EP1017776A1 - Bleaching activators in the form of granules - Google Patents

Bleaching activators in the form of granules

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Publication number
EP1017776A1
EP1017776A1 EP98947521A EP98947521A EP1017776A1 EP 1017776 A1 EP1017776 A1 EP 1017776A1 EP 98947521 A EP98947521 A EP 98947521A EP 98947521 A EP98947521 A EP 98947521A EP 1017776 A1 EP1017776 A1 EP 1017776A1
Authority
EP
European Patent Office
Prior art keywords
granules
bleach activator
bleach
ammonium
granules according
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.)
Granted
Application number
EP98947521A
Other languages
German (de)
French (fr)
Other versions
EP1017776B1 (en
Inventor
Matthias LÖFFLER
Gerd Reinhardt
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
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Filing date
Publication date
Application filed by Clariant GmbH filed Critical Clariant GmbH
Publication of EP1017776A1 publication Critical patent/EP1017776A1/en
Application granted granted Critical
Publication of EP1017776B1 publication Critical patent/EP1017776B1/en
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
    • 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
    • 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
    • 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
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
    • 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
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions

Definitions

  • Bleach activators are important components in detergents, stain salts and machine dishwashing detergents. They enable a bleaching effect even at temperatures below 60 ° C by reacting with a source of hydrogen peroxide - usually perborates or percarbonates - with the release of an organic peroxyacid.
  • a large number of reactive organic compounds with an O-acyl or N-acyl group are suitable as bleach activators.
  • Representative examples such as N, N, N ', N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzene sulfonate (STHOBSylAcu) tetraacetate ), Di-N-acetyldimethylgiyoxin (ADMG) and 1-phenyl-3-acetylhydantoin (PAH) are in the patents GB-A-836 988, GB-A-907 356, EP-A-0 098 129 and EP-A -0 120 591.
  • cationic bleach activators that contain a quaternary ammonium group have become more important because they are highly effective bleach activators.
  • Such cationic bleach activators are described, for example, in GB-A-1 382 594, US-A-4 751 015, EP-A-0 284 292 and EP-A-0 331 229.
  • R ⁇ R 2 and R 3 are alkyl, alkenyl or aryl groups, form a special class of cationic bleach activators.
  • Compounds of this type and their use as bleach activators in bleaching agents are described in EP-A-303 520, EP-A-464 880, EP-A-458 396 and US-4 883 917. In all the compounds described there, the nitrogen atom of the ammonium group is substituted by alkyl, alkenyl or aryl groups.
  • Another class of ammonium nitriles is described in German patent application 19 605 526.
  • Bleach activators are usually used in granular form in detergents in order to ensure sufficient storage stability and to release the bleach-activating effect only in the wash cycle.
  • EP-A-0 037 026 describes a process for producing easily soluble activator granules with active ingredients of between 90 and 98% by weight.
  • the pulverulent bleach activator is homogeneously mixed with likewise pulverulent cellulose or starch ethers and then sprayed with water or an aqueous solution of the cellulose ether, granulated at the same time and then dried.
  • Similar granules can be produced by spray-drying aqueous slurries containing the activator and the cellulose ether.
  • Granules consisting of bleach activator, cellulose ethers and additives of an organic C 3 -C 6 carbon or hydroxy carboxylic acid are described in WO 90/01 535 and WO 92/13 798. While in WO 90/01 535 the organic carboxylic acid is incorporated into the granulate core to accelerate its solubility, in WO 92/13 798 the carboxylic acid is applied to the finished granulate in an additional coating step.
  • the acidic protective coat is intended to prevent spotting of the bleaching agent and to protect the color of the fabric.
  • WO 94/03 395 claims for the same purpose the use of acidic polymer compounds with a water solubility> 5 g / l (at 20 ° C.) and molar masses of 1000 to 250,000.
  • Also known (GB-A 1 507 312) are granules of bleach activators in which mixtures of soaps and free fatty acids are used as granulating aids.
  • An anhydrous manufacturing process is known from EP-A-0 075 818.
  • the bleach activator is pressed together with an organic binder, for example a fatty alcohol ethoxylate, by compacting under pressure to give particles with a diameter of 0.5 to 3 mm.
  • the bleach activator to be granulated is a solid and has a high melting point. This is necessary so that it does not react and decompose with the binder or existing water during production.
  • such activators are preferred which have a melting point of preferably at least 100 ° C., in particular at least 150 ° C.
  • Suitable granules for use in stain salts represent a further problem.
  • Modern formulations consist of mixtures of percarbonate and bleach activator granules.
  • inert materials such as sodium carbonate, hydrogen carbonate or sulfate are often added.
  • Inert binders or coatings would be of great interest for this area of application.
  • Inorganic materials as carriers for bleach activators are known per se.
  • liquid activators such as diacetylmethylamine, diacetylbutylamine or acetylcaprolactam
  • inorganic adsorbents such as diatomaceous earth, magnesium-aluminum, sodium or calcium aluminum silicates, activated silica or aluminum oxide
  • particles can also be produced in which a bleach activator which is solid per se is deposited in a finely divided form on an inorganic carrier material.
  • the activator and carrier material are first mixed intimately and an organic solvent (ethanol or toluene) is added, the activator going into solution. Subsequent distillation of the solvent causes the activator to be deposited on the carrier in finely divided form.
  • the preferred particle size distribution of the particles according to the invention is between 60 and 250 ⁇ m.
  • EP-A-0 240 057 discloses bleach activator granules which are prepared by mixing an activator with inorganic or organic salts, film-forming polymers and small amounts of smectites or aluminum silicates and subsequent granulation in the presence of water. After granulation has taken place, an expensive drying stage is necessary in order to obtain storage-stable granules.
  • Bleach activator granules which are obtained by mixing and pressing dry bleach activator and smectites (bentonite) in the absence of water, are known from DE-A 44 39 039. Essentially only TAED is used there as a bleach activator. However, the influence of TAED on washing performance is essentially independent of whether the TAED is in granular form or as a powder.
  • the invention thus relates to bleach activator granules consisting essentially of an ammonium nitrile and a layered silicate.
  • These granules are obtained by mixing the two components, compressing and crushing the agglomerates obtained to the desired particle size.
  • ammonium nitriles which have a melting point above 60 ° C. in granular form can be used for the granules.
  • the ammonium nitriles described in the above-mentioned literature come into question, in particular the compounds described in DE 19 605 526. Compounds of the formula are very particularly preferred
  • R 1 and R 2 C r C 4 alkyl preferably methyl and X is an anion, for example chloride or methosulfate.
