EP1570040B1 - Procede ii de neutralisation a sec - Google Patents

Procede ii de neutralisation a sec Download PDF

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Publication number
EP1570040B1
EP1570040B1 EP03767728A EP03767728A EP1570040B1 EP 1570040 B1 EP1570040 B1 EP 1570040B1 EP 03767728 A EP03767728 A EP 03767728A EP 03767728 A EP03767728 A EP 03767728A EP 1570040 B1 EP1570040 B1 EP 1570040B1
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EP
European Patent Office
Prior art keywords
acid
fluidized bed
acids
process according
preferred
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EP03767728A
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German (de)
English (en)
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EP1570040A2 (fr
Inventor
Bernhard Orlich
Gerhard Blasey
Hans-Friedrich Kruse
Wilfried Rähse
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • 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
    • C11D11/0088—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 the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

  • the present invention relates to a process for the preparation of surfactant granules.
  • it relates to a process which makes it possible to produce easily soluble surfactant granules or detergent and cleaner compositions in a cost-optimized manner.
  • anionic surfactants fall in the course of the manufacturing process in their acid form and must be converted with suitable neutralizing agents in their alkali or alkaline earth metal salts.
  • This neutralization step can be carried out with solutions of alkali metal hydroxides or else with solid alkaline substances, in particular sodium carbonate.
  • the surfactant salts are obtained in the form of aqueous formulations, wherein water contents in the range of about 10 to 80 wt .-% and in particular in the range of about 35 to 60 wt .-% are adjustable.
  • products of this type have paste-like to cuttable properties, the flowability and pumpability of such pastes being restricted or even lost even in the range of about 50% by weight of active substance, so that further processing of such pastes, in particular during their incorporation in Solid mixtures, for example, in solid detergents and cleaning agents, considerable problems arise.
  • anionic detergent surfactants in a dry, in particular free-flowing form.
  • FAS fatty alcohol sulfates
  • European patent application EP-A-0 678 573 (Procter & Gamble) describes a process for producing free-flowing surfactant granules having bulk densities above 600 g / l in which anionic surfactant acids with an excess of neutralizing agent form a paste containing at least 40% by weight of surfactant be reacted and this paste with one or more powder (s), at least one of which must be spray-dried and contains the anionic polymer and cationic surfactant is mixed, wherein the resulting granules can be optionally dried.
  • this document reduces the proportion of spray-dried granules in the detergents and cleaners, but does not completely avoid the spray-drying.
  • European Patent Application EP-A-0 438 320 discloses a batch process for the preparation of surfactant granules having bulk densities above 650 g / l.
  • a solution of an alkaline inorganic substance in water, with the possible addition of other solids is mixed with the anionic surfactant acid and granulated in a high-speed mixer / granulator with a liquid binder.
  • neutralization and granulation are carried out in the same apparatus, but in separate process steps, so that the process can only be operated batchwise.
  • European patent application EP-A-0 402 112 discloses a continuous neutralization / granulation process for producing FAS and / or ABS granules from the acid in which the ABS acid is at least 62% pure NaOH is neutralized and then granulated with the addition of auxiliaries, for example ethoxylated alcohols or alkylphenols or a above 48.9 ° C melting polyethylene glycol having a molecular weight between 4000 and 50,000.
  • auxiliaries for example ethoxylated alcohols or alkylphenols or a above 48.9 ° C melting polyethylene glycol having a molecular weight between 4000 and 50,000.
  • European Patent Application EP-A-0 508 543 discloses a process in which a surfactant acid is neutralized with an excess of alkali to form an at least 40 wt% surfactant paste, which is subsequently conditioned and granulated, with a Direct cooling with dry ice or liquid nitrogen takes place.
  • the liquid surfactant mixtures disclosed in this document contain sodium or potassium salts of alkylbenzenesulfonic acids or alkylsulfuric acids in amounts of up to 80% by weight, ethoxylated nonionic surfactants in amounts of up to 80% by weight and at most 10% by weight of water.
  • the surfactant mixtures to be sprayed contain between 40 and 92% by weight of a surfactant mixture and more than 8 to at most 60% by weight of water.
  • the surfactant mixture is in turn at least 50% of polyalkoxylated nonionic surfactants and ionic surfactants.
  • a process for producing a liquid surfactant mixture from the three components anionic surfactant, nonionic surfactant and water is described in EP 507 402 (Unilever).
  • the surfactant blends disclosed herein, which are said to contain little water, are prepared by combining equimolar amounts of neutralizing agent and anionic surfactant acid in the presence of nonionic surfactant.
  • German laid - open specification DE-A-42 32 874 discloses a process for preparing washing and cleaning-active Anionentensidgranulate by neutralization of anionic surfactants in their acid form.
  • a neutralizing agent solid powdery substances, in particular sodium carbonate, disclosed here, which reacts with the anionic surfactant to anionic surfactant, carbon dioxide and water.
  • the granules obtained have surfactant contents of about 30% by weight and bulk densities of less than 550 g / l
  • the European patent application EP 642 576 (Henkel KGaA) describes a two-stage granulation in two successive mixers / granulators, wherein in a first, low-speed granulator 40-100 wt .-%, based on the total amount of the ingredients used, the solid and liquid components vorgranuliert and in a second, high-speed granulator, the pregranulate is optionally mixed with the remaining ingredients and transferred into a granule.
  • German Offenlegungsschrift DE-A-43 14 885 discloses a process for preparing washing and cleaning-active Anionentensidgranulate by neutralization of the acid form of anionic surfactants with a basic compound, wherein the hydrolysis-sensitive acid form of a hydrolysis-sensitive anionic surfactant with the neutralizing agent without release of Water is converted.
  • the neutralizing agent used is sodium carbonate, which reacts in this process to form sodium bicarbonate.
  • US-A-5 929 021 describes a process for preparing a granular detergent or cleaning composition or component having a bulk density of between 300 and 1300 g / l, comprising mixing a particulate starting material in a low or high speed mixer / graniator, adding a liquid binder to the mixer / granulator and subjecting the obtained mixture to partial granulation to produce a partially granulated mixture, transferring the partially granulated mixture to a fluidized bed or a rotating bowl mixer / granulator, adding further liquid binder to the mixture for a sufficient time to allow granulation to complete and thereby obtain the granular powder composition of desired bulk density.
