WO2008135450A1 - A builder system for a detergent composition - Google Patents

A builder system for a detergent composition Download PDF

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Publication number
WO2008135450A1
WO2008135450A1 PCT/EP2008/055226 EP2008055226W WO2008135450A1 WO 2008135450 A1 WO2008135450 A1 WO 2008135450A1 EP 2008055226 W EP2008055226 W EP 2008055226W WO 2008135450 A1 WO2008135450 A1 WO 2008135450A1
Authority
WO
WIPO (PCT)
Prior art keywords
builder
builder system
detergent composition
calcium carbonate
weight
Prior art date
Application number
PCT/EP2008/055226
Other languages
English (en)
French (fr)
Inventor
Subir Kumar Das
Amitava Pramanik
Arpita Sarkar
Gopa Kumar Velayudhan Nair
Original Assignee
Unilever Plc
Unilever N.V.
Hindustan Unilever Limited
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., Hindustan Unilever Limited filed Critical Unilever Plc
Priority to BRPI0810888-9A2A priority Critical patent/BRPI0810888A2/pt
Priority to AT08736623T priority patent/ATE483785T1/de
Priority to DE602008002918T priority patent/DE602008002918D1/de
Priority to EP08736623A priority patent/EP2139980B1/en
Priority to CN2008800146364A priority patent/CN101675154B/zh
Publication of WO2008135450A1 publication Critical patent/WO2008135450A1/en
Priority to ZA2009/06842A priority patent/ZA200906842B/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
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/1233Carbonates, e.g. calcite or dolomite
    • 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
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/10Carbonates ; Bicarbonates
    • 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

