EP1232239B1 - Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel - Google Patents
Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel Download PDFInfo
- Publication number
- EP1232239B1 EP1232239B1 EP00979590A EP00979590A EP1232239B1 EP 1232239 B1 EP1232239 B1 EP 1232239B1 EP 00979590 A EP00979590 A EP 00979590A EP 00979590 A EP00979590 A EP 00979590A EP 1232239 B1 EP1232239 B1 EP 1232239B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- particle
- alkali metal
- component
- acidic component
- alkaline
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 22
- 238000005406 washing Methods 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000012459 cleaning agent Substances 0.000 title description 6
- 239000002245 particle Substances 0.000 claims description 38
- 239000003599 detergent Substances 0.000 claims description 17
- 239000004615 ingredient Substances 0.000 claims description 17
- 230000002378 acidificating effect Effects 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 230000009969 flowable effect Effects 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 1
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims 1
- -1 alkylaryl sulfonic acids Chemical class 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000003513 alkali Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229940045872 sodium percarbonate Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 208000001840 Dandruff Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- 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
-
- 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
- C11D3/3942—Inorganic per-compounds
Definitions
- the present invention relates to a process for the preparation of particulate detergents or cleaners.
- Particulate detergents and cleaners usually consist of a variety of ingredients, which are usually incorporated into a plurality of particulate components in the entire agent because of mutual incompatibilities.
- examples of such mutually incompatible ingredients are bleach and bleach activator, which are to react with each other under conditions of use in aqueous solution and then give a desired increased bleaching performance, but not allowed to react with each other during storage, since they are no longer available for the desired application stand.
- a less striking example of the non-optimal interaction of individual ingredients of detergents and cleaners results from their pH-dependent performance.
- anionic surfactants and builders for example, require an alkaline pH to fully develop their performance.
- both dirt particles as well as most textile fibers form an increasing number of negative charges with increasing pH, which leads to increasing repulsion among them and is therefore beneficial to the desired washing result.
- textile washing has been carried out with more or less alkaline wash liquors since ancient times. The same applies analogously to aqueous solutions for cleaning hard surfaces, for example in the context of machine cleaning methods for dishes.
- Detergent ingredient is understood to mean a substance whose addition to water, which has a pH of 7, leads to an acidic or alkaline pH.
- mp is the total mass of the particles to be treated and r is their mean particle radius.
- a particle to be treated according to the invention may optionally contain all ingredients of a detergent or cleaning agent, ie it is possible with the method according to the invention to coat a finished washing or cleaning agent.
- a detergent or cleaning agent ie it is possible with the method according to the invention to coat a finished washing or cleaning agent.
- Such alkaline ingredients are preferably alkali silicates, alkali aluminosilicates, alkali phosphates, alkali carbonates, alkali metal perborates and alkali percarbonates, and mixtures thereof, with sodium being the preferred alkali metal.
- liquid or pasty acidic component preference is given to applying the liquid or pasty acidic component, optionally in molten form, in a mixer or granulator to the optionally heated particles consisting at least proportionally of an alkaline detergent or cleaning agent ingredient.
- Particularly good coatings are achieved by applying the acidic component to the particle over a period of 5 minutes to 20 minutes.
- the inventive method is, presumably - without this theory To be bound by the neutralization reaction of the acidic coating material with the alkaline particle on its surface and to a certain extent under its surface, a particularly dense and comparatively little or slowly water-soluble coating marafffen having a reliable tightness after entry into an aqueous system and thus enables the production of detergents and cleaners with a step-shaped pH profile.
- the particles obtainable according to the invention contain in their core almost exclusively the constituents of the particle originally used. This core is surrounded by a layer in which increasingly higher concentrations of acidic coating material or its salt formed with the alkaline component occur from the inside to the outside, wherein the outer surface can be formed entirely of acidic coating material.
- Components of the particle of alkaline material, in addition to the alkali component may be all customary with this compatible ingredients of detergents and cleaners, as long as they are solid or ready to confection.
