MXPA00005226A - Aqueous cleaning compositions in dispersed lamellar phase - Google Patents

Abstract

Compositions described herein are aqueous detergent compositions, preferably hard surface cleaning compositions, which contain a flexible lamellar sheet phase dispersed in the aqueous phase. The compositions are viscous, provide excellent soap scum and hard water properties and are easy to rinse. Such compositions are formulated by using an alkylaryl detergent composition in combination with an alcohol and/or cationic surfactant, together with a hydrotropic solvent, in an acidic system further optionally comprising a peroxide.

Description

AQUEOUS CLEANING COMPOSITIONS IN DISPERSED LAMINAR PHASE 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 synthetic detergent solvents and surfactants, soluble in organic water to clean hard surfaces is well established. Known liquid detergent compositions comprise organic cleaning solvents, detergent surfactants, and optional builders and / or abrasives. Liquid cleaning compositions have the great advantage that they can be applied to hard surfaces in pure or cntrated form whereby a relatively high level of, for example, surfactant material and / or organic solvent is supplied directly to the soil. Therefore, liquid cleaning compositions have the potential to provide superior removal of greasy dirt, grease, soapy cream as compared to diluted wash solutions, for example, those prepared from powder cleaning compositions. It is often convenient to increase the viscosity of liquid cleaners on hard surfaces. A higher viscosity may allow a more specific supply of the product during use. In addition, a higher viscosity can promote better action of the product on non-horizontal surfaces, such as toilets, bathtubs, showers and the like. The improved surface coverage and adhesion allows an improved cleaning action of the surfactant / solvent system. A product with shear thinning viscosity is particularly preferred because it can be packaged and sold as a spray or liquid product, is easy to use, and can provide good adhesion and coverage on surfaces. These are important attributes of the product that limit the amount of product spent, during use, through runoff. Additionally, a liquid, viscous thinning product with shear stress may be less irritating in use and may be perceived as softer. The viscosity and thinning properties with shear stress can be obtained by methods known in the art, such as the use of shear thinning gums or polymers. However, thickeners, such as gums or polymers have disadvantages since they increase the cost of the formula, and only provide a benefit, thicken. They do not participate in the actual cleaning of the surface and therefore represent "inert" materials. In many cases, these polymers leave films or veins on surfaces, and often are not sufficiently thin with shear for use in applications with spray bottles. Preferably, the viscosity is constructed by a "self-thickener" system wherein the surfactant / solvent active in the composition is used to provide viscosity. Said approach has several advantages against polymeric thickeners. First, surfactant / solvent systems are often cheaper than polymers.

Second, surfactants / solvents can provide a dual benefit by providing both viscosity and cleanliness. Thickening polymers tend to compete for sites on surfaces and can inhibit the action of the cleaning system. Third, the judicious selection of surfactants / solvents allows for improved compatibility at an acidic pH and / or with optional additives, such as peroxide. Many polymeric thickeners are ineffective at a pH of less than 4, or are not compatible with optional active agents such as peroxide. Finally, surfactant residues tend to be rinsed more easily. It is known in the art how to formulate self-thickened compositions where thickening is achieved without the use of polymeric thickeners, see for example, EP 518 401 and EP 21 581, incorporated herein by reference. However, for many purposes these particular non-polymeric thickener approaches are not convenient, because the viscosity is obtained at the cost of producing compositions that exhibit very stable foaming, leading to difficulties in rinsing. This was suggested by WO 95/33024, incorporated herein by reference, through the use of a combination of amine oxide and primary or secondary mono-branched alkylsulfate or sulfonate surfactants in acidic media. The limitations of this approach are that it requires a specific selection of surfactant, and the desired viscosities are not achieved unless the product has a pH of more than 3, thus limiting the range of hard water removal efficiency. Additionally, it has been discovered that the compositions of the present invention can incorporate high levels of hydrotropic solvent, resulting in an improved soap scum removal, while retaining the desired viscosity profiles. Compositions that are chemically similar to those of the present invention but that do not predominantly exhibit a flexible laminar phase structure do not provide the same level of cleanliness. Although not intended to be limited by theory, it is believed that the laminar structure provides better coverage and / or more contact of the surfactant with the dirt. The present invention provides viscous acid hard surface cleaning compositions suitable for removing the dirt commonly found in the bath, said compositions becoming viscous by a self-thickened system, but which are easy to rinse. These acid hard surface cleaning compositions remove the soapy cream and the hard water marks. The invention may provide viscous acid hard surface cleaning compositions with thinning properties with suitable shear stress for delivery in liquid or spray packages and which are not irritable in use. The compositions can have disinfectant properties achieved through the selection of active ingredients, including citric acid and cationic surfactants, and can be used with or without additives such as hydrogen peroxide for additional mold / moisture prevention benefits.

