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EP1489160B1 - 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
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
Authority
EP
European Patent Office
Prior art keywords
psi
peg
washing
phosphoric acid
compositions 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.)
Expired - Lifetime
Application number
EP04013587A
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German (de)
English (en)
Other versions
EP1489160A1 (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
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.)
Filing date
Publication date
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Publication of EP1489160A1 publication Critical patent/EP1489160A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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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  • 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)

Claims (12)

  1. Corps moulés à action détergente ou nettoyante, caractérisés en ce qu'ils comprennent du polysuccinimide (PSI) en combinaison avec des polyéthylèneglycols (PEG) et/ou de l'acide phosphorique.
  2. Compositions selon la revendication 1, caractérisées en ce qu'elles comprennent du PSI en combinaison avec du PEG.
  3. Compositions selon la revendication 1, caractérisées en ce qu'elles comprennent du PSI en combinaison avec de l'acide phosphorique.
  4. Compositions selon les revendications 1 à 3, caractérisées en ce que l'on utilise du PSI présentant un poids moléculaire moyen de 500 à 20 000.
  5. Compositions selon les revendications 1 à 4, caractérisées en ce que l'on utilise du PEG en quantités de 0,5 à 20 % en poids.
  6. Compositions selon les revendications 1 à 5, caractérisées en ce que l'on utilise de l'acide phosphorique en quantités de 0,5 à 25 % en poids.
  7. Compositions selon la revendication 1, caractérisée en ce que l'on utilise des agents de désintégration supplémentaires.
  8. Compositions selon la revendication 1, caractérisées en ce qu'elles comprennent des constituants supplémentaires, tels qu'ils sont habituellement utilisés dans des détergents ou agents nettoyants et des adoucisseurs d'eau.
  9. Procédé de production de corps moulés à action détergente ou nettoyante comprenant du PSI et du PEG et/ou de l'acide phosphorique, caractérisé en ce que le PSI est d'abord mélangé avec du PEG et/ou avec de l'acide phosphorique, avant que ceux-ci soient mélangés avec les constituants supplémentaires éventuels et compressés pour donner lieu aux corps moulés, de préférence des tablettes.
  10. Utilisation de PSI en combinaison avec du PEG et/ou de l'acide phosphorique dans des corps moulés à action détergente ou nettoyante.
  11. Utilisation d'un corps moulé détergent selon l'une quelconque des revendications 1 à 8 dans des machines à laver domestiques.
  12. Procédé de lavage employant un corps moulé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le corps moulé est introduit dans la liqueur de lavage par l'intermédiaire du dispositif de distribution de la machine à laver domestique.
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
DE10327682A DE10327682A1 (de) 2003-06-20 2003-06-20 Wasch- oder reinigungsaktive Formkörper für den Gebrauch im Haushalt
DE10327682 2003-06-20

Publications (2)

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

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE59006160D1 (de) * 1989-08-09 1994-07-21 Henkel Kgaa Herstellung verdichteter granulate für waschmittel.
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
DE10101671A1 (de) * 2000-08-25 2002-03-14 Bayer Ag Verfahren zur Konditionierung stehender und fließender Wassersysteme
DE10124903A1 (de) * 2001-05-22 2002-11-28 Bayer Ag Thixotrope Dispersionen von Polysuccinimid und deren Anwendung
CA2451368A1 (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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Publication number Publication date
DE502004001838D1 (de) 2006-12-07
MXPA04005922A (es) 2005-01-13
ATE343624T1 (de) 2006-11-15
DE10327682A1 (de) 2005-01-05
EP1489160A1 (fr) 2004-12-22
CA2471354A1 (fr) 2004-12-20
BRPI0401972A (pt) 2005-01-25
US20040259756A1 (en) 2004-12-23

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