EP0070474B1 - Verfahren zur Herstellung umhüllter körniger Bleichaktivatoren - Google Patents

Verfahren zur Herstellung umhüllter körniger Bleichaktivatoren Download PDF

Info

Publication number
EP0070474B1
EP0070474B1 EP82106147A EP82106147A EP0070474B1 EP 0070474 B1 EP0070474 B1 EP 0070474B1 EP 82106147 A EP82106147 A EP 82106147A EP 82106147 A EP82106147 A EP 82106147A EP 0070474 B1 EP0070474 B1 EP 0070474B1
Authority
EP
European Patent Office
Prior art keywords
weight
water
starch
bleach activator
ratio
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
Application number
EP82106147A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0070474A1 (de
Inventor
Herbert Dr. Saran
Martin Dr. Witthaus
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT82106147T priority Critical patent/ATE11566T1/de
Publication of EP0070474A1 publication Critical patent/EP0070474A1/de
Application granted granted Critical
Publication of EP0070474B1 publication Critical patent/EP0070474B1/de
Expired legal-status Critical Current

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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic 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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected

Definitions

  • Bleach activators are taken to mean compounds which react in aqueous solutions containing hydrogen peroxide or perhydrates to form peracids which have a bleaching action.
  • the particularly effective bleach activators include N-acylated amines, amides and glycolurils, such as those described in DE-B-11 62 967, DE-B-12 91 317, DE-A-20 38 106 and DE-B-15 94 865 are known.
  • DE-B-11 62967 proposes to provide these bleach activators with a water-soluble coating agent before further use, in particular before use in detergents and bleaching agents, the coating agent being able to consist, for example, of carboxymethyl cellulose.
  • This coating agent dissolved in water, can be sprayed onto the activator in finely divided form, after which the coated material is dried.
  • the recommendation is made to granulate the activator before coating, but there are no indications as to how and with which granulation aids this should be carried out. If one works according to the specifications of DE-B-11 62 967 and sprays such a bleach activator, for example tetraacetylethylene diamine, with an aqueous carboxymethyl cellulose solution in a granulator, considerable problems arise. This is because aqueous solutions containing more than 5% by weight of carboxymethyl cellulose can no longer be handled in industrial granulation processes because of their high viscosity and gel-like nature.
  • DE-A-20 48 331 discloses a process for the production of coated, granulated bleach activators, in which the activator is first mixed dry with an agent suitable for coating or granulation and, in a second step, sprayed with water or with granulation aids or film formers dissolved in water and is granulated.
  • water-soluble skeleton salts customary in detergents such as water-phosphates, polyphosphates, carbonates and silicates of alkali metals, or water-insoluble fillers, such as silica, magnesium silicate or magnesium oxide, are proposed.
  • the same water-soluble, water of crystallization salts can also be used as a granulating aid or the dry premixes can be sprayed with an aqueous solution of film-forming substances such as cellulose derivatives or other water-soluble polymers of natural or synthetic origin and granulated at the same time.
  • this process is only useful for the production of granules with a comparatively low content of bleach activators, that is to say those with less than 50% by weight.
  • the granules can therefore only be used in areas where the high proportion of additives does not interfere.
  • DE-C-21 38584 and DE-A-2207974 disclose processes for the production of coated bleach activators, in which molten mixtures of polyglycol and fatty acids with bleach activators dispersed therein are sprayed into a falling space by means of nozzles or rotating disks and the droplets formed by means of a cooler Air can be frozen.
  • the bleach activator is very effectively protected against decomposition. Problems can arise during use, however, since the prills can only be completely dissolved at temperatures above the melting point. Additions of fatty alcohols or their ethoxylates and sulfates, as described in DE-A- 23 38 412 and DE-A-25 35 731 are described, bring only a gradual improvement.
  • the invention has for its object to develop a process for the production of uniformly coated and therefore very stable bleach activator grains of uniform quality and good solubility in cold water, which have a high content of 90% or more by weight of active substance.
  • the aqueous slurry is advantageously prepared by first preparing a solution or swelling of the cellulose ether or starch or starch ether and then stirring in the powdery bleach activator.
  • cellulose ethers are methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, carboxymethyl cellulose (as sodium salt) and methyl carboxymethyl cellulose (sodium salt).
  • depolymerized starch can be considered as starch.
  • Suitable starch ethers are, for example, carboxymethyl starch, hydroxyethyl starch and methyl starch.
  • Sodium carboxymethyl cellulose has proven to be particularly suitable.
  • N-acylated amines, diamines, amides and glycolurils are suitable as bleach activators.
  • These are, for example, tetraacetylmethylene diamine, tetraacetylethylene diamine, diacetylaniline, diacetyl-p-toluidine, 1,3-diacetyl-5,5-dimethylhydantoin, tetraacetylglycoluril, tetrapropionylglycoluril, 1,4-diacetyl-2,5-diketopiacyl -3,6-dimethyl-2,5-diketopiperazine.
  • Tetraacetylethylenediamine is preferably used as the bleach activator.
  • the bleach activator preferably has the following particle size distribution determined by sieve analysis:
  • the number of sieves is expediently carried out with an air jet sieve in order to avoid errors which occur due to agglomeration of fine particles due to electrostatic charging.
