EP0835926B1 - Procédé de production d'un activateur de blanchiment sous forme de granules enrobés - Google Patents

Procédé de production d'un activateur de blanchiment sous forme de granules enrobés

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Publication number
EP0835926B1
EP0835926B1 EP97116693A EP97116693A EP0835926B1 EP 0835926 B1 EP0835926 B1 EP 0835926B1 EP 97116693 A EP97116693 A EP 97116693A EP 97116693 A EP97116693 A EP 97116693A EP 0835926 B1 EP0835926 B1 EP 0835926B1
Authority
EP
European Patent Office
Prior art keywords
coating
granules
activator
coated
coating substance
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
EP97116693A
Other languages
German (de)
English (en)
Other versions
EP0835926A3 (fr
EP0835926A2 (fr
Inventor
Johannes Dr. Himmrich
Georg Dl. Borchers
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 Produkte Deutschland 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
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Publication of EP0835926A3 publication Critical patent/EP0835926A3/fr
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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • 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
    • C11D3/3907—Organic compounds

Definitions

  • Bleach activators are important ingredients in detergents, stain salts and machine dishwashing detergents. They allow a bleaching effect even at relatively low temperatures by reacting with hydrogen peroxide - usually perborates or percarbonates - to release an organic peroxycarboxylic acid.
  • the achievable bleaching result is determined by the nature and reactivity of the peroxycarboxylic acid formed, the structure of the bond to be perhydrolized 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 application in granulated form to prevent hydrolysis in the presence of alkaline detergent ingredients and to ensure a sufficient shelf life.
  • EP-A-0 037 026 describes a process for preparing a readily soluble activator granulate from 90 to 98% activator with 10 to 2% cellulose ether, starch or starch ether.
  • Granules consisting of bleach activator, film-forming polymers and additions of an organic C 3 -C 6 -carboxylic, hydroxycarboxylic or etheric carboxylic acid are mentioned in WO 90/01535.
  • EP-A-0 468 824 discloses granules of bleach activator and a film-forming polymer which is more soluble at pH 10 than at pH 7.
  • DE-OS-44 39 039 describes a process for the preparation of an activator granules by mixing a dry bleach activator with a dry, inorganic binder material containing water of hydration, compressing this mixture into larger agglomerates and comminuting these agglomerates onto the catalyst desired grain size.
  • An anhydrous preparation process by compaction of the bleach activator without the use of water with at least one water-swellable excipient is known from EP-A-0 075 818.
  • a disadvantage of these Aktivatorgranulaten is that the properties of the granules are essentially determined by the binder and the granulation method used and often in addition to the advantages described in the literature also some disadvantages, e.g. not optimal release of active ingredient, low abrasion resistance, high dust content, insufficient storage stability, segregation in the powder or color damage of the fabric when used in detergents and cleaners.
  • a coating step is often carried out subsequently to the granulation step.
  • Common methods are coating in mixers (mechanically induced fluidized bed) or enveloping in fluidized bed apparatus (pneumatically induced fluidized bed).
  • WO-92/13798 describes a coating for a bleach activator with a water-soluble organic acid melting above 30 ° C. and in WO-94/03305 a coating with a water-soluble acidic polymer for reducing the color damage of the laundry.
  • WO-94/26862 discloses the coating of a granulate consisting of bleach activator and water- and / or alkali-soluble polymer with an organic compound which melts between 30.degree. C. and 100.degree. C. to reduce segregation in the powdery end product.
  • the activator granules are placed in a Lödige ploughshare mixer, circulated at room temperature at 160 to 180 rpm without using the chopper and then sprayed with the hot melt.
  • Disadvantage of this method is a very poor coating quality, which indeed causes a reduction of segregation in the powdery end product, but has no effect on the other granule properties, such as drug release, abrasion resistance, dust content or storage stability.
  • the positive effect on the segregation behavior is probably on attributable droplet-shaped solidification of the coating substance on the granule surface, whereby a hooking of the granules in the bulk material is effected.
  • Object of the present invention was the development of a coating process for activator granules, which allows a targeted adjustment of the granular properties in a wide range with simultaneous optimal utilization of the coating material.