  • Granules can contain one or more of these ammonium nitriles or additionally also bleach activators of another structure, for example N, N, N ', N'-tetraacetylethylene diamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), Sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxin (ADMG) and 1-phenyl-3-acetylhydantoin (PAH).
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • GPA glucose pentaacetate
  • TAX xylose tetraacetate
  • SBOBS sodium 4-benz
  • Layered silicates in particular smectites such as montmorillonites, saponites or hectorites with ion exchange capacities of preferably 50 to 100 meq / 100 g, as well as illites, attapulgites and kaolinites, serve as binders for the formation of the granules.
  • smectites such as montmorillonites, saponites or hectorites with ion exchange capacities of preferably 50 to 100 meq / 100 g, as well as illites, attapulgites and kaolinites, serve as binders for the formation of the granules.
  • Bentonites such as those sold under the names ⁇ Laundrosil DGA and Laundrosil EX 0242 from Süd-Chemie, Kunststoff (DE) are particularly preferred.
  • layered silicates can also be used in acid-modified form, as are available in the commercial products ⁇ Tonsil EX 519, Tonsil Optimum 210 FF, Tonsil Standard 310 FF and 314 FF, and ⁇ Opazil SO from Süd-Chemie, Kunststoff (DE) stand.
  • the granules according to the invention can also contain other auxiliaries, such as, for example, those which influence the pH during storage and use.
  • auxiliaries such as, for example, those which influence the pH during storage and use.
  • organic carboxylic acids or their salts such as citric acid in anhydrous or hydrated form, glycolic acid, succinic acid, maleic acid or lactic acid.
  • additives which influence the bleaching capacity are also possible, such as complexing agents, polycarboxylates and iron or manganese-containing metal complexes, as described in EP-A-0 458 397 and EP-A-0 458 398.
  • the weight ratio of ammonium nitrile to inorganic binder material is usually 50:50 to 98: 2, preferably 70:30 to 96: 4.
  • the amount of any additives depends in particular on their type. For example, acidifying additives and organic catalysts for increasing the performance of peracid are used in amounts of 0 to 20% by weight, in particular in amounts of 1 to 10% by weight, based on the total weight. added, however, metal complexes in concentrations in the ppm range.
  • the mixture of ammonium nitrile and binder is first mixed intimately in a mixing unit (eg ploughshare mixer). In a second step, the mixture becomes larger particles pressed. Roller compactors are suitable for this. The compacts are then subjected to comminution (grinding) and comminuted to the desired grain size. Toothed washer rollers and / or strainers are suitable for this purpose.
  • Fine fraction and coarse material are screened off and returned to the process. While the coarse fraction is directly re-crushed, the fine fraction is added to the grain compacting stage.
  • the grain size of the product is generally in the range from 100 to 2000 ⁇ m, preferably 300 to 1800 ⁇ m.
  • the bulk density of the granules according to the invention is therefore above 500 kg / m 3 , preferably above 600 kg / m 3 .
  • the granules obtained in this way are directly suitable for use in detergents and cleaning agents. In a special form of use, however, they can be provided with a coating envelope.
  • the granules according to the invention are coated with a film-forming substance in an additional step, as a result of which the product properties can be significantly influenced.
  • 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 acids.
  • these coating materials i.a. the dissolving behavior is delayed in order to prevent interactions between the bending activator and the enzyme system at the beginning of the washing process. If the intended granulate is to be used in machine dishwashing detergents, waxes with melting points of 40 to 50 ° C are particularly suitable.
  • Acidic coating materials increase and suppress the storage stability of the granules in highly alkaline formulations containing percarbonates Color damage due to spotting. Additions of a dye are also possible.
  • the coating materials are generally applied by spraying the melted coating materials or coating materials dissolved in a solvent.
  • the coating material can be applied in amounts of from 0 to 20, preferably from 1 to 10,% by weight, based on the total weight, on the granule core according to the invention.
  • the products according to the invention are characterized by good storage stability in powder detergent, cleaning and disinfectant formulations. They are ideal for use in heavy-duty detergents, stain salts, machine dishwashing detergents, powdered all-purpose cleaners and denture cleaners.
  • the granules according to the invention are used in combination with a hydrogen peroxide source in these formulations.
  • a hydrogen peroxide source examples include perborate monohydrate, perborate tetrahydrate, percarbonates and hydrogen peroxide adducts with urea or amine oxides.
  • the formulation can have further constituents, such as organic or inorganic builders and co-builders, surfactants, enzymes, optical brighteners and perfume.
  • Trimethylammonium acetonitrile toluenesulfonate (1) and N-cyanomethyl-N-methylpiperazinium toluenesulfonate (2) were used as activators, each as a powder and as activator granules granules 1 and granules 2 according to Example 1.
  • Dispensing chamber given 8.0 g of percarbonate as well
  • ammonium nitriles trimethylammonium acetonitrile toluenesulfonate (1) and N-cyanomethyl-N-methylpiperazinium toluenesulfonate (2) and TAED (3) were tested in non-granulated form: 2.7 g bleach activator powder 1 3.1 g bleach activator powder 2 2.3 g TAED powder bleach activator 2 kg of terry cloth were used as fiber, 10 bleachable stains (tea, red wine, curry, grass from the Krefeld laundry research) were used as test stains. The laundry was washed in the main wash at 40 ° C. The evaluation is carried out by determining the whiteness after washing by adding the reflectance differences, measured with ELREPHO 2000 (Datacolor).
  • T 40 ° C; Tea, red wine, curry, grass

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Detergent Compositions (AREA)

Abstract

The invention concerns bleaching activators in the form of granules, based on ammonium nitrile and laminated silicate, obtained by mixing two constituents, compacting and crushing to give them the required granular size.

Description

Bleichaktivator-GranulateBleach activator granules
Bleichaktivatoren sind wichtige Bestandteile in Waschmitteln, Fleckensalzen und Maschinengeschirrspüimitteln. Sie ermöglichen eine bleichende Wirkung bereits bei Temperaturen unter 60°C, indem sie mit einer Quelle für Wasserstoffperoxid - meist Perborate oder Percarbonate - unter Freisetzung einer organischen Peroxysäure reagieren.Bleach activators are important components in detergents, stain salts and machine dishwashing detergents. They enable a bleaching effect even at temperatures below 60 ° C by reacting with a source of hydrogen peroxide - usually perborates or percarbonates - with the release of an organic peroxyacid.
