EP0496188A1 - Limescale removing composition - Google Patents

Limescale removing composition Download PDF

Info

Publication number
EP0496188A1
EP0496188A1 EP91870011A EP91870011A EP0496188A1 EP 0496188 A1 EP0496188 A1 EP 0496188A1 EP 91870011 A EP91870011 A EP 91870011A EP 91870011 A EP91870011 A EP 91870011A EP 0496188 A1 EP0496188 A1 EP 0496188A1
Authority
EP
European Patent Office
Prior art keywords
composition
compositions
limescale
maleic acid
acid
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
EP91870011A
Other languages
German (de)
French (fr)
Other versions
EP0496188B1 (en
Inventor
Eddy Vos
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AT91870011T priority Critical patent/ATE159542T1/en
Priority to DE69128025T priority patent/DE69128025T2/en
Priority to EP91870011A priority patent/EP0496188B1/en
Priority to DK91870011.3T priority patent/DK0496188T3/en
Priority to ES91870011T priority patent/ES2108040T3/en
Priority to TR92/0040A priority patent/TR25673A/en
Priority to MX9200253A priority patent/MX9200253A/en
Priority to JP50619292A priority patent/JP3217356B2/en
Priority to BR9205495A priority patent/BR9205495A/en
Priority to US08/090,073 priority patent/US6001792A/en
Priority to PCT/US1992/000250 priority patent/WO1992013058A1/en
Priority to CA002100096A priority patent/CA2100096C/en
Priority to AR92321662A priority patent/AR244786A1/en
Publication of EP0496188A1 publication Critical patent/EP0496188A1/en
Application granted granted Critical
Publication of EP0496188B1 publication Critical patent/EP0496188B1/en
Priority to GR970402530T priority patent/GR3025119T3/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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

Definitions

  • 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.
  • 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.
  • limescale deposits are removed by using a cleaning composition comprising an acid which "dissolves" limescale, typically phosphoric acid.
  • an acid which "dissolves" limescale typically phosphoric acid.
  • 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.
  • compositions for the removal of limestone traces on laundry contain maleic 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 maleic acid.
  • J 61 28 3700 discloses detergent compositions for bathroom which comprises a maleic 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. Maleic acid is not mentioned.
  • compositions according to the invention are aqueous compositions comprising 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; said compositions having a pH as is of from 1.0 to 4.0.
  • the present invention is partly based on the finding that Maleic 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 maleic acid. This percentage is calculated on the basis of the molecular weight of the acid form, but maleic anhydride is equally convenient for use in the compositions according to the present invention. Indeed, maleic 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 maleic 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 maleic acid.
  • compositions according to the invention have a pH as is of from 1.0 to 4.0.
  • 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 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.
  • compositions according to the present invention also comprise a nonionic surfactant system.
  • 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.
  • 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(CH2CH2O)nH, 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.
  • Nonionic 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
  • compositions according to the invention may additionally comprise optional ingredients such as colorants, bactericides, perfumes, thickeners, and the like.
  • the limescale removing (LSR) capacity of different solutions was measured by soaking a marble block of 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.
  • NS stands for "not soluble” i.e. the tested acid is not soluble in the tested composition.

Landscapes

  • 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 an pH as is of from 1.0 to 4.0. These compositions are effective in removing limescale from hard surfaces.

Description

    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.
  • 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 maleic 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 maleic acid.
  • J 61 28 3700 (abstract) discloses detergent compositions for bathroom which comprises a maleic 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. Maleic acid is not mentioned.
    • Summary of the invention
  • The compositions according to the invention are aqueous compositions comprising 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; said compositions having a pH as is of from 1.0 to 4.0.
    • Detailed description of the invention.
  • The present invention is partly based on the finding that Maleic 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 maleic acid. This percentage is calculated on the basis of the molecular weight of the acid form, but maleic anhydride is equally convenient for use in the compositions according to the present invention. Indeed, maleic 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 maleic 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 maleic acid.
  • The compositions according to the invention have a pH as is of from 1.0 to 4.0. 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 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 maleic 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(CH2CH2O)nH, 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. Nonionic 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 maleic acid, and effect of surfactants. :
  • The limescale removing (LSR) capacity of different solutions was measured by soaking a marble block of 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 maleic acid.
    • Composition B is an aqueous composition comprising 8% maleic acid and 3% of a , C8-12 alcohol 6 times ethoxylated (nonionic surfactant)
    • Composition C is an aqueous solution comprising 8% maleic 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
    -
    LSR/clean marble block: 0.78 0.88 0.89
    LSR/ soap scum covered: 0.60 0.36 0.86