Definitions

  • the invention relates to a builder system for use in detergent compositions.
  • the invention more particularly relates to a builder system that ensures faster removal of Calcium ions from washing solutions while being less expensive than Phosphate and Zeolite based building systems.
  • Soaps which are alkali metal salts of fatty acids have traditionally been used for personal washing applications.
  • Soaps have also been used for washing laundry. When washing laundry with soaps, the efficiency of washing is lower when washed in hard water.
  • Hard water refers to water having high levels of dissolved Calcium and Magnesium salts. The dissolved Calcium and Magnesium ions react very quickly with the alkali metal cation (sodium or potassium) of the soap, leading to formation of Calcium soap which is insoluble in water and therefore leading to poor detergency. With the advent of synthetic detergents which are alkali metal salts of long chain acids of petroleum origin, the same problem persists.
  • Most popular synthetic detergents include linear alkyl benzene sulphonates, alpha olefin sulphonates, and primary alkyl sulphates which belong to the class of anionic surfactants.
  • Surfactants of the non-ionic, cationic, amphoteric and zwitterionic character are also known. Cleaning performance of most synthetic surfactants are also affected by the washing in hard water.
  • detergency builders are alkali metal carbonates, silicates, phosphates and structured compounds like Zeolites. Alkali metal carbonates like Sodium Carbonate, commonly referred to as soda ash is a very inexpensive and widely used builder in low cost detergent formulations.
  • Premium detergents use builders like phosphates and/or Zeolites since they have better building properties but are more expensive. There has been continuous work to develop more efficient and faster building systems using less expensive materials. Further, use of phosphates in detergents, is believed by many to be responsible for the eutrophication of rivers and other natural waters bodies. Thus a lot of effort has been made to develop faster building systems using sodium carbonate as the main raw material.
  • EP0234818 discloses a detergent composition containing (i) a detergent active system comprising a mixture of (a) an anionic non-soap detergent active; (b) a non-ionic detergent active; and (c) soap; (ii) a water- soluble alkali metal carbonate; and (iii) a water-insoluble particulate carbonate material which is a seed crystal for Calcium carbonate; characterised in a specific combination of weight ratios of the various detergent actives.
  • the builder system in this publication is a mixture of soda and Calcium carbonate. There have been many improvements to this technology and many products launched which are improvements over this basic technology where combination of soda and Calcium carbonate is used.
  • the present inventors have determined that the best building systems available presently using sodium carbonate as the basic builder still do not provide the desired fast building and there is scope for improvement on this technology which can be perceived by the consumers in the cleanliness of their washed laundry or in terms of costs of the products.
  • the present inventors have found that use of the specific builder system disclosed in EP0234818 along with a specific co-builder provides for very fast building never before achieved with similar systems .
  • US7186677 (Henkel, 2007) describes a method for producing surfactant granules having good solubility and varying bulk densities comprising (a) providing a mixture of anionic surfactant acids and builder acids having a weight ratio of 1:100 to 1:20 of builder acid to surfactant acid; and (b) contacting the mixture with at least one solid neutralising agent.
  • the builder acid is selected from citric, tartaric, succinic, malonic, adipic, maleic, fumaric, oxalic, gluconic, nitrilotriacetic, aspartic, ethylenediaminetetracetic, among many other acids wherein the builder acid has a particle size below 200 ⁇ m.
  • the invention provides for a builder system for a detergent composition comprising:
  • the water solubility of the co-builder is more than 1 g/1 at 25 0 C.
  • di-carboxylic acids are oxalic, malonic and succinic acid.
  • the invention relates to a builder system for a detergent composition.
  • One component of the builder system is a water soluble alkali metal carbonate.
  • the alkali metal is preferably sodium or potassium, sodium being preferred.
  • the most preferred alkali metal carbonate is sodium carbonate.
  • the alkali metal carbonate is preferably present in an amount in the range of 10% to 90%, more preferably 25% to 90%, most preferably 45% to 80% by weight of the builder system.
  • a seed for precipitating Calcium carbonate is meant a compound which has the ability to act as a seed for precipitation of Calcium carbonate in aqueous media.
  • the seed for precipitating Calcium carbonate is a substantially water insoluble particulate material. This water insoluble particulate material may be present in the builder system or generated insitu when the builder system is dispersed in water. The more preferred aspect provides for the substantially water insoluble particulate material to be present in the builder system. A particularly preferred substantially water insoluble particulate material is
  • Calcium carbonate may be calcite, or aragonite; and is more preferably Calcite. Calcite is preferably High Surface Area Calcite.
  • the Calcium carbonate seed has a surface area greater than 20 m 2 /g, more preferably greater then 30 m 2 /g, most preferably greater than 60 m 2 /g.
  • the seed for precipitating Calcium carbonate is preferably present in an amount in the range of 5% to 50%, more preferably from 10% to 40%, most preferably from 15% to 30% by weight of the builder system.
  • the builder system of the invention comprises a co-builder which is a di-carboxylic acid or a salt thereof.
  • the co- builder preferably has water solubility of more than 1 g/1 at 25 0 C.
