EP0601990B1 - Self-thickened acidic cleaning composition - Google Patents
Self-thickened acidic cleaning composition Download PDFInfo
- Publication number
- EP0601990B1 EP0601990B1 EP93870120A EP93870120A EP0601990B1 EP 0601990 B1 EP0601990 B1 EP 0601990B1 EP 93870120 A EP93870120 A EP 93870120A EP 93870120 A EP93870120 A EP 93870120A EP 0601990 B1 EP0601990 B1 EP 0601990B1
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- EP
- European Patent Office
- Prior art keywords
- composition
- acid
- compositions
- weight
- composition according
- 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.)
- Revoked
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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 188 025 teaches that quaternary ammonium salts can be used to thicken an acidic peroxygen-based solution, provided they are combined with a strong mineral acid.
- US-4 612 135 discloses a sanitary cleaning composition comprising phosphoric acid, oxalic acid, a nonionic surfactant and a fluorinated quaternary ammonium surfactant.
- the quaternary ammonium surfactants according to the present invention are not disclosed.
- US-4 016 089 discloses a denture cleaning concentrate consisting essentially of an aqueous solution containing orthophosphoric acid, alkyl phenyl polyglycolether, quaternary ammonium germicide and a chemical indicator for pH which undergoes a colour change at pH about 4.5.
- compositions according to the present invention are aqueous compositions comprising from 0.1% to 45% by weight of the total composition of 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, said thickening system comprises from 0.5% to 15% by weight of the total compositions of a mixture of a nonionic surfactant according to the formula R(CH 2 CH 2 O) n H, wherein R is a primary or secondary, straight or branched alcohol rest having from 8 to 24 carbon atoms, preferably from 12 to 18, and n is from 1 to 15, 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
- 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.
- Nonionic surfactants for use herein are compounds having the general formula R(CH 2 CH 2 O) n H, wherein R represents a hydrophobic moiety, as defined below, and n represents the average number of ethylene oxide moieties. These compounds are typically obtained by condensing ethylene oxide and with a hydrocarbon having a hydroxyl group, in the presence of an acidic or basic catalyst.
- the hydrophobic moiety of the nonionic compound is a primary or secondary, straight or branched alcohol having from 8 to 24 carbon atoms, preferably 12 to 18, 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@.
- 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)
Description
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.
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
EP-A-0518401. 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 188 025 teaches that quaternary ammonium salts can be used to thicken an
acidic peroxygen-based solution, provided they are combined with a strong
mineral acid.
US-4 612 135 discloses a sanitary cleaning composition comprising phosphoric
acid, oxalic acid, a nonionic surfactant and a fluorinated quaternary ammonium
surfactant. The quaternary ammonium surfactants according to the present
invention are not disclosed.
US-4 016 089 discloses a denture cleaning concentrate consisting essentially
of an aqueous solution containing orthophosphoric acid, alkyl phenyl
polyglycolether, quaternary ammonium germicide and a chemical indicator for
pH which undergoes a colour change at pH about 4.5.
The compositions according to the present invention are aqueous compositions
comprising from 0.1% to 45% by weight of the total composition of 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, said thickening system comprises from 0.5% to 15% by
weight of the total compositions of a mixture of a nonionic surfactant according
to the formula R(CH2CH2O)nH, wherein R is a primary or secondary, straight or
branched alcohol rest having from 8 to 24 carbon atoms, preferably from 12 to 18,
and n is from 1 to 15, 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 a C1-4
hydrocarbon chains, said compositions being free of a cold-water soluble
inorganic peroxy compound.
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.
Nonionic surfactants for use herein are
compounds having the general formula
R(CH2CH2O)nH, wherein R represents a
hydrophobic moiety, as defined below,
and n represents the average
number of ethylene oxide moieties. These compounds are
typically obtained by condensing ethylene oxide and
with a hydrocarbon having a
hydroxyl group, in the
presence of an acidic or basic catalyst. In the present
invention, the hydrophobic moiety of the nonionic compound is
a primary or secondary, straight or branched alcohol
having from 8 to 24 carbon atoms, preferably 12
to 18, 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@.
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.
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.
