WO2001031110A1

WO2001031110A1 - Low odor, hard surface abrasive cleaner with enhanced soil removal

Info

Publication number: WO2001031110A1
Application number: PCT/US2000/028372
Authority: WO
Inventors: David Peterson; Michael H. Robbins; Maria G. Ochomogo; Malcolm A. Deleo; Hanneliese S. Selbach
Original assignee: The Clorox Company
Priority date: 1999-10-25
Filing date: 2000-10-13
Publication date: 2001-05-03
Also published as: AR026213A1; AU1083601A

Abstract

The invention provides an aqueous, hard surface abrasive cleaner, with the following components: a) either an anionic, nonionic, amphoteric surfactant, and mixtures thereof with optionally, a quaternary ammonium surfactant, the surfactants being present in a cleaning - effective amount; b) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25°C, the at least one organic solvent present in a solubilizing - or dispersion - effective amount; c) Tetrapotassium ethylenediamine - tetraacetate (K4EDTA) as a chelating agent, the K4EDTA present in an amount effective to enhance soil removal in the cleaner; d) an abrasive in an abrasive-effective amount; and e) the remainder, water.

Description

IN THE UNITED STATES PATENT AND TRADEMARK OFFICE

Title: LOW ODOR, HARD SURFACE ABRASIVE CLEANER WITH ENHANCED SOIL REMOVAL

Inventor(s): David Peterson, Michael H. Robbins, Maria G. Ochomogo, Malcolm DeLeo and Hanneliese S. Selbach

Related Applications: This is a continuation-in-part of co-pending application Serial No. 08/731 ,653, filed October 17, 1996; and Provisional Application

Serial No. 60/139,604, filed June 17, 1999.

Background of the Invention 1. Field of the Invention The invention relates to a hard surface abrasive cleaner especially effective on bathroom soils, such as soap scum. Preferably, the hard surface abrasive cleaner contains a surface safe abrasive. Even more preferably, the hard surface abrasive cleaner is capable of spray-dispensing from a pump or trigger sprayer or other suitable dispenser.

2. Brief Statement of the Related Art

A number of hard surface cleaners have been specially formulated to target bathroom soils. These include products containing liquid hypochlorite for combating mildew and fungus; products with quaternary ammonium compounds as bacteriostats; and acidic cleaners, such as those containing phosphoric or other strong mineral acids.

These cleaners will typically include buffers, dyes, fragrances, and the like in order to provide performance and/or aesthetic enhancements.

Co-pending and parent application Serial No. 08/731 ,653, filed October 17,

1996, of Robbins et al., entitled "Low Odor, Hard Surface Cleaner with Improved Soil Removal," of common assignment, discloses and claims a low odor hard surface cleaner which includes amine oxide, quaternary ammonium compound and tetrapotassium ethylenediaminetetraacetate for enhanced and proficient soil removal. There is no mention of abrasives therein. Its disclosure is incorporated herein by reference thereto. Co-pending application Serial No. 08/807,187, filed February 2, 1997, of Zhou et al., entitled "Antimicrobial Hard Surface Cleaner," also of common assignment, discloses and claims an antimicrobial hard surface cleaner which includes amine oxide, quaternary ammonium compound and tetrasodium EDTA, in which a critical amine oxide: EDTA ratio results in enhanced non-streaking and non-filming performance. Its disclosure is incorporated herein by reference thereto.

Mills et al., U.S. Patent 5,814,591, further of common assignment, discloses and claims a hard surface cleaner which includes surfactants and tetraammonium EDTA for proficient soap scum and soil removal. Its disclosure is incorporated herein by reference thereto.

However, none of the art discloses, teaches or suggest the combination of an abrasive with tetrapotassium (or tripotassium) EDTA in a liquid, abrasive cleaner, the K₄EDTA acting as an effective chelating agent which additionally suφrisingly enhances the soil removing, especially soap scum-removing, ability of the liquid cleaners formulated therewith. Additionally, unlike some of the prior chelating agents, tetrapotassium EDTA has very low to no odor, which is a significant beneficial attribute to the inventive cleaners hereof. Moreover, none of the art discloses, teaches or suggests the use of surface safe abrasives combined with K₄EDTA in a preferred embodiment of this invention.

Summary of the Invention and Objects The invention provides an aqueous, hard surface abrasive cleaner, said cleaner comprising: an aqueous hard surface cleaner with improved soil, especially soap scum, removal comprising:

(a) either an anionic, nonionic, amphoteric surfactant, and mixtures thereof with optionally, a quaternary ammonium surfactant, said surfactants being present in a cleaning - effective amount;

(b) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25°C, said at least one organic solvent present in a solubilizing - or dispersion - effective amount; (c) Tetrapotassium ethylenediamine - tetraacetate (K₄EDTA) as a chelating agent, said K₄EDTA present in an amount effective to enhance soil removal in said cleaner;

(d) an abrasive in an abrasive-effective amount; and (e) the remainder, water.

