EP1570040A2 - Procede ii de neutralisation a sec - Google Patents

Procede ii de neutralisation a sec

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Publication number
EP1570040A2
EP1570040A2 EP03767728A EP03767728A EP1570040A2 EP 1570040 A2 EP1570040 A2 EP 1570040A2 EP 03767728 A EP03767728 A EP 03767728A EP 03767728 A EP03767728 A EP 03767728A EP 1570040 A2 EP1570040 A2 EP 1570040A2
Authority
EP
European Patent Office
Prior art keywords
acid
acids
fluidized bed
weight
preferred
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP03767728A
Other languages
German (de)
English (en)
Other versions
EP1570040B1 (fr
Inventor
Bernhard Orlich
Gerhard Blasey
Hans-Friedrich Kruse
Wilfried Rähse
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication of EP1570040A2 publication Critical patent/EP1570040A2/fr
Application granted granted Critical
Publication of EP1570040B1 publication Critical patent/EP1570040B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—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 method for producing surfactant granules.
  • it relates to a process which allows easily soluble surfactant granules or detergent and cleaning agent compositions to be produced in a cost-optimized manner.
  • anionic surfactants thus occur in their acid form in the course of the production process and must be converted into their alkali metal or alkaline earth metal salts using suitable neutralizing agents.
  • This neutralization step can be carried out with solutions of alkali metal hydroxides or with solid alkaline substances, in particular sodium carbonate.
  • the surfactant salts are obtained in the form of aqueous preparation forms, water contents being adjustable in the range from about 10 to 80% by weight and in particular in the range from about 35 to 60% by weight.
  • Products of this type have a paste-like to cutable quality at room temperature, the flowability and pumpability of such pastes being restricted or even being lost in the range of approximately 50% by weight of active substance, so that such pastes are further processed, in particular when incorporated into them Solid mixtures, for example in solid washing and cleaning agents, considerable problems arise.
  • anionic detergent surfactants in dry, in particular free-flowing, form.
  • anionic detergent surfactants in dry, in particular free-flowing, form.
  • free-flowing anionic surfactant powders or granules in particular those of fatty alcohol sulfates (FAS)
  • FAS fatty alcohol sulfates
  • Conventional drying technology for example in a spray tower.
  • the preparations obtained are often hygroscopic, clump together with the absorption of water from the air during storage and also tend to clump in the finished detergent product. Due to the necessarily high water content of the pastes processed in the spray tower, the energy input in such spray processes is comparatively high.
  • Granulation is an alternative to spray drying surfactant pastes.
  • Patent literature also has a broad state of the art for the non-tower manufacture of detergents and cleaning agents. Many of these processes are based on the acid form of the anionic surfactants, since this surfactant class represents the largest proportion of wash-active substances in terms of quantity and the anionic surfactants occur in the course of their production in the form of the free acids which have to be neutralized to the corresponding salts.
  • European patent application EP-A-0 678 573 (Procter & Gamble) describes a process for producing free-flowing surfactant granules with bulk densities above 600 g / l, in which anionic surfactant acids with an excess of neutralizing agent form a paste with at least 40% by weight of surfactant are reacted and this paste is mixed with one or more powder (s), at least one of which must be spray-dried and which contains anionic polymer and cationic surfactant, the resulting granules optionally being able to be dried.
  • this document reduces the proportion of spray-dried granules in the detergents and cleaning agents, it does not completely avoid spray drying.
  • European patent application EP-A-0 438 320 discloses a batch process for the production of surfactant granules with bulk densities above 650 g / l.
  • Anionic surfactant acid is added to a solution of an alkaline inorganic substance in water, possibly with the addition of other solids, and granulated in a high-speed mixer / granulator with a liquid binder. Neutralization and granulation take place in the same apparatus, but in separate process steps, so that the process can only be operated in batches.
  • ABS acid contains at least 62% NaOH is neutralized and then granulated with the addition of auxiliaries, for example ethoxylated alcohols or alkylphenols or a polyethylene glycol melting above 48.9 ° C. with a molecular weight between 4000 and 50,000.
  • auxiliaries for example ethoxylated alcohols or alkylphenols or a polyethylene glycol melting above 48.9 ° C. with a molecular weight between 4000 and 50,000.
  • EP-A-0 508 543 (Procter & Gamble) mentions a process in which a surfactant acid is neutralized with an excess of alkali to form an at least 40% by weight surfactant paste, which is then conditioned and granulated, one 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 a maximum of 10% by weight of water.
  • the surfactant mixtures to be sprayed on contain between 40 and 92% by weight of a surfactant mixture and more than 8 to a maximum of 60% by weight of water.
  • the surfactant mixture in turn consists of at least 50% polyalkoxylated nonionic surfactants and ionic surfactants.
  • a method 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 mixtures disclosed here 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 (Henkel KGaA) discloses a process for the preparation of washable and cleaning-active anionic surfactant granules by neutralizing anionic surfactants in their acid form.
  • Solid, powdery substances in particular sodium carbonate, are disclosed as neutralizing agents, which react with the anionic surfactant acids to form anionic surfactant, carbon dioxide and water.
  • the granules obtained have surfactant contents of around 30% by weight and bulk densities of less than 550 g / l.
  • European laid-open specification EP 642 576 (Henkel KGaA) describes two-stage granulation in two consecutive mixers / granulators, with 40-100% by weight, based on the total amount of constituents used, of the solid and liquid constituents in a first, low-speed granulator pre-granulated and in a second, high-speed granulator, the pre-granules are mixed with the remaining constituents, if necessary, and transferred to a granulate.
  • European patent EP 772 674 (Henkel KGaA) describes a process for the production of surfactant granules by spray drying, in which anionic surfactant acid (s) and highly concentrated alkaline solutions are separately charged with a gaseous medium and mixed in a multi-component nozzle, neutralized and sprayed into one Hot gas stream can be spray dried. The finely divided surfactant particles obtained in this way are then agglomerated in a mixer to give granules with bulk densities above 400 g / l.
