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)

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Cited By (8)

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Citations (10)

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• 1993
  • 1993-06-25 EP EP93870120A patent/EP0601990B1/fr not_active Revoked
  • 1993-06-25 DE DE1993621566 patent/DE69321566T2/de not_active Revoked
  • 1993-06-25 ES ES93870120T patent/ES2123633T3/es not_active Expired - Lifetime

Patent Citations (10)

Non-Patent Citations (2)

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