  • the invention thus provides a process for producing a coated bleach activator granules, wherein a bleach activator granules in a mechanically induced fluidized bed coated with a coating substance and simultaneously at 30 to 100 ° C, but equal to or below the melting or softening temperature of the coating substance, during a period from 1 to 180 minutes, tempered.
  • activators As base granules all activators can be used which have a melting point of above 100 ° C in granulated form.
  • activator substances are tetraacetylethylenediamine (TAED), tetraacetylglucoluril (TAGU), diacetyldioxohexahydrotriazine (DADHT), acyloxybenzenesulphonates (eg nonanyloxybenzenesulphonate [NOBS], benzoyloxibenzenesulphonate [BOBS]), acylated sugars (eg: pentaacetylglucose [PAG]) or compounds as described in EP Pat.
  • activators are N-acylated amines, amides, lactams, activated carboxylic acid esters, carboxylic anhydrides, lactones, acyls, carboxylic acid amides, acyl lactams, acylated ureas and oxamides, in addition, however, in particular also nitriles, which may also contain a quaternized ammonium group in addition to the nitrile group. Also, mixtures of different bleach activators may be present in the base granules.
  • These base granules may contain the usual granulation aids, which should have a melting point of about 100 ° C.
  • these granulation aids can be used as
  • the bleach activator base granules may contain other additives that improve properties such as storage stability and bleach activating ability.
  • additives include inorganic acids, organic acids such as mono- or polybasic carboxylic acids, hydroxycarboxylic acids and / or ether carboxylic acids and their salts, complexing agents, metal complexes and ketones.
  • the abovementioned additives can be used as individual substances or as mixtures.
  • These base granules are prepared by mixing the dry bleach activator with the dry granulation aid, compressing this mixture to form larger agglomerates and comminuting these agglomerates to the desired particle size.
  • the ratio of bleach activator to granulation aid is usually 50:50 to 98: 2, preferably 70:30 to 96: 4 wt .-%.
  • the amount of the additive depends in particular on its nature.
  • acidifying additives and organic catalysts to increase the performance of the peracid in amounts of 0 to 20 wt .-%, in particular in amounts of 1 to 10 wt .-%, based on the total weight, added, metal complexes in concentrations in the ppm range.
  • further substances which do not soften or melt in this temperature range can be present in dissolved or suspended form, for example polymers (for example homo-, co- or propylene copolymers of unsaturated carboxylic acids and / or Sulfonic acids and their alkali salts, cellulose ethers, starch, starch ethers, polyvinylpyrrolidone); Organic substances (for example mono- or polybasic carboxylic acids, hydroxycarboxylic acids or ether carboxylic acids having 3 to 8 carbon atoms and salts thereof); dyes; Inorganic substances (for example: silicates, carbonates, bicarbonates, sulfates, phosphates, phosphonates).
  • polymers for example homo-, co- or propylene copolymers of unsaturated carboxylic acids and / or Sulfonic acids and their alkali salts, cellulose ethers, starch, starch ethers, polyvinylpyrrolidone
  • Organic substances for example mono- or polybasic
  • the content of coating substance may be from 1 to 30% by weight, preferably from 5 to 15% by weight, based on coated activator granules.
  • mixers mechanically induced fluidized bed
  • mixers for example, plowshare mixers (continuous and batchwise), ring layer mixers or even Schugi mixers are possible.
  • the heat treatment takes place directly in the mixer.
  • Granulated coolers or fluid bed coolers can be used to cool the coated granules.
  • the coating substance can be sprayed on via a single-substance or a two-component nozzle device.
  • the heat treatment consists in a heat treatment at a temperature of 30 to 100 ° C, but equal to or below the melting or softening temperature of the respective shell substance. Preference is given to working at a temperature which is just below the melting or softening temperature.
  • the particle size of the coated bleach activator granules is from 0.1 to 2.0 mm, preferably from 0.2 to 1.0 mm and particularly preferably from 0.3 to 0.8 mm.
  • the exact temperature during the heat treatment or the temperature difference to the melting point of the coating substance is dependent on the coating quantity, the annealing time and the properties desired for the coated bleach activator granules and must be determined for the respective system in preliminary experiments.
  • the duration of the heat treatment is 1 to 180, preferably 3 to 60, particularly preferably 5 to 30 minutes.
