HARD SURFACE ACID CLEANER

Abstract: Hard surface acid cleaners providing fast acting and effec­ tive cleaning results across a wide variety of problematic cleaning areas, comprise alkyl aryl sulfonic acids and at least 50.0% by weight of water. Suitable alkyl aryl sulfonic acids are alkyl benzene sul­ fonic acids of the general structure wherein R is alkyl averaging 5 to 20 carbon atoms in length and wherein R₁ and R₂ are H or alkyl averaging 5 to 20 carbon atoms; and when R₁ is alkyl, R₂ is H. Additionally, solvents, antimicrobial compounds, defoamers, thickeners and other cleaning adjuvants may be added to these hard surface acid cleaners.

Description: HARD SURFACE ACID CLEANER There are many examples of hard surface cleaner in tho art, containing some sort of anionic surfactant, solvent, perhaps a dye and a fragrance to impart a pleasing color and odor, and mostly water, Hoot of these prior art cleaners suffer from one or more disadvantages. ror example, some cleaners are effective only on hard water stains. An example of this clays of cleaner la a highly acidic toilet bowl cleaner containing hydrochloric acid. Hard water stains are mineral stains caused by the deposition of calcium or magnesium salts present in hard water. Certain other cleaners Fay be effective only against soap scum stains, caused when a fatty acid soap, such as a sodium lauryl fatty acid soap precipitates in hard water containing alkaline earth metal salts, such as calcium, magnesium, or barium, causing the familiar soap scum stain. Still other cleaners may be effective only on greasy/oily stains. Generally speaking, these are cleaners which have either at least some water miscible solvent, and/or some higher amount of nonionic and/or anionic surfactants. None of the prior art cleaners have addresses all three of those 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 those cleaners, requiring purchago of other cleaners which will effectively remove the target stain. This will result in addud exponso es a particular cleaner must be purchasod for a particular stain. Furthermore, many of the prior art cleaners are very slow-acting. That is, after being applied to a 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 is 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 alkyl benzene 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 as an atonic surfactant. This was recognized in Kappler. et al, U.S. 3,969,282 which utilized alkyl benzene sulfonic acid in combination with a nonionic surfactant as a storage compound to be neutralized with alkali metal salts prior to using them to launder fabrics. Further, Reid, U.s. 3,463,736 showed that linear alkyl benzene sulfonic acids could be neutralized with triethanolamine to act as a cleaner. However. it was not realised in the art that linear alkyl benzene sulfonic acids can be utilized as hard surface cleaners themselves. this invention relates ts an improved, hard surface acid cleaner preferably having a pH of no more than approximately 6.5 comprising: (a) alkyl aryl sulfonic acidt and (b) at least 50.01 by weight water. The preferred alkyl aryl sulfonic acidir a linear alkyl benzene sulfonic acid surfactant of the general structure EMI3.1 wherein R is an alkyl averaging 5 to 20 carbons. ln a further embodiment, this hard surface acid cleaner further comprises (c) a solvent selected from straight chain alkanols 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 carbons, and mixtures thereof. In yet another embodiment, the hard surface acid cleaner further comprises (d) an antinicrobial compound selected from: (i) a substituted phenol of the general structure; EMI4.1 wherein R1, R2, R3, R4, and R5 can separately be a phenyl group, C1 or H, and R6 can be H or Nai (ii) a quaternary ammonium compound; and (iii) mixtures thereof. In yet another embodiment, the hard surface cleaner further comprises (e) a thickener selected from gums, polysaccharides and resine. In still another embodiment, the hard surface acid cleaner further comprises (f) a defoamer selected from the dialkyl polysiloxane polymers. The hard surface acid cleaner of this invention can aZro include at least one other cleaning adjuvant selected from 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 (3) greasy oily stains. The present invention is a hard surface acid cleaner which has surprisingly effective and fast cleaning results on all thres problem areas: (1) soap acums; (2) hard water stains: and (3) greasy/oily stains. The surprising revelation was that alkyl aryl rulfonio acid compounds, most specifically, linear alkyl benzene sulfonic acids, ("HLAS") were responsible for the improved cleaning in all three area. These alkyl benzene sulfonic acid surfactants are not neutralized with alkali metal, alkaline earth metal, or ammonium salts as are the typical detergents using substituted alkyl benzene sulfonates. The linear alkyl benzene rulfonic acids used in this invention are, as previously mentioned, commonly neutralized with sodium or other alkali metal salts to mako common cleaners. near alkyl benzene sulfonic acid itself is produced by a two step synthesis, in which benzene is first alkylated with some alkyl chloride in the presence of catalyst. Next, the alkylated benzene is reacted with sulfonating reactant. A third step, which does not concern the present invention. can occur when the thus produced linear alkyl benzene sulfonic acid is neutralized with an alkali metal hydroxide, such as NaOH, to produce the sodium salt, which is commonly called "LAS." Linear alkyl benzene sulfonic acid--which was introduced for heavy industrial use, after it was discovered that branched alkyl benzene sulfonate ("ABS) war significantly less bio-degradable--is produced by many companies, including Continental Oil Company under the brand name of Conoco 8A-597, and Pilot Chemical Coapany under the brand name Calsoft LbS-99, Witco Chemical Corporation undor the brand name of Witco 1298 Soft Acid and Stepan Chemical Company under the brand name of Bio Soft 8-100. Linear alkyl benzene sulfonic acid has the general structure EMI6.1 wherein R is alkyl averaging 5 to 20 carbon atoms. Most preferable for use in the formulas of this invention are dodecylbenzeno sulfonic acids, wherein R averages about 11.4 carbon atoms in length. Other alkyl aryl sulfonic acids suitable for use in this invention include alkylated diphenyl oxide disulfonates of the general structure EMI6.2 wherein R1 is H and R2 is alkyl, averaging S to 20 carbon atoms in length. When R1 is alkyl, R2 is H. Preferably, a range of 0.001% to 50.0% particularly, 1.0% to 30.08 and most preferably 5.0% to 15% by weight of acid surfactant is present in compositions of this invention. Further, the preferred surfactant of this invention will cause the formulae of this invention to have pH' of no more than 6.5, and preferably, below 3. An example of a suitable alkyl sulfonic acid is Dowrax 2AO manufactured by Dow Chemical Company corresponding to the structure immediately above when R1 is H and R2 averages 12 carbon. In a further embodiment, solvents are added to the acid surfactants of this invention. Solvents appropriate for use in thir invantion include straight chain0 primary, s@condary and tertiary C1-10 alkanols, C5-10 alicyclic alcohol, C2-8 dialkyl ethers, C3¯20 acyl and axyl glycol ethers and mixtures thereof. 1. Alkanols: appropriate alkanol solvents in this invention have the general formula R-OH wherein R can be a straight, or substituted carbon chain of 1-10 carbon atoms. Solvents of this type include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec butanol, tert butanol, hexanol, heptanol, etc. 2. Aliphatic Cyclic Alcohols (Alicylics): Further appropriate solvents herein are ring structures such as cyclohexanol, cyclooctanol, cyclodecanol, etc. These alicyclics preferably average 5-10 carbon atoms in their ring structures. 