MXPA94004665A - Composition in microemulsion ac - Google Patents

Abstract

An acidic thickened microemulsion composition which contains alpha hydroxy aliphatic acids and is effective in removing soap scum

Description

COMPOSITION IN ACID MICROEMULSION Inventors: Regis Lysy, Maurice Marchal and Claude Blanvalet all of Belgian nationality, with addresses in VOIE Collette, 28 B-4877, B-4877 OLNE, Ru D Center, 23 B-6960 Oster-Manhay and Rué Rossy, 61 B 4031 Angleur , Belgium respectively.

Owner: COLGATE-PALMOLIVE COMPANY, of North American nationality, with address at 300 Park Avenue New York, New York 10022, United States of America.

Extract of the Invention * An acidic thickened microemulsion composition which contains alpha hydroxy aliphatic acids and is effective in removing soap scum.

Field of the Invention This invention relates to a hard surface cleaner, such as bath tubs, sinks, tiles, * Porcelain and articles of ena, which removes dross slag, slag lime and grease from such surfaces if they damage them. More particularly, the invention relates to an acrylic microemulsion which can be sprayed onto the surface to be cleaned, and removed without the usual rinsing and leaving the surface cleaned bright and twinkling. The invention also relates to a method for using such compositions.

Background of the Invention Hard surface cleaners, such as bathroom cleaners and scrubbing cleaners, have known for many years. Scrubbing cleaners typically include a soap or synthetic organic detergent or an active surface agent and an abrasive. Such products can scrape relatively smooth surfaces and can eventually cause them to appear opaque. These products are often ineffective in removing the slag from * (usually calcium and magnesium carbonates embedded) e normal use. Because lime slag can be removed by chemical reactions with an acidic medium, various acidic cleaners have been produced and these have found varying degrees of success. In some cases such cleaners have failed because the acid used was too strong to damage the surfaces that were being cleaned. Other times, the acidic compound of the cleaner reacted ob ectly with other components of the product which adversely affected the detergent or the perfume. Some cleaners required subsequent rinsing to avoid leaving objectionable deposits on the cleaned surfaces. As a result of the research carried out in efforts to overcome the aforementioned disadvantages, an improved liquid cleaning composition in the form of a stable microemulsion has recently been made which is an effective cleaner for removing soap scum, lime scoria and greasy dirt from the hard surfaces, such as bathroom surfaces and which does not require rinsing after use. Such product is described in the patent application of the United States of North America will be No. 120,250 with respect to a "Cleaning Composition and Stable Microemulsion" presented on November 12, 1987 by Loth, Blanvalet and Valenge, whose application is incorporated herein by reference . In particular, Example 3 of that application describes a transparent and acidic oil-in-water microemulsion which is described there as being successfully used to clean wall tiles from a shower of slag from the slag of lime slag which was adhered to them. The cleaning was effected by applying the cleaner to the walls followed by a minimum or cleaned rinse after which the walls were allowed to dry to a good shine.

The microemulsion cleaner described in the patent application is effective for removing slag from lime and lime.

* Soap scum from hard surfaces and is easy to use, but it has been found that its mixture of acidic agents (succinic, glutaric and adipic acid) can damage the surfaces of some hard accessories, such as those of the materials which are not resistant to acid. One such material is u enamel that has been used extensively in Europe as a coating for bath tubs, here mentioned as in European ename. It has been described as white enamel zirconium or enamel white zirconium powder and has the advantage of being resistant to detergents, which makes it suitable for use in tubs, sinks, shower tiles and enamel items of bathroom . However, such enamel is sensitive to acids and is severely damaged by the use of acidic microemulsion cleaner based on the three organic carboxylic acids previously mentioned.

That problem has been solved by the patent of the European Patent Office No.0336878A2, in which * Additional acidic materials are incorporated in the cleaning with the organic acids and rather than exacerbate the problem, these avoid the damage to such enamel europe surfaces by such organic acids. Also, a mixture of such additional acids, phosphonic and phosphoric acids surprisingly further improve the safety of the aqueous cleaner for use on such European enamel surfaces and decrease the cost of the cleaner. The present compositions of this invention allow the cleaning of European enamel surfaces, as well as any other acid-resistant surfaces of bath tubs and other surfaces of the bathroom. The product can be used on several other materials that are especially susceptible to attack by the acidic medium, such as marble. The present compositions employ alpha hydroxy aliphatic acids in place of the mixture of succinic glutaric and adipic acids previously used in the aqueous microemulsion. The present compositions employ the aliphatic hydroxyacids being less harmful to European enamel or other surfaces susceptible to acid such as marble that mixes succinic, glutaric and adipic acids. Additionally, it is contemplated that the present inventions may be thickened with a Xanthan gum as described in United States Patent Application No. 07 / 950,370, filed September 1992.

