WO2015067438A1 - Composition pour le nettoyage de surfaces dures - Google Patents

Composition pour le nettoyage de surfaces dures Download PDF

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Publication number
WO2015067438A1
WO2015067438A1 PCT/EP2014/071903 EP2014071903W WO2015067438A1 WO 2015067438 A1 WO2015067438 A1 WO 2015067438A1 EP 2014071903 W EP2014071903 W EP 2014071903W WO 2015067438 A1 WO2015067438 A1 WO 2015067438A1
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WO
WIPO (PCT)
Prior art keywords
fatty acid
composition
surface cleaning
weight
hard surface
Prior art date
Application number
PCT/EP2014/071903
Other languages
English (en)
Inventor
Sumanth Kumar ARNIPALLY
Punam Bandyopadhyay
Anshul Gupta
Suresh Murigeppa Nadakatti
Original Assignee
Unilever N.V.
Unilever Plc
Conopco, Inc., D/B/A Unilever
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 Unilever N.V., Unilever Plc, Conopco, Inc., D/B/A Unilever filed Critical Unilever N.V.
Publication of WO2015067438A1 publication Critical patent/WO2015067438A1/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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid compositions
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates
    • 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

Definitions

  • the present invention is in the field of hard surface cleaning compositions. It particularly relates to a composition in the form of a paste for superior soil removal from hard surfaces.
  • Hard surfaces are generally cleaned using liquid compositions or pastes.
  • the cleaning compositions may be applied in diluted or undiluted form, in a spray, or rubbed using a cloth and any other convenient way.
  • the cleaning composition may be rinsed from the surface after the cleaning.
  • hard surface cleaning compositions typically comprise one or more surfactants and they often contain one or more abrasives dispersed therein. Combinations of these together with electrolytes are generally used to form a suspending system as is well known in the art.
  • the surfactants are generally chosen to be anionic, nonionic, cationic, or zwitterionic.
  • One or more surfactants selected from amongst primary alcohol sulphates, alkyl benzene sulphonates, alcohol ethoxylates, alkyl ether sulphates, fatty acid soaps and secondary alkyl sulphonates are most commonly employed. Present day consumers appreciate if a surface could be made easier to clean, after deposition of soil or stains. Tough soil removal remains to be desired.
  • Soils on hard surfaces can become more difficult to remove if not cleaned soon after deposition. When not cleaned promptly, soils can become more adherent to surfaces, more sticky and generally tougher, and require more effort to clean. While not being bound by theory, this more difficult removal of soils can arise from the effects of drying out of soils, from chemical changes in soils, from reactions of soils with environmental agents such as oxygen, etc. Some soils are more susceptible than others to toughening reactions and processes. Soils comprising or containing chemically unsaturated oils and fats can become very tough and difficult to clean over time, especially when exposed to elevated temperatures. Even light can cause such fatty soils to toughen over time. As well as environmental factors, the processes of toughening of soils can be affected by the nature and composition of the surface on which the soil is located.
  • IN 204326 discloses the selective use of anionic surfactant that has been neutralised using one or more minerals from the dolomites group thereby resulting in a dolomite salt of the corresponding anionic surfactant ⁇ e.g., neutralisation of linear alkyl benzenesulphonic acid (LAS acid) resulted in dolomites-LAS (DoLAS)), either alone or in combination with other surfactants in cleaning compositions, gives significantly superior soil removal from hard surfaces or fabric as compared to the formulations with other conventional surfactants.
  • anionic surfactant that has been neutralised using one or more minerals from the dolomites group thereby resulting in a dolomite salt of the corresponding anionic surfactant ⁇ e.g., neutralisation of linear alkyl benzenesulphonic acid (LAS acid) resulted in dolomites-LAS (DoLAS)), either alone or in combination with other surfactants in cleaning compositions, gives significantly superior soil removal from hard surfaces or fabric as compared to the formulations with other conventional surfactants.
  • Hard surface cleaning compositions in the form of pastes or liquids which provide superior soil removal from hard surfaces remain to be desired.
  • a stable hard surface cleaning composition in the form of a paste with no grittiness and having a superior soil removal from hard surfaces can be obtained by the addition of one or more of fatty acid or fatty acid esters or a mixture thereof to an anionic surfactant that has been obtained by neutralisation of the precursor using at least one dolomite.
  • the present invention provides a hard surface cleaning composition
  • a hard surface cleaning composition comprising 0.5 to 40% by weight of one or more surfactants wherein at least 50% of the total surfactant is anionic that has been obtained by neutralising an acid precursor with one or more minerals from the dolomites group; 1 to 8% by weight of one or more of fatty acid or fatty acid esters or mixtures thereof and water.
  • the invention provides a process for preparing a hard surface cleaning composition comprising the steps in sequence of adding water to the acid precursor, neutralizing at least 50% of the acid precursor of an anionic surfactant with one or more minerals from the dolomites group, neutralizing any further precursor acid and optionally adding other surfactants; and adding fatty acid/fatty acid esters to the above mix.
  • the invention provides the use of an surfactant system wherein at least 50% of the total surfactant is anionic that has been obtained by neutralizing the acid precursor with one or more minerals from the dolomites group; and one or more of fatty acid or fatty acid esters or mixtures thereof for improved tough soil removal from hard surfaces.
  • a hard surface cleaning composition has been described herein which essentially comprises an anionic surfactant that has been obtained by neutralisation of the precursor using at least one dolomite, one or more of fatty acid or fatty acid esters or mixtures thereof; and water.