  • anionic surfactant acid (s) and highly concentrated alkaline solutions are separately charged with a gaseous medium and mixed in a multi-component nozzle, neutralized and sprayed into one Hot gas stream can be spray dried.
  • the finely divided surfactant particles obtained in this way are then agglomerated in a mixer to give granules with bulk densities above 400 g / l.
  • German Offenlegungsschrift DE-A-43 14 885 discloses a process for producing washable and cleaning-active anionic surfactant granules by neutralizing the acid form of anionic surfactants with a compound having a basic action, the hydrolysis-sensitive acid form of a hydrolysis-sensitive anionic surfactant containing the neutralizing agent without the release of Water is implemented.
  • Sodium carbonate is preferably used as the neutralizing agent, which reacts to sodium hydrogen carbonate in this process.
  • the present invention was based on the object of providing a continuous process which makes it possible to produce detergents and cleaning agents without or with reduced use of spray drying steps. Furthermore, in A further cost optimization can be achieved compared to the methods disclosed in the prior art.
  • the process to be provided should also enable the direct and economically attractive processing of the acid forms of detergent raw materials, the disadvantage of energy-intensive water evaporation or the use of energy-intensive methods
  • the bulk densities of the granules to be produced should be able to be varied 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 using a non-tower process.
  • the end products are superior to the products that can be produced by prior art methods.
  • the bulk density of the end products should be adjustable by means of the procedure.
  • the end products of the process according to the invention should have a high solubility.
  • the present invention relates to a method for producing detergent granules with a bulk density of between 350 and 700 g / l, comprising the steps: i) mixing a solid carrier material with a first portion of a liquid binder in a premixer; ii) transferring the resulting partially granulated mixture into a fluidized bed and fluidizing this mixture to form a fluidized bed; iii) spraying a second portion of a liquid binder by means of a spray device onto the fluidized bed formed in the fluidized bed, and further granulation, characterized in that the premixer is a rotating one
  • rotating reactors are those mixers which are distinguished by a movable or rotating reactor housing or a moving mixing vessel. Reactors of this type can furthermore have static and / or movable mixing and / or cutting tools However, preference is given to rotating reactors in which the material to be mixed is lifted up by wall friction and then falls freely through the mixer space due to its own gravity. Free-fall mixers are used as preferred "rotating reactors”.
  • Containers of such a free-fall mixer are those with simple geometric shapes ( Cylinder, single or double cone, cubes, etc.)
  • Preferred mixing containers also have obtuse-angled inner corners, since this facilitates both the free movement of the mixing material and the emptying and cleaning of the container after the end of the process of the container is preferably transferred to the mixture in the interior in such a way that the reaction mixture is mixed and loosened as irregularly as possible.
  • a directional movement component occurs in preferred continuous processes according to the invention in order to ensure the continuous mass transport.
  • Rotation about a container axis drum or rotary tube mixer
  • axes that do not match the geometric axes of the container or are perpendicular to its symmetry planes tumble mixer
  • vibrate preferably with, are particularly suitable as types of movement for the free-fall mixer high amplitude and low frequency as well as changing directions of the deflections, so that irregular shaking or tumbling movements occur.
  • the solid support material moving 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.
  • Rotating reactors 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 according to the invention offer alternating, inclined walls to the material carried up and falling again in the case of rotating or tumbling movements and thus deflecting, expanding or narrowing the space, shifting and dividing the flow of material.
  • Such mixers can have fixed internals for better loosening of the material to be mixed (e.g. lifting bars), but preferred mixers, unlike the high or low speed mixers customary in the prior art, have no mixing or cutting tools.
  • Methods according to the invention are particularly preferred in which double cone mixers with rotatable containers without mixing tools are used as free-fall mixers, the double cone mixers being divided into a mixing zone and a post-mixing zone and having a knock-off bar which is fastened to an end plate and from there traverses the entire mixing zone and if necessary 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 can have a width of 50 to 150 mm, preferably 75 to 130 mm.
  • the upper edge of the knock-off bar is at a distance from the inner mixer wall which is preferably a maximum of 10% of the drum diameter of the narrowest point of the rotatable container, preferably a maximum of 5% of the narrowest point of the rotatable container and in particular less than 2.5% of the narrowest point of the rotatable container Container.
  • the distance to the nearest inner mixer wall can be greater than in the mixing zone; Values between 100 and 300 mm are quite common.
  • Free-fall mixers which rotate about their horizontal axis, preferably about their slightly inclined axis, are particularly suitable for continuous operation. Due to the inclination of the axis of rotation, the mix has its own Gravity causes a directional movement, which enables the mixture to be continuously discharged from the mixer. In addition to the inclination of the axis of rotation, such a directional movement can of course also be produced by a continuous introduction of anionic surfactant acids and solid neutralizing agent. For the product properties, in particular for the adjustment of the bulk density and the solubility of the reaction products, it has proven to be advantageous if the angle of inclination of the axis of rotation of a preferably used rotatable container correlates with a certain number of revolutions.
  • Methods according to the invention are therefore particularly preferred in which the rotatable container of the free-fall mixer has an inclination angle ⁇ of 0 to 20 °, in particular 0 to 15 °, very particularly preferably 1 to 15 °, and the movement of the rotatable container of the free-fall mixer is controlled by the drive is simultaneously set 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 is preferably less than 20 minutes, preferably between 1 and 600 seconds, particularly preferably between 1 and 300 seconds and in particular between 1 and 120 seconds.
  • the speed 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 transferred into a fluidized bed in the process according to the invention.
  • the reaction mixture can be transferred, for example, via a conveying device. If this conveyor and metering screw extends into the post-mixing zone (it is also possible to connect the conveyor directly to the discharge unit), it is preferred that the screw only protrude at most into the second half of the length of the post-mixing zone and therefore not into the part of the post-mixing zone , which still contains the tee.