Summary of the Invention According to the present invention, an aqueous acidic cleaner for bath tubs and other hard surface articles, which are acid resistant or are of enamel zirconium acid wherein the cleaner has a pH in the range of 1 to ß • 4 and the cleaner removes lime slag, soap scum and greasy dirt from the surfaces of such articles if damaging such surfaces, comprises: a detersive proportion of at least one synthetic organic detergent which is capable of removing the oily dirt from such surfaces; a slag ratio of soap slag and lime slag of an aliphatic alpha-hydroxy acid (s) having 3 to 5 carbon atoms; an aminoalkylene phosphonic acid in proportion, to avoid damage to the zirconium enamel blanc surfaces of the articles to be cleaned by alpha-hydroxy aliphatic acid; phosphoric acid and an aqueous medium for the detergent, alpha-hydroxy aliphatic acid, phosphoric acid and aminoalkylene phosphonic acid.

Detailed description of the invention The present thickened acidic microemulsion compositions comprise approximately by weight: * (a) from 1 to 9 percent of an anionic sulfactant such as an ammonium sulphonate or alkali metal C14_17; an alkoxylammonium sulphate or C8.C18 alkali metal sulfate or an ethoxylated alkyl ether sulfate of ammonium or alkaline metal C8-C18; (b) From 0 to 5 percent of a nonionic sulfactant such as an Ethylene Oxide C13.15 Fatty Alcohol 7: 1 / P04: 1; »(C) 0 1 0.7 percent of a condom such as an alkali metal benzoate such as a sodium benzoate; (d) From 0 to 1.0 percent of a rubber thickener has a molecular weight of about 1,000,000 to 10,000,000 such as the Kelzan T sold by Merck & Co.; (e) From 0 to 0.3 percent of an alkali metal hydroxide; (f) From 0 to 1.0 of phosphoric acid more preferably from 0.05 to 1.0 percent. (g) From 0 to 0.5 percent of an amino trimethyphosphonic acid, more preferably from 0.01 to 0.3%; (h) From 0 to O.l percent of a dye; (i) From 0 to 2.0. percent of a perfume; (j) From 2 to 9 percent of at least one aliphatic hydroxyhydric acid having from 2 to about 6 carbon atoms; (k) The remainder being water, wherein the composition has a pH of about 1 about 4, more preferably about 2.7 to about 3.3 and a Brookfield viscosity of about 5 to 1,000 centipoise cps, more preferably about from 30 to about 600 centipoise at room temperature using a spindle No. 2 and 50 revolutions per minute.

In the present compositions, the synthetic organic detergent can be any suitable anionic, non-ionic amphoteric, ampholytic, switerionic or cationic detergent or a mixture thereof, but anionic and nonionic detergents are preferred as well as mixtures thereof.

The nonionic sulfactant which may be employed in the present liquid detergent composition is present in amounts of from about 0 to 5 percent, preferably from 0.5 to 4.5 percent, more preferably from 1 to 4 percent, by weight of the composition and proportion to a superior performance in the removal of dirt.

F The water-soluble nonionic surfactants used in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates, the secondary aliphatic alcohol ethoxylates, the alkylphenol ethoxylates and the condensates of ethylene oxide-propylene oxide on primary alkanols, such as Plurafacs (BASF) and condensates d ethylene oxide with fatty acid esters sorbitan such com Tweens (ICI). Organic nonionic synthetic detergents are generally the condensation products of an aromatic hydrophobic compound of organic aliphatic alkyl and hydrophilic ethylene oxide groups. Virtually any hydrophobic compound having a carbido, hydroxy, amid or amino group with a free hydrogen subject to nitrogen can be condensed with the ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water-soluble non-ionic detergent. . In addition, the length of hydrophobic polyethenoxy e and the hydrophilic elements.

The class of non-ionic detergent includes the condensation products of a higher alcohol (eg, an alkane containing from about 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with about 5 to 30 moles of oxide of ethylene, for example lauryl or myristyl alcohol condensed with about 1 mole of ethylene oxide (EO), tridecanol condensed with about 6 moles of ethylene oxide, myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of myristyl alcohol, the condensation product of ethylene oxide with a coconut fatty alcohol cut containing a mixture of fatty alcohols with the alkyl chains varying from 10 to about 14 carbon atoms in length and where the condensate already contains be about 6 moles of ethylene oxide per mole of total alcohol or about 9 moles of ethylene oxide per mole of alcohol and alcohol ethoxylates of f tallow containing from 6 ethylene oxide to 11 ethylene oxide per mole of alcohol.