3. Dialkyl ethers: the dialkyl ethers suitable for use as solvents in this invention have a general structure wherein It R and R1 are equal, and each comprise a carbon chain of at least 1. Preferably, the dialkyl ethers herein comprise two to eight carbon atoms in average chain length. Examples of thir particular group of solvents include dimethyl ether, diethyl ether, and dipropyl ether. 4. Glycol ethers: particularly preferred as solvents in this invention are the glycol ethers having the general structure R-O-R1-OH, wherein R is an alkoxy of I to 20 carbon atoms, or aryloxy ot at least 6 carbon atoms, and R1 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 C320 glycol ethers. Examples of particularly preferred solvents include 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 butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, ethylene glycol phenyl ether, and propylene glycol phenol ether. These glycol ethers are especially preferred because they are colorless liquids with mild, pleasant odors. They are very miscible with water, and have been found to be especially stable with the acid surfactants noted above. Addition of 0.001-25.01 by weight of any of the solvents disclosed to this hard surface acid cleaner appears desirable, andespecially preferred is .1 to 158 by weight of added solvent. As will be further discussed in greater detail, addition of solvents to the hard surface acid cleaners herein provides surprisingly even greater cleaning benefits. In yet another enbodizent of this invention, antimicrobial compounds are added to the novel hard surface cleaners of this invention which are selected from substituted phenols and quaternary ammonium compounds. 1. Substituted phenols: suitable antimicrobial compounds can be selected from the substituted phenols having the general structure EMI9.1 wherein R1, R2, R3, R4, and R5 can be separately phenyl group, C1, H, and the alkali zetal salts chereof, and R6 can be K or Na. Phenols suitable for use in this invention. include those .o1d by Dow Chemical Company under the brand name Dowicide, such as sodium o-phenyl phenol tetrahydrate (Dowicide A), o-phenyl phanol (Dowicide I), 2,4,5 trichloro-phenol (Dowicide II), 2,4,5 trichloro-phenol, sodium salt, 1/2 hydrate (Dowicide B), and pentachlorophenol (Dowicide EC-7). Further phenols include ortho-benzyl-para-chlorophenol sold under the brand name Santophen I by Monsaranto Chemical Corporation. 2. Quaternary Ammonium Compounds: particular. surprisingly effective antimicrobial compounds suitable for use in this invention are quaternary ammonium conpounds. One would normally expect that quaternary am@onium compounds, some of which are cationic surfactante, having essentially positively charged species in aqueous solution, would react with tho anionic surfactants in equilibrium with the acid surfactants disclosed above and cause a precipitate to for However, the quaternary ammonium compounds used as antimicrobial compounds in this invention are miscible with the mixture of acid surfactant and solvent in the formula and do not precipitate. Instead, a thickening is seen to occur with a preferred percentage of up to 5.08 of quaternary 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 cleaners. Suitable quaternary ammonium compounds include the ammonium salts of the general structure EMI10.1 wherein R and R1 are alkyls of C5 to C20 and Ais an acid stable anion. Preferred anions include Cl ; Br-, I, SO4-, ClO4-, ClO3-, and NO3-. Other anions stable in the acid surfactants of this invention are possible. R1 can also be an alkyl benzyl group (in which case R is a methyl group). Preferably R and E are both alkyl groups. Further particularly preferred are C7 to C12 dialkyl dimethyl ammonium