  • the fluidized bed can be a mechanical as well as a pneumatic fluidized bed. However, methods 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.
  • These fluidized bed apparatuses can be operated continuously and discontinuously.
  • the air is preferably blown through the perforated porous base.
  • the bulk density of the partially granulated mixture when it enters the pneumatic fluidized bed is preferably between 300 and 700 g / l, particularly preferably between 350 and 650 g / l and in particular between 400 and 600 g / l.
  • the air enters through the porous bottom preferably at least the loosening rate. From the initial fixed bed, the fluidized bed is created, the fluidized bed, which has continuum properties similar to a liquid because of the easy mobility of the particles.
  • the mix is preferably almost non-cohesive.
  • intensive mixing is only possible at 2 to 6 times the loosening speed;
  • Gas inflow velocities which are at least 2 times, preferably at least 4 times, particularly preferably at least 6 times and in particular at least 8 times the loosening rate are therefore preferred in the process according to the invention.
  • the loosening speed w can be calculated from the equilibrium of forces between the weight F g of the bed and the pressure force F p - the pressure drop ⁇ p multiplied by the base area A across the flowed-through layer - with the aid of the Ergun equation. The result is:
  • W L 42.9 • (1 - ⁇ L ) • v / d p ⁇ ⁇ (1 + 3.11 • 10 "4 [ ⁇ L 3 / (1 - ⁇ L ) 2 ] ⁇ g • d p 3 ⁇ [p s / p f ] / v 2 ) 0 ' 5 - 1 ⁇
  • ⁇ L are the porosity of the layer before loosening, v the kinematic viscosity of the air, d p the Sauter diameter d 32 of the particles in the layer p s , p f the solids or air density
  • the floors are divided into sectors which are periodically more or less aerated. This creates changing circulations of larger areas of the fluidized material.
  • the temperature of the inflowing air can be regulated, the temperature deviating from the outside temperature in particularly preferred method variants, that is to say either colder or warmer than the temperature of the surrounding outside air and / or different temperatures for different areas of the fluidized bed the incoming air can be selected.
  • methods are preferred in which:
  • the temperature of the cold air used is less than 15 ° C., preferably less than 13 ° C. and in particular 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 between 2 and 100 cm, preferably between 4 and 80 cm, particularly preferably between 8 and 60 cm and in particular between 10 and 40 cm. Spraying can be carried out using single-substance or high-pressure spray nozzles, two-substance spray nozzles or three-substance spray nozzles.
  • a high mass pressure (5-15 MPa) is required for spraying with single-substance spray nozzles, while spraying in two-substance spray nozzles is carried out with the aid of a compressed air stream (at 0.15-0.3 MPa).
  • Spraying with two-substance spray nozzles is cheaper, especially with regard to possible blockages of the nozzle, but more expensive due to the high compressed air consumption.
  • there are the three-substance spray nozzles which in addition to the compressed air flow for atomization, another air guidance system that is to prevent blockages and droplet formation on the nozzle.
  • two-substance spray nozzles preferably two-substance spray nozzles with a liquid bore between 2 and 6 mm, in particular between 3 and 5 mm, is particularly preferred.
  • the preferred distance of the spray device from the base plate of a fluidized bed preferably used in step iii) is at least 30 cm, preferably at least 60 cm, particularly preferably at least 80 cm and in particular at least 100 cm.
  • the spray head of the spray device is located above the surface of the fluidized bed.
  • the distance of the spraying 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 solubility or bulk density, of granules produced according to the invention can be advantageously influenced, in particular, by the distance of the spraying device from the surface of the fluidized bed.
  • the drop diameter of the sprayed-on liquid binder 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, particularly 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 loading of the fluidized bed by 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), particularly preferably between 0.002 and 2.0 kg / (m 2 s) and in particular between 0.004 and 2.0 kg / (ms).
  • the volume loading of the fluidized bed by the sprayed binder in step iii) is between 0.0001 and 6.0 kg / (m 3 s) in preferred variants of the process according to the invention.
  • the liquid binder is fed to the solid carrier material in two portions in the process according to the invention.
  • the first portion of the liquid binder in step i) is 55 to 90% by weight, preferably between 65 and 90% by weight, particularly preferably between 76 and 90% by weight. -% and in particular between 80 and 90 wt .-% of the total liquid binder used.
  • This preferred distribution of the binder addition gives process products which are characterized by an optimized solubility and a low bulk density in the range from 300 to 700 g / l.
  • Processes according to the invention are preferably 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 carrier materials.
  • Anionic surfactants are particularly suitable as liquid binders.
  • anionic surfactant acid (s) preferably one or more substance (s) from the group of the carboxylic acids, the sulfuric acid half-esters and the sulfonic acids, preferably from the group of the fatty acids, the fatty alkyl sulfuric acids and the alkylarylsulfonic acids, are used as liquid binders, especially from the group of C 8 . ⁇ e-, especially the Cg. 1 3- alkylbenzenesulfonic acids used. These are described below.
  • the compounds mentioned should have longer-chain hydrocarbon radicals, that is to say they should have at least 6 carbon atoms in the alkyl or alkenyl radical.
  • the C chain distributions of the anionic surfactants are usually in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.
  • Carboxylic acids which are used as soaps in detergents and cleaning agents in the form of their alkali metal salts, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage.
  • Carboxylic acids which can be used as an anionic surfactant in acid form in the context of the present invention are, for example, 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 (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), triacidic acid (melotinic acid), triacidic acid (melotonic acid), and melonic acid unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidinic acid), 9c, 12c-oc
  • Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C 8, 6% by weight C 10 48 wt .-% C 12 18 wt .-% C14, 10 wt .-% C ⁇ ⁇ , 2 wt .-% C18, 8 wt .-% C 1 ⁇ - 1 wt .-% C 18 • •), palm kernel oil fatty acid (about 4 wt .-% C 8, 5 wt .-% C 10) 50 parts by weight 12% C, 15 wt .-% C 14, 7 wt .-% C 16> 2 wt .-% C 18 15 wt .-% C 18 - 1 wt .-% C 18 "), Tallow fatty acid (approx.
