EP1036839A2 - Tablets and particulate detergents comprising cross-linked polyvinylpyrrolidone and its use - Google Patents

Tablets and particulate detergents comprising cross-linked polyvinylpyrrolidone and its use Download PDF

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Publication number
EP1036839A2
EP1036839A2 EP00103131A EP00103131A EP1036839A2 EP 1036839 A2 EP1036839 A2 EP 1036839A2 EP 00103131 A EP00103131 A EP 00103131A EP 00103131 A EP00103131 A EP 00103131A EP 1036839 A2 EP1036839 A2 EP 1036839A2
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Prior art keywords
cross
particles
compact
grain size
detergents
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EP00103131A
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German (de)
French (fr)
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EP1036839A3 (en
Inventor
Werner Dr. Bertleff
Folker Dr. Ruchatz
Richard Dr. Baur
Robert Heinz
Peter Palm
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the invention relates to the use of cross-linked polyvinylpyrrolidone as an addition to compact, particulate washing and Detergents to increase their rate of decay when brought together with water, the particles of the cross-linked Polyvinylpyrrolidons with a grain size of 50 to 400 ⁇ m have a method for producing the compact, particulate Detergents and cleaning agents, as well as the compact, particulate Detergents and cleaning agents themselves.
  • Compact detergent and cleaning agent formulations are included Help different agglomeration, compacting or Tableting technologies.
  • washing and Compact detergent products for example in the form from tablets, it is difficult to balance between sufficient strength and sufficient rapid dissolution or produce rapid disintegration when exposed to water.
  • detergent tablets must be placed in the dispenser be dosed into the washing machine when brought together with Water within a period of less than a minute disintegrate.
  • With a slight degree of compaction of detergent tablets becomes a satisfactory rate of decay achieved in the application, but often not the desired one Fracture hardness or abrasion resistance.
  • So made Tablets have a low breaking strength and tend to to crumble and break during transport.
  • the compact detergents and cleaning agents produced in this way show an increased, but not yet sufficient high decay rate, especially with compact ones Detergents and cleaning agents are used to increase the shape and Breaking strength were compressed with higher compression pressures. Furthermore, the compact washing and washing machines produced in this way Detergent has the disadvantage that the disintegrant before compacting in a complex process step into one granular form must be transferred.
  • the invention is therefore based on the object of providing additives the decay rate of compact, further increase particulate detergents and cleaning agents and that do not have the disadvantages mentioned above.
  • cross-linked polyvinylpyrrolidone as an additive to compact, particulate Detergents and cleaning agents to increase their rate of decay when brought together with water
  • the Particles of cross-linked polyvinylpyrrolidone have a grain size have from 50 to 400 microns.
  • compact, particulate detergents and cleaning agents are to be understood as washing or cleaning-active moldings, in particular tablets such as detergent tablets, dishwasher tablets, bleach tablets, stain remover tablets or water softening tablets, in particular laundry detergent tablets for laundry use in the household, in particular for machine use.
  • the term Shaped body is not limited to the tablet shape. In principle, any spatial shape, such as tablets, spheres, strands, rings, bars or scales, is possible, which can be imposed on the starting materials if necessary due to an outer container.
  • Crosslinked polyvinylpyrrolidone is preferably the crosslinked polyvinylpyrrolidone used as a tablet disintegrant in the pharmaceutical industry, such as, for example, Kollidon CL (R) or Luvicross (R) (trade name of BASF-Aktiengesellschaft, Ludwigshafen, see Volker Bühler, Kollidon - Polyvinylpyrrolidone for the pharmaceutical industry, BASF August 1993, p. 156 f.) Understood.
  • Kollidon CL R
  • Luvicross Luvicross
  • the particles of the cross-linked polyvinylpyrrolidone used have a grain size of 50 to 400 microns, preferably 80 to 300 ⁇ m.
  • cross-linked is particularly preferred Polyvinylpyrrolidone
  • the particles of the cross-linked Polyvinyl pyrrolidones with a grain size of 50 to 400 ⁇ m, preferably 80 to 300 ⁇ m, and at least 10% by weight, preferably 15% by weight, particularly preferably 25% by weight of the particles Have grain size less than 200 microns.
  • this grain size distribution which, in a manner known per se, with a broad grain size distribution, by polymerization such as popcorn polymerization and drying producible solid polyvinylpyrrolidone (Kollidon CL® or Luvicross®) directly and without further granulation steps by appropriate classification, such as separated by sieving or sifting and so the grain size distribution set. Drying takes place in a manner known per se Way, for example by roller drying.
  • polymerization such as popcorn polymerization and drying producible solid polyvinylpyrrolidone (Kollidon CL® or Luvicross®) directly and without further granulation steps by appropriate classification, such as separated by sieving or sifting and so the grain size distribution set. Drying takes place in a manner known per se Way, for example by roller drying.
  • the invention further relates to compact, particulate washing and Detergent, crosslinking the aforementioned Polyvinylpyrrolidone in amounts of 0.5 to 20% by weight, preferably 0.5 to 10% by weight, particularly preferably 0.5 to 5 wt .-%, to increase their rate of decay at Bring together with water included.
  • the particles of cross-linked polyvinylpyrrolidones according to their preferred Use a grain size of 50 to 400 microns and at least 10% by weight of the particles have a grain size of less than 200 ⁇ m.
  • compact, particulate detergents and cleaning agents have been developed already explained above.