BRIEF DESCRIPTION OF THE INVENTION The detergent cleaning compositions for hard surfaces of the present are predominantly in the form of flexible laminar sheets dispersed in an aqueous phase. Said compositions provide excellent cleaning of soapy cream; properties of good removal of hard water - dirt; low levels of foam; and excellent rinsing characteristics. The viscosity of the product is provided by rheology of thinning with shear stress achieved through phase chemistry, specifically the formation of lathering surfactant sheets dispersed in the aqueous phase. The invention particularly relates to aqueous detergent compositions comprising: a. from about 1% to about 5% of alkylarylsulfonate detergent surfactant; b. from about 0.3% to about 2% nonionic alcohol and / or ionic cation surfactant; c. from about 1% to about 8% of one, or more, hydrotropic solvents; d. optionally, an effective amount, up to 5% hydrogen peroxide; and e. the remainder an aqueous solvent system and wherein the cleaning compositions comprise predominantly flexible laminar sheets dispersed in an aqueous phase and have a pH of about 0.5 to about 6. Flexible laminar sheets comprising surfactant provide improved viscosity and cleanliness. It is believed that the improved cleaning is the direct result of the laminar sheets, because the laminar structure allows greater contact of the surfactant with the dirt.

DETAILED DESCRIPTION OF THE INVENTION The compositions of the invention are especially useful for cleaning soils commonly found in the bathroom. These include dust particles, 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. Alkylarylsulfonate Alkylarylsulfonates are essential components of the invention. Suitable alkylarylsulfonates can be neutralized with any alkali metal such as lithium, sodium, potassium and the like, or alternatively can be neutralized with a C1-C9 ammonium salt derivative or ammonium such as monoethanolamine, diethylamine, tri-isopropanolamine and the like. They can be produced by any suitable process, leading to the formation of "2-lower phenyl" or "2-higher phenyl" derivatives, although the "2-lower phenyl" derivatives are generally preferred. 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 BASF Aktiengesellschaft (ESA / 1550, D-67056). Ludwigshafen, Germany). 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% alkylarylsulfonate surfactant, most preferably from about 1% to about 4.5% alkylarylsulfonate surfactant and still most preferably from about 1.2% to about 4% surfactant surfactant. alkylarylsulfonate. The alkylarylsulfonates of the invention may have an average chain length of from about 8 carbon atoms to about 14 carbon atoms, most preferably from about 9 carbon atoms to about 13 carbon atoms, still most preferably about 9 atoms of carbon to approximately 13 carbon atoms. The chain length distribution can vary from about 8 carbon atoms to about 16 carbons. Linear and / or branched alkylarylbenzene sulphonate mixtures are suitable. The ammonium and sodium salts of alkylbenzenesulfonates of Cu a C-? 2 are more preferred in the context of the present invention. Examples of commercially available sodium alkylbenzene sulphonates, particularly preferred include Polystep A-13® available from Stepan, suspension of Calsoft L-40® available from Pilot Chemical Company (11756 Burke Street, Santa Fe Springs, California) and Witconate P1059® available from Wítco Corporation (Greenwich, Connecticut). Alternatively, the desired alkylarylsulfonate surfactant can be produced in situ by neutralization of the corresponding alkylarylsulfonic acid. Examples of suitable alkylarylsulfonic acids include Biosoft® 100 available from Stepan Company, Calsoft LAS-99® available from Pliot Chemical, and Lutensit A-LABS® available from BASF AG in Germany.

