EP0601990A1 - Self-thickened acidic cleaning composition - Google Patents

Self-thickened acidic cleaning composition Download PDF

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Publication number
EP0601990A1
EP0601990A1 EP93870120A EP93870120A EP0601990A1 EP 0601990 A1 EP0601990 A1 EP 0601990A1 EP 93870120 A EP93870120 A EP 93870120A EP 93870120 A EP93870120 A EP 93870120A EP 0601990 A1 EP0601990 A1 EP 0601990A1
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EP
European Patent Office
Prior art keywords
compositions
acid
composition according
composition
self
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.)
Granted
Application number
EP93870120A
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German (de)
French (fr)
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EP0601990B1 (en
Inventor
Michel Jean Carrie
Eddy Vos
Axel Koenig
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Procter and Gamble Co
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Procter and Gamble Co
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to PCT/US1993/011680 priority Critical patent/WO1994013769A1/en
Priority to US08/446,758 priority patent/US5656580A/en
Priority to CA002150914A priority patent/CA2150914C/en
Priority to MX9307695A priority patent/MX9307695A/en
Publication of EP0601990A1 publication Critical patent/EP0601990A1/en
Application granted granted Critical
Publication of EP0601990B1 publication Critical patent/EP0601990B1/en
Anticipated expiration legal-status Critical
Revoked 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
    • 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
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D1/835—Mixtures of non-ionic with cationic 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
    • 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
    • C11D3/2082—Polycarboxylic 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
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers 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 10 to 700 cps at 60 rpm shear rate at 20°c, characterized in that 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 R1R2R3R4N+ X ⁇ , wherein X is a counteranion, R1 is a C12 ⁇ 20 hydrocarbon chain and R2, R3 and R4 are independently selected from H or C1 ⁇ 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 R1R2R3R4N+ X ⁇ , wherein X is a counteranion, R1 is a C12 ⁇ 20 hydrocarbon chain and R2, R3 and R4 are independently selected from H or C1 ⁇ 4 hydrocarbon chains.
  • R1 is a C14 ⁇ 18 hydrocarbon chain, most preferably C16 or C18, and R1, R2 and R3 are all three methyl, and 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(CH2CH2CH2O) m (CH2CH2O) 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 nonionic 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.
  • compositions are prepared by mixing the listed ingredients in the listed proportions.
  • Dobanol 23-3 @ 1.6 2.9 2.1 0.8 0.5 pH as is 1.0 0.9 0.9 0.9 0.9 Viscosity (cps at 60rpm) 47 29 70 270 20 VI VII VIII IX CTAB 3.0 4.2 4.2 5.0 Maleic acid 10.0 12.6 4.2 10.0
  • 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.

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

Abstract

Acidic cleaning compositions are disclosed which are self-thickened. The thickening system comprises a mixture of a cationic surfactant and a nonionic surfactant. The compositions are especially suitable for the removal of limescale.