The invention further comprises a method of cleaning soils from hard surfaces by applying said inventive cleaner to said soils, and removing both from said surface.

It is therefore an object of this invention to improve soil, such soap scum, removal from hard surfaces.

It is another object of this invention to improve the performance of a liquid cleaner by combining an abrasive with K₄EDTA, which enhances the removal of soils from the hard surface cleaned.

It is also an object of this invention to provide a hard surface abrasive cleaner, which is effective on oily and particulate soils.

It is a further object of this invention to provide a low to no odor hard surface abrasive cleaner.

It is a still further object of this invention to provide a surface safe abrasive cleaner.

It is yet another object of this invention to provide a surface safe abrasive cleaner by the use of a coated abrasive.

It is an additional object of this invention to provide a sprayable abrasive cleaner.

Detailed Description of the Invention The invention provides an improved, all puφose abrasive cleaner especially adapted for the complete and speedy removal of tough soils from a hard surface. These types of cleaners are intended to clean hard surfaces by application of a metered discrete amount of the abrasive cleaner, which is typically accomplished by pouring or dispensing a suitable amount of liquid cleaner onto a surface and wiping with repeated motions over a stain or soil to remove the same. Generally, a surface cleaning tool or workpiece, such as a cloth, sponge, mop, or the like, is used. Preferably, the cleaner and the soil are then removed with a water rinse. In an especially preferred embodiment of the invention, sprayable abrasives are delivered via a pump or trigger sprayer onto the surface to be cleaned or onto the workpiece used to apply the cleaner. The cleaner can be preferably an emulsion, a single phase dispersion, or, a suspoemulsion, having a viscosity generally less than about 100,000 Centipoise ("cps"), more preferably less than about 10,000 cps and most preferably less than about 1,000 cps. The presence of the abrasive will tend to opacify the liquid cleaner. The cleaner itself has the following ingredients:

(a) an anionic, nonionic or amphoteric surfactant, and mixtures thereof with optionally, a quaternary ammonium surfactant, said surfactants being present in a cleaning - effective amount;

(b) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25°C, said at least one organic solvent present in a solubilizing - or dispersion - effective amount; (c) Tetrapotassium ethylenediamine - tetraacetate (K₄EDTA) as a chelating agent, said potassium EDTA present in an amount effective to enhance soil, especially soap scum, removal in said cleaner;

(d) an abrasive in an abrasive-effective amount; and (d) the remainder, water.

Additional adjuncts in small amounts such as buffers, fragrance, dye and the like can be included to provide desirable attributes of such adjuncts.

In the application, effective amounts are generally those amounts listed as the ranges or levels of ingredients in the descriptions which follow hereto. Unless otherwise stated, amounts listed in percentage ("%'s") are in weight percent (based on 100% active) of the composition. 1. Solvents

The solvent is a water soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25°C. It is preferably selected from C,_.6 alkanol, C,_ ₆ diols, C,_₂₄ alkylene glycol ethers, and mixtures thereof. The alkanol can be selected from methanol, ethanol, n-propanol, isopropanol, butanol, pentanol, hexanol, their various positional isomers, and mixtures of the foregoing. It may also be possible to utilize in addition to, or in place of, said alkanols, the diols such as methylene, ethylene, propylene and butylene glycols, and mixtures thereof.

It is preferred to use an alkylene glycol ether solvent in this invention. The alkylene glycol ether solvents can include ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, propylene glycol n-propyl ether, propylene glycol monobutyl ether, diethylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol N-butyl ether and mixtures thereof. Preferred glycol ethers are ethylene glycol monobutyl ether, also known as butoxyethanol, sold as butyl Cellosolve by Union

Carbide, and also sold by Dow Chemical Co., 2-(2-butoxyethoxy) ethanol, sold as butyl Carbitol, also by Union Carbide, propylene glycol n-propyl ether, and dipropylene glycol N-butyl ether (DPNB), available from a variety of sources. Another preferred alkylene glycol ether is propylene glycol t-butyl ether, which is commercially sold as Arcosolve PTB, by Arco Chemical Co. The n-butyl ether of propylene glycol is also preferred. Other suppliers of preferred solvents include Union Carbide. Certain teφene and teφene derivatives, such as, without limitation, d-Limonene, are also suitable for use. If mixtures of solvents are used, the amounts and ratios of such solvents used are important to determine the optimum cleaning performances of the inventive cleaner. It is preferred to limit the total amount of solvent to no more than 50%, more preferably no more than 25%, and most preferably, no more than 15%, of the cleaner. A preferred range is about 1-15%. These amounts of solvents are generally referred to as dispersion- effective or solubilizing effective amounts, since the other components, such as surfactants, are materials which are assisted into solution by the solvents. The solvents are also important as cleaning materials on their own, helping to loosen and solubilize greasy soils for easy removal from the surface cleaned. 2. Surfactants

