CA1217690A - Hard surface acid cleaner - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Hard surface acid cleaners providing surprisingly fast acting and effective cleaning results across a wide variety of problematic cleaning areas, and methods for making the same are made by combining alkyl aryl sulfonic acids and water.

The preferred alkyl aryl sulfonic acids are alkyl benzene sulfonic acids of the general structure wherein R is alkyl averaging 5 to 20 carbon atoms in length.

Additionally, solvents, antimicrobial compounds, defoamers, thickeners and other cleaning adjuvants may be added to these hard surface acid cleaners.

Description

I

DESCRIPTION

HARD SURFACE ACID COREY

There are many example of hard surface cleaners in the art, containing some sort ox anionic ~uractant, solvent, perhaps a dye and a fragrance to impart a pleasing color and odor, and mostly water. Most of these prior art cleaners suffer from one or more di~advan~ages~ For example, Rome cleaners are effective only on hard water Tony. An example of this clays of cleaner is a highly acidic toilet bowl cleaner containing hydrochloric acid. Hard water stains axe mineral stains caused by the deposition of calcium or magnesium salts present in hard water. Certain other cleaners may be effective only against soap scum stains, caused when a Patty acid soap, such as a sodium laurel fatty acid soap precipitates in hard water containing alkaline earth metal salts, such a calcium, magnesium, or barium, causing the familiar soap SCUM stain.
Still other cleaners may be effective only on grossly stains. Generally speaking, these are cleaner which have either at least some water miscible solvent, and/or sure higher amount of non ionic and/or anionic suxfactants.
one of the prior art cleaner have addressed all three of these problematic areas together. As mentioned, a particular cleaner may be effective against a particular stain or cleaning problem, but not against the others. Thus, ineffective cleaning results may occur against certain stains using some of these cleaners, requiring purchase of other cleaners which will effectively remove the target Tony This will result in added expense as a particular cleaver mutt be purchased for a particular stain.

Furthermore, many ox the prior art cleaner are very slow acting That it after being applied to target stain for long periods of time, they may show some cleaning effect, but this slow action is considered a great disadvantage and inconvenience.

Thus, heretofore no single cleaner has been formulated which will satisfactorily clean all three types of stains.
There is also a need for an effective all purpose hard surface cleaner which it faster than the prior art cleaners. There is thus a long felt need for a multipurpose household cleaner capable of quickly and effectively cleaning all three types of stain.

Linear alkyd Bunsen sulfonic acid has been well known in the detergent and cleaner field as a storage compound which, upon neutralization with generally, an alkali metal salt, is available for use an anionic surfactant. This was recognized in Coupler, et at, USE 3,969,282 which utilized alkyd Bunsen sulfonic acid in combination with a non ionic sur~actant as a storage compound to be neutralized with alkali I metal salts prior to using them to launder fabrics. Further, Reid, US. 3,463,736 showed that linear alkyd Bunsen sul~onic acids could be neutralized with triethanola~ine to act as a cleaner. However, it was not realized in the art that linear alkyd Bunsen sulfonic acids can be utilized as hard surface cleaners themselves.

I

DISCLOSURE OF THE INVENTION
.

This invention relates Jo an improved hard surface acid cleaner having a pi of no more ken approximately 6.5 comprising:

(a) alkyd aureole sulonic acid; and (b) at least 50.0% by weight water.

The preferred alkyd aureole ~ulfonic acid it a linear alkyd Bunsen sulfonic acid surfactant of the general structure wherein R is an alkyd averaging 5 to 20 carbons.

In a further embodiment, this hard uric acid cleaner further comprises I a solvent selected from straight chain alXanols averaging 1 to 10 carbon, alicyclic alkanols averaging 5 to 10 carbons, dialkyl ethers averaging 2 to 8 carbons, and glycol ethers averaging 3 to 20 carbon, and mixtures thereof.

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I

In yet another embodiment the hard Sergei acid cleaner further comprises (d) an antimicrobial compound selected from:
(i) a substituted phenol of thy general structure;
lR6 I Al wherein Al, R2~ R3, R4, and R5 can separately be a phenol group, Of or H, and R6 can be H or pa;
(ii) a qua ternary ammonium compound; and (iii) mixtures thereof.

