WO1997045515A1 - Improvements relating to limescale removing compositions - Google Patents

Improvements relating to limescale removing compositions Download PDF

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Publication number
WO1997045515A1
WO1997045515A1 PCT/EP1997/002161 EP9702161W WO9745515A1 WO 1997045515 A1 WO1997045515 A1 WO 1997045515A1 EP 9702161 W EP9702161 W EP 9702161W WO 9745515 A1 WO9745515 A1 WO 9745515A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
fatty acid
limescale
compositions
acids
Prior art date
Application number
PCT/EP1997/002161
Other languages
English (en)
French (fr)
Inventor
Marilena Coruzzi
Luciano Novita
Original Assignee
Unilever Plc
Unilever N.V.
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 Unilever Plc, Unilever N.V. filed Critical Unilever Plc
Priority to DE69710728T priority Critical patent/DE69710728T2/de
Priority to CA002254844A priority patent/CA2254844C/en
Priority to BR9709268A priority patent/BR9709268A/pt
Priority to EP97921788A priority patent/EP0912676B1/en
Priority to AU27725/97A priority patent/AU723832B2/en
Publication of WO1997045515A1 publication Critical patent/WO1997045515A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/37Mixtures of compounds all of which are anionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2075Carboxylic acids-salts thereof
    • C11D3/2082Polycarboxylic acids-salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/04Carboxylic acids or salts thereof
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143Sulfonic acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146Sulfuric acid esters
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • the present invention relates to compositions for the removal of limescale and/or other mineral deposits from hard surfaces.
  • Limescale mainly comprises calcium and magnesium carbonates, and can contain lesser amounts of soap scum, protein, particulates and other soils. Limescale is formed on evaporation of water containing said soils. While the deposit formed by evaporation is initially paste-like, it hardens with time to form a recalcitrant deposit.
  • Conventional cleaning compositions are generally buffered at alkaline pH so as to attack fatty soils. Limescale is resistant to the action of alkali and specialist cleaning compositions, of acid pH, are used to remove it.
  • Limescale removing compositions of maleic acid in combination with nonionic surfactants, either in further combination with ionic detergents or with phosphoric acid are known. In the absence of nonionic surfactants cleaning efficiency is greatly reduced.
  • Maleic acid is known to be a particularly effective limescale remover and is less prone to attack surfaces than the inorganic acids.
  • EP 0496188 (P&G) relates to compositions with 1-15% nonionic and 4-25% of maleic acid, having a pH of 1-4.
  • Preferred compositions are formulated at pH 1-4 and comprise maleic and nonionic at specified levels but which are substantially free of both ionic detergents and phosphoric acid.
  • GB-B-2149419 (Colgate-Palmolive, filed November 1983) relates to an acidic liquid cleaning composition of pH 3-5 which comprises a surfactant, water, a mmoi proportion of a non-sequestering acid which reacts with Ca and Mg soaps of higher fatty acids in soap scum (examples include glutaric acid) and a lessei minoi proportion of an acid which forms a water insoluble calcium salt (phosphoric acid is given as an example) , both acids being partially neutralised to a pH of 3-5.
  • EP-B-0411708 (Colgate-Palmolive: filed 31 July 1989) relates to an acidic (pH 1-4) aqueous cleaner for baths which are acid resistant or of zirconium white enamel which comprises surfactant, a C2-CJ0 organic ac ⁇ .d other than oxalic and malonic acid, an anunoalkylenephosphonic acid and phosphoric acid.
  • EP-B-0040343 (BASF: filed 16 May 1980) is a granted
  • European patent which relates to a composition comprising ethoxylated alcohol nonionic surfactant and C4-C8 aliphatic dicarboxylic acids or mixtures of such.
  • the acids are present as 'colour stabilizers' and include a mixture of succinic, adipic and glutaric acids in the examples of the patent.
  • EP 0606712 (Clorox: published July 1994) relates to pH approx 2-3.5 cleaning formulations for the removal of mineral deposits which contain 3-10% in total of both a weak acid and its conjugate base at a molar ratio of 1:30 to 30:1 in which the weak acid has a pKa of 2-3.5.
  • the compositions disclosed in this specification comprise citric acid (a tricarboxylic acid) and sodium citrate dihydrate as the limescale removing acids.
  • limescale-removing compositions of pH 1-5 comprising:
  • a limescale-removing composition of pH 1-5 comprising:
