EP1489160B1 - Shaped bodies having detergent or cleaning action for use in a household - Google Patents

Shaped bodies having detergent or cleaning action for use in a household Download PDF

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Publication number
EP1489160B1
EP1489160B1 EP04013587A EP04013587A EP1489160B1 EP 1489160 B1 EP1489160 B1 EP 1489160B1 EP 04013587 A EP04013587 A EP 04013587A EP 04013587 A EP04013587 A EP 04013587A EP 1489160 B1 EP1489160 B1 EP 1489160B1
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EP
European Patent Office
Prior art keywords
psi
peg
washing
phosphoric acid
compositions according
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EP04013587A
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German (de)
French (fr)
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EP1489160A1 (en
Inventor
Thomas Dr. Klein
Alfred Dr. Mitschker
Holger Dr. Schmidt
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/042—Acids
    • 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
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides

Definitions

  • the invention relates to washing or cleaning active moldings, primarily tablets such as detergent tablets, dishwasher tablets, patch salt tablets or water softening tablets for household use, containing polysuccinimide in combination with polyethylene glycol and / or phosphoric acid, in particular for machine use, and a process for producing these Shaped bodies and their use.
  • Washing or cleaning-active moldings in particular tablets, have a number of advantages over powdered detergents, such as advantageous handling, simple metering and low packaging volume requirements.
  • problems arise from the fact that to achieve a sufficient shape and breakage resistance during the compression of the powdery constituents relatively high pressing pressures must be applied. Due to the high degree of compression, such tablets often have inadequate disintegration and release properties when they are used, as a result of which the active substance in the washing or cleaning agent is released too slowly and the risk of residue formation arises, in particular on textiles after the wash cycle.
  • polysuccinimide PSI
  • PSI polysuccinimide
  • Partially hydrolysed PSI as formed by reaction of PSI with water or NaOH in sub-stoichiometric megnenes (based on succinimide units), is in the middle between sodium polyaspartate and PSI in terms of hygroscopicity and can be a compromise between fast-solubility requirements for washing and cleaning-active moldings and hygroscopicity. Partially hydrolyzed PSI is much more soluble in water than unchanged PSI.
  • disintegrating agents known from the pharmaceutical production can be used.
  • disintegrants are swellable phyllosilicates such as bentonites, natural products and natural derivatives based on starch and cellulose, alginates and like, potato starch, methyl cellulose and / or hydroxypropyl cellulose but also microcrystalline cellulose, sugars such as sorbitol. These disintegrants can be mixed with the granules to be compacted, but already incorporated into the granules to be pressed.
  • binder / disintegrant in particular polyethylene glycol
  • binder / disintegrating agents are again known disintegrants, for example starches and starch derivatives, commercially available cellulose derivatives such as crosslinked or modified cellulose, microcrystalline cellulose fibers, crosslinked polyvinylpyrrolidones, phyllosilicates, etc.
  • the proposed solutions in the washing and cleaning agent area contribute to an improvement in the disintegration properties of washing or cleaning tablets.
  • the improvement achieved is in many cases not sufficient.
  • the proportion of sticky organic substances in the tablets, for example on anionic and / or nonionic surfactants increases or one of the ingredients itself, as in the case of PSI, is very poorly soluble in water, these solutions are not very helpful.
  • no detergent tablets are available on the market, which are based on PSI and meet the high demands of the consumer.
  • tablets do not have the sufficiently high rate of disintegration, although the breaking strength is often sufficient.
  • the object of the invention was to provide washing or cleaning active moldings which include polysuccinimide (PSI) and which do not have the abovementioned disadvantages.
  • PSI polysuccinimide
  • a process for the preparation of these improved washing or cleaning-active moldings based on PSI should be provided.
  • the invention therefore in a first embodiment, a washing or cleaning active moldings containing PSI and polyethylene glycol and / or phosphoric acid.
  • the agents according to the invention contain PSI in combination with PEG.
  • the agents according to the invention contain PSI and phosphoric acid.
  • shaped body is not limited to the tablet form. In principle, any spatial form is possible, which may optionally be imposed on the starting materials due to an outer container. Cylindrical bodies can have a height which is smaller or larger or equal to the diameter of the base. It is also conceivable, however, an angular, for example, a rectangular, in particular a square, but also a diamond-shaped or trapezoidal a round or oval base of the molding. Further embodiments include triangular or more than quadrilateral surfaces of the molding.
  • the shaped bodies according to the invention Due to the excellent disintegration properties of the shaped bodies according to the invention, it is possible, but not absolutely necessary, to give the shaped bodies by means of a metering device directly into the aqueous liquor of a machine process; Rather, it is also possible to place the molded body or bodies in the dispensing rings of the commercial household appliances, in particular the washing appliances. Accordingly, the spatial shape of the molded body is adapted in a preferred embodiment of the invention in their dimensions of the dispensing chamber commercial household appliances.
  • the shaped body has a plate-like or tabular structure with alternately thick long and / or thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which represent the short thin segments, broken and into the machine or The dispensing chamber of the machine can be entered.
  • This principle of the "bar-shaped” means can also be realized in other geometric shapes, for example vertical triangles, which are connected to one another on one side only on one side.
  • homogeneous or heterogeneous shaped bodies in particular tablets, are provided, these tablets preferably having a diameter of 20 to 60 mm, in particular 40 +/- 10 mm.
  • the height of these tablets is preferably 10 to 30 mm and in particular 15 to 25 mm.
  • the weight of the individual shaped bodies, in particular of the tablets is preferably from 15 to 60 g and in particular from 25 to 40 g per tablet or tablet;
  • the consistency of the tablets or tablets usually has values above 1 kg / dm 3 , preferably from 1.1 to 1.4 kg / dm 3 .
  • the water hardness range or the pollution 1 or more, for example 2 to 4 moldings, in particular tablets, can be used.
  • Further shaped bodies according to the invention can also have smaller diameters or dimensions, for example 10 mm.
  • a homogeneous shaped body is understood as meaning those in which the ingredients of the shaped body are homogeneously distributed. Accordingly, heterogeneous shaped bodies are understood to mean those which do not have a homogeneous distribution of their constituents. Heterogeneous shaped bodies can be produced, for example, by pressing the various constituents not into a uniform shaped body but into a shaped body having a plurality of layers, ie at least two layers. It is also possible that these different layers have different decay and dissolution rates. This can result in advantageous performance properties of the molded body.
  • the layer structure of the moldings can be carried out in a stack, wherein a solution process of the inner layer (s) at the edges of the molding takes place already when the outer layers are not yet completely dissolved or disintegrated; but it can also be a complete wrapping of the inner layer (s) by the each further outward layers are achieved, which leads to a prevention of premature dissolution of components of the inner layer (s).
  • a tablet consists of at least three layers, ie two outer and at least one inner layer, wherein at least in one of the inner layers, a peroxide bleach is contained, while in the stacked tablet, the two outer layers and the shell-shaped Tablet the outermost layers, however, are free of peroxide bleach. It is likewise possible to spatially separate peroxide bleaching agents and any bleach activators or bleach catalysts and / or enzymes present in a molding or tablet from one another. Such embodiments have the advantage that even in cases where the detergent or bleach body or the detergent or bleach tablet is placed in direct contact with the fabrics in the washing machine or hand basin, no stains ("spotting ”) are to be feared by bleach and the like on the textiles.
  • heterogeneous shaped bodies can be found, for example, in European Patent Application EP-A-0 716 144, the content of which is included in the present application.
  • PSI PSI and its use as a conditioning agent for standing and flowing water systems due to its dispersing properties, thermal stability and hardness stabilizer properties are known from DE-A 101 01 671.
  • PSI in the sense of the present invention is understood to mean PSI itself, its copolymers, partial hydrolysates or hydrolysates.
  • Partial hydrolysates for the purposes of the present invention are polysuccinimides whose polymer units have been partially converted into aspartate units, that is to say copolymers of succinimide units and aspartate units. These partial hydrolysates may also be in spray granulated form.
  • PSI can be prepared on an industrial scale by thermal polymerization of maleic anhydride and ammonia or their derivatives (see US-A 3,846,380, US-A 4,839,461, US-A 5,219,952 or US-A 5,371,180).
  • PSI is obtained by thermal polymerization of aspartic acid (US Pat. No. 5,051,401), if appropriate in the presence of acidic catalysts / solvents (US Pat. No. 3,052,655).
  • PSI accumulates in the chemical synthesis as a polymer having an average molecular weight of 500 to 20,000, preferably 3,000 to 5,000, on.
  • Polysuccinimide is considered to be a chemical precursor of polyaspartic acid, to which it slowly hydrolyzes with water.
  • the pH of the resulting solution is between pH 1 to 4, preferably 2 to 3. This is not only the good stone-dissolving, but also the dispersing effect of the released by PSI polyaspartic acid against poorly soluble calcium salts or other poorly soluble substances to bear. Due to their acidity, the resulting acidic solution also leads to the direct dissolution of possibly formed calcium carbonate incrustations.
  • the PSI to be used according to the invention is used in amounts of from 0.01 to 20% by weight, preferably from 0.1 to 10% by weight and more preferably in an amount of from 0.5 to 5% by weight.
  • the PEG is preferably used in an amount of 0.5 to 20 wt .-%.
  • Suitable polyethylene glycols are those having a high degree of ethoxylation, for example polyethylene glycols having a molecular weight of more than 2,000, preferably from 2,000 to 12,000, particularly preferably from 2,000 to 6,000.
  • the phosphoric acid to be used according to the invention is used in an amount of 0.5% by weight to 25% by weight.
  • so-called explosives are suitable for this purpose.
  • Starch and starch derivatives, cellulose and cellulose derivatives, for example microcrystalline cellulose, CMC, MC, alginic acid and its salts, carboxymethylamylopectin, polyacrylic acid, polyvinylpyrrolidone and polyvinylpolypyrrolidone, are among the preferred disintegrants to be converted into granular or cogranulated form .
  • the disintegrant granules can be prepared in a conventional manner, for example by spray drying or hot steam drying of aqueous preparation forms or by granulation, pelleting, extrusion or roll compaction. It may be advantageous to the disintegrants additives, granulation aids, carriers or laminating the known type to add (cogranulated form).
  • additives are non-surfactant active substances of detergents or cleaners, in particular bleach activators and / or bleach catalysts; particularly preferred is a disintegrant granule containing as an additive tetraacetylethylenediamine (TAED) and / or other bleach activators of the conventional type.
  • TAED tetraacetylethylenediamine
  • Such disintegrant granules can advantageously be prepared by co-granulation of the disintegrant with the additive. By such a cogranulation, the distribution of the disintegrating agent in the shaped body, in particular in the tablet, can be increased, which in certain cases can likewise lead to an improvement in the disintegration rate of the shaped body.
  • washing and cleaning-active moldings according to the invention may contain further constituents, such as are customarily used in detergents and cleaners and water softeners.
  • these include, in particular, anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, inorganic and organic, water-soluble or water-insoluble builder substances and cobuilders, bleaching agents, in particular peroxygen bleaches, but also active chlorine compounds, which are advantageously coated, bleach activators and bleach catalysts, enzymes and enzyme stabilizers, foam inhibitors , Graying inhibitors, substances that prevent the re-soiling of textiles, so-called soil repellents, and conventional inorganic salts such as sulfates and organic salts such as phosphonates, optical brighteners and dyes and perfumes.
  • conventional silver protectants is also recommended.
  • Preferred anionic surfactants include those based on petrochemicals, such as alkylbenzenesulfonates, alkanesulfonates or alkyl (ether) sulfates with odd chain lengths, as well as those on a native basis, for example fatty alkyl sulfates or fatty alkyl (ether) sulfates, soaps, sulfosuccinates, etc. Particular preference is given to optionally in combination with small quantities of soap - alkylbenzenesulfonates and / or various chain cuts of alkyl sulfates or alkyl ether sulfates.
  • alkylbenzenesulfonates the C 11 -C 13 -alkylbenzenesulfonate and C 12 -alkylbenzenesulfonate are preferred
  • preferred chain cuts in the alkyl (ether) sulfates include C 12 to C 16 , C 12 to C 14 , C 14 to C 16 , C 16 to C 18 or C 11 to C 15 or C 13 to C 15 .
  • the preferred nonionic surfactants include, in particular, the C 12 -C 18 -fatty alcohols ethoxylated with an average of 1 to 7 mol of ethylene oxide per mole of alcohol and the corresponding C 11 -C 17 alcohols, in particular C 13 -C 15 alcohols, but also known from the washing or cleaning agent range higher ethoxylated alcohols of the specified chain length, amine oxides, alkyl polyglycosides, polyhydroxy fatty acid amides, fatty acid methyl ester ethoxylates and gemini surfactants.
  • Particularly preferred inorganic builders to be used according to the invention are conventional phosphates, with preference for the tripolyphosphate, zeolites, in particular zeolite A, zeolite P, zeolite X and any mixtures thereof, but also carbonates, bicarbonates and crystalline and amorphous silicates having secondary washing capacity consideration.
  • the usual co-builders include, in particular, (co) polymeric salts of (poly) carboxylic acids, for example copolymers of acrylic acid and maleic acid, but also polycarboxylic acids and their salts, such as citric acid, tartaric acid, glutaric acid, succinic acid, polyaspartic acid, etc.
  • the person skilled in the art is aware of these usable organic cobuilders and their quantities from numerous publications in the washing and cleaning agent area.
  • the bleaching agents used are above all the peroxide bleaching agents currently in use, such as perborate or percarbonate, above all also in combination with the customary bleach activators and bleach catalysts, in particular in the field of dishwashing detergents, but also the active chlorine compounds already mentioned above.
  • proteases but also lipases, amylases, cellulases and peroxidases as well as any desired combinations of these enzymes are of particular interest in the enzymes.
  • anionic surfactant-containing compounds are used, which are different anionic surfactants - for example, alkyl sulfates and alkylbenzenesulfonates and / or soap or alkyl sulfates and sulfated Fettklareglycerinester - and / or Anionentenside in combination with nonionic surfactants, for example alkyl sulfates of different chain length, optionally also several types of alkyl sulfates having various chain portions in combination with ethoxylated alcohols and / or other nonionic surfactants mentioned above.
  • anionic and nonionic surfactants can be predominantly accommodated in two different compounds.
  • Finely divided zeolites, silicic acids, sulfates, calcium stearates, phosphates and / or acetates, as well as the disintegrant granules, are particularly suitable as powdering agents for use in accordance with the invention.
  • a preferred embodiment of the invention Ensure that dust particles and particles smaller than 0.2 mm are completely separated before mixing with the disintegrant granules.
  • the PSI-containing moldings according to the invention have excellent decomposition properties due to PEG and / or phosphoric acid and thus enable the use of PSI only. This can be tested, for example, under critical conditions in a conventional household washing machine (used directly in the wash liquor by means of a conventional metering device, fine washing program or colored laundry, washing temperature of 40 ° C. at most) or in a beaker at a washing temperature of 25 ° C.
  • the actual production of the inventive PSI and PEG and / or phosphoric acid-containing molded body is carried out first by mixing with the remaining components and subsequent Informour, in particular compression into tablets, using conventional methods (for example, as in the conventional patent literature for tabletting, especially on the Washing or cleaning agent area, in particular as described in the above-mentioned patent applications and the article “tableting: state of the art", S ⁇ FW-Journal, 122th year, pp. 1016-1021 (1996)) can be used.
  • the drying and granulation took place in a laboratory fluidized-bed granulator (for example GPCG 3. 1 from Inprotec AG) under the conditions given in the table. After about 30 minutes each was interrupted and the coverings removed from the wall and floor and possibly mortared. Thereafter, the remainder of the solution / suspension was sprayed, trying to keep the product temperature as low as possible. The resulting materials were sieved through a 1 mm sieve to remove very large agglomerates. In all experiments, the granulation was good, but it also produced a lot of dust, which suggests that the material dries quickly. Free-flowing materials were obtained which consisted of hard and brittle particles, mostly smaller than 0.5 mm.
  • the bulk density was between 400 and 480 g / l, which is partly due to the high dust content.
  • the partial hydrolysates react neutral to acidic after granulation (product V3, for example, produces a pH of 6.5 in 4% solution in water).
  • Fig. 1 shows the amount of dissolved PSI's as a function of time, with the various curves Tabs with stearic acid at pH 8 Tabs with stearic acid pH 10 Tabs with alkyl PEG pH 8 Tabs with alkyl PEG pH 10 represent.