  • the process to be provided should also allow the direct and economically attractive processing of the acid forms of detergent raw materials, but avoid the disadvantage of energy-consuming evaporation of water or the use of energy-consuming high-speed mixer or high shear mixer as much as possible.
  • the bulk densities of the granules to be produced should be variable within wide limits, and it was a particular object of the present invention to be able to achieve the low bulk densities of conventional spray-drying products by means of a non-tower process.
  • the end products are superior to the products which can be prepared by prior art processes; in particular, the bulk density of the end products should be adjustable by the process control. Furthermore, the end products of the process according to the invention should have a high solubility.
  • rotary reactors are those mixers which are characterized by a movable or rotating reactor housing or a moving mixing vessel. Such reactors can furthermore comprise static and / or mobile mixing and / or cutting tools, but preference is given to rotating reactors in which the mixture is taken up by wall friction and then falls freely through the mixer space due to its own gravitational force.
  • Preferred mixing containers also have as obtuse-angled inner corners, as this both the free movement of the mix than The movement of the container is preferably transferred to the mix in the interior, that as irregular as possible cluttering and loosening of the reaction mixture takes place continuous process according to the invention on a directed component of motion in order to ensure the continuous mass transfer.
  • the types of movement for the free-fall mixer are, in particular, rotation about a container axis (drum or rotary tube mixer) or about axes that do not coincide with geometric axes of the container or perpendicular to its symmetry planes (tumble mixer), or vibrate, preferably with high amplitude and low frequency and changing directions of the rashes, so the irregular shaking or tumbling movements occur.
  • the solid support material moved in the rotating reactor forms a falling powder curtain, wherein the first portion of the liquid binder introduced in step i) of the process according to the invention is preferably sprayed onto this powder curtain.
  • Rotary reactors which are preferred in the context of the present invention are free-fall mixers, preferably drum mixers, tumble mixers, cone mixers, double-cone mixers or V mixers.
  • the free-fall mixers used in accordance with the invention provide, in the case of rotating or tumbling movements, walls alternately upraised and falling back inside, and thus diversion, widening or narrowing of the space, displacement and division of the material flow.
  • Such mixers may have fixed internals for better loosening of the mix (eg lift rails), however, unlike the conventional high or low speed mixers of the prior art, preferred mixers have no mixing or cutting tools.
  • double-cone mixers with rotatable containers without mixing tools are used as free-fall mixers, the double-cone mixers being subdivided into a mixing zone and a post-mixing zone and having a knock-off strip which is fastened to an end plate and from there passes through the entire mixing zone and optionally extends into the post-mixing zone.
  • the ratio of the length of the mixing zone to the length of the post-mixing zone is preferably at least 1: 1.
  • the tee bar may have a width of 50 to 150 mm, preferably from 75 to 130 mm.
  • the top edge of the stripper has a distance from the internal mixer wall which is preferably at most 10% of the drum diameter of the narrowest point of the rotatable container, preferably at most 5% of the narrowest point of the rotatable container and more preferably less than 2.5% of the narrowest point of the rotatable container Container.
  • the distance to the nearest inner mixer wall may well be greater than in the mixing zone; Values between 100 and 300 mm are quite common.
  • the rotatable container of the tumbler mixer has an inclination angle ⁇ of 0 to 20 °, in particular from 0 to 15 °, most preferably from 1 to 15 ° and the movement of the rotatable container of the tumbler over the drive is set simultaneously to 20 to 70 revolutions per minute and in particular to 30 to 60 revolutions per minute.
  • the residence time of the reaction mixture in the rotatable container in preferred embodiments of the present inventive method is preferably less than 20 minutes, preferably between 1 and 600 seconds, more preferably between 1 and 300 seconds and in particular between 1 and 120 seconds.
  • the velocity of the solid in the rotating reactor is preferably between 0.2 and 20 m / sec, particularly preferably between 0.4 and 15 m / sec, very particularly preferably between 0.8 and 7 m / sec and in particular between 1.5 and 3 m / sec.
  • the reaction mixture After passing through the post-mixing zone, the reaction mixture is converted into a fluidized bed in the process according to the invention.
  • the transfer of the reaction mixture can be carried out for example via a conveying device. If this conveying and metering screw leads into the post-mixing zone (a direct connection of the conveying device to the discharge unit is also possible), then it is preferred that the screw only projects maximally into the second length half of the post-mixing zone and thus not into the part of the post-mixing zone that still includes the tee bar.
  • the fluidized bed may be both a mechanical and a pneumatic fluidized bed.
  • processes according to the invention in which the fluidized bed in step ii) is a pneumatic fluidized bed are preferred.
  • the movement of the mixture components is generated by blowing air into the initially stationary mixture.
  • the operation of these fluidized bed apparatuses can be continuous and discontinuous.
  • the air is preferably blown through the perforated porous floor.
  • the bulk density of the partially granulated mixture entering the pneumatic fluidized bed is preferably between 300 and 700 g / l, more preferably between 350 and 650 g / l and in particular between 400 and 600 g / l.
  • the air enters through the porous soil, preferably at least at the rate of loosening. From the initial fixed bed is formed the fluidized bed, the fluidized bed, which due to the easy mobility of the particles has continuum properties similar to a liquid.
  • the mix is preferably almost cohesive.
  • the temperature of the cold air used is in preferred process variants less than 15 ° C, preferably less than 13 ° C and especially less than 10 ° C.
  • the temperature of the hot air has values above 28 ° C., preferably above 35 ° C., particularly preferably above 40 ° C. and in particular above 50 ° C.
  • a second portion of a liquid binder is sprayed onto the fluidized bed formed in the fluidized bed by means of a spray device.
  • the fluidized bed in step iii) has a depth of between 2 and 100 cm, preferably between 4 and 80 cm, more preferably between 8 and 60 cm and in particular between 10 and 40 cm.
  • the spraying can be carried out by means of single-component or high-pressure spray nozzles, two-component spray nozzles or three-component spray nozzles.
  • single-substance spray nozzles the application of a high melt pressure (5-15 MPa) is required, while the spraying in two-component spray nozzles by means of a compressed air stream (at 0.15-0.3 MPa) takes place.
  • spraying with two-component spray nozzles is more favorable, in particular with regard to possible clogging of the nozzle, but is more complicated due to the high compressed air consumption.
  • the three-component spray nozzles which in addition to the Preßluftstrom for atomization another air ducting system to prevent clogging and dripping at the nozzle.