A preferred group of the above nonionic surfactants are the Neodol ethoxylates (Shell Co.) which are higher aliphatic primary alcohol containing about 9-15 carbon atoms, such as Cg-Cn alkanol condensed with 8 moles of ethylene oxide. (Neodol 91-8), alkanol (C12.13 condensed with 6.5 moles of ethylene oxide (Neodol 23-6.5), C12.1 alkanol condensed with 12 moles of ethylene oxide (Neodol 25-12), C14-15 alkanol condensed with 13 moles of ethylene oxide (Neo 45-13), and the like Such etoxamers have an HL value (lipophilic hydrophobic balance) of about 8 to 15 and have a good O / W emulsification while the etoxamers co values of Lipophilic hydrophobic balance down to 8 contains less than 5 ethylene oxide groups and tends to be poor emulsifiers and poor detergents.

The satisfactorily additional water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing from 8 to 18 carbon atoms in a branched straight chain configuration condensed with 5 to 30 moles of ethylene oxide. Examples of commercially available nonionic detergents of the above type are secondary alkanol Cll-15 condensed with either 9 ethylene oxide (Tergitol 15-S-9) or 12 EO (Tergitol 15 S-12) marketed by Carbide Union.

Other suitable nonionic detergents include condensates of polyethylene oxides of one mole of alkyl phene containing from about 8 to 18 carbon atoms in a straight or branched chain alkyl group with about 30 moles of ethylene oxide. The specific examples of what «2C ethoxylates of alkyl phenol include nonyl condensate co P about 9.5 moles of ethylene oxide per mole of noni phenol, dinonyl phenol condensed with about 12 moles of ethylene oxide per mole of phenol, dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol and di isoctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol. Commercially available nonionic surfactants of this type include Igepal CO-63 (nonyl phenol ethoxylate) marketed by GAF Corporation.

Among the satisfactory non-ionic detergents are the water-soluble condensation products of C8-C2 alkanol with a heteric mixture of ethylene oxide and d-propylene oxide wherein the weight ratio of ethylene oxide to propylene oxide is from about 2.5: 1 to 4: 1, preferably 2.8: 1 to 3.3: 1, with the total of the ethylene oxide and the propylene oxide (including the finished ethanol or the propanol group) being from 60 to 85%, preferably from 70 to 80%, by weight. Such detergents are commercially available from BASF-Wyandotte and a particularly preferred detergent is a condensate of C10-C16 alkanol with ethylene oxide and propylene oxide, the proportion by weight of ethylene oxide to propylene oxide being 3: 2.1 and the Total alkox content being around 75% by weight.

Condensates of 2 to 30 moles of ethylene oxide co mono- and tri-esters of C10-C20 alkanoic acid of sorbitan having a lipophilic hydrophobic blance HLB of 8 to 15 can also be used as the ingredient of non-ionic detergent in the shampoo described. These surfactants are well known and are available from Imperial Chemical Industries under the trade name Tween. Suitable surfactants include polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate polyoxyethylene (20) sorbitan tristearate.

Other suitable water soluble nonionic detergents which are less preferred are marketed under the trade name "Pluronics". The compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide or propylene glycol. The molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4000 and preferably 200 to 2,500. The addition of polyoxyethylene radicals to the hydrophobic portion tends to increase the solubility of the molecule as a whole to make the surfactant soluble in water. The molecular weight of the block polymers varies from 1000 to 15.00 and the polyethylene oxide content may comprise 20% 80%. Preferably, these surfactants will be in liquid form and satisfactory surfactants are available as classes L62 and L64.

The anionic surfactant, used in the microemulsion composition, constitutes about 1% to 9%, preferably 2% to 8%, more preferably 2% to 7%, by weight.

The anionic surfactant which can be used in the present microemulsion detergent of the invention is soluble in water such as triethanolamine salt and includes the sodium, potassium, ammonium and ethanolammonium salts of C18 C18 alkyl sulfates such as lauryl sulfate, sulfate myristyl and the like; C8-C18 ethoxylated alkyl ether sulfates; the sulfonates of C8-C16 alkyl benzene; the C10-C20 paraffin sulfonates; the alpha olefin sulfonates containing about 10-24 atoms d # carbon; the C8-Clg alkyl sulphoacetates; the esters of C 8 -C 18 alkyl sulfosuccinate; the C8-C18 acyl isethionates the C8-C18 acyl taurates. The preferred anionic surfactants are water-soluble alkyl sulfates.