The surfactant is an anionic, nonionic, amphoteric surfactant, or mixtures thereof. Optionally, a quaternary ammonium surfactant can be added.

a. Anionic, Nonionic and Amphoteric Surfactants

The anionic surfactant is, for example, a linear or branched C_6.14 alkylbenzene sulfonate, alkane sulfonate, alkyl sulfate, alkyl ether sulfate, or generally, a sulfated or sulfonated C_6.]4 surfactant. Witconate NAS, for example, is a 1 -octane-sufonate, from Witco Chemical Company. Pilot L-45, a C,,_₅ alkylbenzene sulfonate (which are referred to as "LAS"), from Pilot Chemical Co., Biosoft S100 and S130 (non-neutralized linear alkylbenzene sulfonic acid, which is referred to as "HLAS") and S40 from Stepan Company; sodium dodecyl sulfate and sodium lauryl sulfate. Pilot also produces Calfoam ES-302, an alkylethersulfate. The use of acidic surfactants having a higher actives level may be desirable due to cost-effectiveness, if neutralized by buffers or other alkaline ingredients during the formulation of the cleaner.

The nonionic surfactants are selected from alkoxylated alcohols, alkoxylated phenol ethers, and other surfactants often referred to as semi-polar nonionics, such as the trialkyl amine oxides. The alkoxylated phenol ethers include octyl- and nonylphenol ethers, with varying degrees of alkoxylation., such as 1-10 moles of ethylene oxide per mole of phenol. The alkyl group can vary from C_6.16, although octyl- and nonyl chain lengths are readily available. Various suitable products available from Rohm and Haas under the trademark Triton, such as Triton N-57, N-101, N-l 11, X-45, X-100, X-102, and from Mazer Chemicals under the trademark Macol, from GAF Coφoration under the trademark Igepal, from Texaco Chemical Company under the trademark Surfonic. The alkoxylated alcohols include ethoxylated, and ethoxylated and propoxylated C_6.]5 alcohols, with about 2-10 moles of ethylene oxide, or 1-10 and 1-10 moles of ethylene and propylene oxide per mole of alcohol, respectively. Exemplary surfactants are available from Shell Chemical under the trademarks Neodol and Alfonic; Huntsman; and Tergitol from Union Carbide. The semi-polar amine oxides are also preferred, although, for the invention, a mixture of nonionic and amine oxide surfactants can also be used. The amine oxides, referred to as mono-long chain, di-short chain, trialkyl amine oxides, have the general configuration: R'

R-NO

R"

wherein R is C₆.₂₄ alkyl, and R' and R" are both C alkyl, or C_M hydroxyalkyl, although R' and R" do not have to be equal. These amine oxides can also be ethoxylated or propoxylated. The preferred amine oxide is lauryl amine oxide. The commercial sources for such amine oxides are Barlox 10, 12, 14 and 16 from Lonza Chemical

Company, Varox by Witco and Ammonyx by Stepan Co.

A further preferred semi-polar nonionic surfactant is alkylamidoalkylenedialkylamine oxide. Its structure is shown below:

O R²

" I

Rⁱ -C-NH-(CH₂)_n-NO

I R³

O

II wherein R¹ is C_5.20 alkyl, R² and R³ are C_M alkyl, R¹ -C-NH-(CH₂)_n- or -(CH₂) _p-OH, although R² and R³ do not have to be equal or the same substituent, and n is 1-5, preferably 3, and p is 1-6, preferably 2-3. Additionally, the surfactant could be ethoxylated (1-10 moles of EO/mole) or propoxylated (1-10 moles of PO/mole).

This surfactant is available from various sources, including from Lonza Chemical Company, as a cocoamidopropyldimethyl amine oxide, sold under the brand name Barlox C.

Additionally semi-polar surfactants include phosphine oxides and sulfoxides.

The amphoteric surfactant is typically an alkylbetaine or a sulfobetaine. One group of preferred amphoterics are alkylamidoalkyldialkylbetaines. These have the structure: R²

R^I-C-NH-(CH₂)_m-N⁺-(CH₂)_nCOO-

O R³

wherein R¹ is C_6.20 alkyl, R² and R³ are both C alkyl, although R² and R³ do not have to be equal, and m can be 1 -5, preferably 3, and n can be 1-5, preferably 1. These alkylbetaines can also be ethoxylated or propoxylated. The preferred alkylbetaine is a cocoamidopropyldimethyl betaine called Lonzaine CO, available from Lonza Chemical

Co. Other vendors are Henkel KGaA, which provides Velvetex AB, and Witco Chemical Co., which offers Rewoteric AMB-15, both of which products are cocobetaines.