  • Bleach activators whose particle size distribution is within the above scheme, lead to products with particularly favorable powder or storage properties and a higher dissolution rate in cold water.
  • the weight ratio of bleach activator (component A) to the cellulose or starch ethers or starch (component B) is 99: 1 to 90 10, preferably 97: 3 to 93: 7 with a ratio of water to the sum of the solids of 1.7 : 1 to 1: 1, preferably from 1.5 1 to 1.3: 1.
  • the proportions should be selected so that the aqueous batch can still be pumped and sprayed when heated. This means that batches with higher proportions of component (B) require a higher water content than those with lower proportions of (B).
  • further substances can be added to the aqueous batch which are stable with bleach activators or under the conditions of spray drying and which, when used later, impart advantageous properties to the compositions themselves or to a detergent mixed therewith .
  • These include polyglycols and nonionic surfactants, especially linear, e.g. B. of saturated and unsaturated fatty alcohols or methyl-branched, ie derived from oxo alcohols, alkyl polyglycol ethers with an average of 4 to 25 glycol ether groups or equivalent polyglycol ether derivatives of alkylphenols, alkylamines, thioalcohols, fatty acids and Fatty acid amides.
  • polyglycols and nonionic surfactants especially linear, e.g. B. of saturated and unsaturated fatty alcohols or methyl-branched, ie derived from oxo alcohols, alkyl polyglycol ethers with an average of 4 to 25 glycol ether groups or equivalent polyglycol
  • the amount of these additives can be up to 10, e.g. B. 1 to 5 wt .-%. based on the dry spray product. Such additives reduce the tendency to dust.
  • Dyes and pigments can also be added, furthermore powdery, in particular microfine silica or finely divided zeolites, phosphates such as sodium tripolyphosphate and neutral salts such as sodium sulfate.
  • the proportion of these substances should preferably be small, ie below 10% by weight, based on the dry product, in order not to question one of the essential advantages of the process, namely the provision of a product with a high active substance content. In those cases in which the process products are to be added directly to a detergent, the proportion of such substances that are valuable in terms of washing technology can also be significantly higher and up to 50% by weight of the dry spray product.
  • foam inhibitors are customary known defoamers, preferably organopolysiloxanes, and mixtures thereof with microfine silica. Examples of these are polydimethylsiloxane with a content of approx. 1-10% by weight of microfine silica.
  • the proportion of such polysiloxane defoamers can be 0.5 to 5% by weight, preferably 1 to 4% by weight, based on the finished spray product.
  • the defoamer is advantageously mixed into the aqueous batch after the component (B) has been dissolved or swelled in order to avoid creaming of the silicone liquid.
  • organopolysiloxanes it is advisable not to add surfactants to the aqueous batch in order to avoid a loss of activity with regard to the foam-suppressing properties.
  • Spray drying is carried out in conventional drying chambers which are fed with hot air or hot combustion gases.
  • they consist of cylindrical towers into which the hot gases flow in cocurrent, but preferably in countercurrent, i.e. H. preferably in the lower part of the tower, introduced tangentially at a temperature of preferably 120 ° C to 150 ° C and discharged at the tower head with an outlet temperature of preferably 50 to 85 ° C and directed to the decontamination systems.
  • the aqueous batches to be dried are fed to the top of the drying tower via high-pressure lines and sprayed through spray nozzles, of which several are usually arranged in a circle. Rotating spray plates can also be used instead of the high pressure spray nozzles.
  • the dried spray material can be discharged at the bottom of the tower, for example via screw conveyors or rotary locks.
  • the drying is conducted in such a way that the material to be sprayed has a water content of not more than 3% by weight, preferably 0.5 to 2% by weight, after leaving the tower.
  • the water or crystal water possibly bound in co-sprayed compounds is not included.
  • the bleach activators which are normally sensitive to heat, remain largely stable under the spray conditions selected.
  • the particular advantages can be seen in the fact that the formation of dust and oversize particles is comparatively low and the spray-on products have a largely uniform particle size range of 0.2 to 2 mm, usually 70 to 90% by weight within a desired particle size of 0 , 4 to 1.6 mm. Products with this grain spectrum are particularly suitable for use in spray-dried detergents, which generally have a similar grain spectrum, which is why the mixtures do not tend to separate during transport.
  • the bleach activators are distinguished by a high storage stability.
  • the activator powder used had the following grain spectrum, determined by sieve analysis using an air jet sieve (Alpine) (in% by weight):
  • the batch was sprayed with an hourly throughput of 2 t in the drying tower.
  • the inlet temperature of the air conducted in countercurrent was 160 ° C.
  • the outlet temperature 80 ° C. was 160 ° C.
  • the residual water content of the spray product was 0.5% by weight.
  • the fraction of the sieve fraction from 0.4 to 1.6 mm was 75% by weight.
  • the product largely corresponded to that of Example 1.
  • Example 2 was repeated, with 2 wt .-% of TAED by a foam-suppressing acting polydimethylsiloxane (SiO z content about 4%) has been replaced.
  • the fraction of the sieve fraction between 0.4 and 1.6 mm rose to 76% by weight at the expense of the dust fraction.
  • the product was equivalent to that of Example 1.
  • Example 4 was repeated, but the TAED was replaced by TAGU.
  • the proportion of the sieve fraction between 0.4 and 1.6 mm was 78.5%.
  • the properties of the spray product corresponded to that of Example 4.

