EP1489160A1 - Corps moules a action detergente ou nettoyante a usage menager - Google Patents

Corps moules a action detergente ou nettoyante a usage menager Download PDF

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Publication number
EP1489160A1
EP1489160A1 EP04013587A EP04013587A EP1489160A1 EP 1489160 A1 EP1489160 A1 EP 1489160A1 EP 04013587 A EP04013587 A EP 04013587A EP 04013587 A EP04013587 A EP 04013587A EP 1489160 A1 EP1489160 A1 EP 1489160A1
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EP
European Patent Office
Prior art keywords
psi
peg
phosphoric acid
washing
agent according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP04013587A
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German (de)
English (en)
Other versions
EP1489160B1 (fr
Inventor
Thomas Dr. Klein
Alfred Dr. Mitschker
Holger Dr. Schmidt
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.)
Lanxess Deutschland GmbH
Original Assignee
Bayer Chemicals AG
Lanxess Deutschland GmbH
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.)
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Publication of EP1489160A1 publication Critical patent/EP1489160A1/fr
Application granted granted Critical
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Anticipated expiration legal-status Critical
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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
    • C11D3/02—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 tablets, primarily tablets such as Detergent tablets, dishwasher tablets, stain remover 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 the production of these moldings and their use.
  • Shaped or active cleaning moldings in particular tablets, have powdery form A number of advantages, such as advantageous handling, simple Dosage and low need for packaging volumes.
  • advantages arise in that to achieve sufficient dimensional and fracture resistance when pressing of the powdery components, relatively high pressures must be applied. Due to the high compression, tablets of this type often have insufficient disintegration and Dissolving properties when used, whereby the active substance in the washing or Detergent is released too slowly and the risk of residue formation in particular on textiles after washing.
  • polysuccinimide In the case of the use of polysuccinimide (PSI), its extremely slow aggravates Solubility in water is added, which is why it was only used in slow-release applications in the past was used (see DE-A 11 01 671).
  • polysuccinimide is an ideal component of washing or cleaning active moldings, since it is the dispersant in contact with alkali Forms polyaspartate.
  • the big advantage of polysuccinimide is its very low hygroscopy, because functional groups forming ionic bridges or hydrogen bonds absence. Thus the admixing of hygroscopicity reducing substances such as hydrophobic modified silicon dioxide or magnesium stearate avoidable.
  • Partially hydrolyzed PSI such as It is obtained by reacting PSI with water or NaOH in sub-stoichiometric megnen ( on succinimide units) is in the middle in terms of hygroscopicity Sodium polyaspartate and PSI and can be a compromise for washing and cleaning active moldings be between the requirements of quick solubility and hygroscopicity.
  • partially hydrolyzed PSI is soluble in water much faster than unchanged PSI.
  • At least the particles which contain surfactants and builders are with a solution or dispersion of a binder / disintegrant, in particular polyethylene glycol, envelops.
  • binders / disintegrants are again known disintegrants, for example Starches and starch derivatives, commercially available cellulose derivatives such as cross-linked or modified cellulose, microcrystalline cellulose fibers, cross-linked polyvinylpyrrolidones, Layered silicates etc.
  • the proposed solutions contribute to one in the detergent and cleaning agent sector Improve the disintegration properties of washing or cleaning active tablets.
  • the improvement achieved is not sufficient.
  • the share in sticky organic substances in the tablets, for example on anionic and / or non-ionic surfactants or one of the ingredients itself, as in the case of PSI only increases very much is poorly soluble in water, these solutions are not very helpful.
  • This is one of the Reasons why there are no detergent tablets on the market based on PSI are built and meet the high demands of the consumer.
  • Dishwashing detergents and detergent additives often have tablets sufficient breaking strength does not reveal the sufficiently high rate of decay.
  • the acceleration of the disintegration and dissolution rates of Be an advantage, especially for phases that contain active ingredients at the beginning of the cleaning process or should act at lower temperatures, as in the present case, the PSI.
  • the object of the invention was to provide washing or cleaning active molded articles which include polysuccinimide (PSI) and which include the above Do not have disadvantages. Likewise, there should be a process for making these improved washers cleaning-active moldings based on PSI are provided.