  • a second aspect of the present invention provides for the use, as a low temperature stabilising additive in a limescale removing composition
  • a limescale removing composition comprising l-15%wt of a dicarboxylic acid and l-30%wt of an anionic surfactant other than fatty acid, of 0.1-10%wi of a fatty acid.
  • Dicarboxylic acids suitable for use in the present invention include adipic, glutaric and succinic acid and mixtures thereof.
  • the mixtures are preferred as these are commercially available.
  • Typical mixtures which can be found m the marketplace comprise 30-35% adipic acid, 45- 50% glutaric acid and 10-18% succinic acid.
  • Such a mixture is available in the marketplace as Sokalan DCS (TM, ex. BASF) .
  • Another suitable mixture is available as Radimix (TM, ex. Radici).
  • TM Ex. Radici
  • the use of essentially pure acids is not excluded but these have limited commercial availability and the mixed acids are preferred.
  • Typical levels of total dicarboxylic acid in the product range from 2-10%wt. Levels of 3-5% are preferred for dilute compositions and levels of 6-9% for concentrates.
  • Fatty acids suitable for use m the compositions of the present invention include moncarboxylic acids with an average carbon chain length in the range C10-C18, preferably C12-C16.
  • C14 average chain length linear fatty acids are particularly preferred. Longer chain length fatty acids are less soluble m the absence of expensive hydrotropes (such as alcohol and alkaryl sulphonates) or organic solvents. Suitable fatty acids are available in the marketplace as PRIFAC 7907 (TM ex. Umchema) .
  • Typical levels of fatty acids range from 0.1-3%wt on product, with a range of 0.1-l%wt being particularly preferred. Typical levels in dilute compositions are 0.25%wt with 0.5%wt being used in more concentrated products.
  • the anionic surfactant comprises one or more of the group comprising: primary and secondary alcohol sulphates, alcohol alkoxy sulphates, primary and secondary alkane sulphonates and alkyl aryl sulphonates.
  • the preferred anionic surfactants are the alcohol alkoxy sulphates, preferably the ether-sulphates. Most preferably C ⁇ n -C, average chain length ether sulphates with an average of 0.5-3 moles of ethoxylation. Lauryl ether sulphate (1EO) is a suitable anionic surfactant for compositions of the invention.
  • Preferred levels of anionic surfactant range from 2-14%wt. Preferably 3-7%wt surfactant is present in dilute compositions and 8-12%wt is present in concentrated compositions.
  • compositions of the invention comprise one or more corrosion inhibitors.
  • Phosphoric acid is a suitable corrosion inhibitor, and when present is conveniently employed at a level of 0.1-5%wt with levels of 0.5%wt being used in ditute product and l%wt being used in concentrated products. pH :
  • the pH of the composition is below the pKa of the fatty acid being employed.
  • the pKa of a C12-C16 fatty acid will be close to 4.9, consequently the pH of the compositions will generally be below this figure.
  • the pH of the compositions of the invention falls into the range 3.0-4.5, with a pH of around 3.5 being typical.
  • Sodium hydroxide or another suitable base is used to regulate the pH if required. Typical levels of base in the products of the invention are 0.1-l%wt.
  • Preferred levels of perfume range from 0.1-2%wt. Acid stable perfumes are available from a variety of sources including the Quest company.
  • compositions of the present invention include opacifiers, colours, preservatives and fluorescers.
  • the present invention provides a limescale- removing compositions of pH 3.0-4.9, comprising:
  • Preferred formulations for direct use comprise:
  • compositions were prepared by mixing of the components. Compositions were prepared with proportions as given in Table 1 below, all components being given in wt% as 100%wt.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Fodder In General (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
PCT/EP1997/002161 1996-05-24 1997-04-25 Improvements relating to limescale removing compositions WO1997045515A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE69710728T DE69710728T2 (de) 1996-05-24 1997-04-25 Zusammensetzungen zum entfernen von kalkstein
CA002254844A CA2254844C (en) 1996-05-24 1997-04-25 Improvements relating to limescale removing compositions
BR9709268A BR9709268A (pt) 1996-05-24 1997-04-25 Composição removedora de inscrustação de cal e uso da mesma
EP97921788A EP0912676B1 (en) 1996-05-24 1997-04-25 Improvements relating to limescale removing compositions
AU27725/97A AU723832B2 (en) 1996-05-24 1997-04-25 Improvements relating to limescale removing compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9610965.7 1996-05-24
GBGB9610965.7A GB9610965D0 (en) 1996-05-24 1996-05-24 Improvements relating to limescale removing compositions

