EP1192241B1 - Procede de realisation de corps moules a agent de lavage et de nettoyage - Google Patents

Procede de realisation de corps moules a agent de lavage et de nettoyage Download PDF

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Publication number
EP1192241B1
EP1192241B1 EP00938813A EP00938813A EP1192241B1 EP 1192241 B1 EP1192241 B1 EP 1192241B1 EP 00938813 A EP00938813 A EP 00938813A EP 00938813 A EP00938813 A EP 00938813A EP 1192241 B1 EP1192241 B1 EP 1192241B1
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Prior art keywords
weight
process according
mass
deformable
masses
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German (de)
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EP1192241A1 (fr
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Thomas Holderbaum
Dieter Jung
Christian Nitsch
Bernd Richter
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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

Definitions

  • the present invention relates to a novel process for the preparation of single- and multi-phase detergent tablets.
  • Detergent tablets are widely described in the art and are becoming increasingly popular with consumers because of their ease of use. Tableted detergents have a number of advantages over powdered products: they are easier to dose and handle and, due to their compact structure, have advantages in storage and transport. There is therefore an extremely wide state of the art for washing and makesmittelformkörpem. which is also reflected in an extensive patent literature.
  • developers of tablet-shaped products came up with the idea of releasing certain ingredients in the washing or cleaning process via differently shaped areas of the moldings in order to improve cleaning success.
  • pharmaceutics core / shell tablets and ring / core tablets in particular multilayer molded bodies have prevailed that are offered today for many areas of washing and cleaning or hygiene.
  • optical differentiation of the products is becoming increasingly important, so that single-phase and monochrome shaped body in the field of washing and cleaning were largely displaced by multi-phase moldings.
  • Commercially available two-layer molded articles with one white and one colored phase or with two differently colored layers are currently commercially available.
  • point tablets, toroidal tablets, coated tablets, etc. which currently have a rather minor importance.
  • the production of said moldings always comprises at least one tabletting step in which a particulate premix is converted into a compact mold by applying pressure.
  • a particulate premix is converted into a compact mold by applying pressure.
  • coat / core tablets, etc. different premixes are pressed up or pressed into one another.
  • Multi-layer detergent tablets for automatic dishwashing are described, for example, in European Patent Application EP 224 128 (Henkel KGaA).
  • the two layers have solubility differences. which leads to advantageous application properties.
  • Multi-phase cleaning tablets for the WC are described for example in EP 055 100 (Jeyes Group).
  • This document discloses toilet cleaner blocks comprising a molded body of a slow-dissolving detergent composition. in which a bleach tablet is embedded.
  • This document simultaneously discloses the most varied embodiments of multiphase moldings. The production of the moldings is carried out according to the teaching of this document either by inserting a compressed bleach tablet into a mold and molding this tablet with the detergent composition, or by pouring a portion of the detergent composition into the mold. followed by insertion of the compressed bleach tablet and possibly subsequent pouring with further detergent composition.
  • EP 481 547 also describes multi-phase detergent tablets which are to be used for automatic dishwashing.
  • These shaped bodies are in the form of core / shell tablets and are produced by stepwise compression of the constituents. First, the compression of a bleaching composition into a shaped body which is placed in a semi-filled with a polymer composition die, which is then filled with another polymer composition and a bleach molded body is pressed with a polymer jacket. The process is then repeated with an alkaline detergent composition to give a three-phase molded body.
  • British Patents GB 2 298 867 A and GB 1 048 831 disclose laundry detergent tablets which have improved hardness properties due to partially or fully hydrated builders. Simple production processes are described without going into the applied extruding pressures.
  • the production of moldings should work safely without large technical effort in large series without the moldings have disadvantages in terms of stability or inaccuracies in the dosage would be feared.
  • the present invention was based on the object. to provide a novel manufacturing process for detergent tablets, which is superior to the previous Tablettier- and extrusion technology with respect to the protection of the ingredients from thermal stress, pressure and shear, the apparatus is less expensive and procedural economical cheaper and higher throughputs. In addition, the process should be used without much effort for the production of three- or multi-phase moldings.
  • the invention relates to a process for the preparation of detergent tablets in which one produces a deformable mass (s) and feeds them at a pressure of less than 10 bar outlet openings and cuts off the exiting material strands on molded body dimensions and allowed to harden.
  • the deformable and post cure thermosetting masses are supplied to the orifices at even lower pressures to be pressure sensitive To protect ingredients.
  • Preferred processes are characterized in that the deformable mass (s) are fed to the outlet openings at a pressure below 35 bar, preferably below 30 bar, more preferably below 20 bar.
  • the method according to the invention provides for the processing of deformable masses which harden or solidify after molding into compact shaped bodies.
  • the process according to the invention is operated at low pressures and starts from deformable masses. These deformable masses are not particulate, but dough-like or plastic and harden after the shaping processing.
  • a preferred way in the context of the present invention to supply the deformable masses to the outlet openings is to feed them between two rollers, which have opposite directions of rotation. This will cause the mass to be between the rollers. depending on the width of the gap between the rollers and the roller speed promoted under low pressure in the direction of the outlet openings. Depending on the number of roller pairs and outlet openings and depending on the configuration of these openings result in single or multi-phase material strands, which may have different shapes and / or colors. These strands of material are cut into sections of predetermined length and allowed to harden the individual strand sections to the finished detergent tablets.
  • Single-phase moldings are advantageously produced by supplying a deformable mass with a roller pair to an outlet opening.
  • Preferred methods are characterized in that a deformable mass drawn between two rolls, discharged as a strand of material from outlet openings, cut to the desired shape of the molded body and allowed to cure.
  • suitable apparatuses are available for example from the company Hosokava Bepex GmbH under the name "torsion bar roller press DP".
  • the outlet openings of such apparatus can be configured, for example, circular, triangular, square, rectangular, heart-shaped, crescent-shaped, etc.
  • the first-mentioned openings then require cylindrical, prismatic, cubic or tetragonal, tetragonal or orthorhombic shaped bodies.
  • the drawings show in the figures 27 and 29 to 42 by way of example some possible embodiments for outlet openings.
  • Two-phase moldings can be produced in a corresponding manner with two pairs of rollers.
  • preferred processes are characterized in that two deformable masses of different composition are drawn in between two pairs of rolls and discharged from outlet openings as filled, hollow or multi-layered strands of material, cut to the desired shape dimension and allowed to harden.
  • outlet openings As filled, hollow or multi-layered strands of material, cut to the desired shape dimension and allowed to harden.
  • Apparatuses suitable for such processes according to the invention are available from Hosokava Bepex GmbH under the name "Double Torsion Roller Press DDP".
  • FIGS. 15, 16, 17, 19, 21, 23 and 25 show an example of some cross-sections of outlet openings for different masses.
  • strands and moldings result, in which one part, except for the cut surfaces, is completely enclosed by the other part.
  • the other cited figures show strands or shaped bodies in which one part is or only partly embedded in the other part. Again, a rotation of the strands of material prior to cutting to achieve special optical effects is possible.
  • the process according to the invention can also be used without difficulty for the preparation of three-phase molded bodies.
  • Completely analogous to the previous embodiments, such methods according to the invention are carried out by three differently composite, plastically deformable masses drawn between three pairs of rollers and discharged as one-, two- or three-fold, hollow, two- or three-layer strands of material from outlet openings, to the desired shape of the molded body be cut off and allowed to cure.
  • washing and cleaning agent tablets are obtained; which have the shape of interlaced segments and reminiscent of rope or braids.
  • the flexibility of the method according to the invention with regard to the change of shapes and aesthetic design is thus far superior to the previously known methods.
  • the ratio of the phases with one another can be chosen freely, and it can be advantageous from an aesthetic point of view if one phase is at least 1/100, preferably at least 1/20 and in particular at least 1/10 of the volume or weight of the other Phase (s).
  • the weight ratio of the masses to one another is in the range from 1: 1 to 1: 100, preferably from 1: 2 to 1:75 and in particular from 1: 2.5 to 1:30 (two-phase molding) or in the range from 1 : 1.1 to 1: 100: 100, preferably from 1: 1: 2 to 1:75:75 and especially from 1: 1: 2.5 to 1:30:30 (three-phase molding).
  • the ratio of the surfaces of the individual molded body phases is preferably in similar ranges.
  • the strands of material become at a speed of 0.2 m / min to 30 m / min, preferably between 0.25 m / min to 20 m / min, more preferably from 0.5 m / min to 15 m / min and especially 1 m / min up to 10 m / min discharged from the outlet openings.
  • the method according to the invention is not limited in terms of the shape and size of the outlet openings.
  • the products to be produced and their size or mass which in the case of such products is usually in the range from 5 to 500 g, preferably from 10 to 250 g, more preferably from 15 to 100 g and in particular between 20 and 50 g
  • methods are preferred in which the outlet openings opening areas of 50 mm 2 to 2500 mm 2 , preferably from 100 mm 2 to 2000 mm 2 , more preferably from 200 mm 2 to 1500 mm 2 and in particular from 300 mm 2 to 1000 mm 2 under particular Preferred 350 mm 2 to 750 mm 2 , have.
  • the cutting of the material strands emerging from the outlet openings can take place according to the known methods of the prior art, for example by rotating knives, lowerable blades or wires etc.
  • the mass of the finished shaped bodies depends on the one hand on the size of the outlet openings, on the other hand on the length the sections. If conventional washing and cleaning agent tablets are to be provided for conventional purposes, such as detergent tablets or automatic dishwashing detergent tablets, processes are preferred in which the material strands emerging from the outlet openings are placed on a Length of 10 to 100 mm, preferably from 12.5 to 75 mm, particularly preferably from 15 to 60 mm and in particular from 20 to 50 mm, are cut off.
  • the limits mentioned can also be exceeded or fallen short of.
  • the hardened "bars" obtained in this way can then be introduced as depot blocks in washing machines or dishwashers, where a defined part of the block dissolves per wash or rinse cycle, while the remainder remains in the machine or its dosing system for the next cleaning cycle.
  • the strand sections are allowed to harden.
  • the curing takes place in different ways (see below), so that the curing can optionally be assisted or accelerated by suitable measures. It is thus possible, for example, to superficially initiate or accelerate a reactive curing process by activating activators.
  • the irradiation with radioactive rays can also be used for radiation-curing compounds. as well as UV radiation for UV-active masses.
  • the curing is carried out by internal and external drying and / or cooling, so that preferred methods are characterized in that the curing of cut on molded body material strands by superficial drying and / or cooling, in particular by blowing with cold air, is supported.
  • the hardening of the deformable mass (s) can be effected by different mechanisms, the time-delayed water binding, the cooling below the melting point, the evaporation of solvents, the crystallization, by chemical reaction (s), in particular polymerization and the change of rheological properties, e.g. by altered shearing of the mass (s) as the most important hardening mechanisms in addition to the already mentioned beam softening by UV, alpha-beta or gamma rays are mentioned.
  • a deformable, preferably plastic, mass is produced, which can be processed shaping without great pressures. After the shaping processing, curing then takes place by suitable initiation or waiting of a certain period of time. If masses are processed which have self-hardening properties without further initiation, this must be taken into account during processing in order to avoid hardening during shaping processing and thus blockages and process disruptions.
  • the curing of the deformable mass (s) takes place by time-delayed water binding.
  • the time-delayed water binding in the inventively processed masses can be realized in turn in different ways.
  • masses that contain hydratable, anhydrous raw materials or low hydration grade raw materials that can convert into stable higher hydrates, as well as water are suitable.
  • a shaping processing with low pressures is then no longer possible, and there are handling stable shaped body, which can optionally be further treated and / or packaged.
  • the staggered water binding can also be effected, for example, by incorporating hydrated water-containing salts, which dissolve in their own water of crystallization when the temperature increases, into the masses. If the temperature drops later, the water of crystallization becomes tied again, which leads to a loss of shaping processability by simple means and to a solidification of the masses.
  • the swelling of natural or synthetic polymers as time-delayed water binding mechanism can be used in the context of the method according to the invention.
  • suitable swelling agent e.g. Water, diols, glycerol, etc.
  • suitable swelling agent e.g. Water, diols, glycerol, etc.
  • the most important mechanism of curing by time-delayed water binding is the use of a combination of water and anhydrous or low-raw materials that hydrate slowly.
  • anhydrous or low-raw materials that hydrate slowly.
  • preferred ingredients of the deformable masses are, for example, phosphates, carbonates, silicates and zeolites.
  • the resulting hydrate forms have low melting points, since in this way a combination of the curing mechanisms is achieved by internal drying and cooling.
  • Preferred processes are characterized in that the deformable mass (s) 10 to 95 wt .-%, preferably 15 to 90 wt .-%, particularly preferably 20 to 85 wt .-% and in particular 25 to 80 wt. % anhydrous substances which pass through hydration in a hydrate form having a melting point below 120 ° C, preferably below 100 ° C and in particular below 80 ° C.
  • the deformable properties of the compositions can be influenced by the addition of plasticizing aids such as polyethylene glycols, polypropylene glycols, waxes, paraffins, nonionic surfactants, etc. Further information on the mentioned classes of substances can be found below.
  • Raw materials preferably to be incorporated into the deformable masses come from the group of phosphates, with alkali metal phosphates being particularly preferred. These Substances are used in the preparation of the masses in anhydrous or low-form and set the desired plastic properties of the masses with water and optional plasticizing aids. After the shaping processing, the hardening of the shaped and cut strands is then carried out by hydration of the phosphates.
  • 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 reacts acidic, it is formed when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate potassium phosphate primary or monobasic potassium phosphate, KDP
  • KH 2 PO 4 is a white salt of 2.33 gcm -3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light 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 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. 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.
  • Sodium and potassium phosphates where cyclic representatives. the sodium or potassium metaphosphates and chain types that can distinguish sodium and potassium polyphosphates, respectively. Especially for the latter, a variety of names are in use: Melted or calcined 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.). Pentapotassium. 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
  • phosphates are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.
  • the deformable mass (s) comprise phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate), in amounts of 20 to 80 wt .-%, preferably from 25 to 75 wt .-% and in particular from 30 to 70 wt .-%, each based on the mass.
  • phosphate preferably alkali metal phosphate (s), more preferably pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate)
  • the weight ratio of phosphate (s) to water in the deformable mass is less than 1: 0.3, preferably less than 1: 0.25 and in particular less than 1: 0, 2 is.
  • the deformable mass (s) contain 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 Wt .-% and in particular from 10 to 30 wt .-%, each based on the mass.
  • the weight ratio of carbonate (s) and / or bicarbonate (s) to water in the deformable mass is less than 1: 0.2, preferably less than 1: 0.15 and in particular less than 1 : Is 0.1.
  • ingredients which may be present in the deformable masses instead of or in addition to the said phosphates and / or carbonates / bicarbonates. are silicates, with the alkali metal silicates and including particularly the amorphous and / or crystalline potassium and / or sodium disilicates are preferred.
  • 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 an integer from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514 .
  • 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, with ⁇ -sodium disilicate being obtainable for example by the method / described in the international patent application WO-A-91 08,171th
  • 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.
  • Such so-called X-ray-amorphous silicates which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 .
  • Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the deformable mass (s) comprise silicate (s), preferably alkali metal silicates. particularly preferred crystalline or amorphous alkali disilicates, in amounts of 10 to 60 wt .-%, preferably of 15 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the mass.
  • silicate preferably alkali metal silicates. particularly preferred crystalline or amorphous alkali disilicates, in amounts of 10 to 60 wt .-%, preferably of 15 to 50 wt .-% and in particular from 20 to 40 wt .-%, each based on the mass.
  • the weight ratio of silicate (s) to water in the deformable mass is less than 1: 0.25, preferably less than 1: 0.2 and in particular less than 1: 0.15.
  • zeolites are also suitable as an important component in the compositions to be processed according to the invention.
  • these substances are preferred builders.
  • Zeolites have the general formula M 2 / n O ⁇ Al 2 O 3 ⁇ x SiO 2 ⁇ y H 2 O in which M is a cation of valency n, x stands for values which are greater than or equal to 2 and y can assume values between 0 and 20.
  • the zeolite structures are formed by linking AlO 4 tetrahedra with SiO 4 tetrahedra, this network being occupied by cations and water molecules.
  • the cations in these structures are relatively mobile and can be exchanged to varying degrees by other cations.
  • the intercrystalline "zeolitic" water can be released continuously and reversibly, while with some zeolite types, structural changes are accompanied by water release or uptake.
  • the "primary binding units” AlO 4 tetrahedra and SiO 4 tetrahedra
  • secondary binding units which are in the form of single or multiple rings.
  • S4R, S6R, and S8R 4-. 6- and 8-membered rings
  • D4R most common types: D4R as a square or D6R as a hexagonal prism
  • S8R four- and six-membered double-ring prisms
  • D4R as a square or D6R as a hexagonal prism
  • These "secondary subunits” combine different polyhedra called Greek letters. Most common here is a Dahlflächner, consisting of six squares and eight equilateral hexagons and is referred to as " ⁇ ". With these units, a variety of different zeolites can be realized. So far, 34 natural zeolite minerals and about 100 synthetic zeolites have been known.
  • the best known zeolite, zeolite 4 A is a cubic composite of ⁇ -cages linked by D4R subunits. It belongs to the zeolite structure group 3 and its three-dimensional network has pores of 2.2 ⁇ and 4.2 ⁇ size, the formula unit in the unit cell can be with Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] ⁇ 27 H 2 O describe.
  • zeolites of the faujasite type are used in the process according to the invention.
  • the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which is characterized by the double-six-membered subunit D6R (cf. Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92).
  • the zeolite structural group 4 also includes the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5.
  • the latter two synthetic zeolites have no mineral analogs.
  • Faujasite-type zeolites are composed of ⁇ -cages linked tetrahedrally via D6R subunits, with the ⁇ -cages resembling the carbon atoms in the diamond.
  • the three-dimensional network of the faujasite-type zeolites used in the process according to the invention has pores of 2.2 and 7.4 ⁇ , the unit cell also contains 8 cavities of about 13 ⁇ diameter and can be represented by the formula Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] . 264 H 2 O.
  • the network of zeolite X contains a void volume of about 50%, based on the dehydrated crystal.
  • the term "faujasite type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4.
  • zeolite X zeolite Y and faujasite as well as mixtures of these compounds can therefore also be used according to the invention, the pure zeolite X being preferred.
  • Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which need not necessarily belong to the zeolite structure group 4 can be used according to the invention, with the advantages of the process according to the invention becoming particularly evident when at least 50% by weight of the powdering agent consist of a zeolite of the faujasite type.
  • zeolite of the faujasite type 0.5 wt .-%, based on the weight of the resulting shaped body
  • the powdering agent consist exclusively of one or more faujasite-type zeolites, zeolite X in turn being preferred.
  • the aluminum silicates which are preferably used in the process according to the invention are commercially available, and the methods for their preparation are described in standard monographs.
  • Examples of commercially available X-type zeolites can be described by the following formulas: Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] .xH 2 O, K 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] .xH 2 O, Ca 40 Na 6 [(AlO 2 ) 86 (SiO 2 ) 106 ] xH 2 O, Sr 21 Ba 22 [(AlO 2) 86 (SiO 2) 106] ⁇ x H 2 O, where x can take values between 0 and 276 and have pore sizes of 8.0 to 8.4 ⁇ .
  • a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) which is marketed by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® is also commercially available and preferably usable in the context of the process according to the invention 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.
  • Y-type zeolites are commercially available us can be, for example, by the formulas Na 56 [(AlO 2 ) 56 (SiO 2 ) 136 ] xH 2 O, K 56 [(AlO 2 ) 56 (SiO 2 ) 136 ] xH 2 O, where x is numbers between 0 and 276 and has pore sizes of 8.0 ⁇ .
  • Preferred processes are characterized in that the deformable mass (s) zeolite (s), preferably zeolite A, zeolite P, zeolite X and mixtures thereof, 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 mass.
  • zeolite preferably zeolite A, zeolite P, zeolite X and mixtures thereof, 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 mass.
  • the particle sizes of the faujasite-type zeolites preferably used in the process according to the invention are preferably in the range from 0.1 to 100 .mu.m, preferably between 0.5 and 50 .mu.m and in particular between 1 and 30 .mu.m, in each case measured using standard particle size determination methods.
  • the average particle size of the solids used in the deformable mass (s) is below 400 ⁇ m, preferably below 300 ⁇ m and in particular below 200 ⁇ m.
  • the mean particle size represents the arithmetic mean of the individual particle sizes, which may still vary.
  • Particularly preferred processes are characterized in that less than 10% by weight, preferably less than 5% by weight and in particular less than 1% by weight of the solids used in the deformable mass (s) have particle sizes above 1000 ⁇ m ,
  • the upper particle size range can be narrowed even further, so that particularly preferred processes are characterized in that less than 15 wt .-%, preferably less than 10 wt .-% and in particular less than 5 wt .-% of the deformable Mass (s) of solids used have particle sizes above 800 microns.
  • the fluctuation range around the average particle size is at most 50%, preferably at most 40% and in particular at most 30% of the average particle size, ie the particle sizes are minimally 0.7 and, at most, 1.3. times the mean particle size.
  • the weight ratio of water to certain ingredients in accordance with the invention preferably to be processed masses. After processing, this water is preferably bound in the form of water of hydration, so that the Anlagensend employment preferably have a significantly lower free water content.
  • Preferred end products of the process according to the invention are essentially anhydrous, ie in one state. in which the content of liquid, ie not in the form of water of hydration and / or water of constitution present water below 2 wt .-%, preferably below 1 wt .-% and in particular even below 0.5 wt .-%, in each case based on the moldings , lies.
  • the shaped bodies less than 10 wt .-%, preferably less than 5 wt .-%, more preferably less than 1 wt .-% and in particular less than 0.5 wt .-% free water. Accordingly, water can essentially only be present in chemically and / or physically bound form or as a constituent of the raw materials or compounds present as solid, but not as a liquid, solution or dispersion in the end products of the process according to the invention.
  • the moldings advantageously have a total water content of not more than 15% by weight, with this water not being present in liquid free form, but chemically and / or physically bound, and it is particularly preferred that the Content of not bound to zeolite and / or silicates water in the solid premix not more than 10 wt .-% and in particular not more than 7 wt .-% is.
  • particularly preferred process end products not only have an extremely low proportion of free water, but are preferably themselves still able to bind further free water.
  • the water content of the moldings is 50 to 100% of the calculated water binding capacity.
  • the water binding capacity is the ability of a substance (here: the end product of the process) to absorb water in chemically stable form and ultimately indicates. How much water in the form of stable hydrates can be bound by a substance or a shaped body.
  • the value WBV can be calculated for all hydrate-forming substances which are used in the compositions to be processed according to the invention. About the percentage of these substances then gives the total water binding capacity of the recipe. In preferred Anlagensend.n the water content is then between 50 and 100% of this calculated value.
  • the deformable mass (s) during processing have a water content of from 2.5 to 30% by weight, preferably from 5 to 25% by weight and in particular from 7.5 to 20% by weight .-%, in each case based on the mass, on.
  • Another mechanism for curing the processed in the process according to the invention masses is the cooling in the processing of the masses above their softening point. Methods in which the hardening of the deformable mass (s) by cooling below the melting point are therefore preferred.
  • meltable or softenable masses Under the influence of temperature softenable masses can be easily assembled by mixing the desired other ingredients with a meltable or softenable material and the mixture is heated to temperatures in the softening of this substance and processed molding at these temperatures.
  • waxes, paraffins, polyalkylene glycols, etc. are particularly preferably used as meltable or softenable substances. These are described below.
  • the meltable or softenable substances should have a melting range (solidification range) in such a temperature range, with the remainder Ingredients of the masses to be processed are not exposed to high thermal stress. On the other hand, however, the melting range must be sufficiently high in order to still provide a handleable molding at at least slightly elevated temperature. In preferred compositions according to the invention, the meltable or softenable substances have a melting point above 30 ° C.
  • meltable or softenable substances do not show a sharply defined melting point, as usually occurs in the case of pure, crystalline substances, but instead have a melting range which may be several degrees Celsius.
  • the meltable or softenable substances preferably have a melting range of between about 45 ° C and about 75 ° C. That is, in the present case, the melting range occurs within the specified temperature interval and does not denote the width of the melting range.
  • the width of the melting range is at least 1 ° C, preferably from about 2 to about 3 ° C.
  • waxes are understood to mean a series of naturally or artificially produced substances which generally melt above 40 ° C. without decomposition and are already relatively low-viscosity and non-stringy just above the melting point. They have a strong temperature-dependent consistency and solubility.
  • the waxes are divided into three groups, the natural waxes, chemically modified waxes and the synthetic waxes.
  • Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, Japan wax, Esparto grass wax, cork wax, guaruma wax, rice germ oil wax. Sugarcane wax, ouricury wax, or montan wax, animal waxes such as beeswax. Shellac wax, spermaceti, lanolin (wool wax), or raffia fat, mineral waxes such as ceresin or ozokerite (earth wax), or petrochemical waxes such as petrolatum. Paraffin waxes or microwaxes.
  • the chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. It is also possible to use as meltable or softenable substances for the compositions which cure by cooling, and compounds from other substance classes which meet the stated requirements with regard to the softening point. Suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG), proved. Also suitable are synthetically produced waxes from lower carboxylic acids and fatty alcohols, for example dimyristyl tartrate, which is available under the name Cosmacol® ETLP (Condea).
  • esters of lower alcohols can be used with fatty acids from natural sources.
  • This class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate.
  • Shellac for example shellac KPS three-ring SP (Kalkhoff GmbH) can also be used according to the invention as meltable or softenable substances.
  • Wax alcohols are higher molecular weight. water-insoluble fatty alcohols with usually about 22 to 40 carbon atoms.
  • the wax alcohols are, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • the coating of the solid particles coated according to the invention may optionally also contain wool wax alcohols, among which triterpenoid and steroid alcohols, for example lanolin.
  • fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol bonds may also be used as part of the meltable or softenable substances.
  • meltable or softenable substances in the masses to be processed include those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG), with polyethylene glycols having molecular weights of between 1500 and 36,000 being preferred, and those having molecular weights of from 2000 to 6000 being particularly preferred and those having molecular weights of 3,000 to 5,000 are particularly preferred. Also, corresponding processes, which are characterized in that the plastically deformable mass (s) at least one substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) contains / are preferred.
  • masses to be processed are particularly preferred, which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as sole meltable or softenable substances.
  • PPG propylene glycols
  • PEG polyethylene glycols
  • Polypropylene glycols which can be used according to the invention are polymers of propylene glycol which correspond to the general formula I satisfy, where n can take values between 10 and 2000.
  • Preferred PPG have molecular weights between 1000 and 10,000, corresponding to values of n between 17 and about 170.
  • Polyethylene glycols which can preferably be used according to the invention are polymers of ethylene glycol which correspond to general formula II H- (O-CH 2 -CH 2 ) n -OH (II) satisfy, where n can take values between 20 and about 1000.
  • the abovementioned preferred molecular weight ranges correspond to preferred ranges of the value n in formula IV of about 30 to about 820 (exactly: from 34 to 818), especially preferably from about 40 to about 150 (exactly: from 45 to 136) and especially from about 70 to about 120 (exactly: from 68 to 113).
  • the masses to be processed according to the invention contain in the predominant proportion paraffin wax. That is, at least 50% by weight of the total contained meltable or softenable substances, preferably more, consist of paraffin wax. Particularly suitable are paraffin wax contents (based on the total amount of meltable or softenable substances) of about 60% by weight, about 70% by weight or about 80% by weight, with even higher proportions of, for example, more than 90% by weight. are particularly preferred. In a particular embodiment of the invention, the total amount of the meltable or softenable substances used of at least one mass consists exclusively of paraffin wax.
  • paraffin waxes have the advantage over the other natural waxes mentioned that there is no hydrolysis of the waxes in an alkaline detergent environment (as is to be expected, for example, in the wax esters), since paraffin wax contains no hydrolyzable groups.
  • Paraffin waxes consist mainly of alkanes, as well as low levels of iso- and cycloalkanes.
  • the paraffin to be used according to the invention preferably has substantially no constituents with a melting point of more than 70 ° C., more preferably of more than 60 ° C. Shares of high-melting alkanes in the paraffin can fall below this melting temperature in the detergent leaving unwanted wax residue on the surfaces to be cleaned or the property to be cleaned. Such wax residues usually lead to an unsightly appearance of the cleaned surface and should therefore be avoided.
  • Preferably to be processed masses contain as meltable or softenable substances at least one paraffin wax having a melting range of 50 ° C to 60 ° C, with preferred A process characterized in that the deformable mass (s) contains a paraffin wax having a melting range of 50 ° C to 55 ° C.
  • the content of the paraffin wax used at ambient temperature (usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible.
  • the proportion of solid wax constituents increases, the end-of-processability of the process end products increases against impacts or friction on other surfaces, resulting in longer-lasting protection.
  • High levels of oils or liquid wax components can lead to a weakening of the moldings or moldings areas, whereby pores are opened and the active ingredients are exposed to the aforementioned environmental influences.
  • the meltable or softenable substances may contain, in addition to paraffin as the main constituent, one or more of the abovementioned waxes or waxy substances.
  • the mixture forming the meltable or softenable substances should be such. that the mass and the molded body or molded body component formed therefrom are at least largely water-insoluble.
  • the solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C and preferably be below 5 mg / l.
  • meltable or softenable substances should have the lowest possible water solubility, even in water at elevated temperature, in order to avoid as much as possible a temperature-independent release of the active substances.
  • the principle described above is the delayed release of ingredients at a certain time in the cleaning cycle and can be particularly advantageous when rinsing in the main rinse at a lower temperature (for example 55 ° C), so that the active substance from the rinse aid particles only in the rinse cycle at higher Temperatures (about 70 ° C) is released.
  • compositions to be processed according to the invention are characterized in that they comprise, as meltable or softenable substances, one or more substances having a melting range from 40 ° C. to 75 ° C. in amounts of from 6 to 30% by weight, preferably from 7.5 to 25 Wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the mass.
  • solutions or dispersions of the desired ingredients can be prepared in one or more suitable, volatile solvents which, after the shaping processing step, release and harden the solvent (s).
  • suitable solvents are, for example, lower alkanols, aldehydes, ethers, esters, etc., the selection of which is carried out depending on the further composition of the masses to be processed.
  • Particularly suitable solvents for such processes in which the hardening of the deformable mass (s) takes place by evaporation of solvents are ethanol, propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl- 2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, 3-methyl-1-butanol; 3-methyl-2-butanol, 2-methyl-2-butanol, 2-methyl-1-butanol, 1-hexanol and the acetic acid esters of the abovementioned alcohols, in particular ethyl acetate.
  • the evaporation of said solvents can be accelerated by the shaping and cutting subsequent heating, or by air movement. Combinations of the measures mentioned are suitable for this purpose, for example, the blowing of the cut moldings with hot or hot air.
  • the crystallization as a mechanism underlying the curing can be used, for example, by melting of crystalline substances as the basis of one or more molding masses. After processing such systems go into a higher order state, which in turn leads to the curing of the entire formed body.
  • the crystallization can also be carried out by crystallization from supersaturated solution.
  • supersaturation is the term for a metastable state in which, in a closed system, more of a substance is present than is required for saturation.
  • a supersaturated solution obtained, for example, by supercooling thus contains more solute than it is likely to contain in thermal equilibrium.
  • the excess of dissolved matter may be made by seeding with germs or dust particles or by shaking the system for instant crystallization.
  • the term "supersaturated" always refers to a temperature of 20 ° C. Dissolve in a particular solvent at a temperature of 20 ° C of a substance x grams in liters, the solution in the context of the present invention is to be described as “supersaturated” if it contains (x + y) grams of the substance in liters where y> 0.
  • solutions which are used with an increased temperature as the basis of a mass to be processed and are processed at this temperature at which more dissolved substance is in the solution than those which are present are also to be termed "supersaturated" 20 ° C in the same amount of solvent would solve.
  • the present invention means the maximum amount of a substance. which can absorb the solvent at a certain temperature, ie the proportion of the solute in a saturated at the temperature of the solution. If a solution contains more solute than it should be in thermodynamic equilibrium at a given temperature (eg, supercooling), it is called supersaturated. By seeding with germs can cause the excess precipitates as a bottom body of the now only saturated solution. However, a solution that is saturated with respect to a substance can dissolve other substances (eg you can dissolve sugar in a saturated saline solution).
  • the state of supersaturation can, as described above, be achieved by slow cooling or by supercooling of a solution, as long as the solute is more soluble in the solvent at higher temperatures.
  • Other ways to achieve supersaturated solutions include the combination of two solutions whose ingredients react to another substance, which does not precipitate immediately (prevented or delayed precipitation reactions). The latter mechanism is particularly suitable as a basis for the formation of compositions to be processed according to the invention.
  • the state of supersaturation can be achieved with any type of solution, although the application of the principle described in the present application, as already mentioned, is used in the production of detergents and cleaners.
  • some systems tend to form supersaturated solutions in principle.
  • the underlying material systems ecologically, toxicologically or for economic reasons can not be used.
  • processes according to the invention with the last-mentioned curing mechanism are particularly preferred in which a supersaturated aqueous solution is used as the basis for at least one mass to be processed.
  • the state of supersaturation in the context of the present invention refers to the saturated solution at 20 ° C.
  • the state of supersaturation can be easily reached.
  • Processes according to the invention in which the composition which sets by crystallization has a temperature between 35 and 120 ° C, preferably between 40 and 110 ° C, more preferably between 45 and 90 ° C and especially between 50 and 80 ° C. are preferred in the context of the present invention.
  • the prepared detergent tablets are usually neither stored at elevated temperatures nor later applied at these elevated temperatures, cooling of the mixture results in precipitation of the solute content from the supersaturated solution contained above the saturation limit at 20 ° C in the solution.
  • the supersaturated solution can thus be divided on cooling into a saturated solution and a bottom body. But it is also possible that by recrystallization and hydration phenomena the supersaturated solution solidifies on cooling to a solid. This is the case, for example, when certain hydrazine-containing salts dissolve on heating in their water of crystallization. On cooling, supersaturated solutions are often formed here, which solidify by mechanical action or addition of seed to give a solid-the salt containing water of crystallization as the thermodynamically stable state at room temperature.
  • the supersaturated solution used as the basis of the hardening mass solidifies at room temperature to a solid. It is preferred here that the previously supersaturated solution can not be reconverted into a supersaturated solution after solidification to a solid by heating to the temperature at which the supersaturated solution was formed. This is the case, for example, with the phosphonates mentioned.
  • the supersaturated solution serving as the basis of the hardening composition can - as mentioned above - be obtained in several ways and then be processed according to the invention after optional addition of further ingredients.
  • a simple way is for example. in that the supersaturated solution used as the basis of the hardening mass is prepared by dissolving the solute in heated solvent. Become in this way in the heated solvent higher amounts of the solute dissolved than would dissolve at 20 ° C, so there is a supersaturated in the context of the present invention solution that either hot (see above) or cooled and can be added in the metastable state in the mixer.
  • Another way is to add a non-supersaturated solution with a gas or other liquid or solution so that the solute in the solution reacts to a less soluble substance or dissolves more poorly in the mixture of solvents.
  • the combination of two solutions, each containing two substances which react with each other to a poorly soluble substance, is also a method for producing supersaturated solutions, as long as the less soluble material fails instantaneously.
  • Processes which are likewise preferred in the context of the present invention are characterized in that the supersaturated solution which serves as the basis of the hardening composition is prepared by combining two or more solutions. Examples of such ways of producing supersaturated solutions are discussed below.
  • the supersaturated aqueous solution is obtained by combining an aqueous solution of one or more acidic ingredients of detergents and cleaners, preferably from the group of surfactant acids, builder acids and complexing acids, and an aqueous alkali solution, preferably an aqueous alkali hydroxide solution, especially an aqueous sodium hydroxide solution becomes.
  • the supersaturated aqueous solution is obtained by combining an aqueous phosphonic acid solution with concentrations above 45% by weight, preferably above 50% by weight and in particular above 55 wt .-%, each based on the phosphonic acid and an aqueous sodium hydroxide solution with concentrations above 35 wt .-%, preferably above 40 wt .-% and in particular above 45 wt .-%, each based on the sodium hydroxide solution.
  • the curing of the deformable mass (s) according to the invention can also be effected by chemical reaction (s), in particular polymerization.
  • chemical reaction s
  • all chemical reactions are suitable which, starting from one or more liquid to pasty substances, lead to solids by reaction with (another) substance (s).
  • chemical reactions that do not abruptly lead to the mentioned state change, are suitable.
  • From the variety of chemical reactions that lead to the solidification phenomenon particularly reactions are suitable in which the construction of larger molecules is made of smaller molecules. These, in turn, preferably include reactions in which many small molecules react to (a) larger molecule (s).
  • polyreactions polymerization, polyaddition, polycondensation
  • polymer-analogous reactions are so-called polyreactions (polymerization, polyaddition, polycondensation) and polymer-analogous reactions.
  • the corresponding polymers, polyadducts (polyaddition products) or polycondensates (polycondensation products) then give
  • co-builders may be selected, for example, from the groups of the polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid. Polyacetals, dextrins, etc. come. These classes of substances are described below.
  • Another mechanism by which the hardening of the deformable mass (s) can take place in the context of the method according to the invention is curing by changing the rheological properties.
  • Preferred end products of the process according to the invention that is to say preferred detergent tablets, furthermore contain one or more surfactants. Accordingly, it is preferred that at least one of the masses to be processed contains surfactant (s).
  • surfactant in the detergent tablets according to the invention can anionic. nonionic, cationic and / or amphoteric surfactants or mixtures thereof are used. From an application point of view, preference is given to mixtures of anionic and 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.
  • surfactants of the sulfonate type preferably come C 9-13 alkyl benzene sulfonates, olefin sulfonates. ie mixtures of alkene and hydroxyalkanesulfonates
  • disulfonates as obtained for example from C 12-18 monoolefins with endoder internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, 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 containing 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 is a synthetic. contain on a petrochemical basis produced 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 prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
  • sulfuric acid monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight-chain or branched C 7-21 alcohols such as 2-methyl-branched C 9-11 alcohols
  • ethylene oxide (EO) or C 12-18 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 including the soaps may be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases such as mono-, di-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.
  • nonionic surfactants are preferably alkoxylated, advantageously ethoxylated.
  • primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in which the alcohol radical may be linear or preferably 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 radical may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture , as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals from alcohols of native origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol.
  • 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.
  • 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 described 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-tallow alkyl-N, N-dihydroxyethylaminoxid, and the fatty acid alkanolamides may 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 (III) 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 (IV) 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.
  • C 1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical. its alkyl chain with at least two hydroxyl groups substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this 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 and cleaning agent tablets are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.
  • surfactant (s) preferably anionic (s) and / or nonionic surfactant (s)
  • amounts of from 5 to 40% by weight preferably from 7.5 to 35% by weight .-%, particularly preferably from 10 to 30 wt .-% and in particular from 12.5 to 25 wt .-%, in each case based on the weight of the molded article.
  • 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.
  • surfactants in automatic dishwashing detergent tablets is preferably restricted to the use of small amounts of nonionic surfactants.
  • Detergent tablets preferably to be used as detergent tablets are characterized in that they contain total surfactant contents below 5% by weight, preferably below 4% by weight, more preferably below 3% by weight and in particular below 2 wt .-%, each based on their total weight, have.
  • 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.
  • detergent tablets for automatic dishwashing produced 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 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.
  • EO ethylene oxide
  • 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 highly viscous 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. Also nonionic surfactants which have waxy consistency at room temperature. are 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 complexed 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 consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially 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 Cfhemicals.
  • 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 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.
  • the above information related in part to the final process products which - as mentioned above - can also be designed in two, three or four phases.
  • the deformable mass (s) of total surfactant contents are below 5% by weight, preferably below of 4 wt .-%, more preferably below 3 wt .-% and in particular below 2 wt .-%, each based on the mass, have.
  • the detergent tablets according to the invention may contain further ingredients customary in detergents and cleaners from the group of bleaches.
  • disintegration aids so-called tablet disintegrating agents
  • these substances are suitable, for example, for accelerating the release of individual shaped body regions in relation to other regions.
  • This can be realized in the method according to the invention in that only one of the masses to be processed contains such substances, or that several masses contain such substances in different amounts.
  • 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. Contains only one mass Disintegration aids, so the above information refers only to the weight of this mass.
  • 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 bound by an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • 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 pure cellulose as a cellulose-based disintegrant. which is free of cellulose derivatives.
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
  • Detergent tablets and detergent tablets which contain disintegrating agents in granular or optionally cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and international patent application WO98 / 40463 (Henkel). Further details of the production of granulated, compacted or cogranulated cellulose explosives can be found in these publications.
  • the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
  • the above-mentioned coarser disintegration aids based on cellulose described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from Rettenmaier.
  • Microcrystalline cellulose may be used as another cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact.
  • Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 ⁇ m and can be compacted, for example, into granules having an average particle size of 200 ⁇ m.
  • preferred detergent tablets also contain a disintegration aid, preferably a cellulose-based disintegration assistant, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the molding weight.
  • a disintegration aid preferably a cellulose-based disintegration assistant, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight. -% and in particular from 4 to 6 wt .-%, each based on the molding weight.
  • the detergent tablets according to the invention may additionally comprise a gas-evolving effervescent system which is incorporated in one or more of the masses to be processed.
  • the gas-developing effervescent system can consist of a single substance. which releases a gas on contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which on contact with water Oxygen releases.
  • 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 alkali metal carbonates or bicarbonates 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 for washing technical interest.
  • 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.
  • the content of individual masses of the substances mentioned may well be higher.
  • boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used.
  • the other solid mono-, oligo- and polycarboxylic acids are tartaric acid.
  • Oxalic acid and polyacrylic acid are also usable.
  • 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.
  • At least one of the moldable compositions contains bleaching agents selected from the group consisting of oxygen or halogen bleaches, especially 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 mass.
  • bleaching agents selected from the group consisting of oxygen or halogen bleaches, especially 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 mass.
  • sodium percarbonate has particular significance.
  • sodium gercarbonate is a non-specific term used for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts of sodium carbonate.
  • the commercial product has the average composition 2 Na 2 CO 3 ⁇ 3 H 2 O 2 and is therefore no peroxycarbonate.
  • Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm -3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.
  • the industrial production of sodium percarbonate is predominantly produced by precipitation from aqueous solution (so-called wet process).
  • aqueous solutions of sodium carbonate and hydrogen peroxide, Kristallisierysstoff (for example, polyphosphates, polyacrylates) and stabilizers are combined and the sodium percarbonate by salting-out agent (mainly sodium chloride) (for example, Mg 2+ ions) like.
  • the precipitated salt which still contains 5 to 12 wt .-% mother liquor, is then removed by centrifugation and dried in fluid bed dryers at 90 ° C.
  • the bulk density of the finished product may vary between 800 and 1200 g / l, depending on the manufacturing process.
  • the percarbonate is stabilized by an additional coating. Coating methods and materials used for coating are widely described in the patent literature. In principle, all commercially available percarbonate types can be used according to the invention, as described for example by the companies Solvay Interox. Degussa, Kemira or Akzo.
  • bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
  • bleaching agents it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the tablets.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids. Examples being 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.
  • aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxy carboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N -Terephthaloyl-di (6-aminopercapronate) can be used.
  • Chlorinating or bromine-releasing substances can also be used as bleaching agents in machine dishwashing moldings.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • the deformable masses bleach activators from the groups of polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), the N-acylimides, especially N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, especially n-nonanoyl or Isononanoyloxybenzolsulfonat (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 mass.
  • TAED tetraacetylethylenediamine
  • N-acylimides especially N-nonanoylsuccinimide (NOSI)
  • the acylated phenolsulfonates especially n-
  • bleach activators can be incorporated.
  • Bleach activators which support the action of the bleaching agents are, for example, compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes.
  • TAED tetraacetylethylenediamine
  • TAMD tetraacetylmethylenediamine
  • TAHD tetraacetylhexylenediamine
  • PAG pentaacetylglucose
  • DADHT 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine
  • ISA isatoic anhydride
  • 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 acid anhydrides.
  • TAED tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • acylated glycolurils
  • acylated polyhydric alcohols in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), and German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone.
  • PAG pentaacetylglucose
  • pentaacetylfruktose pentaacetylfruktos
  • N-acylated lactams for example N-benzoyl-caprolactam.
  • Hydrophilic substituted acyl acetals and acyl lactams are also preferably used.
  • Combinations of conventional bleach activators can also be used.
  • bleach catalysts can also be incorporated.
  • 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 are useful as bleach catalysts.
  • Bleach activators from the group of the multiply acylated alkylenediamines are preferred. in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methylsulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0, 1 wt .-% to 8 wt .-%, especially 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 (NOSI)
  • 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.
  • a further preferred method is characterized in that at least one of the deformable masses silver protectants from the group of the triazoles, the benzotriazoles, the Bisbenzotriazole, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, more preferably benzotriazole and / or alkylaminotriazole, in quantities 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 mass contains.
  • the said corrosion inhibitors can also be incorporated into the masses to be processed for the protection of the items to be washed or the machine, wherein in the field of automatic dishwashing silver protectants have a special meaning. It is possible to use the known substances of the prior art. In general, 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. In addition, 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.
  • corrosion inhibitors are used in multiphase moldings, it is preferred to separate them from the bleaching agents. Methods in which one of the deformable masses contains bleach while another deformable mass contains corrosion inhibitors are therefore preferred.
  • the separation of the bleach from other ingredients may be advantageous.
  • Inventive methods in which one of the deformable masses contains bleach. while another deformable mass contains enzymes are also preferred.
  • Particularly suitable enzymes are those from the classes of hydrolases, such as proteases, esterases, lipases or lipolytic enzymes.
  • cellulases and other glycosyl hydrolases can be removed by removing pilling and microfibrils contribute to color retention and to increasing the softness of the textile.
  • oxidoreductases for bleaching or inhibiting color transfer.
  • Particularly suitable are from bacterial strains or fungi such as Bacillus subtilis. Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens, as well as enzymatically derived compounds derived from their genetically engineered variants.
  • Bacillus subtilis Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens
  • 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 protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, 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.
  • Als-cellulases are preferably cellobiohydrolases, endoglucanases and - glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • hydrolases such as proteases. Esterases, lipases or lipolytic enzymes, amylases. Glykosylhydrolasen and mixtures of the enzymes mentioned in question. 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 from bacterial strains or fungi such as Bacillus subtilis.
  • 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 examples include 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 .-%, each based on the mass (s), amount.
  • Such enzyme-containing compositions are preferably processed in multi-stranded processes, i.
  • a strand of material containing enzymes there is at least one other strand which is preferably free of enzymes.
  • methods are particularly preferred in which the enzyme-containing material strand is enveloped by an enzyme-free material.
  • a separation of the bleach from the surfactants described above may also be advantageous, so that preferred processes are characterized in that one of the deformable masses contains bleach, while another deformable mass surfactants.
  • nonionic surfactants with particular preference alkoxylated alcohols having 10 to 24 carbon atoms and 1 to 5 alkylene oxide units.
  • ingredients which may be part of one or more masses in the context of the process according to the invention are, for example, co-builders (see above) dyes, optical brighteners, fragrances, soil-release compounds, soil repellents, antioxidants, fluorescers, foam inhibitors, Silicone and / or paraffin oils, color transfer inhibitors, grayness inhibitors, detergency boosters, etc. These 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.
  • GPC gel permeation chromatography
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural Vervandtschaft with the polymers studied. This information differs 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 are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably 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 of which German Patent Application DE-A-195 40 086 discloses that they also have a bleach-stabilizing effect in addition to cobuilder properties.
  • polyacetals which are obtained by reacting dialdehydes with polyolcarboxylic acids. which have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained.
  • 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.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are described, for example, in European Patent Applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and International Patent Applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 .
  • an oxidized oligosaccharide according to the German patent application DE-A-196 00 018.
  • 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.
  • Such co-builders are described, for example, in International Patent Application WO 95/20029 .
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable, especially when the agents also contain bleach. Aminoalkanphosphonate, in particular DTPMP use, or to use mixtures of said phosphonates.
  • the detergent tablets can be wholly or partially dyed with suitable dyes. Special optical effects can be achieved if in the case of the production of moldings from several masses, the masses to be processed are colored differently.
  • 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 substrates such as textile fibers or dishes so as not to stain them.
  • Preferred for use in detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe.
  • a possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1, Part 2: 10020), which is available as a commercial product, for example as Basacid® Green 970 from BASF, Ludwigshafen, and mixtures thereof with suitable blue dyes.
  • Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160), Supranol® Blue GLW (CAS 12219-32-8, CI Acidblue 221 ), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0).
  • the colorant When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, for example the abovementioned Basacid® Green or the abovementioned Sandolan® Blue, colorant concentrations in the range from a few 10 -2 to 10 -3 % by weight are typically selected.
  • the suitable concentration of the colorant in detergents or cleaners is typically between 10 -3 and 10 -4 % by weight.
  • the laundry detergent and cleaning product tablets produced by the process 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 examples are salts of 4,4'-bis [(4-anilino-6-morpholino-6-triazin-2-yl) amino] -stilbene-2,2'-disulfonic acid or similarly constructed compounds which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group.
  • 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.
  • Fragrances are added to the compositions according to the invention in order to improve the aesthetic impression of the products and to provide the consumer, in addition to the performance of the product, a visually and sensory "typical and unmistakable" 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, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral.
  • Citronellal Citronellyloxyacetaldehyde, cyclamenaldehyde. Hydroxycitronellal, Lilial and Bourgeonal, to the ketones eg the Jonone, ⁇ -isomethylionone and methyl-cedrylketon, to the alcohols anethol, citronellol, eugenol. Geraniol.
  • Linalool, phenylethyl alcohol and terpineol the hydrocarbons include mainly the terpenes such as limonene and pinene.
  • terpenes such as limonene and pinene.
  • mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures, such as those available from plant sources, eg Pine. Citrus, jasmine, patchouly. Rose or Ylang-Ylang oil.
  • the content of perfume in the washing and cleaning agent tablets produced according to the invention is up to 2% by weight of the total formulation.
  • the fragrances can be incorporated directly into the compositions of the invention, but it may also be advantageous to apply the fragrances on carriers, which enhance the adhesion of the perfume on the laundry and provide by a slower release of fragrance for long-lasting fragrance of the textiles.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • 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 methylhydroxy-propylcellulose 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 ether, as well as the 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 acid and terephthalic acid polymers.
  • foam inhibitors which can be used in the compositions according to the invention, for example, soaps.
  • Paraffins or silicone oils which may optionally be applied to carrier 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 starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches etc. Polyvinylpyrrolidone is also 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. used
  • compositions according to 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 prepared according to 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. Halogenphenols and Phenolmercuriacetat, which can be completely dispensed with 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 centistokes at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.
  • the agents prepared according to the invention may also contain UV absorbers. which coat the treated textiles and improve the light fastness of the fibers.
  • Links. which have these desired properties. are, for example, the compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position which are active by radiationless deactivation.
  • substituted benzotriazoles. in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural products such as umbelliferone and the body's own urocanic acid suitable.
  • the content of the end products of the process according to the invention was mentioned in part on the individual substances.
  • the end products of the process according to the invention can be provided in a wide variety of geometric forms, this flexibility being one of the many advantages of the process according to the invention.
  • they can be manufactured in a predetermined spatial form and a predetermined size, wherein as a space form come practically all reasonable manageable configurations come into consideration. for example, training as a blackboard.
  • This last embodiment detects the presentation form from the tablet to compact cylinder pieces with a height to diameter ratio above 1.
  • the end products of the method according to the invention can be designed in each case as separate individual elements which corresponds to the predetermined dosage amount of the washing and / or cleaning agent.
  • the formation as tablets, in cylindrical or parallelepiped form may be expedient, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0 5 is preferred.
  • the spatial form of another embodiment of the moldings is adapted in their dimensions of the dispenser of commercial household washing machines, so that the moldings can be metered without dosing directly into the dispenser, where it dissolves during the dispensing process.
  • a use of the detergent tablets via a dosing is easily possible and preferred in the context of the present invention.
  • Another preferred molded article which can be produced has a plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin segments, broken and in the Machine can be entered.
  • This principle of the "bar-shaped" shaped body wash can also be realized in other geometric shapes, for example vertical triangles, which are joined together only on one side thereof.
  • Such "bar-shaped" strand sections can be produced by a post-treatment step after cutting to length. which consists in it. to push a second knife or a second knife set in the cut strand sections without dividing them. Also a superficial shaping or production of positive or negative lettering can take place according to the invention. Accordingly, preferred processes are characterized in that the cut-to-size moldings are subjected to a post-treatment step.
  • the aftertreatment step may include impressions of patterns, shapes, etc., in addition to memorizing lettering.
  • universal detergents prepared according to the invention can be identified by symbols such as glasses, plates, pots, pans, etc., by means of a T-shirt symbol, color detergents prepared according to the invention by a wool symbol, machine dishwashing detergent tablets produced according to the invention.
  • Preferred methods according to the invention therefore comprise, as post-treatment step, an additional shaping step, in particular embossing.
  • the post-treatment step comprises coating the shaped bodies with a pourable material, preferably a pourable material having a viscosity of ⁇ 5000 mPas.
  • the shaped bodies have a density above 800 kgdm -3 , preferably above 900 kgdm -3 , particularly preferably above 1000 kgdm -3 and especially above 1100 kgdm -3 .
  • the advantages of the offer form of a compact detergent or cleaning agent are particularly evident.
  • the present invention provides a process which makes it possible to produce washing and cleaning agent tablets simply and under varying conditions.
  • a preferred curing mechanism is, as described above, in the time-delayed water binding, wherein corresponding washing and cleaning agent shaped bodies are not described in the prior art.

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Claims (46)

  1. Procédé de production de solides moulés de produits de lavage et de nettoyage.
    caractérisé en ce qu'
    on produit une ou des masse(s) moulables et on amène celle(s)-ci avec une pression inférieur à 10 bars, à des orifices de sortie, et on découpe et on laisse durcir complètement les cordons de produit qui sortent, aux dimensions de solides moulés.
  2. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on amène la (les) masse(s) moulable(s) aux orifices de sortie avec une pression en dessous de 8,5 bars, de préférence en dessous de 7,5 bars d'une manière particulièrement préférée en dessous de 6,5 bars et en particulier en dessous de 5 bars.
  3. Procédé selon l'une quelconque des revendications 1 ou 2,
    caractérisé en ce qu'
    on découpe et on laisse durcir complètement une masse moulable interposée entre deux cylindres, évacuée sous forme de cordon de produit des orifices de sortie, à la dimension désirée de solide moulé.
  4. Procédé selon l'une quelconque des revendications 1 à 3,
    caractérisé en ce qu'
    on lamine deux masses composées différemment, moulables, entre deux paires de cylindres, on les extrait des orifices de sortie, sous forme de cordons de produit pleins, creux ou à plusieurs couches, on les découpe à la dimension désirée de solide moulé et on les laisse durcir.
  5. Procédé selon l'une quelconque des revendications 1 à 4,
    caractérisé en ce qu'
    on lamine trois masses composées différentes, moulables, entre trois paires de cylindres, on les extrait par les orifices de sortie sous forme de cordons pleins, une, deux ou trois fois, ou creux, ou à deux ou trois couches, on les découpe à la dimension désirée de solide moulé, et on les fait durcir.
  6. Procédé selon l'une quelconque des revendications 1 à 5,
    caractérisé en ce qu'
    on extrait les cordons de produit à une vitesse de 0,2 m/min à 30 m/min, de préférence entre 0,25 m/min à 20 m/min, d'une manière particulièrement préférée de 0,5 m/min à 15 m/min et en particulier de 1 m/min à 10 m/min, des orifices de sortie.
  7. Procédé selon l'une quelconque des revendications 1 à 6,
    caractérisé en ce que
    les orifices de sortie possèdent des surfaces d'orifice de 50 mm2 à 2500 mm2, de préférence de 100 mm2 à 2000 mm2, d'une manière particulièrement préférée de 200 à 1500 mm2 et en particulier de 300 mm2 à 1000 mm2 avec une préférence particulière de 350 mm2 à 750 mm2.
  8. Procédé selon l'une quelconque des revendications 1 à 7,
    caractérisé en ce que
    l'épaisseur d'au moins un des cordons de produit qui sortent des orifices de sortie est au moins 5 mm, de préférence au moins 7,5 mm et en particulier au moins 10 mm.
  9. Procédé selon l'une quelconque des revendications 1 à 8,
    caractérisé en ce que
    les cordons de produit qui sortent des orifices de sortie, sont découpés à une longueur de 10 à 100 mm, de préférence de 12,5 à 75 mm d'une manière particulièrement préférée de 15 à 60 mm et en particulier de 20 à 50 mm.
  10. Procédé selon l'une quelconque des revendications 1 à 9,
    caractérisé en ce que
    le durcissement complet des cordons de produit découpés aux dimensions de solide moulé est favorisé par un séchage et/ou un refroidissement superficiels, en particulier par soufflage avec de l'air froid.
  11. Procédé selon l'une quelconque des revendications 1 à 10,
    caractérisé en ce que
    la (les) masse(s) moulables(s) renferme(nt) de 10 à 95 % en poids de préférence de 15 à 90 % en poids, d'une manière particulièrement préférée de 20 à 85 % en poids et en particulier de 25 à 80 % en poids de substances anhydres, qui se transforment par hydratation en une forme hydratée ayant un point de fusion en dessous de 120°C, de préférence en dessous de 100°C et en particulier en dessous de 80°C.
  12. Procédé selon l'une quelconque des revendications 1 à 11,
    caractérisé en ce que
    la (les) masse(s) moulable(s) renferme(nt) un (ou des) phosphate(s), de préférence un (ou des) phosphate(s) de métal alcalin, d'une manière particulièrement préférée le triphosphate pentasodique ou pentapotassique (tripolyphosphate de sodium ou de potassium) en quantités allant de 20 à 80 % en poids, de préférence de 25 à 75 % en poids et en particulier de 30 à 70 % en poids, à chaque fois rapporté à la masse.
  13. Procédé selon la revendication 12,
    caractérisé en ce que
    le rapport pondéral du (des) phosphate(s) à l'eau, dans la masse moulable est inférieur à 1:0,3, de préférence inférieur à 1:0,25 et en particulier inférieur à 1:0,2.
  14. Procédé selon l'une quelconque des revendications 1 à 13,
    caractérisé en ce que
    la (les) masse(s) moulable(s) contien(nen)t du (ou des) carbonate(s) et/ou du (ou des) hydrogénocarbonate(s), de préférence des carbonates de métal alcalin et d'une manière particulièrement préférée du carbonate de sodium en des quantités allant de 5 à 50 % en poids, de préférence de 7,5 à 40 % en poids et en particulier de 10 à 30 % en poids, à chaque fois rapporté à la masse.
  15. Procédé selon l'une quelconque des revendications 1 à 14,
    caractérisé en ce que
    la (les) masse(s) moulable(s) renferme(nt) un (ou des) silicate(s), de préférence des silicates de métal alcalin, d'une manière particulièrement préférée des silicates de métal alcalin cristallins ou amorphes, en quantités allant de 10 à 60 % en poids, de préférence de 15 à 50 % en poids et en particulier de 20 à 40 % en poids, à chaque fois rapporté à la masse.
  16. Procédé selon l'une quelconque des revendications 1 à 15,
    caractérisé en ce que
    la ou les masse(s) moulable(s) renferme(nt) de la (des) zéolithe(s), de préférence de la zéolithe A, de la zéolithe P, de la zéolithe X, et des mélanges de base de celles-ci, en quantités allant de 10 à 60 % en poids, de préférence de 15 à 50 % en poids et en particulier de 20 à 40 % en poids, à chaque fois rapporté à la masse.
  17. Procédé selon l'une quelconque des revendications 1 à 16,
    caractérisé en ce que
    la taille moyenne des particules des matières solides introduites dans la (ou les) masse(s) moulable(s) se situe en dessous de 400 µm, de préférence en dessous de 300 µm et en particulier en dessous de 200 µm.
  18. Procédé selon l'une quelconque des revendications 1 à 17,
    caractérisé en ce que
    moins de 10 % en poids, de préférence moins de 5 % et encore mieux moins de 1 % en poids des matières solides mises en jeu dans la (ou les) masses moulable(s) possèdent des tailles de particule au-dessus de 1000 µm.
  19. Procédé selon l'une quelconque des revendications 1 à 18,
    caractérisé en ce que
    moins de 15 % en poids, de préférence moins de 10 % et mieux moins de 5 % en poids des matières solides mises en jeu dans la (les) masse(s) moulable(s) possèdent une taille de particules au-dessus de 800 µm,
  20. Procédé selon l'une quelconque des revendications 1 à 19,
    caractérisé en ce que
    la teneur en eau des solides moulés s'élève de 50 à 100 % de la capacité de liaison de l'eau calculée.
  21. Procédé selon l'une quelconque des revendications 1 à 20,
    caractérisé en ce que
    la (les) masse(s) moulable(s) possède(nt) lors du façonnage une teneur en eau de 2,5 à 30 % en poids de préférence de 5 à 25 % en poids et en particulier de 7,5 à 20 % en poids à chaque fois rapporté à la masse.
  22. Procédé selon l'une quelconque des revendications 1 à 21,
    caractérisé en ce que
    le durcissement complet de (des) masse(s) moulable(s) s'effectue par liaison de l'eau retardée dans le temps.
  23. Procédé selon l'une quelconque des revendications 1 à 21,
    caractérisé en ce que
    le durcissement complet de la (des) masse(s) moulable(s) s'effectue par refroidissement en dessous du point de fusion.
  24. Procédé selon l'une quelconque des revendications 1 à 21,
    caractérisé en ce que
    le durcissement complet de la (des) masse(s) moulable(s) s'effectue par évaporation des solvants.
  25. Procédé selon l'une quelconque des revendications 1 à 21,
    caractérisé en ce que
    le durcissement complet de la (des) masse(s) moulable(s) s'effectue par cristallisation.
  26. Procédé selon l'une quelconque des revendications 1 à 21,
    caractérisé en ce que
    le durcissement de la (des) masse(s) moulable(s) s'effectue par une (ou des) réaction(s) chimique(s) en particulier par polymérisation.
  27. Procédé selon l'une quelconque des revendications 1 à 21,
    caractérisé en ce que
    le durcissement complet de la (des) masse(s) moulable(s) s'effectue par modification des propriétés rhéologiques.
  28. Procédé selon l'une quelconque des revendications 1 à 27,
    caractérisé en ce que
    la (les) masse(s) moulable(s) possède(nt) des teneurs totales en agent tensioactif en dessous de 5 % en poids, de préférence en dessous de 4 % en poids, d'une manière particulièrement préférée en dessous de 3 % en poids et en particulier en dessous de 2 % en poids, à chaque fois rapporté à la masse.
  29. Procédé selon l'une quelconque des revendications 1 à 28,
    caractérisé en ce qu'
    au moins une des masses moulables renferme un agent de blanchiment choisi dans le groupe des agents de blanchiment à oxygène ou à halogène, en particulier un agent de blanchiment chloré avec une préférence particulière pour le perborate de sodium et le percarbonate de sodium, en quantités allant de 2 à 25 % en poids, de préférence de 5 à 20 % en poids, et en particulier de 10 à 15 % en poids, à chaque fois rapporté à la masse.
  30. Procédé selon l'une quelconque des revendications 1 à 29,
    caractérisé en ce qu'
    au moins une des masses moulables renferme des activateurs de blanchiment choisis dans les groupes des alkylènediamines plusieurs fois acylées, en particulier la tétraacétyléthylènediamine (TAED), des N-acylimides, en particulier de la N-nonanoylsuccinimide (NOSI), des phenolsulfonates acylés en particulier le n-nonanoyl ou l'isononanoyloxybenzènesulfonate (n-ou iso NOBS) et le méthylsulfate de n-méthyhnorpholinium acetonitrile (MMA) en quantités de 0,25 à 15 % en poids, de préférence de 0,5 à 10 % en poids et en particulier de 1 à 5 % en poids, à chaque fois rapporté à la masse.
  31. Procédé selon l'une quelconque des revendications 1 à 30,
    caractérisé en ce qu'
    au moins une des masses moulables renferme un agent de protection de l'agent choisi dans le groupe des triazoles, des benzotriazoles, des bis benzotriazoles, des aminotriazoles, des alkylaminotriazoles, et des sels ou des complexes de métal de transition, d'une manière particulièrement préférée de benzotriazole et/ou un alkylaminotriazole, en quantités allant de 0,01 à 5 % en poids, de préférence de 0,05 à 4 % en poids et en particulier de 0,5 à 3 % en poids à chaque fois rapporté à la masse.
  32. Procédé selon l'une quelconque des revendications 1 à 31,
    caractérisé en ce qu'
    au moins une des masses moulables renferme en outre une ou plusieurs substances choisies dans le groupe des enzymes, des inhibiteurs de corrosion, des inhibiteurs de sédimentation, des agents costructurants, des colorants et/ou des parfums en quantités totales allant de 6 à 30 % de préférence de 7.5 à 25 % en poids, et en particulier de 10 à 20 % en poids, à chaque fois rapporté à la masse.
  33. Procédé selon l'une quelconque des revendications 4 à 32.
    caractérisé en ce qu'
    une des masses moulables renferme un agent blanchissant tandis qu'une autre masse moulable renferme des activateurs de blanchiment.
  34. Procédé selon l'une quelconque des revendications 4 à 33,
    caractérisé en ce qu'
    une des masses moulables renferme un agent de blanchiment tandis qu'une autre masse moulable renferme des enzymes.
  35. Procédé selon l'une quelconque des revendications 4 à 34,
    caractérisé en ce qu'
    une des masses moulables renferme un agent de blanchiment tandis qu'une autre masse moulable renferme un agent de protection contre la corrosion.
  36. Procédé selon l'une quelconque des revendications 4 à 34,
    caractérisé en ce qu'
    un des cordons qui sortent des orifices de sortie, renferme des enzymes.
  37. Procédé selon la revendication 36,
    caractérisé en ce que
    le cordon de produit qui contient des enzymes est enrobé par un produit dépourvu d'enzyme.
  38. Procédé selon l'une quelconque des revendications 4 à 37,
    caractérisé en ce qu'
    une des masses moulables renferme un agent de blanchiment tandis qu'une autre masse moulable renferme des agents tensioactifs, de préférence des agents tensioactifs non ioniques, avec une préférence particulière pour des alcools alkoxylés ayant de 10 à 24 atomes de carbone, et de 1 à 5 éléments oxyde d'alkylène.
  39. Procédé selon l'une quelconque des revendications 4 à 38,
    caractérisé en ce qu'
    au moins deux masses moulables renferment le même principe actif en quantités différentes.
  40. Procédé selon l'une quelconque des revendications 1 à 39,
    caractérisé en ce que
    la (les) masse(s) moulable(s) renferme(nt) une cire de paraffine ayant une plage de fusion allant de 50 à 55°C.
  41. Procédé selon l'une quelconque des revendications 1 à 40,
    caractérisé en ce que
    la (les) masse(s) déformable(s) plastiquement renferme(nt) au moins une substance choisie dans le groupe des polyéthylèneglycols (PEG) et/ou des polypropylèneglycols (PPG).
  42. Procédé selon l'une quelconque des revendications 1 à 41,
    caractérisé en ce que
    les solides moulés renferment moins de 10 % en poids, de préférence moins de 5 % en poids, d'une manière particulièrement préférée moins de 1 % en poids et en particulier moins de 0,5 % en poids d'eau libre.
  43. Procédé selon l'une quelconque des revendications 1 à 42,
    caractérisé en ce que
    les solides moulés possèdent une densité supérieure à 800 kg.dm-3, de préférence supérieure à 900 kg.dm-3, d'une manière particulièrement préférée supérieure à 1000 kg.dm-3 et en particulier supérieure à 1100 kg.dm-3.
  44. Procédé selon l'une quelconque des revendications 1 à 43,
    caractérisé en ce qu'
    on soumet les solides moulés à une étape de post-traitement.
  45. Procédé selon la revendication 44,
    caractérisé en ce que
    l'étape de post-traitement comprend le revêtement des solides moulés avec un produit apte à la coulée, de préférence un produit apte à la coulée ayant une viscosité < 5000 mPas.
  46. Procédé selon l'une quelconque des revendications 44 ou 45.
    caractérisé en ce que
    l'étape de post-traitement comprend une étape de modelage supplémentaire, en particulier l'estampage.
EP00938813A 1999-07-03 2000-06-23 Procede de realisation de corps moules a agent de lavage et de nettoyage Expired - Lifetime EP1192241B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19930771A DE19930771A1 (de) 1999-07-03 1999-07-03 Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern
DE19930771 1999-07-03
PCT/EP2000/005811 WO2001002532A1 (fr) 1999-07-03 2000-06-23 Procede de realisation de corps moules a agent de lavage et de nettoyage

Publications (2)

Publication Number Publication Date
EP1192241A1 EP1192241A1 (fr) 2002-04-03
EP1192241B1 true EP1192241B1 (fr) 2004-04-28

Family

ID=7913582

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00938813A Expired - Lifetime EP1192241B1 (fr) 1999-07-03 2000-06-23 Procede de realisation de corps moules a agent de lavage et de nettoyage

Country Status (7)

Country Link
EP (1) EP1192241B1 (fr)
AT (1) ATE265522T1 (fr)
AU (1) AU5406700A (fr)
CA (1) CA2313356A1 (fr)
DE (2) DE19930771A1 (fr)
ES (1) ES2220474T3 (fr)
WO (1) WO2001002532A1 (fr)

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DE10010759B4 (de) * 2000-03-04 2006-04-27 Henkel Kgaa Verfahren zur Herstellung von Formkörpern
DE10010760A1 (de) 2000-03-04 2001-09-20 Henkel Kgaa Mehrphasige Wasch- und Reinigungsmittelformkörper mit nicht-gepreßten Anteilen
DE10134309A1 (de) * 2001-07-14 2003-02-06 Henkel Kgaa Coextrusion von Wasch- und Reinigungsmitteln
DE10211184B4 (de) * 2002-03-14 2004-10-07 Henkel Kgaa Applikation von Hilfsmitteln und Zusatzstoffen für das maschinelle Geschirrspülen
DE10253214A1 (de) * 2002-11-15 2004-06-03 Henkel Kgaa Portionierte Mittel mit unterschiedlichen Bestandteilen
DE10313172B4 (de) * 2003-03-25 2007-08-09 Henkel Kgaa Gestaltsoptimierte Reinigungsmitteltabletten
GB0310775D0 (en) * 2003-05-10 2003-06-18 Unilever Plc Process for producing structured materials
DE10331464A1 (de) * 2003-05-21 2004-12-16 Aweco Appliance Systems Gmbh & Co. Kg Haushaltsmaschinenreiniger
DE10324788A1 (de) * 2003-05-31 2004-12-16 Beiersdorf Ag Dosierbare feste Reinigungszubereitung
GB2404662A (en) * 2003-08-01 2005-02-09 Reckitt Benckiser Cleaning composition
GB2406821A (en) 2003-10-09 2005-04-13 Reckitt Benckiser Nv Detergent body
DE10352961A1 (de) * 2003-11-13 2005-06-23 Henkel Kgaa Stoßbelastungsresistente Tablette
EP1784117B1 (fr) 2004-08-23 2008-01-23 Reckitt Benckiser N.V. Dispositif de distribution de détergent
AU2006310374A1 (en) * 2005-11-07 2007-05-10 Reckitt Benckiser N.V. Dosage element
US8389036B2 (en) 2006-01-13 2013-03-05 Gianpaola Belloli Product obtained from a powdered or granular material and process for obtaining the product
BRPI0707880A2 (pt) 2006-01-21 2011-05-10 Reckitt Benckiser Nv artigo
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Also Published As

Publication number Publication date
DE19930771A1 (de) 2001-01-04
AU5406700A (en) 2001-01-22
WO2001002532A1 (fr) 2001-01-11
DE50006266D1 (de) 2004-06-03
ES2220474T3 (es) 2004-12-16
CA2313356A1 (fr) 2001-01-03
ATE265522T1 (de) 2004-05-15
EP1192241A1 (fr) 2002-04-03

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