EP0131394B1 - Saurer Reiniger für harte Oberflächen - Google Patents

Saurer Reiniger für harte Oberflächen Download PDF

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Publication number
EP0131394B1
EP0131394B1 EP84303999A EP84303999A EP0131394B1 EP 0131394 B1 EP0131394 B1 EP 0131394B1 EP 84303999 A EP84303999 A EP 84303999A EP 84303999 A EP84303999 A EP 84303999A EP 0131394 B1 EP0131394 B1 EP 0131394B1
Authority
EP
European Patent Office
Prior art keywords
hard surface
cleaner
alkyl
surface acid
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP84303999A
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English (en)
French (fr)
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EP0131394A2 (de
EP0131394A3 (en
Inventor
Kin-Man Choy Clement
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clorox Co
Original Assignee
Clorox Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clorox Co filed Critical Clorox Co
Priority to AT84303999T priority Critical patent/ATE32521T1/de
Publication of EP0131394A2 publication Critical patent/EP0131394A2/de
Publication of EP0131394A3 publication Critical patent/EP0131394A3/en
Application granted granted Critical
Publication of EP0131394B1 publication Critical patent/EP0131394B1/de
Expired legal-status Critical Current

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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.
  • solvent some sort of anionic surfactant
  • solvent perhaps a dye and a fragrance to impart a pleasing color and odor
  • Most of these prior cart cleaners suffer from one or more disadvantages.
  • some cleaners are effective only on hard water stains.
  • An example of this class of cleaner is 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 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 storage compound which, upon neutralization with generally, an alkali metal salt, is available for use as an anionic surfactant.
  • Kappler, et al, U.S.-A-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.-A-2,463,936 showed that linear alkyl benzene 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 comprising
  • the hard surface acid cleaner further comprises an antimicrobial compound selected from:
  • the hard surface cleaner further comprises a thickener selected from gums, polysaccharides and resins.
  • the hard surface acid cleaner further comprises 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) greasy/ 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.
  • alkyl aryl sulfonic acid compounds most particularly, 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 hyroxide, 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 sulfonic ("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 sulfonic
  • Linear alkyl benzene sulfonic acid has the general structure (I) above.
  • 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 (II) above.
  • compositions of this invention Preferably, a range of 0.001 % to 50.0% particularly, 1.0% to 30.0% 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 formulas of this invention to have.pH's of no more than 6.5, and preferably, below 3.
  • Solvents appropriate for use in this invention include C l - lo alkanols such as straight chain, primary, secondary and tertiary C 1-10 alkanols, C S - 1o alicyclic alcohols, C 2 - 8 dialkyl ethers, C 3 - 20 glycol ethers such as 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.
  • antimicrobial 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 such 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 when a preferred percentage of up to 5.0% of quaternary ammonium compound. Surpassing 5.0% has a thixotropic effect on the cleaner, and his 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, are alkyls of 5 to 20 carbon atoms, aryl of 6 to 20 carbon atoms or alkylaryl of 7 to 20 carbon atoms provided that only one of R and R, is aryl or alkylaryl; R, may also be hydrogen and A- is an acid stable anion.
  • Preferred anions include CI-, Br-, I-, SO 4 - , CI0 4 -, CI0 3 -, and N0 3 -.
  • R can also be an alkyl benzyl group (in which case R is preferably a methyl group).
  • R and R are both alkyl groups.
  • C 7 to C 12 dialkyl dimethyl ammonium salts are particularly preferred.
  • Other cationic surfactants notably other quaternary ammonium salts and tertiary amine surfactants may be suitable for use as disinfectant compounds.
  • cationic surfactants used as antimicrobial compounds in this invention are compatible with the acid surfactants.
  • a proposed theory, which is not meant herein to be binding is that these acid surfactants, not being neutralized by any alkali metal salts as the more common anionic surfactants are, may exhibit nonionic moieties in solution which act to solublize the cationic surfactants (quaternary ammonium compounds) and keep them from precipitating with the anion form of the acidic surfactants herein.
  • 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 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 mixtures.
  • Further cleaning adjuvants include defoamers, such as dialkyl polysiloxane polymers. Particularly preferred as the defoamers are those sold by Dow-Corning under the trade name DB 100 for 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.
  • Builders 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 salts, 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, 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 enamalled metal sheets (which material is the same as used for manufacturing porcelain kitchen sinks) and allowed to dry (age) for approximatley 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 surprisingly 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)

