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 components in detergents, stain salts and Dishwasher detergents. They already enable a bleaching effect relatively low temperatures by using hydrogen peroxide - mostly perborates or percarbonates - with the release of an organic peroxycarboxylic acid react.
• the achievable bleaching result is determined by the type and reactivity of the Peroxycarboxylic acid formed, the structure of the bond to be hydrolyzed as well as the water solubility of the bleach activator. Since it's mostly one reactive ester or an amide, in many cases it is necessary to use it for that intended use in granular form to hydrolysis in To prevent the presence of alkaline detergent ingredients and a to ensure sufficient storage stability.
• EP-A-0 037 026 describes a process for producing easily soluble activator granules from 90 to 98% activator with 10 to 2% cellulose ether, starch or starch ether.
• Granules consisting of bleach activator, film-forming polymers and additives of an organic C 3 -C 6 carbon-, hydroxycarbon- or ether carboxylic acid are listed 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 producing an activator granulate by mixing a dry bleach activator with a dry, inorganic, hydrate-containing binding material, compressing this mixture to larger agglomerates and comminuting these agglomerates to the desired particle size.
• a water-free manufacturing process by compacting the bleach activator without using water with at least one water-swellable auxiliary is known from EP-A-0 075 818.
• a disadvantage of these activator granules is that the properties of the granules essentially by the binder and the granulation process used are fixed and often in addition to the advantages described in the literature certain disadvantages, e.g. not optimal release of active ingredient, low abrasion resistance, high dust content, insufficient storage stability, segregation in powder or Color damage to the fabric when used in detergents and cleaning agents exhibit.
• WO-92/13798 describes a coating with a bleach activator water-soluble organic acid melting above 30 ° C and in WO-94/03305 a coating with a water-soluble acidic polymer for reduction the color damage of the laundry described.
• WO-94/26862 describes the coating of a granulate consisting of a bleach activator and water and or alkali soluble polymer, with a between 30 ° C and 100 ° C. melting organic compound to reduce segregation in the powdered end product known.
• the activator granulate is in one Lödige ploughshare mixer submitted without using the chopper Room temperature circulated at 160 to 180 rpm and then with the hot Sprayed melt.
• the disadvantage of this method is a very bad one Coating quality, which is a reduction in the segregation in powder
• the end product has no effect on the other granule properties, such as. Active ingredient release, abrasion resistance, dust content or storage stability.
• the positive effect on the segregation behavior is probably on one droplet-like solidification of the coating substance on the granulate surface attributable, which causes the granules to get caught in the bulk material becomes.
• the object of the present invention was to develop a coating process for activator granules, which is a targeted adjustment of the granule properties in a wide range with optimal use of the coating material enables.
• This task was solved by tempering during and / or after the coating.
• the invention thus relates to a method for producing a coated Bleach activator granules, wherein a bleach activator base granules with a Coating substance wrapped and tempered simultaneously or subsequently.
• activators can be used as basic granules, those in granulated Form have a melting point of above 100 ° C.
• Activator substances are tetraacetylethylenediamine (TAED), tetraacetylglucoluril (TAGU), diacetyldioxohexahydrotriazine (DADHT), acyloxybenzenesulfonates (e.g. Nonanyloxybenzenesulfonate [NOBS], benzoyloxybenzenesulfonate [BOBS]), acylated Sugar (e.g.
• PAG pentaacetyl glucose
• activators are N-acylated amines, amides, lactams, activated Carboxylic acid esters, carboxylic anhydrides, lactones, acylals, carboxamides, Acyl lactams, acylated ureas and oxamides, but also in particular Nitriles, which in addition to the nitrile group also a quaternized ammonium group can contain.
• Mixtures of different bleach activators can also Basic granules are available.
• These basic granules can contain the usual granulation aids, which should have a melting point of over 100 ° C.
• Film-forming polymers are suitable here, for example: cellulose ether, starch, starch ether, homo-, co-, graft copolymers of unsaturated carboxylic acids and / or sulfonic acid and salts thereof; Organic substances, e.g. cellulose, crosslinked polyvinylpyrrolidone or inorganic substances, e.g.
• the Bleach activator base granules contain other additives that Properties such as storage stability and bleach activation capacity improve.
• additives include inorganic acids, organic Acids such as mono- or polyvalent carboxylic acids, hydroxycarboxylic acids and / or ether carboxylic acids and their salts, complexing agents, metal complexes and ketones.
• the aforementioned additives can be used as individual substances or as Mixtures are used.
• These basic granules are produced by mixing the dry Bleach activator with the dry granulating agent, pressing this mixture to larger agglomerates and crushing these agglomerates to the desired one Grain size.
