EP0255978A2 - Acidic liquid cleaning composition - Google Patents

Acidic liquid cleaning composition Download PDF

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Publication number
EP0255978A2
EP0255978A2 EP87201455A EP87201455A EP0255978A2 EP 0255978 A2 EP0255978 A2 EP 0255978A2 EP 87201455 A EP87201455 A EP 87201455A EP 87201455 A EP87201455 A EP 87201455A EP 0255978 A2 EP0255978 A2 EP 0255978A2
Authority
EP
European Patent Office
Prior art keywords
detergent
active compound
acid
composition
cationic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP87201455A
Other languages
German (de)
French (fr)
Other versions
EP0255978A3 (en
Inventor
Thomas Stirling
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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 PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0255978A2 publication Critical patent/EP0255978A2/en
Publication of EP0255978A3 publication Critical patent/EP0255978A3/en
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/40—Monoamines or polyamines; 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/92—Sulfobetaines ; Sulfitobetaines
    • 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
    • C11D3/40—Dyes ; Pigments

Definitions

  • Acidic liquid toilet bowl cleaning compositions are well known in the art. They usually consist of an aqueous solution of a strong acid, to which various desirable additives have been added, such as detergent-­active compounds, germicides, perfumes, corrosion inhibitors, colouring agents and so on. As detergent-­active compounds anionic, nonionic and cationic detergents have been suggested for inclusion in such acidic liquid toilet bowl cleaning compositions. When desired, a pleasing colour is imparted to such compositions by adding a suitable dye, such as a blue dye. Such compositions are particularly effective in removing toilet scale deposits, derived from the water supply to the toilet.
  • compositions contain the cationic detergent-active compound in an amount of 0.1-10% by weight. Mixtures of several cationic detergents, as well as of a cationic and a nonionic detergent may also be used.
  • the dyestuffs suitable for use according to the present invention are those which undergo a pH-dependent colour change in the acid pH range, i.e. for the present invention in the range of 2-6 in aqueous solution.
  • Typical examples of such dyestuffs are the triarylmethane types such as Acid Blue 1 (CI 42045), Acid Blue 9 (CI 42090), Acid Violet 17 (CI 42650) and Mordant Blue 1 (CI 43830).
  • the compositions contain from 0.0001-1% by weight of the dyestuff.
  • other dyestuffs which do not undergo a pH-­dependent colour change may additionally be included so as to achieve a change to a desired colour.
  • inorganic acids such as hydrochloric acid, sulphuric acid, nitric acid and sulphamic acid are suitable; the compositions contain the acid in an amount of 0.5-25% by weight.
  • the pH of the compositions of the present invention is below 2, and in most useful cases below 1.
  • compositions of the invention can be thickened by surfactants, by polymeric materials such as xanthan gums, polyacrylates and by inorganic thickeners such as silicas and clays.

Abstract

An acidic, aqueous liquid detergent composition, especially suitable for toilet bowl cleaning, is provided with a colour-change ingredient to enable the user to monitor the concentration of the composition upon dilution with water when using the product.
By including a detergent-active compound which exists in cationic form in the acid composition and a dye which undergoes a pH-dependent colour change in the acid pH range, the required colour change indication is obtained.