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Abstract

Molded article (A), with washing and cleaning activity, contains polysuccinimide (PSI) together with poly(ethylene glycol) (PEG) and/or phosphoric acid. An INDEPENDEN T CLAIM is also included for preparation of (A) by mixing PSI with PEG and/or phosphoric acid before mixing with other optional ingredients, then compressing the mixture, preferably to tablets.

Description

Die Erfindung betrifft wasch- oder reinigungsaktive Formkörper, in erster Linie Tabletten wie Waschmitteltabletten, Geschirrspülmitteltabletten, Fleckensalztabletten oder Wasserenthärtungstabletten für den Gebrauch im Haushalt, enthaltend Polysuccinimid in Kombination mit Polyethylenglykol und/oder Phosphorsäure, insbesondere für den maschinellen Gebrauch, sowie ein Verfahren zur Herstellung dieser Formkörper und ihre Verwendung.The invention relates to washing or cleaning active moldings, primarily tablets such as detergent tablets, dishwasher tablets, patch salt tablets or water softening tablets for household use, containing polysuccinimide in combination with polyethylene glycol and / or phosphoric acid, in particular for machine use, and a process for producing these Shaped bodies and their use.

Wasch- oder reinigungsaktive Formkörper, insbesondere Tabletten, besitzen gegenüber pulverförmigen Mitteln eine Reihe von Vorteilen, wie eine vorteilhafte Handhabung, eine einfache Dosierung sowie geringer Bedarf an Verpackungsvolumina. Probleme ergeben sich jedoch dadurch, dass zur Erreichung einer hinreichenden Form- und Bruchbeständigkeit beim Verpressen der pulverförmigen Bestandteile verhältnismäßig hohe Pressdrucke angewendet werden müssen. Aufgrund der starken Verdichtung weisen derartige Tabletten vielfach unzureichende Zerfall- und Löseeigenschaften bei ihrer Anwendung auf, wodurch die Aktivsubstanz im Wasch- bzw. Reinigungsmittel zu langsam freigesetzt wird und die Gefahr der Rückstandsbildung insbesondere auf Textilien nach dem Waschgang entsteht.Washing or cleaning-active moldings, in particular tablets, have a number of advantages over powdered detergents, such as advantageous handling, simple metering and low packaging volume requirements. However, problems arise from the fact that to achieve a sufficient shape and breakage resistance during the compression of the powdery constituents relatively high pressing pressures must be applied. Due to the high degree of compression, such tablets often have inadequate disintegration and release properties when they are used, as a result of which the active substance in the washing or cleaning agent is released too slowly and the risk of residue formation arises, in particular on textiles after the wash cycle.