  • Sulfuric acid semiesters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the process according to the invention.
  • Their alkali metal, in particular sodium salts, the fatty alcohol sulfates are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are subsequently neutralized.
  • the fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters.
  • alkyl sulfuric acids In terms of quantity, the most important industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SO 3 / air mixtures in special cascade, falling film or tube bundle reactors.
  • Another class of anionic surfactant acids which can be used in the process according to the invention are the alkyl ether sulfuric acids, the salts of which, the alkyl ether sulfates, are distinguished 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 are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question.
  • 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 alkyl ether sulfuric acids concerned.
  • Alkanesulfonic acids and olefin sulfonic acids can also be used as anionic surfactants in acid form in the context of the present invention.
  • Alkanesulfonic acids can contain the sulfonic acid group in a terminal bond (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), only the secondary ones Alkanesulfonic acids are of commercial importance. These are made by sulfochlorination or sulfoxidation of linear hydrocarbons.
  • n-paraffins are reacted with sulfur dioxide and chlorine under irradiation with UV light to give the corresponding sulfochlorides, which, when hydrolysed with alkalis, provide the alkanesulfonates directly, and when reacted with water, the alkanesulfonic acids.
  • di- and polysulfochlorides and chlorinated hydrocarbons can occur as by-products of the radical reaction in the sulfochlorination, the reaction is usually carried out only up to degrees of conversion of 30% and then terminated.
  • alkanesulfonic acids Another process for the production of alkanesulfonic acids is sulfoxidation, in which n-paraffins are reacted with sulfur dioxide and oxygen under irradiation with UV light.
  • This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylpersulfonyl radicals.
  • the reaction with unreacted paraffin provides an alkyl radical and the alkyl persulfonic acid, which breaks down into an alkyl peroxysulfonyl radical and a hydroxyl radical.
  • the reaction of the two radicals with unreacted paraffin gives the alkyl sulfonic acids or water, which reacts with alkyl persulfonic acid and sulfur dioxide to form sulfuric acid.
  • this reaction is usually carried out only up to degrees of conversion of 1% and then stopped.
  • Olefin sulfonates are produced industrially by the reaction of ⁇ -olefins with sulfur trioxide. Intermediate hermaphrodites form here, which cyclize to form so-called sultons. Under suitable conditions (alkaline or acidic hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which can also be used as anionic surfactant acids.
  • alkylbenzenesulfonates as powerful anionic surfactants have been known since the 1930s. At that time, alkylbenzenes were produced by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution.
  • propylene was tetramerized to branched ⁇ -dodecylene and the product was subjected to a Friedel-Crafts reaction
  • Use of aluminum trichloride or hydrogen fluoride converted to tetrapropylene benzene, which was subsequently sulfonated and neutralized.
  • This economical possibility of producing tetrapropylene benzene sulfonates (TPS) led to the breakthrough of this class of surfactants, which subsequently displaced the soaps as the main surfactant in washing and cleaning agents.
  • Linear alkylbenzenesulfonates are made from linear alkylbenzenes, which in turn are accessible from linear olefins.
  • petroleum fractions with molecular sieves are separated on an industrial scale into the n-paraffins of the desired purity and dehydrated to the n-olefins, resulting in both ⁇ - and i-olefins.
  • the resulting olefins are then reacted with benzene in the presence of acidic catalysts to give the alkylbenzenes, the choice of Friedel-Crafts catalyst having an influence on the isomer distribution of the linear alkylbenzenes formed: when using aluminum trichloride, the content of the 2-phenyl isomers is in the mixture with the 3, 4, 5 and other isomers at approx. 30% by weight, on the other hand, if hydrogen fluoride is used as a catalyst, the 2-phenyl isomer content can be reduced to approx.
  • the anionic surfactant in acid form C 8 . ⁇ 6 -, preferably C. 9 13 - Alkylbenzenesulfonic acids are preferred. It is within the scope of the present invention further preferably, C 8-16 -, preferably C. 9 13 - to use alkylbenzenesulfonic acids which are derived from alkylbenzenes and which have a tetralin content below 5% by weight, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes have been prepared by the HF process, so that the C 8 . 16 -, preferably C 9 . 13 -Alkylbenzenesulfonic acids have a 2-phenyl isomer content below 22% by weight, based on the alkylbenzenesulfonic acid.
  • anionic surfactants in their acid form can be used alone or in a mixture with one another in the process according to the invention.
  • the anionic surfactant in acid form, before addition to the solid neutralizing agent (s) contains further, preferably acidic, ingredients of detergents and cleaning agents in amounts of 0.1 to 40% by weight, preferably from 1 to 15% by weight and in particular from 2 to 10% by weight, based in each case on the weight of the mixture containing anionic surfactant acid.
  • Suitable liquid binders in the context of the present invention are, in addition to the “surfactant acids”, the fatty acids, phosphonic acids, polymer acids or partially neutralized polymer acids as well as “builder acids” and “complex builder acids” alone or in any mixtures.
  • As ingredients of detergents and cleaning agents for example Acidic detergents can be added to the anionic surfactant acid before foaming.
  • Ingredients, for example phosphonic acids, which in neutralized form (phosphonates) are components of many detergents and cleaning agents as incrustation inhibitors.
  • the use of (partially neutralized) polymer acids such as polyacrylic acids is also possible according to the invention.
  • so-called small components are available which would otherwise have to be added in complex further steps, for example optical brighteners, dyes, etc., the acid stability being checked in individual cases.
  • Nonionic surfactants are preferred for the anionic surfactant in acid form in amounts of 0.1 to 40% by weight, preferably 1 to 15% by weight and in particular 2 to 10% by weight, in each case based on the weight of the anionic surfactant-containing Mixture, mixed. This addition can improve the physical properties of the mixture containing anionic surfactant acid and make subsequent incorporation of nonionic surfactants into the surfactant granules or the entire detergent and cleaning agent unnecessary.
