EP0912676B1 - Ameliorations concernant des compositions de detartrage - Google Patents

Ameliorations concernant des compositions de detartrage Download PDF

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Publication number
EP0912676B1
EP0912676B1 EP97921788A EP97921788A EP0912676B1 EP 0912676 B1 EP0912676 B1 EP 0912676B1 EP 97921788 A EP97921788 A EP 97921788A EP 97921788 A EP97921788 A EP 97921788A EP 0912676 B1 EP0912676 B1 EP 0912676B1
Authority
EP
European Patent Office
Prior art keywords
acid
compositions
acids
limescale
average
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.)
Expired - Lifetime
Application number
EP97921788A
Other languages
German (de)
English (en)
Other versions
EP0912676A1 (fr
Inventor
Marilena Coruzzi
Luciano Novita
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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 NV filed Critical Unilever PLC
Publication of EP0912676A1 publication Critical patent/EP0912676A1/fr
Application granted granted Critical
Publication of EP0912676B1 publication Critical patent/EP0912676B1/fr
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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D1/02—Anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic 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 minor 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 lesser minor 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-C10 organic acid other than oxalic and malonic acid, an aminoalkylenephosphonic 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.
  • WO 94/09108 discloses general purpose cleaning compositions of pH below 6 comprising anionic surfactants, C10-C18 monocarboxylic acids, a semi-polar solvent, a polycarboxylic acid and a base.
  • anionic surfactants C10-C18 monocarboxylic acids
  • semi-polar solvent a semi-polar solvent
  • polycarboxylic acid a base.
  • the combination of solvent and fatty acid provides a foam-boosting effect at acid pH, but easy rinsing on dilution with mildly alkaline water.
  • limescale-removing compositions of pH 1-5 comprising:
  • a limescale-removing composition of pH 1-5 comprising:
  • 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 in 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).
  • 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 in the compositions of the present invention include monocarboxylic 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 in 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. Unichema).
  • Typical levels of fatty acids range from 0.1-3%wt on product, with a range of 0.1-1%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 10 -C 18 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 1%wt being used in concentrated products.
  • 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 0.1-1%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. TABLE 1 Example 1 2 LES 1EO 5.0 10.0 Fatty Acid 0.25 0.5 Dicarb Acid 4.0 8.0 Phos. Acid 0.5 1.0 Base 0.38 0.76 Preservative 0.016 0.032 Perfume 0.5 1.0 Water to 100 to 100

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Health & Medical Sciences (AREA)
  • Detergent Compositions (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Fodder In General (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Claims (4)

  1. Composition de détartrage de pH 1 - 5, comprenant :
    a) 1 - 15 % en poids d'un acide dicarboxylique ;
    b) 0,1 - 10 % en poids d'un acide gras avec une longueur moyenne de chaîne carbonée de C10 - C16 ; et
    c) 1 - 30 % en poids d'un tensioactif anionique autre qu'un acide gras
    et ne contenant pas de solvants organiques.
  2. Composition selon la revendication 1, dans laquelle l'acide dicarboxylique comprend un ou plusieurs acides parmi l'acide adipique, l'acide glutarique, l'acide succinique et les mélanges de ceux-ci.
  3. Composition selon la revendication 1 ou 2, dans laquelle le tensioactif anionique comprend un ou plusieurs des composants du groupe comprenant : les sulfates d'alcools primaires et secondaires, les alkoxy sulfates d'alcool, les alcanes sulfates primaires et secondaires, les alcanes sulfonates primaires et secondaires et les alkyl aryl sulfonates.
  4. Composition de détartrage de pH 3,0 - 4,9 comprenant :
    a) 2 - 10 % en poids d'un ou de plusieurs acides dicarboxyliques sélectionnés à partir de l'acide adipique, de l'acide succinique et de l'acide glutarique ;
    b) 0,1 - 3,0 % en poids d'un acide gras en C10 - C16 (en moyenne) ;
    c) 2 - 14 % en poids d'un alkoxy sulfate d'alcool en C10 - C18 avec en moyenne 0,5 - 3 moles d'éthoxylation ;
    d) 0 - 5 % d'acide phosphorique ;
    e) 0-5 % de base
    et ne contenant pas de solvants organiques.
EP97921788A 1996-05-24 1997-04-25 Ameliorations concernant des compositions de detartrage Expired - Lifetime EP0912676B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9610965 1996-05-24
GBGB9610965.7A GB9610965D0 (en) 1996-05-24 1996-05-24 Improvements relating to limescale removing compositions
PCT/EP1997/002161 WO1997045515A1 (fr) 1996-05-24 1997-04-25 Ameliorations concernant des compositions de detartrage

Publications (2)

Publication Number Publication Date
EP0912676A1 EP0912676A1 (fr) 1999-05-06
EP0912676B1 true EP0912676B1 (fr) 2002-02-27

Family

ID=10794296

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97921788A Expired - Lifetime EP0912676B1 (fr) 1996-05-24 1997-04-25 Ameliorations concernant des compositions de detartrage

Country Status (10)

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

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2838130B1 (fr) * 2002-04-08 2004-05-28 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

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4581161A (en) * 1984-01-17 1986-04-08 Lever Brothers Company Aqueous liquid detergent composition with dicarboxylic acids and organic solvent
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
ES2097544T5 (es) * 1992-10-16 2000-10-16 Unilever Nv Mejoras en composiciones de limpieza de caracter general.
DE69409254T2 (de) * 1993-11-24 1998-07-16 Unilever Nv Zusammensetzung zum entfernen von kesselstein

Also Published As

Publication number Publication date
DE69710728D1 (de) 2002-04-04
AU2772597A (en) 1998-01-05
DE69710728T2 (de) 2004-07-08
ES2171935T3 (es) 2002-09-16
AU723832B2 (en) 2000-09-07
AR007213A1 (es) 1999-10-13
EP0912676A1 (fr) 1999-05-06
CA2254844C (fr) 2003-10-21
ZA973931B (en) 1998-11-09
WO1997045515A1 (fr) 1997-12-04
GB9610965D0 (en) 1996-07-31
BR9709268A (pt) 1999-08-10
CA2254844A1 (fr) 1997-12-04

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