Als Bleichaktivatoren geeignet sind eine Vielzahl reaktiver organischer Verbindungen mit einer O-Acyl- oder N-Acylgruppe. Repräsentative Beispiele wie N,N,N',N'-Tetraacetylethylendiamin (TAED), Glucosepentaacetat (GPA), Xylosetetraacetat (TAX), Natrium-4-benzoyloxybenzolsulfoπat (SBOBS), Natriumtrimethylhexanoyloxybenzolsulfonat (STHOBS), Tetraacetylglucoluril (TAGU), Tetraacetylcyansäure (TACA), Di-N-acetyldimethylgiyoxin (ADMG) und 1-Phenyl-3-acetylhydantoin (PAH) sind in den Patentschriften GB-A-836 988, GB-A-907 356, EP-A-0 098 129 und EP-A-0 120 591 beschrieben.A large number of reactive organic compounds with an O-acyl or N-acyl group are suitable as bleach activators. Representative examples such as N, N, N ', N'-tetraacetylethylenediamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), sodium trimethylhexanoyloxybenzene sulfonate (STHOBSylAcu) tetraacetate ), Di-N-acetyldimethylgiyoxin (ADMG) and 1-phenyl-3-acetylhydantoin (PAH) are in the patents GB-A-836 988, GB-A-907 356, EP-A-0 098 129 and EP-A -0 120 591.
Mittlerweile haben kationische Bleichaktivatoren, die eine quartäre Ammoniumgruppe enthalten, an Bedeutung gewonnen, da sie hocheffektive Bleichaktivatoren sind. Solche kationischen Bleichaktivatoren sind beispielsweise in GB-A-1 382 594, US-A-4 751 015, EP-A-0 284 292 und EP-A-0 331 229 beschrieben.In the meantime, cationic bleach activators that contain a quaternary ammonium group have become more important because they are highly effective bleach activators. Such cationic bleach activators are described, for example, in GB-A-1 382 594, US-A-4 751 015, EP-A-0 284 292 and EP-A-0 331 229.
Ammoniumnitrile der FormelAmmonium nitriles of the formula
R\ R2, R3 NCH2CN Xθ R \ R 2 , R 3 NCH 2 CN X θ
wobei R\ R2 und R3 Alkyl-, Alkenyl- oder Arylgruppen bedeuten, bilden dabei eine besondere Klasse kationischer Bleichaktivatoren. Verbindungen dieser Art und deren Verwendung als Bleichaktivatoren in Bleichmitteln sind beschrieben in EP-A-303 520, EP-A-464 880, EP-A-458 396 und US-4 883 917. Bei allen dort beschriebenen Verbindungen ist das Stickstoffatom der Ammoniumgruppe durch Alkyl-, Alkenyl- oder Arylgruppen substituiert. Eine weitere Klasse von Ammoniumnitrilen ist in der Deutschen Patentanmeldung 19 605 526 beschrieben.where R \ R 2 and R 3 are alkyl, alkenyl or aryl groups, form a special class of cationic bleach activators. Compounds of this type and their use as bleach activators in bleaching agents are described in EP-A-303 520, EP-A-464 880, EP-A-458 396 and US-4 883 917. In all the compounds described there, the nitrogen atom of the ammonium group is substituted by alkyl, alkenyl or aryl groups. Another class of ammonium nitriles is described in German patent application 19 605 526.
Üblicherweise werden Bleichaktivatoren in granulierter Form in Waschmitteln eingesetzt, um eine ausreichende Lagerstabilität zu gewährleisten und um die bleichaktivierende Wirkung erst im Waschgang freizusetzen.Bleach activators are usually used in granular form in detergents in order to ensure sufficient storage stability and to release the bleach-activating effect only in the wash cycle.
Zur Granulierung von Bleichaktivatoren sind in der Vergangenheit zahlreiche Hilfsstoffe und Verfahren beschrieben worden, in EP-A-0 037 026 wird ein Verfahren zur Herstellung eines leicht löslichen Aktivatorgranulates mit Aktivgehaiten zwischen 90 bis 98 Gew.-% beschrieben. Dazu wird der pulverförmige Bleichaktivator mit ebenfalls pulverförmigen Cellulose- oder Stärkeethern homogen vermischt und anschließend mit Wasser oder einer wäßrigen Lösung des Celluloseethers besprüht, gleichzeitig granuliert und anschließend getrocknet.Numerous auxiliaries and processes have been described in the past for granulating bleach activators; EP-A-0 037 026 describes a process for producing easily soluble activator granules with active ingredients of between 90 and 98% by weight. For this purpose, the pulverulent bleach activator is homogeneously mixed with likewise pulverulent cellulose or starch ethers and then sprayed with water or an aqueous solution of the cellulose ether, granulated at the same time and then dried.
Nach EP-A-0 070 474 können ähnliche Granulate hergestellt werden, indem wäßrige Aufschlämmungen, enthaltend den Aktivator und den Celluloseether, sprühgetrocknet werden. Granulate bestehend aus Bleichaktivator, Celluloseethern und Zusätzen einer organischen C3-C6-Carbon- oder Hydroxycarbonsäure werden in WO 90/01 535 und WO 92/13 798 beschrieben. Während in WO 90/01 535 die organische Carbonsäure in den Granulatkern eingearbeitet wird, um seine Löslichkeit zu beschleunigen, wird in WO 92/13 798 die Carbonsäure in einer zusätzlichen Coatingstufe auf das fertige Granulat aufgebracht. Der saure Schutzmantel soll ein Spotting des Bleichmittels verhindern und zur Farbschonung des Gewebes beitragen. In WO 94/03 395 wird zum gleichen Zweck die Verwendung saurer Polymerverbindungen mit einer Wasserlöslichkeit > 5 g/l (bei 20°C) und Molmassen von 1000 bis 250 000 beansprucht. Ebenfalls bekannt (GB-A 1 507 312) sind Granulate von Bleichaktivatoren, in denen Gemische von Seifen und freien Fettsäuren als Granulierhilfsmittel zum Einsatz kommen. Ein wasserfreies Herstellverfahren ist aus EP-A-0 075 818 bekannt. Dazu wird der Bleichaktivator zusammen mit einem organischen Bindemittel, z.B. einem Fettalkoholethoxylat, durch Kompaktierung unter Druck zu Teilchen mit Durchmessern von 0,5 bis 3 mm verpreßt.According to EP-A-0 070 474, similar granules can be produced by spray-drying aqueous slurries containing the activator and the cellulose ether. Granules consisting of bleach activator, cellulose ethers and additives of an organic C 3 -C 6 carbon or hydroxy carboxylic acid are described in WO 90/01 535 and WO 92/13 798. While in WO 90/01 535 the organic carboxylic acid is incorporated into the granulate core to accelerate its solubility, in WO 92/13 798 the carboxylic acid is applied to the finished granulate in an additional coating step. The acidic protective coat is intended to prevent spotting of the bleaching agent and to protect the color of the fabric. WO 94/03 395 claims for the same purpose the use of acidic polymer compounds with a water solubility> 5 g / l (at 20 ° C.) and molar masses of 1000 to 250,000. Also known (GB-A 1 507 312) are granules of bleach activators in which mixtures of soaps and free fatty acids are used as granulating aids. An anhydrous manufacturing process is known from EP-A-0 075 818. For this purpose, the bleach activator is pressed together with an organic binder, for example a fatty alcohol ethoxylate, by compacting under pressure to give particles with a diameter of 0.5 to 3 mm.