In yet another embodiment, the hard surface cleaner further comprises (e) a thickener selected from gum, polysaccharides and resins.
In still another embodiment, the hard surface acid cleaner further comprises (f) a defamer selected from the dialkyl polysiloxane polymers.
he hard surface acid cleaner of this invention can also include at least one other cleaning ad juvant selected from 20 dyes, pigments, fragrances, and builders.
Surprisingly, the hard surface acid cleaner of this invention has proven to be both effective and fast acting against all three major problem stain , namely, (1) soap scums;

(2) hard water stains; and I greasy oily stain.

DETAILED DESCRIPTION OF E IVY

The prune invention it a hard surface cold cleaner which has surprisingly effective and fast cleaning results on all threw problem area: I soap scums; (2) hard water stains;
and (3) greasy/oily stains The surprising revelation way that alkyd aureole ~ulfonic acid compound, most ~peci~ically/ linear alkyd Bunsen sulfonic acids, ("HAS") were responsible for the improved cleaning in all three awry. These alkyd Bunsen sulfonic acid surfactants are not neutralized with alkali metal, alkaline earth metal, or ammonium alto as are the typical detergents using substituted alkyd Bunsen sulfonate~.
The linear alkyd Bunsen sulfonic acids used in this invention are, as previously mentioned, commonly neutralized with sodium or other alkali metal salts to make common 15 cleaners. Linear alkyd ensign sulfonic acid itself is produced by a two step synthesis, in which Bunsen it first alkylated with some allele chloride in the presence of catalyst. Next, the alkylated Bunsen it reacted with ~ulfonating reactant. A third step, which does not concern I the present invention,c~occurwhen the thus produced linear alkyd Bunsen sul~onic acid is neutralized with an alkali metal hydroxide, such as Noah, to produce the sodium salt, which is commonly called "WAS."
Linear alkyd Bunsen sulfonic acid- which way 25 introduced for heavy industrial use, aster it was discovered that branched alkyd Bunsen sulfonate ("AS") way significantly less biodegradables produced by many Companies including Continental Oil Company under the brand name of Kink SUE;
and Pilot Chemical Company under the brand name Caliphate LAS-99, 30 Witch Chemical Corporation under the brand name of Witch 1298 Soft acid and Steepen Chemical Company under the brand name of Boo Soft S-100.

- Pi Linear alkyd Bunsen clonic acid hag the general structure A

/

wherein R it alkyd averaging 5 to 20 carbon atoms, Most preferable for use in the formula of this invention are dodecylbenzene sulfonic acids, wherein R averages about 11.4 carbon atoms in length.
Other alkyd aureole sulfonic acids suitable for use in this invention include alkylated diphenyl oxide disulfonates of the general structure \ __ / 2 I

H 03S ~03H

wherein Al is H and R2 is alkyd, averaging 5 to 20 carbon atoms in length. When Al is alkyd, R2 is H/

Preferably, a range of 0,001~ to 50.0% particularly, 1.0~ to 30.0% end most preferably 5.0~ to 15% by weight of acid surfactant is present in composition ox this invention.
Further, the preferred surfactant of this invention will cause the formulas of this invention to have pi of no more than 6.5, and preferably, below 3.

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An example of a suitable alXyl sulfonic acid it Dow fax TAO
manufactured by Dow Chemical Company corresponding to the structure immediately above when Al it H and R2 average 12 carbons.
SOVIETS

In a further embodiment, solvents are added to the acid surfactants of this invention. Solvent appropriate for use in this invention include straight chain, primary, secondary and tertiary Of 10 alkanolsl C5_10 alicyclic 10 alcohols, C2 8 dialkyl ethers, C3_20 azalea and aureole glycol ethers and mixtures thereof.

1. Alkanols: appropriate alXanol solvents in this invention have the general formula R-0~ wherein R can be a straight, or substituted carbon chain ox 1-10 carbon atoms.
15 Solvents of this type include methanol, ethanol, n-propanol, isopropanol, n-butanol, sea buttonhole, left buttonhole, hexanol, heptanol, etc.

2. Aliphatic Cyclic Alcohols (Alicylics): Further appropriate solvents herein are ring structures such a I cyclohexanol, cyclooctanol, cyclodecanol, etc. These alicyclics preferably average 5-10 carbon atom in their ring structures.