The amounts of surfactants present are to be somewhat minimized, for piπposes of cost-savings and to generally restrict the dissolved actives which could contribute to leaving behind residues when the cleaner is applied to a surface. However, the amounts added are generally about 0.001-10%, more preferably 0.002-3.00%> surfactant. These are generally considered to be cleaning-effective amounts. On the other hand, if a dilutable concentrate is desired, the upper level of surfactant can be as high as 25%, more preferably around 15%. If a mixture of anionic and nonionic or amphoteric surfactants is used, the ratio of the anionic surfactant to the nonionic or amphoteric surfactant is about 20:1 to 1 :20, more preferably about 10:1 to 1:10.

b. Quaternary Ammonium Surfactant

The invention may further optionally include a cationic surfactant, specifically, a quaternary ammonium surfactant. These types of surfactants are typically used in bathroom cleaners because they are generally considered "broad spectrum" antimicrobial compounds, having efficacy against both gram positive (e.g., Staphylococcus sp.) and gram negative (e.g., Escherischia coli) microorganisms. Thus, the quaternary ammonium surfactant, or compounds, are incoφorated for bacteriostatic/disinfectant puφoses and should be present in amounts effective for such puφoses. The quaternary ammonium compounds are selected from mono-long-chain, tri- short-chain, tetraalkyl ammonium compounds, di-long-chain, di -short-chain tetraalkyl ammonium compounds, trialkyl, mono-benzyl ammonium compounds, and mixtures thereof. By "long" chain is meant about C_6.30 alkyl. By "short" chain is meant C,_.5 alkyl, preferably C,_₃ . Preferred materials include Stepan series, such as BTC 2125 series; Barquat and Bardac series, such as Bardac MB 2050 and Barquat 4250, from Lonza Chemical. Typical amounts of the quaternary ammonium compound range from preferably about 0-5%, more preferably about 0.001-2%.

3. K EDTA

The tetrapotassium ethylene diamine tetraacetate (referred to as "K₄EDTA") is a critical part of the invention. Its use, in place of the standard chelating agent, tetrasodium EDTA, results in not only a suφrisingly complete removal of various soils, including bathroom soap scum soils, but an unexpectedly rapid removal as well. The fact that the tetrapotassium salt of EDTA is so effective versus the tetrasodium salt was quite unexpected since, in other literature, the tetrapotassium salt has not been demonstrated to be a superior performer as compared to the tetrasodium salt. Additionally, in comparison to another favorable salt, tetraamonium EDTA, the inventive tetrapotassium EDTA has a distinct advantage in having low or no odor. This latter advantage is quite significant since the user of a cleaning product will not be favorably inclined to repeat usage of a product whose odor may not please her/him. Moreover, the tetrapotassium EDTA can be used as the sole chelating agent, or a discrete quantity of a co-chelant, such as tetrasodium EDTA may be added, in an amount ranging from about 1-5%. Further, an alternative is to use tripotassium EDTA, since this non-completely neutralized chelant may be more cost-effective to use, especially when combined with a co-builder or buffer.

K₄EDTA and K₃EDTA can favorably be prepared by taking the acid form of EDTA and neutralizing it with KOH in a less than to greater than stoichiometric quantity. For example, to 50g of the acid form of EDTA and 47g deionized water, 76g of KOH solution (45%) can be slowly added, resulting in a 46% K₄EDTA solution. The acid form of EDTA can be obtained from Hampshire Chemicals and Aldrich Chemicals. In the neutralization of the acid form of EDTA, one can, but does not need, to use an excess of alkali. Thus, for example, the level of KOH can vary from a less than stoichiometric quantity to about a 5% excess. The amount of K₄EDTA added should be in the range of 0.01-25%, more preferably 0.01-10%, by weight of the cleaner.

4. Abrasives The insoluble abrasive is generally present in an amount ranging from about 0.05 to 75% by weight of the cleaner, and more preferably between about 0.1 to about 25% by weight. (The percentage by weight of abrasive in the liquid cleaner will rise if water-soluble abrasives, e.g., borax pentahydrate — described below ~ are utilized. Then, an amount at least greater than about 20 wt.% is typically utilized).

In a particularly preferred embodiment, where a sprayable cleaner is desired, the abrasive is present in an amount of about 0.1 to about 8 parts by weight for each about 99.1 to about 92 parts by weight of the base liquid composition, preferably, about 0.5 parts by weight of the abrasive are mixed with about 99.5 parts by weight of the base liquid composition.