  • the use of two-component spray nozzles preferably two-component spray nozzles with a fluid bore of between 2 and 6 mm, in particular between 3 and 5 mm, is particularly preferred.
  • the preferred distance of the spray device from the bottom plate of a fluidized bed preferably used in step iii) is at least 30 cm, preferably at least 60 cm, more preferably at least 80 cm and in particular at least 100 cm.
  • the spray head of the spraying device is located above the surface of the fluidized bed.
  • the distance of the spray device from the surface of the fluidized bed in step iii) is at least 10 cm, preferably at least 30 cm and in particular at least 50 cm.
  • the distance of the spray device from the surface of the fluidized bed is between 15 and 140 cm, preferably between 20 and 130 cm, in particular between 30 and 120 cm and in particular between 40 and 110 cm. It has been found that the product properties, such as the solubility or bulk density of granules produced according to the invention, can be advantageously influenced in particular by the distance of the spray device from the surface of the fluidized bed.
  • the drop diameter of the liquid binder sprayed on is preferably between 1 and 100 ⁇ m, particularly preferably between 2 and 80 ⁇ m, very particularly preferably between 4 and 70 ⁇ m and in particular between 8 and 60 ⁇ m.
  • the temperature of the sprayed binder is preferably between 20 and 70 ° C, preferably between 25 and 60 ° C, more preferably between 30 and 55 ° C and in particular between 40 and 50 ° C.
  • the advantages of the process according to the invention can be realized in particular by those preferred process variants in which the surface load of the fluidized bed through the sprayed binder in step iii) of the process is between 0.0001 and 2.0 kg / (m 2 s), preferably between 0.001 and 2.0 kg / (m 2 s), more preferably between 0.002 and 2.0 kg / (m 2 s) and in particular between 0.004 and 2.0 kg / (m 2 s).
  • the volume loading of the fluidized bed by the sprayed binder in step iii) is in preferred variants of the method according to the invention between 0.0001 and 6, 0 kg / (m 3 s).
  • the liquid binder in the process according to the invention is fed to the solid support material in two portions.
  • the first portion of the liquid binder in step i) is from 55 to 90% by weight, preferably between 65 and 90% by weight, more preferably between 76 and 90% by weight. % and in particular between 80 and 90 wt .-% of the total liquid binder used.
  • the binder addition process products are obtained, which are characterized by an optimized solubility and a low bulk density in the range of 300 to 700 g / l.
  • Preferred processes according to the invention are further characterized in that the bulk density of the granulation mixture after exiting the pneumatic fluidized bed is between 300 and 700 g / l, preferably between 400 and 700 g / l and in particular between 500 and 650 g / l.
  • liquid binders are reacted with solid support materials.
  • Particularly suitable liquid binders are anionic surfactant acids.
  • the liquid binders used are anionic surfactant acid (s), preferably one or more substances from the group of carboxylic acids, sulfuric acid half esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylaryl sulfonic acids. in particular from the group of C 8-16 -, in particular of C 9-13 -alkylbenzenesulfonic acids, used. These are described below.
  • the compounds mentioned should have longer-chain hydrocarbon radicals, ie at least 6 carbon atoms in the alkyl or alkenyl radical.
  • the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.
  • Carboxylic acids which are used in the form of their alkali metal salts as soaps in detergents and cleaners, are obtained industrially, for the most part, from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage.
  • hexanoic acid caproic acid
  • heptanoic acid enanthic acid
  • octanoic acid caprylic acid
  • nonanoic acid pelargonic acid
  • decanoic acid capric acid
  • undecanoic acid etc.
  • fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and unsaturated Sezies 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroseiaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-o
  • Such mixtures are for example coconut oil (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 , 1% by weight C 18 " ), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight C) 12 , 15 wt .-% C 14 , 7 wt .-% C 16 , 2 wt .-% C 18 , 15 wt .-% C 18 , 1 wt .-% C 18 " ), Tallow fatty acid (about 3% by weight C 14 , 26% by weight C 16 , 2% by weight C 16 , 2% by weight C 17 , 17% by weight C 18 , 44% by weight C 18 ' , 3 wt .-
  • Sulfuric acid semi-esters of relatively long-chain alcohols are likewise anionic surfactants in their acid form and can be used in the context of the process according to the invention.
  • Their alkali metal salts, in particular sodium salts, the fatty alcohol sulfates are industrially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur trioxide to the respective alkyl sulfuric acids and subsequently neutralized.
  • the fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters.
  • alkylsulfuric acids The quantitatively most important industrial process for the production of fatty alkylsulfuric acids is the sulfation of the alcohols with SO 3 / air mixtures in special cascade, falling film or tube bundle reactors.
  • anionic surfactant acids which can be used in the process according to the invention are the alkyl ether sulfuric acids whose salts, the alkyl ether sulfates, are characterized by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates.
  • Alkyl ether sulfuric acids like the alkyl sulfuric acids, are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the relevant alkyl ether sulfuric acids.
  • Alkane sulfonic acids and olefin sulfonic acids can also be used in the context of the present invention as anionic surfactants in acid form.
  • Alkanesulfonic acids may contain the sulfonic acid group terminally attached (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), with only the secondary Alkanesulfonic acids have commercial significance. These are prepared by sulfochlorination or sulfoxidation of linear hydrocarbons.
  • Another process for producing alkanesulfonic acids is sulfoxidation in which n-paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation.
  • This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylsulfonyl radicals.
  • the reaction with unreacted paraffin provides an alkyl radical and the alkylpersulfonic acid which decomposes into an alkyl peroxysulfonyl radical and a hydroxyl radical.
  • the reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid.
  • this reaction is usually carried out only up to degrees of conversion of 1% and then terminated.
  • Olefinsulfonates are produced industrially by reaction of ⁇ -olefins with sulfur trioxide. Intermediate zwitterions form, which cyclize to form so-called sultones. Under suitable conditions (alkaline or acid hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkensulfonic acids, both of which can likewise be used as anionic surfactant acids.
  • Alkyl benzene sulfonates as powerful anionic surfactants have been known since the thirties of our century. At that time, monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation produced alkylbenzenes which were sulfonated with oleum and neutralized with sodium hydroxide solution.
  • Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins.
  • large-scale petroleum fractions are separated with molecular sieves in the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both ⁇ - and i-olefins.
