EP1051473B1 - Lagerstabiles bleichaktivator-granulat - Google Patents

Lagerstabiles bleichaktivator-granulat Download PDF

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Publication number
EP1051473B1
EP1051473B1 EP98948913A EP98948913A EP1051473B1 EP 1051473 B1 EP1051473 B1 EP 1051473B1 EP 98948913 A EP98948913 A EP 98948913A EP 98948913 A EP98948913 A EP 98948913A EP 1051473 B1 EP1051473 B1 EP 1051473B1
Authority
EP
European Patent Office
Prior art keywords
granules
bleach activator
storage
acid
stable
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
Application number
EP98948913A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1051473A2 (de
Inventor
Johannes Himmrich
Frank-Peter Lang
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.)
clariant Produkte Deutschland GmbH
Original Assignee
Clariant GmbH
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 Clariant GmbH filed Critical Clariant GmbH
Publication of EP1051473A2 publication Critical patent/EP1051473A2/de
Application granted granted Critical
Publication of EP1051473B1 publication Critical patent/EP1051473B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/02—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
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
    • 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
    • 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 important components in compact detergents, patch salts and machine dishwashing detergents. Already at 40 to 60 ° C they enable one of the Cook linen comparable bleaching result by using Hydrogen peroxide donor (usually perborates or percarbonates) with release react with an organic peroxyacid.
  • Hydrogen peroxide donor usually perborates or percarbonates
  • the achievable bleaching result is determined by the nature and reactivity of formed peroxycarboxylic acid, the structure of the bond to be perhydrolysed and the water solubility of the bleach activator. Since it is usually a reactive ester or an amide, it is necessary in many cases to use it for the intended use in granulated or coated form to to prevent hydrolysis in the presence of alkaline detergent ingredients and to guarantee a sufficient storage stability.
  • EP-A-0 037 026 discloses a method for Production of an easily soluble active granulate with active contents between 90 and 98 wt .-% described.
  • the powdery bleach activator with also powdered cellulose or starch homogeneously mixed and then sprayed with water or an aqueous solution of the cellulose ether, simultaneously granulated and then dried.
  • granules can be prepared by spray-drying aqueous slurries containing the activator and the cellulose ether.
  • Granules consisting of bleach activator, cellulose ethers and additions of an organic C 3 -C 4 -carboxylic or hydroxycarboxylic acid are described in WO 90/01535 and WO 92/13798. While according to WO 90/01535 the organic carboxylic acid is incorporated in the granules to accelerate its solubility, in WO 92/13798 the carboxylic acid is applied to the finished granules in an additional coating stage.
  • the acidic protective coat is intended to prevent spotting of the bleach and contribute to the color of the fabric.
  • WO 94/03395 the use of acidic polymer compounds having a water solubility> 5 g / l (at 20 ° C) and molecular weights of 1000 to 250,000 is claimed for the same purpose.
  • granules of bleach activators blends of Soaps and free fatty acids serve as granulating aids (GB-A-1 507 312).
  • An anhydrous manufacturing method is known from EP-A-0 075 818. This is the Bleach activator together with an organic binder, e.g. one Fatty alcohol ethoxylate, by compaction under pressure to particles with Diameters of 0.5 to 3 mm pressed.
  • an organic binder e.g. one Fatty alcohol ethoxylate
  • the zu granulating bleach activator is a solid and has a high melting point having. This is necessary so that he does not use the binder or in the manufacture Abreacted and decomposed existing water.
  • preferred such activators having a melting point of preferably at least 100 ° C, in particular at least 150 ° C.
  • Inorganic materials as carriers for bleach activators are known per se. So In DE-OS 2,733,849 the adsorption of liquid activators, such as Diacetylmethylamine, diacetylbutylamine or acetalcaprolactam, to inorganic Adsorbents, such as diatomaceous earth, magnesium aluminum silicates, sodium or Calcium aluminum silicates, activated silica or alumina, proposed. However, granules are not described there.
  • particles can be prepared in which a solid bleach activator in finely divided form on inorganic support material is deposited.
  • the activator and support material are first intimately mixed and an organic solvent (ethanol or toluene) added, wherein the activator goes into solution.
  • an organic solvent ethanol or toluene
  • the preferred Grain size distribution of the particles according to the invention is between 60 and 250 ⁇ m.
