WO1994013769A1 - Composition nettoyantes acides auto-epaissies - Google Patents

Composition nettoyantes acides auto-epaissies Download PDF

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Publication number
WO1994013769A1
WO1994013769A1 PCT/US1993/011680 US9311680W WO9413769A1 WO 1994013769 A1 WO1994013769 A1 WO 1994013769A1 US 9311680 W US9311680 W US 9311680W WO 9413769 A1 WO9413769 A1 WO 9413769A1
Authority
WO
WIPO (PCT)
Prior art keywords
compositions
acid
composition according
composition
self
Prior art date
Application number
PCT/US1993/011680
Other languages
English (en)
Inventor
Michel Jean Carrie
Axel Koenig
Eddy Vos
Original Assignee
The Procter & Gamble Company
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
Priority claimed from EP93870120A external-priority patent/EP0601990B1/fr
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to CA002150914A priority Critical patent/CA2150914C/fr
Priority to US08/446,758 priority patent/US5656580A/en
Publication of WO1994013769A1 publication Critical patent/WO1994013769A1/fr

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2082Polycarboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/835Mixtures of non-ionic with cationic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/62Quaternary ammonium compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to cleaning compositions for hard surfaces.
  • the compositions of the present invention are designed for optimum performance in removing limescale and are thickened without the use of a thickener compound.
  • compositions for cleaning hard surfaces including compositions for removing limescale, are well known in the art.
  • Such compositions which are characterized mainly by a strong acidity, are disclosed for instance in EP 496 188.
  • Limescale is mainly found in such places as sinks, toilet bowls and bathtubs, i.e. vertical surfaces. Therefore, it is desirable to give some viscosity to compositions for removing limescale so as to prevent said compositions from running down said vertical surfaces. Indeed thick compositions cling to vertical surfaces, thus they have more time to act on vertical surfaces before they run down said surfaces. It is however undesirable to use thickener compounds in such compositions for various reasons. For instance, thickener compounds may significantly raise formula costs. Also, thickeners may create issues relating to processing and product stability, especially in extreme acidic conditions. Furthermore, thickeners may affect the limescale removing performance of the composition. Finally, thickeners do not contribute to the cleaning performance of the composition.
  • compositions according to the present invention have the advantage that the use of the quaternary ammonium salts cationic surfactants described hereinafter in combination with an acid provides significant disinfectancy benefits. This advantage is particularly useful in a composition which is meant to be used primarily on bathroom and kitchen surfaces.
  • GB 2 071 688 teaches that quaternary ammonium salts can be used to thicken an acidic solution, provided they are combined with an amine or amine oxide.
  • nonionic surfactants are presented as an alternative to the quaternary ammonium salts.
  • EP 188 205 teaches that quaternary ammonium salts can be used to thicken an acidic solution, provided they are combined with a strong mineral acid.
  • compositions according to the present invention are aqueous compositions comprising an acid whereby the pH as is of said compositions is of from 0.1 to 4.5, said compositions further comprising a thickening system whereby said compositions are stable and have a viscosity of from
  • said thickening system comprises from 0.5% to 15% by weight of the total composition of a mixture of a nonionic surfactant with a cationic surfactant according to the formula R 1 R 2 R 3 R 4 N + X-, wherein X is a counteranion, R 1 is a C 12-20 hydrocarbon chain and R 2 , R 3 and R 4 are independently selected from H or C 1-4 hydrocarbon chains.
  • compositions of the present invention are designed for removing limescale or soils comprising limescale as a main component.
  • they comprise, as a first essential ingredient, an organic or inorganic acid, or mixtures thereof.
  • Appropriate acids for use herein are disclosed for instance in EP 411 708, EP 496 188, GB 2 106 927, EP 200 776, and EP 336 878.
  • acids are suitable for use herein from a pure performance viewpoint, it is preferred to avoid the use of strong inorganic acids such as phosphoric acid or HCl, for environmental reasons and for surface safety.
  • Preferred for use herein are organic acids or mixtures thereof.
  • compositions according to the present invention comprise from 0.1% to 45% by weight of the total composition of an acid or mixtures thereof, preferably from 4% to 25%.
  • the compositions according to the present have a pH as is of from 0.1 to 4.5, preferably 0.5 to 2.0, most preferably about 1.0.
  • compositions according to the present invention comprise a thickening system which consists of a mixture of certain cationic surfactants with nonionic surfactants.
  • compositions according to the present invention are free of a thickener compound, i.e. a compound which has the sole purpose of thickening the composition.