• the ratio of bleach activator to granulation aid is usually 50:50 to 98: 2, preferably 70:30 to 96: 4% by weight.
• the amount of the additive depends in particular on its type. So acidifying additives and organic catalysts to increase the performance of peracid in amounts of 0 up to 20 wt .-%, in particular in amounts of 1 to 10 wt .-%, based on the Total weight, added, however, metal complexes in concentrations in ppm Area.
• C 8 -C 31 fatty acids for example: lauric, myristic, stearic acid); C 8 -C 31 fatty alcohols; Polyalkenyl glycols (eg polyethylene glycols with a molecular weight of 1,000 to 50,000 g / mol); Nonionics (e.g.
• C 8 -C 31 fatty alcohol polyalkoxylates with 1 to 100 moles of EO C 8 -C 31 fatty alcohol polyalkoxylates with 1 to 100 moles of EO
• Anionics for example alkanesulfonates, alkylbenzenesulfonates, ⁇ -olefinsulfonates, alkyl sulfates, alkyl ether sulfates with C 8 -C 31 -hydrocarbon radicals
• Polymers eg polyvinyl alcohols
• Waxes for example: montan waxes, paraffin waxes, ester waxes, polyolefin waxes
• Silicones for example: montan waxes, paraffin waxes, ester waxes, polyolefin waxes.
• softening or melting substances in dissolved or suspended form are present, e.g .: polymers (e.g. homo-, co- or plug copolymers unsaturated carboxylic acids and / or sulfonic acids and their alkali salts, Cellulose ether, starch, starch ether, polyvinylpyrrolidone); Organic substances (e.g. mono- or polyvalent carboxylic acids, hydroxycarboxylic acids or Ether carboxylic acids with 3 to 8 carbon atoms and their salts); Dyes; Inorganic substances (e.g. silicates, carbonates, bicarbonates, sulfates, Phosphates, phosphonates).
• polymers e.g. homo-, co- or plug copolymers unsaturated carboxylic acids and / or sulfonic acids and their alkali salts, Cellulose ether, starch, starch ether, polyvinylpyrrolidone
• Organic substances e.g. mono- or polyvalent
• the content of the coating substance is 1 to 30% by weight, preferably 5 to 15% by weight on coated activator granules.
• Mixers mechanically induced Fluidized bed
• fluidized bed apparatus pneumatically induced fluidized bed
• mixers e.g. Ploughshare mixer (continuous and in batches)
• ring-layer mixer or Schugi mixer possible.
• the Tempering can be done using a mixer in a granule preheater and / or in the mixer directly and / or in a downstream of the mixer Fluidized bed.
• Granulate coolers can be used to cool the coated granulate or fluid bed coolers can be used.
• the tempering takes place via the hot gas used for whirling up. That after The granulate coated by the fluidized bed process can be similar to the Mixer process cooled via a granulate cooler or a fluid bed cooler will. Both in the mixer process and in the fluidized bed process can the coating substance via a single-substance or a two-substance nozzle device be sprayed on.
• the tempering consists of 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. It is preferred to work at a temperature that is scarce is below the melting or softening temperature.
• the grain 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 tempering or the temperature difference to The melting point of the coating substance depends on the amount of coating Annealing time and the desired for the coated bleach activator granulate Properties and must be determined for the respective system in preliminary tests.
• the time for the annealing is approximately 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 that the liquid coating agent does not solidify too quickly and thus the possibility has to run as a thin film on the granulate surface.
• the individual droplets solidify too quickly on the cold granulate surface a.
• the surface is only covered with fine individual droplets and still has large coating defects.
• the desired coating effect is thus achieved insufficiently or a significantly higher amount of coating substance is required to achieve a desired coating effect. The latter but reduces the content of activator substance, which is often undesirable.
• the granules obtained in this way can be used directly in washing and Suitable detergents. They are ideal for use in heavy-duty detergents, Stain salts, machine dishwashing detergents, powdered all-purpose cleaners and denture cleaners.
• the invention Granules mostly used in combination with a hydrogen peroxide source. Examples include perborate monohydrate, perborate tetrahydrate and percarbonates as well as hydrogen peroxide adducts with urea or amine oxides.
• detergent ingredients such as organic or inorganic builders and Co-builders, surfactants, enzymes, washing additives, optical brighteners and perfume.
• Example 1 Coating in a Schugi mixer with a downstream fluid bed Tempering and cooling
• TAED 4303 (Hoechst AG) was continuously with a throughput of 480 kg / h metered into a Schugi mixer (Flexomix 160, Hosokawa Schugi) and sprayed with a melt of myristic acid at a temperature of 75 ° C.