B. Nonionic Alcohol or Cationic Surfactant The detergent compositions of the present invention also preferably comprise one, or more non-ionic alcohols, and / or agents cationic surfactants. The combination of the alkylaryl detergent surfactant with the alcohol and / or cationic surfactant is essential to the invention. Cleaning compositions comprising both non-ionic alcohol and cationic surfactant can be employed. As used herein, "non-ionic alcohol" means a linear non-ionic alcohol h? or mono-branched comprising an average of about 8 carbon atoms to about 16 carbon atoms, most preferably from about 9 carbon atoms to about 14 carbon atoms, still most preferably from about 10 carbon atoms to about 13 carbon atoms. Examples of nonionic alcohols Suitable include 2-butyl-1-octanol, 2-methyl-1-undecanol and dodecanol. The linear C10-C13 non-ionic alcohols are most preferred. Examples of commercially available, preferred nonionic alcohols include Neodol 1® and Neodol 23® available from Shell Chemical (1 Shell Plaza, Houston, Texas 77252). It is believed that the best results are achieved when the length of The non-ionic alcohol chain is more closely coupled to that of the alkylarylsulfonate surfactant. For this reason, nonionic alcohols comprising less than 8 carbon atoms or more than 16 carbon atoms are not preferred in the invention. If present, the non-ionic alcohol is present in effective concentrations not exceeding about 2%, most preferably in concentrations of 1.5% or less, most preferably in concentrations of 1.25% or less by weight of the composition. The detergent compositions herein that do not contain a nonionic alcohol will usually comprise one, or more, cationic surfactants. As used herein, cationic surfactants are those which at an acid pH behave substantially as cationic materials. The cationic surfactant is for the purpose of creating viscosity through ion pairing with the alkylsulphonate surfactant described above. Cationic surfactants can also provide disinfectant properties and can be selected to improve said benefits. Preferred cationic materials have hydrophobic chain lengths of from about 8 carbon atoms to about 16 carbon atoms, most preferably from about 10 carbon atoms to about 16 carbon atoms, still most preferably from about 12 carbon atoms to about 14 carbon atoms. Suitable cationic surfactants include quaternary alkyl and alkylbenzylammonium salts (eg, Bardac® 208M from Lonza Incorporated, 1717 Route 208, Fairiawn, New Jersey 07410), ethoxylated quaternary ammonium salts (eg, Ethoquad® surfactants available from Akzo Nobel Chemicals, 300 South Riverside Plaza, Chicago, Illinois), ethoxylated amines (eg, Ethomeen® surfactants available from Akzo Nobel Chemical), alkyldimethylbetaines (for example, Rewoteric AM DML-35® from Witco Corporation) or amidopropylbetaines (for example, Rewoteric AMB 15U® from Witco Corporation) and amine oxides (for example, Barlox 10S® from Lonza Incorporated). The incorporation of quaternary ammonium surfactants is particularly preferred for compositions that will provide antibacterial, fungistatic and fungicidal properties. Quaternary ammonium surfactants are known in the art and include C 10-16 alkyltrimethylammonium, C 8-14 dialkyldimethylammonium and C 10-16 alkyldimethylbenzylammonium derivatives and mixtures thereof. Suitable and commercially available quaternaries C 10-16 alkyltrimethylammonium and C 8 -C 14 dialkyldimethylammonium are available from Witco Corporation under the trade name Adogen®; Suitable C10-16 alkyldimethylammonium surfactants can be purchased from Lonza incorporated under the trade name Bardac®. The level of cationic surfactant in the compositions of the present invention is preferably not greater than 2%, most preferably not greater than 1.5%, still most preferably not greater than 1.25% by weight of the composition. The cationic surfactants can be used alone or in combination with nonionic alcohols for viscosity. The level of cationic surfactant plus nonionic alcohol comprises at least about 0.3%, most preferably at least 0.4%, still most preferably at least 0.5%, and more preferably from about 0.5% to about 2.0% , by weight of the composition.