  • the suitable cationic surfactants for use herein are according to the formula R 1 R 2 R 3 R 4 N + X-, wherein X is a counteranion, R 1 is a C 12-20 hydrocarbon chain and R 2 , R 3 and R 4 are independently selected from H or C 1-4 hydrocarbon chains.
  • R 1 is a C 14-18 hydrocarbon chain, most preferably C 16 or C 18
  • R 1 , R 2 and R 3 are all three methyl
  • X is halogen, preferably bromide or chloride, most preferably bromide. It is also possible to use mixtures of such cationic surfactants without departing from the spirit of the present invention.
  • Suitable nonionic surfactants for use herein include compounds having the general formula RA(CH 2 CH 2 CH 2 O) m (CH 2 CH 2 O) n H, wherein R represents a hydrophobic moiety, A represents a group carrying a reactive hydrogen atom, m represents the average number of propylene oxide moieties and n represents the average number of ethylene oxide moieties. These compounds are typically obtained by condensing ethylene oxide and/or propylene oxide with a hydrocarbon having a reactive hydrogen, e.g. a hydroxyl, carboxyl, or amido group, in the presence of an acidic or basic catalyst.
  • the hydrophobic moiety of the nonionic compound can be a primary or secondary, straight or branched alcohol having from about 8 to about 24 carbon atoms, preferably 12 to 18, m is 0 and n varies from 1 to 15.
  • suitable surfactants for use herein are commercially available, for instance from Shell under the trade name Dobanol @ , or from BASF under the trade name Lutensol @ . It is of course possible to use mixtures of different nonionic surfactants without departing from the spirit of the present invention.
  • compositions according to the present invention comprise from 0.5% to 15% by weight of the total composition of said thickening system, preferably from 1% to 8%.
  • the compositions according to the present invention consequently have a viscosity in the range of from 10 cps to 700 cps at 60 RPM at 20°c, preferably from 20 cps to 200 cps, most preferably 30 cps to 60 cps.
  • the selection of the most appropriate thickening system depends on such factors as the target viscosity, the acid concentration and the limescale removal performance target. In mere terms of viscosity, it has been found that using straight alkyl chains in both the cationic and the nonionnc surfactants provides the best viscosity build up.
  • the combination of the cationic surfactant with the nonionic surfactant allows to build viscosity in an aqueous solution of an acid, even a weak organic acid, whereby this system is stable and the limescale removal performance of said viscosified solution is substantially preserved.
  • An appropriate way to proceed in determining a suitable thickening system for a given composition is to start by defining the desired limescale removing performance for said composition, i.e. the type and concentration of acid, and to prepare a corresponding aqueous solution of said acid. Then various combinations of cationic and nonionic surfactants can be tried in order to obtain the target viscosity as a stable composition.
  • stable it is meant herein that the composition undergoes no phase separation during a substantial period of time in a temperature range of from 0°c to 50°c. The most appropriate system can thus be selected by trial and error.
  • compositions according to the present invention may further comprise such optional ingredients as solvents, bleaches, bactericides, perfumes, dyes and the like, provided they are compatible in the acidic medium of the compositions according to the present invention.
  • compositions according to the present invention are further illustrated by the following examples. Examples
  • compositions are prepared by mixing the listed ingredients in the listed proportions.
  • Viscosity (cps at 60rpm) 30 54 200 41
  • CTAB stands for a C16 trimethyl ammonium bromide
  • Cetrimide stands for C14 trimethyl ammonium bromide
  • STAB stands for C18 trimethyl ammonium bromide
  • Dobanol @ 23-3 is a C12-C13 ethoxylated alcohol with an average degree of ethoxylation of 3, available from Shell
  • Lutensol @ ON 30 is a C8-C12 ethoxylated alcohol with an average degree of ethoxylation of 3.
  • compositions according to the examples above were stable during 10 days at 50°c.

Landscapes

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

Abstract

L'invention concerne des compositions nettoyantes acides qui s'auto-épaississent. Le système d'épaississement comprend un mélange d'un tensioactif cationique et d'un tensioactif non ionique. Les compositions sont particulièrement appropriés pour éliminer le tartre.
PCT/US1993/011680 1992-12-04 1993-12-02 Composition nettoyantes acides auto-epaissies WO1994013769A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA002150914A CA2150914C (fr) 1992-12-04 1993-12-02 Composition nettoyante acide autoepaississante
US08/446,758 US5656580A (en) 1992-12-04 1993-12-02 Acidic cleaning compositions self-thickened by a mixture of cationic and nonionic surfactants

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP92870195.2 1992-12-04
EP92870195 1992-12-04
EP93870120.8 1993-06-25
EP93870120A EP0601990B1 (fr) 1992-12-04 1993-06-25 Composition acide de nettoyage auto-épaissie

Publications (1)

