles of abrasive

Another optional ingredient is additives detergency builders that are effective for cleaning hard surfaces and have lower formation characteristics of films / veins at critical levels. The reinforcing additives of the preferred detergents are the reinforcing additives of the carboxylic acid type detergency described above in the description of polycarboxylic acid, including citric acids and tartaric. Tartaric acid improves cleanliness and can minimize the problem of the formation of films / veins that It usually occurs when additives are added to the detergency to hard surface cleaners.

The detergent builder additive is present at levels that reinforce detergency and additives that they are not involved in the adjustment to an acidic pH described above, are typically present at a level of 0.1% to 0.3%, plus preferably from 0.2% to 2% and most preferably from 0.5 to one%.

The compositions of the present invention they may also contain other different adjuvants known in the technique for detergent compositions. Preferably I don't know used at levels that may cause unacceptable formation of movies / streaks

Non-limiting examples of other adjuvants are: enzymes such as proteases; hydrotropes such as toluenesulfonate  sodium, sodium cumensulfonate or potassium xylenesulfonate; thickeners at a level of 0.01% to 0.5%, preferably 0.05% to 0.4%; and ingredients to improve aesthetics, such as dyes, provided they do not adversely affect the elimination of movies / streaks

Antibacterial agents may be present, in addition to the cationics described above, but preferably only at levels below 0.5%, preferably below 0.4%, to avoid problems of formation of movies / streaks The use of more agents is avoided hydrophobic antibacterials / germicides, such as orthobenzyl-for-chlorophenol. Yes are present, these materials must be maintained at levels by below 0.1%.

Composition Preparation

The compositions of the present invention may Prepare by mixing all the ingredients. In general, an order of preferred addition it is first to incorporate the water, the surfactant of the alkylarylsulfonate type and the organic acid and then the hydrophobic cleaning solvent. Once the solvent is added, it is optimally adjust the pH according to the wishes of the formulator Then the optionally can be added cationic surfactant, peroxide, polymer, perfume and Colorant.

In this report, all values Numeric are approximations based on normal variations and all parts, percentages and relationships are expressed in weight unless otherwise indicated.

Soap foam cleaning : Conventional stained plates used to provide a standard reproducible stained surface are treated with each product and then the surfaces are cleaned with a sponge using a straight-line Gardner washability machine. The number of passes needed to achieve a complete cleaning is measured and recorded. The cleaning index of the soap foam is calculated using the following equation: (number of passes for the control product / number of passes for the experimental product) * 100, where the control product is the Dow Bath Room® spray and the experimental prototypes are the compositions 1-8 described herein. An index higher than 100 suggests a product with excellent soap foam removal properties.

Cleaning of hard water marks : Four marble fragments of each product analyzed with approximate dimensions of ¾ inch x ¾ inch x ¼ inch are weighed with an accuracy of four decimals using an analytical balance. The fragments are placed in 100 ml beakers containing 20 grams of product for 10 minutes. The marble fragments are removed, rinsed and allowed to dry. They are weighed again and the lost weight is calculated. Using the average of four tests for each product, the hard watermark removal rate is calculated as follows: (average weight loss of the marble fragments submerged in the control product / average weight loss of the fragments of marble immersed in experimental compositions) * 100.

Comparisons in elimination trials of soap foam and hard water marks are made in front of a Dow Bath Room® commercial spray product.

Examples

The present invention is also illustrated. using the examples presented below. The following compositions are prepared by mixing the ingredients indicated in the proportions indicated and in the order of addition mentioned.

Composition

Ingredient one 2 3 4 5 6 C_ {12} THE* 1.6 1.6 1.6 1.6 1.6 1.6 C 12 -_ {14} alkyl sulfates 1.0 1.0 1.0 1.0 1.0 1.0 Bardac 208M® ** - - - - - - - - - - - - 0.2 0.2 n-BPP *** 4,5 4,5 4,5 4.0 4,5 4.0 Acid citric 4,5 4,5 4,5 4,5 4,5 4,5 Ammonia (pH adjusted to 3.0) 0.3 0.3 0.3 0.3 0.3 0.3 Rubber xanthan - - - 0.01 0.05 0.01 0.01 0.01 Polyvinylpyrrolidone - - - - - - - - - 0.05 - - - 0.1 Fragrance 0.2 0.2 0.2 0.2 0.2 0.2 * LAS: Rent C 12 linear benzene sulphonate (Calsoft L-40® de Pilot) ** Bardac 208M® is a mixture of quaternary ammonium surfactants marketed by Lonza, Inc. ^ n *** BPP: Dipropylene Glycol n-butyl ether (Dowanol DPnB® from Dow Chemicals) ^ {\ dagger} The composition does not completely eliminate soap foam

The previous formulations were analyzed in front of Dow Bath Room® spray, the best room cleaner US bathroom The trials include a capacity assessment of removal of hard water and soap foam marks.

