CA2100096C - Limescale removing composition - Google Patents
Limescale removing composition Download PDFInfo
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- CA2100096C CA2100096C CA002100096A CA2100096A CA2100096C CA 2100096 C CA2100096 C CA 2100096C CA 002100096 A CA002100096 A CA 002100096A CA 2100096 A CA2100096 A CA 2100096A CA 2100096 C CA2100096 C CA 2100096C
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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
- 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
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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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)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
Cleaning compositions for hard surfaces are described which comprise from 1% to 15% by weight of the total composition of a nonionic surfactant or mixtures thereof, and from 4 % to 25 % by weight of the total composition of maleic acid. The compositions have a pH as is of from 1.0-to 4.0. These compositions are effective in removing limescale from hard surfaces.
Description
LIMESCALE REMOVING COMPOSITION
Technical field The present invention relates to cleaning compositions for hard surfaces. Specifically, compositions are described which are designed to give optimal performance in removing limescale stains and encrustations.
Background Tap water always contains a certain amount of water hardness salts such as calcium carbonate which eventually deposit on surfaces which are often in contact with said Water, resulting in an unaesthetic aspect of said surfaces.
This limescale deposition phenomenon is even more acute in places where water is particularly hard.
Typically, these limescale deposits are removed by using a cleaning composition comprising an acid which "dissolves" limescale, typically phosphoric acid. however, phosphoric acid has become subject to discussions, in relation to environmental questions. It is therefore an object of this invention to find an alternative to phosphoric acid in this particular context.
Technical field The present invention relates to cleaning compositions for hard surfaces. Specifically, compositions are described which are designed to give optimal performance in removing limescale stains and encrustations.
Background Tap water always contains a certain amount of water hardness salts such as calcium carbonate which eventually deposit on surfaces which are often in contact with said Water, resulting in an unaesthetic aspect of said surfaces.
This limescale deposition phenomenon is even more acute in places where water is particularly hard.
Typically, these limescale deposits are removed by using a cleaning composition comprising an acid which "dissolves" limescale, typically phosphoric acid. however, phosphoric acid has become subject to discussions, in relation to environmental questions. It is therefore an object of this invention to find an alternative to phosphoric acid in this particular context.
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In addition, it has been observed that state of the art compositions do not perform equally well on all limescale-containing stains, particularly on limescale-containing stains which are mainly found in the bathroom.
These bathroom-type stains appear to contain not only calcium carbonate, but also soap scum, and it has now been found that soap scum is detrimental to the limescale removing performance of said compositions.
It is therefore an object of the present invention to obviate this issue in providing a cleaning composition for the removal of limescale, said composition possessing a superior limescale removing capacity, said composition being also effective on limescale-containing bathroom-type stains.
DE 33 40 033 describes a composition for the removal of limestone traces on laundry; these compositions contain malefic acid and nonionic surfactants, as well as high amounts of phosphoric acid and urea.
EP 200 776 describes a method to remove precipitates containing mainly calcium carbonate by using a mixture of a Lewis acid and a protonic acid, possibly malefic acid.
J 61 28 3700 (abstract) discloses detergent compositions for bathroom which comprises a malefic acid or anhydride-based polymer and a nonionic surfactant; these compositions also comprise cationic surfactants.
EP 0 336 878 discloses an acidic cleaning composition comprising conventional surfactants and a dicarboxylic acid. Malefic acid is not mentioned.
In addition, it has been observed that state of the art compositions do not perform equally well on all limescale-containing stains, particularly on limescale-containing stains which are mainly found in the bathroom.
These bathroom-type stains appear to contain not only calcium carbonate, but also soap scum, and it has now been found that soap scum is detrimental to the limescale removing performance of said compositions.
It is therefore an object of the present invention to obviate this issue in providing a cleaning composition for the removal of limescale, said composition possessing a superior limescale removing capacity, said composition being also effective on limescale-containing bathroom-type stains.