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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
EP82106147A 1981-07-17 1982-07-09 Verfahren zur Herstellung umhüllter körniger Bleichaktivatoren Expired EP0070474B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82106147T ATE11566T1 (de) 1981-07-17 1982-07-09 Verfahren zur herstellung umhuellter koerniger bleichaktivatoren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19813128336 DE3128336A1 (de) 1981-07-17 1981-07-17 "verfahren zur herstellung umhuellter koerniger bleichaktivatoren"
DE3128336 1981-07-17

Publications (2)

Publication Number Publication Date
EP0070474A1 EP0070474A1 (de) 1983-01-26
EP0070474B1 true EP0070474B1 (de) 1985-01-30

Family

ID=6137170

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82106147A Expired EP0070474B1 (de) 1981-07-17 1982-07-09 Verfahren zur Herstellung umhüllter körniger Bleichaktivatoren

Country Status (7)

Country Link
US (1) US4457858A (enrdf_load_stackoverflow)
EP (1) EP0070474B1 (enrdf_load_stackoverflow)
JP (1) JPS5819400A (enrdf_load_stackoverflow)
AT (1) ATE11566T1 (enrdf_load_stackoverflow)
BR (1) BR8204148A (enrdf_load_stackoverflow)
DE (2) DE3128336A1 (enrdf_load_stackoverflow)
ZA (1) ZA825103B (enrdf_load_stackoverflow)