  • the advantage of the new method over the prior art is that the liquid coating agent does not solidify too quickly and thereby has the opportunity to run as a thin film on the granule surface. This achieves a very uniform coating of the grain in a thin layer with the coating substance and an optimum coating effect when using a minimal amount of coating substance.
  • conventional methods ie without annealing step, occurs too rapid solidification of the individual droplets on the cold granule surface.
  • the surface is occupied only with fine single droplets and still has large coating defects.
  • the desired coating effect is thereby achieved only insufficient or a significantly higher amount of coating substance is required to achieve a desired coating effect.
  • the latter reduces the content of activator substance, which is often undesirable.
  • the properties of the activator granules can be optimized in a targeted manner to the desired requirements by suitably selecting the coating substance, the coating quantity and the temperature control of the process. Above all, the targeted optimization of the following Aktivatorgranulateigenschaften is possible.
  • a delayed reaction with a slight delay in time and release of active substance from the bleaching system with simultaneous rapid enzyme action is advantageous.
  • the enzymes can fully develop their washing power in the first few minutes of the washing process without being damaged by the bleaching system. Only after the enzymes have done their work is then initiated by reaction of the bleach activator with the hydrogen peroxide source, the bleaching process.
  • the reactivity i. the dissolution rate or the rate of peracid formation can be tailored to the enzyme system. In the method, a targeted adjustment of the peracid formation rate with a minimum amount of coating substance and therefore maximum activator content is possible.
  • the abrasion resistance of an activator granulate By coating a granulate with softening or melting substances, the abrasion resistance of an activator granulate can be increased become.
  • the higher the abrasion resistance the greater the better the granulate surface is coated with the coating substance.
  • optimum coating of the coating substance on the granule surface and thus optimum improvement of the abrasion resistance can be effected with a minimum amount of coating.
  • the granules obtained in this way are directly suitable for use in detergents and cleaners. They are ideal for use in heavy-duty detergents, stain salts, machine dishwashing detergents, powdered all-purpose cleaners and denture cleaners.
  • the granules of the invention are usually used in combination with a source of hydrogen peroxide. Examples include perborate monohydrate, perborate tetrahydrate, percarbonates and hydrogen peroxide adducts of urea or amine oxides.
  • the formulation according to the prior art may comprise further detergent ingredients, such as organic or inorganic builders and co-builders, surfactants, enzymes, laundry additives, optical brighteners and perfume.
  • TAED 4303 (Hoechst AG) was continuously metered at a throughput of 480 kg / h into a Schugi mixer (Flexomix 160, Hosokawa Schugi) and sprayed with a 75 ° C. hot melt of myristic acid.
  • the coated material fell directly into a downstream fluidized bed (Hosokawa Schugi) and was tempered there in a first chamber for 5 to 10 minutes at fluidized bed temperatures of about 54 ° C and then in a second chamber at fluidized bed temperatures of about 35 Cooled ° C.
  • TAED 4303 was continuously metered into the Schugi mixer with a throughput of 480 kg / h, sprayed with a 75 ° C hot melt of myristic acid and then directly in the downstream fluidized bed at fluidized bed temperatures of about 35 Cooled ° C.
  • the coating quality of the products was assessed by determining the rate of peracetic acid formation at a temperature of 20 ° C. The slower the peracetic acid formation, the better the degree of coating achieved.
  • the coating quality expressed by the delay in peracetic acid formation, can be markedly improved with the same amount of coating (comparison of products 3 and 4).
  • Example 2 Coating after the fluidized-bed process with subsequent tempering (not according to the invention)
  • 500-600 g of TAED 4303 were introduced into the fluidized bed (fluidized-bed apparatus Strea 1, from Aeromatic) and sprayed with a melt of stearic acid at a temperature of about 80 ° C.
  • the fluidized bed was operated at low temperatures and after completion of spraying again after-cooled for about 5 minutes (prior art).
  • the coated granules were again introduced into the fluidized bed and tempered by the novel process.