Claims (10)

1. Sauer Reiniger für harte Oberflächen, dadurch gekennzeichnet, daß er
(a) eine Alkylarylsulfonsäure der Formel I
Figure imgb0020
worin R ein Alkylrest mit durchschnittlich 5 bis 20 Kohlenstoffatomen ist, oder der Formel II
Figure imgb0021
worin R, und R2 für H oder einen Alkylrest mit durchschnittlich 5 bis 20 Kohlenstoffatomen stehen, und sofern R, eine Alkylrest ist, R2 ein Wasserstoffatom bedeutet,
(b) ein Lösungsmittel, welches unter Cl-,0-Alkanolen, C5-10-alicyclischen Alkanolen, C2-8-Dialkylethern und C3-20-Glykolethern und Gemischen daraus ausgewählt ist, und
(c) mindestens 25 Gew.-% Wasser enthält.
2. Saurer Reiniger für harte Oberflächen nach Anspruch 1, worin die Alkylarylsulfonsäure in einer Menge von 0,001 bis 50,0 Gew.-% des Reinigers vorhanden ist.
3. Saurer Reiniger für harte Oberflächen nach Anspruch 1 oder Anspruch 2, worin das Lösungsmittel in einer Menge von 0,001 bis 25,0 Gew.-% vorhanden ist.
4. Saurer Reiniger für harte Oberflächen nach einem der voranstehenden Ansprüche, welcher eine antimikrobielle Verbindung enthält, die ausgewählt ist unter:
(i) einem substituierten Phenol der allgemeinen Struktur
Figure imgb0022
woring R,, R2, R3, R4, R5 Phenyl, substituiertes Phenyl, CI oder H sein können und R6 für H oder Na steht;
(ii) einer quaternären Ammoniumverbindung, und
(iii) Gemischen davon.
5. Saurer Reiniger für harte Oberflächen nach Anspruch 4, worin die quaternäre Ammoniumverbindung die allgemeine Struktur
Figure imgb0023
aufweist, worin
R und R, gleich oder unterschiedlich sind, R einen Alkylrest mit 5 bis 20 Kohlenstoffatomen, einen Arylrest mit 6 bis 20 Kohlenstoffatomen oder einen Alkylarylrest mit 7 bis 20 Kohlenstoffatomen bedeutet und
R, gleich Wasserstoff oder eine Gruppe R ist und
A ein säurestabiles Anion ist, mit der Maßgabe, daß lediglich einer der Reste R und
R1 Aryl oder Alkylaryl ist.
6. Saurer Reiniger für harte Oberflächen gemäß Anspruch 4 oder Anspruch 5, worin die antimikrobielle Verbindung in einer Menge von 0,001 bis 15,0 Gew.-% vorhanden ist.
7. Saurer Reiniger für harte Oberflächen gemäß einem der voranstehenden Ansprüche, weicher ferner einen Verdicker enthält, der ausgewählt ist unter Gummi, Harzen, Polysacchariden und Gemischen davon.
8. Saurer Reiniger für harte Oberflächen nach einem der voranstehenden Ansprüche, welcher ferner ein Entschäumungsmittel enthält, welches ausgewählt ist unter Dialkylpolysiloxanpolymeren.
9. Verfahren zur Herstellung eines sauren Reingers für harte Oberflächen nach einem der voranstehenden Ansprüche, wobei die Alkylarylsulfonsäure, Wasser und Lösungsmittel gemäß der Definition in Anspruch 3 zusammengegeben werden.
10. Verfahren zur Reinigung einer haren Oberfläche mit verschmutzenden Materialien darauf, wobei die harte Oberfläche mit einem sauren Reiniger für harte Oberflächen gemäß einem der Ansprüche 1 bis 8 in Berührung gebracht wird und die verschmutzenden Materialien und der saure Reiniger für harte Oberflächen von der harten Oberfläche entfernt werden.
EP84303999A 1983-07-07 1984-06-13 Saurer Reiniger für harte Oberflächen Expired EP0131394B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84303999T ATE32521T1 (de) 1983-07-07 1984-06-13 Saurer reiniger fuer harte oberflaechen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US51210083A 1983-07-07 1983-07-07
US512100 1983-07-07