  • the hard surface may be any household or industrial hard surface, but household surfaces are specifically considered. Typical hard surfaces includes glass, tiles and other ceramic materials, metal surfaces, polished stones and polished concrete; more preferably includes stone or concrete kitchen tops, glass window and cooker tops, and tiles.
  • composition according to the invention will essentially comprise an anionic surfactant that has been obtained by neutralisation of an acid precursor with at least one dolomite, which may be combined with other surfactants generally chosen from alkali or alkaline earth metal, alkanolamine or ammonium salts of anionic surfactants and/or nonionic, cationic, amphoteric or zwitterionic detergent surfactants.
  • Suitable anionic detergent surfactants are water soluble salts of organic sulphuric reaction products having in the molecular structure an alkyl radical containing from 8 to 22 carbon atoms, and a radical chosen from sulphonic acid or sulphuric acid ester radicals and mixtures thereof.
  • the preferred water-soluble synthetic anionic detergent surfactant compounds are higher alkyl benzene sulphonates and mixtures with olefin sulphonates and higher alkyl sulphates, and the higher fatty acid monoglyceride sulphates obtained by neutralisation of the precursor using at least one dolomite.
  • the more preferred anionic detergent surfactant compounds are higher alkyl aromatic sulphonates such as higher alkyl benzene sulphonates containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are higher alkyl benzene sulphonates or of higher-alkyl toluene, xylene or phenol sulphonates, alkyl naphthalene sulphonates, diamyl naphthalene sulphonate, and dinonyl naphthalene sulphonate obtained by neutralisation of the precursor using at least one dolomite.
  • higher alkyl aromatic sulphonates such as higher alkyl benzene sulphonates containing from 6 to 20 carbon atoms in the alkyl group in a straight or branched chain, particular examples of which are higher alkyl benzene sulphonates or of higher-alkyl toluene,
  • the anionic surfactant is present in the composition in a concentration of upto 40% by weight, preferably at least 0.5%, more preferably at least 3% or even at least 5% by weight, but typically not more than 35%, still more preferably not more than 30% or even not more than 25% by weight wherein at least 50%, preferably at least 60%, more preferably at least 70%, still more preferably at least 80% but typically not more than 90% of the total surfactant is anionic obtained by neutralisation of the precursor using at least one dolomite.
  • Dolomite according to the invention refers to minerals with an unusual trigonal bar 3 symmetry and with the general formula AB(C03) 2, where A can be either calcium, barium, and/or strontium and B can be iron, magnesium, zinc and/or manganese. It is preferred that A is calcium and B is magnesium.
  • the dolomites can be selected from the naturally occurring materials such as Ankerite Ca(Fe, Mg, Mn) (C03) 2 , Benstonite (Ba, Sr) 6 (Ca, Mn) 6 Mg(C03) 13 , Dolomite
  • CaMg(C03) 2 and Huntite CaMg3(C03) 4 It is particularly preferred to use Dolomite.
  • Suitable nonionic detergent surfactant compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Particular examples include the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in either straight or branched chain configuration with ethylene oxide, such as a coconut oil ethylene oxide condensate having from 2 to 15 moles of ethylene oxide per mole of coconut alcohol; condensates of alkylphenols whose alkyl group contains from 6 to 12 carbon atoms with 5 to 25 moles of ethylene oxide per mole of alkylphenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, the condensate containing from 40 to 80% of polyoxyethylene radicals by weight and having a molecular weight of from 5,000 to 1 1 ,000; tertiary amine oxides of structure R 3 NO, where one group R is an alkyl group of 8 to 18 carbon atoms and the others are each methyl, ethyl or hydroxyethyl groups, for instance dimethyldodecylamine oxide; tertiary phosphine oxides
  • dimethyldodecylphosphine oxide dimethyldodecylphosphine oxide
  • fatty acid alkylolamides alkylene oxide condensates of fatty acid alkylolamides and alkyl mercaptans.
  • the nonionic surfactants can also be selected from a range of alkyl poly glucosides.
  • the amount of nonionic detergent surfactant to be employed in the detergent composition of the invention will generally be from 0.5 to 15% weight of the total surfactant, preferably from 5 to 10% by weight of the total surfactant.
  • the non-ionic surfactant is in a concentration of 0.5 to 15% by weight, preferably from 5 to 10% by weight of the total surfactant. It is also possible optionally to include amphoteric, cationic or zwitterionic detergent surfactants in the compositions according to the invention.
  • Suitable amphoteric detergent-surfactant compounds that optionally can be employed are derivatives of aliphatic secondary and tertiary amines containing an alkyl group of 8 to 18 carbon atoms and an aliphatic radical substituted by an anionic water-solubilizing group, for instance sodium 3-dodecylamino-propionate, sodium 3- dodecylaminopropane sulphonate and sodium N-2-hydroxydodecyl-N-methyltaurate.
  • Suitable cationic detergent-surfactant compounds are quaternary ammonium salts having an aliphatic radical of from 8 to 18 carbon atoms, for instance cetyltrimethyl ammonium bromide.
  • Suitable zwitterionic detergent-surfactant compounds that optionally can be employed are derivatives of aliphatic quaternary ammonium, sulphonium and phosphonium compounds having an aliphatic radical of from 8 to 18 carbon atoms and an aliphatic radical substituted by an anionic water-solubilising group, for instance 3-(N-N-dimethyl- N-hexadecylammonium) propane-1 -sulphonate betaine, 3-(dodecylmethyl sulphonium) propane-1 -sulphonate betaine and 3-(cetylmethylphosphonium) ethane sulphonate betaine.
  • anionic water-solubilising group for instance 3-(N-N-dimethyl- N-hexadecylammonium) propane-1 -sulphonate betaine, 3-(dodecylmethyl sulphonium) propane-1 -sulphonate betaine and 3-(cetylmethylphosphonium) ethane
  • detergent-surfactant compounds are compounds commonly used as surface-active agents given in the well-known textbooks "Surface Active Agents” Vol. 1 , by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, and/or the current edition of "McCutcheon's
  • Emulsifiers and Detergents published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .
  • composition according to the invention comprises a fatty acid or fatty acid esters.
  • the fatty acid is a C4-C28 fatty acid, preferably C8-C24 fatty acid, more preferably C10-C20 fatty acid. Particularly preferred is C12-C18 fatty acid.
