EP2167624B1 - Composition détergente solide - Google Patents

Composition détergente solide Download PDF

Info

Publication number
EP2167624B1
EP2167624B1 EP08761382A EP08761382A EP2167624B1 EP 2167624 B1 EP2167624 B1 EP 2167624B1 EP 08761382 A EP08761382 A EP 08761382A EP 08761382 A EP08761382 A EP 08761382A EP 2167624 B1 EP2167624 B1 EP 2167624B1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
builder
solid detergent
linear alkyl
alkyl benzene
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
EP08761382A
Other languages
German (de)
English (en)
Other versions
EP2167624A1 (fr
Inventor
Subir Kumar Das
Sujitkumar Suresh Hibare
Jojo Joseph
Amitava Pramanik
Aravindakshan Perincheery
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 PL08761382T priority Critical patent/PL2167624T3/pl
Priority to EP08761382A priority patent/EP2167624B1/fr
Publication of EP2167624A1 publication Critical patent/EP2167624A1/fr
Application granted granted Critical
Publication of EP2167624B1 publication Critical patent/EP2167624B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • 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
    • C11D3/12—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
    • 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
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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 solid detergent composition comprising a carbonate builder system.
  • Soaps which are alkali metal salts of fatty acids, have traditionally been used for the purpose of personal washing. 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 is 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 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 soda 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.
  • 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.
  • US 3,703,772 discloses a process for drying detergents wherein aqueous solutions of of heat sensitive synthetic organic detergents are dried by admixing such a solution with a finely divided sorbent material, thereby distributing the solution over a greatly increased area, which speeds drying an prevents hot spots during drying and drying the mixed detergent-sorbent-moisture particles.
  • CA 979772 discloses detergent compositions for fabric washing.
  • Magnesium salt of linear alkyl benzene sulphonic acid is also known and has been used in detergent formulations.
  • US4146551 (Lion, 1979) describes a process for producing the magnesium salt of sulphonic acids and sulfuric esters comprising the step of neutralizing the sulphonic acids and sulphuric esters with an aqueous dispersion containing (1) at least one neutralizing agent selected from the group consisting of magnesium oxide and magnesium hydroxide and (2) at least one neutralizing accelerator selected from the group consisting of benzoic acid, citric acid, malic acid, phosphoric acid, polyphosphoric acid and water soluble salts thereof under a pH of not more than approximately 6.
  • this publication discloses use of magnesium based anionic surfactants, it does not teach specific combination of such surfactants with selected builder systems that provides enhanced building in hard water and thereby enhanced detergency.
  • Indian patent IN204326 (Hindustan Lever Ltd, published in 2003) describes a synergistic abrasive cleaning composition containing selective combination of surfactants and a process for producing the same.
  • the process comprises neutralization of at least 40% of the acid precursor of the anionic surfactant using at least one mineral of the dolomites group and mixing abrasives and other conventional ingredients such that the total amount of surfactant is between 0.5 and 35% and the amount of abrasives is 30-95% and processing the mixture in a regular manner.
  • Dolomite is a mineral having the chemical formula CaMg(CO 3 ) 2 .
  • This prior art publication is directed to hard surface cleaning compositions which comprise Calcium-magnesium salts of anionic surfactants and does not teach combination of magnesium salt of linear alkyl benzene sulphonic acid with selective builder systems for providing enhanced detergency.