3. Dialkyl ethers: the dialkyl ethers suitable for use as solvents in this invention have a general structure R~0-Rl, wherein R and Al are equal, and each comprise a carbon chain of at least 1. Preferably the dialkyl ether herein comprise two to eight carbon atoms in average chain length. Examples of this particular group of solvents include dim ethyl ether, deathly ether, and dipropyl ether.

4. Glycol ether: particularly preferred a solvents in this invention aye the glycol ethers having thy general structure Rural, wherein R it an alkoxy of 1 to 20 carbon atoms, or airlocks of at least 6 carbon atoms, and Al is an ether condensate of propylene glycol and/or ethylene glycol having from one to ten glycol monomer units. Preferred are glycol ethers having one to five glycol monomer units. These are C3_20 glycol ethers-Examples of particularly preferred solvent include 10 propylene glycol methyl ether, dipropylene glycol methyl ether,tripropylene glycol methyl ether, propylene glycol isobutyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol bottle ether, diethylene glycol methyl ether, diethylene gly~ol ethyl ether, diethylene glycol bottle lo ether, ethylene glycol phenol ether, and propylene glycol phenol ether.

These glycol ethers are especially preferred because whey are colorless liquids with mild, pleasant odors. They are very miscible with water, and have been found to be a3pecially I stclble with the acid surfactants noted above.
Addition of 0.001-25.0~ by weight of any of top solvents disclosed to this hard surface acid cleaner appears desirable, and especially preferred it .1 to 15% by weight of added solvent. As will be further discussed in greater detail, 25 addition of solvents to the hard surface acid cleaner herein provides surprisingly even greater cleaning benefits.

ANTIMICROBIAL COMPOUND

In yet another embodiment of this invention, antimicrobial compounds are added to the novel hard surface cleaners of this invention which are selected from substituted phenols and qua ternary ammonium compounds.
1. Substituted phenols: suitable antimicrobial compounds can be selected from the substituted phenols having the general structure ~R6 I

1' R2~ R3, R4, and R5 can be separately phenol group, Of, H, and the alkali metal salts thereof, and 10 R6 can be H or Nay Phenols suitable for use in -this invention include those sold by Dow Chemical Company under the brand name Dodd, such as sodium o-phenyl phenol tetrahydrate (Dodd I), o-phenyl phenol (Dodd I), 2,4,5 triehloro-phenol (Dodd II), 2,4,5 triehloro-phenol, sodium Walt, l/2 lo hydrate (Dodd B), and pentaehlorophenol (Dodd ESSAY.
urethra phenols include ortho-benzyl-para-ehlorophenol told under the brand name Santophen I by Monsanto Chemical Corporation.

2. Qua ternary Ammonium Compounds: particular, surprisingly effective antimicrobial compound suitable for use 20 in this invention are qua ternary ammonium compounds.

One would normally expect that ~uaternary ammonium compounds, some of which are eationie aurfaetants, having essentially positively charged species in aqueous solution, would react with the anionic surfaetant~ in equilibrium with the acid 25 surfactants disclosed above and eye a precipitate to form.

go ,.~

However, the quatexnary ammonium compound used a antimicrobial compounds in this invention are miscible with the mixture of acid reactant and solvent in thy formula and do not precipitate. Instead, a thickening it seen to occur with a preferred percentage of up to 5.0% ox qua ternary ammonium compound. Surpassing 5.0% has a thixotropic effect on the cleaner, and this latter application may be suitable for use as very substantive cleaners, i.e., bathroom leaners.

Suitable qua ternary ammonium compounds include the 10 dialkyldimethyl Amman salts of the general structure To l R N - SHEA A

SHEA
wherein R and Al are alkyds of C5 to C~0, and A it an acid stable anion. Preferred anion include Of , By , I , SUE, C104-, C103-, and NO-. Other anions stable in the acid 15 surfactants of this invention are possible. Al can also be an alkyd Bunnell group (in which R it a methyl grout).

Further particularly preferred are C7 to C12 Delilah dim ethyl ammonium salts. Other cat ionic surfactants, notably other qua ternary ammonium salts and tertiary amine 20 surfactants may be suitable for use as disinfectant compounds.

As previously discussed, it is generally unknown why the cat ionic sur~actants used as antimicrobial compounds in this invention are compatible with the acid sur~actants. One would normally suspect that the qua ternary ammonium compounds 25 would co-precipitate with the anionic form of the acid surfactants. However, a proposed theory, which it not meant herein to be binding, is that these acid surfactants, not being neutralized by any alkali metal salts as the more common anionic sur~actant~ are, may exhibit non ionic moieties in solution which act to syllables the cat ionic surfactants (qua ternary ammonium compounds) and keep the from precipitating loath thy anion form of the ac~alc surfactants herein.