  • PSI polysuccinimide
  • the invention is therefore in a first embodiment, a wash or cleaning-active molded body containing PSI and polyethylene glycol and / or phosphoric acid.
  • a wash or cleaning-active molded body containing PSI and polyethylene glycol and / or phosphoric acid.
  • the agents according to the invention in combination with PEG.
  • the agents according to the invention contain PSI and phosphoric acid.
  • shaped articles which are active in washing or cleaning understand is. These are primarily cylindrical configurations or Tablets used as detergents, dishwashing detergents, bleach (stain salts), if necessary but also as a pretreatment agent, for example as a water softener or bleach can be used.
  • shaped body is not based on the tablet form limited. In principle, any spatial form is possible, which may include the starting materials can be forced due to an outer container. Cylindrical bodies can have a height that is less than or greater than or equal to the diameter of the base is.
  • an angular one for example a rectangular one, in particular one, is also conceivable square, but also a diamond-shaped or trapezoidal, round or oval base of the shaped body.
  • Other configurations include triangular or more than quadrangular Base areas of the molded body.
  • the molded body directly by means of a metering device to put into the aqueous liquor of a mechanical process; it is rather also possible that or the moldings in the induction rings of commercial household machines, in particular of the washing machines. Accordingly, the spatial shape of the molded body in one preferred embodiment of the invention in its dimensions of the induction chamber more commercially available Household machines adjusted.
  • the shaped body has a plate-like or plate-like structure with alternately thick long and / or thin short segments, so that individual segments from this "bolt" at the predetermined breaking points, which represent the short thin segments, canceled and entered into the machine or the induction chamber of the machine can.
  • This principle of the "bar-shaped” means can also be used in other geometric Shapes, for example vertical triangles, only on one of their sides are longitudinally connected to each other, can be realized.
  • homogeneous or heterogeneous moldings 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 tablets, in particular the tablets is preferably 15 to 60 g and in particular 25 to 40 g per tablet or tablet; the consistency of the shaped bodies or tablets, however, usually has values above 1 kg / dm 3 , preferably from 1.1 to 1.4 kg / dm 3 .
  • the water hardness range or the level of contamination 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 around 10 mm.
  • a homogeneous molded body is understood to mean those in which the ingredients of Shaped body are homogeneously distributed. Accordingly, under heterogeneous shaped bodies understood those that do not have a homogeneous distribution of their ingredients. Heterogeneous molded body can be produced, for example, in that the various ingredients are not to be molded into a single molded body, but into one molded body that has several Layers, i.e. has at least two layers. It is also possible that this different layers have different disintegration and dissolution rates. From this This may result in advantageous performance properties of the molded articles.
  • ingredients are contained in the moldings, which are mutually negative affect, so it is possible that the one component in the faster disintegrating and faster integrate soluble layer and the other component into a slower disintegrating layer to incorporate so that the first component can work with a lead time or has already reacted when the second component goes into solution.
  • the layer structure of the moldings can take place in stacks, whereby a dissolution process of the inner layer (s) on the edges of the Shaped body takes place when the outer layers have not yet completely dissolved or have crumbled; but it can also completely encase the inner layer (s) by the layers lying further outside can be reached, which leads to the prevention of premature Solution of components of the inner layer (s) leads.
  • a tablet consists of at least three layers, ie two outer and at least one inner layer, wherein a peroxide bleach is contained in at least one of the inner layers, while in the stack-shaped tablet the two outer layers and in the case of the shell-shaped tablet the outermost layers, however, are free of peroxide bleach. It is also possible to use peroxide bleach and optionally existing bleach activators or bleach catalysts and / or Separate enzymes spatially in a tablet or tablet. Such configurations have the advantage that even in cases where the detergent or Bleach tablets or the detergent or bleach tablets in direct contact added to the textiles in the washing machine or hand basin, none To fear stains ("spotting") by bleaching agents and the like on the textiles are.