  • bleach activator granules which Mixing an activator with inorganic and organic salts, film-forming polymers and small amounts of smectites or aluminum silicates and subsequent granulation in the presence of water.
  • To Granulation is a costly drying step necessary to To obtain storage-stable granules.
  • DE-OS 44 39 039 is an anhydrous and solvent-free Granulating process described, wherein as a binder bentonites, in particular alkaline activated bentonites are used.
  • the invention relates to a storage-stable bleach activator granules, which in the essentially from a bleach activator and an acid-modified phyllosilicate and which is obtainable by mixing the dry bleach activator with the dry, acid-modified phyllosilicate, pressing this mixture to larger agglomerates and crushing these agglomerates to the desired Grain size.
  • mineral-acid-treated phyllosilicates preferably bentonites, in particular smectitic clays from the group of alkali or alkaline earth montmorillonites, saponites or hectorites.
  • bentonites in particular smectitic clays from the group of alkali or alkaline earth montmorillonites, saponites or hectorites.
  • Particularly preferred are the products of this type which are commercially available under the names ®Tonsil EX 519, Tonsil Optimum 210 FF, Tonsil Standard 310 FF and 314 FF and ®Opazil SO from Süd-Chemie, Kunststoff (DE).
  • the aforementioned binding materials are used as individual substances or as mixtures.
  • the alkali and / or alkaline-earth ions are removed between the layered laminates of the sheet silicates and replaced by hydrogen ions.
  • partial removal of the Al and Mg ions from the octahedral layer takes place.
  • What remains is voluminous silica, which is connected via SiO 4 tetrahedra or with the unimpacted bentonite. This leads to a loosening of the crystal structure and to a certain disorientation of the layer packages.
  • the particles of the acid-modified sheet silicates are finer and the specific surface area is greatly increased. These products are, so to speak, an intramolecular combination of amorphous silicic acid and phyllosilicate.
  • bleach activators those having melting points above 60 ° C are used.
  • these are tetraacetylethylenediamine (TAED), tetraacetylglucoluril (TAGU), diacetyldioxohexahydrotriazine (DADHT), Acyloxibenzenesulfonates, such as nonanoyloxibenzenesulfonate sodium (NOBS) or Benzoyloxibenzenesulfonate (BOBS) and acylated sugars, such as pentaacetylglucose (PAG) or compounds as described in EP-A-0 325 100, EP-A-0 492 000 and WO 91/10719 are described.
  • TAED tetraacetylethylenediamine
  • TAGU tetraacetylglucoluril
  • DADHT diacetyldioxohexahydrotriazine
  • NABS nonanoyloxi
  • bleach activators are known in the art activated carboxylic esters, carboxylic anhydrides, lactones, acylals, Carboxylic acid amides, acyl lactams, acylated ureas and oxamides, next to it but in particular also nitriles, which in addition to the nitrile group also a quaternized May contain ammonium group. Mixtures of different bleach activators can also be used.
  • the granules according to the invention may contain further additives such as anionic and nonionic surfactants containing the Consistency and hardness of the granules of the invention, as well as the homogeneous Favorably influence the distribution of bleach activators.
  • Preferred anionic surfactants are alkali metal salts.
  • anionic surfactants are fatty acids, such as oleic acid, ricinoleic acid, palmitic acid, stearic acid and salts thereof, coconut oil salt or hydrogenated coconut oil acid salts, carboxylic acids of polyglycoethers of the general formula A - (OCH 2 - CH 2 ) n - OCH 2 - CO 2 H wherein AC 12 -C 18 alkyl and n is an integer between 5 and 15, are also suitable as anionic additives for the granules of the invention in question.
  • fatty acids such as oleic acid, ricinoleic acid, palmitic acid, stearic acid and salts thereof, coconut oil salt or hydrogenated coconut oil acid salts
  • nonionic surfactants are polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerinated fatty acid esters, polyethoxylated esters of fatty acids and of Sorbitol, polyethoxylated or polyglycerinated fatty amines are preferred.
  • additives include substances that are in the suds with those from the activator liberated peroxycarboxylic acid to form reactive intermediates, such as Dioxiranes or oxaziridines, and thus reactivity can increase.
  • Corresponding compounds are ketones and sulfonimines according to US-A-3 822 114 and EP-A-0 446 982. Additions are possible. which affect the bleaching ability, such as complexing agents, polycarboxylates and Iron- or manganese-containing metal complexes, as in EP-A-0 458 397 and EP-A-0 458 398.
  • the ratio of bleach activator to binder is usually 50:50 to 98: 2, preferably 70:30 to 96: 4, based on the total weight of the granules.
  • the quantities of the additives depend in particular on their type generally sufficient amounts of 0 to 20 wt .-%, in particular amounts of 1 to 10 wt .-%, based on the total weight of the granules.
