WO2006003156A1 - Sodium percarbonate particles, process for their production, their use and detergent compositions containing them - Google Patents
Sodium percarbonate particles, process for their production, their use and detergent compositions containing them Download PDFInfo
- Publication number
- WO2006003156A1 WO2006003156A1 PCT/EP2005/053043 EP2005053043W WO2006003156A1 WO 2006003156 A1 WO2006003156 A1 WO 2006003156A1 EP 2005053043 W EP2005053043 W EP 2005053043W WO 2006003156 A1 WO2006003156 A1 WO 2006003156A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- particles
- sodium percarbonate
- coating
- sodium
- small
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
- C01B15/10—Peroxyhydrates; Peroxyacids or salts thereof containing carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
- C01B15/10—Peroxyhydrates; Peroxyacids or salts thereof containing carbon
- C01B15/106—Stabilisation of the solid compounds, subsequent to the preparation or to the crystallisation, by additives or by coating
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
-
- 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
- C11D3/39—Organic or inorganic per-compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- sodium percarbonate or sodium carbonate peroxyhydrate
- detergent compositions for household fabric washing or dish washing
- detergent compositions contain among other components zeolites as builder material, enzymes, bleach activators and/or perfumes.
- zeolites as builder material
- enzymes enzymes
- bleach activators and/or perfumes.
- a number of proposals have been made to overcome this problem by interposing a layer between the sodium percarbonate and its environment, called a coating layer. For instance, in the British patent application GB 1538893 sodium sulphate is used as one of the constituents of the coating layer, and in the international application WO 96/14389 a magnesium salt is used.
- the aim of the present invention is to provide new sodium percarbonate particles presenting an improved long term stability when they are stored as such or in a formulated product for a long period before being used, compared to known coated sodium percarbonate particles.
- the long term stability of sodium percarbonate particles can be expressed in two different ways.
- the present invention concerns sodium percarbonate particles with a long term stability expressed as heat output at 40 °C measured (as described above) after storage during 12 weeks at 40 °C which is less than 5 ⁇ W/g.
- the long term heat output is less than 4 ⁇ W/g, preferably less than 3 ⁇ W/g, and most preferably less than 2 ⁇ W/g.
- the mean particle size of particles is measured using a sieve set (containing at least 6 sieves of known sieve aperture) to obtain several fractions and weighing each fraction.
- the mean particle size in ⁇ m (MPS) is then calculated according to the formula
- the sodium percarbonate particles of the present invention usually have a 90 % dissolution time of at least 0,1 min, in particular at least 0,5 min. Generally, the 90 % dissolution time is at most 3 min, especially at most 2,5 min.
- the 90 % dissolution time is the time taken for conductivity to achieve 90 % of its final value after addition of the coated sodium percarbonate particles to water at 15 0 C and 2 g/1 concentration.
- the method used is adapted from ISO 3123-1976 for industrial perborates, the only differences being the stirrer height that is 10 mm from the beaker-bottom and a 2 liter beaker (internal diameter 120 mm).
- a sample of dry sodium percarbonate (about 5 g) is placed on the Petri dish which is gently agitated to generate an even particulate layer across the base of the dish and reweighed on the same balance, (W2).
- the sample on the Petri dish is stored in a room, about 2,5 m high, wide and long in an atmosphere maintained for a period of 24 hours at 32 0 C by a thermostat controlled heater and at 80 % Relative Humidity (RH) by introduction of a fine droplet water spray under the control of a humidity detector and weighed on the same balance, (W3).
- RH Relative Humidity
- Moisture Pick-up (g/kg) 1000 x (W3 - W2) / (W2 - Wl).
