WO1992020773A1 - Composition nettoyante - Google Patents

Composition nettoyante Download PDF

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Publication number
WO1992020773A1
WO1992020773A1 PCT/US1992/003426 US9203426W WO9220773A1 WO 1992020773 A1 WO1992020773 A1 WO 1992020773A1 US 9203426 W US9203426 W US 9203426W WO 9220773 A1 WO9220773 A1 WO 9220773A1
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WO
WIPO (PCT)
Prior art keywords
weight
surfactant
oil
composition
carbons
Prior art date
Application number
PCT/US1992/003426
Other languages
English (en)
Inventor
Patrick C. Hu
Raynold Corona
Edward F. Zaweski
Jennifer C. Lewis
Original Assignee
Ethyl Corporation
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 Ethyl Corporation filed Critical Ethyl Corporation
Publication of WO1992020773A1 publication Critical patent/WO1992020773A1/fr

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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
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C11D17/0021—Aqueous microemulsions

Definitions

  • This invention relates to cleaning compositions having improved effectiveness in removing oily soils from substrates.
  • compositions for removing oily soils from laundry, floors, wall tiles, ovens, dishes, and other substrates There are many known compositions for removing oily soils from laundry, floors, wall tiles, ovens, dishes, and other substrates.
  • the cleaning compositions that were used to effect the soil removal were either surfactant solutions or ordinary emulsions, such as the two-phase laundry prespotting composition of U. S. Patent 4,749,516 (Brusky).
  • surfactant solutions or ordinary emulsions such as the two-phase laundry prespotting composition of U. S. Patent 4,749,516 (Brusky).
  • micro- emulsion cleaning compositions have also been employed.
  • microemulsion cleaning compositions include those of U. S. Patent 4,919,839 (Durbut et al.), U. K. Patent Application 2,190,681 (Loth et al.-I), and European Patent Applications 0316726 (Loth et aL-H) and 0368146 (Loth et al.- ⁇ ).
  • microemulsions have been discovered to be more effective cleaners than surfactant solutions or ordinary emulsions. However, it would be desirable to find cleaning compositions which would be even more effective than the known microemulsion cleaning compositions.
  • novel cleaning compositions of the invention are oil-absorbent microemulsion cleaning compositions which have a surfactant content of at least 2% by weight and a mimmum oil absorbency of 0.2% by weight, spontaneously emulsify oil which is contacted therewith until no more oil can be absorbed, and then provide an interfacial tension not higher than 0.1 erg/cm 2 in contact with any excess oil.
  • the cleaning compositions of the invention are microemulsions which remove soil from substrates by the mechanism of spontaneous emulsification - a mechanism which is more efficient than the roll-up mechanism by which most conventional cleaning compositions remove soil. They are more effective cleaners than known microemulsion cleaning compositions because of their providing spontaneous emulsification (i.e., emulsification that occurs without input of energy such as shaking, mixing, or other form of agitation) and a much lower interfacial tension when contacted with excess oil, i.e., an amount of oil exceeding the amount that is spontaneously absorbed thereby.
  • spontaneous emulsification i.e., emulsification that occurs without input of energy such as shaking, mixing, or other form of agitation
  • excess oil i.e., an amount of oil exceeding the amount that is spontaneously absorbed thereby.
  • compositions may have any components which, in combination with the surfactant, provide that spontaneous emulsification and low interfacial tension. However, most commonly, they comprise 2-35%, preferably 3-25% by weight of a surfactant; 0-35%, preferably 0-10% by weight of a co-surfactant; 0.5-20%, preferably 1-15% by weight of an electrolyte; 0.5-45%, preferably 1-40% by weight of an oil; and 15-95%, preferably 40-90% by weight of water.
  • the surfactant used to prepare a cleaning composition of the invention should ordinarily be a surfactant having an HLB number of 3-16, preferably 4-15; and it may be composed of one or more surfactants selected from anionic, cationic, nonionic, and amphoteric surfactants.
  • Exemplary of utilizable surfactants are:
  • anionic surfactants such as the sodium, potassium, calcium, barium, magnesium, ammonium, and hydroxyalkylammonium sulfonates, s ulfates, carboxylates, phosphates, sulfosuccinates, and other succinate derivatives containing an organic hydrophobic moiety of 8-26 carbons, preferably 10-18 carbons, such as the fatty acid soaps, N-acylsarcosinates, alkylbenzenesulfonates, ⁇ -olefinsulfonates, alcohol sulfates, ethoxylated alcohol s ulfates, and ethoxylated alkylphenol sulfates,
  • anionic surfactants such as the sodium, potassium, calcium, barium, magnesium, ammonium, and hydroxyalkylammonium sulfonates, s ulfates, carboxylates, phosphates, sulfosuccinates, and other succinate derivatives containing an organic
  • cationic surfactants such as dodecyldimethylammonium chloride and other quaternary ammonium, phosphonium, and sulfonium halides, acetates, and nitrites, containing a detergent-range hydrophobic moiety
  • nonionic surfactants such as alcohol ethoxylates, alkylphenol ethoxylates, carboxylic acid esters, glycerol esters, polyoxyethylene esters of fatty acids, anhydrosorbitol esters, ethoxylated anhydrosorbitol esters, glycol esters of fatty acids, fatty acid diethanolamides and monoalkanolamides, polyoxyethylene fatly acid amides, ethylene oxide-propylene oxide copolymers, and tert-amine oxides, and
  • amphoteric surfactants such as tetradecyldimethylbetaine, hexadecyldimethylbetaine, and other alkyldimethylbetaines in which the alkyl group contains 12-18 carbons.
  • the surfactants which are apt to be preferred are those comprising or consisting of an anionic surfactant, especially when the anionic surfactant is a sulfate, sulfonate, or phosphate in which the lipophilic portion of the molecule corresponds to one of the formulas:
  • R"CH CR(CH 2 ) m (OCH 2 CH 2 ) n - wherein R and R' represent alkyl groups containing at least six carbons, generally 6-20 carbons; R" is an alkyl group containing at least five carbons, generally 5-20 carbons; m is 1 or 2; and n is 0 or an integer of 1-20.
  • These preferred surfactants include, e.g., the sodium, potassium, and ammonium sulfates, sulfonates, and phosphates in which the lipophilic moiety is 3-hexylundecyl . 2-hexyldecyl, or 3,6,9-trioxa-12-hexyleicosyl (also designated as ⁇ -(3- hexylundecy trioxyethylene).
  • a co-surfactant is sometimes needed to enhance the formation of a microemulsion and modify the rheological properties of the system.
  • a co-surfactant is ordinarily an organic compound having a water solubility of 0.1-50% by weight.