The paraffin sulfonates can be monosulfonates di-sulfonates and are usually mixtures thereof, obtained by sulfonating paraffins of 10 to 20 carbon atoms. The * preferred paraffin sulphonates are those C12.18 carbon atom chains and more preferably are C14_17 chains. The paraffin sulphonates having the sulfonat group (s) distributed along the paraffin chain are described in U.S. Patent No. 4,050,280; 2,507,088; 3,260,744; and 3,372,188; and also in German Patent No. 735,096. Such compounds can be made to specifications and desirably the content of the paraffin sulfonate outside the range of C14_17 will be lower and will be minimized as well as any content of di- or poly-sulfonates.

Examples of other suitable anionic suphonated detergents are the well known higher alkyl mononuclear aromatic sulphonates, such as the higher alkyl benzene sulfonates containing from 9 to 18 or preferably from 9 or 11 to 15 or from 16 carbon atoms in the group d) higher alkyl in a straight or branched chain, or toluene sulfonate of C8.15 alkyl. An alkyl benzene sulfonate # preferred is a linear alkyl benzene sulphonate having a higher content of 3-phenyl (or higher) isomers and its correspondingly low content (well below 50%) of 2 phenyl (or lower) isomers such as those sulfonates e where the ring of benzene is subject mainly to the 3-position or higher (for example 4,5,6 or 7) of the alkyl group d and the content of the isomers in which the benzene ring is held in position 2 or 1 is correspondingly low . Preferred materials are set forth in U.S. Patent No. 3,320,174, especially those in which the alkyls are from 10 to 13 carbon atoms.

The higher alkyl ether sulphates in the present invention are represented by the formula: Wherein R is a secondary primary alkyl group which may be straight or branched having from 10 to 18 carbon atoms, preferably from 12 to 15 especially from 12 to 14, more preferably from 12 to 13 carbon atoms. M is an ammonium cation or. alkali metal and n is a number from 1 to 10 preferably from 1 to 6, especially from 2 or 3. These detergents are produced by sulfonating the corresponding ether alcohol and then neutralizing the sulfuric acid ester resulting therefrom. The sodium and amino salts of the ether sulfates are especially preferred.

The anionic alkyl sulfate detergent compounds which are useful in the present invention have from 6 to 18 in the alkyl group and may be represented by the following general formula: * R2S04M wherein R 2 is a branched straight chain alkyl of from 6 to 8, especially a chain length of 8 to 14 carbon atoms, and M is an ammonium or meta-alkali carbon, especially sodium. Straight chain alkyl groups are preferred.

The active acidic component of the acidic emulsions is an alpha hydroxy aliphatic acid which is strong enough to lower the pH of the microemulsion to one in the range one to four. Several such carboxylic acids can perform this function but those which have been found to effectively remove soap scum and slag from the surfaces of the bathroom in the best way, while not destabilizing the emulsion, are Alf aliphatic hydroxy acids having the structure: X # -OH C02H wherein Y is selected from the group consisting of hydroxy or a group COOH and X is (CH2) nW, wherein W is selected from a group consisting of CH3 or COOH and n is 0, 1 or 2. L alpha hydroxy oliphatic acids are acrylic acid, lactic acid and malic acid, wherein a mixture of lactic acid and malic acid is preferred, wherein the ratio by weight of lactic acid to malic acid is preferred to be about 5: 1 to about 1 : 2.1, more preferably around 4: 1 to about 1: 2.1. The at least one alpha hydroxy aliphatic acid is incorporated in the composition in an amount from about 2 to about 9% by weight, preferably from about 2 to about 7 weight percent.

The aliphatic alpha hydroxy acid, after it is incorporated in the acidic emulsion, can be partially neutralized to produce the desired pH in the emulsion, for greater functional effectiveness, safely.