Description

    Technical field
  • 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.
    • Background of the invention
  • 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.
  • It is therefore desirable to provide limescale removing compositions in the form of self-thickened systems. Self-thickened systems have been disclosed for instance in co-pending EP 92201412.1. In these systems, the thickening effect is obtained by the combination of an anionic surfactant, a nonionic surfactant and an electrolyte. It has however been found that such systems are not optimum for limescale removing compositions. Indeed, this approach does not seem to provide viscosity in a strongly acidic system unless very high levels of ingredients are used, and strong negatives have been observed on limescale removal. Furthermore, the stability of anionic surfactants may be problematic in such strongly acidic conditions.
  • It has now been found that a stable self-thickened effect could be obtained in an acidic medium, without compromising on the limescale removing efficiency of the composition by combining a quaternary ammonium salt surfactant with a nonionic surfactant. This solution has the additional advantage that the thickening system also fulfills a detergent function.
  • Additionally it has been found that the 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. In the '688 patent, 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.
    • Summary of the invention
  • The 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 10 to 700 cps at 60 rpm shear rate at 20°c, characterized in that 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 R₁R₂R₃R₄N⁺ X⁻, wherein X is a counteranion, R₁ is a C₁₂₋₂₀ hydrocarbon chain and R₂, R₃ and R₄ are independently selected from H or C₁₋₄ hydrocarbon chains.
    • Detailed description of the invention
  • The compositions of the present invention are designed for removing limescale or soils comprising limescale as a main component. Thus 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. Although a wide variety of 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. Particularly preferred for use herein are weak organic acids, and particularly preferred is maleic acid which is particularly appealing from both in terms of environmental compatibility and performance. The 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%. Thus, 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.
  • As the second essential ingredient, the compositions according to the present invention comprise a thickening system which consists of a mixture of certain cationic surfactants with nonionic surfactants. In a highly preferred embodiment, the 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 R₁R₂R₃R₄N⁺ X⁻, wherein X is a counteranion, R₁ is a C₁₂₋₂₀ hydrocarbon chain and R₂, R₃ and R₄ are independently selected from H or C₁₋₄ hydrocarbon chains. In a preferred embodiment of the invention, R₁ is a C₁₄₋₁₈ hydrocarbon chain, most preferably C₁₆ or C₁₈, and R₁, R₂ and R₃ are all three methyl, and 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(CH₂CH₂CH₂O)m(CH₂CH₂O)nH, 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. In the present invention, 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. Such 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.
  • The 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 nonionic surfactants provides the best viscosity build up. In the system according to the present invention 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. By 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.
  • The 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.
  • The compositions according to the present invention are further illustrated by the following examples.
    • Examples
  • The following compositions are prepared by mixing the listed ingredients in the listed proportions.
    I II III IV V
    CTAB 3.2 4.2 - - -
    Cetrimide - - 4.2 - -
    STAB - - - 4.2 1.0
    Maleic acid 8.0 8.6 8.6 8.6 8.0
    Dobanol 23-3@ 1.6 2.9 2.1 0.8 0.5
    pH as is 1.0 0.9 0.9 0.9 0.9
    Viscosity (cps at 60rpm) 47 29 70 270 20
    VI VII VIII IX
    CTAB 3.0 4.2 4.2 5.0
    Maleic acid 10.0 12.6 4.2 10.0
    Dobanol 23-3@ 1.6 3.4 1.3 1.6
    Lutensol ON 30@ 0.4 - - 0.4
    pH as is 0.9 0.8 1.1 1.0
    Viscosity (cps at 60rpm) 30 54 200 41
  • In the above examples:
    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.
  • All the compositions according to the examples above were stable during 10 days at 50°c.

Claims (7)

  1. An 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 10 to 700 cps at 60 rpm shear rate at 20°c, characterised in that 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 R₁R₂R₃R₄N⁺ X⁻, wherein X is a counteranion, R₁ is a C₁₂₋₂₀ hydrocarbon chain and R₂, R₃ and R₄ are independently selected from H or C₁₋₄ hydrocarbon chains.
  2. A composition according to claim 1 which comprises from 1% to 8% of said mixture of said nonionic and said cationic surfactant.
  3. A composition according to the preceding claims, wherein said acid is an organic acid.
  4. A composition according to claim 3, wherein said acid is maleic acid.
  5. A composition according to the preceding claims which comprises from 0.1% to 45% by weight of the total composition of said acid, preferably 4% to 25%.
  6. A composition according to the preceding claims wherein said nonionic surfactant is an ethoxylated alcohol having from about 8 to about 24 carbon atoms, preferably 12 to 18, and an average degree of ethoxylation of from 1 to 15.
  7. A composition according to the preceding claims wherein in said cationic surfactant R₁ is a C₁₄₋₁₈ hydrocarbon chain, most preferably C₁₆ or C₁₈, and R₁, R₂ and R₃ are all three methyl, and X is bromide or chloride.
EP93870120A 1992-12-04 1993-06-25 Self-thickened acidic cleaning composition Revoked EP0601990B1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
PCT/US1993/011680 WO1994013769A1 (en) 1992-12-04 1993-12-02 Self-thickneded acidic cleaning composition
US08/446,758 US5656580A (en) 1992-12-04 1993-12-02 Acidic cleaning compositions self-thickened by a mixture of cationic and nonionic surfactants
CA002150914A CA2150914C (en) 1992-12-04 1993-12-02 Self-thickened acidic cleaning composition
MX9307695A MX9307695A (en) 1992-12-04 1993-12-06 SELF-THICKENED ACID CLEANING AQUEOUS COMPOSITION.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP92870195 1992-12-04
EP92870195 1992-12-04

Publications (2)

Publication Number Publication Date
EP0601990A1 true EP0601990A1 (en) 1994-06-15
EP0601990B1 EP0601990B1 (en) 1998-10-14

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Application Number Title Priority Date Filing Date
EP93870120A Revoked EP0601990B1 (en) 1992-12-04 1993-06-25 Self-thickened acidic cleaning composition

Country Status (3)