Additionally, the antimicrobial compounds can apparently be used in combination. Jo loss in stability it seen by combining these two antimicrobial compound Further, either or both of these antimicrobial compound may be present in the invention from approximately 0.001 to 15.0% by wright.
Particularly preferred percentages ox these antimicrobial compounds are from 0.1 to 10~ by weight.

CLEANING ADJUTANTS

Further, approximately 0.0001-25% by weight of further cleaning adjutants may be added to the present invention, These cleaning adjutants include thickeners selected from gums, resins and other polysaccharides, such as xanthan gums, starch, and mixtures.

Further cleaning adjutants include defamers, such as dialXyl polysiloxane polymers. Particularly preferred as the defamers are those sold by Dow-Corning under the trade name Do 100 for 100% dimet~yl polysiloxane~ Further defamer may be applicable for use in this invention, including various cat ionic and non ionic surfactants.

Still further cleaning Advents include dye, pigments, fragrances and builders. The dyes and pigments in this invention are merely limited to those which will not substantially deposit and stain the surface to be cleaned.
Fragrances selected must generally by those which will not be degraded by the low pi of the hard Ursa acid cleaner.
Builders can include many inorganic and organic builders, such as sodium ethylenediaminetetraacetate or HIDEOUT (hydroxyethyl ethylenediaminetriacetic acid). Further builders include many organic acids and their alkali metal salts, erg., citric acid, sodium citrate, sodium lactate, sodium Malta, etc.

Various formulations of the hard surface acid cleaners of this invention were assayed in the three soiling problem area soap scums; (2) hard water stain and (3) oily/greasy stains, as described in the following section, under "EXPERIMENTAL."
Test methodologies and results of aye are set forth in greater detail below.

EXPERIMENT _ A. Synthetic Soap Scum Test Preparation and Method:

A standard soap scum suspend ion was prepared using the following ingredients:
White Ethyl Alcohol 85.0%
Calcium Stewart 5.0%

Distilled ~2 10.0%
100 . 0%

This suspension was applied and boxed onto tilts which were then cleaned with various formulations of the hard surface acid cleaner (1) using a Gardner Wear Tester (i.e., "Scrubbing Test") and (2) by simple application according to the "Soak Test." Impartial panelists were asked to grade the cleaning of the synthetic soap scum stains by the formulations of this invention as well as the performance of competitive cleaners on a 0 to 5 scale, wherein 0 = no cleaning, 5 = total cleaning. The grading was averaged for a number of trials.
These results are reported below in TABLES I,II and III.
Competitive products were also tested. Grading was conducted over various time periods to show that the hard surface acid cleaners of this invention clean effectively much more rapidly than competitive products.

B. Hard Water Stain Test Methods:

Two "premixes" were prepared from the following ingredients:
Premix A % wt. Premix B wit *Nay Sue X 5H205.0% Distilled H20 73.0%
Distilled H2095.0% Ethanol 24.0 Calcium Chloride 2.0 Magnesium Chloride 1.0 100.~% 100.0%

US *Metro 20 (Trademark, PI Corporation) Each premix was sprayed on preheated brown tiles, then baked and allowed to cool.

The tiles were cleaned by applying approximately 4 grams of various formulations of the hard surface acid cleaner, scrubbed and rinsed ("Scrubbing Test"). Impartial panelists then graded the cleaning results on a 0 to 5 scale, as previously discussed.
Competitive products were also compared. Further, in a second test, "Soak Test," formulations were allowed to soak the target stain for time intervals of 30, 20, 10, 5, 3, and 1 minutes, or lo, 5, 3, 2 , 1 minutes and 45 second to demonstrate rapid cleaning efficiency. The results are reported in TABLES I,II and III below. Participants noted also how quickly elective cleaning occurred at the various time intervals.

C. Oily/Greasy Soil Test Methods The following oily/greasy soil mixture was prepared:

Wilson's Lard 60.0 grams Weston Oil 38.0 grams Grumbacher Cobalt Drier 2.0 trams (Cobalt Linoleate) 100.0 grams 'this mixture was applied in a thin layer to precleaned white enameled metal sheets which material is the same a used for manufacturing porcelain kitchen sinks and allowed to dry (age) for approximately 24 hours.