  • the preferred co-surfactants are butanol and 2-hexoxy- ethanol.
  • alcohols, ethoxylated ethers of alcohols and alkylphenols, glycols, glycol ethers, amines, amides, and organic halides are also utilizable, e.g., carbon tetrachloride, methylene chloride, hexylamine, N-methyl-2-pyrrolidone, hexanol, ethylene glycol, diethylene glycol, 3-(3-met ⁇ oxypropoxy)propanol, and an ethoxylated nonylphenol containing three ethoxy groups.
  • the co-surfactant which is preferred in any instance is apt to be the one that will enhance the formation of a microemulsion and modify the rheological properties of the system at the minimum expense.
  • a different co-surfactant such as the known usefulness of chlorinated hydrocarbons in cleaning compositions, might make that co-surfactant or a mixture containing it preferable to a co-surfactant which could accomplish the desired modification of properties at a lower cost.
  • Electrolytes utilizable inpreparing the cleaning compositions include acids, bases, and salts but are usually alkali metal or alkaline earth metal salts (especially the sodium, potassium, barium, calcium, and magnesium salts) or ammonium salts wherein the anion may be inorganic (e.g., halide, hypochlorite, perchlorite, hydroxide, bicarbonate, carbonate, bisulfite, sulfate, sulfonate, nitrate, phosphate, tripolyphosphate, pyrophosphate, or nitrilotriacetate) or organic (e.g., acetate, citrate, polycarboxylate, ethylenecUaminetetraacetate, or carboxymethoxy- succinate).
  • alkali metal or alkaline earth metal salts especially the sodium, potassium, barium, calcium, and magnesium salts
  • ammonium salts wherein the anion may be inorganic (e.g., halide, hypochlorite
  • an electrolyte having bleaching capabilities such as calcium hypochlorite or sodium bisulfite, can have particular value in the cleaning compositions as the sole electrolyte or as a component of an electrolyte mixture.
  • the oils which are used in the cleaning compositions are generally hydrocarbon oils containing 10-60 carbons, although ester and ether oils are also utilizable.
  • oils include, e.g., fatty oils, polyalphaolefins, rapeseed oil, sunflower oil, other triglyceride oils, essential oils, mineral oils, isoparaffinic hydrocarbons, low-odor petroleum solvent having a boiling range of 195-250 ° C, kerosene, pine oil, naphtha, perfume oils, such as those containing terpenes, and other oily materials.
  • the nature of the oil in the microemulsion determines the amount of oily soil that can be absorbed by the composition - larger amounts of oil being absorbable by microemulsions containing an oil which is the same as or very similar to the oily soil to be absorbed.
  • a cleaning composition when a cleaning composition is being formulated for the treatment of a particular type of oily soil, it is preferred to use the same oil or a similar oil in preparing the microemulsion in order to obtain optimum results.
  • adequate cleaning can frequently be achieved with the microemulsions containing different types of oils, especially when the amount of oily soil to be absorbed is low and/or a larger amounts of microemulsion is used.
  • micromeulsions of the invention In the preparation of the micromeulsions of the invention, it is important to appreciate that it is insufficient merely to combine water with the ingredients described above to provide compositions having the aforementioned proportionation of ingredients. Most of the microemulsions thus prepared would be compositions which, like those specifically taught by Durbut et al., would provide interfacial tensions much higher than 0.1 erg/cm 2 , e.g., 1-20 erg/cm 2 , when contacted with excess oil (i.e., more oil than can be spontaneously absorbed) and accordingly would lack the improved cleaning ability of the novel microemulsions.
  • a convenient way of determining the proportions of ingredients to use in preparing a microemulsion of the invention is to (1) choose the particular ingredients which it is desired to employ, (2) add an equal volume of the oil to an aqueous solution of the surfactant and any co-surfactant in order to form a two- phase system, (3) add the electrolyte incrementally until sufficient surfactant has been pushed from the aqueous phase to result in the formation of a surfactant-rich middle-phase microemulsion, (4) analyze the composition of the middle phase, (5) recombine all of the ingredients of the middle phase except for the oil, and (6) incrementally add the oil until the composition contains sufficient oil for a microemulsion to be formed.
  • the microemulsion prepared by this technique is an oil-absorbent microemulsion that provides the desired low interfacial tension when contacted with excess oil, and it retains those characteristics even when the amount of oil used in its preparation is somewhat more than the amount barely enough to result in the formation of a microemulsion.
  • the microemulsions of the invention can be used in neat form (but, unlike the Durbut et al.
  • compositions only occasionally in dilute form) to remove oily soil from laundry, floors, wall tiles, ovens, dishes, and other surfaces; and they may be applied by means of a sponge or cloth or by soaking. Also, they may be modified by the inclusion of minor amounts of additives, such as the dyes, perfumes, and preservatives frequently used in cleaning compositions.
  • the microemulsions are used as spot remover formulations to be applied to laundry prior to washing - an application in which they have been found to be superior to a commercial composition which is sold for this purpose.
  • microemulsions were prepared by (1) adding an equal volume of mineral oil to an aqueous solution of a surfactant and co-surfactant in order to form a two-phase system, (2) adding an electrolyte incrementally until sufficient surfactant has been pushed from the aqueous phase to result in the formation of a surfactant-rich middle-phase microemulsion, (3) analyzing the composition of the middle phase, (4) recombining all of the ingredients of the middle phase except for the oil, and (5) incrementally adding the oil until the composition contained sufficient oil for a microemulsion to be formed.
  • the compositions of the microemulsions thus formed are shown below.
  • Each of these emulsions had an oil absorbency of at least 0.2%, spontaneously emulsified oil in contact therewith until no more oil could be absorbed, and then provided an interfacial tension not higher than 0.1 erg/cm 2 in contact with excess oil.
  • the oil absorbency was determined by adding incremen ⁇ tal amounts of mineral oil to the formulations, providing minimal agitation to accelerate the evaluation of the microemulsion efficacy.
  • the maximum oil absorbency was determined at the point that the isotropic im ⁇ o-emulsion converted to a turbid system.
  • microemulsion of the invention is significantly better than the commercial formulation in removing oily soil by pre- wash application.