DE 33 40 033 describes a composition for the removal of limestone traces on laundry; these compositions contain malefic acid and nonionic surfactants, as well as high amounts of phosphoric acid and urea.
EP 200 776 describes a method to remove precipitates containing mainly calcium carbonate by using a mixture of a Lewis acid and a protonic acid, possibly malefic acid.
J 61 28 3700 (abstract) discloses detergent compositions for bathroom which comprises a malefic acid or anhydride-based polymer and a nonionic surfactant; these compositions also comprise cationic surfactants.
EP 0 336 878 discloses an acidic cleaning composition comprising conventional surfactants and a dicarboxylic acid. Malefic acid is not mentioned.
3 2~.~~~~~
Summary of the invention The compositions according to the invention are aqueous compositions comprising from 1% to ~~% by weig::~ c.' the total composition of a nonionic surfactant or mixtures thereof and from 4% to 25 % by weight of the total composition of malefic acid: said compositions having a pH
as is of from 1.0 to 4Ø
Detailed description of the invention.
The present invention is partly based on the finding that Malefic acid possesses an unexpected superior limescale removing capacity, compared to phosphoric acid and compared to other dicarboxylic acids at equal levels.
Therefore, the compositions according to the invention comprise from 4% to 25% by weight of the total composition of malefic acid. This percentage is calculated on the basis of the molecular weight of the acid form, but malefic anhydride is equally convenient for use in the compositions according to the present invention. Indeed, malefic anhydride is generally cheaper and it is transformed into the acid form when incorporated in an aqueous medium.
It has been observed that the limescale removing capacity of the composition raises with the amount of malefic acid, up to a certain amount where a plateau in the limescale removing performance is reached. Accordingly, the compositions preferably comprise from 6 to 10% of malefic acid.
The compositions according to the invention have a pH
as is of from 1.0 to 4Ø The limescale removing capacity of the composition is strongly dependent on its pH, and the lower the pH, the better the limescale removing performance: the pH of the composition also has an effect on the shine performance of the compositions, and the 4 PCT/t;S92/00250 ~21000~~
higher the pH, the better the shine; one therefore has to balance the pH so as to obtain the desired compromise between limescale removing performance and shine performance. The compositions according to the invention preferably have a pH as is in the range of from 1 to 2, preferably 1.2.
The compositions according to the present invention also comprise a nonionic surfactant system. Indeed, typical limescale removing compositions do not perform optimally on bathroom type soils; this technical problem, which is not recognized in the art, is believed to be due to the soap scum which is present ,together with limescale, in bathroom type soils; indeed, soap scum has now been identified as having a detrimental effect on the limescale removing capacity of the composition.
In response to this issue, it is desirable to formulate a limescale removing composition which also comprises a surfactant system; it has now been found that the use of nonionic surfactants is much more desirable than other surfactants types, in order to address said technical issue and yet preserve an optimum limescale removing performance. Indeed, anionic and cationic surfactants have been found to adversely affect the limescale removing capacity of malefic acid. Therefore, the compositions according to the invention comprise from 1% to 15% by weight of the total composition of a nonionic surfactant or mixtures thereof, preferably from 2% to 4% by weight of the total composition, and the compositions according to the present invention are preferably free of cationic and anionic surfactants.
Nonionic surfactants are conventionally produced by condensing ethylene 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, and include compounds having the general formula RA(CH2CH20)nH, 5 pCT/U592/00250 2loooaa wherein R represents the hydrophobic moiety, A represents the group carrying the reactive hydrogen atom, and n represents the average number of ethylene oxide moieties. R
typically contains from 2 to 22 carbon atoms. Nonic~ic surfactants can also be formed by the condensation of propylene oxide with a lower molecular weight compound. n usually varies from 2 to 24. 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. Preferred nonionic surfactants for use in the compositions according to the invention are the condensation products of ethylene oxide with alcohols having a straight alkyl chain, having from 6 to 22 carbon atoms, wherein the degree of ethoxylation is from 5 to 12 Most preferred are C8-C12 ethoxylated alcohols with a degree of ethoxylation of 6; these surfactants are commercially available from Shell under the trade name Dobanol R 91-6. These nonionics are preferred because they have been found to allow the formulation of a stable product without requiring the addition of stabilizers or hydrotopes. When using other nonionics, it may be necessary to add hydrotopes such as cumene sulphonate or solvents such as butyldiglycolether The compositions according to the invention may additionally comprise optional ingredients such as colorants, bactericides, perfumes, thickeners, and the like.