Thereafter, each panel was cleaned via the Oil Grease Stain "Soak Method," wherein approximately 5 grams of various formulations of the hard surface acid cleaner we e applied and 25 allowed to soak for time interval of 30, 20, 10, 5, 3 and 1 minutes. Competitive products were similarly compared. Speed in cleaning, as previously noted, was scrutinized carefully. The results are reported below in TABLES I,II and III below.

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TABLE III - Perfoxmance9 of Hard Surface Acid Cleaner Versus Competitive Product ("SCRUBBING TEST") Soap Scum Hard Water Exile Formula% wettest Stain Test (Visual Grading) (Visual Grading) 13. 2-Butoxyethanol 5.0%
HLASL 5.0% 4.8 3.7 H20 90.0~

14 . Ethanol . 0%
HAS 5.0% 408 3.5 H20 90 . 0%

15. DOW DBC 1.9 1.3 16. Lucille 1.1 0 9 17. Borax 206 1.3 18. Soft Scrub 2.1 4.0 19. Comet Lydia 3.8 2.3 1) HAS is alkyd Bunsen sulfonic acid, wherein R
averages lo to 14 carbon atoms.

2) "DOW DUB a trademark of Dow Chemical Company.

3) "Lucille" is a trademark of ennui and Fink Company.

4) "Borax" is a trademark ox US, Borax and Chemical Corporation.

5) "Soft Scrub" is a trademark ox The Clucks Company.

6) "Comet Liquid" is a trademark of Procter and Gamble Company.

7) Soap Scum Test was outlined above in "EXPERIMENTAL,"
"A".

8) Hard Water Stain Test was outlined above in "EXPERIMENTAL," "B."

9) Performance was graded by visual assays performed by impartial panelists on a O to 5 scale, wherein O = no cleaning, and 5 = total cleaning. The grading was averaged for a number of trials. Test administrators did not disclose or identify what products the panelists were using.

.

In TABLES IV-V, below, the effect ox adding a solvent, selected from the preferred solvents discussed previously, to the hard surface acid cleaners of this invention was tested.

Surprisingly, it was found that even stronger cleaning performances were obtained without any loss in formula stability.

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o I-n Jo TABLE VI, below, illustrates the effect of adding a germicidal compound to the hard surface acid cleaners of this invention. As previously discussed the preferred germicidal or antimicrobial compounds are chosen from substituted phenols, qua ternary ammonium compounds, or mixtures thereof.
Surprisingly, not only were the phenols stably miscible with the hard surface acid cleaners, but thy qua ternary ammonium compounds as well. Since the qua ternary ammonium compounds are cat ionic species, it positively charged species in aqueous solutions, it was presumed that precipitation would occur upon combination with the acid surfactants of the present invention. Surprisingly, no precipitation occurred, and the qua ternary ammonium compounds also caused a thickening of the formulas when used in percentages of 5.0% or more. Adding more than 5.0% may cause a thixotrope to form, which helps the cleaning formula stay in place when applied to a vertical surface. This is a substantial benefit over other cleaners which are not as substantive and which tend to drain off.
Furthermore, as disclosed in TABLE VI below, the antimicrobial activity of the antimicrobial compounds was very efficacious.

TABLE VI-Effect of Adding an Antimicrobial Compound to the lard Surface Acid Cleaners Formula Gram tram Fungus Positive Negative Bacteria Bacteria 56. (Control) Jo effect Jo Effect No effect 57. HAS 500% Both fresh Both fresh Fresh samples Ethanol Andy 60 day and 60 day effective Xanthan Gum 0.1~ aged samples aged samples Burdock 2~30.25% effective effective 58. HAS 5.0~ south fresh Both fresh Fresh samples Ethanol 5.0~ and 60 day and 60 day effective Xanthan Gum 0.1% aged samples aged samples Santophen 130.25~ effective effective 59. HAS 5.0% Both fresh Both fresh Fresh samples Ethanol 5.0% and 60 day and 60 day effective Xanthan Gum 0.1% aged samples aged samples Burdock 222 ~.125% effective effective Santophen 1 0.125~
60. HAS 5.0% Both fresh Both fresh Fresh samples 2-Butoxyethanol 5.0~ and 60 day and 60 day effective Xanthan Gum 0.1% aged samples aged samples Santophen 13 0.25% effective elective 1) (Control) = 5.0% HAS, 5~0% ethanol, and 0.1% xanthan gum. Xanthan gum is a thickener compatible with the acid surfactants of this invention I) Burdock 22, a trademark of Lyons Chemical Company, is a qua ternary ammonium compound with the following structure:

_ C~3 R 1 Al Of SHEA .

wherein R = Al and R averages 10 carbon atoms in length.