  • the present inventors have determined that when a builder system comprising a water soluble alkali metal carbonate and a seed for precipitating calcium carbonate is used along with a specific anionic surfactant viz. magnesium salt of linear alkyl benzene sulphonic acid, the building properties of this builder system combined with the specific properties of this surfactant interact synergistically to provide enhanced cleaning of soiled fabrics especially when washed in hard water.
  • a specific anionic surfactant viz. magnesium salt of linear alkyl benzene sulphonic acid
  • the solid detergent composition of the invention comprises magnesium salt of linear alkyl benzene sulphonic acid (Mg-LAS).
  • the solid detergent composition is preferably in the powder, granule, bar or tablet form.
  • the more preferred form of the detergent composition is the powder or granule form.
  • the Mg-LAS therein is preferably present as granules in a particle size range larger than 0.3 mm, more preferably larger than 0.5 mm, most preferably larger than 1 mm, and optimally in the range of 1 to 2 mm.
  • the solid detergent composition comprises Mg-LAS in an amount in the range of 5% to 90%, preferably 10% to 50%, most preferably 15% to 35% by weight of the detergent composition.
  • a suitable process to prepare solid form of Mg-LAS is disclosed in our co-pending application 445/MUM/2007 (published as WO2008/107463 ).
  • the process disclosed and claimed therein comprises the step of neutralization of linear alkyl benzene sulphonic acids with a magnesium based alkali in the presence of 3% to 28% water by weight of the reaction mixture in a high shear mixer.
  • Mg-LAS in very high concentration, as high as 90% in solid forms like powder, granule or extrudable bar can be prepared by the above mentioned process.
  • This process has the advantage that only low amounts of alkali are required for complete neutralisation.
  • Preferred amounts for neutralization are from 5% to 100% stoichiometric excess of the magnesium based alkali.
  • Suitable magnesium based alkali are one or more of magnesium carbonate, magnesium bicarbonate, magnesium oxide, magnesium hydroxycarbonate or magnesium hydroxide.
  • a further preferred aspect of the detergent composition of the present invention provides for the Mg-LAS granules to be coated with a water soluble polymer.
  • the water soluble polymers may be poly ethylene oxide, sodium carboxymethyl cellulose, poly vinyl pyrrolidone, poly acrylic acid or poly vinyl alcohol most preferably poly vinyl alcohol. The following processes can be adopted to coat granules of Mg-LAS with water soluble polymers.
  • the preferred process for coating of Mg-LAS comprises the steps of spraying a solution of polymer onto Mg-LAS in a pan granulator.
  • the sprayed product may be dried by heating the pan granulator to a high temperature, in the range of 60°C to 90°C to a moisture content of the granules of less than 10 wt%. Alternately, the sprayed product may be transferred to an oven to be dried.
  • a fluidized bed may also be used for coating the polymer with the use of hot air to dry the granules to the desired moisture content.
  • the preferred amount of polymer coating is from 0.25% to 5%, more preferably 0.5% to 2% and most preferably 0.75% to 1.25% by weight of the Mg-LAS granules.
  • the solid detergent composition of the invention comprises 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 water soluble alkali metal carbonate is present in an amount in the range of 10% to 70%, preferably from 15% to 60%, most preferably from 25% to 50% by weight of the solid detergent composition.
  • 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 detergent composition or generated in situ when the detergent composition is dispersed in water. The more preferred aspect provides for the substantially water insoluble particulate material to be present in the detergent composition.
  • Examples of seed for precipitating calcium carbonate which is generated in situ include generation of particulate zinc oxide by including sodium zincate in the detergent composition, generation of particulate alumina by including sodium aluminate or generation of silica by including alumino silicate in the detergent composition.
  • Suitable substantially water insoluble particulate materials which may be present in the detergent composition are silica, zinc oxide, aluminium oxide, titanium oxide, Zeolite, magnesium oxide or calcium carbonate.
  • Particularly preferred substantially water insoluble particulate material is calcium carbonate.