Experimental Data a) Effect of soap scum on the limescale removing capacity of malefic acid, and effect of surfactants. .
The limescale removing (LSR) capacity of different solutions was measured by soaking a marble block of WO 92/13058 pCT/US92/0025U
Summary of the invention The compositions according to the invention are aqueous compositions comprising from 1% to ~~% by weig::~ c.' the total composition of a nonionic surfactant or mixtures thereof and from 4% to 25 % by weight of the total composition of malefic acid: said compositions having a pH
as is of from 1.0 to 4Ø
Detailed description of the invention.
The present invention is partly based on the finding that Malefic acid possesses an unexpected superior limescale removing capacity, compared to phosphoric acid and compared to other dicarboxylic acids at equal levels.
Therefore, the compositions according to the invention comprise from 4% to 25% by weight of the total composition of malefic acid. This percentage is calculated on the basis of the molecular weight of the acid form, but malefic anhydride is equally convenient for use in the compositions according to the present invention. Indeed, malefic anhydride is generally cheaper and it is transformed into the acid form when incorporated in an aqueous medium.
It has been observed that the limescale removing capacity of the composition raises with the amount of malefic acid, up to a certain amount where a plateau in the limescale removing performance is reached. Accordingly, the compositions preferably comprise from 6 to 10% of malefic acid.
The compositions according to the invention have a pH
as is of from 1.0 to 4Ø The limescale removing capacity of the composition is strongly dependent on its pH, and the lower the pH, the better the limescale removing performance: the pH of the composition also has an effect on the shine performance of the compositions, and the 4 PCT/t;S92/00250 ~21000~~
higher the pH, the better the shine; one therefore has to balance the pH so as to obtain the desired compromise between limescale removing performance and shine performance. The compositions according to the invention preferably have a pH as is in the range of from 1 to 2, preferably 1.2.
The compositions according to the present invention also comprise a nonionic surfactant system. Indeed, typical limescale removing compositions do not perform optimally on bathroom type soils; this technical problem, which is not recognized in the art, is believed to be due to the soap scum which is present ,together with limescale, in bathroom type soils; indeed, soap scum has now been identified as having a detrimental effect on the limescale removing capacity of the composition.
In response to this issue, it is desirable to formulate a limescale removing composition which also comprises a surfactant system; it has now been found that the use of nonionic surfactants is much more desirable than other surfactants types, in order to address said technical issue and yet preserve an optimum limescale removing performance. Indeed, anionic and cationic surfactants have been found to adversely affect the limescale removing capacity of malefic acid. Therefore, the compositions according to the invention comprise from 1% to 15% by weight of the total composition of a nonionic surfactant or mixtures thereof, preferably from 2% to 4% by weight of the total composition, and the compositions according to the present invention are preferably free of cationic and anionic surfactants.
Nonionic surfactants are conventionally produced by condensing ethylene 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, and include compounds having the general formula RA(CH2CH20)nH, 5 pCT/U592/00250 2loooaa wherein R represents the hydrophobic moiety, A represents the group carrying the reactive hydrogen atom, and n represents the average number of ethylene oxide moieties. R
typically contains from 2 to 22 carbon atoms. Nonic~ic surfactants can also be formed by the condensation of propylene oxide with a lower molecular weight compound. n usually varies from 2 to 24. 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. Preferred nonionic surfactants for use in the compositions according to the invention are the condensation products of ethylene oxide with alcohols having a straight alkyl chain, having from 6 to 22 carbon atoms, wherein the degree of ethoxylation is from 5 to 12 Most preferred are C8-C12 ethoxylated alcohols with a degree of ethoxylation of 6; these surfactants are commercially available from Shell under the trade name Dobanol R 91-6. These nonionics are preferred because they have been found to allow the formulation of a stable product without requiring the addition of stabilizers or hydrotopes. When using other nonionics, it may be necessary to add hydrotopes such as cumene sulphonate or solvents such as butyldiglycolether The compositions according to the invention may additionally comprise optional ingredients such as colorants, bactericides, perfumes, thickeners, and the like.