- "Dry sodium percarbonate” is intended to denote sodium percarbonate which has been dried until its moisture content is below 0,3 % by weight (using a Halogen dryer METTLER HR73 equipment in which a cooled sample of about 7,5 g is placed on an aluminum dish, the sample is continuously weighed and dried at 60 0 C until the weight is constant (maximum weight loss of 1 mg in 90 s). The drying can be done for instance in a fluid bed drier having a diameter of 15 cm, during 15 to
- the in-detergent stability is measured as follows : a detergent composition is prepared by dry mixing 15 % by weight of coated sodium percarbonate particles with 90 % by weight of a base detergent composition containing zeolite A (Na) called DECA* base in an amount of about 35 % by weight. Samples (50 g) of the blended composition are transferred into polyethylene-coated cartons which were sealed and the cartons stored in a temperature and humidity controlled cabinet at 32 0 C, 80 % relative humidity for 6 weeks. The available oxygen content (Avox) of the composition was measured at the beginning and end of the storage period, using a standard potassium permanganate titration method and the Avox remaining at the end expressed as a percentage of its starting value is calculated.
- zeolite A Na
- the sodium percarbonate particles of the invention can be coated or uncoated. Preferably, they are coated. When coated, they contain sodium percarbonate core particles which are surrounded by at least one coating layer. This means that the surface of the sodium percarbonate core particles has been treated, at least once, by contacting it with a coating agent or with a mixture of coating agents, so that a layer of that coating agent or mixture is deposited onto the surface of the core particles. It is recommended to have a coating layer as uniform and homogeneous as possible having all around the surface of the core particle a homogeneous chemical structure, a homogeneous thickness with as less holes as possible. The function of this coating layer is to protect the core material from contact with the environment and especially from contact with humidity present in the environment which enhances the decomposition of the core material.
- Particular combinations of coating agents include carbonate/silicate, and boric acid or borate with sulfate and the combination of a) sulfate, carbonate, carbonate/sulfate, bicarbonate, boric acid, borate, boric acid/sulfate, or borate/sulfate, with b) silicate.
- the inorganic coating agent contains sodium silicate, sodium borate, boric acid, sodium carbonate, sodium sulfate, magnesium sulfate or one of their mixtures.
- the coating agent can also be sodium percarbonate itself which can be applied as a solution of sodium percarbonate or by using simultaneously a solution of sodium carbonate and a solution of hydrogen peroxide.
- the presence of these small particles in the coating layer can be detected by using Scanning Electron Microscopy - Energy Dispersive X-ray element mapping of an element which is present in the coating agent or in the small sodium percarbonate particles (but not in both) such as magnesium or sulphur, using the following equipment : FEI Quanta 200, EDX-System: Genesis from the company Edax, under the measurement conditions : High vacuum, 30 kV.
- Figures 1 and 2 show two typical pictures obtained with this method of coated sodium percarbonate containing small sodium percarbonate particles in the coating layer. In these figures, the area around 1 corresponds to the coating layer, 2 corresponds to a small sodium percarbonate particle inside the coating layer, and the area around 3 corresponds to the core particle.
- the small sodium percarbonate particles which can be present can be uncoated. Alternatively, they can be coated.
- the sodium percarbonate core particles obtained according to the first option of step (a) contain commonly more than 1 % by weight of water, the water content being generally up to 15 % by weight.
- the core particles obtained according to the second option contain in general less than 1,5 % by weight of water, in particular less than 1 % by weight of water, a water content of at most 0,8 % by weight being most preferred.
- the core particles obtained according to the third option (direct process) contain typically between 0, 1 and 25 % by weight of water.
- the water content of sodium percarbonate particles is measured, in the framework of the present invention, according to the following method : a sample is heated and the amount of liberated water is measured by the METTLER method described above.
- the drying step (b) of the' process of the present invention can be a distinct step from step (a) or can be carried out simultaneously with step (a) in the same equipment.
- step (a) is carried out according to the first (liquid crystallization process)
- the drying step (b) can be done in any reactor such as in a fluid bed drier, in a rotating drum drier, in an oven or in a circulating air oven.
- Typical temperatures of the hot air are from 50 to 210 0 C, especially from 100 to 160 0 C.