Description

  • The present invention relates to aqueous, acidic liquid cleaning compositions which are suitable for cleaning hard, acid-resistant surfaces such as metallic, vitreous and ceramic surfaces. They are especially suitable for cleaning toilet bowls.
  • Acidic liquid toilet bowl cleaning compositions are well known in the art. They usually consist of an aqueous solution of a strong acid, to which various desirable additives have been added, such as detergent-­active compounds, germicides, perfumes, corrosion inhibitors, colouring agents and so on. As detergent-­active compounds anionic, nonionic and cationic detergents have been suggested for inclusion in such acidic liquid toilet bowl cleaning compositions. When desired, a pleasing colour is imparted to such compositions by adding a suitable dye, such as a blue dye. Such compositions are particularly effective in removing toilet scale deposits, derived from the water supply to the toilet.
  • In order to enable the user of these compositions to monitor the concentration of such products in the water upon dilution when using these products, it would be desirable to include an ingredient giving the user a readily appreciated rating of the concentration present. Such an ingredient would be a pH indicator, the colour of which changes upon dilution, as is for instance suggested for liquid detergents in GB Patent Specification 1 313 180.
  • However, we have found that the performance of such a colour change providing ingredient in acidic toilet bowl cleaners is related to the nature of the detergent-active compound present in the compositions, and that such a colour change is only obtained if the composition contains a detergent-active compound that exists in a cationic form under the acidic conditions of the composition. Cationic surfactants are particularly advantageous in acidic toilet cleaning compositions because of their known germicidal properties.
  • Consequently, the present invention in its broadest aspects relates to an aqueous, acidic liquid cleaning composition comprising an aqueous solution of a strong acid, a detergent-active compound and a dye, which is characterised by the fact that the detergent-active compound exists in a cationic form in the composition and that the dye undergoes a pH-dependent colour change in the acid pH range.
  • Detergent-active compounds which are cationic under the acidic conditions in the composition are e.g. permanent cationics such as the quaternary ammonium and imidazoline compounds, or tertiary amines, tertiary amine oxides, amine ethoxylates, betaines and sulphobetaines. Specific examples are coconut dimethyl amine oxide, coconut trimethyl quaternary ammonium chloride, coconut sulphobetaine.
  • In general, the compositions contain the cationic detergent-active compound in an amount of 0.1-10% by weight. Mixtures of several cationic detergents, as well as of a cationic and a nonionic detergent may also be used.
  • The dyestuffs suitable for use according to the present invention are those which undergo a pH-dependent colour change in the acid pH range, i.e. for the present invention in the range of 2-6 in aqueous solution.
  • Typical examples of such dyestuffs are the triarylmethane types such as Acid Blue 1 (CI 42045), Acid Blue 9 (CI 42090), Acid Violet 17 (CI 42650) and Mordant Blue 1 (CI 43830). In general, the compositions contain from 0.0001-1% by weight of the dyestuff. Optionally, other dyestuffs which do not undergo a pH-­dependent colour change may additionally be included so as to achieve a change to a desired colour.
  • As strong acid, inorganic acids such as hydrochloric acid, sulphuric acid, nitric acid and sulphamic acid are suitable; the compositions contain the acid in an amount of 0.5-25% by weight. The pH of the compositions of the present invention is below 2, and in most useful cases below 1.
  • Other optional ingredients may also be included, such as perfumes, corrosion inhibitors, viscosity modifiers, electrolyte salts, small amounts of anionic detergents, solvents, hydrotropes etc. Thickened compositions are especially desirable since they remain in contact with vertical and inclined surfaces of the toilet for a longer period of time and give improved cleaning. The compositions of the invention can be thickened by surfactants, by polymeric materials such as xanthan gums, polyacrylates and by inorganic thickeners such as silicas and clays.
    • Examples 1-13
  • The following table shows a number of compositions of the present invention which undergo colour change upon dilution with water. The figures are percentages by weight.
    Figure imgb0001

Claims (4)

1. An acidic, aqueous liquid cleaning composition having a pH of below 2, comprising an aqueous solution of a strong acid, a detergent-active compound and a dye which undergoes a pH-dependent colour change, characterised in that the detergent-active compound exists in a cationic form in the composition and the dye undergoes a pH-dependent colour change in the acid pH range.
2. A composition according to claim 1,
characterised in that the detergent-active compound is a permanent cationic detergent-active compound selected from the group consisting of the quaternary ammonium and imidazoline compounds.
3. A composition according to claim 1,
characterised in that the detergent-active compound is only cationic in the acid pH range, selected from the group consisting of tertiary amines, tertiary amine oxides, ethoxylated amines, betaines and sulphobetaines.
4. A composition according to claims 1-3,
characterised in that it is thickened by inclusion therein of a thickening agent.
EP87201455A 1986-08-08 1987-07-30 Acidic liquid cleaning composition Ceased EP0255978A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8619391 1986-08-08
GB868619391A GB8619391D0 (en) 1986-08-08 1986-08-08 Acidic liquid cleaning composition