  • the fluidized bed was gradually heated to temperatures of about 65 to 70 ° C and this product temperature for about 5 to 8 min. kept constant. Subsequently, the tempered product was gradually cooled again.
  • the coating quality expressed by the delay in peracetic acid formation, can be significantly improved for the same amount of coating (comparison of products 6 and 8 or products 7 and 9).
  • tempering The influence of tempering on the coating quality is also reflected in the storage stability of TAED granules in detergent formulations.
  • the storage stability was tested in prefabricated cartons (height: 6.5 cm, width 3.2 cm, depth 2.2 cm) at 38 ° C and 80% relative humidity (RH) over a period of 28 days.
  • Each carton was filled with a homogeneous mixture of 8.0 g of test detergent WMP, 1.5 g of sodium percarbonate and 0.5 g of the TAED granules to be tested and then sealed at the top with Tesafilm. All samples were mixed and bottled the same day.
  • the filled and labeled cartons were then placed in the climatic cabinet at a sufficient distance from each other and stored at 38 ° C / 80% RH.
  • the samples were removed from the climatic chamber, the entire sample at 20 ° C in 1 l of distilled water while stirring with a magnetic stirrer (250 to 280 rev / min) registered and 1 g of sodium percarbonate added.
  • the further determination of the amount of peracetic acid formed was carried out analogously to the information in Example 1. From the maximum value of peracetic acid found then the TAED content of the sample was calculated.
  • the TAED maintenance level represents the percentage TAED content of the sample after storage based on the TAED content of the un-stored sample. Table 3: Storage stability in detergent formulations of TAED granules coated by fluidized bed with subsequent heat treatment Product no.
  • TAED granules TAED retention after storage [%] 0d 3d 6d 9d 15d 23d 28d 5
  • Basic granulate (BG) 100 24 14 12 10 9 8th 6 BG + 10% stearic acid, annealed 100 88 61 56 47 45 45 8th BG + 10% stearic acid, unannealed 100 52 24 20 18 16 15
  • TAED 4303 was continuously metered via a flexible metering screw at 40 kg / h into the fluidized bed apparatus (technical fluidized bed apparatus) and coated with 20% myristic acid.
  • the residence time in the fluidized bed was about 30 minutes.
  • the product discharged through a rotary valve was transported by means of a metering screw to a screening machine, on which the coarse fraction of greater than 1.0 mm and the fine fraction of less than 0.2 mm were separated.
  • the coarse fraction was then comminuted in a mill and then returned together with the fine fraction via a flexible metering screw in the fluidized bed apparatus.
  • the fluidized bed temperature was increased from initially 46 ° C to finally 54 ° C.
  • TAED granules T fluid bed [° C] Peracetic acid [%] dust content 5 min 10 min 20 min [%] 11 Basic granulate (BG) - 75 95 100 - 12 BG + 20% myristic acid 46 66 81 94 30 13 BG + 20% myristic acid 49 48 68 87 15 14 BG + 20% myristic acid 52 38 60 86 10 15 BG + 20% myristic acid 54 20 36 62 5
  • the coating quality as expressed by the retardation of peracid formation, increases significantly and a better dedusting and higher abrasion resistance, expressed by the decreasing dust content ⁇ 0.2 mm of the coated granulate.
  • Example 4 Coating in the ploughshare mixer with simultaneous tempering
  • 1.2 kg of TAED granules according to EP-A-0 037 026 were initially charged in a batch ploughshare mixer (M5R, Lödige) and mixed with a mixing speed of about 150 rpm with 210 g of an 80 ° C hot stearic acid melt sprayed.
  • the contents of the mixer were heated to a temperature of 50 ° C. during the coating step by means of a heating jacket.
  • the coating and annealing time was about 10 minutes.
  • 1.2 kg of TAED granules according to EP-A-0 037 026 were initially charged in a batch ploughshare mixer and mixed at room temperature with mixing at a speed of the mixing tools of about 150 rev / min with 210 g an 80 ° C hot stearic acid melt sprayed.
  • Example 5 Coating in the ploughshare mixer with simultaneous tempering
  • TAED 4303 was continuously metered into the ploughshare mixer (KT-160, Drais company) at throughput rates of 100 to 300 kg / h.
  • the mixer contents were heated to a temperature in the range of 44 to 52 ° C via a heating mantle.
  • the residence time in the mixer was 8 to 12 minutes.
  • a melt of stearic acid with a temperature of 80 ° C in the front part of the mixer was injected (closer to the product entry).
  • the coating amount was 7%.
  • the mixer was operated at a speed of the mixing tools of 90 rpm and without the use of chopper blades.
  • the degree of filling in the mixer was adjusted so that the product just covered the mixing shaft.
  • the coated material was continuously withdrawn from the mixer and passed directly through a sieve (0.2 to 1.0 mm) to separate fine and coarse fractions.

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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)

Claims (9)

  1. Procédé de production d'un activateur de blanchiment sous forme de granulés enrobés, caractérisé en ce que l'on enrobe un granulé d'activateur de blanchiment avec une substance de revêtement dans un lit fluidisé mécaniquement induit et en ce qu'on étuve en même temps de 30 à 100 °C, cependant à une température égale ou inférieure à la température de fusion ou de ramollissement de la substance de revêtement, pendant une durée de 1 à 180 minutes.
  2. Procédé selon la revendication 1, caractérisé en ce que le granulé de base de l'activateur présente un point de fusion de plus de.100 °C.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la substance de revêtement a un point de ramollissement ou de fusion dans la plage de 30 à 100 °C.
  4. Procédé selon une ou plusieurs des revendications 1 à 3, caractérisé en ce qu'on utilise comme activateurs de blanchiment des amines N-acylées, des amides, des lactames, des acyloxybenzène-sulfonates, des sucres acylés, des carboxylates activés, des anhydrides d'acide carboxylique, des lactones, des acylals, des oxamides et/ou des nitriles, qui peuvent contenir un groupe ammonium quaternaire.
  5. Procédé selon une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'on utilise comme substances de revêtement des acides gras, des alcools gras, des polyalkylèneglycols, des agents tensio-actifs non ioniques, des agents tensio-actifs anioniques, des polymères, des cires et/ou des silicones.
  6. Procédé selon une ou plusieurs des revendications 1 à 5, caractérisé en ce que la substance de revêtement contient des polymères, des substances organiques et/ou des substances inorganiques sous forme dissoute ou en suspension.
  7. Procédé selon une ou plusieurs des revendications 1 à 6, caractérisé en ce que la teneur en substance de revêtement est de 1 à 30 % en poids, de préférence de 5 à 15 % en poids, par rapport au granulé d'activateur revêtu.
  8. Procédé selon une ou plusieurs des revendications 1 à 7, caractérisé en ce que la taille de grains du granulé d'activateur de blanchiment revêtu est de 0,1 à 2,0 mm, de préférence de 0,2 à 1,0 mm et de manière particulièrement préférée de 0,3 à 0,8 mm.
  9. Procédé selon une ou plusieurs des revendications 1 à 8, caractérisé en ce que le granulé d'activateur contient jusqu'à 20 % en poids, par rapport au poids du granulé de base de l'activateur, d'un ou de plusieurs additifs choisis dans le groupe constitué des acides inorganiques, des acides organiques, des agents complexants, des cétones et des complexes des métaux.
EP97116693A 1996-10-10 1997-09-25 Procédé de production d'un activateur de blanchiment sous forme de granules enrobés Expired - Lifetime EP0835926B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19641708A DE19641708A1 (de) 1996-10-10 1996-10-10 Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats
DE19641708 1996-10-10

Publications (3)

Publication Number Publication Date
EP0835926A2 EP0835926A2 (fr) 1998-04-15
EP0835926A3 EP0835926A3 (fr) 1999-01-07
EP0835926B1 true EP0835926B1 (fr) 2007-01-24

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ID=7808324

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97116693A Expired - Lifetime EP0835926B1 (fr) 1996-10-10 1997-09-25 Procédé de production d'un activateur de blanchiment sous forme de granules enrobés

Country Status (13)

Country Link
US (3) US6107266A (fr)
EP (1) EP0835926B1 (fr)
JP (1) JP4897988B2 (fr)
KR (1) KR100507515B1 (fr)
AR (1) AR008887A1 (fr)
BR (1) BR9704995A (fr)
CA (1) CA2216193C (fr)
CZ (1) CZ294306B6 (fr)
DE (2) DE19641708A1 (fr)
ES (1) ES2276414T3 (fr)
HU (1) HUP9701617A3 (fr)
PL (1) PL188368B1 (fr)
TW (1) TW418252B (fr)

Families Citing this family (30)