  • ABSS alkylbenzenesulfonic acid
  • alkylbenzenesulfonic acids whose alkylbenzenes were prepared by the HF process, so that the C 8-16 -, preferably C 9-13 -alkyl benzene sulfonic acids used have a content of 2-phenyl isomer of less than 22% by weight. , based on the alkylbenzenesulfonic acid.
  • anionic surfactants in their acid form may be used alone or in admixture with each other in the process of the present invention.
  • the anionic surfactant in acid form before addition to the solid neutralizing agent (s) further, preferably acidic, ingredients of detergents and cleaners in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the anionic surfactant acid-containing mixture, are admixed.
  • Suitable liquid binders in the context of the present invention are also the fatty acids, phosphonic acids, polymer acids or partially neutralized polymeric acids and "builder acids” and “complex builder” acids alone and in any desired mixtures.
  • ingredients of detergents and cleaners which can be added, for example, the anionic surfactant prior to foaming, offer especially acid detergent ingredients on, so for example phosphonic acids, which are in neutralized form (phosphonates) as incrustation inhibitors part of many detergents and cleaners.
  • the use of (partially neutralized) polymer acids such as polyacrylic acids, according to the invention is possible. But it is also possible to mix acid-stable ingredients with the anionic surfactant acid.
  • small components which would otherwise have to be added in complicated further steps, so for example optical brightener, dyes, etc., in which case the acid stability is to be checked.
  • the anionic surfactant in acid form nonionic surfactants in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the anionic surfactant acid-containing Mixture, mixed.
  • This addition can improve the physical properties of the anionic surfactant-containing mixture and make subsequent incorporation of nonionic surfactants into the surfactant granules or the entire detergent and cleaning agent superfluous.
  • the different representatives from the group of nonionic surfactants are described below.
  • the temperature of the mixture to be applied as low as possible is.
  • the liquid binder has a temperature of 20 and 70 ° C., preferably between 25 and 60 ° C., more preferably between 30 and 55 ° C. and in particular between 40 and 50 ° C., when introduced into the free-fall mixer.
  • liquid, acidic component refers to the anionic surfactant acid, which optionally comprises further acidic components.
  • the preferred reaction between anionic surfactant (s) and sodium carbonate is carried out so that the reaction Na 2 CO 3 + 2 anionic surfactant H ⁇ 2 anionic surfactant Na + CO 2 + H 2 O is largely suppressed and in their place the reaction Na 2 CO 3 + anionic surfactant H ⁇ anionic surfactant Na + NaHCO 3 entry.
  • the sodium carbonate is used here in excess, so that unreacted sodium carbonate remains in the product, while sodium bicarbonate is additionally formed in the reaction.
  • the amount of sodium carbonate on average (based on the agent, without taking into account any water of hydration present) is in relation to the amount of sodium bicarbonate on average (based on the agent, without taking into account any water of hydration present) in relation to the invention and must be 5: 1 or more.
  • per gram of NaHCO 3 contained in the process products according to the invention at least 5 grams of Na 2 CO 3 are included.
  • the mass ratio of sodium carbonate to sodium bicarbonate is within narrow limits, and in preferred processes according to the invention the weight ratio of sodium carbonate to sodium bicarbonate in the process end products is 50: 1 to 2: 1, preferably 40: 1 to 2.1: 1, particularly preferably 35: 1 to 2.2: 1 and in particular 30: 1 to 2.25: 1.
  • the content of the inventively preferred means of sodium bicarbonate may vary.
  • the content of the process end products of sodium hydrogencarbonate is from 0.01 to 20% by weight, preferably from 0.1 to 15% by weight, particularly preferably from 0.5 to 10% by weight and in particular from 1 to 10% by weight. -%, in each case based on the total weight of the process end products.
  • the neutralized form of the anionic surfactant acids in short the anionic surfactants, may also be included in varying amounts in the compositions made by the process of the present invention.
  • Suitable anionic surfactant acids are all acids known from the prior art. These have been described in detail above.
  • Preferred processes according to the invention are characterized in that the content of neutralized anionic surfactant acid in the process products is at most 50% by weight, preferably 8 to 42% by weight, particularly preferably 10 to 35% by weight and in particular 15 to 25% by weight. is.
  • the agents prepared by the process according to the invention can have different bulk densities depending on the content of the individual ingredients and other process parameters. Preference is given to processes according to the invention in which the bulk density of the process end products is 300 to 800 g / L, preferably 330 to 650 g / L, particularly preferably 350 to 550 g / L and in particular 400 to 500 g / L.
  • the process products according to the invention preferred method further have a particle size distribution with a mean particle size d 50 below 5000 microns, preferably between 20 and 3000 microns, more preferably between 40 and 2000 microns and in particular between 50 and 1600 microns.
  • the process end products of the process according to the invention are preferably low in water and are preferably characterized by water content, determined by loss of drying at 120 ° C., of less than 15% by weight, preferably less than 10% by weight, particularly preferably less than 5% by weight. -% and in particular of less than 2.5 wt .-%, each based on the total weight of the process end products after leaving the fluidized bed, from.
  • the water content of the process end products preferably ⁇ 15 wt .-%, preferably ⁇ 10 wt .-%, more preferably ⁇ 5 wt .-% and in particular ⁇ 2.5 wt .-%.
  • the low-water process procedure to ensure the desired reaction to sodium bicarbonate is preferred.
  • the raw materials used should therefore be used as far as possible dry, dry or water-poor.
  • Both Anionic surfactant acids are preferred according to the invention to select the highest possible concentrations, as long as the technical process control (moving the anionic surfactant and applying to the sodium carbonate) is properly guaranteed.
  • Another way to promote the formation of sodium bicarbonate and to avoid the formation of carbon dioxide and water is to maintain the lowest possible temperatures. This can be achieved, for example, by cooling, but also by suitable process control or the coordination of the amounts of the reactants.
  • the process according to the invention is based on the reaction or granulation of liquid binders with solid support materials.
  • anionic surfactant acid and sodium carbonate are reacted with each other.
  • other substances may also be present in the reaction mixture which may or may not be involved in the reaction.
  • reactive or inert species may be admixed with either the sodium carbonate or the anionic surfactant acid (s) prior to the reaction; Alternatively, both reactants may contain other reactive or inert ingredients.
  • the sodium carbonate It is preferred in the context of the present invention to admix further ingredients, in particular further preferably solid carrier materials, to the sodium carbonate.