- step (a) is carried out according to the second option (fluid bed granulation process)
- the drying is usually done in the same fluid bed reactor as the one used in step (a). Drying is then simultaneously carried out with step (a).
- Typical temperatures of the fluidizing gas are from 50 to 210 0 C, especially from 100 to 160 0 C.
- step (a) is carried out according to the third option (direct process)
- the drying can be done in any reactor such as a rotating drum drier, an oven, a circulating air oven or a fluid bed reactor which can be the same as the fluid bed reactor used in step (a).
- Typical temperatures of the fluidizing gas are from 50 to 210 0 C, especially from 100 to 160 0 C.
- the dried sodium percarbonate core particles obtained in step (b) contain in general less than 1,5 % by weight of water, in particular less than 1 % by weight of water, a water content of at most 0,8 % by weight being most preferred.
- step (c) it is recommended to have a minimum amount of moisture present in the system to allow to bind the coating layer onto the surface of the core particles and/or to glue the small particles onto the surface of the core particles or in the coating layer.
- This moisture can already be present inside the sodium percarbonate core particles. It can also be added as the diluent of the aqueous solution or slurry of the coating agent or as the diluent of the slurry of the small sodium percarbonate particles, or else it can be added as such.
- the moisture content is usually at least 2 % by weight of the weight of the dried sodium percarbonate core particles, in particular at least 3 % by weight , preferably at least 5 % by weight.
- the drying step (d) of the process of the invention can be carried out under similar conditions as the drying step (b).
- the drying step (d) is preferably carried out simultaneously with the coating step (c) in the same fluid bed equipment.
- the small sodium percarbonate particles are obtained by removing some of the particles generated during the process of the present invention and by recycling them into step (c).
- the small sodium percarbonate particles used in the coating step are recycled from the drying step (b) carried out in drier 5 as follows.
- the drier 5 is in this case a fluid bed drier using an upward flow of fluidizing gas entering the fluid bed via the conduit 17.
- the fluidizing gas leaves the drier 5 at the top through the conduit 18 and carries along fine sodium percarbonate particles. These fine particles are removed from the stream leaving the drier 5 through the conduit 18 with the aid of the separating device 19.
- the fluidizing gas leaves via the conduit 20.
- the thus removed particles are transferred through the conduit 21 into an optional milling device 22 in which particles of a mean size smaller than 100 ⁇ m are obtained.
- the small sodium percarbonate particles used in the coating step are recycled from the sieving devices 7 and/or 15.
- the sieving devices particles with a size smaller than 300 ⁇ m and particles larger than 1800 ⁇ m are separated from the others. The others continue in the process as explained above.
- the separated particles (smaller than 300 and larger than 1800 ⁇ m) are transferred via the conduits 25 and/or 26 into the milling devices 27 a ⁇ Wor 28 in which particles of a mean size smaller than 100 ⁇ m are obtained.
- These small particles are transferred via the conduits 29, 30, 31 and/or 32 and introduced in the first and/or second coating reactors 9 and/or 12.
- the small sodium percarbonate particles used in the coating step are recycled from the drying step (d) carried out in drier 12 as follows.
- the drier 12 is in this case a fluid bed drier using an upward flow of fluidizing gas entering the drier through the conduit 33.
- the fluidizing gas leaves the drier 12 at the top through the conduit 34 and carries along fine coated sodium percarbonate particles. These fine particles are removed from the stream leaving the drier 12 through the conduit 34 with the aid of the separating device 35.
- the fluidizing gas leaves through the conduit 36.
- the thus removed particles are transferred through the conduit 37 into an optional milling device 38 in which particles of a mean size smaller than 100 ⁇ m are obtained. These milled particles are then transferred through the conduits 39 and/or 40 and introduced in the first and/or second coating reactors 9 and/or 12.
- a particularly preferred realization form of the second process of the invention is represented in the figure 4.
