EP0780465B1 - Reinigungsmittel und Verfahren zum Reinigen von empfindlichen Oberflächen - Google Patents

Reinigungsmittel und Verfahren zum Reinigen von empfindlichen Oberflächen Download PDF

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Publication number
EP0780465B1
EP0780465B1 EP95870133A EP95870133A EP0780465B1 EP 0780465 B1 EP0780465 B1 EP 0780465B1 EP 95870133 A EP95870133 A EP 95870133A EP 95870133 A EP95870133 A EP 95870133A EP 0780465 B1 EP0780465 B1 EP 0780465B1
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EP
European Patent Office
Prior art keywords
composition
alkyl
anionic surfactant
compositions
cleaning
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EP95870133A
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English (en)
French (fr)
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EP0780465A1 (de
Inventor
Marc François Theophile Evers
Roberta Margherita Romano
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to AT95870133T priority Critical patent/ATE223958T1/de
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to DE69528182T priority patent/DE69528182T2/de
Priority to ES95870133T priority patent/ES2182883T3/es
Priority to EP95870133A priority patent/EP0780465B1/de
Priority to CA002240882A priority patent/CA2240882C/en
Priority to AU13297/97A priority patent/AU1329797A/en
Priority to BR9612063A priority patent/BR9612063A/pt
Priority to CZ981937A priority patent/CZ193798A3/cs
Priority to US09/091,617 priority patent/US6165285A/en
Priority to JP9522846A priority patent/JP2000500805A/ja
Priority to CN96199914A priority patent/CN1209162A/zh
Priority to PCT/US1996/019402 priority patent/WO1997022679A1/en
Publication of EP0780465A1 publication Critical patent/EP0780465A1/de
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Publication of EP0780465B1 publication Critical patent/EP0780465B1/de
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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