Im Falle des Einsatzes von Polysuccinimid (PSI) kommt erschwerend dessen extrem langsame Löslichkeit in Wasser hinzu, weshalb es in der Vergangenheit nur in slow-release Anwendungen zum Einsatz kam (siehe DE-A 101 01 671). Polysuccinimid ist jedoch ein idealer Bestandteil von wasch- oder reinigungsaktiven Formkörpern, da es im Kontakt mit Alkali das Dispergiermittel Polyaspartat bildet. Der große Vorteil von Polysuccinimid ist dessen sehr geringe Hygroskopie, da ihm ionische Brücken bildende oder Wasserstoffbrücken bildende funktionelle Gruppen völlig fehlen. Somit wird das Beimischen von hygroskopizitätsvermindernden Substanzen wie hydrophob modifiziertes Siliciumdioxid oder Magnesiumstearat vermeidbar. Teilhydrolysiertes PSI, wie es durch Umsetzung von PSI mit Wasser bzw. NaOH in unterstöchiometrischen Megnen (bezogen auf Succinimideinheiten) entsteht, steht hinsichtlich der Hygroskopizität in der Mitte zwischen Natriumpolyaspartat und PSI und kann für wasch- und reinigungsaktive Formkörper ein Kompromiß sein zwischen den Anforderungen Schnelllöslichkeit und Hygroskopizität. Teilhydrolisiertes PSI ist wesentlich schneller in Wasser löslich als unverändertes PSI.In the case of the use of polysuccinimide (PSI) aggravating its extremely slow solubility in water is added, which is why it was used in the past only in slow-release applications (see DE-A 101 01 671). However, polysuccinimide is an ideal component of washing or cleaning active moldings, since it forms the dispersant polyaspartate in contact with alkali. The great advantage of polysuccinimide is its very low hygroscopicity because it completely lacks ionic bridging or hydrogen bonding functional groups. Thus, incorporation of hygroscopicity-reducing substances such as hydrophobically-modified silica or magnesium stearate becomes avoidable. Partially hydrolysed PSI, as formed by reaction of PSI with water or NaOH in sub-stoichiometric megnenes (based on succinimide units), is in the middle between sodium polyaspartate and PSI in terms of hygroscopicity and can be a compromise between fast-solubility requirements for washing and cleaning-active moldings and hygroscopicity. Partially hydrolyzed PSI is much more soluble in water than unchanged PSI.

Das Problem des langsamen Zerfalls von Tabletten mit einer raschen Auflösung der Inhaltsstoffe im Gebiet der Wasch- und Reinigungsmittel ist schon lange bekannt. Gemäß der Lehren aus EP-B 0 523 099 und WO-A-96/06156 können Sprengmittel eingesetzt werden, die von der Arzneimittelherstellung her bekannt sind. Als Sprengmittel werden quellfähige Schichtsilikate wie Bentonite, Naturstoffe und Natur-Derivate auf Stärke- und Cellulose-Basis, Alginate und dergleichen, Kartoffelstärke, Methylcellulose und/oder Hydroxypropylcellulose aber auch mikrokristalline Cellulose, Zucker wie Sorbit genannt. Diese Sprengmittel können mit den zu verpressenden Granulaten vermischt, aber bereits auch in die zu verpressenden Granulate eingearbeitet werden.The problem of the slow disintegration of tablets with a rapid dissolution of the ingredients in the field of detergents and cleaners has long been known. According to the teachings of EP-B 0 523 099 and WO-A-96/06156 disintegrating agents known from the pharmaceutical production can be used. As disintegrants are swellable phyllosilicates such as bentonites, natural products and natural derivatives based on starch and cellulose, alginates and like, potato starch, methyl cellulose and / or hydroxypropyl cellulose but also microcrystalline cellulose, sugars such as sorbitol. These disintegrants can be mixed with the granules to be compacted, but already incorporated into the granules to be pressed.

Gemäß EP-A-0 522 766 werden zumindest die Teilchen, welche Tenside und Builder enthalten, mit einer Lösung oder Dispersion eines Binders/Zerfallhilfsmittels, insbesondere Polyethylenglykol, umhüllt. Andere Binder/Zerfallhilfsmittel sind wiederum bekannte Sprengmittel, beispielsweise Stärken und Stärkederivate, im Handel erhältliche Cellulose-Derivate wie quervemetzte oder modifizierte Cellulose, mikrokristalline Cellulosefasern, quervernetzte Polyvinylpyrrolidone, Schichtsilikate etc.According to EP-A-0 522 766, at least the particles containing surfactants and builders are coated with a solution or dispersion of a binder / disintegrant, in particular polyethylene glycol. Other binder / disintegrating agents are again known disintegrants, for example starches and starch derivatives, commercially available cellulose derivatives such as crosslinked or modified cellulose, microcrystalline cellulose fibers, crosslinked polyvinylpyrrolidones, phyllosilicates, etc.

Gemäß der EP-A-0 711 827 führt der Einsatz von Partikeln, welche zum überwiegenden Teil aus Citrat bestehen, das eine bestimmte Löslichkeit in Wasser aufweist, auch zu einem beschleunigten Zerfall der Tabletten.According to EP-A-0 711 827, the use of particles which consist predominantly of citrate which has a certain solubility in water also leads to an accelerated disintegration of the tablets.

Die genannten Lösungsvorschläge tragen im Wasch- und Reinigungsmittelbereich zu einer Verbesserung der Zerfallseigenschaften von wasch- oder reinigungsaktiven Tabletten bei. Jedoch ist die erreichte Verbesserung in vielen Fällen nicht ausreichend. Insbesondere wenn der Anteil an klebrigen organischen Substanzen in den Tabletten, beispielsweise an anionischen und/oder nichtionischen Tensiden steigt oder einer der Inhaltsstoffe selbst, wie im Falle des PSI, nur sehr schlecht in Wasser löslich ist, sind diese Lösungsvorschläge wenig hilfreich. Dies ist einer der Gründe dafür, däss bis heute keine Waschmitteltabletten im Markt erhältlich sind, die auf Basis von PSI aufgebaut sind und den hohen Anforderungen des Verbrauchers genügen. Aber auch im Geschirrspülmittelbereich und im Bereich der Waschmitteladditive weisen Tabletten bei häufig genügender Bruchfestigkeit nicht die genügend hohe Zerfallsgeschwindigkeit auf. Dabei kann auch im Geschirrspülmittelbereich die Beschleunigung der Zerfalls- und der Auflösegeschwindigkeit von Vorteil sein, insbesondere für Phasen, die Wirkstoffe enthalten, die am Beginn des Reinigungsprozesses bzw. bei tieferen Temperaturen wirken sollen wie im vorliegenden Fall das PSI.The proposed solutions in the washing and cleaning agent area contribute to an improvement in the disintegration properties of washing or cleaning tablets. However, the improvement achieved is in many cases not sufficient. In particular, if the proportion of sticky organic substances in the tablets, for example on anionic and / or nonionic surfactants increases or one of the ingredients itself, as in the case of PSI, is very poorly soluble in water, these solutions are not very helpful. This is one of the reasons why to date no detergent tablets are available on the market, which are based on PSI and meet the high demands of the consumer. But even in the dishwashing detergent sector and in the field of detergent additives, tablets do not have the sufficiently high rate of disintegration, although the breaking strength is often sufficient. It can also be advantageous in the dishwashing detergent range to accelerate the rate of disintegration and dissolution, especially for phases containing active ingredients that are to act at the beginning of the cleaning process or at lower temperatures as in the present case, the PSI.

Dementsprechend bestand die Aufgabe der Erfindung darin, wasch- oder reinigungsaktive Formkörper bereitzustellen, welche Polysuccinimid (PSI) beinhalten und welche die obengenannten Nachteile nicht aufweisen. Ebenso sollte ein Verfahren zur Herstellung dieser verbesserten waschoder reinigungsaktiven Formkörper auf Basis von PSI bereitgestellt werden.Accordingly, the object of the invention was to provide washing or cleaning active moldings which include polysuccinimide (PSI) and which do not have the abovementioned disadvantages. Likewise, a process for the preparation of these improved washing or cleaning-active moldings based on PSI should be provided.