  • This mixture forms the solid bed to which the anionic surfactant acid (s) is / are added - optionally in admixture with other substances.
  • further neutralizing agents can be admixed with the sodium carbonate, solid neutralizing agents being preferred.
  • Aqueous solutions of neutralizing agents can also be applied to the sodium carbonate, as long as the overall water balance of the process (the water content of the final process products) is not burdened beyond said limits. Therefore, the use of low-water or even completely-free raw materials is preferred.
  • the solid support materials additionally comprise one or more substances from the group Sodium hydroxide, sodium sesquicarbonate, potassium hydroxide and / or potassium carbonate.
  • solid support materials carriers which do not take part in the reaction may also be added to the sodium carbonate. These should then have sufficient stability against the added acids to avoid local decomposition and thus unwanted discoloration or other loading of the product.
  • sodium sulfate which is still present today in some countries up to 45 wt .-% in the detergents, the / the solid neutralizing agents is added.
  • reaction mixture can during and / or after the turbulence in step iii) of the method according to the invention further substances are added.
  • addition of powdering agents or surface modifiers is preferred.
  • Amorphous and / or crystalline aluminosilicates such as zeolite A, X and / or P, various types of silicas, calcium stearate, carbonates, sulfates, but also finely divided compounds, for example of amorphous silicates and carbonates, are preferred here.
  • Preferred processes according to the invention are characterized in that the granulation mixture is after-treated after emerging from the pneumatic fluidized bed.
  • the liquid binders used in process steps i) and / or iii) may contain further constituents in addition to the abovementioned anionic surfactants which are preferably used.
  • These other preferred binders include aqueous Polymer solutions or dispersion as well as aqueous solutions of water glass.
  • aqueous polymer solutions particular preference is given to aqueous solutions or dispersions of homo- or copolymers of acrylic acid, in particular polyacrylates and / or copolymers of acrylic acid with methacrylic acid and / or copolymers of acrylic acid with maleic acid. More detailed descriptions of the preferably used polyacrylates such as the copolymeric polycarboxylates can be found below in the text.
  • the surfactant granules prepared by the process according to the invention are particularly suitable for the production of detergents or cleaners, in particular solid detergents or cleaners, for example by further agglomeration, by extrusion or compaction.
  • Such washing or cleaning agents contain in addition to the previously mentioned ingredients such as the anionic surfactants other ingredients, especially from the group of builders, co-builders, bleach, bleach activators, dyes and fragrances, optical brighteners, enzymes, soil-release polymers, etc. These substances are described below for the sake of completeness.
  • Builders are used in detergents or cleaners especially for binding calcium and magnesium.
  • Usual builders which are preferred in the context of the invention in amounts of 22.5 to 45 wt .-%, preferably from 25 to 40 wt .-% and in particular from 27.5 to 35 wt .-%, each based on the total agent which also contains the process end products of the process according to the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates.
  • trisodium citrate and / or pentasodium tripolyphosphate and silicatic builders from the class of alkali metal isilicates.
  • the potassium salts are preferable to the sodium salts because they often have a higher water solubility.
  • Preferred water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium water glasses.
  • Washing or cleaning agents may contain as builders phosphates, preferably alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate).
  • builders phosphates preferably alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate).
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits and also contribute to the cleaning performance.
  • the detergents or cleaning agents may contain condensed phosphates as water-softening substances. These substances form a group of - because of their production also mentioned melting or annealing phosphates - phosphates, which can be derived from acidic salts of orthophosphoric acid (phosphoric acids) by condensation.
  • the condensed phosphates can be classified into the metaphosphates [Mnn (PO 3 ) n ] and polyphosphates (M l n + 2 P n O 3n + 1 or M l n H 2 P n O 3n + 1 ).
  • Metaphosphates are obtained as impurities of the - mistakenly referred to as sodium hexametaphosphate - Graham's salt by melting of NaH 2 PO 4 to temperatures above 620 ° C, wherein also intermediately so-called Maddrell's salt is formed.
  • This and Kurrolsches salt are linear polyphosphates, which are usually not one of the metaphosphates today, but also in the context of the present invention are also used with preference as water-softening substances.
  • the quenched, glassy melt is, depending on the reaction conditions, the water-soluble Graham's salt, (NaPO 3 ) 40-50 , or a glassy condensed phosphate of the composition (NaPO 3 ) 15-20 , known as Calgon.
  • the misleading term hexametaphosphate is still in use.
  • Kurrol's salt (NaPO 3 ) n with n »5000, is also produced from the 600 ° C hot melt of Maddrell's salt, if this is left for a short time at about 500 ° C. It forms high polymer water-soluble fibers.
  • Suitable silicate builders are the crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle.
  • Such so-called X-ray amorphous silicates likewise have a dissolution delay compared with the conventional water glasses.
  • Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the usable finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP ® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2-2.5) SiO 2 • (3.5-5.5) H 2 O can be described.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Acidifying agents are both inorganic acids and organic acids, provided that they are compatible with the other ingredients.
  • the solid mono-, oligo- and polycarboxylic acids are used. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, Fumaric acid, oxalic acid and polyacrylic acid.
  • the anhydrides of these acids can be used as Acidisersstoff, in particular maleic anhydride and succinic anhydride are commercially available.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • a commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight).
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.
  • Customary and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines; Ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • complex-forming polymers ie polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and react with suitable metal atoms usually with the formation of chelate complexes, can be used according to the invention.
  • the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
  • Complexing groups (ligands) of conventional complexing polymers are iminodiacetic, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific. Activities towards ions of different metals.
  • Base polymers of many also commercially significant Complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethylenimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.
  • polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5.
  • Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA are preferred.
  • these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts.
  • alkali metal, ammonium or alkylammonium salts, in particular sodium salts are preferred.
  • Scale inhibiting polymers may also be included in detergents or cleaners. These substances, which could be constructed chemically different, for example, from the groups of low molecular weight polyacrylates having molecular weights between 1000 and 20,000 daltons, with polymers having molecular weights below 15,000 daltons are preferred.
  • Scale-inhibiting polymers may also have co-builder properties.
  • Organic cobuilders which can be used in the compositions which comprise the process end products according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, this group can again be the short chain polyacrylates, the molar masses of 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, may be preferred.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • compositions according to the invention may contain further customary ingredients of cleaning agents, in particular bleaching agents, bleach activators, enzymes, dyes and fragrances being of importance. These substances will be described below.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Detergents or cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenz-amidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidoper-succinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9
  • Chlorine or bromine releasing substances can also be used as bleaching agents in automatic dishwashing agents.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • Bleach activators aid the action of the bleaching agents.
  • Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morph
  • bleach catalysts can also be present in the agents according to the invention.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Bleach activators from the group of the polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred -Methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOS
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt % to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.
  • Detergents or cleaning agents may contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5 percent by weight, based on active protein. The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method.
  • BCA method bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid
  • subtilisin type examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
  • subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvaerd, Denmark.
  • subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ® variants are derived.
  • proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, that under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
  • Examples of usable amylases are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens or B. stearothermophilus and their further developments for use in detergents and cleaners.
  • the enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST.
  • Development products of this ⁇ -amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
  • amyloliquefaciens is marketed by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, likewise from Novozymes.
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); Likewise, fusion products of said molecules can be used.
  • Detergents or cleaners may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also to generate in situ peracids from suitable precursors.
  • lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®.
  • the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens .
  • lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase® , Lipase AP® , Lipase M- AP® and Lipase AML® are available. From the company Genencor, for example, the lipases, or cutinases can be used whose Ranzyme originally isolated from Pseudomonas mendocina and Fusarium solanii .
  • Detergents or cleaners especially those intended for the treatment of textiles, may contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components complement each other advantageously with regard to their various performance aspects.
  • These performance aspects include, in particular, contributions to the primary washing performance, the secondary washing performance of the composition (anti-redeposition effect or graying inhibition) and softening (fabric effect), up to the exercise of a "stone washed" effect.
  • EG endoglucanase
  • Novozymes under the trade name Celluzyme ®.
  • the products Endolase® ® and Carezyme ® likewise available from Novozymes, are based on the 50 kD EG and 43 kD EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ® and Renozyme ®.
  • the 20 kD EG cellulase from Melanocarpus from AB Enzymes, Finland available under the trade names Ecostone® ® and Biotouch ®, can be used.
  • Suitable mannanases for example, under the name Gamanase ® and Pektinex AR ® by the company Novozymes, under the name Rohapec ® B1 L from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, USA.
  • the obtained from B. subtilis ⁇ -glucanase is available under the name Cereflo ® from Novozymes.
  • Detergents and cleaning agents may contain oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) to increase the bleaching effect , Suitable commercial products Denilite® ® 1 and 2 from Novozymes should be mentioned.
  • organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
  • the enzymes used in detergents or cleaning agents either originate from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • the purification of the relevant enzymes is conveniently carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
  • Detergents or detergents may be added to the enzymes in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer.
  • further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
  • a protein and / or enzyme contained in a detergent or cleaning agent can be protected especially during storage against damage such as inactivation, denaturation or disintegration such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or disintegration such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • stabilizers can be used for this purpose.
  • One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, or their salts or esters. Furthermore, peptide aldehydes, that is oligopeptides with reduced C-terminus are suitable. As peptidic protease inhibitors are, inter alia, ovomucoid and leupeptin to mention; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and - propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates can also be used as stabilizers.
  • Lower aliphatic alcohols but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers.
  • di-glycerol phosphate protects against denaturation by physical influences.
  • calcium salts are used, such as calcium acetate or calcium formate and magnesium salts.
  • Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or, such as cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
  • Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors.
  • Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes.
  • Alkylpolyglycosides can stabilize in accordance with the also the enzymatic components of the agent according to the invention and even increase their performance.
  • Crosslinked N-containing compounds perform a dual function as soil release agents and as enzyme stabilizers.
  • Reducing agents and antioxidants such as sodium sulfite or reducing sugars enhance the stability of the enzymes to oxidative degradation.
  • combinatons of stabilizers are used, for example of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.
  • the effect of peptide-aldehyde stabilizers can be enhanced by combination with boric acid and / or boric acid derivatives and polyols and further enhanced according to the additional use of divalent cations, such as calcium ions.
  • liquid enzyme formulations Particularly preferred in the context of the present invention is the use of liquid enzyme formulations.
  • the additional enzymes and / or enzyme preparations preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of 1 to 5 wt .-%, preferably from 1.5 to 4.5 and in particular from 2 to 4 wt .-%, each based on the total agent to use.
  • Dyes and fragrances can be added to detergents or cleaners to improve the aesthetic appearance of the resulting products and to provide the consumer with a visual and sensory "typical and unmistakable" product in addition to performance.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are known e.g.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g.
  • the linear alkanals having 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the ionones, ⁇ -isomethylionone and methylcedryl ketone, among the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrance oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • the fragrances can be incorporated directly into the compositions, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and by slower release of fragrance for long-lasting Fragrance of the textiles provide.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • dyes In order to improve the aesthetic impression of the washing or cleaning agents, it (or parts thereof) can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic dishes, not to stain them.
  • Detergents or cleaning agents may contain as optical brighteners derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g.
  • the process end products of the process according to the invention can not only be mixed with particulate detergents or cleaners, but can also be used in detergent tablets. Surprisingly, the solubility of such tablets improved by the use of the process end products of the method according to the invention in comparison to the same hard and identically composed tablets, which do not include end products of the method according to the invention.
  • Another object of the present invention is therefore the use of the process end products of the process according to the invention for the production of detergents, in particular detergent tablets.
  • washing and cleaning active moldings is done by applying pressure to a mixture to be pressed, which is located in the cavity of a press.
  • the mixture to be tableted is injected directly, i. pressed without previous granulation.
  • the advantages of this so-called Maistablett ist are their simple and cost-effective application, since no further process steps and consequently no other systems are needed. However, these advantages are also faced with disadvantages.
  • a powder mixture, which is to be tabletted directly have sufficient plastic deformability and have good flow properties, furthermore, it must not show any separation tendencies during storage, transport and filling of the die.
  • detergent tablets are pulverulent components which are agglomerated or granulated by suitable processes to give secondary particles having a relatively high particle diameter. These granules or mixtures of different granules are then mixed with individual powdered additives and fed to the tableting. In the context of the present invention, this means that the process end products of the process according to the invention are worked up to a premix with further ingredients, which may also be present in granular form.