Publications (2)

Publication Number Publication Date
EP0255978A2 true EP0255978A2 (en) 1988-02-17
EP0255978A3 EP0255978A3 (en) 1989-03-08

Family

ID=10602444

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87201455A Ceased EP0255978A3 (en) 1986-08-08 1987-07-30 Acidic liquid cleaning composition

Country Status (7)

Country Link
EP (1) EP0255978A3 (en)
JP (1) JPS6343999A (en)
AU (1) AU607708B2 (en)
BR (1) BR8703992A (en)
CA (1) CA1329751C (en)
GB (1) GB8619391D0 (en)
ZA (1) ZA875848B (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2717108A1 (en) * 1994-03-14 1995-09-15 Sgb Cleaning process using range of coloured cleaning prods.
EP0754749A1 (en) * 1995-07-20 1997-01-22 The Procter & Gamble Company Fabric softeners containing water soluble dyes for reduced staining
US5691291A (en) * 1994-10-28 1997-11-25 The Procter & Gamble Company Hard surface cleaning compositions comprising protonated amines and amine oxide surfactants
US5965514A (en) * 1996-12-04 1999-10-12 The Procter & Gamble Company Compositions for and methods of cleaning and disinfecting hard surfaces
US5990064A (en) * 1994-10-28 1999-11-23 The Procter & Gamble Company Compositions and methods for cleaning hard surfaces using protonated amines and amine oxide surfactants
WO2003014282A1 (en) * 2001-08-06 2003-02-20 Colgate-Palmolive Company Color changing liquid cleaning composition
WO2004078896A1 (en) * 2003-03-05 2004-09-16 Unilever Plc Method of treating a textile using a colour changing foam
WO2005003276A1 (en) * 2003-06-18 2005-01-13 Unilever Plc Laundry treatment compositions
WO2006041739A1 (en) * 2004-10-04 2006-04-20 The Procter & Gamble Company A composition with a metal-complexing dye and surfactant
WO2008117235A1 (en) * 2007-03-26 2008-10-02 The Procter & Gamble Company Liquid composition system having a visual indication change
WO2008117233A1 (en) * 2007-03-26 2008-10-02 The Procter & Gamble Company Liquid detergent composition system having a visual indication change
US7651989B2 (en) 2003-08-29 2010-01-26 Kimberly-Clark Worldwide, Inc. Single phase color change agents
US8067350B2 (en) 2005-12-15 2011-11-29 Kimberly-Clark Worldwide, Inc. Color changing cleansing composition
US20140158166A1 (en) * 2012-12-10 2014-06-12 Milliken & Company Cleaning composition and method for using the same
WO2017200496A1 (en) 2016-05-18 2017-11-23 Hayat Kimya Sanayi Anonim Sirketi Dual purpose cleaning composition for limescale removal
US9926519B2 (en) 2012-06-08 2018-03-27 S. C. Johnson & Son, Inc. Self-adhesive detergent compositions with color-changing systems

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4743395A (en) * 1986-09-12 1988-05-10 The Drackett Company Thickened acid cleaner compositions containing quaternary ammonium germicides and having improved thermal stability
JPH01240600A (en) * 1988-03-18 1989-09-26 Seiwa Kogyo Kk Cleaning agent for toilet
GB9000028D0 (en) * 1990-01-02 1990-03-07 Shell Int Research Cleaning of equipment used in a liquid phase oxidation process
JP4884768B2 (en) * 2005-12-28 2012-02-29 花王株式会社 Hard surface cleaner