  • Preferred compact, particulate Detergents and cleaning agents are molded articles that are suitable for washing suitable for laundry, i.e. compact, particulate washing and Cleaning agents which, in addition to the use of cross-linked polyvinylpyrrolidone the usual ingredients of Detergents for laundry included.
  • the compact, particulate detergents and cleaning agents according to the invention are produced in a manner known per se by informing, in particular by compacting or compacting, preferably by pressing the powdery constituents (crosslinked polyvinylpyrrolidone as disintegrant and usual ingredients of washing or cleaning agents, bleaching agents and water softeners) Tableting: state of the art ", S ⁇ FW-Journal, 1996, 122nd year., Pp. 1016-1021).
  • Common ingredients of compact, particulate laundry and Cleaning agents are, for example, ionic, nonionic, cationic, amphoteric and zwitterionic surfactants, inorganic and organic, water-soluble or water-insoluble builder substances and cobuilders, bleaching agents, in particular peroxy bleaching agents, but also active chlorine compounds, which advantageously are coated, bleach activators and bleach catalysts, Enzymes and enzyme stabilizers, foam inhibitors, Graying inhibitors, color transfer inhibitors, optical Brighteners, substances that re-soiling textiles prevent so-called soil repellents, as well as common inorganic Salts such as sulfates and organic salts such as phosphonates, optical brighteners, dyes and fragrances or corrosion inhibitors.
  • ionic, nonionic, cationic, amphoteric and zwitterionic surfactants inorganic and organic, water-soluble or water-insoluble builder substances and cobuilders
  • bleaching agents in particular peroxy bleaching agents, but also active chlorine compounds,
  • Preferred detergents are so-called compact detergents as ingredients at least one surfactant and at least one Builder included.
  • Detergent and cleaning agent is the above-mentioned cross-linked Polyvinylpyrrolidone, preferably in amounts from 0.5 to 20% by weight, particularly preferably 0.5 to 10% by weight, very particularly particularly preferably 0.5 to 5% by weight, based on the weight of the washing and cleaning-active molded body produced, the powdery common ingredients of washing or cleaning agents, Bleaches and water softeners or their powdered form Precursors or sub-components to increase the rate of decay before the final compaction or Tableting step added.
  • the powdery usual ones Ingredients of washing or cleaning agents, bleaching agents and water softeners, the precursors or sub-components of which for example as powder, granules or in the form of strands in front. They have particle sizes in the range of, for example 200 ⁇ m to 3 mm, preferably 250 ⁇ m to 2 mm.
  • the powdery After mixing the powdery, usual ingredients of Detergents or cleaning agents, bleaches and water softeners or their subcomponents with the invention using cross-linked polyvinylpyrrolidone, if necessary after further mixing steps, processing the mixture to aggregated, compact shaped bodies while increasing the Density, e.g. by extruding or pressing the mixture.
  • the mixture can advantageously be so portion that e.g. Tablets or balls in one produces such a size that for a wash in one Washing machine, for example, only one to three tablets or Bullets are required.
  • the diameter of the molded body the made-up mixtures is, for example, 1 to 50 mm, preferably 2 to 35 mm.
  • crosslinked polyvinylpyrrolidone according to the invention as an addition to compact, particulate washing and Detergents leads to a significant increase in Disintegration speed of compact, particulate washing and Detergents when brought together with water. Also in the case of unbreakable, highly compressed molded bodies, disintegration takes less seconds. It doesn't just mean that possible the compact, particulate detergents and cleaning agents by means of a metering device directly into the aqueous To give a fleet of a mechanical process also the compact, particulate detergents and cleaning agents directly in the induction channel of commercially available household machines, especially the washing machines.
  • composition A bulk density approx. 770 g / l
  • crosslinked Polyvinylpyrrolidone Examples 1 and 2: grain size 80 to 400 ⁇ m, Examples 3 and 4: grain size less than 100 ⁇ m
  • Examples 1 and 2 grain size 80 to 400 ⁇ m
  • Examples 3 and 4 grain size less than 100 ⁇ m
  • the mixtures each contained 5% of the invention using cross-linked polyvinylpyrrolidone.
  • the tablets were tested for their dissolution behavior in water (see Table).
  • the hardness of the tablets was measured using a tablet tester from Kraemer, Darmstadt. The device measures that horizontal force required to take a tablet break.
  • a decay time tester from Erweka was used to determine the solubility.
  • the tablets were moved in a disintegration test basket with a sieve bottom in a tempered water bath (30 up and down movements per minute with a lifting height of 20 mm). The time was determined after which there was no residue on the sieve bottom. The results are shown in the table.
  • composition A Alkyl benzene sulfonate 8th Calico coconut soap 1.2
  • Nonionic surfactant 6 (1 mole of C 13 / C 15 fatty alcohol reacted with 7 moles of ethylene oxide Zeolite A 35 sodium 8th Sodium metasilicate x 5.5 H 2 O 6 Sodium citrate 4th Sodium percarbonate 18th Tetraacetylethylenediamine (TAED) 5
  • Complexing agent 0.3 ethylenediaminetetramethylenephosphonate
  • Other ingredients 2.5 fragments, foam attenuators, enzymes, optical brighteners
  • tablets of approx. 3 g and a diameter of 20 mm were produced from the powdered, granulated detergent A and tested for their dissolving behavior in water (see table).
  • the measurement values were determined analogously to Examples 1 to 4 Properties of detergent tablets example Detergent A with PVP of the grain size Pressing force in kN Pressure in MPa Breaking strength in N Dissolution behavior in minutes 1 80 to 400 ⁇ m 6.48 ⁇ 3 ⁇ 5 seconds 2nd 80 to 400 ⁇ m 29.41 12th ⁇ 10 seconds 3rd ⁇ 100 ⁇ m 5.98 ⁇ 3 30 minutes 4th ⁇ 100 ⁇ m 26.39 14 30 minutes Comparative Example 1 without the addition of PVP 4.09 13 8th > 30 minutes Comparative Example 2 without the addition of PVP 7.97 25th 11 > 30 minutes
  • the Particles have a grain size of 80 to 400 ⁇ m, a clear faster disintegration of the detergent tablets at significantly higher Breaking strength is achieved.

