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EP1112342A1 - Corps moules de lavage et de nettoyage contenant des granules tensioactifs speciaux - Google Patents

Corps moules de lavage et de nettoyage contenant des granules tensioactifs speciaux

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Publication number
EP1112342A1
EP1112342A1 EP99946081A EP99946081A EP1112342A1 EP 1112342 A1 EP1112342 A1 EP 1112342A1 EP 99946081 A EP99946081 A EP 99946081A EP 99946081 A EP99946081 A EP 99946081A EP 1112342 A1 EP1112342 A1 EP 1112342A1
Authority
EP
European Patent Office
Prior art keywords
weight
surfactant
granules
acid
detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99946081A
Other languages
German (de)
English (en)
Inventor
Andreas Lietzmann
Dieter Jung
Peter Schmiedel
Hans-Friedrich Kruse
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1112342A1 publication Critical patent/EP1112342A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C11D3/323—Amides; Substituted amides urea or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions

Definitions

  • the present invention is in the field of compact molded articles which have washing and cleaning properties.
  • washing and cleaning agent shaped articles include, for example, detergent shaped articles for washing textiles, cleaning agent shaped articles for machine dishwashing or cleaning hard surfaces, bleaching agent shaped articles for use in washing machines or dishwashers, water softening shaped articles or stain tablets.
  • the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are referred to briefly as detergent tablets.
  • Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage.
  • Tableted detergents and cleaning agents have a number of advantages over powdered ones: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. Consequently, detergent tablets are also described comprehensively in the patent literature.
  • a problem that occurs again and again when using washing and cleaning active molded articles is the too slow disintegration and dissolving speed of the molded articles under application conditions.
  • DE 11 91 509 (Henkel) describes detergent tablets containing tripolyphosphate of modification I and conventional organic detergent substances, preferably 10 to 35 wt.% Detergent substances, 35 to 65 wt.% Tripolyphosphate, 1 to 6 wt. % Of silica or magnesium silicate, 3 to 10% by weight of alkaline inorganic salts, 3 to 10% by weight of urea and up to 10% by weight of other constituents are contained.
  • DE 36 28 406 (Henkel) discloses detergent tablets produced by compressing 10 to 40% by weight of anionic surfactant, 0 to 10% by weight of nonionic surfactant, 3 to 10% by weight of polyvinylpyrrolidone, 0 to 3% by weight. % Silicate and 50 to 80% by weight urea. These detergent tablets are to be used for cleaning motor vehicle windshields.
  • WO 95/18212 (Ecolab Ine) teaches the use of urea in piece-shaped cleaning agents for the dishwasher, which can be produced by mixing an effective amount of a cleaning agent and a part of urea as a curing agent, converting the homogeneous mixture into a mold and then curing it.
  • Inclusion compounds of urea and fatty acids that improve foam behavior are described in IN 145 921 (Hindustan Lever Ltd.). These compounds are added to soap-free detergent bars.
  • JP 07/286199 discloses a process for the production of detergent tablets by mixing an anionic surfactant with a nonionic surfactant in the presence of at least 10% by weight of water and other detergent ingredients, whereby surfactant granules are obtained, and compressing these surfactant granules with granular solubilizers a solubility of at least 20g / 100ml (0 ° C).
  • Preferred solubilizers are potassium carbonate, ammonium sulfate, ammonium chloride, sodium benzoate, Na-benzenesulfonate, p-toluenesulfonic acid-Na, Na-xylene sulfonate, NaCl, citric acid, D-glucose, urea and sucrose.
  • urea is added to the mixture to be treated as an additive in pure form or in the form of defined compounds. None of the cited documents deals with detergent tablets which contain urea in the form of granules which predominantly have different contents. Contains substances. The use of urea in detergent tablets to improve the disintegration times and to enable dosing via the dispenser of household washing machines is not described or suggested in any document.
  • detergent tablets can be produced with the advantages mentioned if they contain surfactant granules containing urea.
  • the invention therefore relates to detergent tablets made of compressed, particulate detergents and cleaning agents which contain urea-containing granules of surfactant.
