WO1995014756A1 - Limescale removing composition - Google Patents

Limescale removing composition Download PDF

Info

Publication number
WO1995014756A1
WO1995014756A1 PCT/EP1994/003790 EP9403790W WO9514756A1 WO 1995014756 A1 WO1995014756 A1 WO 1995014756A1 EP 9403790 W EP9403790 W EP 9403790W WO 9514756 A1 WO9514756 A1 WO 9514756A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
alpha
maleic acid
composition according
hydroxy carboxylic
Prior art date
Application number
PCT/EP1994/003790
Other languages
English (en)
French (fr)
Inventor
Elaine Ann Bowden
Alan John Fry
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
Priority claimed from GB939324126A external-priority patent/GB9324126D0/en
Priority claimed from GB9412377A external-priority patent/GB9412377D0/en
Application filed by Unilever Plc, Unilever N.V. filed Critical Unilever Plc
Priority to EP95900745A priority Critical patent/EP0730628B1/en
Priority to DE69409254T priority patent/DE69409254T2/de
Priority to AU81436/94A priority patent/AU678313B2/en
Priority to BR9408132A priority patent/BR9408132A/pt
Publication of WO1995014756A1 publication Critical patent/WO1995014756A1/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
    • 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
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic 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
    • 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
    • C11D3/2086Hydroxy carboxylic 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
    • 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
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to compositions for the removal of limescale.
  • 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.
  • a plurality of limescale removing compositions are disclosed in EP 0253676. These compositions are thickened by means of an amine or an a ine oxide and comprise an acid which may be organic or inorganic.
  • 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.
  • Maleic acid is produced from petrochemical sources and potentially oxidises to produce rancid odours.
  • Maleic acid is a relatively toxic material and is moderately expensive.
  • Other organic acids, such as citric and lactic acids are available from renewable resources, are less toxic and less prone to oxidation.
  • compositions comprising citric acid together with nonionic surfactants are unstable.
  • limescale-removing compositions of pH 1-4 comprising maleic acid, a nonionic surfactant, an anionic surfactant, a perfume and an alpha- hydroxy carboxylic acid are stable.
  • alpha-hydroxy carboxylic acid is less toxic and less prone to decomposition than an equivalent amount of maleic acid, i.e. an amount which provides comparable limescale- removing performance.
  • the alpha-hydroxy carboxylic acid interacts with the nonionic surfactant to destabilise the product in the absence of the anionic surfactant.
  • compositions comprise a fragrance.
  • a fragrance is important both to meet consumer expectations and to mask any off odours resulting from decomposition of the organic acids.
  • the presence of the anionic detergent is essential in order that the perfume can be solubilised in the composition.
  • Typical levels of maleic acid in the product range from 2- 6%wt. It is preferable that the level of maleic acid is below 4%wt so as reduce toxicity and prevent the development of excessive off odours. The most preferred level of maleic acid falls into the range more than 3.0%wt and less than 4.0%wt.
  • Preferred alpha-hydroxy carboxylic acids are lactic acid, glycolic acid and citric acid.
  • Polycarboxylic acids, particularly citric acid is the most preferred for reasons of cost, ease of availability and weight-effectiveness.
  • citric acid The preferred of citric acid are 2.5-10wt%, most preferably 2.5-7.5wt%. It is particularly preferably that the alpha-hydroxy carboxylic acid should be present in weight excess relative to the maleic acid. Ratio of alpha-hydroxy carboxylic acid to maleic acid is preferably in the range 1-2:1.
  • nonionic surfactants should not include any significant amounts of amine oxide.
  • the preferred nonionic surfactants are alkoxylated alcohols.
  • the preferred alkoxylated alcohols are selected from the group comprising ethoxylated alcohols of the general formula:
  • R x is straight or branched, C 8 to C 18 alkyl or hydroxyalkyl and m is, on average, 1-14.
  • the alkyl chain length is C 8 -C n . It is believed that this reduces the strength of the interaction with the alpha-hydroxy carboxylic acd.
  • the preferred average degree of ethoxylation m is 6-9 for good fatty soil detergency and high solubility in the composition.
  • the nonionic surfactant should have a HLB in the range 12-16.
  • nonionic surfactant ranges from 0.5- 7%wt, more preferably 0.75-3%wt.
  • 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 secondary alkane sulphonates. Most preferably the secondary alkane sulphonate is a C 12 -C 18 average chain length secondary alkane sulphonate.
  • Preferred levels of anionic surfactant range from l-10%wt, more preferably l-6%wt. It is particularly preferred that the weight ratio between the anionic surfactant to nonionic is 3:1-1:1. It is also preferable that the alpha-hydroxy carboxylic acid is present in weight excess over the total surfactant content.
  • a thickener when present are xanthan gums.
  • Preferred xanthan gums are the Kelzan (RTM) series (available from Kelco Corp) . Typical levels of xanthan gum range from 0.05-lwt%.
  • the resulting viscosity of the composition, as measured on a Haake RV2 rotoviscometer (RTM) is preferably in the range 10-200 Pas at 20 reciprocal seconds shear and 25 Celcius, using an MV1 bob. More preferably the thickened compositions have a viscosity of 10-100 mPas under the conditions mentioned above.
  • compositions of the present invention include opacifiers, colours, preservatives and fluorescers.
  • Preferred formulations comprise:
  • compositions having a pH of 1-3 and a viscosity of 3- 7 mPas as measured on a Haake RV2 rotoviscometer (RTM) at 20 reciprocal seconds shear and 25 Celcius, using an MV1 bob.
  • RTM Haake RV2 rotoviscometer
  • compositions were prepared by:
  • compositions were prepared as given in Table 1 below, all components being given as 100%wt.