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

Abstract

Use is claimed of crosslinked polyvinyl pyrrolidone (PVP) particles, of size 50-400 mu , as additives for compacted particulate detergents to increase the disintegration rate when the detergent comes in contact with water. Independent claims are also included for: (i) compacted particulate detergent compositions containing 0.5-20 wt.% of the PVP additive particles of size 50-400 mu with at least 10 wt.% below 200 mu ; and (ii) production of such compositions containing the PVP disintegrating agent by mixing the PVP particles with powdered detergent ingredients and compacting the mixture.

Description

Die Erfindung betrifft die Verwendung von quervernetztem Polyvinylpyrrolidon als Zusatz zu kompakten, teilchenförmigen Wasch- und Reinigungsmitteln zur Erhöhung ihrer Zerfallsgeschwindigkeit beim Zusammenbringen mit Wasser, wobei die Partikel des quervernetzten Polyvinylpyrrolidons eine Korngröße von 50 bis 400 µm aufweisen, ein Verfahren zur Herstellung der kompakten, teilchenförmigen Wasch- und Reinigungsmittel, sowie die kompakten, teilchenförmige Wasch- und Reinigungsmittel selbst.The invention relates to the use of cross-linked polyvinylpyrrolidone as an addition to compact, particulate washing and Detergents to increase their rate of decay when brought together with water, the particles of the cross-linked Polyvinylpyrrolidons with a grain size of 50 to 400 µm have a method for producing the compact, particulate Detergents and cleaning agents, as well as the compact, particulate Detergents and cleaning agents themselves.

Kompakte Wasch- und Reinigungsmittelformulierungen werden mit Hilfe unterschiedlicher Agglomerierungs-, Kompaktierungs- oder Tablettierungstechnologien hergestellt. Im Fall von Wasch- und Reinigungsmittelkompaktprodukten, die beispielsweise in Form von Tabletten vorliegen, ist es schwierig, die Balance zwischen ausreichender Festigkeit und hinreichend rascher Auflösung bzw. raschem Zerfall bei der Einwirkung von Wasser herzustellen. So müssen beispielsweise Waschmitteltabletten, die in die Einspülkammer der Waschmaschine dosiert werden, beim Zusammenbringen mit Wasser innerhalb eines Zeitraums von weniger als einer Minute zerfallen. Bei einem leichten Kompaktierungsgrad von Waschmitteltabletten wird zwar eine zufriedenstellende Zerfallsgeschwindigkeit bei der Anwendung erreicht, jedoch oftmals nicht die gewünschte Bruchhärte bzw. Abriebfestigkeit. So hergestellte Tabletten weisen nur eine geringe Bruchfestigkeit auf und neigen zum Abbröckeln und zerbrechen beim Transport. Auf der anderen Seite führt ein zu starkes Kompaktieren oder Pressen bei der Herstellung von Waschmitteltabletten zu unbefriedigend langen Zerfalls- bzw. Auflösezeiten der Waschmitteltabletten bei der Anwendung.Compact detergent and cleaning agent formulations are included Help different agglomeration, compacting or Tableting technologies. In the case of washing and Compact detergent products, for example in the form from tablets, it is difficult to balance between sufficient strength and sufficient rapid dissolution or produce rapid disintegration when exposed to water. So For example, detergent tablets must be placed in the dispenser be dosed into the washing machine when brought together with Water within a period of less than a minute disintegrate. With a slight degree of compaction of detergent tablets becomes a satisfactory rate of decay achieved in the application, but often not the desired one Fracture hardness or abrasion resistance. So made Tablets have a low breaking strength and tend to to crumble and break during transport. On the other Too much compacting or pressing on the side Manufacture of detergent tablets too long Disintegration or dissolution times of the detergent tablets at Application.

Kompakte bzw. ultrakompakte Wasch- und Reinigungsmittel sind bekannt, vgl. EP-A-340013, EP-A-0518888, DE-A-19649560 und DE-A-19649565. Um die Lösegeschwindigkeit von teilchenförmigen Waschmittelformulierungen zu verbessern, verwendet man als löslichkeitserhöhende Zusätze beispielsweise Copolymerisate aus hydrophoben und hydrophilen Monomeren, z.B. Copolymerisate aus Styrol und Acrylsäure, vgl. WO-A-97/46657. Gemäß den Angaben der WO-A-97/46529 verwendet man zur Erhöhung der Lösegeschwindigkeit von teilchenförmigen Waschformulierungen beispielsweise Additionsprodukte von Ethylenoxid und/oder Propylenoxid an Polyole.Are compact or ultra-compact detergents and cleaning agents known, cf. EP-A-340013, EP-A-0518888, DE-A-19649560 and DE-A-19649565. At the rate of dissolution of particulate To improve detergent formulations is used as Solubility-increasing additives, for example copolymers hydrophobic and hydrophilic monomers, e.g. Copolymers Styrene and acrylic acid, cf. WO-A-97/46657. According to the information provided by the WO-A-97/46529 is used to increase the rate of dissolution of particulate washing formulations, for example Addition products of ethylene oxide and / or propylene oxide Polyols.