salts. Other cationlc surfactants, notably other quaternary ammonium salts and tertiary amin@ surfactants may be suitable for use as disinfectant compounds. As previously discussed, it is generally unknown why the catlonic surfactants used as antinlerobial compounds in this invention are compatible with the acid surfactants. One would normally suspect that the quaternary ammonium compounds would co-precipitate with the anionic form of the acid surfactants. However, a proposed theory, which is not meant herein to be binding, is that these acid surfactants, not being neutralized by any alkali metal saoits as the more common anionic surfactants are, may exhibit nonionic moieties in solution which act to solubilize the cationic surfactants (quaternary ammonium compounds) and keep them from precipitating with the anion form of the acidic surfactants herein. Additionally. the antimicrobial compounds can apparently be used in combination. No loss in stability is seen by combining these two antimicrobial compounds. Further, either or both of these antimicrobial compounds may be present in the invention from approximately 0.001 to 15.0% by weight. Particularly preferred percantages of these antimiorobial compounds are from 0.1 - to 10% by weight. Further, approximately 0.0001-25% by weight of further cleaning adjuvants may be added to the present invention. These cleaning adjuvants include thickeners selected from gums, resine and other polysaccharides, such as xanthan gums, starch, and mixtures. Further cleaning adjuvants include defoamers. such as dialkyl polysiloxane polymers. Particularly preferred as the defomers are those sold by Dow-Corning under the trade name DB 100 for 100%dimethylpolysiloxane. Further defoamer smay be applicable for use in this invention, including various cationic and nonionic surfactants. Still further cleaning adjuvants include dyes, pigments, fragrances and builder. 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 be those which will not be degraded by the low pH of the hard surface acid cleaner. Builders can include many Inorganic and organic builders, such as sodium ethylenediaminetetraacetate or HED1.% (hydroxyethyl ethylenediaminetriacetic acid). Further builders include many organic acids and their alkali metal salts, eg., citric acid, sodium citrate, sodium lactate, sodium maleate, etc. Various formulations of the hard surface acid cleaners of this invention were assayed in the three soiling problem areas: (l) soap scums: (2) hard water stains and (3) oily/greasy stains, as described in the following section, under "EXPERIMENTAL." Test methodologies and results of assays are set forth in greater detail below. EXPERIMENTAL A. Synthetic Soap Scum Test Preparation and Methods A standard soap scum suspension was prepared using the following ingredients: wt.% Ethyl Alcohol 85.08 Calcium Stearate 5.0% Distilled H2O 10.0% 100.0% This suspension was applied and baked onto tiles 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 acum stains by the formulations of this invention as well as the performances of competitive cleaners on a 0 to 5 scale, wherein 0 " no cleaning. S " total cleaning. The grading was averaged for a number of 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 % Wt. "Na2 SiO3 X 5H2O 5.0% Distilled H2O 73.0% Distilled H2O 95.0% Ethanol 24.0% Calcium Chloride 2.0% Magnesium Chloride 1.0% 100.0% 100.0% "Metso 20 # (Trademark, PQ 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, wSoak Test," formulations were allowed to soak the target stain for time intervals' of 30, 20, 10, 5, 3, and 1 minutes, or 10, 5, 3, 2 , l minutes and 45 seconds to demonstrate rapid cleaning efficiency. The results are reported in TABLES I,II and Its below. Participants noted also how quickly effective 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 Wesson Oil 38.0 grams Grumbacher Cobalt Drier 2.0 grams (Cobalt Linoleate) 100.0 grams This mixture war applied in a thin layer to pre-cleaned white enamelled metal sheets (which material is the sass as used for manufacturing procelain kitchen sinks) and allowed to dry (age) for approximately 24 hours. Thereafter, each panel was cleanod via the Oil/Grease Stain "Soak Method, wherein approximately S grams of various formulations of the hard surface aid cleaner were applied and allowed to soak for time intervals of 30, 20. 