Es wurde nun gefunden, dass die Anwendung von PSI in Kombination mit Polyethylenglykolen (PEG) und/oder Phosphorsäure überraschenderweise zu schnell zerfallenden wasch- oder reinigungsaktiven Formkörpem führt obwohl letztere Substanzen Flüssigkeiten sind. Im Rahmen der vorliegenden Erfindung wurde überraschenderweise gefunden, dass PEG und Phosphorsäure echte Lösungsmittel für PSI darstellen. Konzentrierte Lösungen in hochmolekularem PEG (z. B. MG > 2000 d) (d = Dalton) erstarren zu hochviskosen oder gar festen Produkten, die gut tablettierbar sind. Durch Kontakt mit Wasser entstehen aus den Lösungen Dispersionen von PSI mit Wasser, die durch die feindisperse Verteilung der PSI-Partikel eine höhere Löslichkeit zeigen.It has now been found that the use of PSI in combination with polyethylene glycols (PEG) and / or phosphoric acid surprisingly fast-decomposing wash or cleaning-active Formkörpem leads although the latter substances are liquids. It has surprisingly been found within the scope of the present invention that PEG and phosphoric acid are true solvents for PSI. Concentrated solutions in high molecular weight PEG (eg MW> 2000 d) (d = Dalton) solidify to highly viscous or even solid products which are readily tablettable. By contact with water, dispersions of PSI with water are formed from the solutions, which show a higher solubility due to the finely dispersed distribution of the PSI particles.

Gegenstand der Erfindung ist daher in einer ersten Ausführungsform ein wasch- oder reinigungsaktiver Formkörper, enthaltend PSI und Polyethylenglykol und/oder Phosphorsäure. In bevorzugten Ausführungsformen enthalten die erfindungsgemäßen Mittel PSI in Kombination mit PEG. In einer weiteren bevorzugten Ausführungsform enthalten die erfindungsgemäßen Mittel PSI und Phosphorsäure.The invention therefore in a first embodiment, a washing or cleaning active moldings containing PSI and polyethylene glycol and / or phosphoric acid. In preferred embodiments, the agents according to the invention contain PSI in combination with PEG. In a further preferred embodiment, the agents according to the invention contain PSI and phosphoric acid.

Im Rahmen der Arbeiten zur vorliegenden Erfindung wurde gefunden, dass PEG und Phosphorsäure anscheinend als Lösungsvermittler fungieren.As part of the work of the present invention, it has been found that PEG and phosphoric acid appear to function as solubilizers.

Bereits eingangs wurde beschrieben, was unter wasch- oder reinigungsaktiven Formkörpern zu verstehen ist. Es handelt sich dabei in erster Linie um zylinderförmige Ausgestaltungen oder Tabletten, die als Waschmittel, Geschirrspülmittel, Bleichmittel (Fleckensalze), gegebenenfalls aber auch als Vorbehandlungsmittel, beispielsweise als Wasserenthärter oder Bleichmittel eingesetzt werden können. Der Begriff "Formkörper" ist aber nicht auf die Tablettenform beschränkt. Prinzipiell ist jede Raumform möglich, die den Ausgangsstoffen gegebenenfalls aufgrund eines äußeren Behältnisses aufgezwungen werden kann. Zylinderförmige Körper können dabei eine Höhe aufweisen, die kleiner oder größer oder gleich dem Durchmesser der Grundfläche ist. Denkbar ist jedoch auch eine eckige, beispielsweise eine rechteckige, insbesondere eine quadratische, aber auch eine rautenförmige bzw. trapezförmige eine runde oder ovale Grundfläche des Formkörpers. Weitere Ausgestaltungen schließen dreieckige oder mehr als viereckige Grundflächen des Formkörpers ein.Already at the beginning was described what is meant by washing or cleaning active moldings. These are primarily cylindrical designs or tablets which can be used as detergents, dishwashing detergents, bleaches (stain salts), but if appropriate also as pretreatment agents, for example as water softeners or bleaches. The term "shaped body" is not limited to the tablet form. In principle, any spatial form is possible, which may optionally be imposed on the starting materials due to an outer container. Cylindrical bodies can have a height which is smaller or larger or equal to the diameter of the base. It is also conceivable, however, an angular, for example, a rectangular, in particular a square, but also a diamond-shaped or trapezoidal a round or oval base of the molding. Further embodiments include triangular or more than quadrilateral surfaces of the molding.

Aufgrund der hervorragenden Zerfallseigenschaften der erfindungsgemäßen Formkörper ist es möglich, aber nicht zwingend erforderlich, die Formkörper mittels einer Dosiervorrichtung direkt in die wässrige Flotte eines maschinellen Verfahrens zu geben; es ist vielmehr auch möglich, den oder die Formkörper in die Einspülringe der handelsüblichen Haushaltsmaschinen, insbesondere der Waschgeräte, zu plazieren. Dementsprechend ist die Raumform der Formkörper in einer bevorzugten Ausführungsform der Erfindung in ihren Dimensionen der Einspülkammer handelsüblicher Haushaltsmaschinen angepasst.Due to the excellent disintegration properties of the shaped bodies according to the invention, it is possible, but not absolutely necessary, to give the shaped bodies by means of a metering device directly into the aqueous liquor of a machine process; Rather, it is also possible to place the molded body or bodies in the dispensing rings of the commercial household appliances, in particular the washing appliances. Accordingly, the spatial shape of the molded body is adapted in a preferred embodiment of the invention in their dimensions of the dispensing chamber commercial household appliances.

In einer bevorzugten Ausführungsform hat der Formkörper eine platten- oder tafelartige Struktur mit abwechselnd dicken langen und/oder dünnen kurzen Segmenten, so dass einzelne Segmente von diesem "Riegel" an den Sollbruchstellen, welche die kurzen dünnen Segmente darstellen, abgebrochen und in die Maschine bzw. die Einspülkammer der Maschine eingegeben werden können. Dieses Prinzip des "riegelförmigen" Mittels kann ebenfalls in anderen geometrischen Formen, beispielsweise senkrecht stehenden Dreiecken, die lediglich an einer ihrer Seiten längsseitig miteinander verbunden sind, verwirklicht werden.In a preferred embodiment, the shaped body has a plate-like or tabular structure with alternately thick long and / or thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which represent the short thin segments, broken and into the machine or The dispensing chamber of the machine can be entered. This principle of the "bar-shaped" means can also be realized in other geometric shapes, for example vertical triangles, which are connected to one another on one side only on one side.

In einer bevorzugten Ausführungsform der Erfindung werden homogene oder heterogene Formkörper, insbesondere Tabletten bereitgestellt, wobei diese Tabletten vorzugsweise einen Durchmesser von 20 bis 60 mm, insbesondere von 40 +/- 10 mm aufweisen. Die Höhe dieser Tabletten beträgt vorzugsweise 10 bis 30 mm und insbesondere 15 bis 25 mm. Das Gewicht der einzelnen Formkörper, insbesondere der Tabletten, liegt dabei vorzugsweise bei 15 bis 60 g und insbesondere bei 25 bis 40 g pro Formkörper bzw. Tablette; die Stoffdichte der Formkörper bzw. Tabletten weist hingegen üblicherweise Werte oberhalb von 1 kg/dm3, vorzugsweise von 1,1 bis 1,4 kg/dm3 auf. Je nach Art der Anwendung, des Wasserhärtebereichs oder der Verschmutzung können 1 oder mehrere, beispielsweise 2 bis 4 Formkörper, insbesondere Tabletten, eingesetzt werden. Weitere erfindungsgemäße Formkörper können auch kleinere Durchmesser bzw. Abmessungen, beispielsweise um 10 mm, aufweisen.In a preferred embodiment of the invention, homogeneous or heterogeneous shaped bodies, in particular tablets, are provided, these tablets preferably having a diameter of 20 to 60 mm, in particular 40 +/- 10 mm. The height of these tablets is preferably 10 to 30 mm and in particular 15 to 25 mm. The weight of the individual shaped bodies, in particular of the tablets, is preferably from 15 to 60 g and in particular from 25 to 40 g per tablet or tablet; By contrast, the consistency of the tablets or tablets usually has values above 1 kg / dm 3 , preferably from 1.1 to 1.4 kg / dm 3 . Depending on the nature of the application, the water hardness range or the pollution, 1 or more, for example 2 to 4 moldings, in particular tablets, can be used. Further shaped bodies according to the invention can also have smaller diameters or dimensions, for example 10 mm.