Experimental Data a) Effect of soap scum on the limescale removing capacity of malefic acid, and effect of surfactants. .
The limescale removing (LSR) capacity of different solutions was measured by soaking a marble block of WO 92/13058 pCT/US92/0025U
2100~~-~
standardized size in these solutions during 30 minutes;
marble blocks are chemically speaking very similar to lime scale, i.e. contain essentially calcium carbonate. Each marble block is weighed before and after the experiment, and the performance is expressed in grams of marble block "dissolved" during the 30 minutes.
-Composition A in an aqueous solution containing 8% of malefic acid.
-Composition B is an aqueous composition comprising 8%
malefic acid and 3% of a , C8-12 alcohol 6 times ethoxylated (nonionic surfactant) -Composition C is an aqueous solution comprising 8% malefic acid and 3% of Coconut alkyl sulfate (anionic surfactant) This experiment was conducted for these three compositions in two different conditions, either using a clean marble block, or a soap scum covered marble block.
The results were:
Compositions: A ~ B ~ C
________________________________________~____________i_____ LSR/clean marble block: 0.88 ~ 0.89 0.78 ISR/ soap scum covered: 0.36 ~ 0.86 0.60 The above results call for the following comments:
-The different results for composition A show that soap scum is detrimental to the LSR of malefic acid (0.88 vs 0.36).
-The comparable results for composition B shows that the 2~.~~~~
presence of nonionic surfactants addresses this issue (0.89 vs 0.86) -The results for composition C show that anionic surfactants are less efficient in addressing this issue.(0.78 vs 0.60) -comparing the results of all three compositions using the clean marble block shows that nonionic surfactants do not affect the LSR of malefic acid (0.89 vs 0.88) while anionic do (0.78 vs 0.88). This is confirmed when the test is performed using the soap scum covered marble block.
b) Comparison of lime scale removing capacity of different dicarboxylic acids:
Different dicarboxylic acids were tested at 2%, 5% and 10%
in a base composition . Marble blocks of standardized size , were then soaked in each of these compositions, and the LSR
was determined as in the previous test in a) herein above.
NS stands for "not soluble" i.e. the tested acid is not soluble in the tested composition.
The results were:
Base composition (ref): 0.14 Adipic acid: 2%: 0.08 5%: NS
10%: NS
Malic acid: 2%: 0.09 5%: 0.16 10%: 0.25 Fumaric acid: 2%: NS
5%: NS
10%: NS
standardized size in these solutions during 30 minutes;
marble blocks are chemically speaking very similar to lime scale, i.e. contain essentially calcium carbonate. Each marble block is weighed before and after the experiment, and the performance is expressed in grams of marble block "dissolved" during the 30 minutes.
-Composition A in an aqueous solution containing 8% of malefic acid.
-Composition B is an aqueous composition comprising 8%
malefic acid and 3% of a , C8-12 alcohol 6 times ethoxylated (nonionic surfactant) -Composition C is an aqueous solution comprising 8% malefic acid and 3% of Coconut alkyl sulfate (anionic surfactant) This experiment was conducted for these three compositions in two different conditions, either using a clean marble block, or a soap scum covered marble block.
The results were:
Compositions: A ~ B ~ C
________________________________________~____________i_____ LSR/clean marble block: 0.88 ~ 0.89 0.78 ISR/ soap scum covered: 0.36 ~ 0.86 0.60 The above results call for the following comments:
-The different results for composition A show that soap scum is detrimental to the LSR of malefic acid (0.88 vs 0.36).