  • the urea contained in the surfactant-containing granules is the diamide of carbonic acid, which is sometimes also referred to as carbamide, and can be described by the formula H N-CO-NH.
  • Urea forms colorless, odorless crystals with a density of 1.335, which melt at 133 ° C.
  • Urea is soluble in water, methanol, ethanol and glycerin with a neutral reaction.
  • Urea can be prepared according to Wöhler's Synth, by evaporation of an aqueous solution of ammonium cyanate or in the laboratory by exposure to ammonia on phosgene, chloroformate, urethane or carbonic acid diester according to the usual acid amide synthesis.
  • urea is made from carbon dioxide and ammonia via ammonium carbamate, which converts to urea at 135-150 ° C and 35-40 bar in the presence of three times the amount of ammonia. Under these conditions, the hydrolysis of the ammonium carbamate in ammonium carbonate or ammonia and carbon dioxide, which occurs as a side reaction, is suppressed.
  • the surfactant granules contain urea in amounts of 0.1 to 20% by weight, preferably 0.5 to 15% by weight, particularly preferably 1 to 10% by weight and in particular 1 5 to 5 wt .-%, each based on the weight of the surfactant granules.
  • the surfactant granules naturally contain surfactants. These can come from the groups of anionic, nonionic, cationic or amphoteric surfactants, it also being possible, of course, to use mixtures of the types of surfactants mentioned.
  • the surfactant granules in preferred detergent tablets have surfactant contents of 5 to 60% by weight, preferably 10 to 50% by weight and in particular 15 to 40% by weight, based in each case on the weight of the surfactant granules , on.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the preferred surfactants of the sulfonate type are C 1 -C 3 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as those obtained from C 1. 2- ⁇ 8 monoolefmen with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates which are for example obtained from 2- C ⁇ ⁇ 8 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production 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 become.
  • Preferred sulfated fatty acid glycerol esters are the sulfate products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C 2 -C 8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cjo-C 2 o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • Cj 2 -Ci6 alkyl sulfates and Cj 2 - C ⁇ _ alkyl sulfates and C ⁇ 4 -C ⁇ .5 alkyl sulfates are preferred for washing technology reasons.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-2 ⁇ alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2 -methyl-branched C -n alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ⁇ 2- ⁇ . 8 -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 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 which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8- ⁇ 8 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants, including the soaps can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • detergent tablets are preferred in which the anionic surfactant content of the surfactant granules is 5 to 45% by weight, preferably 10 to 40% by weight and in particular 15 to 35% by weight, based in each case the weight of the surfactant granules.
  • preferred surfactant granules have a soap content which exceeds 0.2% by weight, based on the total weight of the detergent tablets.
  • the preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, with preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s) in each case based on the weight of the detergent tablets
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular 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, in which the alcohol radical has a linear or preferably 2-methyl branching may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 2 -C 4 alcohols with 3 EO or 4 EO, C 9 n alcohol with 7 EO, C 3 -C 5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO , C ⁇ . 2-] alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 - 14 - alcohol having 3 EO and Cj 2- ⁇ 8 alcohol containing 5 EO.
  • the specified ethoxy The degrees of lation represent statistical averages, which can be a whole or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants which are 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 with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • APG alkyl polyglycosides
  • Usable alkyl polyglycosides satisfy the general formula RO (G) z , in which R is a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is Is a symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Linear alkyl polyglucosides ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
  • the surfactant granules can preferably contain alkyl polyglycosides, with APG contents of more than 0.2% by weight, based on the total molded body, being preferred.
  • Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R * for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or is an aryl radical or an oxy-alkyl radical with 1 to 8 carbon atoms, C 1 - alkyl or phenyl radicals being preferred
  • [Z] for a linear poly is a hydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, 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, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • detergent tablets are preferred in which the nonionic surfactant content of the surfactant granules is 1 to 15% by weight, preferably 2.5 to 10% by weight and in particular 5 to 7.5% by weight, in each case based on the weight of the surfactant granules.