Families Citing this family (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8304990D0 (en) * 1983-02-23 1983-03-30 Procter & Gamble Detergent ingredients
GB8310080D0 (en) * 1983-04-14 1983-05-18 Interox Chemicals Ltd Bleach composition
US4671972A (en) * 1984-03-16 1987-06-09 Warner-Lambert Company Controlled release encapsulated hypochlorite deactivator for use in denture cleansers
US4552679A (en) * 1984-03-16 1985-11-12 Warner-Lambert Company Method for deodorizing hypochlorite denture cleansing solutions and product containing a delayed release hypochlorite deactivator
DE3422055A1 (de) * 1984-06-14 1985-12-19 Henkel KGaA, 4000 Düsseldorf Waschzusatz
GB8422158D0 (en) * 1984-09-01 1984-10-03 Procter & Gamble Ltd Bleach compositions
GB8607387D0 (en) * 1986-03-25 1986-04-30 Unilever Plc Activator compositions
US5002691A (en) * 1986-11-06 1991-03-26 The Clorox Company Oxidant detergent containing stable bleach activator granules
US5112514A (en) * 1986-11-06 1992-05-12 The Clorox Company Oxidant detergent containing stable bleach activator granules
US4830773A (en) * 1987-07-10 1989-05-16 Ecolab Inc. Encapsulated bleaches
AU605573B2 (en) * 1987-08-12 1991-01-17 Ecolab Inc. Solid cast warewashing composition
US4961755A (en) * 1987-12-29 1990-10-09 Ciba-Geigy Corporation Coated active substances: dye coated with polyethylene oxide-propylene oxide or with ethoxylated stearyldi phenyloxyethyl diethylenetriamine
GB8806016D0 (en) * 1988-03-14 1988-04-13 Danochemo As Encapsulated photoactivator dyes for detergent use
DE3826092A1 (de) * 1988-08-01 1990-02-08 Henkel Kgaa Granulares, bleichaktivatoren enthaltendes bleichhilfsmittel mit verbesserten eigenschaften
US4906399A (en) * 1988-08-19 1990-03-06 Dow Corning Corporation Organosilicon oxygen bleach activator compositions
US5269962A (en) * 1988-10-14 1993-12-14 The Clorox Company Oxidant composition containing stable bleach activator granules
DE3843195A1 (de) * 1988-12-22 1990-06-28 Hoechst Ag Verfahren zur herstellung eines lagerstabilen, leicht loeslichen bleichaktivator-granulats
DE4040654A1 (de) * 1990-12-19 1992-06-25 Henkel Kgaa Granulat mit umhuelltem bleichaktivator
EP0652848A4 (en) * 1992-08-01 1995-07-26 Procter & Gamble COMPOSITIONS OF PEROXYACID-BASED BLEACHING PRECURSORS.
EP0652930A4 (en) * 1992-08-01 1995-08-02 Procter & Gamble LOW - LEVEL GELIFICATION DETERSIVE COMPOSITIONS AND METHOD OF PREPARATION.
WO1994003395A1 (en) * 1992-08-01 1994-02-17 The Procter & Gamble Company Peroxyacid bleach precursor compositions
US5480575A (en) * 1992-12-03 1996-01-02 Lever Brothers, Division Of Conopco, Inc. Adjuncts dissolved in molecular solid solutions
JPH08504867A (ja) * 1992-12-22 1996-05-28 ザ、プロクター、エンド、ギャンブル、カンパニー コートされたペルオキシ酸漂白剤前駆物質組成物
DE4316481A1 (de) * 1993-05-17 1994-11-24 Henkel Kgaa Bleich- und Desinfektionsmittel
DE4439039A1 (de) 1994-11-02 1996-05-09 Hoechst Ag Granulierte Bleichaktivatoren und ihre Herstellung
DE19641708A1 (de) * 1996-10-10 1998-04-16 Clariant Gmbh Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats
US6045588A (en) 1997-04-29 2000-04-04 Whirlpool Corporation Non-aqueous washing apparatus and method
US7534304B2 (en) 1997-04-29 2009-05-19 Whirlpool Corporation Non-aqueous washing machine and methods
DE19740671A1 (de) * 1997-09-16 1999-03-18 Clariant Gmbh Bleichaktivator-Granulate
DE19740668A1 (de) 1997-09-16 1999-03-18 Clariant Gmbh Lagerstabiles Bleichaktivator-Granulat
DE19801186A1 (de) * 1998-01-15 1999-07-22 Henkel Kgaa Verfahren zur Herstellung gefärbter Wasch- und Reinigungsmittel
DE19841184A1 (de) 1998-09-09 2000-03-16 Clariant Gmbh Bleichaktivatorgranulate
AU4358500A (en) * 1999-04-19 2000-11-02 Procter & Gamble Company, The Process for coating a particle with a polymeric coating having unique dissolution characteristics
US6527690B2 (en) 2000-06-02 2003-03-04 Bhaskar Krishna Arumugam Purification of phenyl ester salts
US7513132B2 (en) 2003-10-31 2009-04-07 Whirlpool Corporation Non-aqueous washing machine with modular construction
US7739891B2 (en) 2003-10-31 2010-06-22 Whirlpool Corporation Fabric laundering apparatus adapted for using a select rinse fluid
US7513004B2 (en) 2003-10-31 2009-04-07 Whirlpool Corporation Method for fluid recovery in a semi-aqueous wash process
US7300468B2 (en) 2003-10-31 2007-11-27 Whirlpool Patents Company Multifunctioning method utilizing a two phase non-aqueous extraction process
US7695524B2 (en) 2003-10-31 2010-04-13 Whirlpool Corporation Non-aqueous washing machine and methods
EP1548097B1 (en) * 2003-12-25 2007-05-16 Kao Corporation Process for producing a bleaching activator composition
US20050224099A1 (en) * 2004-04-13 2005-10-13 Luckman Joel A Method and apparatus for cleaning objects in an automatic cleaning appliance using an oxidizing agent
DE102004018790B4 (de) 2004-04-15 2010-05-06 Henkel Ag & Co. Kgaa Wasserlöslich umhüllte Bleichmittelteilchen
EP1740757A1 (en) 2004-04-29 2007-01-10 Unilever N.V. Dry cleaning method
US7966684B2 (en) 2005-05-23 2011-06-28 Whirlpool Corporation Methods and apparatus to accelerate the drying of aqueous working fluids
US20060260064A1 (en) * 2005-05-23 2006-11-23 Luckman Joel A Methods and apparatus for laundering with aqueous and non-aqueous working fluid
GB0710559D0 (en) * 2007-06-02 2007-07-11 Reckitt Benckiser Nv Composition