Definitions

  • the present invention relates to hard surface cleaning compositions.
  • the compositions herein are specifically designed for the safe cleaning of marble, and painted and lacquered wood.
  • marble and lacquered surfaces are two types of surfaces which do require particular attention, when formulating cleaning compositions for their cleaning.
  • marble is mainly composed of calcium carbonate, and is therefore incompatible with cleaning compositions which would be acidic, and/or which would comprise a builder.
  • acidity would "dissolve” marble
  • the builder whose function is specifically to bind ions which are present in water and dirt particles, would also bind the calcium in the marble, thereby turning the surface from very shiny to dull, as the introduced surface irregularities lower the reflectance of the surface.
  • cleaning products formulated at neutral pH and which contain anionics surfactants also damage marble, probably because the anionic surfactants would also bind the calcium in the marble as described hereinabove.
  • the formulation of an alkaline composition free of anionic surfactants would seem indicated in the present circumstances.
  • an alkaline composition does not accommodate the cleaning of lacquered and painted wooden surfaces e.g. lacquered wooden floors.
  • lacquers are typically made out of polyurethanes or polyacrylates or mixtures of both, and paint is mainly pigmented polyacrylates, polyvinylacetates or alkydresins. Indeed such surfaces are permanently damaged by alkalinity. Specifically, alkalinity would destroy the lacquer and therefore give the lacquered surface the appearance of dullness or a colour change. Thus it would appear that formulating a cleaning composition which is suitable for cleaning both marble and lacquered surfaces is hindered by incompatible pH requirements.
  • a liquid composition which is suitable, i.e. safe, for the cleaning of both marble and lacquered surfaces, and which comprises an anionic surfactant so as to provide good cleaning performance, in particular which performs well on grease removal.
  • a liquid composition which comprises at least one anionic surfactant, which is free of strong builders, which is formulated at a mildly acidic to mildly alkaline pH, which comprises positive divalent ions in amounts so as to saturate the anionic surfactant in the composition, and preferably a carbonate of the formula XHCO 3 where X is an alkali metal or ammonium ion.
  • the mildly acidic to mildlly alkaline pH damages neither marble nor lacquers.
  • the positive divalent ions in a saturating amount for the anionic surfactant prevents the damage on marble, while still allowing the anionic surfactant to perform its cleaning action.
  • the present invention encompasses a liquid cleaning composition which comprises at least one anionic surfactant, which is free of strong builders, which is formulated at a mildly acidic to mildly alkaline pH, which comprises positive divalent ions in an amount so as to saturate the anionic surfactant in the composition, and preferably a carbonate of the formula XHCO 3 where X is an alkali metal or ammonium ion.
  • the present invention further encompasses a method of cleaning marble or lacquered surfaces, where an effective amount of said composition is applied to clean said marble or lacquered surfaces, and said composition is removed.
  • compositions herein are liquid compositions. They are typically aqueous and typically comprise from 10 % to 99 % by weight of the total composition, preferably from 15 % to 95 %, most preferably from 30 % to 92 % of water.
  • the compositions herein comprise at least one anionic surfactant, required for cleaning.
  • anionic surfactants for use herein include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 9 -C 20 linear alkylbenzenesulfonates, C 8 -C 22 primary or secondary alkanesulfonates, C 8 -C 24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 6 -C 12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sul
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwart, Perry and Berch).
  • suitable anionic surfactants for use herein include alkyl ester sulfonate surfactants, i.e. linear esters of C 8 -C 20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO 3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty acid substances as derived from tallow, palm oil, etc.
  • alkyl sulfate surfactants hereof which are water soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10 -C 24 linear or branched hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethyl
  • alkyl alkoxylated sulfate surfactants herein which are water soluble salts or acids of the formula RO(A) m SO 3 M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component,
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • a variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
  • compositions of the present invention comprise from 0.1% to 30% by weight of the total composition of said anionic surfactant or mixtures thereof, preferably from 0.1% to 20% most preferably 0.1% to 10% and 0.5% to 5%.
  • compositions herein may comprise additional, non anionic surfactants.
  • suitable such co-surfactants include nonionic, cationic and amphoteric surfactants.
  • Cationic detersive surfactants suitable for use in compositions of the present invention are those having a long-chain hydrocarbyl group.
  • cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula [R 2 (OR 3 ) y ][(R 4 (OR 3 ) y ] 2 R 5 N + X -
  • R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain
  • each R 3 is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures thereof
  • each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups
  • Ampholytic surfactants are also suitable for use in the compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain.
  • One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 for examples of ampholytic surfactants.
  • Zwitterionic surfactants are also suitable for use in the present compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48 for examples of zwitterionic surfactants.
  • Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
  • Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula wherein R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R 5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
  • the R 5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
  • amine oxide surfactants in particular include C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxy ethyl dihydroxy ethyl amine oxides.
  • Nonionic surfactants for use herein are nonionic surfactants.
  • Suitable nonionic surfactants herein comprise polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide.
  • the ethylene oxide is present in an amount equal to from about 5 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol.
  • nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation; and Triton MT X-45, X-114, X-100 and X-102, all marketed by Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are also suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C 11 -C 15 linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C 12 -C 14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C 14 -C 15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation product of C 12 -C 13 linear alcohol with 6.5 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C 14 -C 15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation product of C 14 -C 15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and KyroTM EOB.
  • TergitolTM 15-S-9 the condensation product of C 11 -C 15 linear alcohol with 9 moles ethylene oxide
  • alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose, and galactosyl moieties can be substituted for the glucosyl moieties.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions of the preceding saccharide units.
  • a polyalkkyleneoxide chain joining the hydrophobic moiety and the polysaccharide moiety.
  • the preferred alkyleneoxide is ethylene oxide.
  • Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms.
  • the alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
  • Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses.
  • Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
  • the preferred alkylpolyglycosides have the formula R 2 O(C n H 2n O) t (glucosyl) x wherein R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
  • the glycosyl is preferably derived from glucose.
  • the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position).
  • the additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6- position, preferably predominantely the 2- position.
  • condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use herein.
  • the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility.
  • the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
  • Examples of compounds of this type include certain of the commercially available PluronicTM surfactants, marketed by BASF.
  • nonionic surfactants are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5000 to about 11000.
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • R 1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxypropyl, or a mixture thereof, preferably C 1 -C 4 alkyl, more preferably C 1 or C 2 alkyl, most preferably C 1 alkyl (i.e., methyl); and R 2 is a C 5 -C 31 hydrocarbyl, preferably straight chain C 7 -C 19 alkyl or alkenyl, more preferably straight chain C 9 -C 17 alkyl or alkenyl, most preferably straight chain C 11 -C 17 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Suitable reducing sugards include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH 2 -(CHOH) n -CH 2 OH, -CH(CH 2 OH)-(CHOH) n-1 -CH 2 OH, -CH 2 -(CHOH) 2 (CHOR')(CHOH)-CH 2 OH, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH 2 -(CHOH) 4 -CH 2 OH.
  • R 1 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R 2 -CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.
  • nonionic surfactants herein are polyethylene oxide condensates of alkyl phenols, condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethyelene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are C 8 -C 14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and C 8 -C 18 alcohol ethoxylates (preferaby C 10 avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.
  • Preferred co-surfactants for use herein are nonionic surfactants for their cleaning action on grease.
  • compositions herein may comprise from 0.2% to 90% by weight of the total composition of said co-surfactants or mixtures thereof, preferably from 1% to 50%, most preferably from 2% to 20%.
  • the compositions herein comprise positive divalent ions in amounts so as to saturate the anionic surfactant present in the composition.
  • saturated it is meant herein that there should be enough positive divalent ions to bind substantially all the anionic surfactant - i.e. the negative charges of the anionic surfactant - present in the composition, i.e. at least 75% of the anionic surfactant, preferably at least 80%, most preferably at least 90% or all of anionic surfactant.
  • Different species of anionic surfactants have different number of anions per mole of surfactant.
  • the compositions herein will comprise positive divalent ions in a molar ratio of positive divalent ions to anionic surfactant of at least X:2. And for the purpose of the present invention and the amount of positive divalent ions needed therein, the form - protonated or not - in which the anions of the anionic surfactant are present is not critical.
  • Suitable positive divalent ions for use herein include Mg 2+ , Ba 2+ , Fe 2+ , Ca 2+ , Zn 2+ and Ni 2+ . Most Preferred are Mg 2+ and Ca 2+ , or mixtures thereof.
  • the ions can be introduced in the compositions in any form. As far as Mg is concerned, MgCl 2 has been found to be commercially attractive. However MgSO 4 and MgNO 3 are also suitable source of Mg ions for the compositions herein. Without wishing to be bound by theory, we speculate that the ions herein somehow prevent the builder from binding with the calcium in the marble, without preventing the builder from performing in the cleaning operation.
  • salts of the anionic surfactants and the divalent positive ions can be pre-formed, before they are introduced in the composition