  • Calcium carbonate may be calcite, or aragonite, most preferably calcite. Calcite is preferably high surface area calcite.
  • the water insoluble particulate carbonate seed crystal has a surface area greater than 20 m 2 /g; more preferably greater then 30 m 2 /g, and most preferably greater than 60 m 2 /g.
  • the seed for precipitating calcium carbonate is present in an amount in the range of 3% to 50%, more preferably from 5% to 40%, most preferably from 10% to 30% by weight of the solid detergent composition.
  • the solid detergent composition optionally and preferably comprises a co-builder which is a di-carboxylic acid or salt thereof.
  • the co-builder present in the solid detergent composition preferably has a water solubility of more than 1 g/l at 25°C.
  • Preferred di-carboxylic acids are oxalic acid, malonic acid and succinic acid, most preferred being oxalic acid.
  • the preferred salts of the di-carboxylic acid are alkali metal or ammonium salts, alkal metal salts being more preferred.
  • the most preferred co-builder is di-sodium oxalate.
  • the co-builder is preferably present in the solid detergent composition as a powder i.e in a low particle size.
  • the average particle size of the co-builder is preferably less than 150 microns, more preferably less than 75 microns.
  • the co-builder is preferably present in an amount in the range of 1% to 20%, more preferably 5% to 15%, most preferably 5% to 10% by weight of the solid detergent composition.
  • the solid detergent composition of the invention preferably comprises an additional 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 formulae 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°C 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. These are usually sold as 20% to 50% aqueous solutions.
  • the preferred compound to be used in the composition of the invention is neutral sodium 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 5% to 50%, more preferably 12% to 40% by weight of the solid detergent composition.
  • the use of the solid detergent composition in 2 g/l to 5 g/l of the wash liquor thereby ensures presence of alkali metal silicate in 0.2 g/l to 1 g/l, preferably 0.5 g/l to 0.8 g/l in the wash liquor.
  • a process to prepare a granular detergent composition comprising mixing granules of magnesium salt of linear alkyl benzene sulphonic acid with powders of a water soluble alkali metal carbonate, seed for precipitating calcium carbonate and a co-builder which is a dicarboxylic acid or salt thereof.
  • a process to prepare a detergent composition comprising the steps of:
  • the granules of Mg-LAS used in the above process are coated with a water soluble polymer.
  • 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 using 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 calcium ion concentration was calculated using the formula:
  • Protocol A Protocol used to simulate hand washing.
  • the 48 FH water was taken and the detergent composition was added to it and stirred by hand for 45 seconds at about 70-80 rpm. After letting the solution stay for about 5 minutes, the solution was stirred vigorously for about 10 seconds. Samples were then withdrawn at the desired time points using syringes and filtered using a syringe filter into TARSONTM tubes. The filtrate was used to determine Ca 2+ ion concentration as described earlier.
  • Protocol B (Protocol used to simulate washing machine)
  • the 48 FH water was taken and the detergent composition was added to it and stirred by using an overhead stirrer at about 160-170 rpm. All detergent compositions had a surfactant concentration when in use of 0.7 g/l. The stirring was continued for a total time of 30 minutes. Samples were withdrawn at the desired time points using syringes and filtered using syringe filter into TARSONTM tubes. The filtrate was used to determine Ca 2+ concentration as described earlier.
  • Example 3 Example Surfactant Surfactant, particle size, mm Soda ash, g/l HSAC, g/l STPP, g/l Di-sodium oxalate, g/l Comparative Example A NaLAS 0.5 - 1 1.4 0.3 0.16 - Comparative Example B NaLAS 0.5 - 1 1.5 1.0 - - Example 5 MgLAS 1 - 2 1.5 0.5 - 0.4 Example 6 MgLAS 0.5 - 1.0 1.5 0.5 - 0.4 Example 7 MgLAS 1 - 2; PVA coated 1.5 0.5 - 0.4
  • Di sodium oxalate was used in the above experiments in a particle size of ⁇ 0.075 mm.