* Cited by examiner, † Cited by third party
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DE19641708A1 (de) * 1996-10-10 1998-04-16 Clariant Gmbh Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats
DE10038832A1 (de) * 2000-08-04 2002-03-28 Henkel Kgaa Umhüllte Bleichaktivatoren
DE10057045A1 (de) 2000-11-17 2002-05-23 Clariant Gmbh Teilchenförmige Bleichaktivatoren auf der Basis von Acetonitrilen
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
DE10334046A1 (de) * 2003-07-25 2005-02-10 Clariant Gmbh Verfahren zur Herstellung von granulierten Acyloxybenzolsulfonaten oder Acyloxybenzolcarbonsäuren und deren Salze
DE102004012568A1 (de) * 2004-03-12 2005-12-08 Henkel Kgaa Bleichaktivatoren und Verfahren zu ihrer Herstellung
DE102004012915A1 (de) * 2004-03-17 2005-10-13 Clariant Gmbh Feste Zubereitungen enthaltend einen sensitiven Wirkstoff
CA2647895A1 (fr) * 2006-04-04 2007-10-18 Basf Se Systeme de blanchissement enrobe d'une couche polymere
GB0710559D0 (en) * 2007-06-02 2007-07-11 Reckitt Benckiser Nv Composition
US20100075883A1 (en) * 2008-09-24 2010-03-25 Ecolab Inc. Granular cleaning and disinfecting composition
DE102009017722A1 (de) * 2009-04-11 2010-10-14 Clariant International Limited Bleichmittelgranulate mit Aktivcoating
GB0918914D0 (en) 2009-10-28 2009-12-16 Revolymer Ltd Composite
DE102009057222A1 (de) * 2009-12-05 2011-06-09 Clariant International Ltd. Bleichkatalysator-Compounds, Verfahren zu ihrer Herstellung und ihre Verwendung
DE102010028236A1 (de) * 2010-04-27 2011-10-27 Evonik Degussa Gmbh Bleichmittelpartikel umfassend Natriumpercarbonat und einen Bleichaktivator
GB201019628D0 (en) 2010-11-19 2010-12-29 Reckitt Benckiser Nv Dyed coated bleach materials
GB201106408D0 (en) 2011-04-15 2011-06-01 Revolymer Ltd Novel composite
GB201106391D0 (en) 2011-04-15 2011-06-01 Reckitt & Colman Overseas Novel composite
GB201106377D0 (en) 2011-04-15 2011-06-01 Reckitt & Colman Overseas Novel composite
GB201106409D0 (en) 2011-04-15 2011-06-01 Revolymer Ltd Novel composite
US8728454B1 (en) 2012-10-30 2014-05-20 The Clorox Company Cationic micelles with anionic polymeric counterions compositions thereof
US8765114B2 (en) 2012-10-30 2014-07-01 The Clorox Company Anionic micelles with cationic polymeric counterions methods thereof
US8883705B2 (en) 2012-10-30 2014-11-11 The Clorox Company Cationic micelles with anionic polymeric counterions systems thereof
US8883706B2 (en) 2012-10-30 2014-11-11 The Clorox Company Anionic micelles with cationic polymeric counterions systems thereof
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CZ294306B6 (cs) 2004-11-10
DE19641708A1 (de) 1998-04-16
CA2216193A1 (fr) 1998-04-10
BR9704995A (pt) 1998-11-03
US20030207784A1 (en) 2003-11-06
CZ319897A3 (cs) 1998-04-15
JPH10152697A (ja) 1998-06-09
PL188368B1 (pl) 2005-01-31
US6645927B1 (en) 2003-11-11
HU9701617D0 (en) 1997-11-28
EP0835926A3 (fr) 1999-01-07
US6107266A (en) 2000-08-22
KR100507515B1 (ko) 2005-11-14
AR008887A1 (es) 2000-02-23
PL322521A1 (en) 1998-04-14
DE59712800D1 (de) 2007-03-15
JP4897988B2 (ja) 2012-03-14
HUP9701617A2 (hu) 1998-07-28
KR19980032630A (ko) 1998-07-25
HUP9701617A3 (en) 2000-03-28
EP0835926A2 (fr) 1998-04-15
TW418252B (en) 2001-01-11
CA2216193C (fr) 2006-07-04
ES2276414T3 (es) 2007-06-16

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