3) Santophen 1, a trademark of Monsanto Chemical Company, is a finlike compound with the following structure:

OH
[SUE

Of 4) Gram Positive Bacteria: Representative examples include Bacillus sup., Lactobacillus sup., Streptococcus sup., Staphylococcus sup., etc.
5) Gram negative Bacteria: Representative examples include Escherichia golf, Salmonella sup., Proteus sup., etc.
6) Fungus: Representative examples include Trichophyton mentagrophytes, Tine penis (mostly Athlete' 5 Foot fungi), etc.

Review of TABLES VOW grows that the hard surface acid cleaners of the present invention show surprising efficacy and fast action.
In direct comparison tests with other commercially available cleaners in TABLES I,II and III, the hard surface acid cleaners showed that total cleaning was consistently achieved, whether a "Scrubbing Test" or "Soak Test" was considered, and cleaning results were achieved faster than when using any of the competitive products TABLES IV-V disclosed the even greater cleaning efficiency when using a variety of different solvents of varying structure. Further, using move than one type of solvent as in Example 48 is possible, but in the interest of cost effectiveness may not be as de treble, although such increases still constitute a part of this invention. Lastly, TABLE VI shows that effective antimicrobial action is obtained by adding either a substituted phenol, a qua ternary ammonium compound, or both, with surprisingly no loss in stability prom addition of the qua ternary ammonium compound.
The present invention therefore provides a multipurpose, fist acting and effective hard surface acid cleaner which is effective over the three major problem cleaning area.

Claims (31)

WHAT IS CLAIMED IS:

1. A hard surface acid cleaner comprising, (a) alkyl aryl sulfonic acid; and (b) at least 50.0% by weight water.
(c) a water-miscible organic solvent.

2. The hard surface acid cleaner of claim 1 wherein said alkyl aryl sulfonic acid is an alkyl averaging 5 to 20 carbons atoms; or wherein R1 and R2 are H or alkyl averaging 5 to 20 carbon atoms and when R1 is alkyl, R2 is H.

3. The hard surface acid cleaner of claim 2 wherein said alkyl aryl sulfonic acid is present in an amount of approximately 0.001 to 50.0% by weight of the cleaner.

4. An all purpose hard surface acid cleaner comprising:
a) an acid surfactant of the general structure wherein R is alkyl averaging 5 to 20 carbon atoms or an an acid surfactant of the general structure of an alkyl diphenyl sulfonic acid structure of the following configuration:

wherein R1 and R2 may be C5-20 or H; and R1?R2;
b) a solvent selected from C1-10 alkanols, C5-10 alicyclic alkanols, C2-8 dialkyl ethers, [and] C3-20 glycol ethers and mixtures thereof; and c) at least 25.0% by weight water.

5. The hard surface acid cleaner of claim 4, wherein said acid surfactant is present in an amount from approximately 0.001% to 50.0% by weight and said solvent is present in an amount from approximately 0.001% to 25.0% by weight.

6. The hard surface acid cleaner of claim 4 further comprising (d) an antimicrobial compound selected from:

(i) a substituted phenol of the general structure:

wherein R1, R2, R3, R4, R5 can be phenyl, substituted phenyl, C1, or H; and R6 is H or Na;
(ii)a quaternary ammonium compound; and (iii)mixtures thereof.

7. The hard surface acid cleaner of claim 6, wherein said quaternary ammonium compound is a dialkyl dimethyl ammonium salt of the general structure:

wherein R1 is H, or equal to R, or R and R1 are separately alkyls of 5 to 20 carbon atoms of differing lengths, or R or R1 is aryl of 6 to 20 carbon atoms, or alkylaryl of 7 to 20 carbon atoms, and A- is an acid stable anion.

8. The hard surface cleaner of claim 7 wherein said quaternary ammonium compound is present in an amount from approximately 0.001 to 15.0% by weight.