Phosphoric acid is one of the additional acids that helps protect acid-sensitive surfaces that are being cleaned with the present emulsion cleaner. Being tribasic acid, this can be partially neutralized to obtain an emulsion pH in the desired range. For example, diphosphate can be partially neutralized, for example, NaH2P04, or NH4H2P04 The phosphonic acid, the other of the two additional acids to protect the acid-sensitive surfaces from the dissolution action of the dicarboxylic acids of the present expressed emulsions, apparently only exists theoretically, but their derivatives are stable and are useful in the practice of the present invention. Such are considered to be the phosphonic acids as the term is used in this description. The phosphonic acids are of the OH structure OH Where Y is any suitable substituent, per preferably Y is alkylamino or N-alkylamino substituted. For example, a preferred phosphonic acid component of the present thickened acidic emulsions is aminotri (methylene phosphonic acid) which is of the formula N (CH2PHx03). Among the useful phosphonic acids are ethylene diamine # tetra- (methylene phosphonic), hexamethylene tetra (methylene phosphonic) acid, and ad diethylenetriamine Penta (methylene phosphonic acid). Such class of compounds can be described as aminoalkylene phosphonic acids containing in the ranges d 1 to 3 amino nitrogens, 3 or 4 lower alkylene phosphonic groups in which the lower alkylene is 1 or 2 carbon atom, and 0 to 2 alkylene groups of 2 to 6 carbon atoms each, whose alkylene (s) are / are present and amino nitrogen bonded with a plurality of such amino nitrogen is present in the amino alkylene phosphonic acid. It has been found that such amino alkylene phosphonic acids, which can also be partially neutralized at the desired pH of the microemulsion cleaner, are of a desired stabilizing protection effect in the invented cleaner, especially when present with the phosphate acid, avoiding attack harmful to the European enamel surfaces of the alpha hydroxy aliphatic components of the cleaner.

The thickener which is optionally used in the acidic microemulsion is a xanthan gum called Kelzan T sold by Merck & Co. Xanthan gum is an exocellular hetropolysaccharide having a molecular weight of about 1,000.00 to 10,000.00 and is used in a concentration of about 0. percent by weight, more preferably from 0.1 to about 0. percent by weight, and more preferably 0.2 to 0.6 percent by weight. When used at these concentration levels, the composition retains its microemulsion characteristics in the sense that the essential miscellaneous aggregates are maintained. The composition is still sprayable and will hang well to the vertical wall. Additionally, the compositions having the xanthan gum incorporated therein are thinning cutting which means that the composition can be easily removed from the surface being cleaned without much mechanical action. Other cellulose, hydroxypropyl cellulose, polyacrylamides and polyvinyl alcohol will create the compositions cutting thickening The water used to make the present microemulsions may be tap water but low hardness is preferred, usually less than 150 parts per milliliter (p.p.m.) hardness. Still, useful cleaners can be made of tap waters that are of a higher hardness, up to 3.00 p.p.m. More preferably the water used will be distilled or deionized water, in which the content of the hardness ions is less than 25 p.p.m.

Several other components may be present in the invented cleaners., including preservatives such as sodium benzoate, antioxidants or corrosion inhibitors, with solvents, cosurfactants, multivalent target ions, perfumes, dyes, and terpenes (and terpineois) but various other auxiliaries conventionally used in liquid detergents and cleaners. Dur surface may also be present, provided that these do not interfere with the cleaning and slag removal functions of the cleaner. Of the various auxiliaries (which are identified as such because they are not necessary for the production of an operative cleaner, even though they can be desirable components of the cleaner) the most important ones are considered to be perfumes, which, with the tarpenes , terpenes hydrocarbons (which can be substituted by the perfume or added to these) work as a solvent especially effective for the greasy dirt on the hard surfaces that are being cleaned, and form the dispersed phases of the oil-in-water microemulsions ( o / w). Also of great functional importance are the co-surfactant and the polyvalent target ions, with the former helping to stabilize the microemulsion and the latter being added to improve the detergency, especially for more dilute cleaners, and the polyvalent salts of the anionic detergent employed. more effective detergents against the fatty dirt found in use.

The various perfumes which have been found to be useful in the formation of the dispersed phase of the thickened acidic microemulsion cleaners may be that normally employed in the cleaning products preferably are normally in the liquid state. These include the esters, ethers, aldehydes, alcohols and alkanes used in the perfumery but of greater importance are the essential oils that are of a high terpene content. It appears that terpenes (and terpineols) coact with the detersive components of the microemulsions to improve the detergency of the invented compositions, in addition to form the stable dispersed phase of the microemulsions. In the present invention it has been found that especially when a pine perfume is being used, one can decrease the proportion of such a comparatively expensive perfume and can compensate for this with alpha-terpineol, and in some cases with other terpenes. For example, for each 1% of perfume one can substitute 60 to 90 of this, for example, about 80%, with alpha-terpineol, obtain essentially the same fragrance, with a good cleaning and a microemulsion stability emulsion. Similarly, terpenes and other compounds of terpene and derivative types may be employed but alpha-terpineol is considered to be the best.