  • Preferred fatty acid esters are alkyl esters of fatty acids.
  • Non-limiting examples of fatty acid esters that can be used according to the present invention include methyl laurate.
  • the fatty acid or fatty acid esters may be present in a concentration of 1 to 8%, preferably not less than 2%, more preferably not less than 4%, still more preferably not less than 5% but typically not more than 7.5%, preferably not more than 7% or even not more than 6% by weight of the total composition.
  • the composition further comprises water adding upto a 100% by weight of the total composition, preferably 15 to 98%, more preferably not less than 20%, still more preferably not less than 30% but typically not more than 80%, more preferably not more than 70%, still more preferably not more than 60% or even not more than 40% by weight of the composition. It is found that higher concentrations of water in the composition results in syneresis problem.
  • composition according to the invention can contain other ingredients that aid in their cleaning performance.
  • the composition can contain detergent builders other than the special water-soluble salts such as nitrilotriacetates, polycarboxylates, citrates, dicarboxylic acids, water-soluble phosphates especially polyphosphates, mixtures of ortho- and pyrophosphates, zeolites and mixtures thereof.
  • Such builders can additionally function as abrasives if present in an amount in excess of their solubility in water.
  • Composition according to the invention can also contain a particulate abrasive phase.
  • the particulate phase comprises a particulate abrasive which is insoluble in water.
  • the abrasive may be soluble and present in such excess to any water present in the composition that the solubility of the abrasive in the aqueous phase is exceeded and consequently solid abrasive exists in the composition.
  • Suitable abrasives are selected from, particulate zeolites, calcites, dolomites, feldspar, silicas, silicates, other carbonates, aluminas, bicarbonates, borates, sulphates and polymeric materials such as polyethylene.
  • Preferred abrasives for use in general purpose compositions have a Moh hardness of 2 to 7 although higher hardness abrasives can be employed for specialist applications.
  • Preferred average particle sizes for the abrasive fall in the range 0.5 to 400 microns, preferably 10 to 200 microns.
  • the abrasives other than the special water-soluble salts when employed preferably will form from 30 to 85 wt% by weight of the composition.
  • Composition according to the invention can also contain, in addition to the ingredients already mentioned, various other optional ingredients such as structurants, colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly hypohalites), and preservatives.
  • various other optional ingredients such as structurants, colourants, whiteners, optical brighteners, soil suspending agents, detersive enzymes, compatible bleaching agents (particularly hypohalites), and preservatives.
  • the hard surface cleaning composition according to the invention is prepared by first mixing an acid precursor of an anionic surfactant with water to facilitate neutralization reaction. A Dolomite mineral is then added to the slurry of acid precursor and mixed for 10 min in order to achieve complete neutralization. Completion of the reaction was confirmed by checking pH of the mix. A fatty acid or fatty acid ester is added to the mix after completion of acid precursor-Dolomite neutralization. Subsequently, the optional ingredients like china clay, structurants, colorants, perfume etc are added and processed in a conventional manner.
  • the treatment procedure according to the invention comprises application of the paste in concentrated form contained in Bottles, trigger dispensers, trays, wipes, by spreading uniformly over the surface.
  • the paste is left on the surface for some time and then rinsed or wiped with a tissue paper/cloth till completely dry.
  • the dried treated surface is observed to show superior soil removal.
  • composition may be applied diluted from the bottle or through a trigger dispenser, or by application with a wet cloth.
  • Acid precursor LAS acid (ex Reliance LAS )
  • Dolomite mineral Dolomite
  • the measure of grittness was done through the observation of solid granules while smearing the paste on a petridish. The sample where solid granules were observed was rated as “Yes” and in case of smooth paste without any solid granules was rated as "No” on grittness.
  • Example 1 Effect of concentration of methyl laurate on grittiness and phase
  • Ex1 to Ex5 are example compositions according to the present invention which are compared to Comp A (Comparative example) with no methyl laurate.
  • Example 2 Effect of concentration of dolomite LAS on grittiness and phase separation In this example, different concentrations of dolomite LAS are compared.
  • Ex6 to Ex9 example compositions according to the present invention are compared.
  • Example 3 Effect of a higher concentration of dolomite LAS on grittiness and phase separation
  • Ex10 and Ex1 1 are example compositions according to the present invention which are compared to Comp B (Comparative example) with no methyl laurate.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention porte sur le domaine des compositions de nettoyage de surfaces dures. Elle concerne en particulier une composition sous la forme d'une pâte pour une meilleure élimination des salissures de surfaces dures. Des compositions pour le nettoyage de surfaces dures sous forme de pâtes ou de liquides assurant une meilleure élimination des salissures des surfaces dures ne sont pas encore disponibles. Un objet de la présente invention consiste donc à fournir une composition pour le nettoyage de surfaces dures sous la forme d'une pâte n'ayant pas une structure granuleuse, et ne présentant pas de séparation des phases dans le temps, assurant une meilleure élimination des salissures des surfaces dures. On a constaté qu'une composition stable de nettoyage des surfaces dures, sous la forme d'une pâte n'ayant pas de structure granuleuse et assurant une meilleure élimination des salissures des surfaces dures, peut être obtenue par addition d'un ou plusieurs acides gras ou esters d'acides gras, ou mélanges de ceux-ci, à un tensioactif anionique qui a été obtenu par neutralisation d'un précurseur acide avec au moins une dolomite.
PCT/EP2014/071903 2013-11-07 2014-10-13 Composition pour le nettoyage de surfaces dures WO2015067438A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP13191883.1 2013-11-07
EP13191883 2013-11-07