Für die meisten der genannten Granulierverfahren ist Voraussetzung, daß der zu granulierende Bleichaktivator ein Feststoff ist und einen hohen Schmelzpunkt aufweist. Dies ist notwendig, damit er bei der Herstellung nicht mit dem Binder oder vorhandenem Wasser abreagiert und zersetzt wird. So werden z.B. in DE-OS 2 048 331 solche Aktivatoren bevorzugt, die einen Schmelzpunkt von vorzugsweise mindestens 100°C, insbesondere wenigstens 150°C aufweisen.For most of the granulation processes mentioned, it is a prerequisite that the bleach activator to be granulated is a solid and has a high melting point. This is necessary so that it does not react and decompose with the binder or existing water during production. For example, in DE-OS 2 048 331 such activators are preferred which have a melting point of preferably at least 100 ° C., in particular at least 150 ° C.
Als Bindemittel wurden bisher überwiegend organische Verbindungen verwendet. Hieraus können sich jedoch Probleme ergeben, die die Verwendung der Granulate einschränken.So far, mostly organic compounds have been used as binders. However, this can result in problems which restrict the use of the granules.
Werden oberflächenaktive Verbindungen eingesetzt, wie Seifen, Fettsäuren, anionische Tenside oder Fettalkoholethoxylate, so sind die damit hergestellten Granulate zum Einsatz in Maschinengeschirrspülmitteln ungeeignet, da unter Waschbedingungen Schaumprobleme auftreten, Dies ist selbst bei Verwendung normalerweise schwach schäumender hochethoxylierter Fettalkohole der Fall. Zum Einsatz in Maschinengeschirrspülmitteln werden daher überwiegend Aktivatorgranulate verwendet, deren Bindemittel aus Celluloseethern besteht. Die biologische Abbaubarkeit dieser Produktgruppe ist jedoch mäßig.If surface-active compounds are used, such as soaps, fatty acids, anionic surfactants or fatty alcohol ethoxylates, the granules produced with them are unsuitable for use in machine dishwashing detergents, since foam problems occur under washing conditions. This is the case even when using normally low-foaming, highly ethoxylated fatty alcohols. Activator granules whose binders consist of cellulose ethers are therefore predominantly used for use in machine dishwashing detergents. However, the biodegradability of this product group is moderate.
Ein weiteres Problem stellen geeignete Granulate zum Einsatz in Fleckensalzen dar. Moderne Formulierungen bestehen aus Mischungen von Percarbonat und Bleichaktivator-Granulaten. Um eine exotherme Zersetzung dieser Mischungen bei Herstellung und Lagerung zu unterbinden, werden häufig Inertmaterialien, wie Natriumcarbonat, -hydrogencarbonat oder -sulfat zugegeben. Für diesen Anwendungsbereich wären inerte Binde- oder Coatingmittel von großen Interesse. Anorganische Materialien als Träger für Bleichaktivatoren sind an sich bekannt. So wird in DE-OS 2 733 849 die Adsorption flüssiger Aktivatoren, wie Diacetylmethylamin, Diacetylbutylamin oder Acetylcaprolactam, an anorganische Adsorbentien, wie Kieselgur, Magnesium-Aluminium-, Natrium- oder Calciumaluminiumsilikate, aktivierte Kieselsäure oder Aluminiumoxid, vorgeschlagen.Suitable granules for use in stain salts represent a further problem. Modern formulations consist of mixtures of percarbonate and bleach activator granules. In order to prevent exothermic decomposition of these mixtures during production and storage, inert materials such as sodium carbonate, hydrogen carbonate or sulfate are often added. Inert binders or coatings would be of great interest for this area of application. Inorganic materials as carriers for bleach activators are known per se. In DE-OS 2 733 849, the adsorption of liquid activators, such as diacetylmethylamine, diacetylbutylamine or acetylcaprolactam, on inorganic adsorbents, such as diatomaceous earth, magnesium-aluminum, sodium or calcium aluminum silicates, activated silica or aluminum oxide, is proposed.
Weiterhin können nach GB-A-2 249 104 Partikel hergestellt werden, in denen ein an sich fester Bleichaktivator in fein verteilter Form auf einem anorganischem Trägermaterial abgelagert ist. Hierzu werden Aktivator und Trägermaterial zunächst innig gemischt und ein organisches Lösemittel (Ethanol oder Toluol) hinzugefügt, wobei der Aktivator in Lösung geht. Durch anschließende Abdestillation des Lösemittels wird der Aktivator in feinst verteilter Form auf dem Träger abgelagert. Die bevorzugte Korngrößenverteilung der erfindungsgemäßen Partikel liegt zwischen 60 und 250 μm.According to GB-A-2 249 104 particles can also be produced in which a bleach activator which is solid per se is deposited in a finely divided form on an inorganic carrier material. For this purpose, the activator and carrier material are first mixed intimately and an organic solvent (ethanol or toluene) is added, the activator going into solution. Subsequent distillation of the solvent causes the activator to be deposited on the carrier in finely divided form. The preferred particle size distribution of the particles according to the invention is between 60 and 250 μm.
Daneben sind aus EP-A-0 240 057 Bleichaktivator-Granulate bekannt, die durch Vermischen eines Aktivators mit anorganischen oder organischen Salzen, filmbildenden Polymeren und geringen Mengen von Smectiten oder Aluminiumsilikaten und anschließender Granulierung in Gegenwart von Wasser hergestellt werden. Nach erfolgter Granulierung ist eine kostenintensive Trockenstufe notwendig, um lagerstabile Granulate zu erhalten.In addition, EP-A-0 240 057 discloses bleach activator granules which are prepared by mixing an activator with inorganic or organic salts, film-forming polymers and small amounts of smectites or aluminum silicates and subsequent granulation in the presence of water. After granulation has taken place, an expensive drying stage is necessary in order to obtain storage-stable granules.
Bleichaktivatorgranulate, die durch Vermischen und Verpressen von trockenem Bleichaktivator und Smektiten (Bentonit) in Abwesenheit von Wasser erhalten werden, sind aus DE-A 44 39 039 bekannt. Als Bleichaktivator wird dort im wesentlichen nur TAED benutzt. Der Einfluß von TAED auf die Waschleistung ist jedoch im wesentlichen unabhängig davon, ob das TAED in granulierter Form vorliegt oder als Pulver.Bleach activator granules, which are obtained by mixing and pressing dry bleach activator and smectites (bentonite) in the absence of water, are known from DE-A 44 39 039. Essentially only TAED is used there as a bleach activator. However, the influence of TAED on washing performance is essentially independent of whether the TAED is in granular form or as a powder.