  • the surfactant granules In addition to urea and surfactant (s), the surfactant granules generally contain other ingredients in detergents and cleaning agents. In order to obtain storage-stable and free-flowing surfactant granules, it is preferred if carrier substances are added in the manufacture of the surfactant granules, ie the surfactant granules contain builders. Other ingredients of detergents and cleaning agents, in particular so-called small components such as optical brighteners, polymers, defoamers, phosphonates, colorants and fragrances, can also be part of the surfactant granules.
  • the surfactant granules can be used in the detergent tablets in varying amounts.
  • Detergent tablets according to the invention which contain the urea-containing surfactant granules in amounts of 40 to 95% by weight, preferably 45 to 85% by weight and in particular 55 to 75% by weight, in each case based on the molded article weight preferred.
  • Another object of the present invention is a method for producing the detergent tablets described with advantageous properties, that is, a method for producing detergent tablets by mixing a surfactant-containing granules with finely divided preparation components and subsequent shaping in a known manner which contains the surfactant-containing granulate urea.
  • the urea contents in the surfactant granules are advantageously in the range from 0.1 to 20% by weight, preferably from 0.5 to 15% by weight, particularly preferably from 1 to 10% by weight and in particular from 1, 5 to 5 wt .-%, each based on the weight of the surfactant granules.
  • the granules containing surfactant are not produced by spray drying, but rather by means of a granulation process.
  • press agglomeration processes can also be used, for example. Methods in which the surfactant-containing granules are produced by granulation, agglomeration, press agglomeration or a combination of these methods are therefore preferred.
  • the granulation can be carried out in a large number of apparatuses customarily used in the detergent and cleaning agent industry. For example, it is possible to use the rounding agents commonly used in pharmacy. In such turntable devices, the residence time of the granules is usually less than 20 seconds.
  • Conventional mixers and mixing granulators are also suitable for granulation. As Mixers can be used both high-intensity mixers ("high-shear mixer”) and normal mixers with lower circulation speeds.
  • Suitable mixers are, for example Eirich ® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ® Flexomix, the Fukae ® FS-G mixers (trade marks of Fukae Powtech, Kogyo Co., Japan), the Lödige ® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais ® series T or KT (trademark of Drais- Maschinene GmbH, Mannheim).
  • the residence times of the granules in the mixers are in the range of less than 60 seconds, the residence time also being dependent on the circulation speed of the mixer. The dwell times are reduced accordingly the faster the mixer runs.
  • the residence times of the granules in the mixer / rounder are preferably less than one minute, preferably less than 15 seconds. Dwell times of up to 20 minutes are set in slow-running mixers, for example a Lödige KM, dwell times below 10 minutes being preferred because of the process economy.
  • Preferred granulation processes for the production of surfactant-containing granules are carried out in mixer granulators in which some mixer parts or the entire mixer are heated to temperatures which are at least 20 ° C. above the temperature which the substances to be granulated have at the beginning of the granulation process.
  • some or all of the mixer parts have a temperature of at least 40 ° C.
  • a temperature of 120 ° C for the mixer parts or the entire mixer should not be exceeded. If only parts of the mixer are heated to the temperatures mentioned, these are preferably the mixer walls or the mixer tools.
  • the former can be brought to the desired temperature by a heatable jacket, the latter by built-in heating elements.
  • non-aqueous granulation aids in particular nonionic surfactants, which have a melting point in the range from 20 to 50 ° C.
  • nonionic surfactants which have a melting point in the range from 20 to 50 ° C.
  • the preferred granulation process described allows the bulk density of the surfactant granules to be increased, with undesirable caking on the wall at the same time on the mixer walls can be significantly reduced.
  • the use of the surfactant granules produced in this way in tablettable premixes leads to detergent tablets which, compared to mixtures containing conventionally produced granules, are characterized by a further reduced disintegration time.
  • the surfactant-containing granules are compressed under pressure and under the action of shear forces, homogenized in the process and then discharged from the apparatus in a shaping manner.
  • the technically most important press agglomeration processes are extrusion, roller compaction, pelleting and tableting.