• the coated Material fell directly into a downstream fluid bed (Hosokawa Schugi) and was there in a first chamber for 5 to 10 minutes at fluidized bed temperatures of annealed at approx. 54 ° C and then in a second chamber at fluidized bed temperatures cooled from approx. 35 ° C.
• TAED 4303 was used for comparison purposes (prior art) continuously with a throughput of 480 kg / h in the Schugi mixer dosed, sprayed with a 75 ° C melt of myristic acid and then directly in the downstream fluid bed at fluidized bed temperatures of approx. 35 ° C chilled.
• the coating quality of the products was determined by determining the speed of the Peracetic acid formation assessed at a temperature of 20 ° C. The slower that Peracetic acid formation is the better the degree of coating achieved.
• Peracetic acid formation rate of the TAED granules coated in a Schugi mixer with a downstream fluidized bed products 1 and 4: comparative examples
• Basic granulate (BG, not coated) 75 95 100 2nd BG + 10% myristic acid, annealed 11 21 55 3rd BG + 15% myristic acid, annealed 9 18th 54 4th BG + 15% myristic acid, chilled 39 59 83
• the coating quality can be expressed by the delay in the formation of peracetic acid, improve significantly (Comparison of products 3 and 4).
• Example 2 Coating according to the fluidized bed process with downstream Tempering
• 500 - 600 g TAED 4303 were in the fluidized bed (fluidized bed apparatus Strea 1, from Aeromatic) and with a melt of approx. 80 ° C Sprayed stearic acid. In one case, this was used for comparison purposes Fluidized bed operated at low temperatures and after finishing the Spray again after cooling for about 5 minutes (prior art). In the other The coated granulate fell again according to the method of the invention presented and tempered in the fluidized bed. This became the fluidized bed gradually heated to temperatures of about 65 to 70 ° C and this Product temperature for about 5 to 8 min. kept constant. Then that was annealed product gradually cooled again.
• TAED granules peracetic acid formed [%] 5 min 10 min 20 min 5 Basic granulate (BG) 75 95 100 6 BG + 10% stearic acid, annealed 10th 21 50 7 BG + 20% stearic acid, annealed 12th 22 52 8th BG + 10% stearic acid, untempered 70 85 98 9 BG + 20% stearic acid, untempered 40 60 84 10th BG + 30% stearic acid, untempered 20th 35 60
• the coating quality can be expressed by the delay in the formation of peracetic acid, improve significantly (Comparison of products 6 and 8 or products 7 and 9).
• tempering The influence of tempering on the coating quality is also evident in the Storage stability of TAED granules in detergent formulations.
• the storage stability was tested in prefabricated folding boxes (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 folding box 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 scotch tape. All samples were mixed and filled on the same day.
• the filled and labeled folding boxes were then placed at a sufficient distance from each other in the climate cabinet and stored at 38 ° C / 80% rh.
• the samples were removed from the climate chamber, and the entire sample was introduced at 20 ° C. into 1 l of distilled water with stirring using a magnetic stirrer (250 to 280 rpm) and 1 g of sodium percarbonate were added.
• the amount of peracetic acid formed was further determined analogously to the information in Example 1.
• the TAED content of the sample was then calculated from the maximum value of peracetic acid found.
• the degree of TAED maintenance represents the percentage TAED content of the sample after storage in relation to the TAED content of the unstored sample.
• Example 3 Coating using the fluidized bed process with simultaneous Tempering
• TAED 4303 was continuously fed at 40 kg / h via a flexible dosing screw the fluidized bed apparatus (technical fluidized bed apparatus) metered in and with 20% coated with myristic acid.
• the residence time in the fluidized bed was approximately 30 Minutes.
• the product discharged through a rotary valve was removed using a dosing screw on a screening machine, on which the coarse fraction of greater than 1.0 mm and the fine fraction of less than 0.2 mm separated were.
• the bulk was then crushed in a mill and then together with the fine portion via a flexible dosing screw in the Fluidized bed apparatus returned.
• the Fluid bed temperature increased from initially 46 ° C to finally 54 ° C.
• the coating quality was checked by determining the rate of formation of peracetic acid at a temperature of 20 ° C and the dust content of less than 0.2 mm of the coated TAED granules.
• the slower the formation of peracetic acid the better the degree of coating achieved.
• the lower the dust content the better the dedusting achieved by the coating and the higher the abrasion resistance.
• Peracetic acid formation rate of TAED granules coated in a fluidized bed process with simultaneous tempering (product 11: comparative example) Product no.