10. 5, 3 and 1 minutes. Competitive products were similarly compared. Speed in cleaning. as previously noted was scrutinized carefully. The reaults are reported below in TADLES I,II and III below. TABLE I - Performance 9 of Hard Surface Acid Cleaner versue Competitive Products ("SOAX TEST") EMI15.1 Soap <SEP> Scum <SEP> Test6 <SEP> Oily <SEP> / <SEP> Greasy <SEP> Test7 <SEP> Hard <SEP> Water <SEP> Stain <SEP> Test8 <tb> Example <SEP> Formula/ <tb> Product <SEP> Mame <SEP> % <SEP> wt. <SEP> 10m10 <SEP> 5m <SEP> 3m <SEP> 2m <SEP> 1m <SEP> 45sec <SEP> 30m <SEP> 20m <SEP> 10m <SEP> 5m <SEP> 3m <SEP> 1m <SEP> 30m <SEP> 20m <SEP> 10m <SEP> 5m <SEP> 3m <SEP> 1m <tb> 1. <SEP> 2-Butoxyethanol <SEP> 5.0% <tb> HLAS1 <SEP> 5.0% <SEP> 5.0 <SEP> 4.9 <SEP> 3.8 <SEP> 1.9 <SEP> 0.7 <SEP> 0 <SEP> 5.0 <SEP> 4.9 <SEP> 3.8 <SEP> 1.9 <SEP> 0.7 <SEP> 0 <SEP> 3.4 <SEP> 3.3 <SEP> 3.3 <SEP> 3.1 <SEP> 3.0 <SEP> 2.5 <tb> H2O <SEP> 90.0% <tb> 2. <SEP> Ethanol <SEP> 5.0% <tb> HLAS1 <SEP> 5.0% <SEP> 4.9 <SEP> 4.4 <SEP> 4.1 <SEP> 2.8 <SEP> 1.6 <SEP> 0 <SEP> 4.9 <SEP> 4.4 <SEP> 4.1 <SEP> 2.8 <SEP> 1.6 <SEP> 0 <SEP> 3.4 <SEP> 3.4 <SEP> 3.4 <SEP> 3.4 <SEP> 3.4 <SEP> 2.8 <tb> H2O <SEP> 90.0% <tb> 3. <SEP> DOW <SEP> DBC2 <SEP> 4.1 <SEP> 2.8 <SEP> 1.1 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 4.1 <SEP> 2.8 <SEP> 1.1 <SEP> 0 <SEP> 0.1 <SEP> 0 <SEP> 1.4 <SEP> 1.4 <SEP> 1.4 <SEP> 1.0 <SEP> 0.3 <SEP> 0 <tb> 4. <SEP> Lysol3 <SEP> 1.6 <SEP> 1.4 <SEP> 1.3 <SEP> 1.4 <SEP> 0.6 <SEP> 0.5 <SEP> 1.6 <SEP> 1.4 <SEP> 1.2 <SEP> 1.4 <SEP> 0.6 <SEP> 0.5 <SEP> 1.4 <SEP> 1.1 <SEP> 1.1 <SEP> 0.8 <SEP> 0.3 <SEP> 0 <tb> 5. <SEP> Soft <SEP> Scrub4 <SEP> 2.0 <SEP> 1.0 <SEP> 0.5 <SEP> 1.0 <SEP> 0 <SEP> 0 <SEP> 2.0 <SEP> 1.0 <SEP> 0.5 <SEP> 1.0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> 6. <SEP> Comet <SEP> Liquid5 <SEP> 0.8 <SEP> 0.9 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0.8 <SEP> 0.9 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0.5 <SEP> 0.5 <SEP> 0.1 <SEP> 0 <SEP> 0 <SEP> 0 <tb> 1) "HLAS" is alkyl benezene sulfonic acid. wherein R averages 10 to 14 carbon atoms. 2) "DOW DBC" is a trademark of Dow Chemical Company 3) "Lysol" is a trademark of Lehn and Fink Company 4) "Soft Scrub" is a trademark of The Clo@ox Company 5) "Comet Liquid" is a brand name of Procter and Gamble Company 6) Soap Scum Test was outlined in "EXPERIMENTAL." "A." 7) Oily/Greasy Soil Test was outlined in "EXPERIMENTAL," "C." 8) Hard Water Stain Test was outlined in "EXPERIMENTAL." "B." 9) Performance was graded by visual assays conducted by impartial panelists on a 0 to 5 scale, wherein 0 - no cleaning, and 5 - total cleaning. The grading was averaged for a number of trials. Test adsinistrators did not disclose or identify what products the panelists were using. 10) "n" - Minutes. TABLE II - Performance 6 of Hard Surface Acid Cleaners ( "SOAK TEST" ) Soap Scum Test3 Oily/Greasy Soil Test4 Hard Water Stain Test5 Formula/ Product Name % wt. 30m7 20m 10m 5m 3m 1m 30m 20m 10m 5m 3m 1m 30m 20m 10m 5m 3m 1m 7. HLAS1 2% 4.8 4.8 4.6 3.0 2.0 0.4 5.0 3.4 3.6 3.6 1.4 0.4 1.6 1.5 1.5 1.4 1.4 1.0 8. HLAS 5% 5.0 5.0 5.0 5.0 4.0 5.0 5.0 5.0 5.0 4.8 0.8 3.2 3.1 3.1 2.9 2.8 2.3 9. HLAS 10% 5.0 5.0 5.0 4.8 5.0 4.0 5.0 4.2 5.0 4.6 4.2 4.0 4.0 3.8 3.2 3.0 3.0 3.0 10. Dowfax 2AD2 2% 5.0 4.4 0.2 0.2 0.2 0.2 0.2 0.2 0 0 0 0 0 0 0 0 0 0 0 0 11. Dowfax 2AD 5% 4.0 4.0 2.0 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 3.4 3.3 3.3 3.1 3.0 2.5 12. Dowfax 2AD 10% 5.0 5.0 4.8 3.4 0.4 0.2 0.4 0.2 0.2 0.2 0 0 4.3 4.0 4.0 3.8 3.2 3.0 1) "HLAS" is alkyl benzene sulfonic acid, wherein R average 10 to 14 carbon atoms. 