C. Hydrotropic Solvent The compositions may also comprise one or more hydrotropic solvents at effective levels, typically not less than 2%, preferably from about 2% to about 8%, most preferably from about 2% to about 6%, still very much preferably from about 3% to about 6% by weight of the composition. Through experimentation it has been found that the formation of viscosity requires the use of hydrotropic solvent. By hydrotropic solvent, an agent is intended to help solubilize the hydrophobic ingredients in the compositions. The hydrotropic solvent participates in the formation of viscosity and increases the stability of the composition. Such solvents typically have a C3-C6 hydrocarbon termination attached to about one to three portions of ethylene glycol or propylene glycol. Examples of commercially available hydrotropic solvents based on ethylene glycol chemistry include ethylene glycol monobutyl ether (Butyl Cellosolve® available from Union Carbide, 39 Old Ridgebury road, Danbury, Connecticut), diethylene glycol monobutyl ether (Butyl Carbitol® available from Union Carbide), and mono-ethylene glycol n-hexyl ether (Hexil Cellosolve® available from Union Carbide). Examples of commercially available and suitable hydrotropic solvents based on propylene glycol chemistry include the mono-, di-, and tri-propylene glycol derivatives of propyl and butyl alcohol, which are available from Arco Chemical, 3801 West Chester Pike, Newtown Square, PA 19073) and Dow Chemical (1691 N. Sweede Road, Midland, Michigan) under the trade names Arcosolv® and Dowanol®. The most preferred hydrotropic solvent is dipropylene glycol n-butyl ether, sold under the tradenames Arcosolv DPnB® and Dowanol DPnB®. The amount of hydrotropic solvent may vary depending on the amount of other ingredients present in the composition, however it should be present in concentrations of from about 2% to about 8%, most preferably from about 2% to about 6%, still very preferably from about 3% to about 5% by weight of the total composition. In the absence of a hydrotropic solvent, the compositions of the present invention often appear as milky, low viscosity mixtures that are sometimes indefinitely stable at room temperature conditions. The addition of hydrotropic solvent serves to increase the viscosity of the product to produce more translucent solutions. It is believed that the solvent dilutes the initially obtained phase and transforms it into predominantly flexible lamellar sheets dispersed in the aqueous solvent system. Cryogenic tunnel electron microscope (hereafter Cryo-TEM) measurements indicate that phase chemistry consists of small concentric vesicles that become more flexible and laminar sheets more open at the ends after the addition of hydrotropic solvent.

D. pJH For purposes of removal of hard water spots, the compositions are acidic with a pH of about 0.5 to about 6, most preferably about 1.5 about 5, still most preferably about 2.0 to about 4. For removal of Hard water spots, the pH is typically around 3 or less. The acidity is preferably achieved through the use of one or more organic acids having a pKa of less than about 6, preferably about 4. Such organic acids aid in the formation of phase as well as provide water stain removal properties hard. It has been found that organic acids 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 organic acids include citric acid, benzoic acid, lactic acid, tartaric acid, glycolic acid, succinic acid, glutaric acid, adipic acid, gluconic acid and mixtures thereof. Said acids are commercially available in the market. Examples of more preferred acids include citric acid (available from Aldrich Corporation, 1001 West St. Paul Avenue, Milwaukee, Wisconsin), benzoic acid (available from Aldrich Chemical) and a mixture of succinic, glutaric and adipic acids available from DuPont (Wilmington, Delaware ) sold as "refined AGS di-basic acids". Citric acid is the most preferred. 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.

E. Optional Source of Peroxide Compositions of the invention may comprise peroxide such as hydrogen peroxide, or a source of hydrogen peroxide, for additional disinfectant, fungistatic, and fungicidal 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 stabilizing 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 diethylenetriamine pentaacetate, diethylenetriamine pentamethylenephosphonate, hydroxyethyldiphosphonate, and the like.

