EP2139980B1 - Système adjuvant de détergence ("builder") destiné à une composition détergente - Google Patents

Système adjuvant de détergence ("builder") destiné à une composition détergente Download PDF

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Publication number
EP2139980B1
EP2139980B1 EP08736623A EP08736623A EP2139980B1 EP 2139980 B1 EP2139980 B1 EP 2139980B1 EP 08736623 A EP08736623 A EP 08736623A EP 08736623 A EP08736623 A EP 08736623A EP 2139980 B1 EP2139980 B1 EP 2139980B1
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EP
European Patent Office
Prior art keywords
builder
builder system
detergent composition
calcium carbonate
weight
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.)
Not-in-force
Application number
EP08736623A
Other languages
German (de)
English (en)
Other versions
EP2139980A1 (fr
Inventor
Subir Kumar Das
Amitava Pramanik
Arpita Sarkar
Gopa Kumar Velayudhan Nair
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
Priority to EP08736623A priority Critical patent/EP2139980B1/fr
Publication of EP2139980A1 publication Critical patent/EP2139980A1/fr
Application granted granted Critical
Publication of EP2139980B1 publication Critical patent/EP2139980B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1233—Carbonates, e.g. calcite or dolomite
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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

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.
  • 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 watersoluble 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/l at 25°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.
  • the substantially water insoluble particulate material is Calcium carbonate. 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 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/l at 25°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 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.
  • the powders of the co-builder have an average particle size less than 150 microns, more preferably less than 75 microns.
  • the process of the invention comprises:
  • 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.
  • 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.
  • Table - 1 Comparative Example Sodium carbonate, g/l HSAC g/l Disodium Oxalate, g/l Time, s Concentration of Calcium ions, ppm A 1.5 0 0 60 10.4 B 1.5 0 0 300 1.8 C 1.5 0.5 0 60 4.7 E 1.5 0.5 0 120 1.2 F 1.5 0 0.4 30 3.6 G 1.5 0 0.4 60 1.7
  • HSAC means High Surface Area Calcite with surface area of (20-30) m 2 /g.
  • the comparative examples of the prior art are able to bring 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).
  • Various builder compositions were prepared and added to hard water containing 200 ppm Calcium ions at concentrations as shown in Table -2.
  • the builder system was a dry mix of the sodium carbonate and High Surface Area Calcite (HSAC) to which a solution of disodium oxalate in water was sprayed and mixed.
  • HSAC High Surface Area Calcite
  • Example 6 the disodium oxalate granules were first crushed to a powder to an average particle size of about 145 microns. The disodium oxalate powder was then dry mixed with the sodium carbonate and HSAC. The building kinetics was studied by measuring the Ca 2+ ion concentration, at various time periods.
  • Table-3 indicates that inclusion of a dicarboxylic acid viz. Oxalic acid in a Sodium Carbonate/Calcite building system provides for more efficient building as compared to builder system of the prior art.
  • Detergent compositions were used to clean various test monitors as shown in Table -4.
  • WFK10D composite soil on cotton fabric
  • WFK20D composite soil on poly-cotton fabric
  • WFK30D composite soil on polyester fabric
  • All detergent compositions had sodium linear alkyl benzene sulphonate as the active surfactant at about 0.7 g/l in the wash liquor.
  • the builder systems of the various detergent compositions in the wash liquor were as follows:
  • compositions as per the invention are comparable to the RIN ADVANCED TM composition and about 30% lower than the SURF EXCEL TM 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.
  • 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.

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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)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Claims (11)

  1. Système adjuvant de détergence destiné à une composition détergente, qui comprend :
    (i) un carbonate de métal alcalin soluble dans l'eau ;
    (ii) de 5 % à 50 % en poids du système adjuvant de détergence d'un germe cristallin destiné à précipiter le carbonate de calcium, qui est un carbonate de calcium ; et
    (iii) un co-adjuvant qui est un acide dicarboxylique ou un sel de celui-ci, ledit co-adjuvant ayant une taille moyenne de particules inférieure à 150 microns.
  2. Système adjuvant de détergente selon la revendication 1, ledit co-adjuvant ayant une solubilité dans l'eau supérieure à 1 g/L à 25 °C.
  3. Système adjuvant de détergence selon l'une quelconque des revendications précédentes, ledit acide dicarboxylique étant choisi parmi l'acide oxalique, l'acide malonique ou l'acide succinique.
  4. Système adjuvant de détergence selon l'une quelconque des revendications précédentes, ledit co-adjuvant étant présent en une quantité dans la plage de 2 à 20 % en poids du système adjuvant de détergence.
  5. Système adjuvant de détergence selon l'une quelconque des revendications précédentes, ledit carbonate de métal alcalin étant présent en une quantité variant de 10 à 90 en poids du système adjuvant de détergence.
  6. Procédé de préparation d'un système adjuvant de détergence destiné à une composition détergente qui comprend le mélange de poudres d'un carbonate de métal alcalin soluble, de 5 % à 50 % en poids du système adjuvant de détergence d'un germe cristallin destiné à précipiter le carbonate de calcium, qui est un carbonate de calcium ; et un co-adjuvant qui est un acide dicarboxylique ou un sel de celui-ci, ledit co-adjuvant ayant une taille moyenne de particules inférieure à 150 microns.
  7. Procédé de préparation d'un système d'adjuvant de détergence destiné à une composition détergente selon la revendication 6, qui comprend les étapes consistant à :
    (i) dissoudre l'acide dicarboxylique ou les sels de celui-ci dans l'eau pour former une solution ;
    (ii) mélanger à sec les poudres d'un carbonate de métal alcalin soluble avec 5 % à 50 % en poids du système d'adjuvant de détergence d'un germe cristallin destiné à précipiter le carbonate de calcium, qui est le carbonate de calcium, pour former une mélange de poudres ; et
    (iii) mélanger ladite solution de l'étape (i) avec le mélange de poudres de l'étape (ici).
  8. Composition détergente qui comprend :
    (i) un système adjuvant de détergente selon l'une quelconque des revendications 1 à 5 précédentes ; et
    (ii) un tensioactif choisi dans l'une quelconque des classes anionique, non ionique, cationique, zwitterionique ou amphotère,
  9. Composition détergente selon la revendication 6, ledit système adjuvant de détergence étant présent en une quantité dans la plage de 5 à 80 % en poids de la composition détergente.
  10. Procédé de préparation d'une composition détergente qui comprend l'étape consistant à mélanger à sec des poudres d'un tensioactif choisi dans l'une quelconque des classes anionique, non ionique, cationique, zwitterionique ou amphotère avec le système adjuvant de détergence selon l'une quelconque des revendications 1 à 5 précédentes.
  11. Procédé de préparation d'une composition détergente qui comprend les étapes consistant à :
    (i) dissoudre un acide dicarboxylique ou des sels de celui-ci dans l'eau pour former une solution, ledit acide ou lesdits sels de celui-ci ayant une taille moyenne de particules inférieure à 150 microns ;
    (ii) mélanger à sec des poudres d'un tensioactif choisi dans l'une quelconque des classes anionique, non ironique, cationique, zwitterionique ou amphotère avec un carbonate de métal alcalin soluble dans l'eau et de 5 % à 50 % en poids du système adjuvant de détergente d'un germe cristallin destiné à précipiter le carbonate de calcium, qui est du carbonate de calcium, pour former un mélange de poudres ; et
    (iii) mélanger ladite solution de l'étape (i) avec le mélange de poudres de l'étape (ii).
EP08736623A 2007-05-03 2008-04-29 Système adjuvant de détergence ("builder") destiné à une composition détergente Not-in-force EP2139980B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08736623A EP2139980B1 (fr) 2007-05-03 2008-04-29 Système adjuvant de détergence ("builder") destiné à une composition détergente

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
IN851MU2007 2007-05-03
IN1354MU2007 2007-07-16
EP07120277 2007-11-08
PCT/EP2008/055226 WO2008135450A1 (fr) 2007-05-03 2008-04-29 Système adjuvant de détergence ('builder') destiné à une composition détergente
EP08736623A EP2139980B1 (fr) 2007-05-03 2008-04-29 Système adjuvant de détergence ("builder") destiné à une composition détergente

Publications (2)

Publication Number Publication Date
EP2139980A1 EP2139980A1 (fr) 2010-01-06
EP2139980B1 true EP2139980B1 (fr) 2010-10-06

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EP08736623A Not-in-force EP2139980B1 (fr) 2007-05-03 2008-04-29 Système adjuvant de détergence ("builder") destiné à une composition détergente

Country Status (7)

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

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

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA992423A (en) * 1972-04-28 1976-07-06 The Procter And Gamble Company Crystallization seed-containing detergent composition
GB1437950A (en) * 1972-08-22 1976-06-03 Unilever Ltd 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
GB8609044D0 (en) * 1986-04-14 1986-05-21 Unilever Plc Detergent powders
DK166548B1 (da) * 1991-03-15 1993-06-07 Cleantabs As Phosphatfrit maskinopvaskemiddel
GB9108639D0 (en) * 1991-04-23 1991-06-12 Procter & Gamble Particulate detergent compositions
AU2074397A (en) * 1996-03-15 1997-10-01 Amway Corporation Powder detergent composition having improved solubility
JP2001514698A (ja) * 1997-03-11 2001-09-11 ザ、ユニバーシティ、オブ、ノースカロライナ、アット、チャペル、ヒル 洗剤組成物用の選択された結晶性炭酸カルシウムビルダー
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
GB2429014A (en) * 2005-08-12 2007-02-14 Reckitt Benckiser Inc Powdered hard surface cleaning compositions

Also Published As

Publication number Publication date
ZA200906842B (en) 2011-04-28
DE602008002918D1 (fr) 2010-11-18
CN101675154B (zh) 2013-03-13
WO2008135450A1 (fr) 2008-11-13
BRPI0810888A2 (pt) 2014-10-29
EP2139980A1 (fr) 2010-01-06
ATE483785T1 (de) 2010-10-15
CN101675154A (zh) 2010-03-17

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