2) "Dowfax 2AD," trademark of DOW Chemical Company, is a diphenyl oxide disulfonate, wherein R - H, and R1 is alkyl of 5 tc carbon atoms. 3) Soap Scum Test was outlined in "EXPERIMEMTAL." "A." 4) Oily/Greasy Soil Test was outlined in "EXPERIMEMTAL." "C." 5) Hard Water Stain Test was outlined in "EXPERIMEMTAL." "B." 6) Performance was graded by visual assays conducted by impartial panelists on a 0 to 5 acale, wherein 0 = 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. 7) "m" - mimutes. TABLE III - Performance9 of Hard Surface Acid Cleaner Versus Competitive Products ("SCRUBBING TEST") Soap Scum Hard Water Example Formula % wt. Test7 Stain Test8 (Visual Grading) (Visual Grading) 13. 2-Butoxyethanol 5.0% HLAS1 5.0% 4.8 3.7 H2O 90.0% 14. Ethanol 5.0% HLAS1 5.0% 4.8 3.5 H2O 90.0% 15. DOW DBC2 1.9 1.3 16. Lysol3 1.1 0.9 17. Boraxo4 2.6 1.3 18. Soft Scrub5 2.1 4.0 19. Comet Liquld6 3.8 2.3 averages 10 to 14 carbon atoms. 2) "DOW DBC" is a trademark of Dow Chemical Company. 3) "Lysol" is a trademark of Lehn and Fink Company. 4) "Boraxo" is a trademark of U.8. Borax and Chemical Corporation. 5) "Soft Scrub" is a trademark of Th Clorox Company. 6) "Comet Liquid is a trademark of Procter and Gamble Company. 7) Soap scum Test was outlined above in "EXPERIMENTAL," "A". 8) dard 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 0 " no cleaning, and 5 " total cleaning. The grading was averaged for a number of trialr. Test administrators did not disclose or identify what products the panelists were using. In TABLES lV-V, below, the effect of 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. TASLE IV - Effect of Adding Solvent to the Hard Surface Acid Cleaners ("SOAX TEST") 2,5 Soap Scus Test 3 Example HLAS1 Solvent Other Additive 30m 20m 10m 5m 3m 1m 20. 5.0% 0 0 5.0 4.2 .3 2.6 .2 .0 21. " 0 6.01% DB-1004 4.8 5.0 3.6 1.8 0.4 0.4 22. " 5.0% ethanol 0 5.0 4.8 4.8 4.2 0.6 0.1 23. " 5.0% ethanol 0.01% DB-100 4.6 3.8 4.4 3.8 1.4 0.2 24. " 5.0% iaopropanol 0 5.0 5.0 4.0 3.0 1.2 0.2 25. " 5.0% isopropanol 0,01% DB-100 4.8 4.8 4.4 0.6 0.6 .0 26. " 5.0% diethyl ether 0 5.0 4.0 4.0 0.4 0.2 0.2 1) HLAS is alkyl benzene sulfonic acid, wherein R averages 10 to 20 carbon atoms. 2) "SOAK TEST" was outlined in "EXPERIMENTAL," "A". 3) "SOAP SCUN TEST" was oulined in "EXPERIMENTAL," "A". 4) "DB-100" is Dow-Corning's trademark for 100% dimethyl polysilorans, a defoamer. 5) Performance was graded by visual assays performed by impartial paneliats on a 0 to 5 acale, wherein 0 - no cleaning, ar 5 " total cleaning. The grading was averagod for a number of trials. Test administrators did not disclose or identif@ what products the panelists were using. TABLE V - Effect of Adding Solvent to the Hard Surface Acid Cleaners ("SOAK TEST")2.17 Soap Scom Test3 Example HLAS1 Solvent Other Additive 10m 5m 3m 2m 1m 45 Secs. 27. 5.0% 0 0 4.8 4.8 3.6 3.0 0.4 0.2 28. " 0 0 5.0 5.0 3.2 0.4 0.2 0.2 29. " 0 0 5.0 5.0 3.6 2.2 0.2 0.2 30. " 5.0% Dowanol DM4 0 5.0 4.8 4.8 4.8 2.8 0.6 31. " " 0 5.0 5.0 5.0 4.0 2.0 0.4 32. " 5.0% Dowanol EB5 0 5.0 5.0 4.8 4.8 0.4 0.2 33. " " 0 5.0 4.8 4.8 4.1 3.4 0.6 34. " 5.0% Dowanol DE6 0 5.0 5.0 5.0 3.8 0.2 0.2 35. " " 0 4.8 5.0 5.0 5.0 1.2 0.6 36. " 5.0% Dowanol EM7 0 4.8 5.0 3.4 2.0 0.2 0.2 37. " " 0 4.8 4.8 4.4 3.6 0.8 0.2 38. " 5.0% Dowanol TPM8 0 5.0 5.0 4.8 4.8 0.2 0.2 39. " " 0 4.8 4.8 2.8 0.2 0 0 40. " 5.0% Dowanol DB9 0 4.8 5.0 4.8 4.8 0.2 0.2 41. " " 0 5.0 5.0 4.8 4.6 2.6 1.2 42. " 5.0% Dowanol EE10 0 4.8 5.0 4.0 4.0 1.2 0.2 43. " " 0 5.0 5.0 4.8 3.8 0.8 0.8 44. " 5.0% Dowanol PiPT11 0 5.0 4.0 0.2 0.2 0.2 0.2 45. " " 0 5.0 4.4 3.8 1.6 0 0.4 46. " 5.0% Dowanol DPM12 0 5.0 5.0 5.0 4.0 0.2 0.4 47. " " 0 5.0 5.0 3.8 2.2 0 0 48. " 5.0% Dowanol DPM12 5.0% IPA16 5.0 5.0 5.0 3.2 0.2 0.2 49. " " " 5.0 4.6 5.0 4.6 2.8 0.4 50. " 5.0% Dowanol PM13 0 4.8 3.8 4.8 2.2 1.0 0.2 51. " " 0 4.8 4.8 3.8 2.2 0.2 0 52. " 5.0% Dowanol EPH14 0 5.0 5.0 0.2 3.0 2.0 0 53. " " 0 5.0 5.0 5.0 3.6 0.6 0.4 54. " 5.0% Butyl Oxitol15 0 5.0 5.0 5.0 5.0 4.4 3.2 55. " " 0 5.0 5.0 5.0 5.0 3.4 2.4 1) HLAS is alkyl benxene sulfonic acid, wherein R averages 10 to 14 carbom atoms. 