    The above results call for the following comments:
    • The different results for composition A show that soap scum is detrimental to the LSR of maleic acid (0.88 vs 0.36).
    • The comparable results for composition B shows that the 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 maleic 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
    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
    Maleic acid: 2%: 0.13
    5%: 0.39
    10%: 0.74
  • The above results show that maleic acid has a higher LSR than the other dicarboxylic acids tested.
    Figure imgb0001

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 4.0.
  2. A composition according to claim 1 comprising from 6% to 10% by weight of the total composition of maleic acid
  3. A composition according to claim 1 or 2, having a pH as is of from 1.0 to 2.0, preferably 1.2.
  4. A composition according to any of the preceeding claims comprising from 2% to 4% by weight of the total composition of a nonionic surfactant or mixtures thereof.
  5. A composition according to any of the preceeding claims 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, preferably 8 to 12, said condensation product having a degree of ethoxylation of from 5 to 12, preferably 6.
  6. A composition according to any of the preceeding claims which is substantially free of anionic or cationic surfactant.
  7. A composition according to any of the preceeding claims which is substantially free of phosphoric acid.
EP91870011A 1991-01-22 1991-01-22 Limescale removing composition Expired - Lifetime EP0496188B1 (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
AT91870011T ATE159542T1 (en) 1991-01-22 1991-01-22 SCALE REMOVAL COMPOSITION
DE69128025T DE69128025T2 (en) 1991-01-22 1991-01-22 Composition for removing scale
EP91870011A EP0496188B1 (en) 1991-01-22 1991-01-22 Limescale removing composition
DK91870011.3T DK0496188T3 (en) 1991-01-22 1991-01-22 Composition for removing lime coatings
ES91870011T ES2108040T3 (en) 1991-01-22 1991-01-22 COMPOSITION TO ELIMINATE CALCIUM CARBON CRUST.
TR92/0040A TR25673A (en) 1991-01-22 1992-01-17 CLEANING COMPUTER FOR THE REMOVAL OF THE TIRE LAYER ON THE HARD SURFACES.
JP50619292A JP3217356B2 (en) 1991-01-22 1992-01-21 Composition for removing lime scale
BR9205495A BR9205495A (en) 1991-01-22 1992-01-21 LIME INCRUSTATION REMOVAL COMPOSITION
MX9200253A MX9200253A (en) 1991-01-22 1992-01-21 COMPOSITION TO REMOVE LIMESTONE INCRUSTATION
US08/090,073 US6001792A (en) 1991-01-22 1992-01-21 Limescale removing composition containing maleic acid
PCT/US1992/000250 WO1992013058A1 (en) 1991-01-22 1992-01-21 Limescale removing composition
CA002100096A CA2100096C (en) 1991-01-22 1992-01-21 Limescale removing composition
AR92321662A AR244786A1 (en) 1991-01-22 1992-01-22 A compound for removing calcareous encrustation.
GR970402530T GR3025119T3 (en) 1991-01-22 1997-10-23 Limescale removing composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP91870011A EP0496188B1 (en) 1991-01-22 1991-01-22 Limescale removing composition

Publications (2)

Publication Number Publication Date
EP0496188A1 true EP0496188A1 (en) 1992-07-29
EP0496188B1 EP0496188B1 (en) 1997-10-22

Family

ID=8209009

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91870011A Expired - Lifetime EP0496188B1 (en) 1991-01-22 1991-01-22 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)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0601990A1 (en) * 1992-12-04 1994-06-15 The Procter & Gamble Company Self-thickened acidic cleaning composition
EP0616028A1 (en) * 1993-03-19 1994-09-21 The Procter & Gamble Company Cleaning compositions with short chain nonionic surfactants
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
TR26094A (en) * 1990-10-12 1994-12-15 Saint Gobain Isover THE PHENOL RECINES, THE REINTAINATION PREPARATION METHOD AND THE MINERAL LIF GLUE COMPOSITION CONTAINING THIS RECINDE
US5384063A (en) * 1993-03-19 1995-01-24 The Procter & Gamble Company Acidic liquid detergent compositions for bathrooms
TR26294A (en) * 1991-11-20 1995-03-15 Alsthom Gec AUTOMATIC CUTTER WITH MEDIUM VOLTAGE SALTER AND USE IN MEDIUM TENSIONED DEVICES WITH A CELL.
TR26594A (en) * 1991-12-07 1995-03-15 Hoechst Ag PROCEDURE FOR THE MANUFACTURING OF A MODIFIED FIBER MATERIAL AND THE DYEING OF THE MODIFIED FIBER MATERIAL WITH ANIONIC TEXTILE DYES.
US5399280A (en) * 1993-07-22 1995-03-21 The Procter & Gamble Company Acidic liquid detergent compositions for bathrooms
WO1995014756A1 (en) * 1993-11-24 1995-06-01 Unilever Plc Limescale removing composition
EP0666306A1 (en) * 1994-02-03 1995-08-09 The Procter & Gamble Company Acidic cleaning compositions
EP0666303A1 (en) * 1994-02-03 1995-08-09 The Procter & Gamble Company Limescale removing compositions
DE29511365U1 (en) * 1995-07-16 1995-11-23 Yankee Polish Lüth GmbH + Co, 21465 Reinbek Liquid cleaner
DE19525604A1 (en) * 1995-07-16 1997-01-23 Yankee Polish Lueth Gmbh & Co Liquid cleaner and its use
EP0758017A1 (en) 1995-08-09 1997-02-12 The Procter & Gamble Company Acidic cleaning compositions
US5981455A (en) * 1993-03-19 1999-11-09 The Procter & Gamble Company Cleaning compositions with short chain nonionic surfactants
EP0957156A1 (en) * 1998-05-15 1999-11-17 The Procter & Gamble Company Liquid acidic hard surface cleaning 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 (4)

* 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
EP1679362A1 (en) * 2005-01-10 2006-07-12 The Procter & 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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2106927A (en) * 1981-10-01 1983-04-20 Colgate Palmolive Co Liquid toilet bowl cleaner
EP0141395A2 (en) * 1983-11-05 1985-05-15 Henkel Kommanditgesellschaft auf Aktien Process for the preparation of a laundry treating agent
GB2156831A (en) * 1984-04-06 1985-10-16 Kao Corp Production of maleic acid polymers
EP0089256B1 (en) * 1982-02-26 1986-09-03 Pierre Lagier Scale preventing product for flat irons and boilers, and its use

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3277008A (en) * 1962-04-20 1966-10-04 Pfaudler Permutit Inc Surface cleaning method and composition
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2106927A (en) * 1981-10-01 1983-04-20 Colgate Palmolive Co Liquid toilet bowl cleaner
EP0089256B1 (en) * 1982-02-26 1986-09-03 Pierre Lagier Scale preventing product for flat irons and boilers, and its use
EP0141395A2 (en) * 1983-11-05 1985-05-15 Henkel Kommanditgesellschaft auf Aktien Process for the preparation of a laundry treating agent
GB2156831A (en) * 1984-04-06 1985-10-16 Kao Corp Production of maleic acid polymers

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TR26094A (en) * 1990-10-12 1994-12-15 Saint Gobain Isover THE PHENOL RECINES, THE REINTAINATION PREPARATION METHOD AND THE MINERAL LIF GLUE COMPOSITION CONTAINING THIS RECINDE
TR26294A (en) * 1991-11-20 1995-03-15 Alsthom Gec AUTOMATIC CUTTER WITH MEDIUM VOLTAGE SALTER AND USE IN MEDIUM TENSIONED DEVICES WITH A CELL.
TR26594A (en) * 1991-12-07 1995-03-15 Hoechst Ag PROCEDURE FOR THE MANUFACTURING OF A MODIFIED FIBER MATERIAL AND THE DYEING OF THE MODIFIED FIBER MATERIAL WITH ANIONIC TEXTILE DYES.
EP0601990A1 (en) * 1992-12-04 1994-06-15 The Procter & Gamble Company Self-thickened acidic cleaning composition
US5583265A (en) * 1993-03-19 1996-12-10 Woo; Ricky A.-M. Acidic liquid detergent compositions for bathrooms
US5384063A (en) * 1993-03-19 1995-01-24 The Procter & Gamble Company Acidic liquid detergent compositions for bathrooms
EP0616027A1 (en) * 1993-03-19 1994-09-21 The Procter & Gamble Company Concentrated cleaning compositions
EP0616026A1 (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
US5981455A (en) * 1993-03-19 1999-11-09 The Procter & Gamble Company Cleaning compositions with short chain nonionic surfactants
US5698041A (en) * 1993-03-19 1997-12-16 The Procter & Gamble Company Process for using acidic liquid detergent compositions to clean bathrooms
US5612308A (en) * 1993-03-19 1997-03-18 The Procter & Gamble Company Acidic liquid detergent compositions for bathrooms
EP0616028A1 (en) * 1993-03-19 1994-09-21 The Procter & Gamble Company Cleaning compositions with short chain nonionic surfactants
US5607913A (en) * 1993-07-22 1997-03-04 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
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
EP0666303A1 (en) * 1994-02-03 1995-08-09 The Procter & Gamble Company Limescale removing compositions
EP0666306A1 (en) * 1994-02-03 1995-08-09 The Procter & Gamble Company Acidic cleaning compositions
DE19525604A1 (en) * 1995-07-16 1997-01-23 Yankee Polish Lueth Gmbh & Co Liquid cleaner and its use
DE29511365U1 (en) * 1995-07-16 1995-11-23 Yankee Polish Lüth GmbH + Co, 21465 Reinbek Liquid cleaner
DE19525604C2 (en) * 1995-07-16 1998-09-03 Yankee Polish Lueth Gmbh & Co Liquid cleaner and its use
US5877135A (en) * 1995-07-16 1999-03-02 Yankee Polish Luth Gmbh & Co. Thixotropic liquid sanitary cleanser and its uses
EP0758017A1 (en) 1995-08-09 1997-02-12 The Procter & Gamble Company Acidic cleaning compositions
EP0957156A1 (en) * 1998-05-15 1999-11-17 The Procter & Gamble Company Liquid acidic hard surface cleaning composition
WO1999060086A1 (en) * 1998-05-15 1999-11-25 The Procter & Gamble Company Liquid acidic hard surface cleaning composition
US6537957B1 (en) 1998-05-15 2003-03-25 The Procter & Gamble Company Liquid acidic hard surface cleaning 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