  • the different representatives from the group of nonionic surfactants are described below.
  • the temperature of the mixture to be applied is as low as possible is.
  • the liquid binder has a temperature of 20 and 70 ° C., preferably between 25 and 60 ° C., particularly preferably between 30 and 55 ° C. and in particular between 40 and 50 ° C. when it is introduced into the free-fall mixer.
  • anionic surfactant acid which optionally includes further acidic components, is referred to as “liquid, acidic component”.
  • the sodium carbonate is used 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 hydrate water content that may be present) is related to the amount of sodium bicarbonate on average (based on the agent, without taking into account any hydrate water content that may be present) and must be 5: 1 or more according to the invention. In other words, according to the invention, at least 5 grams of Na 2 CO 3 are contained per gram of the NaHCO 3 contained in the process products.
  • the mass ratio of sodium carbonate to sodium bicarbonate is within narrow limits, the weight ratio of sodium carbonate to sodium bicarbonate in the end products of the process being 50: 1 to 2: 1, preferably 40: 1 to 2.1: 1, in processes preferred according to the invention, particularly preferably 35: 1 to 2.2: 1 and in particular 30: 1 to 2.25: 1.
  • the sodium hydrogen carbonate content of the agents preferred according to the invention can vary.
  • the content of sodium hydrogen carbonate in the end products of the process is 0.01 to 20% by weight, preferably 0.1 to 15% by weight, particularly preferably 0.5 to 10% by weight and in particular 1 to 10% by weight. -%, each based on the total weight of the process end products.
  • the neutralized form of the anionic surfactant acids in short the anionic surfactants, can also be present in varying amounts in the agents produced by the process according to the invention. All acids known from the prior art are suitable as anionic surfactant acids. These have been described in detail above.
  • Preferred processes according to the invention are characterized in that the neutralized anionic surfactant acid content of 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 produced by the process according to the invention can have different bulk densities depending on the content of the individual ingredients and other process parameters.
  • Processes according to the invention are preferred in which the bulk density of the end products of the process 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 of processes preferred according to the invention furthermore have a grain size distribution with an average grain size d 50 below 5000 ⁇ m, preferably between 20 and 3000 ⁇ m, particularly preferably between 40 and 2000 ⁇ m and in particular between 50 and 1600 ⁇ m.
  • the 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 less than 2.5 wt .-%, based in each case on the total weight of the process end products after leaving the fluidized bed.
  • the water content of the end products of the process is preferably ⁇ 15% by weight, preferably ⁇ 10% by weight, particularly preferably ⁇ 5% by weight and in particular ⁇ 2.5% by weight.
  • the low-water procedure is preferred to ensure the desired reaction to sodium hydrogen carbonate.
  • the raw materials used should therefore be used as dry, dried or low in water as possible.
  • anionic surfactant acids are preferably to be chosen in as high a concentration as possible, as long as the technical procedure (moving the anionic surfactant acid and application to the sodium carbonate) is properly guaranteed.
  • Another way of promoting the formation of sodium hydrogen carbonate and avoiding 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 by coordinating the amounts of the reactants. Processes according to the invention are preferred here in which the temperature during the process is kept below 100 ° C., preferably below 80 ° C., particularly preferably below 60 ° C. and in particular below 50 ° C.
  • the process according to the invention is based on the conversion or granulation of liquid binders with solid carrier materials.
  • anionic surfactant acid and sodium carbonate are reacted with one another.
  • the reaction mixture may also contain other substances which may or may not be involved in the reaction.
  • reactive or inert substances can be mixed with either the sodium carbonate or the anionic surfactant (s) before the reaction; alternatively, both reactants can also contain further reactive or inert ingredients.
  • further ingredients in particular further preferably solid carrier materials, to the sodium carbonate.
  • This mixture forms the solid bed onto which the anionic surfactant acid (s) - if appropriate in a mixture with other substances - is / are applied.
  • further neutralizing agents can be added to the sodium carbonate, solid neutralizing agents being preferred.
  • Aqueous solutions of neutralizing agents in particular lyes
  • Methods according to the invention are particularly preferred, in which the solid carrier materials additionally contain one or more substances from the group Sodium hydroxide, sodium sesquicarbonate, potassium hydroxide and / or potassium carbonate.
  • solid carrier materials carriers which do not participate in the reaction can also be added to the sodium carbonate. These should then have sufficient stability with respect to the added acids in order to avoid local decomposition and thus undesirable discoloration or other stress on the product.
  • the solid bed contains further solids from the groups of silicates, aluminum silicates, sulfates, citrates and / or phosphates are preferred here.
  • sodium sulfate which is still contained in the detergents in some countries up to 45% by weight, is admixed with the solid neutralizing agent (s).
  • 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.
  • Preferred methods according to the invention are characterized in that the granulation mixture is aftertreated after exiting the pneumatic fluidized bed.
  • the liquid binders used in process steps i) and / or iii) may also have further constituents in addition to the above-mentioned, preferably used anionic surfactants.
  • These other preferred binders include aqueous ones 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 of polyacrylates and / or copolymers of acrylic acid with methacrylic acid and / or copolymers of acrylic acid with maleic acid. More detailed descriptions of the preferred polyacrylates such as the copolymeric polycarboxylates can be found below in the text.
  • the surfactant granules produced by the process according to the invention are particularly suitable for producing detergents or cleaning agents, in particular solid detergents or cleaning agents, for example by further agglomeration, by extrusion or compacting.
  • Such detergents or cleaning agents contain, in addition to the ingredients mentioned above, such as the anionic surfactant acids, further constituents, in particular from the group of builders, cobuilders, bleaching agents, bleach activators, colorants and fragrances, optical brighteners, enzymes, soil-release polymers, etc. These substances are described below for completeness.