  • Preferred di-carboxylic acids are chosen from oxalic acid, malonic acid or succinic acid, most preferred being oxalic acid.
  • the preferred salts of the di-carboxylic acid are alkali metal or ammonium salts, alkali metal salts being more preferred.
  • the co-builder is present in an amount in the range of 2% to 20%, more preferably from 4% to 12% by weight of the builder system. The invention works best when the co-builder is present as a powder i.e in a low particle size form.
  • the average particle size of the co- builder is preferably less than 150 microns, more preferably less than 75 microns.
  • the co-builder is molecularly dispersed in the detergent composition in which the builder system is present. This can be achieved by dissolving the co-builder in water and spraying the solution onto the detergent composition or the builder system and then drying to the desired moisture content.
  • the builder system of the invention provides for relatively fast building kinetics, faster than prior art systems.
  • the builder system ensures that the Ca 2+ ion concentration in input water reduces from about 200 ppm to less than, or about, 1.2 ppm, more preferably to less than, or about, 1.0 ppm, further more preferably less than, or about, 0.5 ppm, optimally less than, or about, 0.3 ppm, in about 30 seconds.
  • the builder system of the invention is preferably substantially free of phosphate builders. Further, more preferably the builder system is substantially free of Zeolite builders.
  • a process to prepare a builder system for a detergent composition comprising mixing powders of a water soluble alkali metal carbonate, 5% to 50% by weight of the builder system a seed for precipitating Calcium carbonate, which is Calcium carbonate; and a co-builder which is a dicarboxylic acid or a salt thereof.
  • powders of the co-builder having an average particle size less than 150 microns, more preferably less than 75 microns are used.
  • the process of the invention comprises:
  • step (ii) dry mixing powders of a water soluble alkali metal carbonate with 5% to 50% by weight of the builder system a seed for precipitating Calcium carbonate, which is Calcium carbonate to form a powder mix; and (iii) mixing said solution from step (i) with the powder mix of step (ii) .
  • the solution is preferably sprayed onto the powder mix during the mixing step (iii) .
  • a detergent composition comprising (i) the builder system according to the invention and (ii) a surfactant selected from any one of the anionic, non-ionic, cationic, zwitterionic or amphoteric class.
  • the builder system of the invention may be present in an amount in the range of 5% to 80%, more preferably 15% to 60%, most preferably 25% to 50% by weight of the detergent composition.
  • Suitable surfactants are compounds commonly used as surface-active agents given in the well-known textbooks "Surface Active Agents", Volume I by Schwartz and Perry and “Surface Active Agents and Detergents", Volume II by Schwartz, Perry and Berch.
  • a process to prepare a detergent composition comprising dry mixing powders of a surfactant selected from any one of the anionic, non-ionic, cationic, zwitterionic or amphoteric class with the powders of the builder system of the present invention.
  • step (i) dissolving a dicarboxylic acid or salts thereof in water to form a solution; (ii) dry mixing powders of a surfactant selected from any one of the anionic, non-ionic, cationic, zwitterionic or amphoteric class with a water soluble alkali metal carbonate and 5% to 50% by weight of the builder system a seed for precipitating Calcium, which is Calcium carbonate, to form a powder mix; and (iii)mixing said solution from step (i) with the powder mix of step (ii) .
  • the process comprises a step of drying the detergent composition to moisture content of less than 10%.
  • the method involved titration with EDTA (di sodium salt of Ethylene Diamine Tetra Acetic acid) using EBT (Eriochrome Black - T) as indicator.
  • EBT Eriochrome Black - T
  • About 2 ml of the Calcium ion solution was pipetted out into a 150 ml conical flask. The solution was diluted with about 10 ml water. To this was added 5 ml of Ammonia-Ammonium chloride pH 10 buffer. Further, about 35 mg of 1% EBT in potassium nitrate solution was added. A wine red colour was obtained.
  • a standardized EDTA solution was added dropwise from a burette with constant stirring. As more EDTA was added the colour gradually changed from wine red to violet. The end point was identified by a sudden colour change from violet to blue.
  • the Calcium ion concentration was calculated by using the formula:
  • Ca 2+ ion concentration volume of EDTA X strength of EDTA volume of Calcium solution taken.
  • HSAC High Surface Area Calcite with surface area of (20-30) m 2 /g.
  • the comparative examples of the prior art are able to being down the Ca 2+ ion concentration down from 200 ppm to a minimum of about 1.2 to 2 ppm and the time required is about 1 to 2 minutes (Best being Comparative Examples E and G) .
  • Oxalic acid was used in the above experiments in a particle size of ⁇ 0.075 mm.
  • RIN ADVANCEDTM 0.16 g/1 STPP + 1.4 g/1 sodium carbonate + 0. 3 g/1 HSAC
  • STPP is sodium tri poly phosphate.
  • compositions as per the invention are comparable to the RIN ADVANCEDTM composition and about 30% lower than the SURF EXCELTM composition.
  • the water used for cleaning had hardness value of 48 FH.
  • the protocol used for cleaning is given below.
  • the experiments were carried out in a Tergo-to-meter .
  • the various compositions were dissolved in the tergo-o-meter pot for 10 minutes at 90 rpm speed.
  • the test monitors were soaked in the solution for 15 minutes followed by 30 minutes of wash cycle in the pot at 90 rpm.
  • the test monitors were then rinsed three times at a liquid to cloth ratio of 25.
  • the test monitors were then dried.
  • the reflectance of the monitors was then measured. Average of reflectance data ( ⁇ R 460) on three different monitors was taken.