The polyvalent metal ion present in the inventive cleansers can be any suitable ion including, but not limited to magnesium, (usually preferred) aluminum, copper, nickel, iron or calcium. The ion or mixture thereof may be added in any suitable form, sometimes as either oxide or hydroxide but usually as a water soluble salt.

It seems that the polyvalent metal ion reacts with the anionic detergent anion (or replaces the detergent cation, constitutes an equivalent solution in the emulsion) which improves the detergency and generally better other product properties as well. If the polyvalent metal ion reacts with the detergent anion to form a polyvalent tai insoluble product it should be avoided. For example, the calcium reaction with the paraffin sulfate anion to form an insoluble sa, so that the calcium ions, as can be obtained within calcium, should be omitted from any microemulsion cleaners of this invention containing sulfonate detergent. paraffin. Similarly, those polyvalent ions or other components of the invented compositions that will react adversely with other components will also be omitted. As previously mentioned, the polyvalent metal ion will preferably be magnesium, and this will be added to the other emulsion components as a water soluble salt. A preferred salt is magnesium sulfate, usually used with heptahydrate (Epson salts), but other hydrates there or anhydride can also be used. Generally, sulfates d polyvalent metals will be used because the anion d sulfate itself is also the anion of some of the anionic detergents and has been found in such detergents as a by-product of neutralization.

The component (s) with surfactant (s) of the acidic cleaners reduce the interfacial tension or surface tension between the lipophilic drops and the aqueous medium continues at a value that is frequently close to 10"3 dynes / cm. This results in spontaneous disintegrations of the dispersed phase globules until they are made so small as to be invisible to the human eye forming a transparent microemulsion. In such a microemulsion the surface area of the dispersed phase increases greatly and its solvent strength and capacity increase. Fat removal is also increased, so that the acidic microemulsion is significantly more effective as a cleanser to remove greasy dirt than when the dispersed phase globules are of an ordinary emulsified size.Among the cosurfactants that are useful in invented cleansers they are: soluble lower alkanols and water of 2 to 4 carbon atoms per molecule (sometimes preferable 3 or 4): polypropylene glycols from 2 to 18 propoxy units; monoalkyl lower glycol ethers of the formul RO (X) nH, where R is alkyl CM, X is CH2CH2CH20 or CH (CH3) CH20, n is from 1 to 4; monoalkyl esters of the formula R1 s acyl CM and X and n are as described immediately beforehand; the substituted aryl alkanols of 1 to 4 carbon atoms; propylene carbonate; alpha-hydroxy aliphatic acids of 2 to 6 carbon atoms such as mono-di and tri-substituted carboxylic acids aliphatic mono-di and tri-hydroxy of 2 6 carbon atoms; mono-di and lower alkyl triesters of phosphoric acid wherein the lower alkyl is from 1 to 4 carbon atoms; and mixtures thereof.

It is also obvious that other previously identified cosurfactants can be used in combination with alpha hydroxy aliphatic acids which function as cosurfactants. These non-acidic cosurfactants will usually be used in conjunction with the aliphatic alpha hydroxy acid cosurfactants in an amount of from about 0.1 to about 5% by weight, more preferably from about 0.5 to about 4.0% by weight depending on the concentration of aliphatic hydroxyl alpha acid cosurfactant.

Representative of such cosurfactants are lactic, maleic and citric acid, diethylene glycol monobutyl ether, dipropylene glycol mono butyl ether and diethylene glycol mono isobutyl ether, which are considered to be the most effective.

From the above discussion of the useful cosurfactants in the present cleaners it is evident that the malic acid lactic and citric, and a mixture of such components are useful to lower the pH of the product so that it removes the slag from the soap and the slag from lime easily from surfaces that are going to be cleaned, and at the same time this works as surfers, improving the appearance of the product and making it more effective in removing grease from such surfaces. Such similar dual effects can be obtained through the use of other named acidic materials that have cosurfactant activities in the described cleaners.