Aus der Technologie der pharmazeutischen Tablettenherstellung sind zahlreiche Möglichkeiten bekannt, Tabletten gewünschter Festigkeit und Zerfallszeit herzustellen. Als hauptsächlich wirksame Mechanismen, die den Zerfall von Tabletten bewirken, werden die Netzung, Kapillareffekte (Wicking) und Quellung beschrieben, vgl. Drug Development and Industrial Pharma, Band 6 (5) 511-536 (1980). Unter den beschriebenen Produkten, die zu einer verbesserten Löslichkeit von Tabletten führen, werden auch chemisch vernetzte, quellende Produkte wie mikrokristalline vernetzte Carboxymethylcellulose, vernetzte Na-Carboxymethylstärke oder vernetztes Polyvinylpyrrolidon (siehe auch Volker Bühler, Kollidon - Polyvinylpyrrolidone for the pharmaceutical industry, BASF August 1993, S. 156 f.) genannt.From the technology of pharmaceutical tablet production Numerous ways are known to make tablets more desirable Establish strength and disintegration time. As the main effective Mechanisms that cause tablet disintegration are the wetting, capillary effects (wicking) and swelling are described, see. Drug Development and Industrial Pharma, Volume 6 (5) 511-536 (1980). Among the products described that lead to improved Solubility of tablets can also be chemical cross-linked, swelling products such as micro-crystalline cross-linked Carboxymethyl cellulose, cross-linked Na carboxymethyl starch or cross-linked polyvinylpyrrolidone (see also Volker Bühler, Kollidon - Polyvinylpyrrolidone for the pharmaceutical industry, BASF August 1993, p. 156 f.).

Aufgrund des Anteils von nichtionischen Tensiden und anderen niedrigschmelzenden wachsartigen, plastisch verformbaren Massen in Waschmitteln ist der Zusatz von Tablettensprengmitteln, welche aus der Pharmazie bekannt sind, zu kompakten Wasch- und Reinigungsmitteln, speziell bei kompakten Waschmitteln zum Waschen von Wäsche selten erfolgreich.Due to the proportion of non-ionic surfactants and others low melting wax-like, plastically deformable masses in detergents is the addition of tablet disintegrants, which are known from pharmacy to compact detergents and cleaning agents, especially for compact detergents for washing of laundry rarely successful.

Es ist bekannt, daß kompakte Wasch- und Reinigungsmittel (wasch- und reinigungsaktive Formkörper) eine erhöhte Zerfallsgeschwindigkeit aufweisen, wenn sie Sprengmittel, welche aus der Pharmazie bekannt und in der Lage sind, die Porosität bzw. Kapillarität der Formkörper zu erhöhen und ein hohes Adsorptionsvermögen für Wasser besitzen, in einer speziellen, granulierten Form enthalten (DE 197 10 254 A1).It is known that compact washing and cleaning agents (washing and cleaning active moldings) an increased disintegration rate if they have explosives which are made of known to pharmacy and able to reduce porosity or Increase the capillarity of the moldings and a high adsorption capacity own for water, in a special, granulated Form included (DE 197 10 254 A1).

Die auf diese Weise hergestellten kompakten Wasch- und Reinigungsmittel zeigen zwar eine erhöhte, aber eine noch nicht ausreichend hohe Zerfallsgeschwindigkeit, insbesondere bei kompakten Wasch- und Reinigungsmitteln die, die zur Erhöhung der Form- und Bruchfestigkeit mit höheren Preßdrücken verdichtet wurden. Ferner weisen die auf diese Weise hergestellten kompakten Wasch- und Reinigungsmittel den Nachteil auf, daß das Sprengmittel vor der Kompaktierung in einem aufwendigen Verfahrensschritt in eine granulierte Form überführt werden muß.The compact detergents and cleaning agents produced in this way show an increased, but not yet sufficient high decay rate, especially with compact ones Detergents and cleaning agents are used to increase the shape and Breaking strength were compressed with higher compression pressures. Furthermore, the compact washing and washing machines produced in this way Detergent has the disadvantage that the disintegrant before compacting in a complex process step into one granular form must be transferred.

Der Erfindung liegt daher die Aufgabe zugrunde, Additive zur Verfügung zu stellen, die die Zerfallsgeschwindigkeit von kompakten, teilchenförmigen Wasch- und Reinigungsmitteln weiter erhöhen und die die vorstehend genannten Nachteile nicht aufweisen. The invention is therefore based on the object of providing additives the decay rate of compact, further increase particulate detergents and cleaning agents and that do not have the disadvantages mentioned above.

Die Aufgabe wird erfindungsgemäß gelöst mit der Verwendung von quervernetztem Polyvinylpyrrolidon als Zusatz zu kompakten, teilchenförmigen Wasch- und Reinigungsmitteln zur Erhöhung ihrer Zerfallsgeschwindigkeit beim Zusammenbringen mit Wasser, wobei die Partikel des quervernetzten Polyvinylpyrrolidons eine Korngröße von 50 bis 400 µm aufweisen.The object is achieved with the use of cross-linked polyvinylpyrrolidone as an additive to compact, particulate Detergents and cleaning agents to increase their rate of decay when brought together with water, the Particles of cross-linked polyvinylpyrrolidone have a grain size have from 50 to 400 microns.