- a reactor 1 for the manufacture of sodium percarbonate core particles is fed with a carbonate source (preferably an aqueous solution of sodium carbonate) through the conduit 2 and with a hydrogen peroxide source (preferably an aqueous hydrogen peroxide solution) through the conduit 3.
- the reactor 1 is preferably a liquid crystallization reactor.
- the obtained sodium percarbonate core particles are transferred from the reactor 1 via the conduit 4 to a fluid bed reactor 5 which acts simultaneously as colting reactor and as drier.
- the fluidizing gas is entered into the fluid bed 5 via the conduit 6.
- the coating agent is introduced in the fluid bed reactor 5 via the conduit 7.
- Small sodium percarbonate particles are introduced in the fluid bed reactor through one or both of the conduits 16 and 19 as explained in detail below.
- the coated and dried sodium percarbonate particles leave the fluid bed reactor 5 via the conduit 8 and are transferred to a sieving device 9 which eliminates the too small and too large particles in order to obtain particles with a mean size of from 300 to 1600 ⁇ m which are collected as final product via the conduit 10.
- the small sodium percarbonate particles used in the coating step are recycled from the coating step itself as follows.
- the fluid bed coating reactor uses an upward flow of fluidizing gas entering the reactor through the conduit 6.
- the fluidizing gas leaves the reactor 5 at the top through the conduit 11 and carries along fine coated sodium percarbonate particles.
- the separated particles (smaller than 300 and larger than 1800 ⁇ m) are transferred via the conduit 17 into a milling device 18 in which particles of a mean size smaller than 100 ⁇ m are obtained. These small particles are transferred via the conduit 19 and introduced in the coating reactor 5.
- the first and second embodiment can be used simultaneously.
- the coated sodium percarbonate particles of the present invention can advantageously be used as bleaching agent in detergent compositions.
- the present invention therefore concerns also the use of the above described coated sodium percarbonate particles as bleaching agent in detergent compositions.
- Example 1 Sodium percarbonate core particles were prepared in a continuous crystallization process using NaCl as salting out agent in a concentration of about 200 g/1.
- the crystallization reactor was filled with mother liquor at a temperature between 15 and 25 0 C. Solid sodium carbonate was added thereto until saturation is reached as well as a slight excess of a 60 % wt aqueous hydrogen peroxide solution.
- the reactor was continuously stirred and cooled at a temperature of 15- 25 °C.
- the formed sodium percafbonate core particles are continuously withdrawn from the reactor and transferred into a buffer tank and then into a discontinuous centrifuge.
- the sodium percarbaonte core particles leaving the centrifuge are dried in a fluid bed dryer at an off-gas temperature between 50 and 75 0 C.
- M 1 weight fraction in % on sieve i
- k t sieve aperture in ⁇ m of sieve i
- Index i increases with increasing sieve aperture
- Ic n+1 1800 ⁇ m and is the maximum size of particles considered for the span calculation.
- MPS was the mean particle size ass calculated according to the description. The fraction below 600 ⁇ m was milled with a cross-beater mill of the type
- Nozzle Spraying top down onto the PCS
- the final product was taken out of the dryer and cooled.
- the total coating level was 6% by weight of the weight of the coated sodium percarbonate particles.
- the coating layer contained 20 % by weight of PCS fines.