Publications (3)

Publication Number Publication Date
EP0131394A2 EP0131394A2 (de) 1985-01-16
EP0131394A3 EP0131394A3 (en) 1985-11-21
EP0131394B1 true EP0131394B1 (de) 1988-02-17

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EP84303999A Expired EP0131394B1 (de) 1983-07-07 1984-06-13 Saurer Reiniger für harte Oberflächen

Country Status (7)

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EP (1) EP0131394B1 (de)
JP (1) JPH0699704B2 (de)
AT (1) ATE32521T1 (de)
CA (1) CA1217690A (de)
DE (1) DE3469363D1 (de)
ES (2) ES8704887A1 (de)
MX (1) MX159252A (de)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8508010D0 (en) * 1985-03-27 1985-05-01 Unilever Plc Liquid bleaching compositions
GB8625103D0 (en) * 1986-10-20 1986-11-26 Unilever Plc Disinfectant compositions
GB8625974D0 (en) * 1986-10-30 1986-12-03 Unilever Plc Non-aqueous liquid detergent
US4895669A (en) * 1986-11-03 1990-01-23 The Clorox Company Aqueous based acidic hard surface cleaner
DE3637711A1 (de) * 1986-11-05 1988-05-11 Remmers Chemie Gmbh & Co Mittel zur reinigung von mineralischen poroesen bauelementen
US5362422A (en) * 1993-05-03 1994-11-08 The Procter & Gamble Company Liquid hard surface detergent compositions containing amphoteric detergent surfactant and specific anionic surfactant
EP0988064A1 (de) * 1997-06-09 2000-03-29 THE PROCTER & GAMBLE CELLULOSE COMPANY (an Ohio corp.) Verbesserte zusammensetzungen mit unkomplexiertem cyclodextrin zur geruchskontrolle
AR017716A1 (es) 1998-04-27 2001-09-12 Procter & Gamble Articulo de manufactura en la forma de un expendedor atomizador operado no-manualmente
WO1999055814A1 (en) * 1998-04-27 1999-11-04 The Procter & Gamble Company Improved uncomplexed cyclodextrin compositions for odor and wrinkle control
WO1999055815A1 (en) * 1998-04-27 1999-11-04 The Procter & Gamble Company Improved uncomplexed cyclodextrin compositions for odor control
BR9815836A (pt) * 1998-04-27 2000-12-26 Procter & Gamble Composições de ciclodextrina descomplexada aperfeiçoada para controle de odor
CA2350696C (en) 1998-11-25 2007-03-20 The Procter & Gamble Company Improved uncomplexed cyclodextrin compositions for odor control
US20140271762A1 (en) * 2013-03-15 2014-09-18 Ecolab Usa Inc. Non-Sorptive or Minimally Sorptive Disinfectant Wipes

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3463736A (en) * 1966-03-04 1969-08-26 Atlantic Richfield Co Aqueous slurries of triethanolamine salts of linear alkylbenzene sulfonic acids
DK132898A (de) * 1969-10-24
JPS4841133A (de) * 1971-09-29 1973-06-16
JPS5158405A (ja) * 1974-11-18 1976-05-21 Dai Ichi Kogyo Seiyaku Co Ltd Mukisansenekyozonenzai
US3969282A (en) * 1974-12-23 1976-07-13 Basf Wyandotte Corporation Acidic surfactant composition, stock surfactant solution prepared therefrom, and method of washing soiled substrates employing the same
CA1116059A (en) * 1978-05-22 1982-01-12 Allied Corporation Phenol-free and chlorinated hydrocarbon-free photoresist stripper
US4414035A (en) * 1979-05-21 1983-11-08 Petrolite Corporation Method for the removal of asphaltenic deposits

Also Published As

Publication number Publication date
JPS6015499A (ja) 1985-01-26
ES8704887A1 (es) 1987-05-01
ES557353A0 (es) 1988-07-16
ES534403A0 (es) 1987-05-01
MX159252A (es) 1989-05-09
ES8802535A1 (es) 1988-07-16
ATE32521T1 (de) 1988-03-15
JPH0699704B2 (ja) 1994-12-07
CA1217690A (en) 1987-02-10
EP0131394A2 (de) 1985-01-16
DE3469363D1 (en) 1988-03-24
EP0131394A3 (en) 1985-11-21

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