- these include, in particular, other builders, surface-active surfactants, other peroxygen compounds, peroxygen activators, sequestering agents, electrolytes and other auxiliaries, such as dye transfer inhibitors, silver corrosion inhibitors, foam regulators and dyes and perfumes, wherein the presence of peroxygen activators in the particle of alkaline material less preferred is when this particle also contains peroxygen compound.
- the particles produced by the process according to the invention are, preferably after mixing with at least one further particulate component, as Detergents or cleaning agents used, which may be agents for manual or machine washing or cleaning in particular.
- the at least one further component contains at least one active ingredient whose washing or cleaning action at a lower pH than that resulting from the dissolution of the alkali component contained in the particles produced by the method according to the invention is higher than at the pH at dissolution of said particle.
- this active ingredient is selected from enzymes or Enzytrmnischenoder, wherein in the case of the mixtures, the individual active ingredients may also be contained in a plurality of different composite particulate components.
- the at least one further component of such a solubility that it releases as much of the active substance contained in it under the initially lower pH conditions, but essentially only after pH increase by the then higher alkalinity of him surrounding aqueous Systms unfolds its full effect, or otherwise reacts with the then liberated alkali component.
- An example of the last-mentioned variant is a bleach activator which is soluble or formulated in a lower pH and which reacts with a bleaching agent released from the coated particle according to the invention and which, by being already dissolved, can rapidly develop a strong bleaching action.
- 1 kg spheronized sodium percarbonate having an average particle diameter of 400 microns were premixed with 25 g of stearic acid (dandruff) in a cold state. This premix was placed in a commercial ploughshare mixer with stud shovel preheated to 90 ° C (jacket temperature). At speed level 2 and a measured product temperature of 80 ° C was compounded reactive for 20 min. The hot product was removed and can be used after cooling in the usual way, for example for the production of detergents or cleaners.
- Each 100 g of spheronized sodium percarbonate having an average particle diameter of 1400 microns were added in a beaker with 2.5 g or 1.5 g of stearic acid and heated to a product temperature of about 80 ° C with stirring. After the molten stearic acid had been absorbed into the alkaline particles, the mixture was further reactive compounded at about 80 ° C. for a further 20 minutes.
- Fig. 1 the pH curve is reproduced after incorporation into water of the product prepared by application of 1.5 g of stearic acid.
- Fig. 1 also contains the pH curve of the uncoated percarbonate.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19957036A DE19957036A1 (de) | 1999-11-26 | 1999-11-26 | Verfahren zur Herstellung teilchenförmiger Wasch- oder Reinigungsmittel |
| DE19957036 | 1999-11-26 | ||
| PCT/EP2000/011425 WO2001038477A1 (de) | 1999-11-26 | 2000-11-17 | Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1232239A1 EP1232239A1 (de) | 2002-08-21 |