Publications (1)

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WO2015067438A1 true WO2015067438A1 (fr) 2015-05-14

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018091226A1 (fr) * 2016-11-18 2018-05-24 Unilever N.V. Composition aqueuse pour le nettoyage de surfaces dures

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4919847A (en) * 1988-06-03 1990-04-24 Colgate Palmolive Co. Process for manufacturing particulate detergent composition directly from in situ produced anionic detergent salt
WO2008107463A2 (fr) * 2007-03-08 2008-09-12 Unilever Plc Composition de détergent solide et procédé de préparation de celle-ci

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4919847A (en) * 1988-06-03 1990-04-24 Colgate Palmolive Co. Process for manufacturing particulate detergent composition directly from in situ produced anionic detergent salt
WO2008107463A2 (fr) * 2007-03-08 2008-09-12 Unilever Plc Composition de détergent solide et procédé de préparation de celle-ci

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"McCutcheon's Emulsifiers and Detergents", MANUFACTURING CONFECTIONERS COMPANY
H. STACHE: "Tenside-Taschenbuch", 1981, CARL HAUSER VERLAG
SCHWARTZ; PERRY: "Surface Active Agents", vol. 1, 1949, INTERSCIENCE
SCHWARTZ; PERRY; BERCH: "SURFACE ACTIVE AGENTS", vol. 2, 1958, INTERSCIENCE

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018091226A1 (fr) * 2016-11-18 2018-05-24 Unilever N.V. Composition aqueuse pour le nettoyage de surfaces dures

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