Elimination Rate of 280 280 280 250 250 250 Foam soap Index of elimination of 350 370 300 350 210 250 watermarks hard

Claims (12)

1. A surface cleaning composition hard acid comprising:

to)

 from 0.5% to 5% by weight of the detergent surfactant composition of alkylbenzene sulfonate type;

b)

 from 1% to 8% by weight of the hydrophobic cleaning solvent composition selected from the group consisting of: di-propylene glycol mono-butyl ether; tri-propylene glycol mono-butyl ether; ethylene glycol mono-hexyl ether and mixtures of themselves;

C)

 from 2% to 8% by weight of the polycarboxylic acid composition water soluble;

d)

 he remainder an aqueous solvent system, and

where the cleaning compositions are in micellar phase with a pH of the composition from 2 to 4. 2. A composition according to claim 1, which includes:

(to)

from 1% to 4% by weight of the type detergent surfactant composition alkylbenzene sulfonate;

(b)

from 2% to 6% by weight of the composition of one or more solvents hydrophobic cleaners;

(C)

from 2% to 6% by weight of the citric acid composition;

(d)

from 60% to 90% by weight of the composition of said solvent system watery, and

wherein said cleaning composition has a pH of 3. 3. A composition according to claim 1, which includes:

(to)

 from 1.2% to 4.5% by weight of the detergent surfactant composition of alkylbenzene sulphonate type wherein said alkyl group contains from 8 to 14 carbon atoms;

(b)

from 3% to 6% by weight of the composition of one or more solvents hydrophobic cleaners;

(C)

from 3% to 5% by weight of the citric acid composition;

(d)

from 60% to 90% by weight of the composition of said solvent system aqueous.

4. A composition according to the claims 1-3, which also includes: (e) from 0.25% to 4% by weight of the composition of a selected anionic auxiliary surfactant from the group consisting of: C 8 -C 18 alkyl linear or branched sulfates; alkyl ethoxy C 8 -C 18 sulfates; and mixtures thereof; and / or (f) an effective concentration not exceeding 2% by weight of the composition of nonionic alcohol and / or cationic surfactant; I (g) an effective amount of up to 5% by weight of the composition of hydrogen peroxide; and / or (h) an effective amount of up to 0.1% in weight of the composition of a hydrophilic polymer. 5. A composition according to claim 4, wherein said non-ionic alcohol is linear alcohol or mono-branched containing 8 to 16 atoms of carbon; and / or wherein said cationic surfactant contains a hydrophobic chain containing 8 to 16 carbon atoms; I said hydrophilic polymer is selected from the group consisting of: xanthan gum; polystyrene sulfonate; polyvinylpyrrolidone; polyvinylpyrrolidone / acrylate copolymer; polyvinyl pyridine; polyvinyl pyridine n-oxide; and mixtures thereof. 6. A composition according to claim 4, wherein said cationic surfactant is selected from the group that consists of: C 8 -C 18 trialkyl chloride ammonium, dialkyl dimethyl C 8-12 chloride ammonium, alkyl benzyl dimethyl chloride C 8 -C 18 ammonium and alkyl chloride pyridinium dimethyl C 8 -C 18 ammonium. 7. A composition according to the claims 4-6, which comprises from 0.001% to 0.1% by weight of said composition of said hydrophilic polymer. 8. A composition according to the claims 4-7, which comprises from 0.05% to 5% by weight of the composition of said hydrogen peroxide. 9. A composition according to the claims 1-8, wherein said hydrophobic cleaning solvent it is dipropylene glycol n-butyl ether and / or in which said composition contains citric acid as a pH regulator and It has a pH of 3 or lower. 10. A composition according to the claims 1-9, wherein said polycarboxylic acid is select from the group consisting of: citric acid and mixtures of succinic, adipic and glutaric acids. 11. The process to clean a surface that comprises applying to said surface an effective amount of the composition according to any of the claims 1-10 and clarify said surface. 12. The process of claim 11, in the that said surface is stained with mold and said composition contains an effective amount of said hydrogen peroxide, said cationic surfactant and / or said hydrophilic polymer.