- the obtained coated PCS presented a long term stability expressed as heat output at 40 0 C measured after storage during 12 weeks at 40 0 C of less than 2 ⁇ W/g, and expressed as Avox recovery after storage for 8 weeks at 55 °C of 88 % and after storage for 8 weeks at 55 °C of 88 %.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2005800214387A CN1976871B (en) | 2004-06-29 | 2005-06-28 | Sodium percarbonate particles,process for their production, their use and detergent compositions containing them |
BRPI0512739-4A BRPI0512739A (en) | 2004-06-29 | 2005-06-28 | sodium percabonate particles, process for their production and use, and detergent compositions |
JP2007518612A JP2008504206A (en) | 2004-06-29 | 2005-06-28 | Sodium percarbonate particles, methods for their production, their use and detergent compositions containing them |
EP05758573A EP1773716A1 (en) | 2004-06-29 | 2005-06-28 | Sodium percarbonate particles,process for their production ,their use and detergent compositions containing them |
US11/631,020 US8025972B2 (en) | 2004-06-29 | 2005-06-28 | Coated sodium percarbonate particles having excellent long term stability, process for their production, their use and detergent compositions containing them |
US13/190,531 US20110281783A1 (en) | 2004-06-29 | 2011-07-26 | Sodium percarbonate particles, process for their production, their use and detergent compositions containing them |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04103015A EP1612186A1 (en) | 2004-06-29 | 2004-06-29 | Sodium percarbonate particles, process for their production, their use and detergent compositions containing them. |
EP04103015.6 | 2004-06-29 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/190,531 Continuation US20110281783A1 (en) | 2004-06-29 | 2011-07-26 | Sodium percarbonate particles, process for their production, their use and detergent compositions containing them |
Publications (2)
Publication Number | Publication Date |
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WO2006003156A1 true WO2006003156A1 (en) | 2006-01-12 |
WO2006003156A8 WO2006003156A8 (en) | 2007-03-01 |
Family
ID=34929261
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2005/053043 WO2006003156A1 (en) | 2004-06-29 | 2005-06-28 | Sodium percarbonate particles, process for their production, their use and detergent compositions containing them |
Country Status (8)
Country | Link |
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US (2) | US8025972B2 (en) |
EP (2) | EP1612186A1 (en) |
JP (1) | JP2008504206A (en) |
KR (1) | KR20070028472A (en) |
CN (1) | CN1976871B (en) |
BR (1) | BRPI0512739A (en) |
RU (1) | RU2396206C2 (en) |
WO (1) | WO2006003156A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101688161B (en) * | 2007-05-02 | 2012-09-05 | 索尔维公司 | Process for the preparation of coated sodium percarbonate |
CN101679917B (en) * | 2007-05-02 | 2014-04-02 | 索尔维公司 | Process for the preparation of coated sodium percarbonate |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1612186A1 (en) | 2004-06-29 | 2006-01-04 | SOLVAY (Société Anonyme) | Sodium percarbonate particles, process for their production, their use and detergent compositions containing them. |
EP1612185A1 (en) * | 2004-06-29 | 2006-01-04 | SOLVAY (Société Anonyme) | Coated sodium percarbonate particles, process for their production, their use and detergent compositions containing them |
EP1728762A1 (en) * | 2005-06-01 | 2006-12-06 | SOLVAY (Société Anonyme) | Coated sodium percarbonate particles, process for their preparation, their use and detergent compositions containing them |
SI1889901T1 (en) | 2006-07-27 | 2009-02-28 | Evonik Degussa Gmbh | Coated sodium percarbonate particle |
PL1903098T3 (en) | 2006-07-27 | 2009-04-30 | Evonik Treibacher Gmbh | Coated sodium percarbonate particle |
ES2344712T3 (en) | 2006-07-27 | 2010-09-03 | Evonik Degussa Gmbh | COVERED SODIUM PERCARBONATE PARTICLES. |