  • metal complexes on the other hand, concentrations in the ppm range are added.
  • step a For the preparation of the granules is first in a mixing unit (e.g. Pflugscharmischer) the mixture of bleach activator and binder intimately mixed (step a). In a second step, the mixture becomes larger Particles pressed (step b). Suitable for this are u.a. Roller compactors. The Pressings are then subjected to comminution (grinding) and on crushed the desired grain size (step c). Suitable for this purpose Sprocket rollers and / or Passiersiebe.
  • a mixing unit e.g. Pflugscharmischer
  • Fines and coarse material are sieved and returned to the process. While the coarse fraction is fed directly to a further comminution, the fine fraction is added to the compacting stage.
  • the grain size of the product is generally in the range of 100 to 2000 microns, preferably 300 to 1800 microns.
  • the bulk density of the granules according to the invention is above 500 kg / m 3 , preferably above 600 kg / m 3 .
  • the granules obtained in this way are directly for use in washing and Detergents suitable. This includes bleach and disinfectants. In a particularly preferred form of use, however, they can with a Coating shell be provided.
  • the granules according to the invention in an additional step d) with wrapped in a film-forming substance, whereby the product properties considerably can be affected.
  • Suitable coating agents are all film-forming substances, such as waxes, Silicones, fatty acids, soaps, anionic surfactants, nonionic surfactants, cationic Surfactants as well as anionic and cationic polymers, e.g. Polyacrylic acid.
  • the dissolution behavior be delayed to interactions between the bleach activator and the Prevent enzyme system at the beginning of the washing process.
  • the dissolution behavior can be delayed to interactions between the bleach activator and the Prevent enzyme system at the beginning of the washing process.
  • waxes with melting points of 40 to 50 ° C are suitable.
  • Acid coating agents increase the storage stability of the granules in percarbonate-containing, highly alkaline formulations and suppress Color damage due to spotting. Additions of a dye are also possible.
  • the application of the coating materials is usually carried out by spraying the melted or dissolved in a solvent coating materials.
  • the coating material in amounts of 0 to 20, preferably from 1 to 10 wt .-%, based on the total weight, on the inventive Granulated core are applied.
  • the products according to the invention are distinguished by good lab stability powdered washing, cleaning and disinfectant formulations.
  • the granules of the invention are usually in Used in combination with a hydrogen peroxide source.
  • a hydrogen peroxide source examples for this are Perborate monohydrate, perborate tetrahydrate, percarbonates as well Hydrogen peroxide adducts on urea or amine oxides.
  • formulation according to the prior art further Have detergent ingredients, such as organic and inorganic builders and Co-builder, surfactants; Enzymes, brighteners and perfume.
  • detergent ingredients such as organic and inorganic builders and Co-builder, surfactants; Enzymes, brighteners and perfume.
  • This homogeneous mixture is then applied to a Roller compactor Pharmapaktor (Bepex (DE)) with a pressing force of 50 to 60 kN pressed into slugs, then in a two-stage grinding, pre-grinding with toothed disc rollers (company Alexanderwerk (DE)) and crushing in one Passiersieb (Frewitt (DE)) crushed at a mesh size of 2000 microns become.
  • the granules 1 according to the invention have compared to the comparative example Granules 2 at a temperature of 20 ° C a delayed peracetic acid formation on a better stabilization of the activator TAED in granules 1 is due.
  • the example shows that the granules 1 according to the invention have the same active content (92%) has a significantly better storage stability compared to granules 2 (Comparative example).
  • the bleaching activity of active granules is determined by washing tests in a Linitest apparatus (Hereaus, Hanau (DE)). in a beaker with 200 ml of water (15 ° dH), add 1.0 g of standard detergent (WMP) without bleach system (WfK (DE)), 150 mg of sodium perborate monohydrate and 50 mg of activator, add the test stain and then in the Linitest instrument 10 min while heating from 20 ° C to 40 ° C and 20 min at 40 ° C washed. Tissue on cotton (WfK (DE)) is used as the test soil for testing the bleaching activity. The whiteness of the fabrics is determined by means of an Elrepho colorimeter 2000 (Datacolor (DE)). The activators used are granules 1 and granules 2 according to example 2. test soil Remission difference (%) Granules 1 Granules 2 Tea on cotton 26.8 27.2
  • the example shows that the granules 1 of the invention with improved Storage stability has a bleaching activity comparable to the prior art.