Abstract

On améliore l'efficacité de nettoyage d'une composition nettoyante en micro-émulsion en la formulant de façon qu'elle contienne au moins 2 % en poids d'un agent tensioactif, qu'elle puisse absorber au moins 0,2 % en poids d'huile par formation spontanée d'une émulsion lorsqu'elle est placée en contact avec l'huile, et qu'elle présente une tension interfaciale inférieure ou égale à 0,1 erg/cm2 lorsqu'elle entre en contact avec une quantité d'huile supérieure à celle qu'elle peut absorber. Les compositions de l'invention contiennent généralement entre 2 et 35 % en poids d'un agent tensioactif, entre 0 et 35 % en poids d'un co-tensioactif, entre 0,5 et 20 % en poids d'un électrolyte, entre 0,5 et 45 % en poids d'une huile et entre 15 et 95 % en poids d'eau.
PCT/US1992/003426 1991-05-10 1992-04-24 Composition nettoyante WO1992020773A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US69854091A 1991-05-10 1991-05-10
US698,540 1991-05-10

Publications (1)

Publication Number Publication Date
WO1992020773A1 true WO1992020773A1 (fr) 1992-11-26

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PCT/US1992/003426 WO1992020773A1 (fr) 1991-05-10 1992-04-24 Composition nettoyante