  • compositions of Comparative Examples A to C and Example 8 to 12 as shown in Table - 5 were used to wash various test monitors using a protocol that simulates hand washing. This protocol C is described below.
  • Protocol C (Hand wash protocol)
  • the 48 FH water was taken and the detergent composition was added to it and stirred by hand at about 50-60 rpm for about 45 seconds. All detergent compositions had a surfactant concentration when in use of 0.7 g/l.
  • the solution was allowed to stand for 5 minutes after which it was stirred by hand for 10 seconds.
  • the fabric test monitors were then added and allowed to soak for 10 minutes.
  • the test monitors were then washed in a tergo-to-meter at 90 rpm for 30 minutes.
  • the test monitors were then rinsed three times at a liquid to cloth ratio of 25 and then dried. The reflectance of the monitors was then measured. Average of reflectance data on three different monitors was taken.
  • the data on the cleaning performance of various test monitors in terms of ⁇ R* with respect to the reflectance of the original test monitors is shown in Table - 6.
  • the original (unwashed) test monitors used were WFK10D (composite soil on cotton fabric) had an initial reflectance of about 45, WFK20D (composite soil on poly-cotton fabric) of about 40 and WFK30D (composite soil on polyester fabric) of about 40.
  • Example 9 21.3 26.1 21.1
  • Example 10 20.2 29.2 23.2
  • Example 11 17.8 22.4 20.3
  • Example 12 15.2 19.6 22.3
  • the data in Table - 6 indicates that the detergent compositions of the invention provide for similar cleaning on some test monitors and better in most other test monitors as compared to the prior art products.
  • the data also indicates that Mg-LAS of higher particle sizes (Examples 8 to 10) provides for vastly improved cleaning. Further the cleaning of the preferred compositions of the invention (Examples 8 to 10) provide for similar or better cleaning as compared to more expensive Na-LAS+STPP based conventional products.
  • Compositions of Comparative Examples A and C and Examples 13 to 16 as shown in Table - 7 were used to wash various test monitors using protocol C as described above.
  • Table-7 Example Surfactant Surfactant, particle size, mm Soda ash, g/l HSAC, g/l STPP, g/l Oxalic acid, g/l Comparative Example A NaLAS 0.5 - 1 1.4 0.3 0.16 - Comparative Example C NaLAS 0.5 -1 0.89 0.07 1.02 - Example 13 MgLAS 0.3 - 0.12 1.5 0.5 - 0.42 Example 14 MgLAS 1 - 2 1.5 0.5 - 0.42 Example 15 MgLAS 0.5 - 0.3 1.5 0.5 - 0.42 Example 16 MgLAS 1- 2 1.5 0.5 - 0.27
  • Table - 8 indicates that preferred detergent compositions of the invention provide for similar or better cleaning on some test monitors and much better cleaning in most other test monitors as compared to the prior art samples.
  • the data also indicates that Mg-LAS at higher particle sizes > 0.5 mm when combined with co-builder like oxalic acid provides for vastly improved cleaning.
  • compositions of Comparative Examples C and Example 17 and 18 as shown in Table - 9 were used to wash various test monitors using a protocol that simulates machine washing. This protocol D is described below:
  • Protocol D (Washing machine protocol)
  • the 48 FH water was taken in a Tergo-to-meter along with the test monitors and the detergent composition was added to it and stirred for about 10 minutes at 90 rpm. All detergent compositions had a surfactant concentration when in use of 0.7 g/l.
  • the fabric test monitors was then added and allowed to soak for 15 minutes. After this it was run for 30 minutes at 90 rpm.
  • the test monitors were then rinsed three times at a liquid to cloth ratio of 25 and then dried. The reflectance of the monitors was then measured. Average of reflectance data on three different monitors was taken.
  • the data on the cleaning performance of various test monitors in terms of ⁇ R* with respect to the reflectance of the original test monitors is shown in Table - 10.
  • the original (unwashed) test monitors used were WFK10D (composite soil on cotton fabric) had an initial reflectance of about 45, WFK20D (composite soil on poly-cotton fabric) of about 40 and WFK30D (composite soil on polyester fabric) f about 40.
  • the particle size of the disodium oxalate in the above experiments was in the size range of ⁇ 0.075 mm.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Centrifugal Separators (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Claims (10)