  • preferred press agglomeration processes used to produce the surfactant-containing granules are extrusion, roller compaction and pelletization.
  • the surfactant-containing granulate is preferably fed continuously to a planetary roller extruder or a 2-screw extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, the housing and the extruder granulating head of which can be heated to the predetermined extrusion temperature .
  • the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but which can also be below this in the case of extremely high penetration depending on the apparatus used
  • the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife.
  • the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension.
  • the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.8 to 5 mm and in particular in the range from approximately 1.0 to 3 mm.
  • the length / diameter ratio of the chipped primary granules is in the range from approximately 1: 1 to approximately 3: 1. adds the still plastic primary granulate to a further shaping processing step; edges present on the crude extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained.
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press or in the extruder.
  • the production process for the surfactant-containing granules is carried out by means of roller compaction.
  • the granules containing surfactant are metered in between two smooth rollers or with depressions of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
  • the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
  • smooth rollers smooth, unstructured sliver belts are obtained, while by using structured rollers, correspondingly structured slugs or individual pellets can be produced, in which, for example, certain shapes of the later granules or moldings can be specified.
  • the sliver belt is subsequently broken down into smaller pieces by a knocking-off and comminution process and can be processed into granules in this way, which can be further tempered by further surface treatment methods known per se, in particular in an approximately spherical shape.
  • the preparation of the surfactant-containing granules is carried out by means of pelleting.
  • the granules containing surfactant are applied to a perforated surface and pressed through the holes by means of a pressure-producing body.
  • the surfactant-containing granulate is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device.
  • the most varied configurations of the pressure roller and perforated die are conceivable here.
  • ring die press consists of a rotating ring die penetrated by press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
  • the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
  • the surfactant granules containing urea are then mixed with further processing components to form a premix which can then be pressed into detergent tablets.
  • the premix to be treated can contain other ingredients customary in washing and cleaning agents, in particular from the group of builders, disintegration aids, bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors , Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.
  • all or part of the substances mentioned can already be part of the surfactant granules.
  • builders are the most important ingredients in detergents and cleaning agents.
  • all builders usually used in detergents and cleaning agents can be present, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates.
  • Suitable crystalline tikf '-shaped sodium silicates have the general formula NaMSi x O 2x + ⁇ ' HO, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, preferred values for x being 2 , 3 or 4 are.
  • Such crystalline layered 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 represents sodium and x assumes the values 2 or 3.
  • M represents sodium
  • x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 'yH 2 O are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171 .
  • the delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compacting / compaction or by overdrying.
  • the term “amo ⁇ h” is also understood to mean “roentgenamo ⁇ h”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This should be integrated in such a way that the products have microcrystalline areas of size 10 to a few hundred ran, values up to max. 50 ran and especially up to max. 20 ran are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.
  • zeolite of the P and / or X type introduced by the surfactant granules can be inco ⁇ orated into the premix. by adding zeolite as a treatment component.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably a type A, P, X or Y zeolite.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO) n and orthophosphoric acid H PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 like “3 , melting point 60 °) and as a monohydrate (density 2.04 like “ 3 ). Both salts are white powders which are very easily soluble in water, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ) at 200 ° C, at higher temperature in sodium trimetaphosphate (Na PO) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH PO 4 , is a white salt with a density of 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 like "3 , water loss at 95 °), 7 mol.
  • Disodium hydrogen phosphate is obtained by neutralizing phosphoric acid with soda solution using Phenolphthalein produced as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na PO are colorless crystals which have a density of 1.62 gcm "3 as a dodecahydrate and a melting point of 73-76 ° C (decomposition), and a decahydrate (corresponding to 19-20% P 2 O) 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 with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
  • Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O, exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 like " 3 , melting point 94 ° with loss of water).
  • Substances are colorless crystals that are soluble in water with an alkaline reaction.
  • N & ⁇ P O is formed by heating 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 formers and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), JP 2 O 7 , exists in the form of the trihydrate and represents a colorless, hygroscopic powder with a density of 2.33 gcm "3 , which is soluble in water, the pH of the 1% solution at 25 ° being 10.4.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O ⁇ o (sodium tripolyphosphate)
  • Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O ⁇ o (potassium tripolyphosphate), for example in the form of a 50 wt .-% solution (> 23% P 2 O, 25% K 2 O) on the market.