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB855735A (en) * 1958-05-09 1960-12-07 Unilever Ltd Bleaching processes and compositions
CA800223A (en) * 1959-06-19 1968-12-03 General Electric Company Edge winding of electro-magnetic cores
US3715184A (en) * 1967-12-30 1973-02-06 Henkel & Cie Gmbh Method of activating per-compounds and solid activated per-compound compositions
DE2038106A1 (de) * 1970-07-31 1972-02-10 Henkel & Cie Gmbh Aktivatoren fuer Perverbindungen
DE2048331A1 (de) * 1970-10-01 1972-04-06 Henkel & Cie GmbH, 4000 Dusseldorf Feste, pulverförmige bis kornige Mittel zur Herstellung von kaltwirksamen Bleich flotten, insbesondere von kaltwirksamen blei chenden Waschlaugen, und Verfahren zur Her stellung dieser Mittel
US4009113A (en) * 1971-04-30 1977-02-22 Lever Brothers Company Protection of materials
BE786985A (fr) * 1971-08-02 1973-01-31 Henkel & Cie Gmbh Produits auxiliaires de blanchiment
DE2263939C2 (de) * 1972-07-03 1983-01-13 Henkel KGaA, 4000 Düsseldorf Zur Verwendung in perhydrathaltigen Textilwaschmitteln geeignete Bleichaktivator-Tablette
GB1515674A (en) * 1972-07-31 1978-06-28 Henkel & Cie Gmbh Bleaching assistant suitable for use in washing and bleaching agents and a process for its preparation
AT326611B (de) * 1972-07-31 1975-12-29 Henkel & Cie Gmbh Als bestandteil von pulverförmigen wasch- und bleichmitteln geeignetes bleichhilfsmittel
AT339246B (de) * 1974-08-14 1977-10-10 Henkel & Cie Gmbh Als bestandteil von pulverformigen wasch- und bleichmitteln geeignetes bleichhilfsmittel
JPS5229761B2 (enrdf_load_stackoverflow) * 1972-08-17 1977-08-04
JPS526867B2 (enrdf_load_stackoverflow) * 1972-09-14 1977-02-25
US3982892A (en) * 1974-07-12 1976-09-28 Colgate-Palmolive Company Activated peroxy bleach composition
US4259200A (en) * 1979-04-06 1981-03-31 Lever Brothers Company Bleaching and cleaning compositions
DE3011998C2 (de) * 1980-03-28 1982-06-16 Henkel KGaA, 4000 Düsseldorf Verfahren zur Herstellung eines lagerstabilen, leichtlöslichen Granulates mit einem Gehalt an Bleichaktivatoren