  • Builders are mainly used in detergents or cleaning agents to bind calcium and magnesium.
  • Usual builders which in the context of the invention are preferably present in amounts of 22.5 to 45% by weight, preferably 25 to 40% by weight and in particular 27.5 to 35% by weight, in each case based on the total composition , which also contains the 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 silicate builders from the class of alkali disilicates are preferably used for washing or cleaning agents.
  • the potassium salts are preferable to the sodium salts, since they often have a higher solubility in water.
  • Preferred water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium water glasses.
  • Detergents or cleaning agents can contain phosphates as builders, preferably alkali metal phosphates with particular preference for pentasodium or. Pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid 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 cleaning performance.
  • the detergents or cleaning agents can particularly preferably contain condensed phosphates as water-softening substances. These substances form a group of phosphates - also called melting or glow phosphates due to their production - which can be derived from acid salts of orthophosphoric acid (phosphoric acids) by condensation.
  • the condensed phosphates can be divided into the metaphosphates [Mln (PO 3 ) n ] and polyphosphates (M ' n + 2 P n O 3n + ⁇ and M' n H 2 P n ⁇ 3n + 1 ).
  • Metaphosphates are obtained as accompanying substances of Graham's salt, which is falsely referred to as sodium hexametaphosphate, by melting NaH 2 PO 4 at temperatures above 620 ° C, with what is known as Maddrell's salt being formed as an intermediate.
  • This and Kurrol's salt are linear polyphosphates, which today are usually not counted among the metaphosphates, but which can also be used with preference as water-softening substances in the context of the present invention.
  • the quenched, glassy melt is the water-soluble Graham's salt, (NaPO 3 ) 0 -5o> or a glassy condensed phosphate of the composition (NaPO 3 ) i5- 2 o, which is known as Calgon.
  • the misleading name hexametaphosphate is still used for both products.
  • Kurrol's salt (NaPO 3 ) n with n »5000, also arises from the melt of the Maddrell salt, which is hot at 600 ° C, if it is left at 500 ° C for a short time. It forms highly polymeric water-soluble fibers.
  • Suitable silicate builders are the crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 ⁇ 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 represents 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.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite that can be used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • acidifying agents In addition to the builders, acidifying agents, chelating agents or the deposit-inhibiting polymers are further preferred ingredients of detergents or cleaning agents.
  • Both inorganic acids and organic acids are suitable as acidifiers, provided that these are compatible with the other ingredients.
  • the solid mono-, oligo- and polycarboxylic acids can be used in particular for reasons of consumer protection and handling safety. From this group, preference is again given to 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 also be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available.
  • Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, i. H. is at least "bidentate". In this case, normally elongated compounds are closed to form rings by complex formation via an ion. The number of ligands bound depends on the coordination number of the central ion.
  • Common chelate complexing agents preferred in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • Complex-forming polymers that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form 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 can 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 complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl - And crown ether residues with z. T. very specific Activities against ions of different metals.
  • Base polymers of many are also commercially important Complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethylenimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.
  • Hydroxyl groups is at least 5,
  • Dishwashing detergent in amounts above 0.1% by weight, preferably above 0.5% by weight, particularly preferably above 1% by weight and in particular above 2.5% by weight, in each case based on the weight of the Dishwashing detergent included.
  • polycarboxylic acids a) are understood to mean carboxylic acids - also monocarboxylic acids - in which the sum of carboxyl 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. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali, ammonium or alkylammonium salts, in particular sodium salts, are preferred.
  • Deposit-inhibiting polymers can also be contained in washing or cleaning agents. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.
  • Deposit-inhibiting polymers can also have cobuilder properties.
  • Organic cobuilders which can be used in the agents which contain the end products of the process, in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as 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 of these.
  • 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 value of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders or scale inhibitors; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights 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 to the polymers investigated. This information differs significantly from the molecular weight data for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given 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, the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly 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 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 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 agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,
  • Further preferred copolymers are those which preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.
  • Suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon 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.
  • Other suitable organic builder substances are 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.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol can be used.
  • 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 at C 6 of the saccharide ring can be particularly advantageous.
  • Ethylene diamine 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 used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be 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 aminoalkane phosphonates.
  • hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the agents according to the invention can contain further customary ingredients of cleaning agents, bleaching agents, bleach activators, enzymes, dyes and fragrances being of particular importance. These substances are described below.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • Washing or cleaning agents according to the invention can also contain bleaching agents from the group of organic bleaching agents.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) 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, ⁇ -phthalimidanoic acid paproacidaproacid )], o-carboxybenz-amidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidoper-succinate, and (c) aliphatic and araliphatic peroxy- dicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocysebacic acid, diper
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in machine dishwashing agents.
  • Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo- and N-chloramides, 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-dimethylhydanthoin are also suitable.
  • Bleach activators support the effects of the bleach.
  • 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 which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • bleach catalysts can also be contained 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 salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Bleach activators from the group of multiply acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOB) iso , n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6 wt .-% based on the total agent used.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOSI)
  • NOSI N-nonanoylsucc
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (ammin) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in conventional amounts, preferably in an amount of up to 5% by weight, in particular 0.0025% by weight .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used.
  • Detergents or cleaning agents can contain enzymes to increase the washing or cleaning performance, although in principle all enzymes established in the prior art can be used for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred.
  • 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 using known methods, for example the BCA process (bicinchoninic acid; 2,2'-bichinolyl-4,4 '-dicarboxylic acid) or the biuret method can be determined.
  • subtilisin type those of the subtilisin type are preferred.
  • 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 that which can no longer be assigned to the subtilisins in the narrower sense
  • subtilisin Carlsberg is available in further developed form under the trade name Alcalase ® from Novozymes A / S, Bagsva-jrd, Denmark
  • subtilisins 147 and 309 are sold under the trade names Esperase ® and Savinase ® from the company Novozymes
  • the protease from Bacillus lentus DSM 5483 is derived from the variants known as BLAP ® .