  • the potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; also mixtures of sodium tripolyphosphate Phate 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 be used according to the invention.
  • Organic cobuilders which can be used in the detergent tablets according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV Detector was used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn 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 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, methods. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
  • 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 production are, for example, from the European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as the 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 are known.
  • An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring
  • Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are 3 to 15% by weight in formulations containing zeolite and / or silicate.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner (pH 9).
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, hold, be preferred to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the amount of builder is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight.
  • the amount of builders used depends on the intended use, so that bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight) ), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).
  • tablet disintegrants In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times.
  • tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
  • These substances which are also referred to as "explosives” due to their effect, increase their volume when water enters, whereby on the one hand the intrinsic volume increases (swelling) and on the other hand a pressure can be generated by the release of gases, which breaks the tablet into smaller particles disintegrates.
  • Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used.
  • Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 8% by weight and in particular 4 to 6% by weight of a disintegration aid, in each case based on the molded article weight.
  • Disintegration agents based on cellulose are used as preferred disintegration agents in the context of the present invention, so that preferred detergent tablets form such a disintegration agent based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 8% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% »of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%>) undamaged.
  • a subsequent disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, to granules with an average particle size of 200 ⁇ m.
  • the premix to be treated has a bulk density that comes close to that of conventional compact detergents.
  • the premix to be ve ⁇ ress has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular above 700 g / 1.
  • bleaching agents that serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Even when using the bleaching agents it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monophthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, oxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1acid, diperoxyacid, such as 1,12 oxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-l, 4-diacid, N, N-terephthal
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in molded articles for automatic dishwashing.
  • Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,
  • Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium are considered.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • bleach activators can be incorporated into the detergent tablets according to the invention.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • TAED tetraacetyl
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase
  • Bacillus subtilis Bacillus licheniformis
  • Streptomyceus griseus Streptomyceus griseus
  • Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase Differentiate types by their CMCase and Avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight.
  • the detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand 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 methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight.
  • nonionic cellulose ether in each case based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.
  • polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • the shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the Mo ⁇ holino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Dyes and fragrances are added to the detergent tablets according to the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propyl propionyl allyl pentyl propyl.
  • the ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, cc -Isomethylionon and methyl-cedrylketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include tephenols such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the dye content of the detergent tablets according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the total formulation.
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles by slower fragrance release.
  • carrier materials for example, cyclodextrins have proven themselves, the cyclodextrin-perfume complexes additionally being able to be coated with further auxiliaries.
  • the agents according to the invention can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye them.
  • the premix Before the particulate premix is pressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This can be of advantage for the quality and physical properties of both the premix (storage, molding) as well as the finished detergent tablets. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (compare Donald W.
  • the or one of the subsequently mixed fine-particle treatment components is a faujasite-type zeolite with particle sizes below 100 ⁇ m, preferably below 100 ⁇ m and in particular below 5 ⁇ m and at least 0.1 2% by weight>, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be treated.
  • the molded articles according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular feeding them into tablets, whereby conventional methods can be used.
  • the premix is compacted in a so-called die between two punches to form a solid compact.
  • This process which is briefly referred to below as tabletting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molded body being formed being determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing of the premix.
  • the upper punch touches the premix and lowers further in the direction of the lower punch.
  • the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix), the plastic deformation begins, in which the particles flow together and the molded body is formed.
  • the premix particles are also crushed and sintering of the premix occurs at even higher pressures.
  • the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities.
  • the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices.
  • the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.). Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches.
  • eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed.
  • the movement of these rams is comparable to that of a conventional four-stroke engine.
  • the pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being increased accordingly.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
  • Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps.
  • the die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
  • the pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.
  • Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet.
  • All non-stick coatings known from the art are suitable for reducing stamp caking.
  • Plastic coatings, plastic inserts or plastic stamps are particularly advantageous.