Unter einem homogenen Formkörper werden derartige verstanden, in denen die Inhaltsstoffe des Formkörpers homogen verteilt sind. Unter heterogenen Formkörpern werden dementsprechend solche verstanden, die keine homogene Verteilung ihrer Inhaltsstoffe aufweisen. Heterogene Formkörper können beispielsweise dadurch hergestellt werden, dass die verschiedenen Inhaltsstoffe nicht zu einem einheitlichen Formkörper, sondern zu einem Formkörper verpresst werden, der mehrere Schichten, also mindestens zwei Schichten aufweist. Dabei ist es auch möglich, dass diese verschiedenen Schichten unterschiedliche Zerfalls- und Lösegeschwindigkeiten aufweisen. Hieraus können vorteilhafte anwendungstechnische Eigenschaften der Formkörper resultieren. Falls beispielsweise Inhaltsstoffe in den Formkörpern enthalten sind, die sich wechselseitig negativ beeinflussen, so ist es möglich, die eine Komponente in der schneller zerfallenden und schneller löslichen Schicht zu integrieren und die andere Komponente in eine langsamer zerfallende Schicht einzuarbeiten, so dass die erste Komponente mit Vorlaufzeit wirken kann oder bereits abreagiert hat, wenn die zweite Komponente in Lösung geht. Der Schichtaufbau der Formkörper kann dabei stapelartig erfolgen, wobei ein Lösungsvorgang der inneren Schicht(en) an den Kanten des Formkörpers bereits dann erfolgt, wenn die äußeren Schichten noch nicht vollständig gelöst oder zerfallen sind; es kann aber auch eine vollständige Umhüllung der inneren Schicht(en) durch die jeweils weiter außen liegenden Schichten erreicht werden, was zu einer Verhinderung der frühzeitigen Lösung von Bestandteilen der inneren Schicht(en) führt.A homogeneous shaped body is understood as meaning those in which the ingredients of the shaped body are homogeneously distributed. Accordingly, heterogeneous shaped bodies are understood to mean those which do not have a homogeneous distribution of their constituents. Heterogeneous shaped bodies can be produced, for example, by pressing the various constituents not into a uniform shaped body but into a shaped body having a plurality of layers, ie at least two layers. It is also possible that these different layers have different decay and dissolution rates. This can result in advantageous performance properties of the molded body. For example, if ingredients are included in the moldings that interact negatively, it is possible to incorporate one component in the faster disintegrating and faster dissolving layer and to incorporate the other component into a slower disintegrating layer, so that the first component with Lead time or has already reacted when the second component goes into solution. The layer structure of the moldings can be carried out in a stack, wherein a solution process of the inner layer (s) at the edges of the molding takes place already when the outer layers are not yet completely dissolved or disintegrated; but it can also be a complete wrapping of the inner layer (s) by the each further outward layers are achieved, which leads to a prevention of premature dissolution of components of the inner layer (s).

In einer weiteren bevorzugten Ausführungsform der Erfindung besteht eine Tablette aus mindestens drei Schichten, also zwei äußeren und mindestens einer inneren Schicht, wobei mindestens in einer der inneren Schichten ein Peroxid-Bleichmittel enthalten ist, während bei der stapelförmigen Tablette die beiden Deckschichten und bei der hüllenförmigen Tablette die äußersten Schichten jedoch frei von Peroxid-Bleichmittel sind. Ebenso ist es möglich, Peroxid-Bleichmittel und gegebenenfalls vorhandene Bleichaktivatoren oder Bleichkatalysatoren und/oder Enzyme räumlich in einem Formkörper oder Tablette voneinander zu trennen. Derartige Ausgestaltungen weisen den Vorteil auf, dass selbst in Fällen, bei denen der Waschmittel- oder Bleichmittel-Formkörper bzw. die Waschmittel- oder Bleichmittel-Tablette im direkten Kontakt zu den Textilien in die Waschmaschine oder ins Handwaschbecken gegeben wird, keine Verfleckungen ("spotting") durch Bleichmittel und dergleichen auf den Textilien zu befürchten sind.In a further preferred embodiment of the invention, a tablet consists of at least three layers, ie two outer and at least one inner layer, wherein at least in one of the inner layers, a peroxide bleach is contained, while in the stacked tablet, the two outer layers and the shell-shaped Tablet the outermost layers, however, are free of peroxide bleach. It is likewise possible to spatially separate peroxide bleaching agents and any bleach activators or bleach catalysts and / or enzymes present in a molding or tablet from one another. Such embodiments have the advantage that even in cases where the detergent or bleach body or the detergent or bleach tablet is placed in direct contact with the fabrics in the washing machine or hand basin, no stains ("spotting ") are to be feared by bleach and the like on the textiles.

Beispiele für heterogene Formkörper können beispielsweise der europäischen Patentanmeldung EP-A-0 716 144 entnommen werden, deren Inhalt von der vorliegenden Anmeldung mit umfasst wird.Examples of heterogeneous shaped bodies can be found, for example, in European Patent Application EP-A-0 716 144, the content of which is included in the present application.

PSI und dessen Einsatz als Konditionierungsmittel für stehende und fließende Wassersysteme aufgrund seiner Dispergiereigenschaften, Thermostabilität und Härtestabilisatoreigenschaften sind aus DE-A 101 01 671 bekannt.PSI and its use as a conditioning agent for standing and flowing water systems due to its dispersing properties, thermal stability and hardness stabilizer properties are known from DE-A 101 01 671.

Unter PSI im Sinne der vorliegenden Erfindung wird PSI selber, dessen Copolymere, Teilhydrolysate oder Hydrolysate verstanden. Teilhydrolysate im Sinne der vorliegenden Erfindung sind Polysuccinimide, deren Polymerbausteine teilweise in Aspartateinheiten überführt worden sind, das heißt es handelt sich um Copolymere aus Succinimideinheiten und Aspartateinheiten. Diese Teilhydrolysate können auch in sprühgranulierter Form vorliegen.PSI in the sense of the present invention is understood to mean PSI itself, its copolymers, partial hydrolysates or hydrolysates. Partial hydrolysates for the purposes of the present invention are polysuccinimides whose polymer units have been partially converted into aspartate units, that is to say copolymers of succinimide units and aspartate units. These partial hydrolysates may also be in spray granulated form.

PSI kann in großtechnischem Maßstab durch thermische Polymerisation von Maleinsäureanhydrid und Ammoniak oder deren Derivate hergestellt werden (siehe US-A 3 846 380; US-A 4 839 461; US-A 5 219 952 oder US-A 5 371 180).PSI can be prepared on an industrial scale by thermal polymerization of maleic anhydride and ammonia or their derivatives (see US-A 3,846,380, US-A 4,839,461, US-A 5,219,952 or US-A 5,371,180).

Darüber hinaus erhält man PSI durch thermische Polymerisation von Asparaginsäure (US-A 5 051 401) gegebenenfalls in Gegenwart saurer Katalysatoren/Lösungsmittel (US-A 3 052 655).In addition, PSI is obtained by thermal polymerization of aspartic acid (US Pat. No. 5,051,401), if appropriate in the presence of acidic catalysts / solvents (US Pat. No. 3,052,655).

PSI fällt bei der chemischen Synthese als Polymer mit einem mittleren Molgewicht von 500 bis 20 000, bevorzugt 3 000 bis 5 000, an. Polysuccinimid ist als chemischer Vorläufer der Polyasparaginsäure zu betrachten, zu der es mit Wasser langsam hydrolysiert. Der pH-Wert der dabei entstehenden Lösung liegt zwischen pH 1 bis 4, bevorzugt 2 bis 3. Hierdurch kommt nicht nur die gute steinlösende, sondern auch gleichzeitig die dispergierende Wirkung der durch PSI freigesetzten Polyasparaginsäure gegenüber schwerlöslichen Calciumsalzen bzw. anderen schwerlöslichen Stoffen zum Tragen. Die resultierende saure Lösung führt aufgrund ihrer Säurewirkung auch zur direkten Auflösung eventuell gebildeter Calciumcarbonat-Inkrustationnen.PSI accumulates in the chemical synthesis as a polymer having an average molecular weight of 500 to 20,000, preferably 3,000 to 5,000, on. Polysuccinimide is considered to be a chemical precursor of polyaspartic acid, to which it slowly hydrolyzes with water. The pH of the resulting solution is between pH 1 to 4, preferably 2 to 3. This is not only the good stone-dissolving, but also the dispersing effect of the released by PSI polyaspartic acid against poorly soluble calcium salts or other poorly soluble substances to bear. Due to their acidity, the resulting acidic solution also leads to the direct dissolution of possibly formed calcium carbonate incrustations.

Das erfindungsgemäß einzusetzende PSI wird in Mengen von 0,01 bis 20 Gew.-%, bevorzugt 0,1 bis 10 Gew.-% und besonders bevorzugt in Menge von 0,5 bis 5 Gew.-% eingesetzt.The PSI to be used according to the invention is used in amounts of from 0.01 to 20% by weight, preferably from 0.1 to 10% by weight and more preferably in an amount of from 0.5 to 5% by weight.

Im Falle des Einsatzes von Polyethylenglykol (PEG) als Lösungsvermittler wird das PEG vorzugsweise in einer Menge von 0,5 - 20 Gew.-% eingesetzt.In the case of the use of polyethylene glycol (PEG) as a solubilizer, the PEG is preferably used in an amount of 0.5 to 20 wt .-%.

Geeignete Polyethylenglykole sind solche mit hohem Ethoxylierungsgrad, beispielsweise Polyethylenglykole mit einem Molekulargewicht von oberhalb 2000, bevorzugt von 2 000 bis 12 000, besonders bevorzugt von 2 000 bis 6 000.Suitable polyethylene glycols are those having a high degree of ethoxylation, for example polyethylene glycols having a molecular weight of more than 2,000, preferably from 2,000 to 12,000, particularly preferably from 2,000 to 6,000.

Im Falle des Einsatzes von Phosphorsäure als Lösungsvermittler wird die erfindungsgemäß einzusetzende Phosphorsäure in einer Menge von 0,5 Gew.-% bis 25 Gew.-% eingesetzt.In the case of the use of phosphoric acid as a solubilizer, the phosphoric acid to be used according to the invention is used in an amount of 0.5% by weight to 25% by weight.