Landscapes

  • 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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Processing Of Solid Wastes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
PCT/EP1994/003790 1993-11-24 1994-11-12 Limescale removing composition WO1995014756A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP95900745A EP0730628B1 (en) 1993-11-24 1994-11-12 Limescale removing composition
DE69409254T DE69409254T2 (de) 1993-11-24 1994-11-12 Zusammensetzung zum entfernen von kesselstein
AU81436/94A AU678313B2 (en) 1993-11-24 1994-11-12 Limescale removing composition
BR9408132A BR9408132A (pt) 1993-11-24 1994-11-12 Composições estáveis viscosas para remoção de incrustação de cal

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB939324126A GB9324126D0 (en) 1993-11-24 1993-11-24 Limescale removing composition
GB9324126.3 1993-11-24
GB9412377.5 1994-06-21
GB9412377A GB9412377D0 (en) 1994-06-21 1994-06-21 Limescale removing composition

Publications (1)

Publication Number Publication Date
WO1995014756A1 true WO1995014756A1 (en) 1995-06-01

Family

ID=26303909

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/003790 WO1995014756A1 (en) 1993-11-24 1994-11-12 Limescale removing composition

Country Status (7)

Country Link
EP (1) EP0730628B1 (es)
AU (1) AU678313B2 (es)
BR (1) BR9408132A (es)
CA (1) CA2175677A1 (es)
DE (1) DE69409254T2 (es)
ES (1) ES2113723T3 (es)
WO (1) WO1995014756A1 (es)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0758017A1 (en) * 1995-08-09 1997-02-12 The Procter & Gamble Company Acidic cleaning compositions
WO1997045515A1 (en) * 1996-05-24 1997-12-04 Unilever Plc Improvements relating to limescale removing compositions

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049467A (en) * 1976-04-23 1977-09-20 Lever Brothers Company Method and compositions for removal of hard surface manganese ion-derived discolorations
JPS6369895A (ja) * 1986-09-12 1988-03-29 花王株式会社 液体クレンザ−組成物
JPH01217099A (ja) * 1988-02-26 1989-08-30 Kao Corp 液体洗剤組成物
EP0496188A1 (en) * 1991-01-22 1992-07-29 The Procter & Gamble Company Limescale removing composition
WO1994005758A1 (en) * 1992-09-01 1994-03-17 The Procter & Gamble Company Liquid or gel detergent compositions containing calcium and stabilizing agent thereof
EP0601990A1 (en) * 1992-12-04 1994-06-15 The Procter & Gamble Company Self-thickened acidic cleaning composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4049467A (en) * 1976-04-23 1977-09-20 Lever Brothers Company Method and compositions for removal of hard surface manganese ion-derived discolorations
JPS6369895A (ja) * 1986-09-12 1988-03-29 花王株式会社 液体クレンザ−組成物
JPH01217099A (ja) * 1988-02-26 1989-08-30 Kao Corp 液体洗剤組成物
EP0496188A1 (en) * 1991-01-22 1992-07-29 The Procter & Gamble Company Limescale removing composition
WO1994005758A1 (en) * 1992-09-01 1994-03-17 The Procter & Gamble Company Liquid or gel detergent compositions containing calcium and stabilizing agent thereof
EP0601990A1 (en) * 1992-12-04 1994-06-15 The Procter & Gamble Company Self-thickened acidic cleaning composition

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8818, Derwent World Patents Index; AN 88-124390 *
DATABASE WPI Week 8941, Derwent World Patents Index; AN 89-295844 *
See also references of EP0730628A1 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0758017A1 (en) * 1995-08-09 1997-02-12 The Procter & Gamble Company Acidic cleaning compositions
WO1997045515A1 (en) * 1996-05-24 1997-12-04 Unilever Plc Improvements relating to limescale removing compositions
AU723832B2 (en) * 1996-05-24 2000-09-07 Unilever Plc Improvements relating to limescale removing compositions

Also Published As

Publication number Publication date
DE69409254D1 (de) 1998-04-30
AU678313B2 (en) 1997-05-22
AU8143694A (en) 1995-06-13
DE69409254T2 (de) 1998-07-16
ES2113723T3 (es) 1998-05-01
CA2175677A1 (en) 1995-06-01
EP0730628A1 (en) 1996-09-11
BR9408132A (pt) 1997-08-05
EP0730628B1 (en) 1998-03-25

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