Überraschenderweise wurde nun gefunden, daß bei den Bleichaktivatoren vom Typ des Ammoniumnithls sehr große Unterschiede hinsichtlich ihrer Waschleistung zwischen der Pulverform und der Granulatform bestehen.Surprisingly, it has now been found that the bleach activators of the type of ammonium nitride there are very large differences in their washing performance between the powder form and the granulate form.
Gegenstand der Erfindung sind somit Bleichaktivatorgranulate bestehend im wesentlichen aus einem Ammoniumnitril und einem Schichtsilikat.The invention thus relates to bleach activator granules consisting essentially of an ammonium nitrile and a layered silicate.
Diese Granulate werden erhalten durch Mischen der beiden Komponenten, Verpressen und Zerkleinem der dabei erhaltenen Agglomerate auf die gewünschte Korngröße.These granules are obtained by mixing the two components, compressing and crushing the agglomerates obtained to the desired particle size.
Für die Granulate können alle Ammoniumnitrile verwendet werden, die in granulierter Form einen Schmelzpunkt oberhalb von 60°C aufweisen. Insbesondere kommen dabei die in der oben erwähnten Literatur beschriebenen Ammoniumnitrile in Frage, insbesondere die in DE 19 605 526 beschriebenen Verbindungen. Ganz besonders bevorzugt sind Verbindungen der FormelAll ammonium nitriles which have a melting point above 60 ° C. in granular form can be used for the granules. In particular, the ammonium nitriles described in the above-mentioned literature come into question, in particular the compounds described in DE 19 605 526. Compounds of the formula are very particularly preferred
R1 R 1
H3C - NΘ - CH2CN XΘ H 3 C - N Θ - CH 2 CN X Θ
R2 R 2
worin R1 und R2 CrC4 Alkyl, vorzugsweise Methyl und X ein Anion, beispielsweise Chlorid oder Methosulfat, bedeuten.wherein R 1 and R 2 C r C 4 alkyl, preferably methyl and X is an anion, for example chloride or methosulfate.
Granulate können ein oder mehrere dieser Ammoniumnitrile enthalten oder zusätzlich auch Bleichaktivatoren anderer Struktur, beispielsweise N,N,N',N'- Tetraacetylethylendiamin (TAED), Glucosepentaacetat (GPA), Xylosetetraacetat (TAX), Natrium-4-benzoyloxybenzolsulfonat (SBOBS), Natriumtrimethylhexanoyloxybenzolsulfonat (STHOBS), Tetraacetylglucoluril (TAGU), Tetraacetylcyansäure (TACA), Di-N-acetyldimethylglyoxin (ADMG) und 1 -Phenyl-3-acetylhydantoin (PAH). Als Bindemittel zur Bildung der Granulate dienen Schichtsilikate, insbesondere Smektite wie Montmorillonite, Saponite oder Hectorite mit lonenaustauschkapazitäten von bevorzugt 50 bis 100 meq/100 g, daneben Illite, Attapulgite und Kaolinite. Besonders bevorzugt sind Bentonite, wie sie unter der Bezeichnung ©Laundrosil DGA und Laundrosil EX 0242 der Firma Süd-Chemie, München (DE) im Handel sind. Diese Schichtsilikate können auch in sauer modifizierter Form eingesetzt werden, wie sie in den Handelsprodukten ©Tonsil EX 519, Tonsil Optimum 210 FF, Tonsil Standard 310 FF und 314 FF, sowie ©Opazil SO der Firma Süd-Chemie, München (DE) zur Verfügung stehen.Granules can contain one or more of these ammonium nitriles or additionally also bleach activators of another structure, for example N, N, N ', N'-tetraacetylethylene diamine (TAED), glucose pentaacetate (GPA), xylose tetraacetate (TAX), sodium 4-benzoyloxybenzenesulfonate (SBOBS), Sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), tetraacetylglucoluril (TAGU), tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxin (ADMG) and 1-phenyl-3-acetylhydantoin (PAH). Layered silicates, in particular smectites such as montmorillonites, saponites or hectorites with ion exchange capacities of preferably 50 to 100 meq / 100 g, as well as illites, attapulgites and kaolinites, serve as binders for the formation of the granules. Bentonites such as those sold under the names © Laundrosil DGA and Laundrosil EX 0242 from Süd-Chemie, Munich (DE) are particularly preferred. These layered silicates can also be used in acid-modified form, as are available in the commercial products © Tonsil EX 519, Tonsil Optimum 210 FF, Tonsil Standard 310 FF and 314 FF, and © Opazil SO from Süd-Chemie, Munich (DE) stand.
Darüber hinaus können die erfindungsgemäßen Granulate auch noch weitere Hilfsmittel enthalten, wie zum Beispiel solche, die den pH-Wert während der Lagerung und der Anwendung beeinflussen. Dazu zählen organische Carbonsäuren oder deren Salze, wie Zitronensäure in wasserfreier oder hydratisierter Form, Glycolsäure, Bernsteinsäure, Maleinsäure oder Milchsäure. Daneben sind auch Zusätze möglich, die das Bleichvermögen beeinflussen, wie Komplexbildner, Polycarboxylate und eisen- bzw. manganhaltige Metallkomplexe, wie in EP-A-0 458 397 und EP-A-0 458 398 beschrieben.In addition, the granules according to the invention can also contain other auxiliaries, such as, for example, those which influence the pH during storage and use. These include organic carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, succinic acid, maleic acid or lactic acid. In addition, additives which influence the bleaching capacity are also possible, such as complexing agents, polycarboxylates and iron or manganese-containing metal complexes, as described in EP-A-0 458 397 and EP-A-0 458 398.
Das Gewichtsverhältnis von Ammoniumnitril zu anorganischem Bindematerial beträgt üblicherweise 50:50 bis 98:2, vorzugsweise 70:30 bis 96:4. Die Menge eventueller Zusatzstoffe richtet sich insbesondere nach deren Art. So werden acidifizierende Zusätze und organische Katalysatoren zur Leistungssteigerung der Persäure in Mengen von 0 bis 20 Gew.-%, insbesondere in Mengen von 1 bis 10 Gew.-%, bezogen auf das Gesamtgewicht, zugesetzt, Metalikomplexe hingegen in Konzentrationen im ppm Bereich.The weight ratio of ammonium nitrile to inorganic binder material is usually 50:50 to 98: 2, preferably 70:30 to 96: 4. The amount of any additives depends in particular on their type. For example, acidifying additives and organic catalysts for increasing the performance of peracid are used in amounts of 0 to 20% by weight, in particular in amounts of 1 to 10% by weight, based on the total weight. added, however, metal complexes in concentrations in the ppm range.