Optional surfactants and solvents In addition to alkylarylsulfonates and hydrotropic solvents, the compositions of the present invention preferably comprise additional additional anionic surfactants. Such surfactants typically comprise a hydrophobic chain containing from about 8 carbon atoms to about 18, preferably from about 10 to about 16 carbon atoms, and include a higher hydrophilic sulfate, sulfonate or carboxylate group. Examples of suitable anionic surfactants include linear or branched alkyl sulfate detergent surfactant (for example, Stepan AM® from Stepan), paraffinsulfonates (Hostapur SAS® from Hoechst, Aktiengesellschaft, D-6230 Frankfurt, Germany), alkyletoxycarboxylate detergent surfactant ( Neodex® from Shell Chemical Corporation), and the like. In particular, it has been found that alkyl sulfate surfactants are preferred as they offer improved soap cream cleaning benefits. In general, the level of optional anionic surfactants in the compositions herein is from about 0.5% to about 2%, preferably from about • 0.6% to about 1%, by weight of the composition. 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 chain of the alcohol. The typical alkoxylation groups are # 10 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 chain lengths and grades of alkoxylation. The preferred nonionic detergent surfactants for use herein are according to the formula R (X) nH, wherein R is a chain Alkyl 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 of about 4. to about 30, preferably from about 5 to about 8. Other nonionic surfactants Those which 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 N-surfactants. alkylglucosamide. 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. The compositions of the present invention can also include zwitterionic surfactants such as sulfobetaines and hydroxysulfobetaines in effective concentrations, preferably not exceeding 2% by weight of the composition. Other commercial sources of such surfactants can be found in McCutcheon's EMULSIFIERS AND DETERGENTS, North American Edition, 1997, McCutcheon Division, MC Publishing Company, also incorporated herein by reference.

Aqueous solvent system and other solvents The compositions are in aqueous form, comprising at least 60% aqueous solvent by weight of the composition, most preferably from about 60% to about 90% by weight of the composition. The aqueous solvent system may comprise low molecular weight solvents 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, which have been found to substantially reduce the foam created by the composition. Optional components, such as perfumes and other conventional auxiliaries may also be present.

Optional perfume and additional auxiliaries 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 the highly volatile, low-boiling perfume components (which have low boiling points), in these perfumes is to improve the odor of the product's own fragrance, rather than to impact the subsequent odor of the product. the surface that has been cleaned. However, some of the less volatile, high-boiling perfume ingredients can provide a fresh and clean impression to the surfaces, and sometimes it is desirable that these ingredients are deposited and presented 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, Michael, 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, is incorporated herein by reference. The perfume components may 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, linalyl acetate, tetrahydrolinalool, citronellol, citronellyl acetate, dihydromyrcenol, dihydromyrcenyl acetate, tepineol, terpinyl acetate, acetate, 2-phenylethanol, 2-phenylethyl acetate, benzyl alcohol, benzyl acetate, benzyl salicylate, benzyl benzoate, styrallylacetate, amyl salicylate, dimethylbenzylcarbinol, trichloromethylphenylcarbinylmethylphenylcarbinyl acetate, p-tert.butyl-cyclohexyl acetate, isononyl acetate, alpha-n-amylcinnamic aldehyde, 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- methyl-2-pentyl-cyclopentanone, n-decanal, n-dodecanal, 9-decenol-1, isobutyrate phenoxyethyl, phenylacetaldehyde dimethylacetal, phenylacetaldehyde diethylacetal, geranonitrile, citronelonitrile, cedryl acetate, 3-socafyl-cyclohexanol, cedryl ether, isolongifolanone, aubepin nitrile, aubepin, heliotropin, coumarin, eugenol, vanillin, diphenyl oxide, hydroxycitronellal, yonones , methyl yonones, isomethyl yonones, irons, cis-3-hexenol and esters thereof, inzan musk fragrances, tetralin musk fragrances, isocroman musk fragrances, macrocyclic ketones, musk fragrances ^ r10 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, W for example ingredients that have 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 20 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, PG Sammens, JB Taylor and CA Ramsden, Eds., Pp. 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 atoms, the connection capacity of the atom, and the chemical bond. The ClogP values which are the most reliable and widely used calculations for this physicochemical property are preferably used instead of the experimental logP values in the selection of the main solvent ingredients which are useful in the present invention. Other methods that can 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. -Chim. Theor., 19, 71 (1984). The compositions herein may comprise a variety of other optional ingredients, including additional actives and detergency 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 ingredients optional. Preferred builders are the carboxylic acid builders described above as part of the description of the carboxylic acid, including citric and tartaric acids. Tartaric acid improves cleaning and can minimize the problem of film / streaking that normally occurs when O 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 5 about 2%, and still most preferably about 0.5 to about 1.0%. Typically the improvement over acceptable film / grain formation results occurs when the improver is combined with detergent surfactant compositions amphoteric and / or zwitterionic although an improvement is also observed with the less preferred compositions of anionic or anionic / nonionic detergent surfactants. 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 such as xanthan gums, for example Keltrol, or Keltrol RD, typically at a level of about 0.01% about 2%, preferably from about 0.05% to about 0.5%; 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 low levels to avoid film / streaking problems. The most 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%.