| EP1232239B1 true EP1232239B1 (de) | 2006-02-01 |
Family
ID=7930482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00979590A Expired - Lifetime EP1232239B1 (de) | 1999-11-26 | 2000-11-17 | Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US7064099B1 (enExample) |
| EP (1) | EP1232239B1 (enExample) |
| JP (1) | JP5036113B2 (enExample) |
| AU (1) | AU1702501A (enExample) |
| CA (1) | CA2326940A1 (enExample) |
| DE (2) | DE19957036A1 (enExample) |
| ES (1) | ES2255518T3 (enExample) |
| WO (1) | WO2001038477A1 (enExample) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10136211B4 (de) * | 2001-07-25 | 2007-05-24 | Henkel Kgaa | Verfahren zur Herstellung teilchenförmiger Wasch-oder Reinigungsmittel |
| DE102006028750A1 (de) * | 2006-06-20 | 2007-12-27 | Henkel Kgaa | Reinigungsverfahren |
| DE102005041708A1 (de) | 2005-09-02 | 2007-03-08 | Henkel Kgaa | Reinigungsmittel |
| US20090165821A1 (en) * | 2005-09-02 | 2009-07-02 | Henkel Kgaa | Detergents |
| DE102005041709A1 (de) * | 2005-09-02 | 2007-03-08 | Henkel Kgaa | Reinigungsmittel |
| PL1917343T3 (pl) * | 2005-09-02 | 2011-12-30 | Henkel Ag & Co Kgaa | Środek do czyszczenia |
| EP1977064A1 (en) * | 2005-09-06 | 2008-10-08 | Aero Project Consultants Pty Ltd | Luggage security device |
Family Cites Families (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE228458C (enExample) * | ||||
| DE221377C (enExample) * | ||||
| DE140987C (enExample) * | 1903-05-16 | |||
| GB707994A (en) * | 1950-02-13 | 1954-04-28 | Ruhrchemie Ag | Process for the neutralization of sulphonic acids |
| US2671797A (en) * | 1951-02-15 | 1954-03-09 | Ruhrchemie Ag | Neutralization of sulfonic acids and sulfuric acid esters |
| US2975141A (en) * | 1957-02-21 | 1961-03-14 | American Alcolac Corp | Preparation of sulfo detergents |
| FR1457677A (fr) * | 1965-09-23 | 1966-01-24 | Colgate Palmolive Co | Procédé de lavage du linge |
| GB1370626A (en) * | 1971-01-27 | 1974-10-16 | Laporte Industries Ltd | Coated peroxygen compounds |
| DE2318930A1 (de) * | 1972-04-17 | 1973-10-31 | Procter & Gamble | Enzym enthaltende detergenzgemische |
| US3908045A (en) * | 1973-12-07 | 1975-09-23 | Lever Brothers Ltd | Encapsulation process for particles |
| US4327151A (en) * | 1976-08-25 | 1982-04-27 | Lever Brothers Company | Encapsulated bleaches and methods for their preparation |
| LU76548A1 (enExample) * | 1977-01-10 | 1978-09-18 | ||
| CH639416A5 (de) * | 1977-06-27 | 1983-11-15 | Akzo Nv | Detergentienzusammensetzung enthaltend alkalicarbonat. |
| US4297229A (en) * | 1979-10-23 | 1981-10-27 | United States Borax & Chemical Corporation | Particulate borate-soap compositions |
| FR2471222A1 (fr) * | 1979-12-12 | 1981-06-19 | Interox | Procede pour la stabilisation de particules contenant des composes peroxygenes et compositions de blanchiment contenant des particules stabilisees selon ce procede |
| US4421664A (en) * | 1982-06-18 | 1983-12-20 | Economics Laboratory, Inc. | Compatible enzyme and oxidant bleaches containing cleaning composition |
| US4734224A (en) * | 1986-09-15 | 1988-03-29 | The Dial Corporation | Dry neutralization process for detergent slurries |
| GB2209172A (en) * | 1987-08-28 | 1989-05-04 | Unilever Plc | Preparation of solid particulate components for detergents |
| JPH03115496A (ja) * | 1989-09-29 | 1991-05-16 | Kao Corp | 漂白剤及び漂白洗浄剤組成物 |