  • the premix Before the particulate premix is compressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This may be advantageous for the nature and physical properties of both the premix (storage, compression) and the finished detergent tablets. Fine particulate powdering agents are well known in the art, with mostly zeolites, silicates or other inorganic salts are used. Preferably, however, the premix is "powdered” with finely divided zeolite, with faujasite-type zeolites are preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structural group 4 (cf. Donald W.
  • Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which need not necessarily belong to the zeolite structure group 4, can be used as a powdering agent, it being advantageous if at least 50 wt .-% of the powdery powder of a zeolite of faujasite Type persist.
  • detergent tablets which consist of a particulate premix containing granular components and subsequently admixed pulverulent substances, the one or more subsequently admixed pulverulent components comprising a faujasite-type zeolite having particle sizes of less than 100 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m and makes up at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be tabletted.
  • the premixes to be compressed may additionally contain one or more substances from the group of bleaches, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors and corrosion inhibitors. These substances have been described above.
  • the production of the shaped bodies according to the invention takes place firstly by the dry mixing of the constituents, which may be completely or partially pre-granulated, and subsequent informing, in particular pressing into tablets, wherein conventional methods can be used.
  • the premix is compacted in a so-called matrix between two punches to form a solid compressed product.
  • This process in the hereinafter referred to as tableting, is divided into four sections: metering, compaction (elastic deformation), plastic deformation and expulsion.
  • the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix.
  • the upper punch contacts the pre-mix and continues to descend toward the lower punch.
  • the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding.
  • the premix particles are also crushed, and even higher pressures cause sintering of the premix.
  • the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities.
  • the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size.
  • the tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down.
  • eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is the operation of a conventional four-stroke engine comparable.
  • the compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohritch is extended accordingly.
  • the throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies are arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available.
  • Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp.
  • the die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection.
  • these curved paths are supported by additional low-pressure pieces, Nierderzugschienen and lifting tracks.
  • the filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix.
  • the pressing pressure on the premix is individually adjustable via the compression paths for upper and lower punches, wherein the pressure build-up is done by the Vorbeirollen the stamp shank heads on adjustable pressure rollers.
  • Concentric presses can be provided with two Drikn to increase the throughput, with the production of a tablet only a semicircle must be traversed.
  • several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling.
  • suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible.
  • Rotary tablet presses can also be equipped with single or multiple tools, see above that, for example, an outer circle with 50 holes and an inner circle with 35 holes are used simultaneously for pressing. The throughputs of modern rotary tablet presses amount to over one million moldings per hour.
  • Plastic coatings, plastic inserts or plastic stamps are particularly advantageous.
  • Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.
  • Tabletting machines suitable for the purposes of the present invention are available, for example, from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Packaging Systems GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Press AG, Berlin, and Romaco GmbH, Worms.
  • Other providers include Dr. med. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), 1st Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ).
  • the moldings can be made in a predetermined spatial form and predetermined size.
  • a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
  • This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can be designed in each case as separate individual elements, which corresponds to the predetermined dosage amount of the washing and / or cleaning agent.
  • the formation of the portioned compacts as tablets, in cylindrical or cuboidal form may be appropriate, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
  • Commercially available hydraulic presses, eccentric presses or Rotary presses are suitable devices, in particular for producing such compacts.
  • the spatial form of another embodiment of the moldings is adapted in their dimensions of the dispenser of commercial household washing machines, so that the moldings can be metered without dosing directly into the dispenser, where it dissolves during the dispensing process.
  • a use of the detergent tablets via a dosing is easily possible and preferred in the context of the present invention.
  • Another preferred molded article which can be produced has a plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin segments, broken and in the Machine can be entered.
  • This principle of the "bar-shaped" shaped body wash can also be realized in other geometric shapes, for example vertical triangles, which are joined together only on one side thereof.
  • the various components are not pressed into a single tablet, but that moldings are obtained which have multiple layers, ie at least two layers. It is also possible that these different layers have different dissolution rates. This can result in advantageous performance properties of the molded body. If, for example, components are contained in the moldings which interact negatively, it is possible to integrate one component in the faster soluble layer and to incorporate the other component into a slower soluble layer, so that the first component has already reacted, when the second goes into solution.
  • the layer structure of the moldings can be carried out both in a staggered manner, whereby a dissolution process of the inner layer (s) takes place at the edges of the molded article already when the outer layers have not yet completely dissolved, but it is also possible to completely cover the inner layer (s) ) are achieved by the respective outer layer (s), which leads to a prevention of premature dissolution of constituents of the inner layer (s).
  • a shaped body consists of at least three layers, ie two outer and at least one inner layer, at least in one of the inner layers containing a peroxy bleach, while the stacked shaped body, the two outer layers and the envelope-shaped body
  • outermost layers are free of peroxy bleach.
  • peroxy bleach and optionally present bleach activators and / or enzymes spatially in a molding from each other.
  • Such multilayer moldings have the advantage that they can be used not only via a dispensing compartment or via a metering device, which is placed in the wash liquor; Rather, it is also possible in such cases, to give the molding in direct contact with the textiles in the machine without stains caused by bleach and the like to be feared.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article
  • D is the molded article diameter in meters and t the height of the moldings.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Detergent Compositions (AREA)
  • Fats And Perfumes (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Cephalosporin Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Claims (12)

  1. Procédé pour préparer des granulés d'agent de nettoyage ayant une densité apparente comprise entre 350 et 700 g/l, comprenant les étapes consistant à :
    i) mélanger une matière véhicule solide avec une première portion d'un liant liquide dans un pré-mélangeur;
    ii) transférer le mélange résultant partiellement granulé dans une couche fluidisée et fluidiser ce mélange en formant un lit fluidisé;
    iii) pulvériser une deuxième portion d'un liant liquide au moyen d'un dispositif de pulvérisation sur le lit fluidisé formé dans la couche fluidisée, suivi d'une granulation,
    caractérisé en ce que, quant au pré-mélangeur, il s'agit d'un réacteur rotatif.
  2. Procédé selon la revendication 1, caractérisé en ce que, quant au réacteur rotatif dans l'étape i), il s'agit d'un mélangeur à chute libre, de préférence un mélangeur à tambour, un mélangeur à tambour culbuteur, un mélangeur à cône, un mélangeur à double cône ou un mélangeur en V.
  3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que la charge de surface du lit fluidisé par le liant pulvérisé dans l'étape iii) est comprise entre 0,0001 et 2,0 kg/(m2s), de préférence entre 0,001 et 2,0 kg/(m2s), de manière particulièrement préférée entre 0,002 et 2,0 kg/(m2s), et en particulier entre 0,004 et 2,0 kg/(m2s).