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 (6)
- An aqueous cleaning composition comprising from 0.1% to 45% by weight of the total composition of an acid whereby the pH as is of said composition is of from 0.1 to 4.5, said composition further comprising a thickening system whereby said composition is stable and has 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 according to the formula R(CH2CH2O)nH, wherein R is a primary or secondary, straight or branched alcohol rest having from 8 to 24 carbon atoms, preferably from 12 to 18, and n is from 1 to 15, 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 a C1-4 hydrocarbon chains, said composition being free of a cold-water soluble inorganic peroxy compound.
- A composition according to claim 1 which comprises from 1% to 8% of said mixture of said nonionic and said cationic surfactant.
- A composition according to the preceding claims, wherein said acid is an organic acid.
- A composition according to claim 3, wherein said acid is maleic acid.
- A composition according to the preceding claims which comprises from 4% to 25% by weight of the total composition of said acid.
- 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.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002150914A CA2150914C (en) | 1992-12-04 | 1993-12-02 | Self-thickened acidic cleaning composition |
| 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 |
| 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 EP0601990A1 (en) | 1994-06-15 |
| EP0601990B1 true EP0601990B1 (en) | 1998-10-14 |
Family
ID=8212289
Family Applications (1)
| 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)
| Country | Link |
|---|---|
| EP (1) | EP0601990B1 (en) |
| DE (1) | DE69321566T2 (en) |
| ES (1) | ES2123633T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7153817B2 (en) | 2000-02-23 | 2006-12-26 | The Procter & Gamble Company | Detergent tablet |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU678313B2 (en) * | 1993-11-24 | 1997-05-22 | Unilever Plc | Limescale removing composition |
| EP0666305B1 (en) * | 1994-02-03 | 2000-11-08 | The Procter & Gamble Company | Acidic cleaning compositions |
| DE69426259T2 (en) * | 1994-02-03 | 2001-06-07 | The Procter & Gamble Company, Cincinnati | Acidic cleaning compositions |
| EP0758017B1 (en) | 1995-08-09 | 2002-10-23 | The Procter & Gamble Company | Acidic cleaning compositions |
| US5981449A (en) * | 1995-08-09 | 1999-11-09 | 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 |
| EP1679363B1 (en) | 2005-01-10 | 2008-07-09 | The Procter and Gamble Company | Cleaning composition for washing-up or washing machine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0188025A2 (en) * | 1985-01-03 | 1986-07-23 | Unilever N.V. | Liquid bleaching compositions |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4016089A (en) * | 1974-11-11 | 1977-04-05 | Regan Glen B | Denture cleaning concentrate |
| GB2071688B (en) * | 1980-03-13 | 1984-02-08 | Jeyes Ltd | Liquid cleaning and descaling compositions |
| ZA826902B (en) * | 1981-10-01 | 1984-04-25 | Colgate Palmolive Co | Safe 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 |
| JP2837405B2 (en) * | 1985-06-10 | 1998-12-16 | 花王株式会社 | Bathroom cleaning composition |
| US5192460A (en) * | 1988-02-10 | 1993-03-09 | Colgate-Palmolive Company | Safe acidic hard surface cleaner |
| DE4014859A1 (en) * | 1990-05-09 | 1991-11-14 | Henkel Kgaa | USE OF A COMBINATION OF IONIC AND NON-IONIC SURFACES |
| AU624504B2 (en) * | 1990-05-09 | 1992-06-11 | S.C. Johnson & Son, Inc. | Thickened acid cleaner compositions having improved thermal stability |
| EP0496188B1 (en) * | 1991-01-22 | 1997-10-22 | The Procter & Gamble Company | Limescale removing composition |
-
1993
- 1993-06-25 EP EP93870120A patent/EP0601990B1/en not_active Revoked
- 1993-06-25 DE DE1993621566 patent/DE69321566T2/en not_active Revoked
- 1993-06-25 ES ES93870120T patent/ES2123633T3/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0188025A2 (en) * | 1985-01-03 | 1986-07-23 | Unilever N.V. | Liquid bleaching compositions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7153817B2 (en) | 2000-02-23 | 2006-12-26 | The Procter & Gamble Company | Detergent tablet |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69321566D1 (en) | 1998-11-19 |
| DE69321566T2 (en) | 1999-06-02 |
| EP0601990A1 (en) | 1994-06-15 |
| ES2123633T3 (en) | 1999-01-16 |
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