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)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
PCT/EP2008/055226 2007-05-03 2008-04-29 A builder system for a detergent composition WO2008135450A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BRPI0810888-9A2A BRPI0810888A2 (pt) 2007-05-03 2008-04-29 Sistema de builder para uma composição detergente, processo para preparar um sistema de builder, composição detergente e processo para preparar uma composição detergente
AT08736623T ATE483785T1 (de) 2007-05-03 2008-04-29 Buildersystem für eine waschmittelzusammensetzung
DE602008002918T DE602008002918D1 (pt) 2007-05-03 2008-04-29
EP08736623A EP2139980B1 (en) 2007-05-03 2008-04-29 A builder system for a detergent composition
CN2008800146364A CN101675154B (zh) 2007-05-03 2008-04-29 用于洗涤剂组合物的助洗剂系统
ZA2009/06842A ZA200906842B (en) 2007-05-03 2009-10-01 A builder system for a detergent composition

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
IN0851/MUM/2007 2007-05-03
IN851MU2007 2007-05-03
IN1354/MUM/2007 2007-07-16
IN1354MU2007 2007-07-16
EP07120277.4 2007-11-08
EP07120277 2007-11-08

Publications (1)

Publication Number Publication Date
WO2008135450A1 true WO2008135450A1 (en) 2008-11-13

Family

ID=39642897

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/055226 WO2008135450A1 (en) 2007-05-03 2008-04-29 A builder system for a detergent composition

Country Status (7)

Country Link
EP (1) EP2139980B1 (pt)
CN (1) CN101675154B (pt)
AT (1) ATE483785T1 (pt)
BR (1) BRPI0810888A2 (pt)
DE (1) DE602008002918D1 (pt)
WO (1) WO2008135450A1 (pt)
ZA (1) ZA200906842B (pt)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109517673B (zh) * 2018-11-16 2021-03-19 太原理工大学 一种加酶无磷衣物用粉末洗涤剂及其制备方法

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA979772A (en) * 1972-08-22 1975-12-16 Unilever Limited Detergent compositions
CA991942A (en) * 1972-04-28 1976-06-29 Lawrence Benjamin Detergent composition containing crystallization seed and soap
US4473485A (en) * 1982-11-05 1984-09-25 Lever Brothers Company Free-flowing detergent powders
US4619710A (en) * 1984-04-20 1986-10-28 Badger Pharmacal, Inc. Disposer cleaner
EP0242138A2 (en) * 1986-04-14 1987-10-21 Unilever Plc Process for the preparation of detergent powders
EP0504091A1 (en) * 1991-03-15 1992-09-16 Cleantabs A/S A phosphate-free automatic dishwashing composition
WO1992018594A1 (en) * 1991-04-23 1992-10-29 The Procter & Gamble Company Particulate detergent compositions
WO1998040455A1 (en) * 1997-03-11 1998-09-17 The Procter & Gamble Company A selected crystalline calcium carbonate builder for use in detergent compositions
US5990068A (en) * 1996-03-15 1999-11-23 Amway Corporation Powder detergent composition having improved solubility
US6608022B1 (en) * 2003-01-27 2003-08-19 Colgate-Palmolive Company Cleaning compositions in the form of a tablet
RU2235124C1 (ru) * 2003-01-05 2004-08-27 Закрытое акционерное общество "Невская косметика" Чистящее средство
US20070037729A1 (en) * 2005-08-12 2007-02-15 Reckitt Benckiser Inc. Powdered cleaning compositions

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA991942A (en) * 1972-04-28 1976-06-29 Lawrence Benjamin Detergent composition containing crystallization seed and soap
CA979772A (en) * 1972-08-22 1975-12-16 Unilever Limited Detergent compositions
US4473485A (en) * 1982-11-05 1984-09-25 Lever Brothers Company Free-flowing detergent powders
US4619710A (en) * 1984-04-20 1986-10-28 Badger Pharmacal, Inc. Disposer cleaner
EP0242138A2 (en) * 1986-04-14 1987-10-21 Unilever Plc Process for the preparation of detergent powders
EP0504091A1 (en) * 1991-03-15 1992-09-16 Cleantabs A/S A phosphate-free automatic dishwashing composition
WO1992018594A1 (en) * 1991-04-23 1992-10-29 The Procter & Gamble Company Particulate detergent compositions
US5990068A (en) * 1996-03-15 1999-11-23 Amway Corporation Powder detergent composition having improved solubility
WO1998040455A1 (en) * 1997-03-11 1998-09-17 The Procter & Gamble Company A selected crystalline calcium carbonate builder for use in detergent compositions
RU2235124C1 (ru) * 2003-01-05 2004-08-27 Закрытое акционерное общество "Невская косметика" Чистящее средство
US6608022B1 (en) * 2003-01-27 2003-08-19 Colgate-Palmolive Company Cleaning compositions in the form of a tablet
US20070037729A1 (en) * 2005-08-12 2007-02-15 Reckitt Benckiser Inc. Powdered cleaning compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 2004, Derwent World Patents Index; AN 2004-716652, XP002474489, "clean agent" *

Also Published As

Publication number Publication date
DE602008002918D1 (pt) 2010-11-18
BRPI0810888A2 (pt) 2014-10-29
ATE483785T1 (de) 2010-10-15
EP2139980A1 (en) 2010-01-06
ZA200906842B (en) 2011-04-28
EP2139980B1 (en) 2010-10-06
CN101675154A (zh) 2010-03-17
CN101675154B (zh) 2013-03-13

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