Unter kompakten, teilchenförmigen Wasch- und Reinigungsmitteln werden erfindungsgemäß wasch- oder reinigungsaktive Formkörper, insbesondere Tabletten wie Waschmitteltabletten, Geschirrspülmitteltabletten, Bleichmitteltabletten, Fleckensalztabletten oder Wasserenthärtungstabletten, insbesondere Waschmitteltabletten für Wäsche für den Gebrauch im Haushalt, insbesondere für den maschinellen Gebrauch, verstanden. Der Begriff

Figure 00030001
Formkörper" ist nicht auf die Tablettenform beschränkt. Prinzipiell ist jede Raumform, wie beispielsweise Tabletten, Kugeln, Stränge, Ringe, Riegel oder Schuppen möglich, die den Ausgangsstoffen gegebenenfalls aufgrund eines äußeren Behältnisses aufgezwungen werden kann.According to the invention, compact, particulate detergents and cleaning agents are to be understood as washing or cleaning-active moldings, in particular tablets such as detergent tablets, dishwasher tablets, bleach tablets, stain remover tablets or water softening tablets, in particular laundry detergent tablets for laundry use in the household, in particular for machine use. The term
Figure 00030001
Shaped body "is not limited to the tablet shape. In principle, any spatial shape, such as tablets, spheres, strands, rings, bars or scales, is possible, which can be imposed on the starting materials if necessary due to an outer container.

Unter quervernetztem Polyvinylpyrrolidon wird vorzugsweise das als Tablettensprengmittel in der Pharmaindustrie verwendete quervernetzte Polyvinylpyrrolidon, wie beispielsweise Kollidon CL(R) oder Luvicross(R) (Handelsname der BASF-Aktiengesellschaft, Ludwigshafen, siehe Volker Bühler, Kollidon - Polyvinylpyrrolidone for the pharmaceutical industry, BASF August 1993, S. 156 f.) verstanden.Crosslinked polyvinylpyrrolidone is preferably the crosslinked polyvinylpyrrolidone used as a tablet disintegrant in the pharmaceutical industry, such as, for example, Kollidon CL (R) or Luvicross (R) (trade name of BASF-Aktiengesellschaft, Ludwigshafen, see Volker Bühler, Kollidon - Polyvinylpyrrolidone for the pharmaceutical industry, BASF August 1993, p. 156 f.) Understood.

Die Partikel des verwendeten, quervernetzten Polyvinylpyrrolidons weisen eine Korngröße von 50 bis 400 µm, vorzugsweise 80 bis 300 µm, auf.The particles of the cross-linked polyvinylpyrrolidone used have a grain size of 50 to 400 microns, preferably 80 to 300 µm.

Besonders bevorzugt ist die erfindungsgemäße Verwendung von quervernetztem Polyvinylpyrrolidon, wobei die Partikel des quervernetzten Polyvinylpyrrolidons eine Korngröße von 50 bis 400 µm, vorzugsweise 80 bis 300 µm, und mindestens 10 Gew.-%, vorzugsweise 15 Gew.-%, besonders bevorzugt 25 Gew.-% der Partikel eine Korngröße kleiner 200 µm aufweisen.The use of cross-linked is particularly preferred Polyvinylpyrrolidone, the particles of the cross-linked Polyvinyl pyrrolidones with a grain size of 50 to 400 μm, preferably 80 to 300 µm, and at least 10% by weight, preferably 15% by weight, particularly preferably 25% by weight of the particles Have grain size less than 200 microns.

Zur bevorzugten Herstellung dieser Korngrößenverteilung werden die, in an sich bekannter Weise mit breiter Korngrößenverteilung, durch Polymerisation, wie beispielsweise Popcorn-Polymerisation und Trocknung herstellbaren Polyvinylpyrrolidonfestkörper (Kollidon CL® oder Luvicross®) direkt und ohne weitere Granulierungsschritte durch entsprechendes Klassieren, wie beispielsweise durch Sieben oder Sichten getrennt und so die Korngrößenverteilung eingestellt. Die Trocknung erfolgt in an sich bekannter Weise, beispielsweise durch Walzentrocknung.For the preferred production of this grain size distribution which, in a manner known per se, with a broad grain size distribution, by polymerization such as popcorn polymerization and drying producible solid polyvinylpyrrolidone (Kollidon CL® or Luvicross®) directly and without further granulation steps by appropriate classification, such as separated by sieving or sifting and so the grain size distribution set. Drying takes place in a manner known per se Way, for example by roller drying.

Ferner betrifft die Erfindung kompakte, teilchenförmige Wasch- und Reinigungsmittel, wobei sie das vorstehend erwähnte quervernetzte Polyvinylpyrrolidon in Mengen von 0,5 bis 20 Gew.-%, vorzugsweise 0,5 bis 10 Gew.-%, besonders bevorzugt 0,5 bis 5 Gew.-%, zur Erhöhung ihrer Zerfallsgeschwindigkeit beim Zusammenbringen mit Wasser enthalten.The invention further relates to compact, particulate washing and Detergent, crosslinking the aforementioned Polyvinylpyrrolidone in amounts of 0.5 to 20% by weight, preferably 0.5 to 10% by weight, particularly preferably 0.5 to 5 wt .-%, to increase their rate of decay at Bring together with water included.

In einer bevorzugten Ausführungsform weisen die Partikel des quervernetzten Polyvinylpyrrolidons dabei entsprechend ihrer bevorzugten Verwendung eine Korngröße von 50 bis 400 µm und mindestens 10 Gew.-% der Partikel eine Korngröße kleiner 200 µm auf.In a preferred embodiment, the particles of cross-linked polyvinylpyrrolidones according to their preferred Use a grain size of 50 to 400 microns and at least 10% by weight of the particles have a grain size of less than 200 μm.