  1. Composition détergente solide comprenant :
    (i) 5 % à 90 % en poids de la composition détergente de sel de magnésium d'acide sulfonique d'alkyl benzène linéaire ;
    (ii) 10 à 70 % en poids de la composition détergente d'un carbonate de métal alcalin hydrosoluble ; et
    (iii) 3 à 50 % en poids de la composition détergente d'un germe pour précipiter le carbonate de calcium et
    (iv) en option, un co-adjuvant qui est un acide di-carboxylique ou un sel de celui-ci.
  2. Composition détergente solide selon la revendication 1, dans laquelle l'hydrosolubilité dudit co-adjuvant est supérieure à 1 g/l à 25 °C.
  3. Composition détergente solide selon la revendication 1 ou la revendication 2, dans laquelle ledit co-adjuvant a une taille de particule moyenne inférieure à 150 microns.
  4. Composition détergente solide selon l'une quelconque des revendications précédentes, dans laquelle ledit co-adjuvant est présent dans une quantité dans la plage de 1 % à 20 % en poids de la composition détergente.
  5. Composition détergente solide selon l'une quelconque des revendications précédentes, dans laquelle le sel de magnésium d'acide sulfonique d'alkyl benzène linéaire est présent sous forme de granulés dans une plage de tailles de particules supérieure à 0,3 mm.
  6. Composition détergente solide selon l'une quelconque des revendications précédentes, dans laquelle le sel de magnésium d'acide sulfonique d'alkyl benzène linéaire est revêtu avec un polymère hydrosoluble.
  7. Composition détergente solide selon l'une quelconque des revendications précédentes, dans laquelle ledit germe pour précipiter le carbonate de calcium est du carbonate de calcium ayant une surface supérieure à 20 m2/g.
  8. Composition détergente solide selon l'une quelconque des revendications précédentes, comprenant un adjuvant supplémentaire qui est du silicate de métal alcalin.
  9. Procédé de préparation d'une composition détergente en granulés solide consistant à mélanger des granulés de sel de magnésium d'acide sulfonique d'alkyl benzène linéaire avec des poudres d'un carbonate de métal alcalin hydrosoluble, un germe pour précipiter le carbonate de calcium et un co-adjuvant qui est un acide dicarboxylique ou sel de celui-ci.
  10. Procédé selon la revendication 9, comprenant les étapes consistant à :
    (i) préparer la forme granulaire du sel de magnésium de l'acide sulfonique d'alkyl benzène linéaire (Mg-LAS) grâce à la neutralisation des acides sulfoniques d'alkyl benzène linéaire avec un alcalin à base de magnésium en présence de 3 à 28 % d'eau en poids du mélange réactionnel dans un mélangeur à cisaillement élevé ;
    (ii) tamiser éventuellement les granulés de Mg-LAS au tamis à une plage de tailles supérieures à 0,3 mm ; et
    (iii) mélanger lesdits granulés de Mg-LAS avec la poudre de carbonate de métal alcalin hydrosoluble, le germe pour précipiter le carbonate de calcium et le co-adjuvant, qui est un acide dicarboxylique ou sel de celui-ci.
EP08761382A 2007-07-16 2008-06-26 Composition détergente solide Not-in-force EP2167624B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL08761382T PL2167624T3 (pl) 2007-07-16 2008-06-26 Stała detergentowa kompozycja
EP08761382A EP2167624B1 (fr) 2007-07-16 2008-06-26 Composition détergente solide