Publications (1)

Publication Number Publication Date
WO1997045515A1 true WO1997045515A1 (en) 1997-12-04

Family

ID=10794296

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/002161 WO1997045515A1 (en) 1996-05-24 1997-04-25 Improvements relating to limescale removing compositions

Country Status (10)

Country Link
EP (1) EP0912676B1 (es)
AR (1) AR007213A1 (es)
AU (1) AU723832B2 (es)
BR (1) BR9709268A (es)
CA (1) CA2254844C (es)
DE (1) DE69710728T2 (es)
ES (1) ES2171935T3 (es)
GB (1) GB9610965D0 (es)
WO (1) WO1997045515A1 (es)
ZA (1) ZA973931B (es)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2838130A1 (fr) * 2002-04-08 2003-10-10 Rhodia Polyamide Intermediates Formulation solide antitartre a base d'acide adipique et son utilisation en lavage automatique de la vaisselle
US10683468B1 (en) 2017-06-05 2020-06-16 Miguel Angel Regalado, Sr. Water mineral cleaning solutions and related methods
US10988712B1 (en) 2017-06-05 2021-04-27 Miguel Angel Regalado, Sr. Water mineral cleaning solutions and related methods

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0151517A2 (en) * 1984-01-17 1985-08-14 Unilever N.V. Liquid detergent composition
JPS61157593A (ja) * 1984-12-28 1986-07-17 ライオン株式会社 浴室用洗浄剤組成物
WO1994009108A1 (en) * 1992-10-16 1994-04-28 Unilever Plc Improvements in general purpose cleaning compositions
WO1995014756A1 (en) * 1993-11-24 1995-06-01 Unilever Plc Limescale removing composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0151517A2 (en) * 1984-01-17 1985-08-14 Unilever N.V. Liquid detergent composition
JPS61157593A (ja) * 1984-12-28 1986-07-17 ライオン株式会社 浴室用洗浄剤組成物
WO1994009108A1 (en) * 1992-10-16 1994-04-28 Unilever Plc Improvements in general purpose cleaning compositions
WO1995014756A1 (en) * 1993-11-24 1995-06-01 Unilever Plc Limescale removing composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8635, Derwent World Patents Index; Class D25, AN 86-228430, XP002042367 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2838130A1 (fr) * 2002-04-08 2003-10-10 Rhodia Polyamide Intermediates Formulation solide antitartre a base d'acide adipique et son utilisation en lavage automatique de la vaisselle
WO2003085076A1 (fr) * 2002-04-08 2003-10-16 Rhodia Polyamide Intermediates Formulation solide antitartre a base d'acide adipique et son utilisation en lavage automatique de la vaisselle
US10683468B1 (en) 2017-06-05 2020-06-16 Miguel Angel Regalado, Sr. Water mineral cleaning solutions and related methods
US10988712B1 (en) 2017-06-05 2021-04-27 Miguel Angel Regalado, Sr. Water mineral cleaning solutions and related methods

Also Published As

Publication number Publication date
DE69710728D1 (de) 2002-04-04
AR007213A1 (es) 1999-10-13
AU2772597A (en) 1998-01-05
BR9709268A (pt) 1999-08-10
EP0912676B1 (en) 2002-02-27
AU723832B2 (en) 2000-09-07
ES2171935T3 (es) 2002-09-16
CA2254844A1 (en) 1997-12-04
DE69710728T2 (de) 2004-07-08
CA2254844C (en) 2003-10-21
EP0912676A1 (en) 1999-05-06
ZA973931B (en) 1998-11-09
GB9610965D0 (en) 1996-07-31

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