Suitable abrasives useful in the present invention are selected from water- insoluble, non-gritty materials well-known in the literature for their relatively mild abrasive properties. It is highly preferred that the abrasives used herein not be undesirably "scratchy". Abrasive materials having a Mohs hardness in the range of about

1 to 7 are typically used; abrasives having a Mohs hardness of 3, or below, being used to avoid scratches on aluminum or stainless steel finishes. Suitable inorganic abrasives include titanium dioxide, calcium carbonate, pumice, calcium sulfate, silica, alumina, zeolites (aluminosilicates), limestone, dolomite, diatomaceous earth, as well as materials such as Fuller's earth, magnesium carbonate, China clay, attapulgite, calcium hydroxyapatite, calcium orthophosphate and the like, or any other water-insoluble mineral salt. Organic abrasives such as urea-formaldehyde, methylmethacrylate, and melamine-formaldehyde resins; polyethylene spheres, PET and polyvinylchloride (PVC) can be used in order to avoid scratching on certain surfaces, especially plastic surfaces. Other types of abrasives include water soluble materials present in an amount such as to exceed their solubility in water, leaving a portion thereof undissolved. These types of materials include alkali metal bicarbonates, alkali metal phosphates, alkali metal borates, particularly sodium tetraborate decahydrate ("borax") and pentahydrate ("borax pentahydrate"; see co-pending and commonly assigned U.S. Patent Application Serial No. 08/718,059, filed September 17, 1996, entitled "Cleaner with Water Soluble Abrasive," incoφorated herein by reference.). The low Mohs hardness ( 3) materials and the water soluble abrasives are especially suitable for surface safe applications (i.e., mitigation or prevention of scratching or damaging metal or composite surfaces, such as

Formica® or Corian® materials). The "hard" inorganic abrasives can be converted to "soft" organic abrasives by coating the former with synthetic resins (such as coating TiO₂ with a block ethylene oxide/propylene oxide copolymer, Pluronic®, Rohm &

Haas) or water soluble polymer such as polyacrylate (Carbopol®, BASF) or a fatty acid, e.g., stearic acid, by techniques known in the art. Typically, the abrasives have a particle size range of from 1 to 1,000 microns, more preferably between about 1 and 500 microns. For the sprayable embodiment, this is more typically between about 1 and 100 microns, more preferably about 1 and 50 microns.

In one alternative embodiment, the abrasive cleaner is formulated as a suspoemulsion, whereby the abrasive is suspended by means of a mixture of surfactants and a lipid. In this type of system, the preferred abrasive is a relatively small particle size abrasive, such as finely divided silica, titanium dioxide, ultramarine blue, calcium carbonate; water soluble abrasives such as sodium bicarbonate, borax pentahydrate and decahydrate; and organic abrasives. Finely divided silica is especially desirable, with a preferred material being Sident, from Degussa Coφ. It is preferred that the abrasive have a particle size of less than 200 , and especially, less than 50. This particular fine size is easier to incoφorate as a payload in the suspoemulsion and is easier to dispense from a trigger sprayer, which has a relatively small spray orifice. Most liquid abrasive cleaners are pourable, necessitated by the relatively larger particle size of the abrasives, as well as the fact that most other commercial liquid cleaners have a tendency to thicken, which, in a trigger sprayer, would lead to clogging. As well, the inventive suspoemulsions can carry larger amounts of abrasives, indeed, other types of solids, relative to prior liquid compositions (in the form of suspensions, dispersions, mulls, or other forms) without phase separation, which is distinctly advantageous. Preparation of the suspoemulsion is described in Provisional Application Serial No. 60/139,604, filed June 17, 1999, and incoφorated herein by reference. However, generally, in order to best practice the invention, the oil phase and the aqueous phase materials are separately prepared, with the Active being added to the oil phase, or being separately added. The, the two phases are combined, by means of high shear, using a variable high speed mixer. Apparently, in order to blend or cause the emulsion to form, a very high rate of shear is needed when the Active is added. It is thus believed, without limitation of theory, that the Active is coated with the oil phase, and that the surfactants then help to maintain an encapsulate around the Active, and also to maintain the stable suspension of the Active within the emulsion, thus resulting in the suspoemulsion and its attendant advantages. A preferred variable high speed mixer is Dispermat, from VMA-Getzmann GmbH, although other apparatuses are suitable for use.