2) "Soak Test" was outlined in "EXPERIMEMTAL," "A" above. 3) "Soap Scum Test" was outlined in "EXPERIMEMTAL." "A" above. 4) "Dowanol DM" is Dow Chemical Company's trademark for diethylane glycol mathyl ether (CH3OC2H4OC2H4OM) 5) "Dowanol EB" is Dow Chemical Company's trademark for ethylene glycol N-butyl ether (C4N5OC2H4OH) 6) "Dowanol DE" is Dow Chemical Company's trademark for diethylene glycol ethyl ether (C2H5OC2H4C2N4OH) 7) "Dowanol EM" is Dow Chemical Company's trademark for tripropylene glycol methyl ether (CH3OC2H4OH) 8) "Dowanol TPM" is Dow Chemical Company's trademark for tripropylene glycol methyl ether (CH3O[CH2CH(CH3)O]3S) 9) "Dowanol DS" is Dow Chemical Company's trademark for diethylene glycol N-betyl ether (C4H9OC2N4OC2H4OH 10) "Dowanol EE" is Dow Chemical Company's trademark for ethylene glycol ethyl (C2H5OC2H4OH) 11) "Dowanol Pior" is Dow Chemical Company's trademark for propylese glycol isot@tyl ether ( (CH3)2 C2H3OCH2CHOHCH3) 12) "Dowanol DPM" is Dow Chemical Company's trademark for dipropylene glycol methyl ether (CH3O[CN2CH (CH3) O]2N) 13) "Dowanol PM" is Dow Chemical Company's trademark for propylene glycol methyl ether (CH3OCH2CHOHCH3) 14) "Dowanol EPH" is Dow Chemical Company's trademark for ethylene glycol phenyl ether (C6H5OC2H4OH) 15) "Butyl Oxitol" is Shall Chemical Company's trademark for ethylene glycol monobutylether (C4H9OC2H4OH) 16) "IPA" is isopropyl alcohol (2-propanol) 17) Performance was graded by visual assnys performed by impartial panelists on a 0 to 5 scale. wherein 0 - no cleaming, and 5 - total cleaning. The grading was averaged for a number of trials. Test administratorm did not dimclose or identify that products the panelists were using. 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. quaternary aoniun compounds, or mixtures thereof. Surprisingly. not only were the phenols stably miscible with the hard surface acid cleaners, but the quaternary ammonium compounds as well. Since the quaternary ammonium compounds are cationic species, i.e., 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 quaternary ammonium compounds also caused a thickening of the formulas when used in percentages of 5.0% or more. Adding more than 5.08 may cause a thixotrope to for., 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-Iffect of Adding an Antimicrobial Compound to the Hard Surface Acid Cleaners Example Formula Antimicrobial Action Against Gram Gram Fungus6 Positive4 Megative5 Bacteria Bacteria 56. (Control) No effaot No effoct No Effact No effect 57. HLAS 5.0% Both fresh Both fresh Both fresh Fresh samples @thanol 5.0% and @0 day and 60 day and 60 day effective Xanthan Gum 0.1% aged samples aged samples Bardac 222 0.25% effsctive 58. HLAS 5.0% Both fresh Both fresh Fresh samples Ethanol 5.0% and 60 day and 60 day effective Xanthan Gum6 0.1% aged samples aged samples Santophen 130.25% effective effective 59. HLAS 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 Bardac 222 0.125% effective effective Santophen 130.125% 60. HLAS 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 effective 1) (Control) - 5.0% HLAs, 5.0% ethanol, and 0.1% xanthan gum. Xanthan gum is a thiokener compatible with the acid surfactants of this invention 2) Bardac 22, a trademark of Lonza Chemical Company, is a quaternary ammonium compound with the following structure: EMI26.1 Wherein R = R1 and R averages 10 carbon atoms in length. 