Kompakte, teilchenförmige Wasch- und Reinigungsmittel wurden bereits vorstehend erklärt. Bevorzugte kompakte, teilchenförmige Wasch- und Reinigungsmittel sind Formkörper, die sich zum Waschen von Wäsche eignen, also kompakte, teilchenförmige Wasch- und Reinigungsmittel, die neben der erfindungsgemäßen Verwendung von quervernetztem Polyvinylpyrrolidon die üblichen Inhaltsstoffe von Waschmitteln für Wäsche enthalten.Compact, particulate detergents and cleaning agents have been developed already explained above. Preferred compact, particulate Detergents and cleaning agents are molded articles that are suitable for washing suitable for laundry, i.e. compact, particulate washing and Cleaning agents which, in addition to the use of cross-linked polyvinylpyrrolidone the usual ingredients of Detergents for laundry included.

Die erfindungsgemäßen kompakten, teilchenförmige Wasch- und Reinigungsmittel werden in an sich bekannter Weise durch Informbringen, insbesondere durch Kompaktieren oder Verdichten, vorzugsweise durch Verpressen der pulverförmigen Bestandteile (Quervernetztes Polyvinylpyrrolidon als Sprengmittel und übliche Inhaltsstoffe von Wasch- oder Reinigungsmitteln, Bleichmitteln und Wasserenthärtern) hergestellt Tablettierung: Stand der Technik", SÖFW-Journal, 1996, 122. Jahrgang., S. 1016-1021).The compact, particulate detergents and cleaning agents according to the invention are produced in a manner known per se by informing, in particular by compacting or compacting, preferably by pressing the powdery constituents (crosslinked polyvinylpyrrolidone as disintegrant and usual ingredients of washing or cleaning agents, bleaching agents and water softeners) Tableting: state of the art ", SÖFW-Journal, 1996, 122nd year., Pp. 1016-1021).

Übliche Inhaltsstoffe von kompakten, teilchenförmigen Wasch- und Reinigungsmitteln sind beispielsweise ionische, nichtionische, kationische, amphotere und zwitterionische Tenside, anorganische und organische, wasserlösliche oder wasserunlösliche Buildersubstanzen und Cobuilder, Bleichmittel, insbesondere Peroxybleichmittel, aber auch Aktivchlorverbindungen, welche vorteilhafterweise umhüllt sind, Bleichaktivatoren und Bleichkatalysatoren, Enzyme und Enzymstabilisatoren, Schauminhibitoren, Vergrauungsinhibitoren, Farbübertragungsinhibitoren, optische Aufheller, Substanzen, welche das Wiederanschmutzen von Textilien verhindern, sogenannte soil repellents, sowie übliche anorganische Salze wie Sulfate und organische Salze wie Phosphonate, optische Aufheller, Farb- und Duftstoffe oder Korrosionsinhibitoren. Common ingredients of compact, particulate laundry and Cleaning agents are, for example, ionic, nonionic, cationic, amphoteric and zwitterionic surfactants, inorganic and organic, water-soluble or water-insoluble builder substances and cobuilders, bleaching agents, in particular peroxy bleaching agents, but also active chlorine compounds, which advantageously are coated, bleach activators and bleach catalysts, Enzymes and enzyme stabilizers, foam inhibitors, Graying inhibitors, color transfer inhibitors, optical Brighteners, substances that re-soiling textiles prevent so-called soil repellents, as well as common inorganic Salts such as sulfates and organic salts such as phosphonates, optical brighteners, dyes and fragrances or corrosion inhibitors.

Bevorzugte Waschmittel sind sogenannte Kompaktwaschmittel, die als Inhaltsstoffe mindestens ein Tensid und mindestens einen Builder enthalten.Preferred detergents are so-called compact detergents as ingredients at least one surfactant and at least one Builder included.

Zur Herstellung der erfindungsgemäßen kompakten, teilchenförmigen Wasch- und Reinigungsmittel wird das vorstehend erwähnte quervernetzte Polyvinylpyrrolidon, vorzugsweise in Mengen von 0,5 bis 20 Gew.-%, besonders bevorzugt 0,5 bis 10 Gew.-%, ganz besonders besonders bevorzugt 0,5 bis 5 Gew.-%, bezogen auf das Gewicht des hergestellten wasch- und reinigungsaktiven Formkörpers, den pulverigen üblichen Inhaltsstoffen von Wasch- oder Reinigungsmitteln, Bleichmitteln und Wasserenthärtern oder deren pulverförmigen Vorstufen bzw. Teilkomponenten zur Erhöhung der Zerfallsgeschwindigkeit vor dem abschließenden Kompaktierungs- oder Tablettierungsschritt zugesetzt. Die pulverigen, üblichen Inhaltsstoffe von Wasch- oder Reinigungsmitteln, Bleichmitteln und Wasserenthärtern, deren Vorstufen bzw. Teilkomponenten liegen beispielsweise als Pulver, Granulat oder in Form von Strängen vor. Sie haben Teilchengrößen in dem Bereich von beispielsweise 200 µm bis 3 mm, vorzugsweise 250 µm bis 2 mm.To produce the compact, particulate according to the invention Detergent and cleaning agent is the above-mentioned cross-linked Polyvinylpyrrolidone, preferably in amounts from 0.5 to 20% by weight, particularly preferably 0.5 to 10% by weight, very particularly particularly preferably 0.5 to 5% by weight, based on the weight of the washing and cleaning-active molded body produced, the powdery common ingredients of washing or cleaning agents, Bleaches and water softeners or their powdered form Precursors or sub-components to increase the rate of decay before the final compaction or Tableting step added. The powdery, usual ones Ingredients of washing or cleaning agents, bleaching agents and water softeners, the precursors or sub-components of which for example as powder, granules or in the form of strands in front. They have particle sizes in the range of, for example 200 µm to 3 mm, preferably 250 µm to 2 mm.