Publication Number Publication Date
WO1994013769A1 true WO1994013769A1 (fr) 1994-06-23

Family

ID=26132648

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1993/011680 WO1994013769A1 (fr) 1992-12-04 1993-12-02 Composition nettoyantes acides auto-epaissies

Country Status (3)

Country Link
CA (1) CA2150914C (fr)
MX (1) MX9307695A (fr)
WO (1) WO1994013769A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995021231A1 (fr) * 1994-02-03 1995-08-10 The Procter & Gamble Company Preparations detergentes acides
WO1995021232A1 (fr) * 1994-02-03 1995-08-10 The Procter & Gamble Company Compositions d'elimination des depots de calcaire
US5672578A (en) * 1994-02-03 1997-09-30 The Procter & Gamble Company Limescale removing compositions
EP0839898A1 (fr) 1996-11-04 1998-05-06 The Procter & Gamble Company Compositions de nettoyage à épaississement propre
WO1999016854A1 (fr) * 1997-09-30 1999-04-08 Reckitt Benckiser Inc. Compositions acides epaissies pour le nettoyage et la desinfection
WO2000063337A1 (fr) * 1999-04-16 2000-10-26 Reckitt Benckiser Inc. Compositions nettoyantes et desinfectantes acides pour surfaces dures
EP1894989A1 (fr) * 2006-09-01 2008-03-05 The Procter and Gamble Company Composition pâteuse pour articles sanitaires

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4666622A (en) * 1985-01-03 1987-05-19 Lever Brothers Company Stable thickened low pH liquid bleaching compositions containing inorganic peroxy compounds
US4891150A (en) * 1985-12-05 1990-01-02 Joh. A. Benckiser Gmbh Liquid sanitary cleansing and descaling agents and process for their production
US5008030A (en) * 1989-01-17 1991-04-16 Colgate-Palmolive Co. Acidic disinfectant all-purpose liquid cleaning composition
US5100660A (en) * 1989-04-21 1992-03-31 Allied Colloids Limited Thickened acidic aqueous compositions using cross-linked dialkylaminoacrylic microparticles
EP0518401B1 (fr) * 1991-06-14 1995-11-02 The Procter & Gamble Company Compositions de nettoyage à épaississement propre

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4666622A (en) * 1985-01-03 1987-05-19 Lever Brothers Company Stable thickened low pH liquid bleaching compositions containing inorganic peroxy compounds
US4891150A (en) * 1985-12-05 1990-01-02 Joh. A. Benckiser Gmbh Liquid sanitary cleansing and descaling agents and process for their production
US5008030A (en) * 1989-01-17 1991-04-16 Colgate-Palmolive Co. Acidic disinfectant all-purpose liquid cleaning composition
US5100660A (en) * 1989-04-21 1992-03-31 Allied Colloids Limited Thickened acidic aqueous compositions using cross-linked dialkylaminoacrylic microparticles
EP0518401B1 (fr) * 1991-06-14 1995-11-02 The Procter & Gamble Company Compositions de nettoyage à épaississement propre

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995021231A1 (fr) * 1994-02-03 1995-08-10 The Procter & Gamble Company Preparations detergentes acides
WO1995021232A1 (fr) * 1994-02-03 1995-08-10 The Procter & Gamble Company Compositions d'elimination des depots de calcaire
US5672578A (en) * 1994-02-03 1997-09-30 The Procter & Gamble Company Limescale removing compositions
AU701869B2 (en) * 1994-02-03 1999-02-04 Procter & Gamble Company, The Limescale removing compositions
EP0839898A1 (fr) 1996-11-04 1998-05-06 The Procter & Gamble Company Compositions de nettoyage à épaississement propre
WO1999016854A1 (fr) * 1997-09-30 1999-04-08 Reckitt Benckiser Inc. Compositions acides epaissies pour le nettoyage et la desinfection
US6239092B1 (en) 1997-09-30 2001-05-29 Reckitt Benckiser Inc. Thickened acidic, hard surface cleaning and disinfecting compositions particularly useful for ceramic surfaces
WO2000063337A1 (fr) * 1999-04-16 2000-10-26 Reckitt Benckiser Inc. Compositions nettoyantes et desinfectantes acides pour surfaces dures
EP1894989A1 (fr) * 2006-09-01 2008-03-05 The Procter and Gamble Company Composition pâteuse pour articles sanitaires
WO2008026192A1 (fr) * 2006-09-01 2008-03-06 The Procter & Gamble Company Composition pâteuse destinée à des équipements sanitaires

Also Published As

Publication number Publication date
CA2150914A1 (fr) 1994-06-23
MX9307695A (es) 1994-06-30
CA2150914C (fr) 1999-07-13

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