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IN1354MU2007 2007-07-16
EP07120954 2007-11-19
PCT/EP2008/058137 WO2009010375A1 (fr) 2007-07-16 2008-06-26 Composition détergente solide
EP08761382A EP2167624B1 (fr) 2007-07-16 2008-06-26 Composition détergente solide

Publications (2)

Publication Number Publication Date
EP2167624A1 EP2167624A1 (fr) 2010-03-31
EP2167624B1 true EP2167624B1 (fr) 2010-12-01

Family

ID=39758803

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08761382A Not-in-force EP2167624B1 (fr) 2007-07-16 2008-06-26 Composition détergente solide

Country Status (7)

Country Link
EP (1) EP2167624B1 (fr)
CN (1) CN101743299B (fr)
AT (1) ATE490303T1 (fr)
DE (1) DE602008003820D1 (fr)
PL (1) PL2167624T3 (fr)
WO (1) WO2009010375A1 (fr)
ZA (1) ZA200908805B (fr)

Families Citing this family (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112012024674B1 (pt) 2010-04-26 2019-07-02 Novozymes A/S Grânulo, e, composição de detergente granular
ES2528099T3 (es) * 2010-07-27 2015-02-04 Unilever N.V. Composición de detergente
EP2721137B1 (fr) 2011-06-20 2017-11-01 Novozymes A/S Composition particulaire
WO2012175708A2 (fr) 2011-06-24 2012-12-27 Novozymes A/S Polypeptides ayant une activité de protéase et polynucléotides les codant
DK3543333T3 (da) 2011-06-30 2022-02-14 Novozymes As Fremgangsmåde til screening af alfa-amylaser
WO2013007594A1 (fr) 2011-07-12 2013-01-17 Novozymes A/S Granulés enzymatiques stables au stockage
MX2014001594A (es) 2011-08-15 2014-04-25 Novozymes As Polipeptidos que tienen actividad de celulasa y polinucleotidos que los codifican.
EP2751266B1 (fr) 2011-09-22 2017-03-29 Novozymes A/S Polypeptides dotés d'une activité de protéase et polynucléotides codant pour ceux-ci
JP2015500006A (ja) 2011-11-25 2015-01-05 ノボザイムス アクティーゼルスカブ サブチラーゼ変異体およびこれをコードするポリヌクレオチド
CN104011204A (zh) 2011-12-20 2014-08-27 诺维信公司 枯草杆菌酶变体和编码它们的多核苷酸
AU2013213601B8 (en) 2012-01-26 2018-01-18 Novozymes A/S Use of polypeptides having protease activity in animal feed and detergents
US10093911B2 (en) 2012-02-17 2018-10-09 Novozymes A/S Subtilisin variants and polynucleotides encoding same
US20150064773A1 (en) 2012-03-07 2015-03-05 Novozymes A/S Detergent Composition and Substitution of Optical Brighteners in Detergent Composition
WO2013167581A1 (fr) 2012-05-07 2013-11-14 Novozymes A/S Polypeptides ayant une activité de décomposition du xanthane et polynucléotides codant pour ceux-ci
AU2013279440B2 (en) 2012-06-20 2016-10-06 Novozymes A/S Use of polypeptides having protease activity in animal feed and detergents
CN104869841A (zh) 2012-12-21 2015-08-26 诺维信公司 具有蛋白酶活性的多肽和编码它的多核苷酸
WO2014106593A1 (fr) 2013-01-03 2014-07-10 Novozymes A/S Variants d'alpha-amylase et polynucléotides les codant
US20160083703A1 (en) 2013-05-17 2016-03-24 Novozymes A/S Polypeptides having alpha amylase activity
EP3786269A1 (fr) 2013-06-06 2021-03-03 Novozymes A/S Variants d'alpha-amylase et polynucléotides les codant
FI3013956T3 (fi) 2013-06-27 2023-05-23 Novozymes As Subtilaasivariantteja ja niitä koodittavia polynukleotideja
US20160145596A1 (en) 2013-06-27 2016-05-26 Novozymes A/S Subtilase Variants and Polynucleotides Encoding Same
JP2016523098A (ja) 2013-07-04 2016-08-08 ノボザイムス アクティーゼルスカブ 再付着防止効果を有するポリペプチドおよびそれをコードするポリヌクレオチド
EP3611260A1 (fr) 2013-07-29 2020-02-19 Novozymes A/S Variants de protéase et polynucléotides les codants
WO2015014803A1 (fr) 2013-07-29 2015-02-05 Novozymes A/S Variants de protéases et polynucléotides les codant
EP3339436B1 (fr) 2013-07-29 2021-03-31 Henkel AG & Co. KGaA Composition détergente comprenant des variantes de protéases
WO2015049370A1 (fr) 2013-10-03 2015-04-09 Novozymes A/S Composition détergente et utilisation de celle-ci
WO2015091989A1 (fr) 2013-12-20 2015-06-25 Novozymes A/S Polypeptides ayant une activité protéase et polynucléotides codant pour ceux-ci