5. Thickeners

In some of the formulations of this invention, the level of solids is less than 40%, especially in the case of the sprayable abrasive cleaners. In that instance, it is preferred to add at least one thickener. The thickener is typically a water soluble to water dispersible organic polymer, although some inorganic substances, such as finely divided CaCO₃, and other materials may also be suitable for use. Just about any polymer which can thicken an aqueous dispersion is applicable herein as a thickener, preferably hydrolyzable polymers. These can include hydroxycelluloses, alginates, guar gum (galactomannan), xanthan (sometimes spelled xanthum) gum, polyvinyl alcohol, polyvinyl acetate, polyacrylic acid, acrylic acid co-polymers, and mixtures thereof. Preferred hydroxycelluloses include methyl, ethyl and propyl, hydroxymethylcelluloses, hydroxyethylcelluloses and hydroxypropylcelluloses. These products are available from a number of sources, including BASF AG, Rohm and Haas, Union Carbide, Hoechst AG (now Clariant), B.F. Goodrich, and Dow Chemical Company. The molecular weights of the polymer thickeners can vary from about 300 to 500,000 Daltons. The amount added varies from about 0.1 to 20, more preferably 0.1 to about 10.0%.

6. Water and Miscellaneous

Since the cleaner is an aqueous cleaner with relatively low levels of actives, the principal ingredient is water, which should be present at a level of up to about 25%, more preferably up to about 50%, and most preferably, at least about 80%. Where a sprayable embodiment is desired, the water level is at least about 50%, more preferably at least about 60% and most preferably up to 90% by weight. Deionized water is preferred. Small amounts of adjuncts can be added for improving cleaning performance or aesthetic qualities of the cleaner. For example, buffers could be added to maintain constant pH (which for the invention is between about 7-14, more preferably between about 8-13). These buffers include NaOH, KOH, Na₂CO₃, K₂CO₃, K₂C₂O₄, as alkaline buffers, and phosphoric, hydrochloric, sulfuric acids as acidic buffers, and others. KOH,

K₂CO₃, and K₂C₂O₄ are preferred buffers. One way of obtaining tri- and tetrapotassium EDTA is to take the acidic EDTA acid and neutralize it with an appropriate, stoichiometric amount of KOH. Builders, such as phosphates, silicates, and again, carbonates, may be desirable (wherein the amount utilized is less than the amount which would be used to form water soluble abrasives). Further solubilizing materials, such as hydrotropes, e.g.s., cumene, toluene and xylene sulfonates, may also be desirable. Adjuncts for cleaning include additional surfactants, such as those described in Kirk- Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Volume 22, pp. 332-432 (Marcel-Dekker, 1983), and McCutcheon's Soaps and Detergents (N. Amer. 1984), which are incoφorated herein by reference. Aesthetic adjuncts include fragrances, such as those available from Givaudan, IFF, Quest, Sozio, Firmenich, Dragoco and others, and dyes and pigments which can be solubilized or suspended in the formulation, such as diaminoanthraquinones. Water-insoluble solvents may sometimes be desirable as added grease or oily soil cutting agents. These types of solvents include tertiary alcohols, hydrocarbons (alkanes), pine-oil, d-limonene and other teφenes and teφene derivatives, and benzyl alcohols. As stated in 5. above, thickeners, such as calcium carbonate, sodium bicarbonate, aluminum oxide, and polymers, such as polyacrylate, starch, xanthan gum, alginates, guar gum, cellulose, and the like, may be desired additives. The use of some of these thickeners (CaCO₃ or NaHCO₃) is to be distinguished from their potential use as builders, generally by particle size or amount used. Antifoaming agents, or foam controlling agents, may be also desirable, such as silicone defoamers. The amounts of these cleaning and aesthetic adjuncts should be in the range of 0-10%, more preferably 0-2%.

Preferred Embodiment: Sprayable Abrasiver Cleaner

A preferred embodiment of the invention provides an improved sprayable, opaque, liquid abrasive composition. These compositions have improved scouring ability over traditional spray cleaners, because of the inclusion of an abrasive. These compositions are opaque and thus the consumer can readily determine where they have sprayed the product. These compositions have relatively low levels of abrasive and surfactant so that the viscosity remains low and they are readily sprayable. The low surfactant level results in a cleaner that has a relatively low suds level and can be easily wiped away by the consumer. The cleaning ability is excellent without the need for high levels of hydrocarbons, which can cause environmental problems and are expensive. The preferred embodiment has the following most preferred ranges, in weight percent basis:

0.2% to 2% of an anionic, nonionic or amphoteric surfactant or combination thereof; 0.1 % to 8% of an abrasive;

1% to 10%) of a preferably non-hydrocarbon solvent;

0% to 10%) of a chelating agent, especially tetrapotassium EDTA

0.1% to 2% of a polymeric thickener;

0% to 0.5% of a fragrance; and the balance being water and other additives.

In the following Experimental section, the suφrising performance benefits of the various aspects of the inventive cleaner are demonstrated.

EXPERIMENTAL Example 1 The following formulas (wt% actives) were made and the stability of the suspension measured at 100F. The table shows that the invention is compatible with a variety of solvents.

² From J.T.Baker.

³ From BASF Coφ.

⁴ Hamp-ene K4 100 from AKZO Nobel.