Nach dem Mischen der pulverigen, üblichen Inhaltsstoffe von Wasch- oder Reinigungsmitteln, Bleichmitteln und Wasserenthärtern bzw. ihrer Teilkomponenten mit dem erfindungsgemäß zu verwendenden quervernetzten Polyvinylpyrrolidon erfolgt, ggf. nach weiteren Mischschritten, eine Verarbeitung der Mischung zu aggregierten, kompakten Formkörpern unter Erhöhung der Dichte, z.B. durch Extrudieren oder Verpressen der Mischung. Man erhält so beispielsweise Tabletten, Kugeln, Stränge, Ringe oder Schuppen. Man kann die Mischung dabei vorteilhaft so portionieren, daß man z.B. Tabletten oder Kugeln in einer solchen Größe herstellt, daß für einen Waschgang in einer Waschmaschine beispielsweise nur ein bis drei Tabletten oder Kugeln erforderlich sind. Der Durchmesser der Formkörper aus den konfektionierten Mischungen beträgt beispielsweise 1 bis 50 mm, vorzugsweise 2 bis 35 mm.After mixing the powdery, usual ingredients of Detergents or cleaning agents, bleaches and water softeners or their subcomponents with the invention using cross-linked polyvinylpyrrolidone, if necessary after further mixing steps, processing the mixture to aggregated, compact shaped bodies while increasing the Density, e.g. by extruding or pressing the mixture. This gives, for example, tablets, balls, strands, rings or dandruff. The mixture can advantageously be so portion that e.g. Tablets or balls in one produces such a size that for a wash in one Washing machine, for example, only one to three tablets or Bullets are required. The diameter of the molded body the made-up mixtures is, for example, 1 to 50 mm, preferably 2 to 35 mm.

Die erfindungsgemäße Verwendung von quervernetztem Polyvinylpyrrolidon als Zusatz zu kompakten, teilchenförmigen Wasch- und Reinigungsmitteln führt zu einer beträchtlichen Steigerung der Zerfallsgeschwindigkeit von kompakten, teilchenförmigen Wasch- und Reinigungsmitteln beim Zusammenbringen mit Wasser. Auch bei bruchfesten, stark verdichteten Formkörpern wird innerhalb weniger Sekunden der Zerfall erreicht. Dadurch ist es nicht nur möglich die kompakten, teilchenförmigen Wasch- und Reinigungsmittel mittels einer Dosiervorrichtung direkt in die wäßrige Flotte eines maschinellen Verfahrens zu geben sonden auch die kompakten, teilchenförmigen Wasch- und Reinigungsmittel direkt in der Einspülrinne der handelsüblichen Haushaltsmaschinen, insbesondere der Waschgeräte, zu plazieren.The use of crosslinked polyvinylpyrrolidone according to the invention as an addition to compact, particulate washing and Detergents leads to a significant increase in Disintegration speed of compact, particulate washing and Detergents when brought together with water. Also in the case of unbreakable, highly compressed molded bodies, disintegration takes less seconds. It doesn't just mean that possible the compact, particulate detergents and cleaning agents by means of a metering device directly into the aqueous To give a fleet of a mechanical process also the compact, particulate detergents and cleaning agents directly in the induction channel of commercially available household machines, especially the washing machines.

Die nachstehenden Beispiele verdeutlichen die ErfindungThe following examples illustrate the invention

Beispiele 1 bis 4Examples 1 to 4

Aus einem pulverförmigen, granulierten Waschmittel der unten angegebenen Zusammensetzung A (Schüttdichte ca. 770 g/l) und vernetztem Polyvinylpyrrolidon (Beispiel 1 und 2: Korngröße 80 bis 400 µm, Beispiel 3 und 4: Korngröße kleiner 100 µm) wurden in einem Mischer homogene Gesamtmischungen hergestellt, die jeweils mit einer in der Technik üblichen Exzenterpresse (Fa. Korsch, Typ EK 0 DMS) unter den in der Tabelle angegebenen Bedingungen zu Tabletten von ca. 3 g (Durchmesser 20 mm) verpreßt wurden. Die Mischungen enthielten jeweils 5 % des erfindungsgemäß zu verwendenden quervernetzten Polyvinylpyrrolidons. Die Tabletten wurden bezüglich des Auflöseverhaltens in Wasser getestet (siehe Tabelle).From a powdered, granulated detergent the below specified composition A (bulk density approx. 770 g / l) and crosslinked Polyvinylpyrrolidone (Examples 1 and 2: grain size 80 to 400 µm, Examples 3 and 4: grain size less than 100 µm) were in a mixer made homogeneous total mixes, each with a conventional eccentric press (from Korsch, Type EK 0 DMS) under the conditions specified in the table were compressed into tablets of about 3 g (diameter 20 mm). The mixtures each contained 5% of the invention using cross-linked polyvinylpyrrolidone. The tablets were tested for their dissolution behavior in water (see Table).