US20160348035A1 (en) 2014-03-05 2016-12-01 Novozymes A/S Compositions and Methods for Improving Properties of Non-Cellulosic Textile Materials with Xyloglucan Endotransglycosylase
US20160333292A1 (en) 2014-03-05 2016-11-17 Novozymes A/S Compositions and Methods for Improving Properties of Cellulosic Textile Materials with Xyloglucan Endotransglycosylase
WO2015150457A1 (fr) 2014-04-01 2015-10-08 Novozymes A/S Polypeptides présentant une activité alpha-amylase
WO2015189371A1 (fr) 2014-06-12 2015-12-17 Novozymes A/S Variants d'alpha-amylase et polynucléotides codant pour ces derniers
CN116240202A (zh) 2014-07-04 2023-06-09 诺维信公司 枯草杆菌酶变体以及编码它们的多核苷酸
EP3164486B1 (fr) 2014-07-04 2020-05-13 Novozymes A/S Variants de subtilase et polynucléotides codant pour ceux-ci
WO2016079305A1 (fr) 2014-11-20 2016-05-26 Novozymes A/S Variants de alicyclobacillus et polynucléotides codant pour ceux-ci
WO2016087617A1 (fr) 2014-12-04 2016-06-09 Novozymes A/S Variants de subtilase et polynucléotides codant pour ceux-ci
EP3234121A1 (fr) 2014-12-15 2017-10-25 Henkel AG & Co. KGaA Composition de détergent comprenant des variants de subtilase
EP3872175A1 (fr) 2015-06-18 2021-09-01 Novozymes A/S Variants de subtilase et polynucléotides codant pour ceux-ci
EP3106508B1 (fr) 2015-06-18 2019-11-20 Henkel AG & Co. KGaA Composition détergente comprenant des variantes de subtilase
EA036576B1 (ru) * 2015-09-15 2020-11-25 Юнилевер Н.В. Водная композиция для очищения твердых поверхностей
WO2017064253A1 (fr) 2015-10-14 2017-04-20 Novozymes A/S Polypeptides ayant une activité de protéase et polynucléotides codant pour ceux-ci
US10479981B2 (en) 2015-10-14 2019-11-19 Novozymes A/S DNase variants
EP3464582A1 (fr) 2016-06-03 2019-04-10 Novozymes A/S Variants de subtilase et polynucléotides codant pour ceux-ci
WO2018011276A1 (fr) 2016-07-13 2018-01-18 The Procter & Gamble Company Variants dnase de bacillus cibi et leurs utilisations
MX2019002639A (es) * 2016-09-07 2019-07-04 Ecolab Usa Inc Composiciones detergentes solidas y metodos para ajustar la velocidad de dispensacion de los detergentes solidos que utilizan tensioactivos anonicos solidos.
US20230416706A1 (en) 2017-10-27 2023-12-28 Novozymes A/S Dnase Variants
CN111247245A (zh) 2017-10-27 2020-06-05 宝洁公司 包含多肽变体的洗涤剂组合物
AU2019210740B2 (en) 2018-01-26 2022-02-17 Ecolab Usa Inc. Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier
CN111655830A (zh) 2018-01-26 2020-09-11 埃科莱布美国股份有限公司 固化液体阴离子表面活性剂
CN111655829A (zh) 2018-01-26 2020-09-11 埃科莱布美国股份有限公司 用粘合剂及任选载体固化液体氧化胺、甜菜碱和/或磺基甜菜碱表面活性剂
WO2019201793A1 (fr) 2018-04-17 2019-10-24 Novozymes A/S Polypeptides ayant une activité de liaison des hydrates de carbone dans des compositions détergentes et leur utilisation pour réduire les plis de textiles ou de tissus
AU2020242303A1 (en) 2019-03-21 2021-06-24 Novozymes A/S Alpha-amylase variants and polynucleotides encoding same
WO2020207944A1 (fr) 2019-04-10 2020-10-15 Novozymes A/S Variants polypeptidiques
US20220325204A1 (en) 2019-08-27 2022-10-13 Novozymes A/S Detergent composition
WO2021053127A1 (fr) 2019-09-19 2021-03-25 Novozymes A/S Composition détergente
WO2021064068A1 (fr) 2019-10-03 2021-04-08 Novozymes A/S Polypeptides comprenant au moins deux domaines de liaison aux hydrates de carbone
EP3892708A1 (fr) 2020-04-06 2021-10-13 Henkel AG & Co. KGaA Compositions de nettoyage comprenant des variantes de dispersine
WO2022074037A2 (fr) 2020-10-07 2022-04-14 Novozymes A/S Variants d'alpha-amylase
WO2022171780A2 (fr) 2021-02-12 2022-08-18 Novozymes A/S Variants d'alpha-amylase
EP4359518A1 (fr) 2021-06-23 2024-05-01 Novozymes A/S Polypeptides d'alpha-amylase
WO2024123464A1 (fr) * 2022-12-06 2024-06-13 The Procter & Gamble Company Procédé de fabrication d'un flocon de tensioactif détersif anionique d'alkylbenzène sulfonate linéaire de magnésium