  • 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, which is sold under the trade name Protosol ® by Advanced Biochemicals Ltd., Thane, India, which is sold under the trade name Wuxi ® by Wuxi Snyder Bioproducts Ltd., China, and in the trade name 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.
  • amylases examples include the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens or from ⁇ . stearothermophilus and its further developments for use in detergents and cleaning agents.
  • the enzyme from ß. 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 ®.
  • the ⁇ -amylase from ß. Amyloliquefaciens is sold by Novozymes under the name BAN ® , and derived variants from the ⁇ -amylase from ⁇ . stearothermophilus under the names BSG ® and Novamyl ® , also from Novozymes.
  • ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); fusion products of the molecules mentioned can also be used.
  • Washing or cleaning agents can contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate peracids in situ 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 ® available.
  • the Genencor company can use, for example, the lipases or cutinases, their starting enzymes originally isolated from Pseudomonas mendocina and Fusarium solanii.
  • Detergents or cleaning agents can contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement one another with regard to their various performance aspects.
  • These performance aspects include, in particular, contributions to the primary washing performance, to the secondary washing performance of the agent (anti-deposition effect or graying inhibition) and finish (tissue effect), up to the exertion of a “stone washed” effect.
  • EG endoglucanase
  • Novozymes A useful fungal, endoglucanase (EG) -rich cellulase preparation or its further developments are offered by the Novozymes company under the trade name Celluzyme ® .
  • the products Endolase ® and Carezyme ® also available from Novozymes, are based on the 50 kD-EG and the 43 kD-EG from H. insolens DSM 1800.
  • Other possible commercial products from this company are Cellusoft ® and Renozyme ® .
  • the 20 kD EG cellulase from Melanocarpus, which is available from AB Enzymes, Finland, under the trade names Ecostone ® and Biotouch ® can also 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 .beta.-glucanase obtained from B. subtilis is available under the name Cereflo ® from Novozymes.
  • washing and cleaning agents can 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) , Suitable commercial products are Denilite ® 1 and 2 from Novozymes.
  • organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of greatly different redox potentials between the oxidizing enzymes and the soiling.
  • 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 according to known biotechnological processes by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.
  • the enzymes in question are advantageously purified by methods which are in themselves established, for example by means of precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
  • the enzymes can be added to detergents or cleaning agents in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers.
  • the enzymes can be encapsulated both for the solid and for the liquid administration form, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed in a solidified gel are or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals.
  • Additional active ingredients for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in superimposed layers.
  • Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating.
  • a protein and / or enzyme contained in a detergent or cleaning agent can be protected, particularly during storage, against damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or disintegration, for example by physical influences, oxidation or proteolytic cleavage.
  • the proteins and / or enzymes are obtained microbially, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases.
  • stabilizers can be used for this purpose.
  • a group of stabilizers are reversible protease inhibitors.
  • Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used, including above all derivatives with aromatic groups, for example ortho, meta- or para-substituted phenylboronic acids, or their salts or esters.
  • Peptide aldehydes, ie oligopeptides with a reduced C-terminus are also suitable. Ovomucoid and leupeptin may be mentioned as peptide protease inhibitors; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.
  • Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and - propanolamine and their mixtures, aliphatic carboxylic acids up to C 12 , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End group-capped fatty acid amide alkoxylates can also be used as stabilizers.
  • Di-glycerol phosphate also protects against denaturation by physical influences.
  • Calcium salts are also 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.
  • Polymers containing polyamine-N-oxide act simultaneously as enzyme stabilizers and as color transfer inhibitors.
  • Other polymeric stabilizers are the linear C 8 -C 18 polyoxyalkylenes.
  • Alkyl polyglycosides can also stabilize the enzymatic components of the agent according to the invention and even increase their performance.
  • Crosslinked N-containing compounds fulfill a double function as soil release agents and as enzyme stabilizers.
  • Reducing agents and antioxidants such as sodium sulfite or reducing sugars increase the stability of the enzymes against oxidative breakdown.
  • Combinations of stabilizers are preferably used, for example made 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 action of peptide-aldehyde stabilizers can be increased by the combination with boric acid and / or boric acid derivatives and polyols and can be further enhanced by the additional use of divalent cations, such as calcium ions.
  • the use of liquid enzyme formulations is particularly preferred in the context of the present invention.
  • the additional enzymes and / or enzyme preparations preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably 1.5 to 4.5 and in particular from 2 to 4% by weight, based in each case on the total composition.
  • Dyes and fragrances can be added to detergents or cleaning agents to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensorially "typical and distinctive" 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 e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate,
  • ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g.
  • terpenes such as limonene and pinene.
  • perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the fragrances can be incorporated directly into the compositions, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and by slower fragrance release for long-lasting Ensure the fragrance of the textiles.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • dyes In order to improve the aesthetic impression of the washing or cleaning agents, it (or parts thereof) can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to the substrates to be treated with the compositions, such as glass, ceramics or plastic dishes, so as not to stain them.
  • Detergents or cleaning agents can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. 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 structured compounds which are used instead of the morpholino group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • the end products of the process according to the invention can not only be admixed with particulate detergents or cleaning agents, but can also be used in detergent or cleaning agent tablets. Surprisingly, the solubility of such tablets is improved by using the end products of the process according to the invention compared to tablets of the same hardness and of identical composition which do not contain any 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. The production of such tablets using the process end products according to the invention is described below.
  • the washing and cleaning-active molded articles are produced by applying pressure to a mixture to be pressed, which is located in the cavity of a press.
  • a mixture to be tableted is directly, i.e. pressed without previous granulation.
  • the advantages of this so-called direct tableting are its simple and inexpensive use, since no further process steps and consequently no further plants are required.
  • these advantages are offset by disadvantages.
  • a powder mixture that is to be tabletted directly must have sufficient plastic deformability and have good flow properties. Furthermore, it must not show any tendency to segregate during storage, transport and filling of the die.