  • 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 known from DE-A 101 01 671.
  • PSI in the sense of the present invention refers to PSI itself, its copolymers, Part hydrolyzates or hydrolyzates understood.
  • Partial hydrolyzates in the sense of the present Invention are polysuccinimides, the polymer building blocks of which are partially converted into aspartate units have been, that is, copolymers of succinimide units and Aspartate. These partial hydrolyzates can also be in spray-granulated form.
  • PSI can be produced on an industrial scale by thermal polymerization of maleic anhydride and ammonia or derivatives thereof (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-A 5,051,401) optionally in the presence of acidic catalysts / solvents (US Pat. No. 3,052,655).
  • PSI falls as a polymer with an average molecular weight of 500 to 20,000, preferably 3,000 to 5,000.
  • Polysuccinimide is a chemical precursor to polyaspartic acid to which it slowly hydrolyzes with water. The pH of it The resulting solution is between pH 1 to 4, preferably 2 to 3. This does not only result in good stone-removing, but also the dispersing effect of PSI released polyaspartic acid against poorly soluble calcium salts or others poorly soluble substances to wear.
  • the resulting acidic solution leads due to its acidity also for the direct dissolution of possibly formed calcium carbonate incrustations.
  • the PSI to be used according to the invention is used in amounts of 0.01 to 20% by weight, preferably 0.1 up to 10 wt .-% and particularly preferably used in an amount of 0.5 to 5 wt .-%.
  • PEG polyethylene glycol
  • Suitable polyethylene glycols are those with a high degree of ethoxylation, for example Polyethylene glycols with a molecular weight of above 2000, preferably from 2000 to 12,000, particularly preferably from 2,000 to 6,000.
  • the invention Phosphoric acid to be used in an amount of 0.5 wt .-% to 25 wt .-%.
  • so-called explosives are suitable for this.
  • the explosive granules can in a conventional manner, for example by spray drying or superheated steam drying of aqueous preparation forms or by granulation, pelleting, Extrusion or roller compaction can be made.
  • aggregates are Invention non-surfactant active substances of detergents or cleaning agents, in particular Bleach activators and / or bleach catalysts, one is particularly preferred Disintegrant granulate, which as an additive tetraacetylethylenediamine (TAED) and / or contains other bleach activators of the common type.
  • TAED tetraacetylethylenediamine
  • Such disintegrant granules can advantageously can be produced by co-granulating the disintegrant with the aggregate.
  • Such a co-granulation can distribute the disintegrant in the shaped body, especially in the tablet, which in certain cases also becomes a Improvement in the rate of decay of the molded body can result.
  • washing and cleaning-active moldings according to the invention can be further Components, such as those commonly used in detergents or cleaning agents and water softeners are used included.
  • these include anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, inorganic and organic, water-soluble or water-insoluble Builder substances and cobuilders, bleaches, especially peroxide bleaches, however also active chlorine compounds, which are advantageously coated, bleach activators and Bleaching catalysts, enzymes and enzyme stabilizers, foam inhibitors, graying inhibitors, Substances that prevent the re-soiling of textiles, so-called soil repellents, as well as common inorganic salts such as sulfates and organic salts such as phosphonates, optical brighteners and colors and fragrances. In machine dishwashing detergents is additional the use of conventional silver protection agents is recommended.
  • the preferred anionic surfactants include both those based on petrochemicals, such as alkylbenzenesulfonates, alkanesulfonates or alkyl (ether) sulfates with odd chain lengths, and also those based on native ingredients, for example fatty alkyl sulfates or fatty alkyl (ether) sulfates, soaps, sulfosuccinates, etc. optionally in combination with small amounts of soap - alkylbenzenesulfonates and / or various chain cuts of alkyl sulfates or alkyl ether sulfates.
  • 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 moles of ethylene oxide per mole of alcohol and the corresponding C 11 -C 17 alcohols, in particular C 13 -C 15 alcohols, but also those Highly ethoxylated alcohols of the specified chain length, amine oxides, alkyl polyglycosides, polyhydroxy fatty acid amides, fatty acid methyl ester ethoxylates and gemini surfactants known in the detergent or cleaning agent sector.
  • conventional inorganic builders to be used according to the invention are conventional ones Phosphates, with preference for tripolyphosphate, zeolites, especially zeolite A, zeolite P, zeolite X and any mixtures of these play a role, but also Carbonates, bicarbonates as well as crystalline and amorphous silicates with secondary washing ability into consideration.