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2717243A (en) * 1955-09-06 Non-caking alkyl aryl sulfonate
US3703772A (en) * 1971-07-27 1972-11-28 Colgate Palmolive Co Drying of detergents
GB1437950A (en) * 1972-08-22 1976-06-03 Unilever Ltd Detergent compositions
CA1110517A (fr) * 1977-12-22 1981-10-13 Peter L. Dawson Detergent liquide

Also Published As

Publication number Publication date
PL2167624T3 (pl) 2011-05-31
WO2009010375A1 (fr) 2009-01-22
EP2167624A1 (fr) 2010-03-31
DE602008003820D1 (de) 2011-01-13
ATE490303T1 (de) 2010-12-15
CN101743299B (zh) 2012-03-28
CN101743299A (zh) 2010-06-16
ZA200908805B (en) 2011-03-30

Similar Documents

Publication Publication Date Title
EP2167624B1 (fr) Composition détergente solide
EP2154233B1 (fr) Composition d'adjuvant
US4908159A (en) Detergent granules containing simple sugars and a seed crystal for calcium carbonate
SU558648A3 (ru) Моюща композици
US4196093A (en) Production of detergent compositions
EP2366006A1 (fr) Composition solide d'adjuvant
JP3705818B2 (ja) 洗濯方法及び洗浄剤組成物
JPH046760B2 (fr)
EP0050894B1 (fr) Compositions pour l'adoucissement de l'eau à base d'aluminosilicates et compositions détergentes les contenant
CA1069013A (fr) Production de detergents
EP2121588A2 (fr) Composition de détergent solide et procédé de préparation de celle-ci
JP5041469B2 (ja) 洗剤組成物
EP2139980B1 (fr) Système adjuvant de détergence ("builder") destiné à une composition détergente
EP2231531B1 (fr) Système builder pour compositions détergentes
KR100464891B1 (ko) 개질된알루미노실리케이트
ES2357188T3 (es) Composición detergente sólida.
JP3187437B2 (ja) 高密度粒状洗剤組成物
JP3705392B2 (ja) 洗濯方法
JP2005048183A (ja) 層状珪酸塩吸着質およびその用途
ES2353935T3 (es) Sistema mejorador de la detergencia para una composición detergente.
AU2011285135B2 (en) Detergent composition
JPH10195485A (ja) 高嵩密度粒状洗剤組成物の製造方法
JPH04277599A (ja) 洗剤組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20091204

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

DAX Request for extension of the european patent (deleted)
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 602008003820

Country of ref document: DE

Date of ref document: 20110113

Kind code of ref document: P

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20101201

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2357188

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20110419

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110301

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20101201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110301

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

REG Reference to a national code

Ref country code: PL

Ref legal event code: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110302

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110401

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20110401

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

26N No opposition filed

Effective date: 20110902

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008003820

Country of ref document: DE

Effective date: 20110902

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110626

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20120626

Year of fee payment: 5

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120630

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20120630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110626

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20130627

Year of fee payment: 6

Ref country code: DE

Payment date: 20130627

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20130603

Year of fee payment: 6

Ref country code: TR

Payment date: 20130611

Year of fee payment: 6

Ref country code: FR

Payment date: 20130702

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20101201

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20130621

Year of fee payment: 6

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602008003820

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20140626

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602008003820

Country of ref document: DE

Effective date: 20150101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20150227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150101

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140630

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140626

REG Reference to a national code

Ref country code: PL

Ref legal event code: LAPE

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20151029

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140626

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140627

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20140626