  • detergent tablets are extremely difficult to master with many substance mixtures, so that direct tableting is not often used, particularly in the manufacture of detergent tablets.
  • the usual way of producing detergent tablets is therefore based on powdery components (“primary particles”), which are agglomerated or granulated by suitable processes to form secondary particles with a larger particle diameter. These granules or mixtures of different granules are then mixed with individual powdery additives and fed to the tableting.
  • primary particles powdery components
  • these granules or mixtures of different granules are then mixed with individual powdery additives and fed to the tableting.
  • this means that the process end products of the process according to the invention are worked up into a premix with further ingredients, which may also be in granular form.
  • the premix Before the particulate premix is pressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This can be advantageous for the nature and physical properties of both the premix (storage, pressing) and the finished detergent tablets. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably "powdered” with finely divided zeolite, zeolites from faujasite Type 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 structure group 4 (compare Donald W.
  • Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites which do not necessarily have to belong to structure group 4 of the zeolite can also be used as powdering agents, it being advantageous if at least 50% by weight of the powdering agent from a zeolite of faujasite -Type exist.
  • detergent tablets consist of a particulate premix which contains granular components and subsequently admixed powdery substances, the or one of the subsequently admixed powdery components being a zeolite of the faujasite type with particle sizes below 100 ⁇ m, is 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 pressed.
  • the premixes to be pressed can additionally include one or more substances from the group of bleaching agents, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and contain corrosion inhibitors. These substances have been described above.
  • the moldings according to the invention are first produced by dry mixing the constituents, which may be wholly or partially pregranulated, and then providing information, in particular pressing them into tablets, using conventional methods.
  • the premix is compacted in a so-called die between two punches to form a solid compressed product. This process, which takes place in The following, briefly referred to as tableting, is divided into four sections: dosage, compression (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molding being formed being determined by the position of the lower punch and the shape of the pressing tool.
  • the constant metering, even at high molding throughputs, is preferably achieved by volumetric metering of the premix.
  • the upper punch touches the premix and lowers further towards the lower punch.
  • the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed.
  • the premix particles are also crushed and sintering of the premix occurs at even higher pressures.
  • the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities.
  • the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point in time, only the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.).
  • Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down.
  • eccentric tablet presses are preferably used, in which the stamp or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of this press ram is like a conventional four-stroke engine comparable.
  • the pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disc, the number of die holes being correspondingly increased.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of matrices 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 also commercially available.
  • Each die on the die table is assigned an upper and lower stamp, with the pressing pressure being active only by the upper or lower die. Lower stamp, but can also be built up by both stamps.
  • the die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
  • the pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.
  • Rotary presses can also be provided with two filling shoes to increase the throughput, only a semicircle having to be run through to produce a tablet.
  • several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling.
  • jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible.
  • Rotary tablet presses can also be equipped with single or multiple tools that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for pressing. The throughputs of modern rotary tablet presses are over one million tablets per hour.
  • Tableting machines suitable in the context of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, IMAmaschinessysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms.
  • Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (Sl ).
  • the hydraulic double pressure press HPF 630 from LAEIS, D. Tablettierwerkmaschinee are, for example, from the companies Adams Tablettierwerkmaschinee, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hörn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter diarrheabau, Tamm available.
  • Other providers include Senss AG, Reinach (CH) and Medicopharm, Kamnik (Sl).
  • the moldings can be manufactured in a predetermined spatial shape and a predetermined size. Practically all usable configurations come into consideration as the spatial shape, for example the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each be designed as separate individual elements which correspond to the predetermined dosage of the detergents and / or cleaning agents. However, it is also possible to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points.
  • the portioned compacts can be designed as tablets, in cylindrical or cuboid form, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred.
  • Commercial hydraulic presses, eccentric presses or Rotary presses are suitable devices, in particular for the production of such compacts.
  • the spatial shape of another embodiment of the shaped bodies is adapted in its dimensions to the induction chamber of commercially available household washing machines, so that the shaped bodies can be metered directly into the induction chamber without metering aid, where they dissolve during the induction process.
  • the detergent tablets can also be used without problems via a metering aid and are preferred in the context of the present invention.
  • Another preferred molded body that can be produced has a plate-like or sheet-like structure with alternately thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, broken off and into the Machine can be entered.
  • This principle of the "bar-shaped" shaped body detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.
  • the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible for these different layers to have different dissolution rates. This can result in advantageous performance properties of the molded articles. If, for example, components are contained in the moldings which have a mutually negative effect, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution.
  • the layer structure of the shaped bodies can be stacked, the inner layer (s) already loosening at the edges of the shaped body when the outer layers have not yet been completely detached, but the inner layer (s) can also be completely encased ) can be achieved by the layer (s) lying further out, what leads to the premature release of components of the inner layer (s).
  • a shaped body consists of at least three layers, that is to say two outer and at least one inner layer, at least one peroxy bleaching agent being contained in at least one of the inner layers, while in the case of the stacked shaped body the two cover layers and in the case of the shaped body the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in one molded body.
  • Such multilayered moldings have the advantage that they can be used not only via a dispenser or via a metering device which is added to the washing liquor; rather, it is also possible in such cases to put the molded body in direct contact with the textiles in the machine without fear of bleaching and the like.
  • the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the process of melt coating.
  • the breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to
  • ⁇ stands for diametral fracture stress (DFS) in Pa
  • P is the force in N that leads to the pressure exerted on the molded body that causes the molded body to break
  • D is the molded body 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)
EP03767728A 2002-12-12 2003-12-03 Procede ii de neutralisation a sec Expired - Lifetime EP1570040B1 (fr)

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DE10258006A DE10258006B4 (de) 2002-12-12 2002-12-12 Trockenneutralisationsverfahren II
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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

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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
EP1570040B1 (fr) 2007-03-21
WO2004053037A2 (fr) 2004-06-24
ATE357499T1 (de) 2007-04-15

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