  • the compositions herein are formulated at a mildly acidic to mildly alkaline pH. Accordingly, the compositions herein preferably have a pH between 6 and 9, more preferably between 6.5 and 8, and most preferably between 6.5 and 7.5. At lower pH, the composition would damage marble while, at higher pH, it would damage lacquers. Interestingly, even in neutral pH in which the compositions herein can be formulated, damage to marble would be observed in the abscence of the saturating ions.
  • the pH of the compositions herein can be adjusted by any of the means well known to the man skilled in the art, such as addition of NaOH, KOH, MEA,TEA,MDEA,K2CO3,Na 2 CO 3 and the like, or sulphuric acid, nitric acid, hydrochloric acid, acetic acid and the like.
  • compositions herein be free of strong builders.
  • strong builders it is meant herein polycarboxylates and polyphosphates described hereinbelow:
  • Such polycarboxylates include citrate and complexes of the formula: CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B) wherein A is H or OH; B is H or -O-CH(COOX)-CH 2 (COOX); and X is H or a salt-forming cation.
  • a and B are both H, then the compound is oxydissuccinic acid and its water-soluble salts.
  • A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts.
  • TDS tartrate disuccinic acid
  • Still other ether polycarboxylates excluded herein include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulfonic acid, and carboxymethyloxysuccinic acid.
  • ether hydroxypolycarboxylates represented by the structure: HO-[C(R)(COOM)-C(R)(COOM)-O] n -H wherein M is hydrogen or a cation wherein the resultant salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or different and selected from hydrogen, C 1-4 alkyl or C 1-4 substituted alkyl.
  • Excluded ether polycarboxylates are also cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903 particularly dipicolinic acid and chelidanic acid.
  • polycarboxylates herein are mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, benezene pentacarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.
  • carboxylate builders herein are the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28,1973.
  • carboxylates herein are alkali metal, ammonium and substituted ammonium salts of polyacetic acids.
  • polyacetic acid builder salts are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine, tetraacetic acid and nitrilotriacetic acid.
  • alkyliminoacetic builders such as methyl imino diacetic acid, alanine diacetic acid, methyl glycine diacetic acid, hydroxy propylene imino diacetic acid and other alkyl imino acetic acid builders.
  • compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanediotes and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986
  • Succinic acid builders include the C5-C20 alkyl succinic acids and salts thereof, particularly dodecenylsuccinic acid.
  • Alkyl succinic acids excluded herein typically are of the general formula R-CH(COOH)CH 2 (COOH) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., C 10 -C 20 alkyl or alkenyl, or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
  • succinate builders excluded herein are laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate, 2-pentadecenylsuccinate, and the like.
  • excluded builders are sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
  • polycarboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979.
  • polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials are the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • polyphosphonates herein are the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates.
  • compositions herein can further comprise a variety of well known optional ingredients, including perfumes, and dyes.
  • optional ingredients including perfumes, and dyes.
  • the compositions herein are free of builders and they should be substantially free of solvents which would otherwise damage lacquers.
  • compositions herein comprise an effective amount of a carbonate of the formula XHCO 3, where X is an alkali metal, particularly K + , Na + , or NH 4 + .
  • X is an alkali metal, particularly K + , Na + , or NH 4 + .
  • the amount of these compounds needed in the compositions herein can be determined by trial and error, but appears to lie in the range of from 0.05% to 0.4% by weight of the total composition, preferably from 0.05% to 0.1%. Caution needs to be exercised however in that we have observed that too high an amount of XHCO 3 may raise be detrimental to surface safety on lacquered wood.
  • the present invention further encompasses a method of cleaning marble or painted or lacquered wooden surfaces.
  • a method of cleaning marble or painted or lacquered wooden surfaces In that method, an effective amount of a composition as herein before described is applied onto said marble or wooden surface, and said composition is optionally removed.
  • the compositions herein can be used undiluted, i.e. neat, or diluted.
  • the compositions herein are used in diluted form, i.e. at dilution levels of from about 0.5% to 1.5%, depending on how concentrated the product is.
  • the compositions herein are applied to said surface, and left to dry, i.e. no rinsing is required.
  • the product can also be applied neat on the surface to remove the encrustated dirt much more easily.
  • neat usage of the composition will be preferred. In neat usage, it is preferable that the composition should be removed, i.e. rinsed off after it has been applied to clean.
  • compositions were made by mixing the listed ingredients in the listed proportions. These compositions were used neat to clean marble and dilute to clean lacquered wooden floors. Excellent cleaning and surface safety performance was observed.
  • Ingredients Compositions (weight %) Example N 1 2 3 4 NaPS 1.0 3.0 - - NaLAS - - 2.0 - NaAE 2 S - - - 2.0 R-AE X 6.0 4.0 5.0 6.0 Mg 0.08 0.20 0.13 0.12 NaHCO 3 - 0.10 0.11 0.10 Na2HPO4 - - - - Na2H3P3010 - - - - pH 7.1 7.5 7 7.3 water and minors --------------------------------up to 100%-------------------------------------------------------------up to 100%-------------------------------------------------------------------------up to 100%----------------------------------------------------------------