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1313180A (en) * 1970-09-23 1973-04-11 Unilever Ltd Surface active liquids
US4016089A (en) * 1974-11-11 1977-04-05 Regan Glen B Denture cleaning concentrate
US4302253A (en) * 1980-02-19 1981-11-24 R. T. Vanderbilt Company, Inc. Thickeners for acid cleaning compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1313180A (en) * 1970-09-23 1973-04-11 Unilever Ltd Surface active liquids
US4016089A (en) * 1974-11-11 1977-04-05 Regan Glen B Denture cleaning concentrate
US4302253A (en) * 1980-02-19 1981-11-24 R. T. Vanderbilt Company, Inc. Thickeners for acid cleaning compositions

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2717108A1 (en) * 1994-03-14 1995-09-15 Sgb Cleaning process using range of coloured cleaning prods.
US5990064A (en) * 1994-10-28 1999-11-23 The Procter & Gamble Company Compositions and methods for cleaning hard surfaces using protonated amines and amine oxide surfactants
US5691291A (en) * 1994-10-28 1997-11-25 The Procter & Gamble Company Hard surface cleaning compositions comprising protonated amines and amine oxide surfactants
EP0754749A1 (en) * 1995-07-20 1997-01-22 The Procter & Gamble Company Fabric softeners containing water soluble dyes for reduced staining
US5965514A (en) * 1996-12-04 1999-10-12 The Procter & Gamble Company Compositions for and methods of cleaning and disinfecting hard surfaces
WO2003014282A1 (en) * 2001-08-06 2003-02-20 Colgate-Palmolive Company Color changing liquid cleaning composition
WO2004078896A1 (en) * 2003-03-05 2004-09-16 Unilever Plc Method of treating a textile using a colour changing foam
WO2005003276A1 (en) * 2003-06-18 2005-01-13 Unilever Plc Laundry treatment compositions
US7858568B2 (en) 2003-08-29 2010-12-28 Kimberly-Clark Worldwide, Inc. Single phase color change agents
US7651989B2 (en) 2003-08-29 2010-01-26 Kimberly-Clark Worldwide, Inc. Single phase color change agents
WO2006041739A1 (en) * 2004-10-04 2006-04-20 The Procter & Gamble Company A composition with a metal-complexing dye and surfactant
CN101035887B (en) * 2004-10-04 2011-03-09 宝洁公司 A composition with a metal-complexing dye and surfactant
US7550422B2 (en) 2004-10-04 2009-06-23 The Procter & Gamble Company Composition with a metal-complexing dye and surfactant
US8067350B2 (en) 2005-12-15 2011-11-29 Kimberly-Clark Worldwide, Inc. Color changing cleansing composition
WO2008117233A1 (en) * 2007-03-26 2008-10-02 The Procter & Gamble Company Liquid detergent composition system having a visual indication change
WO2008117235A1 (en) * 2007-03-26 2008-10-02 The Procter & Gamble Company Liquid composition system having a visual indication change
US9926519B2 (en) 2012-06-08 2018-03-27 S. C. Johnson & Son, Inc. Self-adhesive detergent compositions with color-changing systems
US20140158166A1 (en) * 2012-12-10 2014-06-12 Milliken & Company Cleaning composition and method for using the same
WO2014092865A3 (en) * 2012-12-10 2014-09-12 Milliken & Company Cleaning composition and method for using the same
US9688946B2 (en) 2012-12-10 2017-06-27 Milliken & Company Cleaning composition and method for using the same
WO2017200496A1 (en) 2016-05-18 2017-11-23 Hayat Kimya Sanayi Anonim Sirketi Dual purpose cleaning composition for limescale removal

Also Published As

Publication number Publication date
JPS6343999A (en) 1988-02-25
GB8619391D0 (en) 1986-09-17
BR8703992A (en) 1988-04-05
AU7654987A (en) 1988-02-11
ZA875848B (en) 1989-04-26
CA1329751C (en) 1994-05-24
EP0255978A3 (en) 1989-03-08
AU607708B2 (en) 1991-03-14

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