Also Published As

Publication number Publication date
JPS5819400A (ja) 1983-02-04
DE3262138D1 (en) 1985-03-14
DE3128336A1 (de) 1983-01-27
US4457858A (en) 1984-07-03
BR8204148A (pt) 1983-07-12
JPH0227400B2 (enrdf_load_stackoverflow) 1990-06-15
ZA825103B (en) 1983-04-27
ATE11566T1 (de) 1985-02-15
EP0070474A1 (de) 1983-01-26

Similar Documents

Publication Publication Date Title
EP0070474B1 (de) Verfahren zur Herstellung umhüllter körniger Bleichaktivatoren
EP0037026B1 (de) Verfahren zur Herstellung eines lagerstabilen, leichtlöslichen Granulates mit einem Gehalt an Bleichaktivatoren
EP0191396B2 (de) Verfahren zur Herstellung eines rieselfähigen Granulats
DE69404543T2 (de) Stabilisiertes Natriumpercarbonatteilchen
DE69019574T2 (de) Detergens-Zusammensetzungen und Verfahren zu ihrer Herstellung.
DE4116701C2 (de) Bleichende Reinigungsmittel-Zusammensetzung
EP0663946B1 (de) Wertstoffe und wertstoffgemische für netz-, wasch- und/oder reinigungsmittel in neuer zubereitungsform
EP0632826B1 (de) Verfahren zur herstellung rieselfähiger wasch- und reinigungsmittelgranulate und/oder -teilgranulate
DE69207727T2 (de) Verfahren zur Herstellung von Salzgranulaten
DE69425534T2 (de) Mischverfahren zur Formulierung von Detergentien
DE3436194C2 (enrdf_load_stackoverflow)
DE2753573A1 (de) Tablettenfoermiges wasch- und reinigungsmittel
DE3036325A1 (de) Verfahren zur verhinderung der gelierung von bicarbonat-carbonat-silikat seifenmischeraufschlaemmungen
EP0515417B1 (de) Verfahren zur herstellung eines schüttfähigen, phosphatfreien entschäumerpräparates
DE19524464A1 (de) Verfahren zur Herstellung von Zuckertensidgranulaten
DE3843195A1 (de) Verfahren zur herstellung eines lagerstabilen, leicht loeslichen bleichaktivator-granulats
US3852212A (en) Method of producing hydrated sodium tripolyphosphate composition
EP0708817B1 (de) Schüttfähiges, phosphatfreies schaumregulierungsmittel
DE2431529A1 (de) Verfahren zur herstellung spruehgetrockneter, nichtionische tenside enthaltender waschmittel
DE2406965C3 (de) Verfahren zur Herstellung von Pulvern quaternärer Ammoniumsalze
DE2365269A1 (de) Lagerbestaendiger, leichtloeslicher waschmittelzusatz und verfahren zu dessen herstellung
DE1617246C3 (de) Verfahren zur Herstellung von rieselfähigen Waschpulvermischungen
WO2003048289A1 (de) Verfahren zur herstellung von bleichaktivatorgranulaten
EP0822974B1 (de) Lagerstabiles, bleichaktivatoren enthaltendes granulat und seine herstellung
DE10002709A1 (de) Verfahren zur Herstellung von wasser- und staubarmen Alkyl- und/oder Alkenylphosphat-Granulaten

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

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

17P Request for examination filed

Effective date: 19830416

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH DE FR IT LI NL

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): AT BE CH DE FR IT LI NL

REF Corresponds to:

Ref document number: 11566

Country of ref document: AT

Date of ref document: 19850215

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3262138

Country of ref document: DE

Date of ref document: 19850314

ET Fr: translation filed
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

26N No opposition filed
ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19920601

Year of fee payment: 11

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

Ref country code: DE

Payment date: 19930617

Year of fee payment: 12

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

Ref country code: AT

Payment date: 19930629

Year of fee payment: 12

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

Ref country code: FR

Payment date: 19930709

Year of fee payment: 12

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

Ref country code: LI

Effective date: 19930731

Ref country code: CH

Effective date: 19930731

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

Ref country code: NL

Payment date: 19930731

Year of fee payment: 12

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

Ref country code: BE

Payment date: 19930824

Year of fee payment: 12

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: AT

Effective date: 19940709

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

Ref country code: BE

Effective date: 19940731

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19940731

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

Ref country code: NL

Effective date: 19950201

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19950331

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

Ref country code: DE

Effective date: 19950401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST