EP1563052B1 - Procede pour produire des corps moules detergents et nettoyants garnis ii - Google Patents

Procede pour produire des corps moules detergents et nettoyants garnis ii Download PDF

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Publication number
EP1563052B1
EP1563052B1 EP03811371A EP03811371A EP1563052B1 EP 1563052 B1 EP1563052 B1 EP 1563052B1 EP 03811371 A EP03811371 A EP 03811371A EP 03811371 A EP03811371 A EP 03811371A EP 1563052 B1 EP1563052 B1 EP 1563052B1
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EP
European Patent Office
Prior art keywords
acid
weight
preferred
tablet
tablets
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP03811371A
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German (de)
English (en)
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EP1563052A2 (fr
Inventor
Thomas Holderbaum
Bernd Richter
Wolfgang Barthel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP1563052A2 publication Critical patent/EP1563052A2/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N1/00—Pretreatment of moulding material

Definitions

  • the present invention relates to a process for producing filled and subsequently sealed detergent tablets. It relates in particular to a process for the production of filled detergent tablets which comprise a base tablet with a trough which is filled and closed.
  • Lately forms of detergents or cleaners have proven to be advantageous in which various active ingredients are located in different areas.
  • various mixed forms are described in the literature in which tablets are combined with other bodies or in which water-soluble or dispersible packages are filled with tablets and / or other forms of preparation.
  • a viable way is to provide a mold (for example, a tablet with a trough or a through hole, a deep-drawn part of water-soluble material, an injection molding of water-soluble material, etc.), which is filled and then sealed, wherein hollow molds made of polymers Sealing plays a prominent role.
  • the filled hollow body can be difficult to move without the filling partially exits and complicates the application of adhesives or the adhesion of the occlusive film on the edges of the mold.
  • the application of adhesives to the edges of the mold is susceptible to interference if the filling is metered before the adhesive application, since the filling can contaminate the applicator tools.
  • a process for producing detergent tablets is disclosed in German Patent Application DE-A-10062582. According to the teaching of this document, a particulate premix is compressed to an extruded part, the wall of the cavity in this part is covered with foil and the cavity is filled with active substances.
  • the problems just described also occur here.
  • the filled moldings are difficult to move without the filling exits partially on the tablet top and there the application of adhesion promoters or the liability of Film difficult.
  • the application of adhesives to the tablet surface is susceptible to interference if the filling is metered in before the adhesive application, since the filling can contaminate the applicator tools.
  • Another problem lies in the exact cutting of the film after sticking, since protruding film seams affect the visual appearance of the tablet.
  • the present invention has for its object to provide a large-scale production compassionsverfahre for filled hollow or molded body of the type described, which is free from the disadvantages mentioned.
  • a fillable body is first produced. This is then filled and closed.
  • the preparation of the fillable body can preferably be made of materials which fulfill a function in the washing or cleaning process, wherein the tabletting of active substance mixtures occupies a prominent role.
  • greater dimensional variability may result from using materials that do not perform a specific function in the washing or cleaning process.
  • water-soluble or -dispersible polymers have an outstanding importance.
  • the disadvantage of using additional "ballast" is compensated by the advantage of greater variability in shape and potential ingredients as well as high aesthetic appeal.
  • Preferred variants of the process according to the invention are therefore characterized in that the production of the open cavity mold in step a) comprises the pressing of a particulate premix into a compressed part (base molding) having at least one cavity.
  • a further preferred embodiment are processes according to the invention, which are characterized in that the production of the open hollow mold in step a) takes place by deep drawing and / or casting and / or injection molding and / or blow molding of a water-soluble or -dispersible polymer or polymer mixture.
  • detergents or cleaners according to the invention are characterized in that they contain the dispersant in amounts above 11% by weight, preferably above 13% by weight, more preferably above 15% by weight, most preferably above 17% by weight. and in particular above 19 wt .-%, each based on the total weight of the dispersion.
  • agents according to the invention which have a dispersion with a proportion by weight of dispersant above 20% by weight, preferably above 21% by weight and in particular above 22% by weight, in each case based on the total weight of the dispersion.
  • the maximum content of preferred dispersions of dispersants according to the invention is preferably less than 63% by weight, preferably less than 57% by weight, more preferably less than 52% by weight, very particularly preferably less than 47 Wt .-% and in particular less than 37 wt .-%.
  • dispersions having a density of above 1.040 g / cm 3 Preference is given to using dispersions having a density of above 1.040 g / cm 3 .
  • dispersions according to the invention having a density of 1040-1670 g / cm 3, preferably 1.120 to 1.610 g / cm 3, particularly preferably 1.210 to 1.570 g / cm 3, most preferably 1.290 to 1.510 g / cm 3 , and in particular between 1.340 and 1.480 g / cm 3 .
  • the density data refer to the densities of the dispersions at 20 ° C.
  • the dispersants used are preferably water-soluble or water-dispersible.
  • the solubility of these dispersants at 25 ° C. is preferably more than 200 g / l, preferably more than 300 g / l, more preferably more than 400 g / l, very preferably between 430 and 620 g / l and especially between 470 and 580 g / l.
  • Dispersions which are preferably used according to the invention are characterized in that they are dissolved in water (40 ° C.) in less than 12 minutes, preferably less than 10 minutes, preferably less than 9 minutes, particularly preferably less than 8 minutes and in particular less Dissolve as 7 minutes.
  • 20 g of the dispersion are introduced into the interior of a dishwashing machine (Miele G 646 PLUS).
  • the main rinse of a standard rinse program (45 ° C) is started.
  • the determination of the solubility is carried out by the measurement of the conductivity, which is recorded via a conductivity sensor.
  • the dissolution process is completed when the maximum conductivity is reached. In the conductivity diagram, this maximum corresponds to a plateau.
  • the conductivity measurement starts with the replacement of the circulation pump in the main wash cycle.
  • the amount of water used is 5 liters.
  • Suitable dispersants in the context of the present invention are preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers.
  • the dispersant may be both a single polymer and mixtures of various water-soluble or water-dispersible polymers.
  • the dispersant or at least 50% by weight of the polymer mixture consists of water-soluble or water-dispersible nonionic polymers from the group consisting of polyvinylpyrrolidones, vinylpyrrolidone-vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.
  • Suitable polyalkylene glycols are, in particular, polyethylene glycols and polypropylene glycols.
  • Polymers of ethylene glycol, those of general formula III H- (O-CH 2 -CH 2 ) n -OH (III) satisfy, where n can assume values between 1 (ethylene glycol) and several thousand.
  • n can assume values between 1 (ethylene glycol) and several thousand.
  • polyethylene glycols there are various nomenclatures that can lead to confusion.
  • Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210.
  • polyethylene glycols for example under the trade name Carbowax® PEG 200 (Union Carbide), Emkapol® 200 (ICI Americas), Lipoxol® 200 MED (HUBS America), Polyglycol® E-200 (Dow Chemical), Alkapol® PEG 300 (Rhone -Poulenc), Lutrol® E300 (BASF) and the corresponding trade name with higher numbers.
  • the average relative molecular weight of at least one of the dispersants used in the detergents or cleaners according to the invention, in particular at least one of the poly (alkylene) glycols used, is preferably between 200 and 36,000, preferably between 200 and 6000 and particularly preferably between 300 and 5000.
  • washing or cleaning agents contain as dispersing agent a nonionic polymer, preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, wherein the weight fraction of the poly (ethylene) glycol on the total weight of all dispersing agents is preferably between 10 and 90% by weight, more preferably between 30 and 80% by weight and in particular between 50 and 70% by weight.
  • a nonionic polymer preferably a poly (alkylene) glycol, preferably a poly (ethylene) glycol and / or a poly (propylene) glycol, wherein the weight fraction of the poly (ethylene) glycol on the total weight of all dispersing agents is preferably between 10 and 90% by weight, more preferably between 30 and 80% by weight and in particular between 50 and 70% by weight.
  • Detergents or cleaning compositions according to the invention in which the dispersion medium is more than 92% by weight, preferably more than 94% by weight, more preferably more than 96% by weight, very particularly preferably more than 98, are particularly preferred Wt .-% and in particular to 100 wt .-% of a poly (alkylene) glycol, preferably poly (ethylene) glycol and / or poly (propylene) glycol, but in particular consists poly (ethylene) glycol.
  • Dispersing agents which also contain poly (propylene) glycol in addition to poly (ethylene) glycol preferably have a ratio of the weight proportions of poly (ethylene) glycol to poly (propylene) glycol between 40: 1 and 1: 2, preferably between 20: 1 and 1: 1, more preferably between 10: 1 and 1.5: 1, and most preferably between 7: 1 and 2: 1.
  • nonionic surfactants which are used alone, but particularly preferably in combination with a nonionic polymer.
  • a detailed description of the usable nonionic surfactants can be found below in the description. Reference is made to this embodiment to avoid repetition at this point.
  • washing or cleaning agents contain as dispersing agent at least one nonionic surfactant, preferably at least one end-capped poly (oxyalkylated) nonionic surfactant, wherein the weight fraction of the nonionic surfactant in the total weight of all dispersants preferably between 1 and 60 wt .-%, particularly preferably between 2 and 50 wt .-% and in particular between 3 and 40 wt.% Is.
  • washing or cleaning agents according to the invention in which the total weight of the nonionic surfactant (s) in the total weight of the composition according to the invention is between 0.5 and 40% by weight, preferably between 1 and 30% by weight, especially preferably between 2 and 25 and in particular between 2.5 and 23 wt .-% is.
  • Preferred washing or cleaning agents according to the invention are characterized in that at least one dispersing agent has a melting point above 25 ° C., preferably above 35 ° C. and in particular above 40 ° C.
  • such agents may for example contain a dispersant having a melting point above 26 ° C, or above 30 ° C, or 35 ° C, or above 42 ° C, or above 50 ° C.
  • dispersants having a melting point or melting range between 30 and 80 ° C, preferably between 35 and 75 ° C, more preferably between 40 and 70 ° C and in particular between 45 and 65 ° C, these dispersants, based on the total weight of the dispersants used, a weight fraction above 10 wt .-%, preferably above 40 wt .-%, more preferably above 70 wt.% And in particular between 80 and 100 wt .-%.
  • Preferred agents according to the invention are dimensionally stable at 20 ° C.
  • dimensionally stable means according to the invention which have an intrinsic dimensional stability, which enables them under normal conditions of manufacture, storage, transport and handling by the consumer to occupy a non-disintegrating spatial form, said this spatial form under the conditions mentioned above longer time, preferably 4 weeks, more preferably, 8 weeks and especially 32 weeks, not changed, that is under the usual conditions of manufacture, storage, transport and handling by the consumer persists in the production-related spatial-geometric shape, that is, does not melt.
  • the detergents or cleaners according to the invention contain at least one dispersant having a melting point below 15 ° C., preferably below 12 ° C. and in particular below 8 ° C.
  • Particularly preferred dispersants have a melting range between 2 and 14 ° C, in particular between 4 and 10 ° C.
  • all substances which are solid or wash-active at room temperature are suitable as dispersed substances, but especially washing or cleaning substances from the group of builders (builders and co-builders), washing or cleaning-active polymers, bleaching agents, bleach activators , the glass corrosion inhibitor, the silver protectant and / or the enzymes.
  • Agents preferred according to the invention are characterized in that the dispersed substances, based on their total weight, at least 20% by weight, preferably at least 30% by weight, particularly preferably at least 40% by weight and in particular at least 50% by weight of builders and / or or bleaches and / or bleach activators and / or washing or cleaning-active polymers and / or glass corrosion inhibitors and / or silver protectants and / or enzymes.
  • compositions according to the invention consist of at least 90% by weight, preferably at least 92% by weight, preferably at least 94% by weight, more preferably at least 96% by weight, particularly preferably at least 98% by weight and most preferably at least 99.5 wt .-% in addition to the above-mentioned preferred dispersants further exclusively from builders and / or bleaches and / or bleach activators and / or washing or cleaning active polymers and / or glass corrosion inhibitors and / or silver protectants and / or enzymes ,
  • open molds are produced in the first step of the process according to the invention, which have at least one cavity.
  • the open molds according to the invention can also be designed such that they have a plurality of cavities which are filled successively or simultaneously with the same or with different active substances.
  • the particle size of the premix compressed in step a) preferably also satisfies certain criteria: Processes in which the particulate premix in step a) has particle sizes between 100 and 2000 .mu.m, preferably between 200 and 1800 .mu.m, more preferably between 400 and 1600 .mu.m and in particular between 600 and 1400 ⁇ m, are preferred according to the invention. A further narrowed particle size in the premixes to be compressed can be adjusted to obtain advantageous molded body properties.
  • the particulate premix compressed in step a) has a particle size distribution in which less than 10% by weight, preferably less than 7.5% by weight and in particular less than 5% by weight of Particles larger than 1600 microns or smaller than 200 microns are.
  • narrower particle size distributions are more preferred.
  • Particularly advantageous process variants are characterized in that the particulate premix compressed in step a) has a particle size distribution at which more than 30% by weight, preferably more than 40% by weight and in particular more than 50% by weight of the particles have a particle size between 600 and 1000 microns.
  • the inventive method is not limited to that only a particulate premix is pressed into a shaped body. Rather, process step a) can also be extended to produce multilayer molded articles in a manner known per se by preparing two or more premixes which are pressed together.
  • the first-filled premix is slightly pre-pressed to get a smooth and parallel to the mold bottom extending top, and end-pressed after filling the second premix to the finished shaped body.
  • a further pre-compression takes place after each premix addition, before the shaped article is end-pressed after the last premix has been added.
  • the cavity described above in the base molding is a trough, so that preferred embodiments of the first method according to the invention are characterized in that in step a) multi-layered moldings having a trough, are prepared in a conventional manner by several different particulate premixes to each other be pressed.
  • step a) first by the dry mixing of the constituents, which may be pre-granulated in whole or in part, and subsequent informing, in particular pressing into tablets, whereby conventional methods can be used.
  • the premix is compacted in a so-called matrix between two punches to form a solid compressed product.
  • This process hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix.
  • the upper punch contacts the pre-mix and continues to descend toward the lower punch.
  • the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding.
  • the premix particles are also crushed, and even higher pressures cause sintering of the premix.
  • the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities.
  • the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size.
  • the tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down.
  • eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine.
  • the compression can each with a top and Lower stamp done, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohritch is extended accordingly.
  • the throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies are arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available.
  • Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp.
  • the die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection.
  • these curved paths are supported by additional low-pressure pieces, Nierderzugschienen and lifting tracks.
  • the filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix.
  • the pressing pressure on the premix is individually adjustable via the compression paths for upper and lower punches, wherein the pressure build-up is done by the Vorbeirollen the stamp shank heads on adjustable pressure rollers.
  • Concentric presses can be provided with two Drik to increase the throughput, with the production of a tablet only a semicircle must be traversed.
  • several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling.
  • suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible.
  • Even rotary tablet presses can be equipped with single or multiple tools, so 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 amount to over one million moldings per hour.
  • Plastic coatings, plastic inserts or plastic stamps are particularly advantageous.
  • Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.
  • step a) takes place at compression pressures of from 0.01 to 50 kNcm -2 , preferably from 0.1 to 40 kNcm -2 and in particular from 1 to 25 kNcm -2 ,
  • Tableting machines suitable for the purposes of the present invention are obtainable, for example, from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMAmaschinessysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell on the lake, KORSCH presses AG, Berlin, as well as Romaco GmbH, Worms.
  • Other providers include Dr. med. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ).
  • the cavity in the molded body produced in step a) can have any shape. It can divide the shaped body, i. an opening at the top and bottom of the molding, but it may also be a not passing through the entire molding cavity, the opening is visible only on a molded body side.
  • the moldings produced according to the invention may take any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid, five, seven and octagonal prismatic and rhombohedral forms are preferred. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. If the shaped bodies according to the invention have corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and bevelled ("touched”) edges is preferred.
  • the moldings produced according to the invention can also be produced in a multiphase manner.
  • two-layer moldings have proven particularly useful.
  • the shape of the cavity can also be chosen freely within wide limits, regardless of the choice of the manufacturing process in step a). For reasons of process economy, through holes whose openings are located on opposite surfaces of the moldings, and wells with an opening on a molded body side have proven.
  • the cavity has the shape of a through hole, the openings of which are located on two opposite mold body surfaces.
  • the shape of such a through hole can be chosen freely, wherein moldings are preferred in which the through hole has circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, heptagonal or octagonal horizontal sections. Even completely irregular hole shapes such as arrow or animal shapes, trees, clouds, etc. can be realized.
  • those with rounded corners and edges or with rounded corners and touched edges are preferred.
  • moldings with a rectangular or square base and circular holes can be made as well as round moldings with octagonal holes, the variety of possible combinations are no limits.
  • moldings with a hole are particularly preferred in which the mold body base area and the hole cross section have the same geometric shape, for example shaped bodies with a square base area and a centrally machined square hole.
  • Particularly preferred are ring shaped bodies, i. circular shaped bodies with a circular hole.
  • the shaped bodies produced according to the invention can also assume any geometric form in this embodiment, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylindrical segments, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, hexagonal, octagonal prismatic and rhombohedral shapes are preferred. Even completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can be realized. If the shaped body has corners and edges, these are preferably rounded off. As additional optical differentiation, an embodiment with rounded corners and bevelled ("touched”) edges is preferred.
  • the shape of the trough can be chosen freely, wherein moldings are preferred in which at least one trough is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, cylinder segment, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal , five-, seven- and octagonal-prismatic as well as rhombohedral form.
  • Completely irregular shapes such as arrow or animal shapes, trees, clouds etc. can also be realized.
  • wells with rounded corners and edges or with rounded corners and chamfered edges are preferred.
  • Particularly preferred are tray molds as described in German Patent Application DE 198 22 973 A1 (Henkel KGaA), to which express reference is made.
  • the size of the trough or the through hole compared to the entire shaped body depends on the desired use of the shaped body. Depending on whether the cavity is to be filled with additional active substance and whether a smaller or larger amount may be included in the active substance, the size of the cavity may vary. Regardless of the intended use, detergent tablets are preferred in which the volume ratio of tablet to cavity is 2: 1 to 100: 1, preferably 3: 1 to 80: 1, particularly preferably 4: 1 to 50: 1 and in particular 5: 1 to 30: 1, is.
  • the volume ratio is calculated from the volume of the finished molded article according to the invention, ie the molded article having the cavity which is closed with the film and the volume of the cavity.
  • the difference between the two volumes gives the volume of the shaped body with a cavity, in which the cavity is not closed with foil.
  • the volume of this "basic shaped body" is 22 cm 3 .
  • the volume used to calculate the ratio is 24 cm 3 , since the trough is closed with foil and thus there is an orthorhombic molded body without trough to the outside.
  • the ratio of the volumes is 12: 1.
  • volume ratios of moldings cavity below 2: 1, which, of course, can also be realized according to the invention, the instability of the walls can increase.
  • the opening (s) of the cavity in such an exemplary shaped body in preferred embodiments of the present invention thus has an area of 0.52 to 13 cm 2 , preferably of 1.04 to 10.4 cm 2 , particularly preferably 1.56 to 7.8 cm 2 and especially 2.08 to 5.2 cm 2 .
  • step b) the cavity is filled with active substance (s), active substance mixtures or active substance preparations.
  • active substance active substance
  • the cavity has more than one opening, it is procedurally expedient to close the second, third and any further openings in order to make the filling technically easier in this way.
  • the cavity of the molded body produced in step a) has more than one opening, it is preferable to carry out the optional step b) - filling - only after (n-1) -first execution of step c), if the number of Openings n is.
  • the Closing the last opening then corresponds to the last-time implementation of method step c), to which further steps can follow.
  • the shaped bodies produced according to the invention consist of a basic shaped body which has one or more cavities, foil (s) which closes / closes this cavity (s) and optionally active substance (s) contained in the cavity (s).
  • the film materials and preferred physical parameters of the films are described below.
  • the ingredients of the basic tablet which may be simultaneously active ingredients contained in the cavity, as well as an enumeration of preferred physical parameters for basic tablets and filling the cavity.
  • the solubility of the filling of the cavity can be specifically accelerated, on the other hand, the release of certain ingredients from this filling can lead to advantages in the washing or cleaning process.
  • Ingredients which are preferably at least partially localized in the cavity are, for example, the surfactants, enzymes, soil-release polymers, builders, bleaches, bleach activators, bleach catalysts, optical brighteners, silver protectants, etc., described below.
  • the base molding in preferred embodiments of the present invention has a high specific gravity.
  • Detergents and cleaning agent tablets which are characterized in that the base tablet has a density above 1000 kgdm -3 , preferably above 1025 kgdm -3 , more preferably above 1050 kgdm -3 and in particular above 1100 kgdm -3 are according to the invention prefers.
  • Process step a) will be explained below with reference to the second preferred process variant of producing the open hollow mold by deep drawing and / or casting and / or injection molding and / or blow molding of a water-soluble or -dispersible polymer or polymer mixture:
  • the melt leaving the extruder is blow-molded.
  • Blow molding methods suitable for the present invention include extrusion blow molding, coextrusion blow molding, injection stretch blow molding and dipping blowing.
  • the wall thicknesses of the moldings can be produced by blow molding partially different, by the wall thicknesses of the preform, preferably along its vertical axis, according to different thicknesses, preferably by regulating the amount of thermoplastic material, preferably by means of an adjusting spindle during application of the preform from the extruder die, is formed.
  • the powdered or liquid filled solid can be blow molded with regions of different outer circumference and uniform wall thickness by varying the wall thicknesses of the preform, preferably along its vertical axis, accordingly different thicknesses, preferably by controlling the amount of thermoplastic material by means of an adjusting spindle during application of the preform from the extruder die, forming.
  • the shaped body can emboss and / or decorate during blow molding in the blow mold.
  • a motif can be mirror images transferred to the molding.
  • the surface of the molding can be virtually any shape.
  • information such as calibration marks, application instructions, danger symbols, brands, weight, filling quantity, expiration date, images, etc. can be applied to the shaped body.
  • the preform and / or the hollow body may be tubular, spherical or bubble-shaped.
  • a spherical shaped body preferably has a shape factor of> 0.8, preferably of> 0.82, preferably> 0.85, more preferably> 0.9 and particularly preferably of> 0.95.
  • the shape factor in the sense of the present invention can be precisely determined by modern particle-measuring techniques with digital image processing.
  • a common method is, for example, the Camsizer® system from Retsch Technology or the KeSizer® from Kemira. These methods are based on the fact that the bodies are irradiated with a light source and the moldings are detected as projection surfaces, digitized and processed by computer technology.
  • the determination of the surface curvature is made by an optical measuring method in which the "shadow cast" of the body to be examined is determined and converted into a corresponding form factor.
  • the underlying principle for determining the shape factor has been described, for example, by Gordon Rittenhouse in "A visual method of estimating two-dimensional sphericity" in the Journal of Sedimentary Petrology, Vol.
  • the measuring limits of this optical analysis method are 15 ⁇ m to 90 mm.
  • Methods for determining the shape factor for larger particles are known to those skilled in the art. These are usually based on the principles of the aforementioned methods.
  • the walls of the hollow bodies produced by blow molding have a wall thickness of between 0.05 and 5 mm, preferably between 0.06 and 2 mm, preferably between 0.07 and 1.5 mm, more preferably between 0.08 and 1 , 2 mm, more preferably from 0.09 to 1 mm, and most preferably from 0.1 to 0.6 mm.
  • the filling opening of the hollow body after filling can be closed in a liquid-tight manner in step c), wherein it is preferable to provide corresponding edges around the filling opening during blow molding.
  • the melt of water-soluble polymer blend leaving the extruder is shaped by means of an injection molding process.
  • Injection molding is carried out in accordance with per se known procedures at high pressures and temperatures with the steps of closing the mold connected to the extruder for injection molding, injecting the polymer at high temperature and high pressure, cooling the injection-molded molding, opening the mold and removing the molded blank , Further optional steps, such as the application of release agents, demolding, etc., are known to the person skilled in the art and can be carried out according to technology known per se.
  • injection molding is carried out at up to 5000 bar, preferably between 2 and 2500 bar, more preferably between 5 and 2000 bar, even more preferably between 10 and 1500 and in particular between 100 and 1250 bar.
  • the temperature of the material to be injection molded is preferably above the melting or softening point of the material and thus also depends on the type and composition of the polymer blend. In preferred inventive method is at temperatures between 100 and 250 ° C, preferably between 120 and 200 ° C and in particular between 140 and 180 ° C, injection-molded.
  • the tools that receive the materials are preferably pre-tempered and have temperatures above room temperature, with temperatures between 25 and 60 ° C and in particular from 35 to 50 ° C are preferred.
  • the thickness of the wall can be varied.
  • the wall should on the one hand be chosen so thin that a rapid dissolution or disintegration is achieved and the ingredients are released quickly into the application fleet, but also a certain minimum thickness is required to give the mold the desired stability, in particular dimensional stability.
  • Preferred wall thicknesses of injection-molded articles are in the range from 100 to 5000 .mu.m, preferably from 200 to 3000 .mu.m, particularly preferably from 300 to 2000 .mu.m and in particular from 500 to 1500 .mu.m.
  • the molded article produced by injection molding does not have walls that are closed on all sides and is open on at least one of its sides-in the case of a spherical or elliptical body in the region of a part of its shell-due to its production.
  • a preparation (s) is / are introduced into the compartment (s) formed inside the molding. This is also done in a known per se way, for example in the context of known from the confectionery industry manufacturing process; It is also possible to proceed in several steps.
  • a one-step procedure is particularly preferred if, in addition to solid preparations, preparations comprising liquid components (dispersions or emulsions, suspensions) or even preparations comprising gaseous components (foams) are to be introduced into shaped articles.
  • a film of appropriate material on a mold having recesses placed, optionally heated and then pulled under negative pressure in the depression.
  • the film can be pressed by pressurization from the top or by a punch in the mold.
  • Preferred wall thicknesses of deep-drawn moldings are in the range from 100 to 5000 .mu.m, preferably from 200 to 3000 .mu.m, particularly preferably from 300 to 2000 .mu.m and in particular from 500 to 1500 .mu.m.
  • the hollow bodies preferably have edges to which the labels can be applied in the later method step.
  • the width of these edges is preferably at least 2 mm.
  • Suitable materials for the hollow bodies of water-soluble or -dispersible polymers are all polymers which can also be used for the closing film. These are described below.
  • the mold can be produced in step a) of the process according to the invention by casting water-soluble or water-dispersible polymers or polymer mixtures or dispersions.
  • the production of the mold in step a) can be carried out with different techniques.
  • a flowable mixture is filled into a corresponding mold. If you let the mixture solidify there, you would get a compact body, no mold. By suitable process control can be ensured that the mixture first solidifies on the wall of the mold. If the mold is turned over after a certain time t, the excess mixture flows off, leaving behind a lining of the mold, which itself forms a hollow mold, which can be demoulded after complete solidification.
  • the turning of the mold is preferably carried out after a time t between 0 and 20 minutes, preferably after a time t between 1 and 17 minutes, more preferably after a time between 2 and 14 minutes, most preferably between 3 and 11 minutes and especially between 4 and 8 minutes.
  • the cavity can only be partially filled.
  • the water-soluble or water-dispersible Polymer or polymer mixture or the water-soluble or water-dispersible dispersion is pressed in these cases with a suitable stamp on the wall of the cavity, where it solidifies to the hollow body.
  • This process variant is quasi an intermediate form between the "Abgtigtechnik" and the casting technique in negative forms of the hollow body.
  • a cooled stamp is used.
  • the temperature of this cooled stamp is preferably between 5 and 20 ° C, more preferably between 8 and 19 ° C, most preferably between 11 and 18 ° C and especially between 14 and 17 ° C.
  • the noses or edges of solidified wash- or cleaning-active preparation are cut or scraped off by knives or removed with a roller from the molds produced by turning or displacement.
  • heated blades or scrapers or rollers are used for cutting or scrapers or rolls.
  • the temperature of these heated knives, scrapers or rollers is preferably at least 35 ° C, preferably at least 45 ° C and in particular between 50 and 90 ° C.
  • the open hollow bodies are produced by tabletting or by other methods, they are filled with active substance (s) in step b) of the process according to the invention.
  • active substance for example, dyes, enzymes, optical brighteners, redispersing agents, complexing agents, etc., so-called minor components
  • the majority of the active substance will be in the Filling are located.
  • prepared detergent tablets are characterized in that the basic tablet builders in amounts of 1 to 100 wt .-%, preferably from 5 to 95 wt .-%, particularly preferably from 10 to 90 wt .-% and in particular from 20 to 85 wt .-%, each based on the weight of the base molding contains.
  • all builders commonly used in detergents and cleaning agents may be present, in particular zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 ⁇ yH 2 O are preferred.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • preferably prepared detergent tablets are characterized in that the base tablet silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous Alkalidisilikate, in amounts of 10 to 60 wt .-%, preferably from 15 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the weight of the base molding contains.
  • the base tablet silicate preferably alkali metal silicates, particularly preferably crystalline or amorphous Alkalidisilikate
  • the finely crystalline, synthetic and bound water-containing zeolite 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 particularly preferred.
  • zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 2 O ⁇ (1-n) K 2 O ⁇ Al 2 O 3 ⁇ (2 - 2.5) SiO 2 ⁇ (3.5-5.5) H 2 O. can be described.
  • the zeolite can be used both as a builder in a granular compound, as well as to a kind of "powdering" of the entire mixture to be pressed, wherein usually both ways for incorporating the zeolite are used in the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate primary or monobasic potassium phosphate, potassium biphosphate, KDP
  • KH 2 PO 4 is a white salt of density 2.33 gcm -3 a melting point 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is readily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Condensation of the NaH 2 PO 4 or the KH 2 PO 4 results in higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain types, the sodium or potassium polyphosphates.
  • cyclic representatives the sodium or potassium metaphosphates and chain types, the sodium or potassium polyphosphates.
  • hot or cold phosphates Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • preferably prepared detergent tablets are characterized in that the base tablet phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate), in amounts of 20 to 80 Wt .-%, preferably from 25 to 75 wt .-%, in particular from 30 to 70 wt .-%, each based on the weight of the base molding contains.
  • the base tablet phosphate preferably alkali metal phosphate (s), more preferably pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate)
  • alkali carriers may be present.
  • Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate.
  • a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate.
  • the basic tablet contains carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonates, more preferably sodium carbonate, in amounts of from 5 to 50% by weight, preferably from 7.5 to 40% by weight. -% and in particular from 10 to 30 wt .-%, each based on the weight of the base molding.
  • carbonate (s) and / or bicarbonate (s) preferably alkali metal carbonates, more preferably sodium carbonate, in amounts of from 5 to 50% by weight, preferably from 7.5 to 40% by weight. -% and in particular from 10 to 30 wt .-%, each based on the weight of the base molding.
  • Particularly suitable organic co-builders in the detergent tablets according to the invention are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Aminoalkanphosphonate - preferably come Ethylenendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question.
  • ETMP Ethylenendiamintetramethylenphosphonat
  • DTPMP Diethylentriaminpentamethylenphosphonat
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%, each based on the base molding.
  • the amount of builders used depends on the intended use, so that bleach tablets may have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight. ), for example, detergent tablets (usually 10 to 50 wt .-%, preferably 12.5 to 45 wt .-%, in particular between 17.5 and 37.5 wt .-%).
  • the said substances from the group of builders and co-builders can of course be part of the compositions contained in the cavity.
  • Prefabricated detergent tablets also contain one or more surfactants.
  • surfactants prepared anionic, nonionic, cationic and / or amphoteric Surfactants or mixtures of these can be used.
  • laundry detergent tablets are preferably mixtures of anionic and nonionic surfactants and detergents tablets nonionic surfactants.
  • the total surfactant content of the tablets in the case of detergent tablets is 5 to 60% by weight, based on the tablet weight, with surfactant contents above 15% by weight being preferred, whereas automatic dishwashing detergent tablets preferably contain less than 5% by weight of surfactant (e ) contain.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which are prepared for example according to US Patents 3,234,258 or 5,075,041 and as Commercial products of the Shell Oil Company under the name DAN® can be obtained are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 -alcohol with 7 EO, C 13-15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters as they are for example, in Japanese Patent Application JP 58/217598, or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (I) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to the teaching of international application WO-A-95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • washing agent and detergent tablets which contain anionic and nonionic surfactant (s) are preferred in the preparation of laundry detergent tablets, with technical advantages resulting from specific proportions in which the individual classes of surfactant are used ,
  • washing and cleaning agent tablets prepared according to the invention are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5 : 1 and 1: 2 is.
  • anionic surfactants Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases may result in washing and cleaning agent tablets which are more suitable for certain fields of application. It is therefore within the scope of the present invention also possible to use detergent tablets in which at least one phase of the tablets is free of anionic surfactants.
  • detergent tablets and detergent tablets which are preferably to be produced as detergent tablets are characterized in that the basic tablet has total surfactant contents below 5% by weight, preferably below 4% by weight, more preferably below 3% by weight and in particular below of 2 wt .-%, each based on the weight of the base molding having.
  • surfactants only weakly foaming nonionic surfactants are usually used in automatic dishwashing detergents. Representatives from the groups of anionic, cationic or amphoteric surfactants, however, have less importance.
  • the machine dishwashing detergent tablets according to the invention contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferred may be methyl branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • the detergent tablets contain a nonionic surfactant having a melting point above room temperature.
  • at least one of the deformable masses in the process according to the invention preferably contains a nonionic surfactant having a melting point above 20 ° C.
  • Preferably used nonionic surfactants have melting points above 25 ° C, particularly preferably used nonionic surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant derived from the Reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, more preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
  • the nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants which may be used with particular preference are available, for example, under the name Poly Tergent® SLF-18 from Olin Chemicals.
  • a further preferred surfactant can be defined by the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ] in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1, 5 and y is a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.
  • Preferred detergent tablets contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, of one or more disintegration aids, in each case based on the weight of the tablet. If only the basic tablet contains disintegration aids, then the details given relate only to the weight of the basic tablet.
  • Preferred disintegrating agents in the context of the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning agent tablets contain such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • alkali celluloses fall into the group of cellulose derivatives.
  • the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
  • the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivative
  • Suitable swellable disintegration aids are, for example, bentonites or other swellable silicates. It is also possible to use synthetic polymers, in particular the superabsorbents or cross-linked polyvinylpyrrolidone used in the hygiene sector.
  • polymers based on starch and / or cellulose are used as swellable disintegration aids. These base substances can be processed alone or in admixture with other natural and / or sythetic polymers to swellable disintegrating agents.
  • a cellulosic material or pure cellulose can be converted by pressure transfer into secondary particles by granulation, compaction or other application, which swell on contact with water and thus serve as a disintegrant.
  • Wood pulp which has been obtained by thermal or chemical-thermal processes from wood or wood chips (sawdust, sawmill waste) has proven to be suitable as a cellulosic material.
  • This cellulosic material from the TMP process (thermo-mechanical pulp) or the CTMP process (chemo-thermo-mechanical pulp) can then be compatibilized by application of pressure, preferably roll-shaped and converted into particle form.
  • pure cellulose can also be used in a completely analogous manner, although it is more expensive from the raw material base.
  • both microcrystalline and amorphous finely divided cellulose and mixtures thereof can be used.
  • Another way is to granulate the cellulose-containing material with the addition of granulation aids.
  • granulation aids for example, solutions of synthetic polymers or nonionic surfactants have proven useful as granulating aids.
  • the primary fiber length of the cellulose or cellulose used in the cellulose-containing material should be less than 200 .mu.m, preference being given to primary fiber lengths of less than 100 .mu.m, in particular less than 50 .mu.m.
  • the secondary particles ideally have a particle size distribution in which more than 90% by weight of the particles are sizes above 200 ⁇ m. A certain proportion of dust can contribute to an improved storage stability of the tablets produced therewith. Shares of a fine dust content of less than 0.1 mm up to 10% by weight, preferably up to 8% by weight, may be present in the disintegrant granules used according to the invention.
  • the finely divided cellulose preferably has apparent densities of from 40 g / l to 300 g / l, very particularly preferably from 65 g / l to 170 g / l. If already granulated types are used, their bulk density is higher and, in an advantageous embodiment, can be from 350 g / l to 550 g / l.
  • the bulk densities of the cellulose derivatives are typically in the range of 50 g / l to 1000 g / l, preferably in the range of 100 g / l and 800 g / l.
  • cellulose-based disintegration aids which, in addition to cellulose, contain other active ingredients or auxiliaries.
  • Suitable here are, for example, compressed disintegrant granules of 60-99% by weight of non-water-soluble, water-swellable cellulose and optionally further, modified water-swellable polysaccharide derivatives, 1-40% by weight of at least one polymeric binder in the form of a polymer or copolymer of (meth) acrylic acid and / or salts thereof, and 0 - 7 wt.% Of at least one liquid, gelling with water surfactant.
  • These disintegrants preferably have a moisture content of from 2 to 8% by weight.
  • the proportion of cellulose in such disintegrant granules is between 60 to 99% by weight, preferably between 60 to 95% by weight.
  • Regenerated celluloses such as viscose can also be used in these disintegrants.
  • Especially regenerated celluloses in powder form are characterized by a very good water absorption.
  • the viscose powder can be produced from cut viscose fiber or by precipitation of the dissolved viscose.
  • Low molecular weight cellulose degraded by electron beam is also suitable, for example, for producing such disintegrant granules.
  • the swellable disintegration aids according to the invention contained in the detergent tablets may contain water-swellable cellulose derivatives such as cellulose ethers and cellulose esters and starch or starch derivatives and other swellable polysaccharides and polygalactomannans, for example ionically modified celluloses and starches such as carboxymethyl-modified cellulose and starch, nonionically modified celluloses and Starches such as alkoxylated celluloses and starches, such as hydroxypropyl and hydroxyethyl starch or hydroxypropyl and hydroxyethyl cellulose and alkyl-etherified products such as methyl cellulose and mixed modified celluloses and starches from the aforementioned modifications, optionally combined with a modification which leads to crosslinking.
  • water-swellable cellulose derivatives such as cellulose ethers and cellulose esters and starch or starch derivatives and other swellable polysaccharides and polygalactomannans
  • Suitable starches are also cold-swelling starches which are formed by mechanical or degrading reactions on the starch grain. Which includes especially swelling starches from extruder and roller dryer processes as well as enzymatically, oxidatively or acid-degrading modified products.
  • Chemically derivatized starches preferably contain substituents attached to the polysaccharide chains in sufficient numbers by ester and ether groups
  • Starches modified with ionic substituents such as carboxylate, hydroxyalkyl or phosphate groups have been found to be particularly advantageous and are therefore preferred. To improve the swelling behavior, the use of easily cross-linked starches has proven itself. Also alkaline treated starches can be used because of their good cold water swellability.
  • the combination of cellulose with cellulose derivatives and / or starch and / or starch derivatives has been proven. The proportions can vary within wide limits, based on the combination, the proportion of cellulose derivatives and / or starch and / or starch derivatives preferably 0.1 to 85 wt.%, Particularly preferably 5 to 50 wt.%.
  • polymers or copolymers of (meth) acrylic acid or mixtures of such polymers or copolymers are used as binders in preferred disintegration aid granules.
  • the polymers are selected from the group of homopolymers of (meth) acrylic acid, from the group of copolymers with the following monomer components of ethylenically unsaturated dicarboxylic acids and / or their anhydrides and / or ethylenically unsaturated sulfonic acids and / or acrylic esters and / or vinyl esters and / or vinyl ethers or their saponification products and / or crosslinkers and / or graft bases based on polyhydroxy compounds.
  • Non-crosslinked polymers or copolymers of (meth) acrylic acid having weight-average molecular weights of 5,000 to 70,000 have proved to be particularly suitable.
  • the copolymers are preferably copolymers of (meth) acrylic acid and ethylenically unsaturated dicarboxylic acids or their anhydrides, such as maleic acid or maleic anhydride, which contain, for example, 40 to 90% by weight of (meth) acrylic acid and 60 to 10% by weight of maleic acid or Contain maleic anhydride whose relative molecular weight, based on free acids, between 3,000 and 100,000, preferably 3,000 to 70,000 and most preferably 5,000 to 50,000.
  • ter- and quattropolymere polycarboxylates composed of (meth) acrylic acid, maleic acid and optionally fully or partially saponified vinyl alcohol derivatives, or those of (meth) acrylic acid, ethylenically unsaturated sulfonic acids and polyhydroxy units, such as sugar derivatives, or such from (meth) acrylic acid, maleic acid, vinyl alcohol derivatives and monomers containing sulfonic acid groups.
  • the polymeric binders are preferably used in the preparation in the form of their aqueous solutions, but can also be used in the form of finely divided powders.
  • the binder polymers are preferably in part or fully neutralized form, the salt formation is preferably carried out with cations of alkali metals, ammonia and amines, or mixtures thereof.
  • the proportion of polymers / copolymers in preferred disintegrants is between 1 and 40% by weight, preferably between 1 and 20% by weight, particularly preferably between 5 and 15% by weight. Polymer contents above 15% in the disintegrant result in harder disintegrant granules, while polymer contents below 1% tend to form soft granules that are less resistant to abrasion.
  • Suitable polymer binders are also crosslinked polymers of (meth) acrylic acid. They are preferably used as finely divided powders and preferably have average particle sizes of 0.045 mm to 0.150 mm and are preferably used with 0.1 to 10 wt.%. Although particles having an average particle size of more than 0.150 mm also give good disintegrant granules, but after dissolution of the pellets produced with the granules visually visible as particles swelling bodies, which are deposited clearly visible, for example in the case of textile washes on the fabric in a disturbing manner.
  • a particular embodiment of the invention is the combination of soluble poly (meth) acrylate homo- and copolymers and the aforementioned finely divided crosslinked polymer particles.
  • disintegrant granules contain one or more liquid, water-gelling surfactants selected from the group of nonionic, anionic or amphoteric surfactants, which may be present in amounts of up to 7% by weight, preferably up to 3.5% by weight can. If the surfactant content in the disintegrant is too high, in addition to an increased abrasion of the tablets produced therewith, also worse swelling properties result.
  • the nonionic surfactants have been described in detail above.
  • Disintegration aids which are preferably used according to the invention are distinguished by a special swelling kinetics, the extent of which does not change linearly as a function of time, but already reaches a very high level after a very short time. Of particular interest is the swelling behavior in the first 10 seconds after contact with water.
  • the specific water absorption capacity of preferably used disintegration assistant can be determined gravimetrically and is preferably 500 to 2000%.
  • the liquid uptake (also referred to as specific porosity) of preferred disintegrants is in a range of more than 600 ml / kg, preferably more than 750 ml / kg, in particular in the range 800 to 1000 ml / kg.
  • Granulated disintegrant granules are initially produced by mixing the granule constituents with customary mixing processes. For example, mixers from Vomm, Lödige, Schugi, Eirich, Henschel or Fukae can be used. In this first step of mixing and granulating, precompounds are produced by agglomeration processes.
  • these precompounds are mechanically compacted.
  • the compression using pressure can be done in various ways.
  • the products can between two pressure surfaces in roller compactors, z. B. smooth or profiled, be compacted.
  • the output of the Kompaktates takes place as a strand.
  • Compacting methods in dies with punches or cushion rolls result in compact forms such as tablets or briquettes.
  • Roller compactors, extruders, roller or die presses, but also granulation presses can be used as compacting machines.
  • pelleting presses Compaction with pelleting presses has proved particularly suitable, granules being obtained by suitable process control which can be dried without further comminution.
  • suitable pelleting presses are e.g. produced by the companies Amandus Kahl and Fitzpatrick.
  • the coarse, compacted particles are comminuted, e.g. Mills, shredders or roller mills are suitable.
  • the comminution can be carried out before or after drying.
  • preferred water contents of 2 to 8% by weight, preferably 2.5 to 7% by weight and more preferably 3 to 5% by weight, can be set.
  • conventional dryers such as e.g. Drum dryers (e.g., temperatures of 95-120 ° C) or fluidized bed dryers (e.g., temperatures of 70-100 ° C).
  • Suitable swellable disintegration aids are also coprocesses which are obtained from polysaccharide material and insoluble disintegrants.
  • polysaccharide materials the abovementioned substances from the groups powdery cellulose, microcrystalline cellulose and mixtures thereof are particularly suitable here;
  • Insoluble disintegrants which can be considered here in particular are insoluble polyacrylic acid monopolymers, insoluble polyacrylamide monopolymers, insoluble polyacrylic acid-polyacrylamide copolymers and mixtures thereof.
  • the content of the individual components in these disintegrating agents may vary within wide limits, for example from 1 to 60% by weight of insoluble polyacrylic product disintegrating agent and from 40 to 99% by weight of cellulose.
  • Preferred is a content of 3 to 60% by weight of insoluble polyacrylic product disintegrant and 40 to 97% by weight of cellulose.
  • Even more preferred is a content of 5 to 30% by weight of insoluble polyacrylic product disintegrant and 70 to 95% by weight of cellulose.
  • small quantities of further disintegrating agents for example various starches, effervescent mixtures, e.g. sodium carbonate and sodium bisulfate, etc., these amounts being offset by appropriate deductions in the amount of cellulose, i. be compensated.
  • This suitable disintegrant can be obtained by coprocessing a cellulose as defined above with an insoluble disintegrant as defined above by wet or dry compression under pressure.
  • coprocessing is meant herein dry compaction e.g. between counter-rotating compacting rolls at pressures of 20-60 kN, preferably 30-50 kN, or wet compaction after addition of water, by kneading or pressing of wet-plastic masses through a sieve, a perforated disc or an extruder and final drying understood.
  • the detergent tablets according to the invention can also contain a gas-evolving effervescent system both in the basic tablet and in the cavity.
  • the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water.
  • the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas. While here a variety of systems is thinkable and executable that release, for example, nitrogen, oxygen or hydrogen, the bubble system used in the detergent tablets according to the invention can be selected both on the basis of economic as well as ecological aspects.
  • Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • the sodium and potassium salts are clearly preferred over the other salts for reasons of cost.
  • the relevant pure alkali metal carbonates or bicarbonates do not have to be used; Rather, mixtures of different carbonates and bicarbonates may be preferred.
  • the effervescent system is 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10 wt .-% of an Acidisersstoffs, in each case based on the entire molded body used.
  • Acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts.
  • Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • Sokalan® DCS commercially available and likewise preferably usable as acidifying agent in the context of the present invention is Sokalan® DCS (trademark of BASF), a mixture of succinic acid (maximum 31% by weight), glutaric acid (maximum 50% by weight) and adipic acid ( at most 33% by weight).
  • detergent tablets and cleansing agent tablets in which a substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures thereof is used as the acidifying agent in the effervescent system.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimido-peroxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in the dishwashing detergent tablets produced according to the invention.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • the bleaching agents are usually used in automatic dishwasher detergents in amounts of from 1 to 30% by weight, preferably from 2.5 to 20% by weight and in particular from 5 to 15% by weight, based in each case on the composition.
  • the stated proportions relate to the weight of the base molding.
  • Bleach activators which aid in the action of the bleaches may also form part of the base molding.
  • Known bleach activators are compounds containing one or more N- or. Contain O-acyl groups, such as substances from the class of anhydrides, esters, imides and acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morph
  • Hydrophilic substituted acyl acetals and acyl lactams are also preferably used.
  • Combinations of conventional bleach activators can also be used.
  • the bleach activators are usually used in automatic dishwashing detergents in amounts of from 0.1 to 20% by weight, preferably from 0.25 to 15% by weight and in particular from 1 to 10% by weight, based in each case on the composition. In the context of the present invention, the stated proportions relate to the weight of the base molding.
  • bleach catalysts can also be incorporated into the active substance particles.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or - carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Bleach activators from the group of the polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred -Methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOS
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt % to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.
  • bleaching agents selected from the group consisting of oxygen or halogen bleaches, in particular chlorine bleaches, with particular preference to sodium perborate and sodium percarbonate, in amounts of from 2 to 25% by weight. preferably from 5 to 20 wt .-% and in particular from 10 to 15 wt .-%, each based on the weight of Basic molded article contains, are an inventively preferred embodiment of the present invention.
  • the base molding and / or the active substance (s) in the cavity contain bleach activators.
  • Detergent tablets prepared according to the invention in which the base tablet contains bleach activators from the groups of the polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium acetonitrile-methyl sulfate (MMA), in amounts of 0.25 to 15 wt .-%, preferably from 0.5 to 10 wt .-% and in particular of 1 to 5 wt .-%, each based on the weight of the base molding contains, are also preferred.
  • TAED tetraacetylethylenedi
  • the detergent tablets produced according to the invention may contain corrosion inhibitors, in particular in the base tablet for the protection of the ware or the machine, with particular silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art.
  • silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • the base tablet contains silver protectants from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes, more preferably benzotriazole and / or Alkylaminotriazole, in amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the weight of the base molding.
  • silver protectants from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes, more preferably benzotriazole and / or Alkylaminotriazole, in amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the weight of the base molding.
  • the trough filling contain silver protection agent, wherein the base molding either also contains silver protection agent or is free of such compounds.
  • further classes of substances are suitable for incorporation into detergents and cleaners.
  • washing and cleaning agent shaped bodies produced according to the invention are preferred in which the basic shaped body further comprises one or more substances from the groups of enzymes, corrosion inhibitors, scale inhibitors, cobuilders, dyes and / or fragrances in total amounts of 6 to 30 wt .-%, preferably from 7.5 to 25 wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the base molding contains.
  • the detergent tablets according to the invention may contain further ingredients customary in detergents and cleaners from the group of dyes, perfumes, optical brighteners, enzymes, foam inhibitors, silicone oils, antiredeposition agents, grayness inhibitors, dye transfer inhibitors and Contain corrosion inhibitors.
  • Suitable enzymes in the basic moldings are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants.
  • the hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%.
  • preferred detergent tablets are characterized in that the base tablet contains protease and / or amylase.
  • the detergent tablets according to the invention can contain the enzyme (s) in two fundamentally different regions (in the base tablet and / or in the cavity as active substance or active substance mixture) allows tablets to be molded with very precisely defined enzyme release and action provide.
  • the table below gives an overview of possible enzyme distributions in detergent tablets according to the invention: Basic tablet cavity amylase - protease - lipase - Amylase + protease - Amylase + lipase - Protease + lipase - Amylase + protease + lipase - - amylase - protease - lipase - Amylase + protease - Amylase + lipase - Protease + lipase - Amylase + protease + lipase amylase amylase amylase amylase protease amylase Amylase + protease amylase amylase protease amylase amylase amylase amylase protease amylase Amy
  • Dyes and fragrances can be added to the detergent tablets according to the invention both in the base tablet and in the preparations contained in the cavity in order to improve the aesthetic impression of the resulting products and to give the consumer, in addition to the performance, a "typical and unmistakable" visual and sensory To provide product.
  • perfume oils or fragrances individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, ⁇ -isomethylionone and Methylcedrylketon to the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrance oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • the fragrances can be incorporated directly into the detergents and cleaners according to the invention, but it can also be advantageous to apply the fragrances to carriers, which enhance the adhesion of the perfume to the laundry and ensure a lingering fragrance of the textiles through a slower release of fragrance.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • the agents according to the invention can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the treated with the agents substrates such as textiles, glass, ceramics or plastic tableware, not these to stain.
  • the detergent tablets according to the invention may contain one or more optical brighteners. These fabrics, also called “whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellow tinge.
  • Optical brighteners are organic dyes that convert part of the invisible UV radiation of sunlight into longer-wavelength blue light. The emission of this blue light complements the "gap" in the light reflected from the textile so that a fabric treated with optical brightener appears whiter and brighter to the eye. Since the mechanism of action of brighteners requires their application to the fibers, a distinction is made depending on the "fibers to be dyed", for example, brighteners for cotton, polyamide or polyester fibers.
  • the commercially available brighteners suitable for detergent incorporation essentially comprise five structural groups on the stilbene, diphenylstilbene, coumarin-quinoline, diphenylpyrazoline and the combination of benzoxazole or benzimidazole with conjugated systems.
  • An overview of common brighteners can be found, for example, in G. Jakobi, A. Lohr "Detergents and Textile Washing" , VCH Verlag, Weinheim, 1987, pages 94 to 100 .
  • Suitable salts are, for example, salts of 4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] stilbene-2,2'-disulphonic acid or compounds of similar construction which are used in place of the morpholino Group a Diethanolaminooeuvre, a methylamino group, an anilino group or a 2-Methoxyethylaminoxx carry.
  • brighteners of the substituted diphenylstyrene type may be present, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used.
  • the detergent tablets may also contain components which positively influence the oil and grease washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • Suitable foam inhibitors which can be used in the compositions according to the invention are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, e.g. degraded starch, aldehyde levels, etc. Also polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions
  • compositions of the invention may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • compositions of the invention may contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungiostats and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, although it is entirely possible to do without these compounds.
  • the agents may contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
  • External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • External antistatic agents are described for example in the patent applications FR 1,156,513, GB 873 214 and GB 839 407.
  • the lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed herein are useful as antistatics for textiles or as additives to laundry detergents, with the additional benefit of providing a softening effect.
  • silicone derivatives can be used in the compositions according to the invention. These additionally improve the rinsing behavior of the agents by their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones are in the range between 100 and 100,000 at 25 ° C Centistokes, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.
  • the agents according to the invention may also contain UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers.
  • Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2 and / or 4 position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • preferably prepared detergent tablets are characterized in that the active substance contained in the space enclosed by the foil and the shaped body contains at least one active substance from the group of enzymes, surfactants, soil-release polymers, disintegration aids, bleaching agents, Bleach activators, bleach catalysts, silver protectants and mixtures thereof.
  • ingredients can be separated from each other, either to a storage stability improving separation of incompatible ingredients or to a controlled release certain Active substances can be used.
  • the base tablet or the active substance contained in the space enclosed by the foil and the tablet contains bleach, while the other region of the tablet contains bleach activators.
  • prepared detergent tablets are characterized in that the base tablet or d contains the active substance contained in the space enclosed by the foil and the tablet, bleach, while the other portion of the tablet contains enzymes.
  • a separation of bleaching agents and corrosion inhibitors or silver protectants can be achieved.
  • Detergent tablets in which the base tablet or the active substance contained in the space enclosed by the foil and the tablet Bleach contains, while the other portion of the shaped body contains deformable mass corrosion inhibitor, are also preferred.
  • washing and cleaning agent tablets are also preferred in which the base tablet or the active substance contained in the space enclosed by the foil and the tablet contains bleach, while the other region of the tablet is surfactants, preferably nonionic surfactants, with particular preference to alkoxylated alcohols to 24 carbon atoms and 1 to 5 alkylene oxide units.
  • the individual regions can also have a different content of the same ingredient, whereby advantages can be achieved.
  • Detergent tablets in which the base tablet and the active substance contained in the space enclosed by the foil and the tablet contain the same active ingredient in different amounts are preferred.
  • the term "different amount” refers, not to the absolute amount of the ingredient in the relevant part of the molding, but to the relative amount, based on the phase weight, so represents a wt .-% statement, based on the individual area, So the basic molding or cavity filling, dar.
  • the optional substance to be incorporated into the cavity is preferably particulate.
  • active substance in the context of the present invention is not limited to pure substances. On the contrary, it denotes pure active substances, mixtures of active substances and forms of preparation, so that there are no limits to formulation freedom.
  • particulate matter is included in the cavity (s)
  • the filling optionally to be introduced into the cavity is preferably solid, with particulate fillings being particularly preferred. If the cavities of the shaped bodies are filled with particulate compositions, preference is given to processes in which the particulate composition (s) in step b) have a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l has / have.
  • the film which closes off the cavity (s) is punched out to match the size of the surface of the mold and held in place by means of a vacuum.
  • "Matching the size of the surface of the mold” means that the film completely covers the cavity and closes.
  • the film does not protrude beyond the edge of the mold, but this has more aesthetic than technical reasons.
  • a sealing edge around the cavity can be sufficient, wherein the width of the sealing edge is preferably at least 1 mm.
  • the punched label is held in place by vacuum. Preferably, this is done with the help of the robot, who has also carried out the punching process.
  • the vacuum promotes the formation of a smooth film surface, which does not curl even when applying adhesive and is preferably in the range of 100 to 1000 mbar, particularly preferably from 250 to 950 mbar and in particular from 500 to 900 mbar.
  • the film closes the cavity and thus secures the filling from falling out.
  • the film must be suitably attached to the hollow body.
  • geometrical form-fitting can be used here, but with regard to large-scale production, the gluing of the film is the method of choice. For this you can use prefabricated films, which have self-adhesive properties. These are glued similar to a "sticker" on the top of the filled mold. With regard to the price of such films, however, methods according to the invention are preferred in which the surface of the hollow mold and / or the underside of the labels are provided with adhesive and the labels are then adhered to the mold.
  • the film is preferably made of water-soluble material.
  • the polymers used as film materials may consist of a single material or a blend of different materials.
  • Preferred film materials come from the group (optionally acetalized) polyvinyl alcohol (PVAL) and / or PVAL copolymers, polyvinylpyrrolidone, polyethylene oxide, polyethylene glycol, gelatin and / or copolymers and mixtures thereof.
  • polyvinyl alcohols are particularly preferred.
  • Polyvinyl alcohols (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure in small proportions (about 2%) also structural units of the type contain.
  • polyvinyl alcohols which are available as white-yellowish powders or granules with degrees of polymerization in the range of about 100 to 2500 (molar masses of about 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , so still contain a residual content of acetyl groups.
  • the polyvinyl alcohols are characterized by the manufacturer by indicating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.
  • polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
  • Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable. The water solubility can be reduced by aftertreatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
  • Polyvinyl alcohol is largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allows water vapor to pass through.
  • the film material comprises polyvinyl alcohols and / or PVAL copolymers whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • the degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680, and most preferably between about 260 to about 1500.
  • the film comprises polyvinyl alcohols and / or PVAL copolymers whose average degree of polymerization is between 80 and 700, preferably between 150 and 400, particularly preferably between 180 and 300 and / or their molecular weight ratio MW (50%).
  • MW molecular weight ratio
  • to MG (90%) is between 0.3 and 1, preferably between 0.4 and 0.8 and in particular between 0.45 and 0.6.
  • polyvinyl alcohols described above are widely available commercially, for example under the trademark Mowiol® (Clariant).
  • Polyvinyl alcohols which are particularly suitable for the purposes of the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88 and Mowiol® 8-88.
  • ELVANOL® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont)
  • ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.)
  • Gohsenol® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK).
  • ERKOL types from Wacker.
  • a further preferred group of water-soluble polymers which can serve as a film material according to the invention are the polyvinylpyrrolidones. These are sold, for example, under the name Luviskol® (BASF).
  • Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (IV) which are prepared by free-radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators.
  • free-radical initiators peroxides, azo compounds
  • polyvinylpyrrolidones have molar masses in the range of about 2500-750000 g / mol, which are characterized by the specification of the K values and - depending on K value - have glass transition temperatures of 130-175 °. They are called white, hygroscopic powder or aqueous. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
  • copolymers of vinylpyrrolidone with other monomers in particular VinylpyrrolidonNinylester copolymers, such as those sold under the trademark Luviskol® (BASF).
  • Luviskol® VA 64 and Luviskol® VA 73, in each case vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred nonionic polymers.
  • the vinyl ester polymers are vinyl ester-accessible polymers having the moiety of formula (V) as a characteristic building block of the macromolecules.
  • V formula (V)
  • the polymerization of the vinyl esters is carried out free-radically by different processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization).
  • Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (IV) and (V)
  • PEG polyethylene glycols
  • V polyethylene glycol
  • PEGs are prepared industrially by anionic ring-opening polymerization of ethylene oxide (oxirane), usually in the presence of small amounts of water. Depending on the reaction procedure, they have molar masses in the range of about 200-5,000,000 g / mol, corresponding to degrees of polymerization of about 5 to> 100,000.
  • PEG polyethylene glycols
  • PEOX polyethylene oxides
  • Gelatine is also suitable as a film material according to the invention, this being preferably used together with other polymers.
  • Gelatine is a polypeptide (molar mass: approx. 15,000 to> 250,000 g / mol) which is mainly produced by hydrolysis of the skin and bones of Obtained from collagen under acidic or alkaline conditions.
  • the amino acid composition of gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as a water-soluble coating material is extremely widespread, especially in pharmacy in the form of hard or soft gelatin capsules. In the form of films, gelatin has little use because of its high price compared to the polymers mentioned above.
  • polymers which are suitable according to the invention are water-soluble amphopolymers.
  • Amphoteric polymers ie polymers which contain both free amino groups and free -COOH or SO 3 H groups in the molecule and are capable of forming internal salts, are zwitterionic polymers which contain quaternary ammonium groups in the molecule. COO - - or -SO 3 - groups, and summarized those polymers containing -COOH or SO 3 H groups and quaternary ammonium groups.
  • amphopolymer which can be used according to the invention is the acrylic resin obtainable under the name Amphomer®, which is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.
  • Amphomer® is a copolymer of tert-butylaminoethyl methacrylate, N- (1,1,3,3-tetramethylbutyl) acrylamide and two or more monomers from the group of acrylic acid, Represents methacrylic acid and its simple esters.
  • amphopolymers are composed of unsaturated carboxylic acids (for example acrylic and methacrylic acid), cationically derivatized unsaturated carboxylic acids (for example acrylamidopropyltrimethylammonium chloride) and, if appropriate, further ionic or nonionic monomers, terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride, such as those mentioned under the name Merquat ® 2001 N are commercially available, according to the invention are particularly preferred ampho polymers.
  • unsaturated carboxylic acids for example acrylic and methacrylic acid
  • cationically derivatized unsaturated carboxylic acids for example acrylamidopropyltrimethylammonium chloride
  • further ionic or nonionic monomers, terpolymers of acrylic acid, methyl acrylate and methacrylamidopropyltrimonium chloride such as those mentioned under the name Merquat ® 2001 N are commercially available, according to the
  • amphoteric polymers are, for example, the octylacrylamide / methyl methacrylate / tert-butylaminoethyl methacrylate / 2-hydroxypropyl methacrylate copolymers available under the names Amphomer® and Amphomer® LV-71 (DELFT NATIONAL).
  • Short-chain carboxylic acids or alcohols are to be understood as meaning those having 1 to 8 carbon atoms, it being possible for the carbon chains of these compounds to be interrupted, if appropriate, by divalent hetero groups such as -O-, -NH-, -S-.
  • Terpolymers of crotonic acid, vinyl acetate and an allyl or methallyl ester comprise monomer units of the general formulas (IV) and (VI) (see above) and monomer units of one or more allyl or methallyl esters of the formula X: wherein R 3 is -H or -CH 3 , R 2 is -CH 3 or -CH (CH 3 ) 2 and R 1 is -CH 3 or a saturated straight or branched C 1-6 alkyl radical and the sum of the carbon atoms in the radicals R 1 and R 2 is preferably 7, 6, 5, 4, 3 or 2.
  • Cationic polymers preferred according to the invention are quaternized cellulose derivatives and polymeric dimethyldiallylammonium salts and their copolymers.
  • Cationic cellulose derivatives, in particular the commercial product Polymer® JR 400, are very particularly preferred cationic polymers.
  • the film adherently bonded to the shaped body forms the washing and cleaning agent shaped bodies produced according to the invention.
  • the structure of the molded body according to the invention reminds of a "drum", in which a cavity is closed by a film.
  • the composition of the shaped body and of the film must be matched to the filling in order to prevent premature destruction of the film or loss of active substance through the molded article. This is required in the incorporation of solid substances in the cavity only to a minor extent (chemical incompatibilities), so that preferably prepared detergent tablets more active ingredient in particulate form, preferably in powdered, granular, extruded, pelleted, prilled, flaky or tableted form, contain.
  • the closed cavity through the film can be completely filled with additional active substance.
  • attractive visual effects can be realized.
  • production methods for detergent tablets are preferred in which the volume ratio of the space enclosed by the foil and the shaped body to the active substance contained in this space is 1: 1 to 100: 1, preferably 1.1: 1 to 50: 1, particularly preferably 1.2: 1 to 25: 1 and in particular 1.3: 1 to 10: 1.
  • a 1: 1 volume ratio means that the cavity is completely filled.
  • the proportion of the further active substance in the cavity can make up different proportions of the overall shaped body.
  • the weight ratio defined above is the ratio of the mass of the unfilled shaped body ("base molding") to the mass of the filling. The mass of the film is not taken into account in this calculation.
  • the time at which the substance contained in the cavity is released can be predetermined.
  • the film can be virtually instantaneously soluble, so that the active substance contained in the cavity is dosed at the beginning of the washing or cleaning cycle in the washing or cleaning liquor.
  • the film may be so poorly soluble that only the shaped body is dissolved and the active substance contained in the cavity is thereby released.
  • detergent tablets in which the active substance contained in the space enclosed by the film and the molded body dissolves more slowly than the base tablet are also preferred embodiments of the present invention.
  • the base moldings produced in step a) are fed to the filling or sealing stations on a conveyor belt, wherein the conveyor belt has a feed rate of 0.01 to 1 m / s, preferably 0.02 to 0 , 5 m / s, more preferably from 0.03 to 0.3 m / s and in particular from 0.05 to 0.2 m / s.
  • the filling of the shaped bodies with active substance (s), i. with liquid (s) and / or particulate preparations is preferably also in the way that several base moldings are filled simultaneously.
  • methods according to the invention are preferred in which the filling of the basic shaped bodies takes place by means of a filling system which operates at 5 to 30 cycles per minute, preferably at 10 to 25 cycles per minute and in particular at 15 to 20 cycles per minute.
  • 1440 molded parts per minute can be filled at a cycle rate of 20 cycles per minute.
  • the adhesive application can be done for example by application rollers, which are provided on one side continuously with adhesive.
  • the molded body top side or the lower side of the film is then guided past the rotating applicator roll and thus provided with adhesive.
  • An embodiment of the present invention therefore provides that the top of the filled base moldings is provided by means of application rollers with adhesive.
  • the tablet surface is more or less rough, so that the application of adhesive to the tablet surface can be technically difficult.
  • powder residues on the tablet surface can contaminate the adhesive roller and impair the system run and the adhesion of the film to the molded body.
  • a preferred embodiment of the present invention therefore provides to provide the labels with adhesive and then put on the filled base moldings.
  • methods according to the invention are preferred in which the underside of the labels held in place by vacuum is provided with adhesive by applicator rollers.
  • Methods which are likewise preferred in accordance with the invention are therefore characterized in that the upper side of the filled base moldings is provided with adhesive by means of a casting machine which can cast any desired line shape onto the surface in a computer-controlled manner.
  • adhesives it is possible to use substances which impart adequate adhesiveness to the shaped body surfaces to which they are applied, so that the films applied in the subsequent process step adhere permanently to the surface.
  • the substances mentioned in the relevant adhesives literature and in particular in the monographs are suitable for this purpose, whereby in the context of the present invention the application of melts, which act as adhesion promoters at elevated temperatures but are no longer tacky after cooling, but a special one Meaning.
  • Particularly preferred adhesives in the context of the present invention are solutions of polyvinyl alcohols (see above) and dispersions of polyacrylates.
  • the amount of adhesive applied per molded article may vary depending on the size of the molded article, its composition and its surface roughness, and in preferred processes of the present invention is 0.05 to 0.3 grams per tablet.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Claims (12)

  1. Procédé pour préparer des corps moulés d'agent de lavage et de nettoyage
    a) en préparant un moule creux ouvert ("corps moulé de base"), qui présente au moins une cavité;
    b) en remplissant ladite ou lesdites cavités avec une ou plusieurs substances actives sous forme liquide, sous forme de gel, sous forme pâteuse ou solide,
    c) en fermant les ouvertures des cavités (remplies) avec une feuille,
    caractérisé en ce que
    des étiquettes qui s'adaptent à la dimension de la surface du moule creux sont découpées à partir de la feuille et sont maintenues au moyen d'un vide, les étiquette étant appliquées ensuite sur le moule creux.
  2. Procédé selon la revendication 1, caractérisé en ce que la préparation du moule creux ouvert dans l'étape a) comprend le pressage d'un pré-mélange sous forme de particules en une pièce pressée (corps moulé de base), qui présente au moins une cavité.
  3. Procédé selon la revendication 1, caractérisé en ce que la préparation du moule ouvert se réalise à l'étape a) par emboutissage et/ou par coulée et/ou à l'aide d'un moulage par injection et/ou par soufflage d'un polymère ou d'un mélange de polymères, soluble ou dispersif dans l'eau.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la surface du moule creux et/ou le dessous des étiquettes sont munis de colle puis collés ensuite sur le moule creux.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que les corps moulés de base préparés dans l'étape a) sont introduits sur une bande convoyeuse des postes de remplissage ou de scellage, la bande convoyeuse présentant une vitesse d'avancement de 0,01 à 1 m/s, de préférence de 0,02 à 0,5 m/s, de manière particulièrement préférée de 0,03 à 0,3 m/s, et en particulier de 0,05 à 0,2 m/s.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que les corps moulés de base préparés dans l'étape a) sont disposés les uns à côté des autres, et derrière les uns les autres, sur une plate-forme de sorte que plusieurs corps moulés de base peuvent être remplis simultanément puis scellés simultanément.
  7. Procédé selon la revendication 6, caractérisé en ce qu'au moins 4, de préférence au moins 6, de manière particulièrement préférée au moins 10, et en particulier au moins 12 corps moulés de base, sont disposés les uns à côté des autres.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le remplissage des corps moulés de base se réalise au moyen d'une installation de remplissage, qui fonctionne à raison de 5 à 30 cycles par minute, de préférence de 10 à 25 cycles par minute, et en particulier de 15 à 20 cycles par minute.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que plusieurs étiquettes sont découpées simultanément, maintenues à l'aide d'un vide et collées, après application d'une colle sur la surface des comprimés et/ou le dessous des étiquettes.
  10. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le côté supérieur des corps moulés de base remplis sont munis de colle au moyen de rouleaux d'application.
  11. Procédé selon l'une quelconque des revendications 1 à 9, caractérisé en ce que le côté supérieur des corps moulés de base remplis est muni de colle au moyen d'une installation de coulée, qui peut verser sous la commande d'un ordinateur une forme linéaire quelconque sur la surface.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que le dessous des étiquettes maintenues au moyen d'un vide est muni de colle au moyen de rouleaux d'application.
EP03811371A 2002-11-21 2003-11-12 Procede pour produire des corps moules detergents et nettoyants garnis ii Expired - Lifetime EP1563052B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10254314A DE10254314B4 (de) 2002-11-21 2002-11-21 Verfahren zur Herstellung befüllter Wasch- und Reinigungsmittelformkörper II
DE10254314 2002-11-21
PCT/EP2003/012624 WO2004046298A2 (fr) 2002-11-21 2003-11-12 Procede pour produire des corps moules detergents et nettoyants garnis ii

Publications (2)

Publication Number Publication Date
EP1563052A2 EP1563052A2 (fr) 2005-08-17
EP1563052B1 true EP1563052B1 (fr) 2006-06-07

Family

ID=32308626

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Application Number Title Priority Date Filing Date
EP03811371A Expired - Lifetime EP1563052B1 (fr) 2002-11-21 2003-11-12 Procede pour produire des corps moules detergents et nettoyants garnis ii

Country Status (7)

Country Link
US (1) US20050225003A1 (fr)
EP (1) EP1563052B1 (fr)
AT (1) ATE329004T1 (fr)
AU (1) AU2003302123A1 (fr)
DE (2) DE10254314B4 (fr)
ES (1) ES2266918T3 (fr)
WO (1) WO2004046298A2 (fr)

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DE10253479A1 (de) * 2002-11-16 2004-06-03 Henkel Kgaa Befüllte Muldentabletten und Verfahren zu ihrer Herstellung II
DE102004051619A1 (de) * 2004-10-22 2006-04-27 Henkel Kgaa Wasch- oder Reinigungsmittel
DE102004051620A1 (de) * 2004-10-22 2006-04-27 Henkel Kgaa Wasch- oder Reinigungsmittel
DE102004051553B4 (de) * 2004-10-22 2007-09-13 Henkel Kgaa Wasch- oder Reinigungsmittel
DE102004062327A1 (de) * 2004-12-20 2006-06-29 Henkel Kgaa Mehrphasiger Wasch- oder Reinigungsmittelformkörper
US11338548B2 (en) 2005-06-09 2022-05-24 United States Gypsum Company Light weight gypsum board
US9840066B2 (en) 2005-06-09 2017-12-12 United States Gypsum Company Light weight gypsum board
US11306028B2 (en) 2005-06-09 2022-04-19 United States Gypsum Company Light weight gypsum board
US9802866B2 (en) 2005-06-09 2017-10-31 United States Gypsum Company Light weight gypsum board
US8980817B2 (en) * 2007-01-18 2015-03-17 Reckitt Benckiser N.V. Dosage element and a method of manufacturing a dosage element
CN101675153B (zh) 2007-05-04 2014-09-24 埃科莱布有限公司 含水溶性镁化合物的清洁组合物及其使用方法
US20090270566A1 (en) * 2008-04-23 2009-10-29 Fina Technology, Inc. Olefin Polymerization Processes and Catalysts for Use Therein
US8740993B2 (en) 2012-03-23 2014-06-03 Ecolab Usa Inc. Method for reduced encrustation of textiles using a polymer comprising maleic acid, vinyl acetate, and alkyl acrylate
US8623151B2 (en) 2012-03-23 2014-01-07 Ecolab Usa Inc. Terpolymer containing maleic acid, vinyl acetate, and alkyl acrylate monomers for aluminum protection
US10399899B2 (en) 2012-10-23 2019-09-03 United States Gypsum Company Pregelatinized starch with mid-range viscosity, and product, slurry and methods related thereto
US9540810B2 (en) 2012-10-23 2017-01-10 United States Gypsum Company Pregelatinized starch with mid-range viscosity, and product, slurry and methods related thereto
US9828441B2 (en) 2012-10-23 2017-11-28 United States Gypsum Company Method of preparing pregelatinized, partially hydrolyzed starch and related methods and products
WO2024007284A1 (fr) * 2022-07-08 2024-01-11 广州洁生日化有限公司 Feuille de détergent respectueuse de l'environnement, et procédé de préparation et appareil de préparation de feuille associés

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US3908340A (en) * 1974-03-25 1975-09-30 Anderson Bros Mfg Co Apparatus for feeding and applying individual lids to containers
US4589943A (en) * 1984-03-08 1986-05-20 American Bank Note Company Apparatus and procedure for applying adhesive labels
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DE19932765A1 (de) * 1999-07-14 2001-01-18 Henkel Kgaa Befüllte Wasch- und Reinigungsmittelformkörper
DE10010760A1 (de) * 2000-03-04 2001-09-20 Henkel Kgaa Mehrphasige Wasch- und Reinigungsmittelformkörper mit nicht-gepreßten Anteilen
DE10062582A1 (de) * 2000-12-15 2002-06-27 Henkel Kgaa Befüllte Wasch- und Reinigungsmittelformkörper
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Also Published As

Publication number Publication date
US20050225003A1 (en) 2005-10-13
WO2004046298A2 (fr) 2004-06-03
DE50303740D1 (de) 2006-07-20
WO2004046298A3 (fr) 2004-07-15
ATE329004T1 (de) 2006-06-15
AU2003302123A1 (en) 2004-06-15
AU2003302123A8 (en) 2004-06-15
ES2266918T3 (es) 2007-03-01
DE10254314B4 (de) 2004-10-14
DE10254314A1 (de) 2004-06-09
EP1563052A2 (fr) 2005-08-17

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