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0684300A2 (fr) * 1994-05-27 1995-11-29 Unilever Plc Composition tensio-active et composition de nettoyage la contenant
EP0706371A1 (fr) * 1993-06-28 1996-04-17 The Procter & Gamble Company Compositions detergentes liquides a faible pouvoir moussant
WO1997000843A1 (fr) * 1995-06-20 1997-01-09 Albemarle Corporation Composes a chaine ramifiee et leur utilisation
WO2005042689A1 (fr) * 2003-10-20 2005-05-12 Unilever N.V. Composition de microemulsion amelioree

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1302430A (fr) * 1960-05-10 1962-08-31 Exxon Research Engineering Co Produits d'addition de l'oxyde d'éthylène et d'alcools supérieurs et leurs sulfates
US3786003A (en) * 1971-11-04 1974-01-15 Shell Oil Co Liquid detergent compositions
EP0072488A1 (fr) * 1981-08-14 1983-02-23 S.C. Johnson & Son, Inc. Composition de pré-détachage du linge à faible teneur de solvant
GB2144763A (en) * 1983-08-11 1985-03-13 Procter & Gamble Liquid detergent compositions with magnesium salts
EP0160762A1 (fr) * 1984-04-07 1985-11-13 The Procter & Gamble Company Microémulsion de nettoyage huile dans l'eau stabilisées
GB2190681A (en) * 1986-05-21 1987-11-25 Colgate Palmolive Co Microemulsion all-purpose liquid cleaning composition
US4749516A (en) * 1985-09-24 1988-06-07 S. C. Johnson & Son, Inc. Anionic emulsion pre-spotting composition
EP0316726A2 (fr) * 1987-11-12 1989-05-24 Colgate-Palmolive Company Composition de nettoyage stable sous forme de microémulsion
US4919839A (en) * 1989-02-21 1990-04-24 Colgate Palmolive Co. Light duty microemulsion liquid detergent composition containing an aniocic/cationic complex
EP0368146A2 (fr) * 1988-11-07 1990-05-16 Colgate-Palmolive Company Composition détergente sous forme de microémulsion stable
EP0418986A2 (fr) * 1989-09-22 1991-03-27 Colgate-Palmolive Company Procédé pour absorber une souillure lipophile d'une surface dans une composition détergente de cristaux liquides

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1302430A (fr) * 1960-05-10 1962-08-31 Exxon Research Engineering Co Produits d'addition de l'oxyde d'éthylène et d'alcools supérieurs et leurs sulfates
US3786003A (en) * 1971-11-04 1974-01-15 Shell Oil Co Liquid detergent compositions
EP0072488A1 (fr) * 1981-08-14 1983-02-23 S.C. Johnson & Son, Inc. Composition de pré-détachage du linge à faible teneur de solvant
GB2144763A (en) * 1983-08-11 1985-03-13 Procter & Gamble Liquid detergent compositions with magnesium salts
EP0160762A1 (fr) * 1984-04-07 1985-11-13 The Procter & Gamble Company Microémulsion de nettoyage huile dans l'eau stabilisées
US4749516A (en) * 1985-09-24 1988-06-07 S. C. Johnson & Son, Inc. Anionic emulsion pre-spotting composition
GB2190681A (en) * 1986-05-21 1987-11-25 Colgate Palmolive Co Microemulsion all-purpose liquid cleaning composition
EP0316726A2 (fr) * 1987-11-12 1989-05-24 Colgate-Palmolive Company Composition de nettoyage stable sous forme de microémulsion
EP0368146A2 (fr) * 1988-11-07 1990-05-16 Colgate-Palmolive Company Composition détergente sous forme de microémulsion stable
US4919839A (en) * 1989-02-21 1990-04-24 Colgate Palmolive Co. Light duty microemulsion liquid detergent composition containing an aniocic/cationic complex
EP0418986A2 (fr) * 1989-09-22 1991-03-27 Colgate-Palmolive Company Procédé pour absorber une souillure lipophile d'une surface dans une composition détergente de cristaux liquides

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0706371A1 (fr) * 1993-06-28 1996-04-17 The Procter & Gamble Company Compositions detergentes liquides a faible pouvoir moussant
EP0706371A4 (fr) * 1993-06-28 1996-04-24
EP0684300A2 (fr) * 1994-05-27 1995-11-29 Unilever Plc Composition tensio-active et composition de nettoyage la contenant
EP0684300A3 (fr) * 1994-05-27 1999-08-04 Unilever Plc Composition tensio-active et composition de nettoyage la contenant
WO1997000843A1 (fr) * 1995-06-20 1997-01-09 Albemarle Corporation Composes a chaine ramifiee et leur utilisation
WO2005042689A1 (fr) * 2003-10-20 2005-05-12 Unilever N.V. Composition de microemulsion amelioree

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