Zur Herstellung der Granulate wird zunächst in einem Mischaggregat (z.B. Pflugscharmischer) die Mischung aus Ammoniumnitril und Bindemittel innig vermischt. In einem zweiten Schritt wird das Gemisch zu größeren Partikeln verpreßt. Geeignet hierfür sind u.a. Walzenkompaktoren. Die Preßlinge werden anschließend der Zerkleinerung (Mahlung) unterworfen und auf die gewünschte Korngröße zerkleinert. Zu diesem Zweck eignen sich Zahnscheibenwaizen und/oder Passiersiebe.To produce the granules, the mixture of ammonium nitrile and binder is first mixed intimately in a mixing unit (eg ploughshare mixer). In a second step, the mixture becomes larger particles pressed. Roller compactors are suitable for this. The compacts are then subjected to comminution (grinding) and comminuted to the desired grain size. Toothed washer rollers and / or strainers are suitable for this purpose.
Feinanteil und Grobgut werden abgesiebt und in den Prozeß zurückgeführt. Während der Grobanteil direkt einer erneuten Zerkleinerung zugeführt wird, wird der Feinanteil der Korn paktierstufe zugesetzt. Die Korngröße des Produktes liegt im allgemeinen im Bereich von 100 bis 2000 μm, vorzugsweise 300 bis 1800 μm. Das Schüttgewicht der erfindungsgemäßen Granulate liegt damit oberhalb 500 kg/m3, vorzugsweise oberhalb 600 kg/m3.Fine fraction and coarse material are screened off and returned to the process. While the coarse fraction is directly re-crushed, the fine fraction is added to the grain compacting stage. The grain size of the product is generally in the range from 100 to 2000 μm, preferably 300 to 1800 μm. The bulk density of the granules according to the invention is therefore above 500 kg / m 3 , preferably above 600 kg / m 3 .
Die auf diese Weise erhaltenen Granulate sind direkt zum Einsatz in Wasch- und Reinigungsmitteln geeignet. In einer besonderen Verwendungsform können sie jedoch mit einer Coatinghülle versehen werden.The granules obtained in this way are directly suitable for use in detergents and cleaning agents. In a special form of use, however, they can be provided with a coating envelope.
Hierzu wird das erfindungsgemäße Granulat in einem zusätzlichen Schritt mit einer filmbildenden Substanz umhüllt, wodurch die Produkteigenschaften erheblich beeinflußt werden können.For this purpose, the granules according to the invention are coated with a film-forming substance in an additional step, as a result of which the product properties can be significantly influenced.
Als Coatingmaterial geeignet sind alle filmbildenden Substanzen, wie Wachse, Silikone, Fettsäuren, Seifen, anionische Tenside, nichtionische Tenside, kationische Tenside, sowie anionische und kationische Polymere, z.B. Polyacrylsäuren. Durch Verwendung dieser Coatingmaterialien kann u.a. das Auflöseverhalten verzögert werden, um auf diese Weise Wechselwirkungen zwischen dem Bieichaktivator und dem Enzymsystem zu Beginn des Waschprozesses zu unterbinden. Soll das bestimmungsgemäße Granulat in Maschinengeschirrspülmitteln Verwendung finden, eignen sich hierzu vor allem Wachse mit Schmelzpunkten von 40 bis 50°C.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 acids. By using these coating materials, i.a. the dissolving behavior is delayed in order to prevent interactions between the bending activator and the enzyme system at the beginning of the washing process. If the intended granulate is to be used in machine dishwashing detergents, waxes with melting points of 40 to 50 ° C are particularly suitable.
Saure Coatingmaterialien erhöhen die Lagerstabilität der Granulate in hochalkalischen Formulierungen, die Percarbonate enthalten, und unterdrücken Farbschäden durch Spotting. Zusätze eines Farbstoffes sind ebenfalls möglich.Acidic coating materials increase and suppress the storage stability of the granules in highly alkaline formulations containing percarbonates Color damage due to spotting. Additions of a dye are also possible.
Das Aufbringen der Coatingmaterialien erfolgt in der Regel durch Aufsprühen der geschmolzenen oder in einem Lösemittel gelösten Coatingmaterialien. Gemäß der Erfindung kann das Coatingmaterial in Mengen von 0 bis 20, vorzugsweise von 1 bis 10 Gew.-%, bezogen auf das Gesamtgewicht auf den erfindungsgemäßen Granulatkern aufgebracht werden.The coating materials are generally applied by spraying the melted coating materials or coating materials dissolved in a solvent. According to the invention, the coating material can be applied in amounts of from 0 to 20, preferably from 1 to 10,% by weight, based on the total weight, on the granule core according to the invention.
Die erfindungsgemäßen Produkte zeichnen sich durch eine gute Lagerstabilität in pulverförmigen Wasch-, Reinigungs- und Desinfektionsmittelformulierungen aus. Sie sind ideal zum Einsatz in Vollwaschmitteln, Fleckensalzen, Maschinengeschirrspülmitteln, pulverförmigen Allzweckreinigern und Gebißreinigern.The products according to the invention are characterized by good storage stability in powder detergent, cleaning and disinfectant formulations. They are ideal for use in heavy-duty detergents, stain salts, machine dishwashing detergents, powdered all-purpose cleaners and denture cleaners.
In diesen Formulierungen werden die erfindungsgemäßen Granulate in Kombination mit einer Wasserstoffperoxidquelle eingesetzt. Beispiele dafür sind Perborat- Monohydrat, Perborat-Tetrahydrat, Percarbonate sowie Wasserstoffperxoid-Addukte an Harnstoff oder Aminoxiden. Daneben kann die Formulierung dem Stand der Technik entsprechend weitere Bestandteile aufweisen, wie organische oder anorganische Builder und Co-Builder, Tenside, Enzyme, optische Aufheller und Parfüm.The granules according to the invention are used in combination with a hydrogen peroxide source in these formulations. Examples include perborate monohydrate, perborate tetrahydrate, percarbonates and hydrogen peroxide adducts with urea or amine oxides. In addition, according to the prior art, the formulation can have further constituents, such as organic or inorganic builders and co-builders, surfactants, enzymes, optical brighteners and perfume.