• Fluid bed temperature decreases the coating quality expressed by the delay of peracid formation, and you get a better dedusting and higher abrasion resistance, expressed by the decreasing proportion of dust ⁇ 0.2 mm of the coated granulate.
• Example 4 Coating in a ploughshare mixer with simultaneous tempering
• 1.2 kg of TAED granules according to EP-A-0 037 026 were in a batch ploughshare mixer (M5R, Fa. Lödige) and mixed with a The speed of the mixing tools is approx. 150 rpm with 210 g at 80 ° C Sprayed stearic acid melt.
• the mixer content was during the Coating step heated to a temperature of 50 ° C over a heating jacket.
• the coating and annealing time was approx. 10 minutes.
• WO-94/26826 1.2 kg TAED granules according to EP-A-0 037 026 in one Batch ploughshare mixer submitted and at room temperature with thorough mixing with a speed of the mixing tools of approx. 150 U / min with 210 g of an 80 ° C sprayed hot stearic acid melt.
• the coating quality was checked by determining the rate of formation of peracetic acid at a temperature of 20 ° C.
• Peracetic acid formation rate of TAED granules coated in a ploughshare mixer with tempering during the coating step products 16 and 18; comparative examples
• the coating can have a positive effect Achieve segregation behavior in the powder (product 18), but the improvement many other properties, here for example the delay of the Peracetic acid formation is only by tempering, i.e. by the invention Process possible (product 17).
• the positive effect on the segregation behavior caused by the coating without Annealing is probably due to the droplet-like solidification of the The coating substance can be attributed to the surface of the granules, causing them to get caught of the granules in the bulk material is effected. However, this is not a positive effect many other properties connected.
• Example 5 Coating in a ploughshare mixer with simultaneous tempering
• TAED 4303 was in continuous with throughputs from 100 to 300 kg / h dosed the ploughshare mixer (KT-160, Drais).
• the Mixer content via a heating jacket at temperatures in the range of 44 to 52 ° C tempered.
• 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 (closer to the product entry) injected.
• the coating amount was 7%.
• the mixer was at a speed of 90 rpm and the mixing tools operated without using the chopper knife.
• the degree of filling in the mixer was like this set that the product just covered the mixing shaft.
• the coated Material was continuously withdrawn from the mixer and directly through a sieve (0.2 to 1.0 mm) to separate fine and coarse particles.
• the coating quality was checked by determining the rate of formation of peracetic acid at a temperature of 20 ° C.
• Peracetic acid formation rate of TAED granules coated in a ploughshare mixer with simultaneous tempering product 19: comparative example
• Prod.No. TAED granules T mix [° C] Peracetic acid [%] 5 min 10 min 20 min 19th Basic granulate --- 75 95 100 20th BG + 7% stearic acid 44 72 95 99 21 BG + 7% stearic acid 48 70 90 98 22 BG + 7% stearic acid 52 60 80 94

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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)

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• 1996
  • 1996-10-10 DE DE19641708A patent/DE19641708A1/de not_active Withdrawn
• 1997
  • 1997-09-22 CA CA002216193A patent/CA2216193C/fr not_active Expired - Fee Related
  • 1997-09-25 ES ES97116693T patent/ES2276414T3/es not_active Expired - Lifetime
  • 1997-09-25 DE DE59712800T patent/DE59712800D1/de not_active Expired - Lifetime
  • 1997-09-25 EP EP97116693A patent/EP0835926B1/fr not_active Expired - Lifetime
  • 1997-10-07 US US08/939,170 patent/US6107266A/en not_active Expired - Lifetime
  • 1997-10-08 AR ARP970104657A patent/AR008887A1/es unknown
  • 1997-10-08 KR KR1019970051487A patent/KR100507515B1/ko not_active Expired - Fee Related
  • 1997-10-08 TW TW086114779A patent/TW418252B/zh not_active IP Right Cessation
  • 1997-10-08 HU HU9701617A patent/HUP9701617A3/hu unknown
  • 1997-10-09 PL PL97322521A patent/PL188368B1/pl not_active IP Right Cessation
  • 1997-10-09 CZ CZ19973198A patent/CZ294306B6/cs not_active IP Right Cessation
  • 1997-10-09 BR BR9704995A patent/BR9704995A/pt not_active Application Discontinuation
  • 1997-10-09 JP JP27750497A patent/JP4897988B2/ja not_active Expired - Fee Related
• 2000
  • 2000-07-21 US US09/621,492 patent/US6645927B1/en not_active Expired - Fee Related
• 2003
  • 2003-05-12 US US10/436,472 patent/US20030207784A1/en not_active Abandoned

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