Preparation of the composition The compositions herein can be made by mixing all the ingredients. In general, a preferred order of addition is first to incorporate water, alkylarylsulfonate surfactant and organic acid, followed by optional anionic, nonionic, and / or zwitterionic surfactants. The mixture initially becomes turbid and becomes less opaque as the hydrotropic solvent is added; the addition of hydrotropic solvent also results in a substantial increase in the viscosity of the product resulting from the formation of more flexible and more open vesicles at the ends and / or sheet sheets. In most cases, the addition of hydrotropic solvent causes the solution to become translucent or transparent. Once the solvent is added, the pH is adjusted to optimum as desired by the formulator. Optional peroxide, perfume and dye can be added. The compositions herein eventually reach a viscosity of 50 cP to 200 cP, measured using a Brookfield viscometer at a shear rate of 60 RPM with spindle # 2. 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 .

Chemical Experiment of phases by Cryo-TEM: The samples were prepared in a controlled environment vitrification system (CEVS) that is described in J. Electron Microsc. Tech, 1988, 10, 87-111, said article is incorporated herein by reference. A drop of 5μl of the sample solution is placed on a carbon-coated polymer backing film with holes in the film, said film mounted on the surface of a standard 300 mesh TEM grid (Ted Pella, Inc., Catalog # 01883). The drop was dried with filter paper until reduced to a thin film (10-200 nm) of the sample covering the holes (2-8μm) of the support film. The sample is vitrified by rapid immersion through a synchronous obturator in the bottom of CEVS in liquid ethane to its freezing point. The glassy specimen is transferred under liquid nitrogen to a Philips CM12 microscope or a CM120 microscope with integrated biofilter for imaging. The temperature of the sample is kept below -170 ° C through the test. The images are recorded on Kodak SO-163 film or by a slow-scan CCD camera with Gatan Digital Micrograph programs.

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. The cleaning index of soapy cream is calculated using the following equation: (# passes for control product / # passes for experimental product) * 100, where the control product is Mastro Lindo (Italy) and the experimental prototypes are compositions 1 -8 described herein. Indices of more than 100 indicate products with superior soap-cream removal properties.

Hard water cleaning: Four pieces of marble for each tested product of approximate dimensions 3 / "x 3 /" x 1 / "are weighed to four decimal places using an analytical balance The pieces are placed in 100 ml beakers They contain 20 grams of the product for a total of 10 minutes.The pieces of marble are removed, rinsed and left to dry, then reweighed and the weight loss recorded, using averages of four tests for each product, the index of hard water removal 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.

EXAMPLES - EXPERIMENTAL DATA The present invention is also illustrated by the following examples and data. The following compositions are made by mixing the ingredients listed in the proportions listed in the listing order of addition. Said soap removal comparisons are made against a commercially available product sold in Italy, Mastro Lindo a product formulated at a pH of 3.7.