9. The hard surface acid cleaner of claim 6 wherein said substituted phenol is present in an amount from approximately 0.001 to 15.0% by weight.

10. The hard surface acid cleaner of claim 6 further comprising (e) a thickener selected from gums, resins, polysaccharides, and mixtures thereof.

11. The hard surface acid cleaner of claim10 further comprising (f) a defoamer selected from dialkyl polysiloxane polymers.

12. A method of making a hard surface acid cleaner, comprising combining (a) Alkyl aryl sulfonic acid and (b) at least 50.0% by weight water.

13. The method of claim 12 wherein said alkyl aryl sulfonic acid is wherein R is an alkyl averaging 5 to 20 carbon atoms;
or wherein R1 and R2 are H or alkyl averaging 5 to 20 carbon atoms; and when R1 is alkyl, R2 is H.

14. The method of claim 13 wherein said alkyl anyl sulfonic acid is present in an amount of approximately 0.001 to 50.0% by weight of the cleaner.

15. A method of making an all purpose hard surface acid cleaner comprising combining:
a) an acid surfactant of the general structure wherein R is alkyl averaging 5 to 20 carbon atoms or an acid surfactant of the general structure of an alkyl diphenyl sulfonic acid structure of the following configuration:

wherein R1 and R2 may be C5-20 or H; and R1?R2 ;
b) a solvent selected from C1-10 alkanols, C5-10 alicyclic alkanols, C2-8 dialkyl ethers, C3-20 glycol ethers and mixtures thereof; and c) at least 25.0% by weight water.

16. The method of claim 15 wherein said acid surfactant is present in an amount from approximately 0.001% to 50.0% by weight and said solvent is present in an amount from approximately 0.001% to 25.0% by weight.

17. The method of claim 15 further comprising (d) an antimicrobial compound selected from:

(i) a substituted phenol of the general structure:

wherein R1, R2, R3 R4, R5 can be H,phenyl, substituted phenyl, or C1, and R6 is H or Na;

(ii) a quaternary ammonium compound; and (iii)mixtures thereof.

18. The method of claim 17 wherein said quaternary ammonium compound is a dialkyl dimethyl ammonium salt of the general structure wherein R is H, or equal to R1, or R and R1 are separately alkyls of 5 to 20 carbon atoms of differing lengths, or R or R1 is aryl of 6 to 20 carbon atoms or alkylaryl of 7 to 20 carbon atoms, and A- is an acid stable anion.

19. The method of claim 18 wherein said quaternary ammonium compound is present in an amount from approximately 0.001% to 15.0% by weight.

20. The method of claim 17 wherein said substituted phenol is present in an amount from approximately 0.001% to 15.0% by weight.

21. The method of claim 17 further comprising (e) a thickener selected from gums, resins, polysaccharides, and mixtures thereof.

22. The method of claim 21 further comprising (f) a defoamer selected from dialkyl polysiloxane polymers.

23. A method for cleaning hard surfaces having soiling materials thereon comprising combining:
(a) an alkyl aryl sulfonic acid; and (b) at least 50.0% by weight water to form a hard surface acid cleaner: contacting said hard surfaces with said hard surface acid cleaner; and removing said soiling materials and said hard surface acid cleaner from said hard surfaces.

24. An improved method for cleaning hard surfaces having soiling materials deposited thereon by contacting said hard surface with a hard surface cleaner and removing said soiling materials and said hard surface cleaner, wherein the improvement comprises combining:
(a) an alkyl aryl sulfonic acid; and (b) at least 50.0% by weight water to form said hard surface cleaner.

25. The hard surface acid cleaner of claim 1 further comprising (d) an antimicrobial compound.

26. The method of claim 12 wherein the step of combining further comprises (c) a water - misible organic solvent.

27. The method of claim 26 wherein the step of combining further comprises (d) an antimicrobial compound.

28. The hard surface acid cleaner of claim 6 wherein said antimicrobial compound is a mixture of said substituted phenol and said quaternary ammonium compound.

29. The hard surface acid cleaner of claim 28 wherein said mixture is present in an amount from approximately 0.001 to 15.0%
by weight.

30. The method of claim 17 wherein said antimicrobial compound is a mixture of said substitute phenol and said quaternary ammonium compound.

31. The method of claim 30 wherein said mixture is present in an amount of approximately 0.001 to 15-0% by weight.