In invented cleansers it is important that the proportions of the components are in certain ranges so that the product must be more effective in removing the greasy dirt, slag from lime and soap scum, and other deposits from the hard surfaces submitted. to the treatment, as to protect such surfaces during such treatment As previously mentioned the detergent must be present in a detersive proportion, sufficient to remove the oily and greasy soils; the proportion (s) of the aliphatic alpha hydroxy acid (s) must be sufficient to remove the soap slag and lime slag, the phosphonic acid or the mixture of Phosphoric and phosphonic acids should be sufficient to avoid damage to the acid-sensitive surface by the alpha-hydroxy aliphatic acid (s), and the aqueous medium should be a solvent and a suspending medium for the required components. and for any auxiliaries that may be present as well. Normally, such percentages of components will be by weight from 0 to 1.0 percent of xanthan gum. 1 to 9% synthetic organic anionic detergent (s) from 0 to 5% synthetic organic non-ionic detergent (s) (s), from two to 9% aliphatic alpha hydroxy acids, of 0. 0.5 6.6% of the phosphoric acid or a mono-salt thereof and 0.005 to 2 of phosphonic acid (s), 0 to 0.6% of alkylene phosphoric acid (s), or mono-phosphonic salt (s) ( s) of 1 same; and the remainder being water and auxiliary (s) if any were present. Of the alpha hydroxy aliphatic acids it is preferred that a mixture of lactic and malic acids be used. The proportion of the aliphatic alpha-hydroxy acid to the aminoalkyl phosphonic acid in the present composition is about 5: 1 about 250: 1 more preferably about 2: 1 about 10.1 and the proportion of the aliphatic hydroxy acid The phosphoric acid is around 5: 2 to 25: 1.

Usually it will be present in the cleaning especially when an anionic surfactant is present 0.0 to 5 percent and preferably 0.1 to 3.0% of a polyvalent ion preferably magnesium or aluminum, and more preferably magnesium. Also, the percentage of the perfume will normally be in the range of 0.2 to 2%, preferably being in the range 0.5 to 1.5% of whose perfume at least 1.0% is terpene terpineol. The terpineol is alpha-interpineol and is preferably added to allow a reduction in the amount of perfume, with the total perfume (including alpha-terpineol) being from 50 to 90% terpineol, preferably 80% thereof.

The pH of the various preferred microemulsion cleaners is usually 1 to 4, preferably 1.5 to 3. e.t.3. The water content of the microemulsions will usually be in the range of about 75 to 90% preferably about 80 to 85 percent and the content of auxiliaries will be from 0 to 5%, usually about 1 to 3 percent. If the pH is not in the desired range it will usually be adjusted with either sodium hydroxide or a suitable acid, such as sulfuric acid, solution, but normally the pH will rise and it will not be lowered, and if it is going down it can be used instead of this more d the mixture of alpha hydroxy acid.

Liquid cleaners can be manufactured mediant * merely mixing the various components thereof with orders or additions not being critical. However, it is desirable that the xanthan gum be optionally added first mixed with the water, several water-soluble components that are mixed together into the xanthan gum solution, the oil-soluble components to be mixed together in a separate operation, and the Two mixtures are to be combined, with the part of oil soluble being added to the soluble part of water (in the water) with shake or other agitation.

In some cases, such a procedure may be varied to avoid any undesired reactions in the components. For example, one will not add concentrated phosphoric acid directly to the magnesium sulfate or to the dye, however such additions will be of aqueous solutions, preferably diluted of the components.

The cleaner can be desirably packaged manually operated spray assortment containers, which are usually and preferably are made of a synthetic inorganic polymeric plastic material, such as polyethylene, polypropylene or polyvinyl chloride (PVC). Tail containers also preferably include nylon or other non-reactive plastic closures, spray nozzle, dip tube and associated dispenser parts, and the resulting cleaner package is ideally suited for use in "spray and clean" applications. However, in some cases, such as when the slag deposits of soap and scoria dime are very heavy, the cleaner may be left until it has dissolved the tank (s) and can then be cleaned or rinsed or multiple applications made by multiple removals until the deposits have disappeared.

The following examples illustrate but do not limit the invention. All the parts, proportions and percentages in the examples, the specification and clauses are by weight and the temperatures are in degrees centigrade unless indicated otherwise.

TABLE 1 COMPONENTS% (BY WEIGHT) A B C Sulfate Lauril Sodium 4.00 3.0 4.0 Benzoate Na C13.15 0.30 0.3 0.3 Magnesium Sulfate Heptahydrate 1.50 1.5 1.5 Malic acid 2.0 2.0 Lactic acid 2.0 3.0 Citrus acid 4.

Aminotri 0.25 0.25 0.2 Methylphosphonic acid 0.425 0.425 042 phosphoric acid Perfume (contains around 40% of terpenes) 0.8 0.8 0.

Tint 0.002 0.002 aooB Water rest rest _E_ pH 3.0 3.0 3.0 Viscosity Brookfield 10 10 10 RT, # 2 Sorpins spindle (cps) rest 100.00 The microemulsion is made by dissolving the optional xanthan gum and the benzoates and then dissolving the detergent into the water, after which the rest of the water-soluble materials are added to the water. the detergent solution, with agitation, except for the perfume and the adjusting agent (solution of sodium hydroxides). The pH is adjusted to 3.0 and then the perfume is stirred into the aqueous solution, instantly generating the desired microemulsion, which is transparent blue.