| JP2918991B2 (ja) * | 1990-05-25 | 1999-07-12 | 三菱瓦斯化学株式会社 | 漂白洗浄剤組成物 |
| WO1992017404A1 (de) * | 1991-03-26 | 1992-10-15 | Henkel Kommanditgesellschaft Auf Aktien | Stabilisiertes natriumpercarbonat |
| DE4128826A1 (de) * | 1991-08-30 | 1993-03-04 | Henkel Kgaa | Wasch- und/oder reinigungsverfahren |
| WO1993004982A1 (de) * | 1991-09-03 | 1993-03-18 | Degussa Ag | Lagerstabil verkapseltes natriumpercarbonat und verfahren zu seiner herstellung |
| US5486317A (en) * | 1992-02-14 | 1996-01-23 | The Procter & Gamble Company | Process for making detergent granules by neutralization of sulphonic acids |
| DE4209924A1 (de) * | 1992-03-27 | 1993-09-30 | Henkel Kgaa | Stabilisiertes Percarbonat (II) |
| GB9226796D0 (en) * | 1992-12-23 | 1993-02-17 | Solvay Interox Ltd | Process for stabilising alkali percarbonate particles,particles obtained thereby and washing and/or bleaching compositions containing them |
| US5443751A (en) * | 1993-03-05 | 1995-08-22 | Church & Dwight Co. Inc. | Powder detergent composition for cold water washing of fabrics |
| DE4344831A1 (de) * | 1993-12-29 | 1995-07-06 | Solvay Interox Gmbh | Beschichtete Alkalimetallperoxosalze und Verfahren zu deren Herstellung |
| US5489399A (en) * | 1994-11-02 | 1996-02-06 | Rengo Co., Ltd. | Carbon dioxide gas generating compositions |
| US5573697A (en) * | 1995-05-31 | 1996-11-12 | Riddick; Eric F. | Process for making high active, high density detergent granules |
| JP3705818B2 (ja) * | 1995-09-04 | 2005-10-12 | 花王株式会社 | 洗濯方法及び洗浄剤組成物 |
| DE19606343A1 (de) * | 1996-02-21 | 1997-08-28 | Hoechst Ag | Bleichmittel |
| GB9712587D0 (en) * | 1997-06-16 | 1997-08-20 | Unilever Plc | Production of detergent granulates |
| GB9712580D0 (en) * | 1997-06-16 | 1997-08-20 | Unilever Plc | Production of detergent granulates |
| GB9713748D0 (en) * | 1997-06-27 | 1997-09-03 | Unilever Plc | Production of detergent granulates |
| CN1192091C (zh) * | 1997-07-14 | 2005-03-09 | 普罗格特-甘布尔公司 | 通过控制附聚颗粒大小制备低密度洗涤剂组合物的方法 |
| JPH11279593A (ja) * | 1998-03-26 | 1999-10-12 | Kao Corp | 液体漂白剤組成物 |
| GB2337054A (en) * | 1998-05-08 | 1999-11-10 | Procter & Gamble | Effervescent particle |
| DE19957038A1 (de) | 1999-11-26 | 2001-05-31 | Henkel Kgaa | Wasch- und Reinigungsmittel |
-
1999
- 1999-11-26 DE DE19957036A patent/DE19957036A1/de not_active Withdrawn
-
2000
- 2000-11-17 WO PCT/EP2000/011425 patent/WO2001038477A1/de not_active Ceased
- 2000-11-17 JP JP2001540232A patent/JP5036113B2/ja not_active Expired - Fee Related
- 2000-11-17 ES ES00979590T patent/ES2255518T3/es not_active Expired - Lifetime
- 2000-11-17 AU AU17025/01A patent/AU1702501A/en not_active Abandoned
- 2000-11-17 DE DE50012170T patent/DE50012170D1/de not_active Expired - Lifetime
- 2000-11-17 EP EP00979590A patent/EP1232239B1/de not_active Expired - Lifetime
- 2000-11-22 US US09/718,943 patent/US7064099B1/en not_active Expired - Fee Related
- 2000-11-27 CA CA002326940A patent/CA2326940A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001038477A1 (de) | 2001-05-31 |
| DE19957036A1 (de) | 2001-05-31 |
| JP5036113B2 (ja) | 2012-09-26 |
| JP2003514982A (ja) | 2003-04-22 |
| US7064099B1 (en) | 2006-06-20 |
| DE50012170D1 (de) | 2006-04-13 |
| CA2326940A1 (en) | 2001-05-26 |
| EP1232239A1 (de) | 2002-08-21 |
| ES2255518T3 (es) | 2006-07-01 |
| AU1702501A (en) | 2001-06-04 |
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