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EP (1) EP0601990B1 (en)
DE (1) DE69321566T2 (en)
ES (1) ES2123633T3 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995014756A1 (en) * 1993-11-24 1995-06-01 Unilever Plc Limescale removing composition
EP0666305A1 (en) * 1994-02-03 1995-08-09 The Procter & Gamble Company Acidic cleaning compositions
EP0666304A1 (en) * 1994-02-03 1995-08-09 The Procter & Gamble Company Acidic cleaning compositions
EP0758017A1 (en) 1995-08-09 1997-02-12 The Procter & Gamble Company Acidic cleaning compositions
EP0875551A1 (en) * 1997-04-30 1998-11-04 The Procter & Gamble Company Self-thickened acidic cleaning compositions
US5981449A (en) * 1995-08-09 1999-11-09 The Procter & Gamble Company Acidic cleaning compositions
GB2348885A (en) * 1999-04-16 2000-10-18 Reckitt & Colman Inc Hard surface cleaning and disinfecting composition
EP1679363A1 (en) 2005-01-10 2006-07-12 The Procter and Gamble Company Cleaning composition for washing-up or washing machine

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0004130D0 (en) 2000-02-23 2000-04-12 Procter & Gamble Detergent tablet

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US4016089A (en) * 1974-11-11 1977-04-05 Regan Glen B Denture cleaning concentrate
GB2071688A (en) * 1980-03-13 1981-09-23 Jeyes Ltd Liquid Cleaning and Descaling Compositions
GB2106927A (en) * 1981-10-01 1983-04-20 Colgate Palmolive Co Liquid toilet bowl cleaner
DD230552A3 (en) * 1983-07-07 1985-12-04 Domal Stadtilm Veb ACID, LIQUID CLEANING AGENTS
US4612135A (en) * 1983-08-05 1986-09-16 Sanitary Products Corp. All-purpose sanitary cleaning composition
JPS61283696A (en) * 1985-06-10 1986-12-13 花王株式会社 Detergent composition for bathroom
EP0411708A2 (en) * 1989-07-31 1991-02-06 Colgate-Palmolive Company Safe acidic hard surface cleaner
WO1991017233A1 (en) * 1990-05-09 1991-11-14 Henkel Kommanditgesellschaft Auf Aktien Use of a combination of ionic and non-ionic tensides
AU5482490A (en) * 1990-05-09 1991-12-05 S.C. Johnson & Son, Inc. Thickened acid cleaner compositions having improved thermal stability
EP0496188A1 (en) * 1991-01-22 1992-07-29 The Procter & Gamble Company Limescale removing composition

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GB8500116D0 (en) * 1985-01-03 1985-02-13 Unilever Plc Liquid bleaching compositions

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4016089A (en) * 1974-11-11 1977-04-05 Regan Glen B Denture cleaning concentrate
GB2071688A (en) * 1980-03-13 1981-09-23 Jeyes Ltd Liquid Cleaning and Descaling Compositions
GB2106927A (en) * 1981-10-01 1983-04-20 Colgate Palmolive Co Liquid toilet bowl cleaner
DD230552A3 (en) * 1983-07-07 1985-12-04 Domal Stadtilm Veb ACID, LIQUID CLEANING AGENTS
US4612135A (en) * 1983-08-05 1986-09-16 Sanitary Products Corp. All-purpose sanitary cleaning composition
JPS61283696A (en) * 1985-06-10 1986-12-13 花王株式会社 Detergent composition for bathroom
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995014756A1 (en) * 1993-11-24 1995-06-01 Unilever Plc Limescale removing composition
AU678313B2 (en) * 1993-11-24 1997-05-22 Unilever Plc Limescale removing composition
EP0666305A1 (en) * 1994-02-03 1995-08-09 The Procter & Gamble Company Acidic cleaning compositions
EP0666304A1 (en) * 1994-02-03 1995-08-09 The Procter & Gamble Company Acidic cleaning compositions
EP0758017A1 (en) 1995-08-09 1997-02-12 The Procter & Gamble Company Acidic cleaning compositions
WO1997006228A1 (en) * 1995-08-09 1997-02-20 The Procter & Gamble Company Acidic cleaning compositions
US5981449A (en) * 1995-08-09 1999-11-09 The Procter & Gamble Company Acidic cleaning compositions
EP0758017B1 (en) * 1995-08-09 2002-10-23 The Procter & Gamble Company Acidic cleaning compositions
EP0875551A1 (en) * 1997-04-30 1998-11-04 The Procter & Gamble Company Self-thickened acidic cleaning compositions
GB2348885A (en) * 1999-04-16 2000-10-18 Reckitt & Colman Inc Hard surface cleaning and disinfecting composition
EP1679363A1 (en) 2005-01-10 2006-07-12 The Procter and Gamble Company Cleaning composition for washing-up or washing machine

Also Published As

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EP0601990B1 (en) 1998-10-14
DE69321566D1 (en) 1998-11-19
ES2123633T3 (en) 1999-01-16
DE69321566T2 (en) 1999-06-02

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