-The comparable results for composition B shows that the 2~.~~~~
presence of nonionic surfactants addresses this issue (0.89 vs 0.86) -The results for composition C show that anionic surfactants are less efficient in addressing this issue.(0.78 vs 0.60) -comparing the results of all three compositions using the clean marble block shows that nonionic surfactants do not affect the LSR of malefic acid (0.89 vs 0.88) while anionic do (0.78 vs 0.88). This is confirmed when the test is performed using the soap scum covered marble block.
b) Comparison of lime scale removing capacity of different dicarboxylic acids:
Different dicarboxylic acids were tested at 2%, 5% and 10%
in a base composition . Marble blocks of standardized size , were then soaked in each of these compositions, and the LSR
was determined as in the previous test in a) herein above.
NS stands for "not soluble" i.e. the tested acid is not soluble in the tested composition.
The results were:
Base composition (ref): 0.14 Adipic acid: 2%: 0.08 5%: NS
10%: NS
Malic acid: 2%: 0.09 5%: 0.16 10%: 0.25 Fumaric acid: 2%: NS
5%: NS
10%: NS
8 g PCT/US92/00250 2~.~0~~
succinic acid: 2%: 0.11 5%: 0.19 10%: NS
Lactic acid: 2%: 0.10 5%: 0.18 10%: 0.27 Glutaric acid: 2%: 0.11 5%: 0.15 10%: 0.18 Malefic acid: 2%: 0.13 5%: 0.39 10%: 0.74 The above results show that malefic acid has a higher LSR
than the other dicarboxylic acids tested.
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succinic acid: 2%: 0.11 5%: 0.19 10%: NS
Lactic acid: 2%: 0.10 5%: 0.18 10%: 0.27 Glutaric acid: 2%: 0.11 5%: 0.15 10%: 0.18 Malefic acid: 2%: 0.13 5%: 0.39 10%: 0.74 The above results show that malefic acid has a higher LSR
than the other dicarboxylic acids tested.
2100~~~ 9 O O O N
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Claims (7)
1. An aqueous cleaning composition for hard surfaces comprising from 1% to 15% by weight of the total composition of a nonionic surfactant or mixtures thereof, from 4% to 25%
by weight of the total composition of maleic acid, said composition having a pH as is of from 1.0 to 4Ø
by weight of the total composition of maleic acid, said composition having a pH as is of from 1.0 to 4Ø
2. A composition according to claim 1 comprising from 6%
to 10% by weight of the total composition of maleic acid.
to 10% by weight of the total composition of maleic acid.
3. A composition according to claim 1 having a pH as is of from 1.0 to 2Ø
4. A composition according to claim 2 comprising from 20 to 4% by weight of the total composition of a nonionic surfactant or mixtures thereof.
5. A composition according to claim 1, 2, 3 or 4 wherein the nonionic surfactant is a condensation product of ethylene oxide with an alcohol, said alcohol having a straight alkyl chain comprising from 6 to 22 carbon atoms, said condensation product having a degree of ethoxylation of from 5 to 12.