Example 2 The following formulas (wt% actives) were made and the stability of the suspension measured at 100F. The table shows that the invention is compatible with a variety of thickeners.

Example 3 The following formulas (wt% actives) were made and the stability of the suspension measured at 100F. The table shows that the invention is compatible with a variety of abrasives.

¹ Nonionic surfactant from Union Carbide Chemical & Plastics Inc.

² Silica from Degussa AG.

³ From Quantum Chemical.

⁴ Calcium carbonate from ECC International.

⁵ Benwood 2213 from Suzorite Mineral Products, Inc.

⁶ Valfour 100 from PQ Coφ.

⁷ NB012 from CR Minerals Coφ.

Example 4 The following formulas (wt% actives) were made and the stability of the suspension measured at 100F. The table shows that the invention is compatible with a variety of surfactants.

Example 5 The following formulas (wt% actives) were made and the stability of the suspension measured at 100F. The table shows that the invention is not stable in the presence of high surfactant levels.

Example 6 The following formulas (wt% actives) were made and the stability of the viscosity measured at 70F. The table shows that the low viscosity of the invention was suitable for spraying.

^■Brookfield RVT, spindle No.4, 5 RPM, room temperature. ² Product of the Clorox Company.

Example 7 Sprayable abrasive cleaners containing tetrapotassium EDTA.

Formula A

Tetrapotassium EDTA 2.0% actives

Tergitol Min-Foam IX 0.5%

Titanium dioxide 0.4%

Dipropylene glycolbutylether 5.0%

Xanthan gum 0.35%

Fragrance 0.1%

Formula B

Tetrapotassium EDTA 2.0% actives

Tergitol Min-Foam IX 0.5%

Calcium Carbonate (Microwhite 15) 8.0%

Dipropylene glycolbutylether 5.0%

Xanthan gum 0.35%

Fragrance 0.1 %

These inventive formulas A and B were then tested for cleaning performance on bathroom soil against three commercial formulas. In this test, bathroom soil removal is measured using a testing apparatus which measures the cumulative amount of soil removed at each cycle, with a maximum of 50 cycles. In any case, in this test, the higher score achieved is more preferred.

The results were

a. Contains 50% calcium carbonate and citrate as a chelating agent. b. Contains tetrasodium EDTA as a chelating agent. c. Contains tetrapotassium EDTA as a chelating agent.

As can be seen from the above performance data, the combination of abrasive with tetrapotassium EDTA gives performance superior to commercial cleaners without tetrapotassium EDTA and abrasive or with only abrasive or tetrapotassium EDTA.

Examples 8-9 The following Examples depict formulas which have been produced for various potential commercial product executions:

Formula A (thick)

Tetrapotassium EDTA 2.0% actives

Tergitol Min-Foam IX 0.5%

Titanium dioxide 0.5%

Dipropylene glycolbutylether 5.0%

Carbopol 674 (thickener) 0.5%

Fragrance 0.1%

Formula B (thin)

Tetrapotassium EDTA 2.0% actives

Tergitol Min-Foam IX 0.5%

Calcium Carbonate (Microwhite 15) 4.0%

Dipropylene glycolbutylether 5.0%

Xanthan gum 0.35%

Fragrance 0.1% Example 10 is an example of a suspoemulsion version of the invention:

EXAMPLE 10 Sprayable Surface Safe Abrasive Cleaner

¹ Sident 9, Degussa Coφ. (particle size 50μ)

² Aerosil R-972, Degussa Coφ. (particle size ~ 14 nm) ³Triglyeride of Castor Oil, Rheox

⁴Xanthan Gum, Kelco ⁵Chelant

⁶Pluronic PI 04, BASF Coφ. ⁷Pluronic L92, BASF Coφ. ⁸Pluronic 25R4, BASF Coφ. ⁹C₁₂amine oxide, Stepan Co.

In the above example, the first two co-thickeners are combined with the mineral oil to form an oil phase, with slow heating to about 50°C/122°F until fully blended. This first oil phase is allowed to cool to ambient temperature. Next, the first three surfactants are dissolved in a quantity of water, with slow heating to about 50°C/122°F until fully blended, and this mixture is also allowed to cool. Using a variable high speed mixing apparatus, for example, Dispermat (VMA-Getzmann GmbH) (other potentially useful mixers include Microfluidizer (Arthur D. Little) and apparatuses from Hobart; ball mixers, rollers and other devices may also be suitable), the abrasive is slowly mixed into the water/surfactants mixture at about 4,000 φm. Thereafter, the last co-thickener/adhering agent is added, slowly. The oil phase mixture is then introduced, at much higher shear, about 8,000 rpm, and processed well. Finally, the last surfactant and the chelating agent are added. The resulting abrasive liquid cleaner is capable of being dispensed from a trigger sprayer, unlike prior formulations which are too viscous and whose abrasive particle sizes were too large for effective metering from a trigger sprayer.