Herstellungs- und AnwendungsbeispieleManufacturing and application examples
Beispiel 1 (Herstellung)Example 1 (Production)
In einem 50 I Lödige-Mischer werden jeweils 10 kg einer Mischung aus 92 Gew.-% Ammoniumnitril (Trimethylammoniumacetonitril Toluolsulfonat = Granulat 1 oder N-Cyanomethyl-N-methyipiperazinium Toluolsulfonat = Granulat 2) und 8 Gew.-% Bentonit (©Laundrosil DGA) mit einer Drehzahl von 70 U/min über einen Zeitraum von 10 min intensiv gemischt. Diese homogene Mischung wird anschließend auf einem Walzenkompaktor Pharmapaktor (Fa. Bepex (DE)) mit einer Preßkraft von 50 bis 60 kN zu Schülpen verpreßt, die dann in einer zweistufigen Mahlung, Vormahlung mit Zahnscheibenwalzen (Fa. Alexanderwerk (DE)) und Zerkleinerung in einem Passiersieb (Fa. Frewitt (DE)) bei einer Maschenweite von 2000 μm zerkleinert werden.10 kg of a mixture of 92% by weight ammonium nitrile (trimethylammonium acetonitrile toluenesulfonate = granulate 1 or N-cyanomethyl-N-methyipiperazinium toluenesulfonate = granulate 2) and 8% by weight bentonite (© Laundrosil DGA ) intensively mixed at a speed of 70 rpm over a period of 10 min. This homogeneous mixture is then on a roller compactor Pharmapaktor (Fa. Bepex (DE)) with a pressing force of 50 to 60 kN pressed into flakes, which are then subjected to a two-stage grinding, pre-grinding with toothed disk rollers (Fa. Alexanderwerk (DE)) and comminution in a sieve (Fa. Frewitt (DE )) crushed with a mesh size of 2000 μm.
Man erhält 5,3 kg Granulat mit einer Korngrößenverteilung von 200 bis 1600 μm (Ausbeute: 53 %), sowie 2,8 kg Feinanteil < 200 μm (28 %), die durch erneute Kompaktierung rezykliert werden können, und 1 ,9 kg Grobanteil > 1600 μm (19 %), die durch erneute Mahlung aufgearbeitet werden können.This gives 5.3 kg of granules with a particle size distribution of 200 to 1600 μm (yield: 53%), as well as 2.8 kg of fine fraction <200 μm (28%), which can be recycled by further compacting, and 1.9 kg of coarse fraction > 1600 μm (19%), which can be worked up by grinding again.
Beispiel 2 (Lagerstabilität)Example 2 (storage stability)
Zur Bestimmung der Lagerstabilität wurden 10 g Standardwaschmittel WMP ohne Bleichsystem (WfK (DE)) mit 1 ,5 g Natriumperborat-Monohydrat und 0,5 g Aktivator bzw. Aktivatorgranulat enthaltend 0,5 g Aktivator homogen vermischt und die Mischung anschließend in Faltschachteln bei 38°C und 80 % relativer Luftfeuchtigkeit im Klimaschrank gelagert (Schnelltest). In bestimmten Zeitabständen wurde der verbleibende Aktivator-Gehalt durch iodometrische Titration ermittelt.To determine the storage stability, 10 g of standard washing agent WMP without bleaching system (WfK (DE)) were mixed homogeneously with 1.5 g of sodium perborate monohydrate and 0.5 g of activator or activator granules containing 0.5 g of activator, and the mixture was then packed in folding boxes at 38 ° C and 80% relative humidity stored in a climatic cabinet (quick test). At certain intervals, the remaining activator content was determined by iodometric titration.
Als Aktivatoren wurden Trimethyiammoniumacetonitril Toluolsulfonat (1 ) und N-Cyanomethyl-N-methylpiperazinium Toluolsulfonat (2) jeweils als Pulver sowie als Aktivatorgranulate Granulat 1 und Granulat 2 gemäß Beispiel 1 verwendet. Trimethylammonium acetonitrile toluenesulfonate (1) and N-cyanomethyl-N-methylpiperazinium toluenesulfonate (2) were used as activators, each as a powder and as activator granules granules 1 and granules 2 according to Example 1.
Tabelle 1Table 1
Dieses Beispiel zeigt, daß die Ammoniumnitrile in pulverisierter Form schnell an Aktivgehalt verlieren. In granulierter Form dagegen sind die Aktivatoren lagerstabil.This example shows that the ammonium nitriles quickly lose their active content in powdered form. In granular form, however, the activators are stable on storage.
Beispiel 3 (Bleichaktivität)Example 3 (bleaching activity)
Die Bleichaktivität der erfindungsgemäßen Granulate wurde unter praxisnahenThe bleaching activity of the granules according to the invention was found to be practical
Bedingungen in einer Mehrkomponenten-Waschmaschine Öko-Lavamat 6753Conditions in a multi-component washing machine Öko-Lavamat 6753
(AEG, Nürnberg) an Bleichtestgeweben in Gegenwart reiner Testwäsche geprüft.(AEG, Nuremberg) tested on bleach test fabrics in the presence of pure test laundry.
Entsprechend der Dosiervorschrift für Wasserhärtebereich 3 wurden 70 gAccording to the dosing specification for water hardness range 3, 70 g
Referenzwaschmittel (WMP) in die dafür vorgesehenen Einspülkammern derReference detergent (WMP) in the provided detergent dispenser
Waschmaschine gegeben. Als Bleichkomponente wurden in die dafür vorgeseheneGiven washing machine. As a bleaching component, the
Einspülkammer 8,0 g Percarbonat gegeben sowieDispensing chamber given 8.0 g of percarbonate as well
2,93 g Bleichaktivatorgranulat 1 (92 %ig) gemäß Beispiel 1 ,2.93 g bleach activator granules 1 (92%) according to Example 1,
3,37 g Bleichaktivatorgranulat 2 (92 %ig) gemäß Beispiel 1 ,3.37 g bleach activator granules 2 (92%) according to Example 1,
2,52 g Bleichaktivatorgranulat 3 (92 %ig) auf Basis TAED gemäß Beispiel 1 aus2.52 g of bleach activator granules 3 (92%) based on TAED according to Example 1
DE-A 44 39 039.DE-A 44 39 039.