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  • 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)
  • Cosmetics (AREA)
EP98948913A 1997-09-16 1998-09-05 Lagerstabiles bleichaktivator-granulat Expired - Lifetime EP1051473B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19740668 1997-09-16
DE19740668A DE19740668A1 (de) 1997-09-16 1997-09-16 Lagerstabiles Bleichaktivator-Granulat
PCT/EP1998/005627 WO1999014306A2 (de) 1997-09-16 1998-09-05 Lagerstabiles bleichaktivator-granulat

Publications (2)

Publication Number Publication Date
EP1051473A2 EP1051473A2 (de) 2000-11-15
EP1051473B1 true EP1051473B1 (de) 2005-06-01

Family

ID=7842497

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98948913A Expired - Lifetime EP1051473B1 (de) 1997-09-16 1998-09-05 Lagerstabiles bleichaktivator-granulat

Country Status (11)

Country Link
US (1) US6270690B1 (enExample)
EP (1) EP1051473B1 (enExample)
JP (1) JP4183110B2 (enExample)
AR (1) AR015721A1 (enExample)
AT (1) ATE296873T1 (enExample)
CZ (1) CZ2000960A3 (enExample)
DE (2) DE19740668A1 (enExample)
ES (1) ES2243008T3 (enExample)
PL (1) PL193631B1 (enExample)
TW (1) TW401458B (enExample)
WO (1) WO1999014306A2 (enExample)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10038832A1 (de) * 2000-08-04 2002-03-28 Henkel Kgaa Umhüllte Bleichaktivatoren
DE10054693A1 (de) * 2000-11-03 2002-05-08 Clariant Gmbh Reinigungsmittel für Zahnprothesen
DE10142124A1 (de) 2001-08-30 2003-03-27 Henkel Kgaa Umhüllte Wirkstoffzubereitung für den Einsatz in teilchenförmigen Wasch- und Reinigungsmitteln
DE10159388A1 (de) * 2001-12-04 2003-06-12 Henkel Kgaa Verfahren zur Herstellung von umhüllten Bleichaktivatorgranulaten
DE10161766A1 (de) * 2001-12-15 2003-06-26 Clariant Gmbh Bleichaktivator-Co-Granulate
DE10304131A1 (de) 2003-02-03 2004-08-05 Clariant Gmbh Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren
EP1725271B1 (en) 2004-03-05 2011-05-11 Gen-Probe Incorporated Method for deactivating nucleic acids
US8969283B2 (en) * 2009-02-05 2015-03-03 American Sterilizer Company Low odor, hard surface sporicides and chemical decontaminants

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
GB1507312A (en) 1974-12-04 1978-04-12 Unilever Ltd Encapsulation of particles
DE2733849A1 (de) 1977-07-27 1979-02-15 Basf Ag Feste kaltbleichaktivatoren fuer aktivsauerstoff abgebende verbindungen enthaltende wasch- und reinigungsmittel
DE3011998C2 (de) 1980-03-28 1982-06-16 Henkel KGaA, 4000 Düsseldorf Verfahren zur Herstellung eines lagerstabilen, leichtlöslichen Granulates mit einem Gehalt an Bleichaktivatoren
IE51848B1 (en) * 1980-11-06 1987-04-15 Procter & Gamble Bleach activator compositions,preparation thereof and use in granular detergent compositions
DE3128336A1 (de) 1981-07-17 1983-01-27 Henkel KGaA, 4000 Düsseldorf "verfahren zur herstellung umhuellter koerniger bleichaktivatoren"
EP0075818B2 (de) 1981-09-28 1990-03-14 BASF Aktiengesellschaft Körniger Bleichaktivator
GB8607388D0 (en) * 1986-03-25 1986-04-30 Unilever Plc Activator compositions
US5318714A (en) * 1988-03-14 1994-06-07 Novo Nordisk A/S Stabilized particulate composition
DE3826092A1 (de) 1988-08-01 1990-02-08 Henkel Kgaa Granulares, bleichaktivatoren enthaltendes bleichhilfsmittel mit verbesserten eigenschaften
GB8907346D0 (en) * 1989-03-31 1989-05-17 Ecc Int Ltd Detergent granules
GB9023006D0 (en) * 1990-10-23 1990-12-05 Bp Chem Int Ltd Bleach activators
GB9102507D0 (en) 1991-02-06 1991-03-27 Procter & Gamble Peroxyacid bleach precursor compositions
WO1994003395A1 (en) 1992-08-01 1994-02-17 The Procter & Gamble Company Peroxyacid bleach precursor compositions
DE4439039A1 (de) * 1994-11-02 1996-05-09 Hoechst Ag Granulierte Bleichaktivatoren und ihre Herstellung
GB2294694A (en) * 1994-11-05 1996-05-08 Procter & Gamble Solid detergent composition
GB2294705A (en) * 1994-11-05 1996-05-08 Procter & Gamble Bleaching compositions
GB9424009D0 (en) * 1994-11-29 1995-01-18 Procter And Gamble The Company Peroxyacid bleach precursor compositions

Also Published As

Publication number Publication date
PL339435A1 (en) 2000-12-18
ES2243008T3 (es) 2005-11-16
WO1999014306A2 (de) 1999-03-25
JP4183110B2 (ja) 2008-11-19
AR015721A1 (es) 2001-05-16
EP1051473A2 (de) 2000-11-15
PL193631B1 (pl) 2007-02-28
US6270690B1 (en) 2001-08-07
TW401458B (en) 2000-08-11
JP2001518529A (ja) 2001-10-16
CZ2000960A3 (cs) 2001-08-15
DE59812838D1 (de) 2005-07-07
ATE296873T1 (de) 2005-06-15
DE19740668A1 (de) 1999-03-18
WO1999014306A3 (de) 1999-05-14

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