EP0496188A1 - Limescale removing composition - Google Patents

Limescale removing composition Download PDF

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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
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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
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German (de)
French (fr)
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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
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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 DE69128025T priority Critical patent/DE69128025T2/en
Priority to AT91870011T priority patent/ATE159542T1/en
Priority to ES91870011T priority patent/ES2108040T3/en
Priority to EP91870011A priority patent/EP0496188B1/en
Priority to DK91870011.3T priority patent/DK0496188T3/en
Priority to TR92/0040A priority patent/TR25673A/en
Priority to JP50619292A priority patent/JP3217356B2/en
Priority to MX9200253A priority patent/MX9200253A/en
Priority to US08/090,073 priority patent/US6001792A/en
Priority to PCT/US1992/000250 priority patent/WO1992013058A1/en
Priority to BR9205495A priority patent/BR9205495A/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

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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

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.

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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 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
DE69128025T DE69128025T2 (en) 1991-01-22 1991-01-22 Composition for removing scale
AT91870011T ATE159542T1 (en) 1991-01-22 1991-01-22 SCALE REMOVAL COMPOSITION
ES91870011T ES2108040T3 (en) 1991-01-22 1991-01-22 COMPOSITION TO ELIMINATE CALCIUM CARBON CRUST.
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
TR92/0040A TR25673A (en) 1991-01-22 1992-01-17 CLEANING COMPUTER FOR THE REMOVAL OF THE TIRE LAYER ON THE HARD SURFACES.
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
JP50619292A JP3217356B2 (en) 1991-01-22 1992-01-21 Composition for removing lime scale
PCT/US1992/000250 WO1992013058A1 (en) 1991-01-22 1992-01-21 Limescale removing composition
BR9205495A BR9205495A (en) 1991-01-22 1992-01-21 LIME INCRUSTATION REMOVAL 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

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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
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
EP0616028A1 (en) * 1993-03-19 1994-09-21 The Procter & Gamble Company Cleaning compositions with short chain nonionic surfactants
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
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.
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.
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
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
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

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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
JP6882341B2 (en) * 2016-05-19 2021-06-02 エコラボ ユーエスエー インコーポレイティド Cleaning composition for use with calcite stones
KR200497203Y1 (en) 2021-04-15 2023-08-31 (주)서원하이텍 Fishing lure assembly

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

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