The cleaner has been packed in a tight polyethylene bottle equipped with polypropylene spray nozzles which are adjustable to the spray and closed spray positions. In use the microemulsion is sprayed onto the "bath ring" of a bath tub, which also includes lime slag, in addition to soap scum and oily dirt. The application rate is about 5 milliliters per 5 meters of ring (which is about 3 centimeters wide). After the application of the wait of about 2 minutes the ring is cleaned with a sponge and cleaned with water; It has been found that greasy dirt, soap scum and even slag of lime have effectively removed. In those cases where lime scree is particularly thick or adhered, a second application may be desirable, but this is considered to be the norm.

The tub surface can be rinsed because it is easy to rinse a bath tub (or shower) but no rinsing is necessary.

Sometimes the dry cleaning will be sufficient but if you want to remove any acidic residue the surface can be cleaned with a sponge with clean water with a damp cloth but in this case it is not necessary to use more than 10 times the weight of the cleaner applied . In other words, the surface does not require being thoroughly rinsed with water, and it will still be clean and bright (as long as it was originally bright). In other uses of the cleaner, this can be used to clean shower tiles, bathroom floor tiles, kitchen tiles, sinks and enamel items generally, without damaging the surfaces thereof. It is recognized that many of these surfaces are resistant to acid but commercial product should be able to be used without damaging even less resistant surfaces, such as enamel europe (often on set iron or steel sheet base which is in some It is a characteristic of the cleaning described above (and other cleaners of this invention) that this can effectively clean hard surfaces but that it contains ionizable acids and therefore should not be applied to surface sensitive to water. However, it has been found that these damage the baths of European white enamel, in this

Claims (8)

example, which are seriously affected by the cleaning with preparations exactly the same as in this example except for the omission in these of the phosphonic acid or of the phosphonic-phosphoric acid mixture. Claims Having described the invention, it is considered as a novelty and therefore the property contained in the following clauses is claimed as property:

1. A composition in acidic microemulsion bath pads and other hard surface items, which are resistant to acid to white zirconium enamel and have pH in the range of 1 to 4 that removes lime slag, soap scour and the greasy dirt of the surfaces of such articles without damaging such surfaces, comprising a detergent proportion of synthetic organic detergent, which P able to remove greasy dirt from such surfaces; a lime scale slag and soap slag removal ratio of an aliphatic alpha hydroxy acid, an amino alkylene phosphonic acid, water and a perfume.

2. A composition as claimed in clause 1 characterized in that said alpha hydroxyl aliphatic acid has from 2 to 6 carbon atoms and the aminoalkylene phosphonic acid contains from 1 to 3 amino nitrogen (s), or 4 lower alkylene phosphidic acid groups and from 0 to lower alkylene groups of 2 to 6 carbon atoms each, which alkylene (s) is / are present and connects (n) to amino nitrogen when a plurality of such nitrogen is present in the amino alkylene phosphonic acid.

3. A composition as claimed in clause 2 characterized in that the proportion of said aliphatic aliphatic hydroxy acid to said amino alkylene phosphonic acid is § the range from 5: 1 to 250: 1.

4. A composition as claimed in clause 3 characterized in that the synthetic organic detergent is a C8.18 alkyl sulfate surfactant.

5. A composition as claimed in clause 1 characterized in that a phosphoric acid is also present which improves the action of the amino-vinylene phosphonic acid to protect the surface of white zirconium enamel from the articles being cleaned against the action of the aliphatic alpha hydroxy acid (s) and the proportion of phosphoric acid being in the range of 2: to 10: 1 with respect to the aminoalkylene phosphonic acid and the proportion of alpha hydroxy aliphatic acid to phosphoric acid is in the range of 5: 2 to 25: 1.

6. A composition as claimed in clause 5 characterized in that it comprises from 1 to 9 percent of * detergent (s) or synthetic organic anion (s), from 1 to 6 percent synthetic organic anionic detergent, from 2 to 9 percent aliphatic alpha hydroxy acid, from 0.05 to 1% of phosphoric acid and from 0.01 to 0.3% of the aminoalkylene phosphonic acid (s).

7. A composition as claimed in clause 1 characterized in that said aliphatic alpha hydroxy acid is a mixture of malic acid and lactic acid.

8. A composition as claimed in clause 1, characterized in that said alpha aliphatic acid and citric acid. In testimony of which I sign the present and Mexico D.F. on June 20, 1994. Jos' An Utonio Miranda L. Representative