Composition LAS: linear C12 alkylbenzene sulphonate (Calsoft L-40® from Pilot) * Bardac 208M® is a mixture of quaternary ammonium surfactants sold by Lonza, Incorporated. *** n-BPP: dipropylene glycol n-butyl ether (Dowanol DPnB® by Dow Chemical) f f The composition does not completely remove the soapy cream Data analysis: All compositions include a C12 alkylbenzene sulfonate as the selection anionic surfactant and all except composition 1 include the required hydrotropic solvent. Compositions 1, 2 and 3 illustrate the impact of hydrotropic solvent on phase chemistry and on the viscosity of the product. Unlike conventional products, the hydrotropic solvent (n-BPP) increases the viscosity of the product by transforming the concentric vesicular structures into flexible laminar sheets. The result is an improvement in the cleaning of soapy cream. The phase chemistry and viscosity of compositions 4-8 are formed using long chain alcohols instead of surfactants Cationic W Compositions 4 and 5 show a flexible laminar phase structure, while the phase structure of compositions 6 and 7, which are chemically very similar to composition 5, consist of vesicles concentric. The differences in cleaning performance between compositions 6 and 7 and compositions 4 and 5 are attributed to differences in phase chemistry. Composition 8 uses the combination of long chain alcohol plus quaternary ammonium surfactant to create a high viscosity product comprising flexible laminar sheets. Note that the composition additionally contains peroxide, has high viscosity and shows excellent performance in the cleaning of soapy cream. The hard water test was limited to products that showed the strongest results in the soap-cream test. Note that the three preferred compositions have excellent hard water removal properties.

Claims (11)

NOVELTY OF THE INVENTION CLAIMS

1. - A viscous aqueous hard surface detergent composition containing a flexible sheet sheet phase comprising: a) from about 1% to about 5% of alkylarylsulfonate detergent surfactant; b) from about 0.3% to about 2% nonionic alcohol and / or cationic surfactant; c) from about 1% to about 8% of one, or more, hydrotropic solvents; d) optionally, an effective amount, up to 5% peroxide; and e) the remainder an aqueous solvent system, said composition having a pH of about 0.5 to about 6.

2. A composition according to claim 1, further characterized in that it comprises a) from about 1% to about 4.5% by weight of the alkylarylsulfonate surfactant composition; b) from about 0.4% to about 1.5% by weight of the composition of said nonionic alcohol and / or cationic surfactant; from about 2% to about 6% of one, or more, hydrotropic solvents; up to 5% by weight of the composition of said peroxide which is hydrogen peroxide; and from about 60% to about 90% by weight of the composition of said aqueous solvent system, said composition having a pH of from about 1.5 to about 5.

3. - A composition according to claim 2, further characterized in that it comprises from about 1.2% to about 4% alkylarylsulfonate surfactant, b) from? about 0.5% to about 1.25% by weight of the composition of 5 said nonionic alcohol and / or cationic surfactant; from about 3% to about 6% of one, or more, hydrotropic solvents; from about 0.5% to about 3% by weight of the composition of said hydrogen peroxide; and from about 60% to about 90% by weight of the composition of said aqueous solvent system, said composition 10 having a pH of from about 2.0 to about

4. 4. A composition according to any of claims 1-3, further characterized in that said alkylarylsulfonate detergent surfactant is an alkylbenzene sulfonate wherein said alkyl group contains from about 8 to approximately 14 atoms 15 carbon.

5. A composition according to claim 4, further characterized in that said nonionic alcohol is a linear, or mono-branched alcohol containing from about 8 to about 16 carbon atoms and / or wherein said cationic surfactant contains 20 a hydrophobic chain containing from about 8 to about 16 carbon atoms.

6. A composition according to claim 5, further characterized in that said cationic surfactant is selected from the group consisting of dialkyldimethylammonium surfactants from C8 to Cu, alkyltrimethylammonium surfactants of C-? Or C? 6, surfactants of C 10 -C 16 alkyldimethylbenzylammonium and mixtures thereof.

7. A composition according to claim 5, further characterized in that the hydrogen peroxide is present at levels of about 0.05% to about 3%.

8. A composition according to any of claims 1-7, further characterized in that said hydrotropic solvent comprises a hydrocarbon portion containing from about 3 to about 6 carbon atoms attached to about 1 to about 3 portions of oxide of ethylene and / or propylene.

9. A composition according to any of claims 1-8, further characterized in that it comprises citric acid as a pH adjuster and having a pH of about 3 or less.

10. The method of cleaning a surface consisting of applying an effective amount of the composition according to any of claims 1-9 to said surface and rinsing said surface.

11. The process according to claim 10, further characterized in that said surface is fouled with mold and said composition contains an effective amount of hydrogen peroxide.