Die Verwendung von PEG und/oder Phosphorsäure führt überraschenderweise zu einem schnellen Abbau des PSI aus den Formkörpern bzw. den Tabletten in eine wasserlösliche Form, so dass erst durch diese Maßnahme der Einsatz von PSI in Wasch- und Reinigungsmitteln möglich wird.The use of PEG and / or phosphoric acid surprisingly leads to a rapid degradation of the PSI from the moldings or the tablets in a water-soluble form, so that only by this measure, the use of PSI in detergents and cleaners is possible.

Neben den erfindungsgemäß einzusetzenden Komponenten PSI und PEG und/oder Phosphorsäure können weitere die Auflösung der Tabletten unterstützende Mittel eingesetzt werden.In addition to the components PSI and PEG and / or phosphoric acid to be used according to the invention, further agents assisting the dissolution of the tablets can be used.

Beispielsweise eignen sich dafür sogenannte Sprengmittel.For example, so-called explosives are suitable for this purpose.

Zu den bevorzugten Sprengmitteln, welche in eine granulare bzw. in eine cogranulierte Form zu überführen sind, zählen Stärke und Stärke-Derivate, Cellulose und Cellulosederivate, beispielsweise mikrokristalline Cellulose, CMC, MC, Alginsäure und deren Salze, Carboxymethylamylopectin, Polyacrylsäure, Polyvinylpyrrolidon und Polyvinylpolypyrrolidon. Die Sprengmittelgranulate können auf herkömmliche Art und Weise, beispielsweise durch Sprühtrocknung oder Heißdampftrocknung wässriger Zubereitungsformen oder durch Granulierung, Pelletierung, Extrusion oder Walzenkompaktierung hergestellt werden. Dabei kann es von Vorteil sein, den Sprengmitteln Zuschlagsstoffe, Granulierhilfsmittel, Träger oder Kaschiermittel der bekannten Art zuzusetzen (cogranulierte Form). Zuschlagsstoffe sind in einer bevorzugten Ausführungsform der Erfindung nicht-tensidische Wirksubstanzen von Wasch- oder Reinigungsmitteln, insbesondere Bleichaktivatoren und/oder Bleichkatalysatoren, besonders bevorzugt ist dabei ein Sprengmittelgranulat, welches als Zuschlagstoff Tetraacetylethylendiamin (TAED) und/oder andere Bleichaktivatoren der gängigen Art enthält. Derartige Sprengmittelgranulate können vorteilhafterweise durch Cogranulation des Sprengmittels mit dem Zuschlagsstoff hergestellt werden. Durch eine derartige Cogranulation kann die Verteilung des Sprengmittels in dem Formkörper, insbesondere in der Tablette, vergrößert werden, was in bestimmten Fällen ebenfalls zu einer Verbesserung der Zerfallsgeschwindigkeit des Formkörpers führen kann.Starch and starch derivatives, cellulose and cellulose derivatives, for example microcrystalline cellulose, CMC, MC, alginic acid and its salts, carboxymethylamylopectin, polyacrylic acid, polyvinylpyrrolidone and polyvinylpolypyrrolidone, are among the preferred disintegrants to be converted into granular or cogranulated form , The disintegrant granules can be prepared in a conventional manner, for example by spray drying or hot steam drying of aqueous preparation forms or by granulation, pelleting, extrusion or roll compaction. It may be advantageous to the disintegrants additives, granulation aids, carriers or laminating the known type to add (cogranulated form). In one preferred embodiment of the invention, additives are non-surfactant active substances of detergents or cleaners, in particular bleach activators and / or bleach catalysts; particularly preferred is a disintegrant granule containing as an additive tetraacetylethylenediamine (TAED) and / or other bleach activators of the conventional type. Such disintegrant granules can advantageously be prepared by co-granulation of the disintegrant with the additive. By such a cogranulation, the distribution of the disintegrating agent in the shaped body, in particular in the tablet, can be increased, which in certain cases can likewise lead to an improvement in the disintegration rate of the shaped body.

Die Einsatzmengen solcher Sprengmittel sind dem Fachmann aus der DE-A 197 10 254 bekannt, deren Inhalt von der vorliegenden Anmeldung mit umfasst wird.The amounts of such disintegrants are known to the person skilled in the art from DE-A 197 10 254, the content of which is included in the present application.

'Darüber hinaus können die erfindungsgemäßen Wasch- und reinigungsaktiven Formkörper weitere Bestandteile, wie sie üblicherweise in Wasch- oder Reinigungsmitteln und Wasserenthärtem eingesetzt werden, enthalten. In erster Linie zählen hierzu anionische, nichtionische, kationische, amphotere und zwitterionische Tenside, anorganische und organische, wasserlösliche oder wasserunlösliche Buildersubstanzen und Cobuilder, Bleichmittel, insbesondere Peroxidbleichmittel, aber auch Aktivchlorverbindungen, welche vorteilhafterweise umhüllt sind, Bleichaktivatoren und Bleichkatalysatoren, Enzyme und Enzymstabilisatoren, Schauminhibitoren, Vergrauungsinhibitoren, Substanzen, welche das Wiederanschmutzen von Textilien verhindern, sogenannte soil repellents, sowie übliche anorganische Salze wie Sulfate und organische Salze wie Phosphonate, optische Aufheller und Farb- und Duftstoffe. In maschinellen Geschirrspülmitteln ist zusätzlich der Einsatz von herkömmlichen Silberschutzmitteln empfehlenswert..In addition, the washing and cleaning-active moldings according to the invention may contain further constituents, such as are customarily used in detergents and cleaners and water softeners. These include, in particular, anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, inorganic and organic, water-soluble or water-insoluble builder substances and cobuilders, bleaching agents, in particular peroxygen bleaches, but also active chlorine compounds, which are advantageously coated, bleach activators and bleach catalysts, enzymes and enzyme stabilizers, foam inhibitors , Graying inhibitors, substances that prevent the re-soiling of textiles, so-called soil repellents, and conventional inorganic salts such as sulfates and organic salts such as phosphonates, optical brighteners and dyes and perfumes. In automatic dishwashing detergents, the use of conventional silver protectants is also recommended.

Zu den bevorzugten anionischen Tensiden zählen sowohl solche auf petrochemischer Basis wie Alkylbenzolsulfonate, Alkansulfonate oder Alkyl(ether)sulfate mit ungeraden Kettenlängen, als auch solche auf nativer Basis, beispielsweise Fettalkylsulfate oder Fettalkyl(ether)sulfate, Seifen, Sulfosuccinate etc. Besonders bevorzugt sind - gegebenenfalls in Kombination mit geringen Mengen an Seife - Alkylbenzolsulfonate und/oder verschiedene Kettenschnitte von Alkylsulfaten bzw. Alkylethersulfaten. Während bei Alkylbenzolsulfonaten das C11-C13-Alkylbenzolsulfonat und C12-Alkylbenzolsulfonat bevorzugt sind, umfassen bei den Alkyl(ether)sulfaten bevorzugte Kettenschnitte C12 bis C16, C12 bis C14, C14 bis C16, C16 bis C18 oder C11 bis C15 bzw. C13 bis C15.Preferred anionic surfactants include those based on petrochemicals, such as alkylbenzenesulfonates, alkanesulfonates or alkyl (ether) sulfates with odd chain lengths, as well as those on a native basis, for example fatty alkyl sulfates or fatty alkyl (ether) sulfates, soaps, sulfosuccinates, etc. Particular preference is given to optionally in combination with small quantities of soap - alkylbenzenesulfonates and / or various chain cuts of alkyl sulfates or alkyl ether sulfates. While in alkylbenzenesulfonates the C 11 -C 13 -alkylbenzenesulfonate and C 12 -alkylbenzenesulfonate are preferred, preferred chain cuts in the alkyl (ether) sulfates include C 12 to C 16 , C 12 to C 14 , C 14 to C 16 , C 16 to C 18 or C 11 to C 15 or C 13 to C 15 .

Zu den bevorzugten nichtionischen Tensiden zählen insbesondere die mit durchschnittlich 1 bis 7 Mol Ethylenoxid pro Mol Alkohol ethoxylierten C12-C18-Fettalkohole und die entsprechenden C11-C17-Alkohole, insbesondere C13-C15-Alkohole, aber auch die aus dem Wasch- oder Reinigungsmittelbereich bekannten höher ethoxylierten Alkohole der angegebenen Kettenlänge, Aminoxide, Alkylpolyglykoside, Polyhydroxyfettsäureamide, Fettsäuremethylesterethoxylate und Gemini-Tenside.The preferred nonionic surfactants include, in particular, the C 12 -C 18 -fatty alcohols ethoxylated with an average of 1 to 7 mol of ethylene oxide per mole of alcohol and the corresponding C 11 -C 17 alcohols, in particular C 13 -C 15 alcohols, but also known from the washing or cleaning agent range higher ethoxylated alcohols of the specified chain length, amine oxides, alkyl polyglycosides, polyhydroxy fatty acid amides, fatty acid methyl ester ethoxylates and gemini surfactants.