EP1905738A1 (en) * | 2006-09-28 | 2008-04-02 | Evonik Degussa GmbH | Process for preparing granular sodium percarbonate |
EP1939275A1 (en) * | 2006-12-29 | 2008-07-02 | Solvay SA | Non-oxidiser percarbonate particles |
EP2080544B1 (en) | 2007-12-19 | 2010-12-01 | Evonik Degussa GmbH | Method for manufacturing coated sodium percarbonate particles |
US7638474B1 (en) | 2008-08-05 | 2009-12-29 | The Clorox Company | Natural laundry detergent compositions |
DE102010028236A1 (en) * | 2010-04-27 | 2011-10-27 | Evonik Degussa Gmbh | Bleaching agent particles comprising sodium percarbonate and a bleach activator |
EP3003979B1 (en) * | 2013-05-24 | 2019-08-14 | Solvay SA | Non-oxidizer particles |
EP3181670B1 (en) * | 2015-12-17 | 2019-01-30 | The Procter and Gamble Company | Automatic dishwashing detergent composition |
EP3181671A1 (en) | 2015-12-17 | 2017-06-21 | The Procter and Gamble Company | Automatic dishwashing detergent composition |
CN112877152B (en) * | 2021-02-06 | 2022-05-06 | 濮阳宏业环保技术研究院有限公司 | Coated sodium percarbonate material and preparation method and application thereof |
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KR100366556B1 (en) * | 2000-04-26 | 2003-01-09 | 동양화학공업주식회사 | Granular coated sodium percarbonate and process for preparing them |
FI109685B (en) * | 2001-01-26 | 2002-09-30 | Kemira Chemicals Oy | Process for preparing sodium percarbonate granules with improved stability |
DE10140838A1 (en) * | 2001-08-21 | 2003-03-06 | Degussa | Process for the production of sodium percarbonate |
EP1612185A1 (en) * | 2004-06-29 | 2006-01-04 | SOLVAY (Société Anonyme) | Coated sodium percarbonate particles, process for their production, their use and detergent compositions containing them |
EP1612186A1 (en) | 2004-06-29 | 2006-01-04 | SOLVAY (Société Anonyme) | Sodium percarbonate particles, process for their production, their use and detergent compositions containing them. |
EP1728762A1 (en) * | 2005-06-01 | 2006-12-06 | SOLVAY (Société Anonyme) | Coated sodium percarbonate particles, process for their preparation, their use and detergent compositions containing them |
US7638474B1 (en) * | 2008-08-05 | 2009-12-29 | The Clorox Company | Natural laundry detergent compositions |
-
2004
- 2004-06-29 EP EP04103015A patent/EP1612186A1/en not_active Withdrawn
-
2005
- 2005-06-28 KR KR1020067027767A patent/KR20070028472A/en not_active Application Discontinuation
- 2005-06-28 WO PCT/EP2005/053043 patent/WO2006003156A1/en active Application Filing
- 2005-06-28 JP JP2007518612A patent/JP2008504206A/en active Pending
- 2005-06-28 CN CN2005800214387A patent/CN1976871B/en not_active Expired - Fee Related
- 2005-06-28 EP EP05758573A patent/EP1773716A1/en not_active Withdrawn
- 2005-06-28 RU RU2007103184/15A patent/RU2396206C2/en not_active IP Right Cessation
- 2005-06-28 US US11/631,020 patent/US8025972B2/en not_active Expired - Fee Related
- 2005-06-28 BR BRPI0512739-4A patent/BRPI0512739A/en not_active IP Right Cessation
-
2011
- 2011-07-26 US US13/190,531 patent/US20110281783A1/en not_active Abandoned
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101688161B (en) * | 2007-05-02 | 2012-09-05 | 索尔维公司 | Process for the preparation of coated sodium percarbonate |
CN101679917B (en) * | 2007-05-02 | 2014-04-02 | 索尔维公司 | Process for the preparation of coated sodium percarbonate |
Also Published As
Publication number | Publication date |
---|---|
JP2008504206A (en) | 2008-02-14 |
EP1773716A1 (en) | 2007-04-18 |
EP1612186A1 (en) | 2006-01-04 |
US20110281783A1 (en) | 2011-11-17 |
US8025972B2 (en) | 2011-09-27 |
RU2007103184A (en) | 2008-08-10 |
WO2006003156A8 (en) | 2007-03-01 |
KR20070028472A (en) | 2007-03-12 |
RU2396206C2 (en) | 2010-08-10 |
US20070275243A1 (en) | 2007-11-29 |
CN1976871A (en) | 2007-06-06 |
CN1976871B (en) | 2012-04-04 |
BRPI0512739A (en) | 2008-04-08 |
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