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que le lit fluidisé dans l'étape iii) présente une profondeur comprise entre 2 et 100 cm, de préférence entre 4 et 80 cm, de manière particulièrement préférée entre 8 et 60 cm, et en particulier entre 10 et 40 cm.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que la charge volumique du lit fluidisé par le liant pulvérisé dans l'étape iii) est comprise entre 0,0001 et 6,0 kg/(m3s).
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que la distance séparant le dispositif de pulvérisation de la plaque de fond dans l'étape iii) est d'au moins 30 cm, de préférence d'au moins 60 cm, de manière particulièrement préférée d'au moins 80 cm, et en particulier d'au moins 100 cm.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que la distance séparant le dispositif de pulvérisation de la surface du lit fluidisé dans l'étape iii) est d'au moins 10 cm, de préférence d'au moins 30 cm, et en particulier d'au moins 50 cm.
  8. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que le diamètre de gouttelette du liant liquide pulvérisé est compris entre 1 et 100 µm, de préférence entre 2 et 80 µm, préférentiellement entre 4 et 70 µm et en particulier entre 8 et 60 µm.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que la densité apparente du mélange partiellement granulé lors de l'entrée dans la couche fluidisée pneumatique est comprise entre 300 et 700 g/l, de préférence entre 350 et 650 g/l, et en particulier entre 400 et 600 g/l.
  10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que la densité apparente du mélange de granulation à la sortie de la couche fluidisée pneumatique est comprise entre 300 et 700 g/l, de préférence entre 400 et 700 g/I et en particulier entre 500 et 650 g/l.
  11. Procédé selon l'une des revendications 1 à 10, caractérisé en ce que la première portion du liant liquide dans l'étape i) constitue de 55 à 90% en poids de tout le liant liquide mis en oeuvre.
  12. Procédé selon l'une des revendications 1 à 11, caractérisé en ce que le mélange de granulation est post-traité en sortant de la couche fluidisée pneumatique.
EP03767728A 2002-12-12 2003-12-03 Procede ii de neutralisation a sec Expired - Lifetime EP1570040B1 (fr)

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DE10258006 2002-12-12
DE10258006A DE10258006B4 (de) 2002-12-12 2002-12-12 Trockenneutralisationsverfahren II
PCT/EP2003/013613 WO2004053037A2 (fr) 2002-12-12 2003-12-03 Procede ii de neutralisation a sec

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JP (1) JP2006509855A (fr)
AT (1) ATE357499T1 (fr)
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DE (2) DE10258006B4 (fr)
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Families Citing this family (5)

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DE102004016497B4 (de) * 2004-04-03 2007-04-26 Henkel Kgaa Verfahren zur Herstellung von Granulaten und deren Einsatz in Wasch- und/oder Reinigungsmitteln
FR2933897B1 (fr) * 2008-07-18 2011-05-20 Eurotab Dispositif pour former des tablettes par compaction a volume constant
BR112012011994A2 (pt) * 2009-11-18 2016-05-10 Kao Corp método para produzir grânulos detergentes
DE102012217877A1 (de) * 2012-10-01 2013-08-14 Henkel Ag & Co. Kgaa Nontower-Verfahren
US10287535B2 (en) * 2014-04-15 2019-05-14 Ecolab Usa Inc. Solid block comprising one or more domains of prismatic or cylindrical shape and production thereof

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3425948A (en) * 1966-01-03 1969-02-04 Wyandotte Chemicals Corp Composition and process for light-weight surfactant products
JPS5230962B2 (fr) * 1972-12-12 1977-08-11
US4587029A (en) * 1983-06-27 1986-05-06 The Chemithon Corporation Intermediate product for use in producing a detergent bar
US4828721A (en) * 1988-04-28 1989-05-09 Colgate-Palmolive Co. Particulate detergent compositions and manufacturing processes
CA2085349A1 (fr) * 1990-06-26 1991-12-27 Raymond D. Young Detersif granulaire contenant un agent de blanchiment et utilisable sur plusieurs surfaces
DE4216774A1 (de) * 1992-05-21 1993-11-25 Henkel Kgaa Verfahren zur kontinuierlichen Herstellung eines granularen Wasch und/oder Reinigungsmittels
EP0862611B1 (fr) * 1995-11-06 2001-09-12 Kao Corporation Procede de production de granules de silicate de metal alcalin cristallin et detergent granulaire d'une densite elevee
GB9526097D0 (en) * 1995-12-20 1996-02-21 Unilever Plc Process
GB9712583D0 (en) * 1997-06-16 1997-08-20 Unilever Plc Production of detergent granulates
GB9713748D0 (en) * 1997-06-27 1997-09-03 Unilever Plc Production of detergent granulates
CN1218027C (zh) * 1997-07-14 2005-09-07 普罗格特-甘布尔公司 通过控制在流化床干燥器中的附聚制备低密度洗涤剂组合物的方法
ATE278765T1 (de) * 1997-07-14 2004-10-15 Procter & Gamble Verfahren zur herstellung von waschmitteln mit niedriger schüttdichte durch kontrolle der düsenhöhe im fliessbett
JP2002507629A (ja) * 1997-07-14 2002-03-12 ザ、プロクター、エンド、ギャンブル、カンパニー 粒子サイズによって塊状化を制御することによる低密度の洗剤組成物の作製方法
DE19818966A1 (de) * 1998-04-28 1999-11-04 Henkel Kgaa Verfahren zur Herstellung von wasch- oder reinigungsaktiver Granulate
US6440342B1 (en) * 1998-07-08 2002-08-27 The Procter & Gamble Company Process for making a low density detergent composition by controlling nozzle height in a fluid bed dryer

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US20050245425A1 (en) 2005-11-03
JP2006509855A (ja) 2006-03-23
DE10258006A1 (de) 2004-07-08
ES2283832T3 (es) 2007-11-01
AU2003292173A1 (en) 2004-06-30
DE50306872D1 (de) 2007-05-03
WO2004053037A3 (fr) 2004-08-26
AU2003292173A8 (en) 2004-06-30
DE10258006B4 (de) 2006-05-04
EP1570040A2 (fr) 2005-09-07
WO2004053037A2 (fr) 2004-06-24
ATE357499T1 (de) 2007-04-15

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