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Cleaning Or Drying Semiconductors (AREA)

Claims (6)

  1. Verfahren zum Reinigen von Marmor- oder bemalten oder lackierten Holzoberflächen, wobei eine wirksame Menge einer flüssigen Reinigungszusammensetzung, welche mindestens ein anionisches Tensid umfaßt, welche frei an starken Polycarboxylat- und Polyphosphat-Buildern ist, welche bei einem schwach sauren bis schwach alkalischen pH formuliert ist, welche positive zweiwertige Ionen in Mengen umfaßt, um im wesentlichen das gesamte in der Zusammensetzung vorliegende, anionische Tensid zu binden, aufgebracht wird, um die Marmor- oder bemalten oder lackierten Holzoberflächen zu reinigen, und die Zusammensetzung wahlweise entfernt wird.
  2. Flüssige Reinigungszusammensetzung, umfassend mindestens ein anionisches Tensid, welche frei ist an starken Polycarboxylat- und Polyphosphat-Buildern, welche bei einem schwach sauren bis schwach alkalischen pH formuliert ist, welche positive zweiwertige Ionen in Mengen enthält, um im wesentlichen das gesamte in der Zusammensetzung vorliegende, anionische Tensid zu binden, und eine wirksame Menge eines Carbonats der Formel XHCO3, worin X ein Alkalimetall oder Ammoniumion ist.
  3. Verfahren nach Anspruch 1 oder Zusammensetzung nach Anspruch 2, welche in einem pH-Bereich von 6 bis 9, vorzugsweise 6,5 bis 8, am meistsen bevorzugt 6.5 bis 7,5. formuliert ist.
  4. Zusammensetzung oder Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei die Zusammensetzung 0,1 bis 30 Gew.-% der Gesamtzusammensetzung, vorzugsweise 0,1 bis 20 Gew.-%, am meisten bevorzugt 0,1 bis 10 Gew.-%, des anionischen Tensids umfaßt.
  5. Zusammensetzung oder Verfahren nach mindestens einem der vorangehenden Ansprüche, wobei die Zusammensetzung weiterhin ein nichtionisches Co-Tensid beinhaltet.
  6. Zusammensetzung oder Verfahren nach mindestens einem der vorangehenden Ansprüche. wobei die positiven zweiwertigen Ionen Mg2+, Ca2+ oder Mischungen hiervon sind.
EP95870133A 1995-12-18 1995-12-18 Reinigungsmittel und Verfahren zum Reinigen von empfindlichen Oberflächen Expired - Lifetime EP0780465B1 (de)

Priority Applications (12)

Application Number Priority Date Filing Date Title
DE69528182T DE69528182T2 (de) 1995-12-18 1995-12-18 Reinigungsmittel und Verfahren zum Reinigen von empfindlichen Oberflächen
ES95870133T ES2182883T3 (es) 1995-12-18 1995-12-18 Composicion limpiadora y metodo de limpieza de superficies delicadas.
EP95870133A EP0780465B1 (de) 1995-12-18 1995-12-18 Reinigungsmittel und Verfahren zum Reinigen von empfindlichen Oberflächen
AT95870133T ATE223958T1 (de) 1995-12-18 1995-12-18 Reinigungsmittel und verfahren zum reinigen von empfindlichen oberflächen
AU13297/97A AU1329797A (en) 1995-12-18 1996-12-06 Cleaning composition and method for the cleaning of delicate surfaces
BR9612063A BR9612063A (pt) 1995-12-18 1996-12-06 Composição e método de limpeza para a limpeza de superfícies delicadas
CA002240882A CA2240882C (en) 1995-12-18 1996-12-06 Cleaning composition and method for the cleaning of delicate surfaces
CZ981937A CZ193798A3 (cs) 1995-12-18 1996-12-06 Čisticí směs a způsob čištění choulostivých povrchů
US09/091,617 US6165285A (en) 1995-12-18 1996-12-06 Method for the cleaning of delicate surfaces
JP9522846A JP2000500805A (ja) 1995-12-18 1996-12-06 クリーニング組成物およびデリケートな表面のクリーニング法
CN96199914A CN1209162A (zh) 1995-12-18 1996-12-06 用于清洗精致表面的清洗组合物和方法
PCT/US1996/019402 WO1997022679A1 (en) 1995-12-18 1996-12-06 Cleaning composition and method for the cleaning of delicate surfaces