6. A composition according to claim 1, 2, 3 or 4 which is substantially free of anionic or cationic surfactant.
7. A composition according to claim 1, 2, 3 or 4 which is substantially free of phosphoric acid.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP91870011.3 | 1991-01-22 | ||
| EP91870011A EP0496188B1 (en) | 1991-01-22 | 1991-01-22 | Limescale removing composition |
| PCT/US1992/000250 WO1992013058A1 (en) | 1991-01-22 | 1992-01-21 | Limescale removing composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2100096A1 CA2100096A1 (en) | 1992-07-23 |
| CA2100096C true CA2100096C (en) | 2001-01-16 |
Family
ID=8209009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002100096A Expired - Fee Related CA2100096C (en) | 1991-01-22 | 1992-01-21 | Limescale removing composition |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0496188B1 (en) |
| JP (1) | JP3217356B2 (en) |
| AR (1) | AR244786A1 (en) |
| AT (1) | ATE159542T1 (en) |
| BR (1) | BR9205495A (en) |
| CA (1) | CA2100096C (en) |
| DE (1) | DE69128025T2 (en) |
| DK (1) | DK0496188T3 (en) |
| ES (1) | ES2108040T3 (en) |
| GR (1) | GR3025119T3 (en) |
| MX (1) | MX9200253A (en) |
| TR (1) | TR25673A (en) |
| WO (1) | WO1992013058A1 (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2667865B1 (en) * | 1990-10-12 | 1992-12-11 | Saint Gobain Isover | PHENOLIC RESIN, PROCESS FOR PREPARING THE RESIN, AND SIZING COMPOSITION OF MINERAL FIBERS CONTAINING THE SAME. |
| FR2683939B1 (en) * | 1991-11-20 | 1993-12-31 | Gec Alsthom Sa | MEDIUM VOLTAGE SELF-DISCONNECTING CIRCUIT BREAKER AND APPLICATION TO A CELL AND A MEDIUM VOLTAGE STATION. |
| TW211595B (en) * | 1991-12-07 | 1993-08-21 | Hoechst Ag | |
| EP0616028A1 (en) * | 1993-03-19 | 1994-09-21 | The Procter & Gamble Company | Cleaning compositions with short chain nonionic surfactants |
| ES2123633T3 (en) * | 1992-12-04 | 1999-01-16 | Procter & Gamble | CLEANING COMPOSITION OF SELF-HEAVY ACID CHARACTER. |
| US5981455A (en) * | 1993-03-19 | 1999-11-09 | The Procter & Gamble Company | Cleaning compositions with short chain nonionic surfactants |
| US5384063A (en) * | 1993-03-19 | 1995-01-24 | The Procter & Gamble Company | Acidic liquid detergent compositions for bathrooms |
| EP0616026A1 (en) * | 1993-03-19 | 1994-09-21 | The Procter & Gamble Company | Concentrated cleaning compositions |
| EP0616027A1 (en) * | 1993-03-19 | 1994-09-21 | The Procter & Gamble Company | Concentrated cleaning compositions |
| WO1994021772A1 (en) * | 1993-03-19 | 1994-09-29 | The Procter & Gamble Company | Acidic liquid detergent compositions for bathrooms |
| US5399280A (en) * | 1993-07-22 | 1995-03-21 | The Procter & Gamble Company | Acidic liquid detergent compositions for bathrooms |
| BR9408132A (en) * | 1993-11-24 | 1997-08-05 | Unilever Nv | Viscous stable compositions for removing lime scale |
| PT666303E (en) * | 1994-02-03 | 2001-08-30 | Procter & Gamble | COMPOSITIONS FOR REMOVAL OF CALCARY SCREW |
| EP0666306B1 (en) * | 1994-02-03 | 1999-12-08 | The Procter & Gamble Company | Acidic cleaning compositions |
| DE29511365U1 (en) * | 1995-07-16 | 1995-11-23 | Yankee Polish Lueth Gmbh & Co | Liquid cleaner |
| DE19525604C2 (en) * | 1995-07-16 | 1998-09-03 | Yankee Polish Lueth Gmbh & Co | Liquid cleaner and its use |
| ATE226623T1 (en) | 1995-08-09 | 2002-11-15 | Procter & Gamble | ACIDIC CLEANING COMPOSITIONS |