  • the usual cobuilders include (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 knows the organic cobuilders which can be used and their amounts from numerous publications in the field of detergents and cleaning agents.
  • peroxide bleaches such as perborate or Percarbonate
  • bleach activators and bleach catalysts especially in the field of dishwashing detergents but also those that are already continuing Active chlorine compounds used above.
  • the enzymes include not only proteases but also lipases, amylases, cellulases and Peroxidases and any combination of these enzymes are of particular interest.
  • anionic surfactant-containing compounds used which different anionic surfactants - for example alkyl sulfates and alkylbenzenesulfonates and / or soap or else alkyl sulfates and sulfonated fatty acid glycerol esters - and / or Anionic surfactants in combination with nonionic surfactants, for example various alkyl sulfates Chain length, optionally also several types of alkyl sulfates with different Chain sections in combination with ethoxylated alcohols and / or other above contain nonionic surfactants.
  • anionic and nonionic Surfactants are mainly contained in two different compounds.
  • Powdering agents to be used according to the invention as in the case of Disintegrant granules, especially finely divided zeolites, silicas, sulfates, calcium stearates, Phosphates and / or acetates into consideration.
  • Disintegrant granules especially finely divided zeolites, silicas, sulfates, calcium stearates, Phosphates and / or acetates into consideration.
  • a preferred embodiment of the invention Make sure that dust and particles smaller than 0.2 mm before mixing with the Disintegrant granules are separated as completely as possible.
  • the PSI-containing molded articles according to the invention have PEG and / or Phosphoric acid has excellent disintegration properties and therefore enables its use from PSI. This can be done, for example, under critical conditions in a conventional household washing machine (Use directly in the wash liquor using a conventional dosing device, Delicates program or colored laundry, washing temperature maximum 40 ° C) or in one Beaker can be tested at a washing temperature of 25 ° C.
  • the dissolution behavior of the PSI-containing wash-active molded bodies was determined using the Fluorescence spectroscopy examined. So shows an aqueous solution of the thermally produced Polyaspartic acid after excitation with UV light with a maximum at 334 nm one Fluorescence emission at 411 nm (maximum).
  • a washing process is therefore claimed, wherein the molded article containing PSI and PEG and / or phosphoric acid via the induction device the household washing machine is introduced into the wash liquor.
  • the drying and granulation took place in a laboratory fluidized bed granulator (for example GPCG3.1 from Inprotec AG) under the conditions given in the table. After about 30 minutes each was interrupted and the coverings were removed from the wall and floor and, if necessary, ground. The rest of the solution / suspension was then sprayed, trying to keep the product temperature as low as possible. The materials obtained were sieved through a 1 mm sieve to remove very large agglomerates. The granulation was good in all experiments, but a lot of dust was also generated, which suggests that the material dries quickly. Free-flowing materials were obtained which consisted of hard and brittle particles, the majority of which were smaller than 0.5 mm.
  • the bulk density was between 400 and 480 g / l, which is partly due to the high dust content.
  • laboratory tests attempt Degree of ring opening% NaOH amount g PH value Supply air temperature. ° C Ablufttemp. ° C Ferntemp. ° 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
  • the partial hydrolyzates react neutral to acidic after granulation (product V3 e.g. produced in 4% solution in water pH 6.5).
  • Compresses of PSI and stearic acid were used for the dissolution behavior PSI and alkyl polyethylene glycols (7-10 EO; 60:40) compared.
  • the latter decay (if manufactured with low pressure) in minutes in an aqueous dispersion in which PSI quickly resolves.
  • the rate of dissolution is especially in alkaline environments, such as typical for detergent formulations, fast.
  • Fig. 1 shows the amount of PSI's dissolved as a function of time, with the different 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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  • 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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP04013587A 2003-06-20 2004-06-09 Corps moules a action detergente ou nettoyante a usage menager Expired - Lifetime EP1489160B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10327682 2003-06-20
DE10327682A DE10327682A1 (de) 2003-06-20 2003-06-20 Wasch- oder reinigungsaktive Formkörper für den Gebrauch im Haushalt