  • Rotating punches have also proven to be advantageous, with the upper and lower punches being designed to be rotatable if possible.
  • a plastic insert can generally be dispensed with.
  • the stamp surfaces should be electropolished here. It was also shown that long pressing times are advantageous. These can be set with pressure rails, several pressure rollers or low rotor speeds. Since the fluctuations in the hardness of the tablet are caused by the fluctuations in the pressing forces, systems should be used which limit the pressing force.
  • elastic stamps, pneumatic compensators or resilient elements can be used in the force path.
  • the pressure roller can also be designed to be resilient.
  • Tableting machines suitable in the context of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, IMA Ve ⁇ ackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms.
  • Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liveeool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Me- diopharm Kamnik (SI).
  • the hydraulic double pressure press HPF 630 from LAEIS, D. Tablettierwerkmaschinee are, for example, from the companies Adams Tablettierwerkmaschinee, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hörn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter negligencebau, Tamm available.
  • Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).
  • the molded body can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section.
  • This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points.
  • the portioned compacts as tablets, in cylinder or cuboid form can be expedient, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred.
  • Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.
  • the spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process.
  • the detergent tablets without problems using a metering aid and is preferred in the context of the present invention.
  • Another preferred molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, broken off and into the Machine can be entered.
  • This principle of the "bar-shaped" shaped body detergent can also be realized in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.
  • the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous application properties of the molded body. If both for example, components are contained in the moldings that mutually influence each other negatively, so it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted if the second goes into solution.
  • the layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, but it is also possible for the inner layer (s) to be completely encased ) by the respective outer layer (s), which leads to the premature dissolution of components of the inner layer (s).
  • a molded body consists of at least three layers, that is to say two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleaching agent, while in the case of the stacked molded body the two outer layers and in the case of the molded body the outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in a molded body.
  • Such multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine without the risk of bleaching from bleaching agents and the like.
  • the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the melt coating method.
  • colored particles can also be incorporated into the molded body as optical differentiation respectively.
  • a white molded body can be colored homogeneously with colored, for example blue, red, green, yellow, etc., speckles.
  • the amount of colored speckles and their particle size should be adapted to the rest of the premix which forms the shaped body matrix from which the speckles emerge optically.
  • a tableting mixture has a particle size range of 200 to 1800 ⁇ m
  • speckles that move in the same or coarser particle size range only achieve a homogeneous distribution above a threshold value of> 6% by weight, based on the tablet composition. Smaller quantities then lead to an optically unsightly accumulation of speckles in some shaped body areas, while other areas remain almost unspotted. In order to achieve a homogeneous impression even at lower use concentrations of colored particles, it is advisable to reduce the particle size of the colored speckle particles.
  • a homogeneous distribution of the speckles is achieved with 2 to 3% by weight> color speckle particles if these particle sizes have between 200 and 800 ⁇ m.
  • a homogeneous speckling which can be calibrated in the manner described above by adapting the speckle particle size and quantity to the premix, also makes it possible to visualize a layer structure of the shaped bodies.
  • two- or multi-layer molded bodies can be produced, one layer of which is undyed, while a second layer is highlighted by sprinkles.
  • This concept can also be applied, for example, to three-layer tablets in which one layer is undyed, the second is speckled and the third is colored through.
  • cores or other sub-areas can also be colored or sprinkled into core-coated tablets, ring-core tablets or dot tablets. The person skilled in the art has hardly any limits when varying these implementation options for optical differentiation.
  • ⁇ stands for diametral fracture stress (DFS) in Pa
  • P is the force in N that leads to the pressure exerted on the molded body that causes the molded body to break
  • D is the molded body diameter in meters and t the height of the molded body.
  • Another object of the present invention is the use of urea in surfactant-containing granules, which, after mixing with finely divided processing components, are pressed in a manner known per se to form detergent tablets, for improving the stability and solubility of detergent tablets.
  • urea in detergent and cleaning agent granules, which are mixed after mixing with other components to form detergent and detergent tablets, the physical properties of the tablets can be improved, as the following examples show:
  • a tower powder containing surfactant was produced by spray drying and was used as the basis for a surfactant-containing granulate.
  • the tower powder was granulated with other components (zeolite, NaOH, anionic surfactant acid, nonionic surfactant, silicate, polymer) in a 50 liter ploughshare mixer from Lödige.
  • the granulation batch according to the invention contained 2% by weight> urea.
  • the granulation batch of the comparative example contained no urea, which is why the percentages by weight in Table 2 differ from those of the example according to the invention.
  • the amounts of the solids and liquids used and the order of addition to the mixer are given in Table 2.
  • the granules were dried in a fluidized bed apparatus from Glatt at a supply air temperature of 60 ° C. over a period of 30 minutes. After drying, fine particles ⁇ 0.6 mm and coarse particles> 1.6 mm were screened off.
  • the surfactant granules E and V were then processed with further components to form a compressible premix, after which the Koring eccentric press led to tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g).
  • the pressure was adjusted so that two series of molded bodies were obtained (El, E2 or VI and V2), which differ in their hardness.
  • Table 1 shows the composition of the spray-dried tower powder.
  • Table 3 shows the composition of the premixes to be eaten (and thus the shaped body).
  • Table 1 Composition of the spray-dried tower powder [% by weight]
  • Composition 92% by weight Cj 2-18 fatty alcohol sulfate 3% by weight »sodium carbonate balance water, salts
  • the hardness of the tablets was measured by deforming the tablet until it broke, the force acting on the side surfaces of the tablet and the maximum force which the tablet withstood being determined.
  • the urea which was subsequently mixed in was compacted on a roller compactor (type Alexanderwerk) and the ground slag was sieved in the particle size range between 0.6 and 1.6 mm in order to achieve a particle size distribution corresponding to the surfactant granulate .
  • the tablets corresponded in diameter, height and weight to the tablets described above and were examined using the same methods. The experimental data are shown in Table 5:
  • Table 5 shows that the incorporation of urea into the surfactant granules provides tablets which, compared to tablets which only contain urea, are distinguished by better disintegration rates at high tablet hardness.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé de production de corps moulés de lavage et de nettoyage qui se distinguent par une dureté élevée, ce qui leur confère une stabilité au transport et à la manipulation, et qui ont d'excellentes propriétés de désintégration. Ces caractéristiques sont dues au fait que les corps moulés contiennent un granulé tensioactif qui, à son tour, contient du carbamide.
EP99946081A 1998-09-10 1999-09-01 Corps moules de lavage et de nettoyage contenant des granules tensioactifs speciaux Withdrawn EP1112342A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19841360 1998-09-10
DE1998141360 DE19841360A1 (de) 1998-09-10 1998-09-10 Wasch- und Reinigungsmittelformkörper mit speziellem Tensidgranulat
PCT/EP1999/006414 WO2000015754A1 (fr) 1998-09-10 1999-09-01 Corps moules de lavage et de nettoyage contenant des granules tensioactifs speciaux

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EP1112342A1 true EP1112342A1 (fr) 2001-07-04

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WO (1) WO2000015754A1 (fr)

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DE10129228B4 (de) * 2001-06-19 2006-03-02 Henkel Kgaa Gelbildung verhindernde Zusätze zu Tensiden und Waschmittelformulierungen und ihre Anwendung in Wasch-und Reinigungsmitteln

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DE2404494A1 (de) * 1974-01-31 1975-08-14 Blendax Werke Schneider Co Reinigungsmittel fuer zahnprothesen
DE4010533A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Tablettierte wasch- und/oder reinigungsmittel fuer haushalt und gewerbe und verfahren zu ihrer herstellung
JPH07286199A (ja) * 1994-04-15 1995-10-31 Lion Corp タブレット洗剤組成物の製造方法
CA2167971C (fr) * 1995-02-01 2008-08-26 Paula J. Carlson Bloc de nettoyage a l'acide et methode de fabrication correspondante

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Title
See references of WO0015754A1 *

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WO2000015754A1 (fr) 2000-03-23

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