Als erfindungsgemäß bevorzugt einzusetzende anorganische Builder kommen insbesondere herkömmliche Phosphate, mit Bevorzugung des Tripolyphosphats, Zeolithe, wobei besonders Zeolith A, Zeolith P, Zeolith X und beliebige Mischungen aus diesen eine Rolle spielen, aber auch Carbonate, Hydrogencarbonate sowie kristalline und amorphe Silikate mit Sekundärwaschvermögen in Betracht. Zu den üblichen Cobuildern zählen vor allem (co-)polymere Salze von (Poly-)Carbonsäuren, beispielsweise Copolymere der Acrylsäure und der Maleinsäure, aber auch Polycarbonsäuren und deren Salze wie Citronensäure, Weinsäure, Glutarsäure, Bernsteinsäure, Polyasparaginsäure etc. Der Fachmann kennt die einsetzbaren organischen Cobuilder und deren Einsatzmengen aus zahlreichen Veröffentlichungen auf dem Wasch- und Reinigungsmittelgebiet.Particularly preferred inorganic builders to be used according to the invention are conventional phosphates, with preference for the tripolyphosphate, zeolites, in particular zeolite A, zeolite P, zeolite X and any mixtures thereof, but also carbonates, bicarbonates and crystalline and amorphous silicates having secondary washing capacity consideration. The usual co-builders include, in particular, (co) polymeric salts of (poly) carboxylic acids, for example copolymers of acrylic acid and maleic acid, but also polycarboxylic acids and their salts, such as citric acid, tartaric acid, glutaric acid, succinic acid, polyaspartic acid, etc. The person skilled in the art is aware of these usable organic cobuilders and their quantities from numerous publications in the washing and cleaning agent area.

Als Bleichmittel werden vor allem die zur Zeit gängigen Peroxidbleichmittel wie Perborat oder Percarbonat, vor allem auch in Kombination mit den gängigen Bleichaktivatoren und Bleichkatalysatoren, insbesondere auf dem Gebiet der Geschirrspülmittel aber auch die bereits weiter oben genannten Aktivchlorverbindungen eingesetzt.The bleaching agents used are above all the peroxide bleaching agents currently in use, such as perborate or percarbonate, above all also in combination with the customary bleach activators and bleach catalysts, in particular in the field of dishwashing detergents, but also the active chlorine compounds already mentioned above.

Bei den Enzymen sind nicht nur Proteasen sondern auch Lipasen, Amylasen, Cellulasen und Peroxidasen sowie beliebige Kombinationen dieser Enzyme von besonderem Interesse.Not only proteases but also lipases, amylases, cellulases and peroxidases as well as any desired combinations of these enzymes are of particular interest in the enzymes.

In einer bevorzugten Ausführungsform der Erfindung werden Aniontensid-haltige Compounds eingesetzt, welche verschiedene Aniontenside - beispielsweise Alkylsulfate und Alkyllbenzolsulfonate und/oder Seife oder aber Alkylsulfate und sulfierte Fettsäureglycerinester - und/oder Anionentenside in Kombination mit Niotensiden, beispielsweise Alkylsulfate verschiedener Kettenlänge, gegebenenfalls auch mehrere Typen von Alkylsulfaten mit verschiedenen Kettenabschnitten in Kombination mit ethoxylierten Alkoholen und/oder anderen obengenannten nichtionischen Tensiden enthalten. Beispielsweise können auch anionische und nichtionische Tenside überwiegend in zwei verschiedenen Compounds untergebracht sein.In a preferred embodiment of the invention anionic surfactant-containing compounds are used, which are different anionic surfactants - for example, alkyl sulfates and alkylbenzenesulfonates and / or soap or alkyl sulfates and sulfated Fettsäureglycerinester - and / or Anionentenside in combination with nonionic surfactants, for example alkyl sulfates of different chain length, optionally also several types of alkyl sulfates having various chain portions in combination with ethoxylated alcohols and / or other nonionic surfactants mentioned above. For example, anionic and nonionic surfactants can be predominantly accommodated in two different compounds.

Als erfindungsgemäß gegebenenfalls einzusetzende Puderungsmittel kommen wie auch bei den Sprengmittelgranulaten vor allem feinteilige Zeolithe, Kieselsäuren, Sulfate, Calciumstearate, Phosphate und/oder Acetate in Betracht. In einer bevorzugten Ausführungsform der Erfindung ist darauf zu achten, dass Staubanteile und Partikel kleiner 0,2 mm vor dem Vermischen mit den Sprengmittelgranulaten möglichst vollständig abgetrennt werden.Finely divided zeolites, silicic acids, sulfates, calcium stearates, phosphates and / or acetates, as well as the disintegrant granules, are particularly suitable as powdering agents for use in accordance with the invention. In a preferred embodiment of the invention Ensure that dust particles and particles smaller than 0.2 mm are completely separated before mixing with the disintegrant granules.

Die erfindungsgemäßen PSI-enthaltenden Formkörper weisen aufgrund von PEG und/oder Phosphorsäure hervorragende Zerfalleigenschaften auf und ermöglichen somit erst den Einsatz von PSI. Dies kann beispielsweise unter kritischen Bedingungen in einer üblichen Haushaltswaschmaschine (Einsatz direkt in der Waschflotte mittels herkömmlicher Dosiervorrichtung, Feinwaschprogramm oder Buntwäsche, Waschtemperatur maximal 40°C) oder in einem Becherglas bei einer Waschtemperatur von 25°C getestet werden.The PSI-containing moldings according to the invention have excellent decomposition properties due to PEG and / or phosphoric acid and thus enable the use of PSI only. This can be tested, for example, under critical conditions in a conventional household washing machine (used directly in the wash liquor by means of a conventional metering device, fine washing program or colored laundry, washing temperature of 40 ° C. at most) or in a beaker at a washing temperature of 25 ° C.

Das Auflöseverhalten der PSI-haltigen waschaktiven Formkörper wurde mit Hilfe der Fluoreszenzspekroskopie untersucht. So zeigt eine wässrige Lösung der thermisch hergestellten Polyasparaginsäure nach Anregung mit UV-Licht mit einem Maximum bei 334 nm eine Fluoreszenzemission bei 411 nm (im Maximum).The dissolution behavior of PSI-containing wash-active moldings was investigated by fluorescence spectroscopy. Thus, an aqueous solution of the thermally prepared polyaspartic acid after excitation with UV light with a maximum at 334 nm fluorescence emission at 411 nm (at maximum).

In einer weiteren Ausführungsform der Erfindung wird deshalb ein Waschverfahren beansprucht, wobei der PSI und PEG und/oder Phosphorsäure enthaltende Formkörper über die Einspülvorrichtung der Haushaltswaschmaschine in die Waschflotte eingebracht wird.In a further embodiment of the invention, therefore, a washing process is claimed, wherein the PSI and PEG and / or phosphoric acid-containing molded body is introduced via the Einspülvorrichtung the household washing machine in the wash liquor.

Die eigentliche Herstellung der erfindungsgemäßen PSI und PEG und/oder Phosphorsäure enthaltenden Formkörper erfolgt zunächst durch das Vermischen mit den restlichen Bestandteilen und anschließendes Informbringen, insbesondere Verpressen zu Tabletten, wobei auf herkömmliche Verfahren (beispielsweise wie in der herkömmlichen Patentliteratur zu Tablettierungen, vor allem auf dem Wasch- oder Reinigungsmittelgebiet, insbesondere wie in den obengenannten Patentanmeldungen und dem Artikel "Tablettierung: Stand der Technik", SÖFW-Journal, 122. Jahrgang, S. 1016-1021 (1996) beschrieben) zurückgegriffen werden kann.The actual production of the inventive PSI and PEG and / or phosphoric acid-containing molded body is carried out first by mixing with the remaining components and subsequent Informbringen, in particular compression into tablets, using conventional methods (for example, as in the conventional patent literature for tabletting, especially on the Washing or cleaning agent area, in particular as described in the above-mentioned patent applications and the article "tableting: state of the art", SÖFW-Journal, 122th year, pp. 1016-1021 (1996)) can be used.

BeispieleExamples Herstellung von Teilhydrolysaten von PolysuccinimidPreparation of partial hydrolysates of polysuccinimide Ansatz:Approach:

Aus 500 g Baypure® DSP (Polysuccimimid rein als Feststoff) und 615 g Wasser wurde eine Suspension hergestellt und mittels Rotor/Stator (X40/38E2) auf Stufe 2 homogenisiert. Dann wurde je nach gewünschtem Ringöffnungsgrad die entsprechende Menge NaOH (45 %ig) langsam zugegeben, sodass eine Temperatur von 50°C nicht überschritten wurde (Wasserbad). Nach Abkühlen auf Raumtemperatur wurde der pH-Wert (siehe Tabelle) gemessen und die Lösung/Suspension versprüht.From 500 g of Baypure® DSP (pure polysuccimimide as solid) and 615 g of water, a suspension was prepared and homogenized by means of rotor / stator (X40 / 38E2) at stage 2. Then, depending on the desired ring opening degree, the appropriate amount of NaOH (45%) was slowly added so that a temperature of 50 ° C was not exceeded (water bath). After cooling to room temperature, the pH (see table) was measured and the solution / suspension was sprayed.

