Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/43—Solvents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
  • C11D1/24—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds containing ester or ether groups directly attached to the nucleus

Definitions

• hard surface cleaners in the art, containing some sort of anionic surfactant, solvent, perhaps a dye and a fragrance to impart a pleasing color and odor, and mostly water.
• Host of these prior art cleaners suffer from one or more disadvantages.
• some cleaners are effective only on hard water ataina.
• An example of this class of cleaner ia a highly acidic toilet bowl cleaner containing hydrochloric acid.
• Hard water stains are mineral atains 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 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.
• 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 anionic surfactant.
• 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.
• Reid, U.S. 3,463,736 showed that linear alkylbenzene sulfonic acids could be neutralized with triethanolamine to act as a cleaner.
• linear alkyl benzene sulfonic acids can be utilized as hard surface cleaners themselves.
• This invention relates to an improved, hard surface acid cleaner preferably having a pH of no more than approximately 6.5 comprising:
• the preferred alkyl aryl sulfonic acid is a linear alkyl benzene sulfonic acid surfactant of the general structure wherein R is an alkyl averaging 5 to 20 carbons.
• this hard surface acid cleaner further comprises (c) a solvent selected from straight chain alkanols averaging 1 to 10 carbons, 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.
• the hard surface acid cleaner further comprises (d) an antimicrobial compound selected from:
• the hard surface cleaner further comprises (e) a thickener selected from gums, polysaccharides and resins.
• 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 also include at least one other cleaning adjuvant selected from dyes, pigments, fragrances, and builders.
• the hard surface acid cleaner of this invention has proven to be both effective and fast-acting against all three major problem stains, namely, (1) soap scums: (2) hard water stains: and (3) greaay oily stains.
• the present invention is a hard surface acid cleaner which has surprisingly effective and fast cleaning results on all three problem areas: (1) soap scums; (2) hard water stains; and (3) greasy/oily stains.
• the surprising revelation was that alkyl aryl sulfonic acid compounds, most specifically, linear alkyl benzene sulfonic acids, (“HLAS") were responsible for the improved cleaning in all three areas.
• HLAS linear alkyl benzene sulfonic acids
• linear alkyl benzene sulfonic acids used in this invention are, as previously mentioned, commonly neutralized with sodium or other alkali metal salts to make common cleaners.
• Linear 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 aalt, 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") was significantly less bio-degradable--is produced by many companies, including Continental Oil Company under the brand name of Conoco SA-597. and Pilot Chemical Company under the brand name Calsoft LAS-99, ) Witco Chemical Corporation under the brand name of Witco 1298 Soft Acid and Stepan Chemical Company under the brand name of Bio Soft S-100.
• ABS branched alkyl benzene sulfonate
• Linear alkyl benzene sulfonic acid has the general structure wherein R is alkyl averaging 5 to 20 carbon atoms. Most preferable for use in the formulas of this invention are dodecylbenzene sulfonic acids, wherein R averages about 11.4 carbon atoms in length.
• alkyl aryl sulfonic acids suitable for use in this invention include alkylated diphenyl oxide disulfonates of the general structure wherein R 1 is H and R 2 is alkyl, averaging 5 to 20 carbon atoms in length. When R 1 is alkyl, R 2 is H.
• compositions of this invention Preferably, a range of 0.001% to 50.0% particularly, 1.0% to 30.0% and moat 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 formulas of this invention to have pH's of no more than 6.5. and preferably, below 3.
• alkyl sulfonic acid is Dowfax 2AO manufactured by Dow Chemical Company corresponding to the structure immediately above when R 1 is H and R 2 averages 12 carbons.
• solvents are added to the acid surfactants of this invention.
• Solvents appropriate for use in this invention include straight chain, primary, secondary and tertiary C 1-10 alkanols, C 5-10 alicyclic alcohols, C 2-8 dialkyl ethers, C 3-20 acyl and aryl glycol ethers and mixtures thereof.
• solvents examples include propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol isobutyl ether, ethylene glycol methyl ether, ethylane 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.
• 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.
• aantimiorobial compounds are added to the novel hard surface cleaners of this invention which are selected from substituted phenols and quaternary ammonium compounds.
• quaternary ammonium compounds some of which are cationic surfactants, having essentially positively charged species in aqueous solution, would react with the anionic surfactants in equilibrium with the acid surfactants disclosed above and cause a precipitate to form.
• 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 5.0% of quaternary ammonium compound. Surpassing 5.01% 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 wherein R and R 1 are alkyls of C5 to C 20 , and A is an acid stable anion.
• Preferred anions include C1 - , 8r - , I - , SO 4 - , ClO 4 -, ClO 3 - , and NO 3 - .
• R 1 can also be an alkyl benzyl group (in which case R is a methyl group).
• R and R 1 are both alkyl groups. Further particularly preferred are C 7 to C 12 dialkyl dimethyl ammonium salts. Other cationic surfactants, notably other quaternary ammonium salts and tertiary amins surfactants may be suitable for use as disinfectant compounds.
• 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 percentages of these antimicrobial compounds are from 0.1 - to 10% by weight.
• cleaning adjuvants include thickeners selected from gums, resins and other polysaccharides, such as xanthan gums, starch, and sixtures.
• 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 fos 100%dimethylpolysiloxane. Further defoamers may be applicable for use in this invention, including various cationic and nonionic surfactants.
• Still further cleaning adjuvants include dyes, 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 be those which will not be degraded by the low pH of the hard surface acid cleaner.
• Buildere can include many inorganic and organic builders, such as sodium ethylenediaminetetraacetate or HEDTA (hydroxyethyl ethylenediaminetriacetic acid). Further builders include many organic acids and their alkali metal salta, eg., citric acid, sodium citrate, sodium lactate, sodium maleate, etc.
• a standard soap scum suspension was prepared using the following ingredients:
• 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 10, 5, 3, 2 , 1 minutes and 45 seconds to demonstrate rapid cleaning efficency. The results are reported in TABLES I,II and III below. Participants noted also how quickly effective cleaning occurred at the various time intervals.
• This mixture was applied in a thin layer to pre-cleaned white enamelled metal sheets (which material is the same as used for manufacturing procelain kitchen sinks) and allowed to dry (age) for approximately 24 hours.
• the preferred germicidal or antimicrobial compounds are chosen from substituted phenols, quaternary ammonium 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.
• 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.
• 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 major problem cleaning areas.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Publications (3)

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Cited By (14)

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• 1983
  • 1983-10-21 CA CA000439460A patent/CA1217690A/en not_active Expired
  • 1983-12-14 JP JP58235994A patent/JPH0699704B2/ja not_active Expired - Lifetime
  • 1983-12-15 MX MX199762A patent/MX159252A/es unknown
• 1984
  • 1984-06-13 EP EP84303999A patent/EP0131394B1/de not_active Expired
  • 1984-06-13 DE DE8484303999T patent/DE3469363D1/de not_active Expired
  • 1984-06-13 AT AT84303999T patent/ATE32521T1/de not_active IP Right Cessation
  • 1984-07-04 ES ES534403A patent/ES8704887A1/es not_active Expired
• 1987
  • 1987-01-15 ES ES557353A patent/ES8802535A1/es not_active Expired

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