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP95870133A EP0780465B1 (de) 1995-12-18 1995-12-18 Reinigungsmittel und Verfahren zum Reinigen von empfindlichen Oberflächen

Publications (2)

Publication Number Publication Date
EP0780465A1 EP0780465A1 (de) 1997-06-25
EP0780465B1 true EP0780465B1 (de) 2002-09-11

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EP (1) EP0780465B1 (de)
JP (1) JP2000500805A (de)
CN (1) CN1209162A (de)
AT (1) ATE223958T1 (de)
AU (1) AU1329797A (de)
BR (1) BR9612063A (de)
CA (1) CA2240882C (de)
CZ (1) CZ193798A3 (de)
DE (1) DE69528182T2 (de)
ES (1) ES2182883T3 (de)
WO (1) WO1997022679A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6001935A (en) 1997-11-10 1999-12-14 Stephan Company Durable hydrophilic polymer coatings
WO2005017083A1 (de) * 2003-08-14 2005-02-24 Henkel Kommanditgesellschaft Auf Aktien Reiniger zur schonenden behandlung säureempfindlicher carbonat-haltiger oberflächen
ATE481470T1 (de) * 2006-07-14 2010-10-15 Ecolab Inc Alkalisches bodenreinigungsmittel und bodenreinigungsverfahren
CN103013719A (zh) * 2012-11-15 2013-04-03 隋丽梅 一种居室环境清洁剂及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3546124A (en) * 1968-11-18 1970-12-08 Joseph Fleischer Cleansing solutions
US3998750A (en) * 1975-06-30 1976-12-21 The Procter & Gamble Company Liquid detergent composition
JPH0715112B2 (ja) * 1986-05-02 1995-02-22 花王株式会社 浴室用洗浄剤組成物
US5378409A (en) * 1990-11-16 1995-01-03 The Procter & Gamble Co. Light duty dishwashing detergent composition containing an alkyl ethoxy carboxylate surfactant and ions
US5252245A (en) * 1992-02-07 1993-10-12 The Clorox Company Reduced residue hard surface cleaner
SK280406B6 (sk) * 1992-08-25 2000-01-18 Unilever Nv Priehľadná vodná kvapalná čistiaca zmes na tvrdý p
US5393468A (en) * 1993-07-14 1995-02-28 Colgate Palmolive Company Hard surface cleaner
EP0639833A1 (de) * 1993-08-19 1995-02-22 The Procter & Gamble Company Verwendung von Magnesiumionen in Reinigungsmitteln für harte Oberflächen zur Verbesserung des Glanzes und entsprechende Reinigungsmittel
US5415813A (en) * 1993-11-22 1995-05-16 Colgate-Palmolive Company Liquid hard surface cleaning composition with grease release agent

Also Published As

Publication number Publication date
AU1329797A (en) 1997-07-14
JP2000500805A (ja) 2000-01-25
EP0780465A1 (de) 1997-06-25
BR9612063A (pt) 1999-05-04
ES2182883T3 (es) 2003-03-16
DE69528182D1 (de) 2002-10-17
CZ193798A3 (cs) 1998-12-16
ATE223958T1 (de) 2002-09-15
CA2240882C (en) 2001-08-21
CA2240882A1 (en) 1997-06-26
CN1209162A (zh) 1999-02-24
WO1997022679A1 (en) 1997-06-26
DE69528182T2 (de) 2003-04-30

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