Publications (2)

Publication Number Publication Date
EP1489160A1 true EP1489160A1 (fr) 2004-12-22
EP1489160B1 EP1489160B1 (fr) 2006-10-25

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EP04013587A Expired - Lifetime EP1489160B1 (fr) 2003-06-20 2004-06-09 Corps moules a action detergente ou nettoyante a usage menager

Country Status (7)

Country Link
US (1) US20040259756A1 (fr)
EP (1) EP1489160B1 (fr)
AT (1) ATE343624T1 (fr)
BR (1) BRPI0401972A (fr)
CA (1) CA2471354A1 (fr)
DE (2) DE10327682A1 (fr)
MX (1) MXPA04005922A (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202006002452U1 (de) * 2006-02-16 2006-05-24 Lanxess Deutschland Gmbh Formkörper für den Sanitärbereich

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002016731A2 (fr) * 2000-08-25 2002-02-28 Bayer Aktiengesellschaft Procede de conditionnement de systemes d'eaux stagnantes et d'eaux courantes
EP1260539A1 (fr) * 2001-05-22 2002-11-27 Bayer Ag Dispersions thixotropes contenant du polysuccinimide et leur utilisation
WO2003014193A1 (fr) * 2001-08-03 2003-02-20 The Procter & Gamble Company Derives de polyaspartate destines a etre utilises dans des compositions detergentes

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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 (de) * 1986-08-07 1988-02-11 Bayer Ag Polyasparaginamidsaeure
US4911856A (en) * 1988-11-30 1990-03-27 Ecolab Inc. Low acid, soluble salt containing aqueous-organic softening agents for detersive systems
US4971714A (en) * 1988-11-30 1990-11-20 Ecolab Inc. Detersive system with an improved hardness ion complexing agent
US5051401A (en) * 1989-04-07 1991-09-24 University Of South Alabama Inhibition of mineral deposition by phosphorylated and related polyanionic peptides
DE4010533A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Tablettierte wasch- und/oder reinigungsmittel fuer haushalt und gewerbe und verfahren zu ihrer herstellung
KR927003783A (ko) * 1989-08-09 1992-12-18 게오르그 차이트 세제용 압축과립의 제조방법
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
DE4322410A1 (de) * 1993-07-06 1995-01-12 Bayer Ag Verfahren zur Herstellung von Polysuccinimid und Polyasparaginsäure
DE4429550A1 (de) * 1994-08-19 1996-02-22 Henkel Kgaa Verfahren zur Herstellung von Wasch- oder Reinigungsmitteltabletten
GB9422924D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions
DE19710254A1 (de) * 1997-03-13 1998-09-17 Henkel Kgaa Wasch- oder reinigungsaktive Formkörper für den Gebrauch im Haushalt

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002016731A2 (fr) * 2000-08-25 2002-02-28 Bayer Aktiengesellschaft Procede de conditionnement de systemes d'eaux stagnantes et d'eaux courantes
DE10101671A1 (de) * 2000-08-25 2002-03-14 Bayer Ag Verfahren zur Konditionierung stehender und fließender Wassersysteme
EP1260539A1 (fr) * 2001-05-22 2002-11-27 Bayer Ag Dispersions thixotropes contenant du polysuccinimide et leur utilisation
WO2003014193A1 (fr) * 2001-08-03 2003-02-20 The Procter & Gamble Company Derives de polyaspartate destines a etre utilises dans des compositions detergentes

Also Published As

Publication number Publication date
DE502004001838D1 (de) 2006-12-07
MXPA04005922A (es) 2005-01-13
EP1489160B1 (fr) 2006-10-25
CA2471354A1 (fr) 2004-12-20
US20040259756A1 (en) 2004-12-23
ATE343624T1 (de) 2006-11-15
DE10327682A1 (de) 2005-01-05
BRPI0401972A (pt) 2005-01-25

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