The invention is further defined and delineated by the Claims which follow hereto.

Claims

Claims 1. An aqueous hard surface cleaner with improved soil removal comprising:

(a) an anionic, nonionic, amphoteric surfactant, and mixtures thereof with optionally, a quaternary ammonium surfactant, the total amount of said surfactant being present in a cleaning effective amount;

(b) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25°C, said at least one organic solvent present in a solubilizing - or dispersion - effective amount;

(c) Tetrapotassium ethylenediamine - tetraacetate (K₄EDTA) or tripotassium ethylenediamine - tetraacetate (K₃EDTA) as a chelating agent, said K₄EDTA or

K₃EDTA present in an amount effective to enhance soil removal in said cleaner;

(d) At least one abrasive in an abrasive-effective amount; and

(e) the remainder, water.

2. The cleaner of Claim 1 wherein said surfactant is an anionic surfactant of

(a), which further comprises a linear or branched C₆.₁₄ alkylbenzene sulfonate, alkane sulfonate, alkyl sulfate, and mixtures thereof.

3. The cleaner of Claim 1 wherein said surfactant of (a) is a nonionic surfactant, which further comprises an alkoxylated alkylphenol ether, an alkoxylated alcohol, or a semi-polar nonionic surfactant.

4. The cleaner of Claim 3 wherein said nonionic surfactant is a semi-polar nonionic surfactant selected from the group consisting of mono-long-chain alkyl, di- short-chain trialkyl amine oxides, alkylamidodialkyl amine oxides, phosphine oxides and sulfoxides.

5. The cleaner of Claim 4 wherein said nonionic surfactant of (a) is a mono-long-chain, di-short-chain trialkyl amine oxide.

6. The cleaner of Claim 4 wherein said nonionic surfactant is an ethoxylated alkylphenol ether selected from the group consisting of ethoxylated octylphenol ethers, ethoxylated nonylphenol ethers, and mixtures thereof.

7. The cleaner of Claim 6 wherein said nonionic surfactant is an ethoxylated octylphenol, ethoxylated with 1-10 moles of ethylene oxide.

8. The cleaner of Claim 1 wherein said organic solvent of (b) is selected from the group consisting of alkanols, diols, glycol ethers, and mixtures thereof.

9. The cleaner of Claim 8 wherein said organic solvent is a C,_₂₄ glycol ether.

10. The cleaner of Claim 1 further comprising d) a quaternary ammonium compound.

11. The cleaner of Claim 10 wherein said quaternary ammonium compound is selected from the group consisting of mono-long-chain, tri-short-chain, tetraalkyl ammonium compounds, di-long-chain, di-short-chain tetra-alkyl ammonium compounds, trialkyl, mono-benzyl ammonium compounds, and mixtures thereof.

12. The cleaner of claim 1 further comprising (e) at least one adjunct selected from the group consisting of builders, buffers, fragrances, thickeners, dyes, pigments, foaming stabilizers, water-insoluble organic solvents, and hydrotropes.

13. The cleaner of claim 1 wherein said chelating agent of (c) is prepared by neutralizing the acid form of EDTA.

14. The cleaner of claim 13 wherein the neutralizing agent is potassium hydroxide.

15. The cleaner of claim 14 wherein said potassium hydroxide is present in a less than stoichiometric to slightly greater than stoichiometric amount.

16. The cleaner of claim 1 wherein the abrasive cleaner is capable of spray dispensing.

17. The cleaner of claim 16 wherein the abrasive particle size is less than or equal to 100 microns.

18. The cleaner of claim 16 wherein the abrasives have a Mohs hardness of 1 to 7.

19. The cleaner of claim 16 wherein the abrasive cleaner is in the form of a suspoemulsion.

20. A method for removing a soil from a hard surface, said method comprising applying to said soil a hard surface cleaner which comprises: (a) either an anionic, nonionic, amphoteric surfactant, and mixtures thereof with optionally, a quaternary ammonium surfactant, the total amount of said surfactant being present in a cleaning effective amount;

(b) at least one water-soluble or dispersible organic solvent having a vapor pressure of at least 0.001 mm Hg at 25°C, said at least one organic solvent present in a solubilizing or dispersion - effective amount;

(c) Tetrapotassium ethylenediamine - tetraacetate (K₄EDTA) or tripotassium ethylenediamine - tetraacetate (K₃EDTA) as a chelating agent, said K₄EDTA or K₃EDTA present in an amount effective to enhance soil removal in said cleaner;

(d) At least one abrasive in an abrasive-effective amount; and (e) the remainder, water.

21. The method of Claim 20 further comprising removing said soil and said cleaner from said surface.