Zum Vergleich wurden die Ammoniumnitrile Trimethylammoniumacetonitril Toluolsulfonat (1 ) und N-Cyanomethyl-N-methylpiperazinium Toluolsulfonat (2) sowie TAED (3) in nicht granulierter Form geprüft: 2,7 g Bleichaktivator Pulver 1 3,1 g Bleichaktivator Pulver 2 2,3 g Bleichaktivator TAED Pulver Als Ballaststoff wurden 2 kg Frotteegewebe verwendet , als Testanschmutzungen 10 bleichbare Anschmutzungen (Tee, Rotwein, Curry, Gras der Wäschereiforschung Krefeld). Die Wäsche wurde im Hauptwaschgang bei 40°C gewaschen. Die Auswertung erfolgt durch Bestimmung des Weißgrades nach der Wäsche durch Addition der Remissionsdifferenzen, gemessen mit ELREPHO 2000 (Datacolor).For comparison, the ammonium nitriles trimethylammonium acetonitrile toluenesulfonate (1) and N-cyanomethyl-N-methylpiperazinium toluenesulfonate (2) and TAED (3) were tested in non-granulated form: 2.7 g bleach activator powder 1 3.1 g bleach activator powder 2 2.3 g TAED powder bleach activator 2 kg of terry cloth were used as fiber, 10 bleachable stains (tea, red wine, curry, grass from the Krefeld laundry research) were used as test stains. The laundry was washed in the main wash at 40 ° C. The evaluation is carried out by determining the whiteness after washing by adding the reflectance differences, measured with ELREPHO 2000 (Datacolor).
Tabelle 2 RemissionsdifferenzenTable 2 Remission differences
T = 40°C; Tee, Rotwein, Curry, GrasT = 40 ° C; Tea, red wine, curry, grass
Dieses Beispiel zeigt, daß bei den Ammoniumnitrilen durch die Granulierung eine sehr wesentliche Steigerung der Bleichleistung erreicht werden kann. Dies ist überraschend, weil bei dem in der Praxis weit verbreiteten Aktivator TAED die Granulierung keinen wesentlichen Einfluß auf die Bleichleistung hat. This example shows that in the case of ammonium nitriles, a very substantial increase in the bleaching performance can be achieved by the granulation. This is surprising because with the activator TAED, which is widely used in practice, the granulation has no significant influence on the bleaching performance.

Claims

Patentansprüche: Claims:
1. Bleichaktivatorgranulat aus einem oder mehreren Ammoniumnitrilen und Schichtsilikat, erhalten durch Mischen der beiden Komponenten, Verpressen und Zerkleinern der dabei erhaltenen Agglomerate auf die gewünschte Korngröße.1. bleach activator granules of one or more ammonium nitriles and layered silicate, obtained by mixing the two components, pressing and comminuting the agglomerates obtained to the desired particle size.
2. Bleichaktivatorgranulat nach Anspruch 1 , dadurch gekennzeichnet, daß es zusätzlich zu den Ammoniumnitrilen Bleichaktivatoren anderer Struktur enthält.2. bleach activator granules according to claim 1, characterized in that it contains bleach activators of a different structure in addition to the ammonium nitriles.
3. Bleichaktivatorgranulat nach Anspruch 1 , dadurch gekennzeichnet, daß es als Ammoniumnitril eine Verbindung der Formel3. bleach activator granules according to claim 1, characterized in that it is a compound of the formula as ammonium nitrile
enthält, wobei R1 und R2 C,-C4-Alkyl und X ein Anion bedeuten.contains, wherein R 1 and R 2 are C, -C 4 alkyl and X is an anion.
4. Bleichaktivatorgranulat nach Anspruch 1 , dadurch gekennzeichnet, daß es als Schichtsilikat natürliche oder sauer modifizierte Bentonite enthält.4. bleach activator granules according to claim 1, characterized in that it contains natural or acid-modified bentonites as layered silicate.
5. Bleichaktivatorgranulat nach Anspruch 1 , dadurch gekennzeichnet, daß es im wesentlichen aus Ammoniumnitril und Schichtsilikat im Gewichtsverhältnis 50:50 bis 98:2 besteht.5. bleach activator granules according to claim 1, characterized in that it consists essentially of ammonium nitrile and layered silicate in a weight ratio of 50:50 to 98: 2.
6. Bleichaktivatorgranulat nach Anspruch 1 , dadurch gekennzeichnet, daß es eine Korngröße von 100 bis 2000 μm aufweist.6. bleach activator granules according to claim 1, characterized in that it has a grain size of 100 to 2000 microns.
7. Bleichaktivatorgranulat nach Anspruch 1 , dadurch gekennzeichnet, daß das Granulat bis zu 20 Gew.-%, bezogen auf das Gewicht des Granulats ein oder mehrere Zusätze in Form von anorganischen Säuren, organischen Säuren, Komplexbildnern, Ketonen und Metallkomplexen enthält.7. bleach activator granules according to claim 1, characterized in that the granules up to 20 wt .-%, based on the weight of the granules or contains several additives in the form of inorganic acids, organic acids, complexing agents, ketones and metal complexes.
8. Wasch-, Reinigungs-, Bleich- und Desinfektionsmittel, enthaltend ein Bleichaktivatorgranulat gemäß einem oder mehreren der Ansprüche 1 bis 7. 8. washing, cleaning, bleaching and disinfecting agents containing a bleach activator granulate according to one or more of claims 1 to 7.
EP98947521A 1997-09-16 1998-09-05 Bleaching activators in the form of granules Expired - Lifetime EP1017776B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19740671 1997-09-16
DE19740671A DE19740671A1 (en) 1997-09-16 1997-09-16 Bleach activator granulate containing ammonium nitrile and layered silicate
PCT/EP1998/005628 WO1999014302A1 (en) 1997-09-16 1998-09-05 Bleaching activators in the form of granules

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EP1017776A1 true EP1017776A1 (en) 2000-07-12
EP1017776B1 EP1017776B1 (en) 2003-12-03

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EP (1) EP1017776B1 (en)
JP (1) JP4210428B2 (en)
KR (1) KR100500184B1 (en)
CN (1) CN1270626A (en)
AR (1) AR017107A1 (en)
AT (1) ATE255628T1 (en)
AU (1) AU9440398A (en)
BR (1) BR9812315A (en)
CA (1) CA2304252A1 (en)
DE (2) DE19740671A1 (en)
DK (1) DK1017776T3 (en)
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DK1017776T3 (en) 2004-03-15
WO1999014302A1 (en) 1999-03-25
US6133216A (en) 2000-10-17
US6063750A (en) 2000-05-16
JP4210428B2 (en) 2009-01-21
DE19740671A1 (en) 1999-03-18
AU9440398A (en) 1999-04-05
JP2001516800A (en) 2001-10-02
ATE255628T1 (en) 2003-12-15
DE59810362D1 (en) 2004-01-15
CA2304252A1 (en) 1999-03-25
CN1270626A (en) 2000-10-18
AR017107A1 (en) 2001-08-22
ES2212345T3 (en) 2004-07-16
TW512173B (en) 2002-12-01
KR20010024052A (en) 2001-03-26
BR9812315A (en) 2000-08-29
EP1017776B1 (en) 2003-12-03

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