| ATE293673T1 (en) * | 1998-05-15 | 2005-05-15 | Procter & Gamble | LIQUID, ACIDIC CLEANING COMPOSITION FOR HARD SURFACES |
| GB0004130D0 (en) | 2000-02-23 | 2000-04-12 | Procter & Gamble | Detergent tablet |
| EP1679362A1 (en) * | 2005-01-10 | 2006-07-12 | The Procter & Gamble Company | Cleaning composition for washing-up or washing machine |
| EP1679363B1 (en) | 2005-01-10 | 2008-07-09 | The Procter and Gamble Company | Cleaning composition for washing-up or washing machine |
| WO2017201404A1 (en) * | 2016-05-19 | 2017-11-23 | Ecolab Usa Inc. | Cleaning compositions for use with calcite-based stone |
| KR200497203Y1 (en) | 2021-04-15 | 2023-08-31 | (주)서원하이텍 | Fishing lure assembly |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3277008A (en) * | 1962-04-20 | 1966-10-04 | Pfaudler Permutit Inc | Surface cleaning method and composition |
| ZA826902B (en) * | 1981-10-01 | 1984-04-25 | Colgate Palmolive Co | Safe liquid toilet bowl cleaner |
| FR2522318A1 (en) * | 1982-02-26 | 1983-09-02 | Foucart Patrick | INDUSTRIAL PRODUCT FOR PREVENTING INCREASE IN STEAM IRONING BOILERS, STEAM BOILERS FOR PRESSING AND INDUSTRIAL STEAM BOILERS, AND USE THEREOF IN IRONS AND BOILERS |
| DE3340033A1 (en) * | 1983-11-05 | 1985-05-15 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING A LAUNDRY TREATMENT PRODUCT |
| JPS60212411A (en) * | 1984-04-06 | 1985-10-24 | Kao Corp | Preparation of polymaleic acid and its copolymer |
| US5192460A (en) * | 1988-02-10 | 1993-03-09 | Colgate-Palmolive Company | Safe acidic hard surface cleaner |
| US5008030A (en) * | 1989-01-17 | 1991-04-16 | Colgate-Palmolive Co. | Acidic disinfectant all-purpose liquid cleaning composition |
-
1991
- 1991-01-22 ES ES91870011T patent/ES2108040T3/en not_active Expired - Lifetime
- 1991-01-22 DK DK91870011.3T patent/DK0496188T3/en active
- 1991-01-22 AT AT91870011T patent/ATE159542T1/en not_active IP Right Cessation
- 1991-01-22 DE DE69128025T patent/DE69128025T2/en not_active Expired - Lifetime
- 1991-01-22 EP EP91870011A patent/EP0496188B1/en not_active Expired - Lifetime
-
1992
- 1992-01-17 TR TR92/0040A patent/TR25673A/en unknown
- 1992-01-21 BR BR9205495A patent/BR9205495A/en not_active Application Discontinuation
- 1992-01-21 CA CA002100096A patent/CA2100096C/en not_active Expired - Fee Related
- 1992-01-21 JP JP50619292A patent/JP3217356B2/en not_active Expired - Fee Related
- 1992-01-21 WO PCT/US1992/000250 patent/WO1992013058A1/en active Application Filing
- 1992-01-21 MX MX9200253A patent/MX9200253A/en not_active IP Right Cessation
- 1992-01-22 AR AR92321662A patent/AR244786A1/en active
-
1997
- 1997-10-23 GR GR970402530T patent/GR3025119T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06505293A (en) | 1994-06-16 |
| AR244786A1 (en) | 1993-11-30 |
| TR25673A (en) | 1993-07-01 |
| MX9200253A (en) | 1992-07-01 |
| ATE159542T1 (en) | 1997-11-15 |
| JP3217356B2 (en) | 2001-10-09 |
| DK0496188T3 (en) | 1997-12-15 |
| DE69128025D1 (en) | 1997-11-27 |
| CA2100096A1 (en) | 1992-07-23 |
| BR9205495A (en) | 1994-03-01 |
| ES2108040T3 (en) | 1997-12-16 |
| GR3025119T3 (en) | 1998-01-30 |
| DE69128025T2 (en) | 1998-04-16 |
| EP0496188A1 (en) | 1992-07-29 |
| WO1992013058A1 (en) | 1992-08-06 |
| EP0496188B1 (en) | 1997-10-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |