EP2154233A1 - Bauzusammensetzung - Google Patents

Bauzusammensetzung Download PDF

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Publication number
EP2154233A1
EP2154233A1 EP08168065A EP08168065A EP2154233A1 EP 2154233 A1 EP2154233 A1 EP 2154233A1 EP 08168065 A EP08168065 A EP 08168065A EP 08168065 A EP08168065 A EP 08168065A EP 2154233 A1 EP2154233 A1 EP 2154233A1
Authority
EP
European Patent Office
Prior art keywords
composition
builder composition
builder
alkali metal
range
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.)
Granted
Application number
EP08168065A
Other languages
English (en)
French (fr)
Other versions
EP2154233B1 (de
Inventor
Subir Kumar Das
Jojo Joseph
Amitava Pramanik
Arpita Sarkar
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 EP2154233A1 publication Critical patent/EP2154233A1/de
Application granted granted Critical
Publication of EP2154233B1 publication Critical patent/EP2154233B1/de
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
    • C11D3/04—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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • 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
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth

Definitions

  • the invention relates to a builder composition for use in a detergent composition which is efficient in softening hard water which contains both calcium and magnesium ions.
  • the invention also relates to a solid detergent composition comprising the builder composition of the invention.
  • the invention relates to a builder composition.
  • a builder composition is meant a composition that softens hard water.
  • softening is meant a process where the amount of dissolved alkaline earth metal ions e.g. calcium and magnesium ions present in hard water is reduced to a desired low concentration. This low concentration of the dissolved alkaline earth metal ions is believed to enhance utilisation of the surfactant used for cleaning surfaces especially fabrics thereby providing better and more economical cleaning products to the consumer. This invention more particularly is applicable for washing laundry.
  • Soaps which are alkali metal salts of fatty acids have been used for washing laundry.
  • the efficiency of washing is lower when washed in hard water i.e. 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 and magnesium soap which is insoluble in water and therefore washing in hard water gives poor cleaning.
  • synthetic detergents which are alkali metal salts of long chain synthetic acids of petroleum origin, similar problems persist.
  • Popular synthetic detergents are 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. Soiled laundry when washed with synthetic surfactants in hard water also gives poor cleaning as compared to cleaning with softer water.
  • detergency builders Compounds that react preferentially with the dissolved calcium and magnesium ions present in hard water, known as detergency builders, have been used in detergent compositions.
  • detergency builders are alkali metal carbonates, silicates, phosphates and structured compounds like zeolites.
  • Sodium carbonate also known as soda ash is an inexpensive and widely used builder in 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 and 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 river and other natural waters systems. Thus a lot of effort has been put into developing faster and/or more efficient building systems using sodium carbonate as the main raw material.
  • US3957695 (1976, Lever Bros. Co) discloses a detergent composition based on sodium carbonate as a detergency builder which also contains a finely divided calcium carbonate having a surface area of about 30 to 100 m 2 /g, together with a detergent active compound or mixture of compounds, which does not form during use, an insoluble calcium salt.
  • the composition may also additionally comprise from about 5 to about 30% of sodium silicate, by weight of the composition.
  • US4049586 (1977, Procter & Gamble Co.) describes a particulate detergent product consisting essentially of: (a) from about 0.5% to about 50% by weight of dry admixed calcium carbonate particles having a mean diameter of from about 0.01 to about 0.50 micron; (b) from about 5% to about 70% by weight of a builder selected from the group consisting of the alkali metal carbonates, bicarbonates, and sesquicarbonates and mixtures thereof; (c) from about 5% to about 70% by weight of alkali metal pyrophosphate; and (d) from about 5% to about 40% by weight of a water-soluble detergent selected from the group consisting of anionic, nonionic, zwitterionic, and ampholytic detergents and mixtures thereof.
  • the composition may also additionally comprise from about 5 to about 40% of sodium silicate, by weight of the composition.
  • detergent compositions which comprise precipitating builders like sodium carbonate and sodium silicate along calcium carbonate have been known and used for some time now.
  • compositions of the prior art does not give as fast and as complete a building as would be desirable in order to deliver enhanced cleaning of consumer fabrics when they are washed in hard water.
  • the present inventors have determined that when two precipitating builders viz. alkali metal carbonate and alkali metal silicate are used along with a seed for precipitating calcium carbonate, the inclusion of a selective class of building enhancers provides for better building, both in the extent, as well as the rate of reduction of dissolved calcium ions as well as in dissolved magnesium ions, which help in cleaning of soiled fabrics, when washed in hard water.
  • a builder composition comprising:
  • a detergent composition comprising a surfactant and a builder composition according to the first aspect of the present invention.
  • the invention provides for a method for softening of hard water especially for cleaning of soiled fabrics.
  • the composition is more effective when the input hard water has both dissolved calcium and dissolved magnesium ions.
  • the method comprises dissolving/dispersing four materials in water viz. (i) an alkali metal carbonate; (ii) a alkali metal silicate (iii) calcium carbonate and (iv) a building enhancer which is a compound capable of precipitating magnesium ions from water selected from the group comprising alkali or alkaline earth metal oxides or hydroxides and alkali metal aluminate, zincate or titanate
  • Preferred building enhancers are hydroxides of sodium or potassium; calcium oxide; calcium hydroxide; and aluminate, zincate, and titanate of sodium or potassium. More preferred building enhancers are calcium oxide, calcium hydroxide or alkali metal aluminate or zinctate.
  • the building enhancer is preferably present in the range of 0.1 to 7.5%, more preferably 0.1 to 5% and most preferably from 1 to 3% by weight of the builder composition.
  • the inclusion of these selective building enhancers helps in the removal of Mg ions. It is believed that the presence of the building enhancers maintains the required solution pH leading to magnesium ion removal by way of precipitation as magnesium hydroxide. In that process, free Ca ion concentration increases which is precipitated as calcium carbonate due to the presence of the precipitating builders.
  • the builder composition comprises a sequestrant selected from amino polycarboxylic acid, amino polyphosphonic acid, nitrilo triacetic acid or salts thereof.
  • Amino polycarboxylic acids are compounds that have the formula: In the above formula, when R is -CH 2 -COOH then the compound is ethylene diamine tetraacetic acid (EDTA).
  • Amino polyphosphonic acids are compounds that have the formula: In the above formula, when R is -CH 2 -PO 3 H 2 then the compound is ethylene diamine tetramethyl phosphonic acid. This compound is available under the brand name DEQUEST 204 TM .
  • R when R is then the compound is diethylene triamine pentamethyl phosphonic acid. This compound is available under the brand name DEQUEST 206 TM .
  • Nitrilo triacetic acid has the chemical formula C 6 H 9 NO 6 and is also known as amino triacetic acid.
  • preferred sequestrants are sodium or potassium salt of ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, ethylenediamine tetramethyl phosphonic acid or diethylenetriamine pentamethyl phosphonic acid.
  • the sequestrant is thus preferably present in a delayed release form in order to achieve the desired dissolution profile.
  • the inventors have determined that one way to achieve this is to incorporate the sequestrant in a defined particle size range i.e. 0.3 to 3 mm more preferably in the range of 0.75 to 2 mm.
  • the builder composition comprises a precipitating builder that is alkali metal silicate.
  • the alkali metal silicate is preferably sodium silicate or potassium silicate, more preferably sodium silicate.
  • Sodium silicate is a colorless compound of oxides of sodium and silica. It has a range of chemical formula varying in sodium oxide (Na 2 O) and silicon dioxide or silica (SiO 2 ) contents. It is soluble in water and it is prepared by reacting silica (sand) and sodium carbonate at a high temperature ranging from 1200 to 1400°C. Aqueous solution of sodium silicate is called water glass.
  • Sodium silicates varying in ratio of Na 2 O:SiO 2 from 1:1.6 to 1:4 are known as colloidal silicates.
  • the preferred compound to be used in the composition of the invention is alkaline sodium silicate or sodium meta silicate. This has a concentration in water in the range of 27 - 39% and a Na 2 O:SiO 2 ratio in the range of 3.0 to 3.5.
  • the alkali metal silicate is preferably present in the range of 1 % to 40% by weight of the builder composition.
  • the builder composition of the invention comprises another precipitating builder that is 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 the range of 5 to 70%, more preferably in the range of 10 - 50% by weight of the builder composition.
  • the builder composition of the invention comprises a seed for precipitating calcium carbonate that is calcium carbonate.
  • Calcium carbonate may be calcite, or aragonite, most preferably calcite.
  • Calcite is preferably high surface area calcite.
  • the calcium carbonate has a surface area greater than 18 m 2 /g, more preferably greater then 30 m 2 /g, most preferably greater than 60 m 2 /g.
  • Calcium carbonate is preferably present in the range of 5 to 40 % by weight of the builder composition.
  • the builder composition of the invention ensures that the Ca 2+ ion concentration in input hard water reduces from about 140 ppm to about less than 1 ppm in about less than 2 minutes and in optimal conditions to less than 0.3 ppm in less than 2 minutes.
  • the builder composition of the invention also ensures that the Mg 2+ ion concentration in input hard water reduces from about 40 ppm to less than about 6 ppm in less than 2 minutes, and in optimal conditions to less than about 2 ppm in less than 2 minutes.
  • the method of the invention has the advantage that it requires significantly low amount of conventional sequestering builders like water soluble phosphates.
  • the composition of the invention is substantially free of water soluble phosphate builders.
  • the builder composition of the invention comprises a seed capable of precipitating magnesium ions.
  • seeds are magnesium carbonate and dolomite.
  • a preferred aspect of the invention provides for magnesium carbonate or dolomite to be present in 5 to 40% by weight of the builder composition.
  • a detergent composition comprising a builder composition of the first aspect of the invention and a surfactant selected from any one of the anionic, non-ionic, cationic, zwitterionic or amphoteric class.
  • the invention also provides for a method of cleaning a fabric comprising contacting the soiled fabric with water which has been built by the builder composition of the invention, the water additionally comprising a surfactant.
  • Suitable anionic synthetic detergents are linear alkyl benzene sulphonates, alpha olefin sulphonates and primary alkyl sulphates.
  • Linear alkyl benzene sulphonates are ideally suited since they are widely and inexpensively available and have very good surfactant action.
  • Sodium or magnesium salts of LAS acids may be used.
  • the method of the invention works better when the surfactant is delivered in a delayed mode in water with respect to the precipitating builders and the calcium carbonate. It is preferred that the surfactant is in dissolved state 15 to 600 seconds, more preferably 30 to 480 seconds, further more preferably 45 to 300 seconds after the water has been built by the method of the invention.
  • the present inventors prefer the surfactant to be magnesium salt of linear alkyl benzene sulphonic acid.
  • a way to ensure delayed dissolution of the surfactant in water is to include the magnesium salt of linear alkyl benzene sulphonic acid in a particle size in the range of 0.1 to 2 mm.
  • the builder composition is preferably present in the range of 5 to 80% by weight of the detergent composition.
  • the surfactant is preferably present in 5 to 90%, preferably 10 to 50%, more preferably 15 to 35% by weight of the detergent composition.
  • the detergent composition is preferably in the solid form e.g. in the powder, granule, bar or tablet form. The more preferred form of the detergent composition is the powder or granule form.
  • the alkali metal carbonate is preferably present in 10 to 70%, more preferably 15 to 60%, and further more preferably 25 to 50% by weight of the detergent composition.
  • the calcium carbonate is preferably present in 3 to 50%, more preferably from 5 to 40%, most preferably from 10 to 30% by weight of the detergent composition.
  • the solution was stirred for 45 seconds using a glass rod.
  • a sample was withdrawn with the help of a syringe at pre-determined time periods after the addition of the builders, and filtered through a microfilter into 5cc glass vials.
  • the Ca 2+ ion and Mg 2+ ion concentrations were determined by EDTA titration as shown below:
  • the method involved titration with EDTA (di sodium salt of elthylene diamine tetra acetic acid) using EBT (Eriochrome Black - T) as indicator.
  • EBT Eriochrome Black - T
  • About 2 ml of the test solution was pipetted out into a 150 ml conical flask.
  • the solution was diluted using about 10 ml water.
  • To this was added 5 ml of ammonia-ammonium chloride pH 10 buffer.
  • 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 total (of calcium and magnesium) ion concentration was calculated using the formula:
  • Total ion concentration vol of EDTA * strength of EDTA/ vol of test solution taken.
  • Table-1 indicates that better building, both in terms of lower final hardness of water and faster kinetics of building, are obtained when a builder composition of the invention is used as compared to builder composition of the prior art.
  • Example 2 Experiments using a builder composition of Example 2 were carried out as shown in Table -1 except that additionally a sequestrant viz. ethylene diamine tetraacetic acid (EDTA) was used either along with the other ingredients or at some delay with respect to the other ingredients. The results are summarized in Table - 2 along with the result for Example - 2 for comparison. Table - 2 Example 2 Example 6 Example 7 Example 8 Concentration of EDTA, ppm Not added 30 30 60 EDTA particle size, mm - As solution As solution 0.85-1.7 Mode of EDTA addition - 2 minutes after others Along with others Along with others Time, minutes Total FH Total FH Total FH Total FH 0 48 48 48 48 2 7 5 5 3 5 3.5 3.5 4 2 15 1.25 1 1 0.5
  • Example 9 is a detergent composition as per the invention.
  • Example 10 is a detergent composition similar to Example 9 but without the building enhancer included.
  • Examples 11 is product "Rin Advanced" which is one of the best sodium carbonate based detergent product available in the Indian market.
  • the compositions of examples 9 and 10 are given in Table-3.
  • Table - 3 Example 9 10 11
  • Surfactant Mg LAS MgLAS NaLAS Surfactant concentration wt% 20.0 20.0 16.0 Sodium carbonate, wt% 30.0 30.0 35.0 ForcalU, wt% 16.7 16.7 8.0 Sodium silicate, wt% 25.0 25.0 - Calcium hydroxide, wt% 1.7 - - STPP, wt% - - 6.0 Others, wt% To 100 To 100 To 100 To 100 To 100
  • Table-4 indicates that improved cleaning is obtained with a detergent composition on inclusion of a builder enhancer of the invention. Further the composition of the invention provides better cleaning as compared to one of the best commercially available product of this class.
  • the invention thus provides for a builder composition which gives faster building as compared to methods available in the present state of the art especially when the hard water contains both calcium and magnesium ions. Consequently the soiled fabrics are cleaned better.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)
EP08168065A 2008-08-14 2008-10-31 Bauzusammensetzung Not-in-force EP2154233B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IN1723MU2008 2008-08-14

Publications (2)

Publication Number Publication Date
EP2154233A1 true EP2154233A1 (de) 2010-02-17
EP2154233B1 EP2154233B1 (de) 2010-09-22

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP08168065A Not-in-force EP2154233B1 (de) 2008-08-14 2008-10-31 Bauzusammensetzung

Country Status (12)

Country Link
EP (1) EP2154233B1 (de)
CN (1) CN102124091B (de)
AR (1) AR073026A1 (de)
AT (1) ATE482264T1 (de)
BR (1) BRPI0917258A2 (de)
CL (1) CL2011000310A1 (de)
DE (1) DE602008002756D1 (de)
EA (1) EA017243B1 (de)
ES (1) ES2353470T3 (de)
MX (1) MX2011001665A (de)
WO (1) WO2010018043A1 (de)
ZA (1) ZA201100431B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011147646A1 (en) * 2010-05-24 2011-12-01 Unilever Nv Builder composition and process for building

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MX2011001665A (es) 2011-03-25
EA017243B1 (ru) 2012-10-30
CN102124091A (zh) 2011-07-13
BRPI0917258A2 (pt) 2015-11-10
EP2154233B1 (de) 2010-09-22
AR073026A1 (es) 2010-10-06
WO2010018043A1 (en) 2010-02-18
CN102124091B (zh) 2013-02-13
ZA201100431B (en) 2012-03-28
DE602008002756D1 (de) 2010-11-04
ATE482264T1 (de) 2010-10-15
EA201100348A1 (ru) 2011-08-30
CL2011000310A1 (es) 2011-08-05

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