3) Santophen 1, a trademark of Monsanto Chemical Company is a phenolic compound with the following structures EMI27.1 4) Gram Positive Bacterias Representative examples include Bacillus sp., Lactobacillus sp., Streptococcus sp., Staphylococcus sp., etc. 5) Gram Negative Bacteria: Representative examples include Escherichia coli, Salmonella sp., Proteus sp.., etc. 6) Fungus: Ropresentative examples include Trichophyton mentagrophytes, Tinea pedis (mostly Athlete's Foot fungi), etc. Review of TABLES l-VT shows that the hard surface acid cleaners of the present invention show surprising efficacy and fast action. In direct comparison tests with other couercially available cleaners in TABLES I, 11 and III, the hard surface acid cleaner 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 structures. Further, using more than one type of solvent as in Example.48 is possible, but in the interest of cost effectiveness may not be as desirable, 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 quaternary ammonium compound, or both, with suprisingly no loss in stability from addition of the quaternary ammonium compound. The present invention therefore provides a multipurpose. fast acting and effective hard surface acid cleaner which is effective over the three najor problem cleaning areas.

Claims: CLAIMS 1. A hard surface acid cleaner comprising: (a) alkyl aryl sulfonic acid; and (b) at least 50.0% by weight water. 2. The hard surface acid cleaner as claimed in Claim 1 wherein said alkyl aryl sulfonic acid is EMI29.1 wherein R is an alkyl averaging 5 to 20 carbons atoms; or EMI29.2 wherein R1 and R2 are H or alkyl averaging 5 to 20 carbon atoms and when R1 is alkyl, R2 is H. 3. An all-purpose hard surface acid cleaner comprising 3. An all-purpose hard surface acid cleaner comprising (a) an alkyl aryl sulfonic acid as defined in Claim 2 (b) a solvent selected from C1 10 alkanols, C5-10 alicyclic alkanols, C28 dialkyl ethers and C3 20 glycol ethers and mixtures thereof: and (c) at least 25.0% by weight water. 4. The hard surface acid cleaner as claimed in any one of Claims 1 to 3 wherein said alkyl aryl sulfonic acid is present in an amount of approximately 0.001 to 50.0% by weight of the cleaner. 5, The hard surface acid cleaner as claimed in Claim 3 or Claim 4 wherein the solvent is present in an amount from approximately 0.001% to 25.0% by weight. 6. The hard surface acid cleaner as claimed in any preceding claim and comprising an antimicrobial compound selected from: (i) a substituted phenol of the general structure: EMI30.1 wherein R1, R28 R31 R4, R5 can be phenyl, substituted phenyl, Cl1 or H; and R6 is H or Na; (ii) a quaternary ammonium compound; and (iii) mixtures thereof. 7, The hard surface acid cleaner as claimed in Claim 6, wherein the quaternary ammonium compound has the general structure: EMI30.2 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 as claimed in claim 6 or claim 7 wherein said antimicrobial compound is present in an amount from approximately 0.001 to 15.056 by weight. 9. The hard surface acid cleaner as claimed in any preceding claim further comprising a thickener selected from gums, resins, polysaccharides, and mixtures thereof. 10. The hard surface acid cleaner as claimed in any preceding claim further comprising a defoamer selected from dialkyl polysiloxane polymers. 11. A method of making a hard surface acid cleaner, as claimed in any preceding claim comprising combining the alkyl aryl sulfonic acid, water and, if required, a solvent as defined in Claim 3. 12. A method for cleaning hard surfaces having soiling materials thereon comprising contacting said hard surfaces with a hard surface acid cleaner as claimed in any one of claims 1 to 10; and removing the soiling materials and the hard surface acid cleaner from the hard surfaces.

Inventors: CLEMENT, KIN-MAN CHOY
Applicants: THE CLOROX COMPANY
Application year: 1984
Main classification: C11D1
IPC codes: C11D1, C11D3