Granulation:Granulation:

Die Trocknung und Granulation erfolgte in einem Labor-Wirbelbettgranulator (beispielsweise GPCG3. 1 der Firma Inprotec AG) unter den in der Tabelle angegebenen Bedingungen. Nach ca. 30 Minuten wurde jeweils unterbrochen und die Beläge von Wand und Boden entfernt und gegebenenfalls gemörsert. Danach wurde der Rest der Lösung/Suspension versprüht, wobei versucht wurde, die Produkttemperatur möglichst niedrig zu halten. Die erhaltenen Materialien wurden über ein 1 mm Sieb abgesiebt, um sehr große Agglomerate zu entfernen. In allen Versuchen war die Granulation gut, es wurde jedoch auch sehr viel Staub erzeugt, was darauf schließen lässt, dass das Material schnell abtrocknet. Es wurden freifließende Materialien erhalten, die aus harten und spröden Partikel bestanden, die größtenteils kleiner 0,5 mm waren. Das Schüttgewicht bewegte sich zwischen 400 und 480 g/l, was teilweise auch auf den hohen Staubanteil zurückzuführen ist. Je niedriger der Ringöffnungsgrad war, desto niedriger konnte die Produkttemperatur gewählt werden. Tabelle 1 Laborversuche Versuch Ringöffnungsgrad % NaOH Menge g pH-Wert Zulufttemp. °C Ablufttemp. °C Produkttemp. °C Sprühdruckbar Menge nach Sieben g V1 50 222 8,28 140 74-80 83-90 1,0 300 V2** 50 444 7,5 140 64-90 77-90 1,0 930 V3 40 178 7,5 140 68-80 74-90 1,0 330 V4 30 133 6,6 140 65-80 72-90 1,0 340 * Trocknungsverlust mit IR-Waage bestimmt, 160°C, 60 min, 2,5 g
** bei der Verwendung von Leitungswasser (17-18°C Härte) wurde eine etwas höhere Viskosität der DSP Suspension beobachtet. The drying and granulation took place in a laboratory fluidized-bed granulator (for example GPCG 3. 1 from Inprotec AG) under the conditions given in the table. After about 30 minutes each was interrupted and the coverings removed from the wall and floor and possibly mortared. Thereafter, the remainder of the solution / suspension was sprayed, trying to keep the product temperature as low as possible. The resulting materials were sieved through a 1 mm sieve to remove very large agglomerates. In all experiments, the granulation was good, but it also produced a lot of dust, which suggests that the material dries quickly. Free-flowing materials were obtained which consisted of hard and brittle particles, mostly smaller than 0.5 mm. The bulk density was between 400 and 480 g / l, which is partly due to the high dust content. The lower the ring opening degree, the lower the product temperature could be selected. <b><u> Table 1 </ u></b> Laboratory tests attempt Ring opening degree% NaOH amount g PH value Supply air temperature. ° C Ablufttemp. ° C Produkttemp. ° C Sprühdruckbar Quantity after seven g V1 50 222 8.28 140 74-80 83-90 1.0 300 V2 ** 50 444 7.5 140 64-90 77-90 1.0 930 V3 40 178 7.5 140 68-80 74-90 1.0 330 V4 30 133 6.6 140 65-80 72-90 1.0 340 * Loss of drying determined with IR balance, 160 ° C, 60 min, 2.5 g
** When using tap water (17-18 ° C hardness), a slightly higher viscosity of the DSP suspension was observed.

Die Teilhydrolysate reagieren nach der Granulation neutral bis sauer (Produkt V3 z.B. erzeugt in 4 %iger Lösung in Wasser einen pH von 6,5).The partial hydrolysates react neutral to acidic after granulation (product V3, for example, produces a pH of 6.5 in 4% solution in water).

Für das Auflöseverhalten wurden Komprimate aus PSI und Stearinsäure (90:10) mit solchen aus PSI und Alkyl-Polyethylenglykolen (7-10 EO; 60:40) verglichen. Die letzteren zerfallen (sofern mit niedrigem Pressdruck hergestellt) in Minuten in eine wässrige Dispersion, in welcher PSI schnell in Lösung geht. Die Lösegeschwindigkeit ist insbesondere in alkalischer Umgebung, wie für Waschmittelformulierungen typisch, schnell.For dissolution behavior, compressed PSI and stearic acid (90:10) were compared with those from PSI and alkyl polyethylene glycols (7-10 EO, 60:40). The latter disintegrate (if prepared at low pressure) in minutes into an aqueous dispersion in which PSI rapidly dissolves. The dissolution rate is fast, especially in an alkaline environment, as typical for detergent formulations.

Die Konzentration als Funktion der Zeit wurde mit Hilfe der Fluoreszenzspektroskopie bestimmt (Anregung 334 nm, Flureszenzemission 411 nm), wobei die Eigenfluoreszenz der thermisch aus Maleinsäureanhydrid und Ammonium hergestellten Polyasparaginsäure genutzt wurde. Fig. 1 zeigt die Menge gelösten PSI's in Abhängigkeit von der Zeit, wobei die verschiedenen Kurven

Figure imgb0001
   Tabs mit Stearinsäure bei pH 8
Figure imgb0002
   Tabs mit Stearinsäure pH 10
Figure imgb0003
   Tabs mit Alkyl-PEG pH 8
Figure imgb0004
   Tabs mit Alkyl-PEG pH 10
darstellen.The concentration as a function of time was determined by means of fluorescence spectroscopy (excitation 334 nm, fluorescence emission 411 nm), using the autofluorescence of the polyaspartic acid thermally prepared from maleic anhydride and ammonium. Fig. 1 shows the amount of dissolved PSI's as a function of time, with the various curves
Figure imgb0001
Tabs with stearic acid at pH 8
Figure imgb0002
Tabs with stearic acid pH 10
Figure imgb0003
Tabs with alkyl PEG pH 8
Figure imgb0004
Tabs with alkyl PEG pH 10
represent.

Claims (12)

  1. Washing- or cleaning-active shaped bodies, characterized in that they comprise polysuccinimide (PSI) in combination with polyethylene glycols (PEG) and/or phosphoric acid.
  2. Compositions according to Claim 1, characterized in that they comprise PSI in combination with PEG.
  3. Compositions according to Claim 1, characterized in that they comprise PSI in combination with phosphoric acid.
  4. Compositions according to Claims 1 to 3, characterized in that PSI with an average molar weight of from 500 to 20 000 is used.
  5. Compositions according to Claims 1 to 4, characterized in that PEG is used in amounts of from 0.5 to 20% by weight.
  6. Compositions according to Claims 1 to 5, characterized in that phosphoric acid is used in amounts of from 0.5 to 25% by weight.
  7. Compositions according to Claim 1, characterized in that additional disintegrants are used.
  8. Compositions according to Claim 1, characterized in that they comprise further constituents as are customarily used in detergents or cleaners and water softeners.
  9. Process for the preparation of washing- or cleaning-active shaped bodies comprising PSI and PEG and/or phosphoric acid, characterized in that the PSI is firstly mixed with PEG and/or with phosphoric acid before these are mixed with the optional additional constituents and compressed to give the shaped bodies, preferably tablets.
  10. Use of PSI in combination with PEG and/or phosphoric acid in washing- or cleaning-active shaped bodies.
  11. Use of a detergent shaped body according to any of Claims 1 to 8 in domestic washing machines.
  12. Washing process using a shaped body according to any of Claims 1 to 8, characterized in that the shaped body is introduced into the wash liquor via the dispensing device of the domestic washing machine.
EP04013587A 2003-06-20 2004-06-09 Shaped bodies having detergent or cleaning action for use in a household Expired - Lifetime EP1489160B1 (en)

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US3052655A (en) * 1958-08-01 1962-09-04 Sidney W Fox Thermal polymerization of amino acid mixtures containing aspartic acid or a thermal precursor of aspartic acid
US3846380A (en) * 1972-10-31 1974-11-05 M Teranishi Polyamino acid derivatives and compositions containing same
DE3626672A1 (en) * 1986-08-07 1988-02-11 Bayer Ag POLYASPARAGINAMID ACID
US4971714A (en) * 1988-11-30 1990-11-20 Ecolab Inc. Detersive system with an improved hardness ion complexing agent
US4911856A (en) * 1988-11-30 1990-03-27 Ecolab Inc. Low acid, soluble salt containing aqueous-organic softening agents for detersive systems
US5051401A (en) * 1989-04-07 1991-09-24 University Of South Alabama Inhibition of mineral deposition by phosphorylated and related polyanionic peptides
DE4010533A1 (en) * 1990-04-02 1991-10-10 Henkel Kgaa Prodn. of high-density detergent granules
DK0486592T3 (en) * 1989-08-09 1994-07-18 Henkel Kgaa Preparation of compacted granules for detergents
GB9114184D0 (en) * 1991-07-01 1991-08-21 Unilever Plc Detergent composition
US5219952A (en) * 1992-09-18 1993-06-15 Donlar Corporation Production of high molecular weight polysuccinimide and high molecular weight polyaspartic acid from maleic anhydride and ammonia
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DE4429550A1 (en) * 1994-08-19 1996-02-22 Henkel Kgaa Process for the production of detergent tablets
GB9422924D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
DE19710254A1 (en) * 1997-03-13 1998-09-17 Henkel Kgaa Shaped or active cleaning moldings for household use
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DE10124903A1 (en) * 2001-05-22 2002-11-28 Bayer Ag Thixotropic dispersions of polysuccinimide and their application
JP2004537627A (en) * 2001-08-03 2004-12-16 ザ プロクター アンド ギャンブル カンパニー Polyaspartate derivatives for use in detergent compositions

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