Publication number Publication date
ATE159542T1 (en) 1997-11-15
TR25673A (en) 1993-07-01
ES2108040T3 (en) 1997-12-16
JP3217356B2 (en) 2001-10-09
CA2100096C (en) 2001-01-16
DE69128025D1 (en) 1997-11-27
DE69128025T2 (en) 1998-04-16
JPH06505293A (en) 1994-06-16
AR244786A1 (en) 1993-11-30
BR9205495A (en) 1994-03-01
GR3025119T3 (en) 1998-01-30
MX9200253A (en) 1992-07-01
CA2100096A1 (en) 1992-07-23
DK0496188T3 (en) 1997-12-15
EP0496188B1 (en) 1997-10-22
WO1992013058A1 (en) 1992-08-06

Similar Documents

Publication Publication Date Title
EP0496188B1 (en) Limescale removing composition
US7935668B2 (en) Particulate
EP0666306B1 (en) Acidic cleaning compositions
JPH01156399A (en) Aqueous detergent composition containing diethylene glycol monohexyl ether solvent
EP0666305B1 (en) Acidic cleaning compositions
WO1993007247A1 (en) Low-phosphate machine diswashing detergents
JPS5925895A (en) Stable liquid detergent composition
US6133218A (en) Aqueous based solvent free cleaner compositions containing two nonionic surfactants
US5977048A (en) Aqueous based solvent free cleaning degreaser compositions containing alcohol alkoxylates, polyoxyalkylene block copolymers, and fatty alcohols having oxyethylate moieties
EP0666303B1 (en) Limescale removing compositions
GB2227021A (en) Phosphate-and silicate-free cleaning compositions
US5672578A (en) Limescale removing compositions
US6001792A (en) Limescale removing composition containing maleic acid
US5545348A (en) Non-Phosphate high carbonate machine dishwashing detergents containing maleic acid homopolymer
US6180589B1 (en) Polyether hydroxycarboxylate copolymers
US5342537A (en) Rapid cooling system cleaning formulations
WO1992005238A1 (en) Liquid detergent compositions
JPH073288A (en) Detergent composition for hard surface
EP0601990A1 (en) Self-thickened acidic cleaning composition
USH1680H (en) Secondary alkyl sulfate-containing hard surface cleaning compositions
JPS63292000A (en) Stable liquid detergent composition
US5965509A (en) Aqueous based solvent free cleaner compositions containing a blend of polyoxyalkylene block copolymers and fatty alcohols oxyethylate moieties
JP4784060B2 (en) Low foam detergent
US5880082A (en) Aqueous based solvent free cleaning compositions containing alcohol alkoxylates, alkoxylated fatty alcohols and fatty alcohols having oxyethylate moieties
US5958859A (en) Aqueous based solvent free cleaner compositions containing a blend of polyoxyalkylene block copolymers

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17P Request for examination filed

Effective date: 19930115

17Q First examination report despatched

Effective date: 19951213

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 159542

Country of ref document: AT

Date of ref document: 19971115

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: RITSCHER & SEIFERT PATENTANWAELTE VSP

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69128025

Country of ref document: DE

Date of ref document: 19971127

ET Fr: translation filed
REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2108040

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed
REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3025119

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20001211

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20001212

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20001222

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20010103

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20010124

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20010129

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20010326

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20010327

Year of fee payment: 11

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020122

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020122

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020131

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020131

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020131

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020131

BERE Be: lapsed

Owner name: THE PROCTER & GAMBLE CY

Effective date: 20020131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020812

EUG Se: european patent has lapsed

Ref document number: 91870011.3

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020801

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20100115

Year of fee payment: 20

Ref country code: GB

Payment date: 20091211

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20100114

Year of fee payment: 20

Ref country code: FR

Payment date: 20100125

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20100129

Year of fee payment: 20

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20110121

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20110301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20110121

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20110123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20110122