Die Härte der Tabletten wurde mit Hilfe eines Tablettentestgeräts der Fa. Kraemer, Darmstadt, bestimmt. Das Gerät mißt die horizontale Kraft, die erforderlich ist, um eine Tablette zu zerbrechen.The hardness of the tablets was measured using a tablet tester from Kraemer, Darmstadt. The device measures that horizontal force required to take a tablet break.

Zur Bestimmung der Löslichkeit wurde ein Zerfallzeit-Testgerät der Fa. Erweka benutzt. Dazu wurden die Tabletten in einem Zerfalltestkorb mit Siebboden in einem temperierten Wasserbad bewegt (30 Auf- und Abwärts-Bewegungen pro Minute mit einer Hubhöhe von 20 mm). Man bestimmte die Zeit, nach der sich kein Rückstand mehr auf dem Siebboden befand. Die Ergebnisse sind in der Tabelle angegeben. Waschmittel der Zusammensetzung A (alle Angaben in Gew.-%) Alkylbenzolsulfonat 8 Kalikokosseife 1,2 Nichtionisches Tensid 6 (1 Mol C13/C15-Fettalkohol, umgesetzt mit 7 Mol Ethylenoxid Zeolith A 35 Natriumcarbonat 8 Natriummetasilikat x 5,5 H2O 6 Natriumcitrat 4 Natriumpercarbonat 18 Tetraacetylethylendiamin (TAED) 5 Komplexbildner 0,3 (Ethylendiamintetramethylenphosphonat) Copolymer Acrylsäure/Maleinsäure 70:30, Molmasse 70000 4 Natriumsulfat 3 Übrige Bestandteile 2,5 (Duftstoffe, Schaumdämpfer, Enzyme, opt. Aufheller) Schüttdichte ca. 770 g/l Teilchengröße ca. 700-1000 µm A decay time tester from Erweka was used to determine the solubility. For this purpose, the tablets were moved in a disintegration test basket with a sieve bottom in a tempered water bath (30 up and down movements per minute with a lifting height of 20 mm). The time was determined after which there was no residue on the sieve bottom. The results are shown in the table. Detergent of composition A (all figures in% by weight) Alkyl benzene sulfonate 8th Calico coconut soap 1.2 Nonionic surfactant 6 (1 mole of C 13 / C 15 fatty alcohol reacted with 7 moles of ethylene oxide Zeolite A 35 sodium 8th Sodium metasilicate x 5.5 H 2 O 6 Sodium citrate 4th Sodium percarbonate 18th Tetraacetylethylenediamine (TAED) 5 Complexing agent 0.3 (ethylenediaminetetramethylenephosphonate) Copolymer acrylic acid / maleic acid 70:30, molecular weight 70000 4th Sodium sulfate 3rd Other ingredients 2.5 (fragrances, foam attenuators, enzymes, optical brighteners) Bulk density approx. 770 g / l Particle size approx. 700-1000 µm

Vergeichsbeispiel 1 und 2Comparative Examples 1 and 2

Zu Vergleichszwecken wurden aus dem pulverförmigen, granulierten Waschmittel A Tabletten von ca. 3 g und einem Durchmesser von 20 mm hergestellt und bezüglich des Auflöseverhaltens in Wasser getestet (siehe Tabelle). Die Bestimmung der Meßwerte erfolgte analog zu den Beispiele 1 bis 4 Eigenschaften der Waschmitteltabletten Beispiel Waschmittel A mit PVP der Korngröße Preßkraft in kN Preßdruck in MPa Bruchkraft in N Auflöseverhalten in Minuten 1 80 bis 400 µm 6,48 < 3 < 5 Sekunden 2 80 bis 400 µm 29,41 12 < 10 Sekunden 3 < 100 µm 5,98 < 3 30 Minuten 4 < 100 µm 26,39 14 30 Minuten Vergleichsbeispiel 1 ohne Zusatz von PVP 4,09 13 8 > 30 Minuten Vergleichsbeispiel 2 ohne Zusatz von PVP 7,97 25 11 > 30 Minuten For comparison purposes, tablets of approx. 3 g and a diameter of 20 mm were produced from the powdered, granulated detergent A and tested for their dissolving behavior in water (see table). The measurement values were determined analogously to Examples 1 to 4 Properties of detergent tablets example Detergent A with PVP of the grain size Pressing force in kN Pressure in MPa Breaking strength in N Dissolution behavior in minutes 1 80 to 400 µm 6.48 <3 <5 seconds 2nd 80 to 400 µm 29.41 12th <10 seconds 3rd <100 µm 5.98 <3 30 minutes 4th <100 µm 26.39 14 30 minutes Comparative Example 1 without the addition of PVP 4.09 13 8th > 30 minutes Comparative Example 2 without the addition of PVP 7.97 25th 11 > 30 minutes

Es ist deutlich zu sehen, daß durch Zusatz des erfindungsgemäß zu verwendenden quervernetzten Polyvinylpyrrolidons, wobei die Partikel eine Korngröße von 80 bis 400 µm aufweisen, ein deutlich schnellerer Zerfall der Waschmitteltabletten bei deutlich höherer Bruchfestigkeit erreicht wird.It can be clearly seen that by adding the invention crosslinked polyvinylpyrrolidones to be used, the Particles have a grain size of 80 to 400 µm, a clear faster disintegration of the detergent tablets at significantly higher Breaking strength is achieved.

Claims (5)

Verwendung von quervernetztem Polyvinylpyrrolidon als Zusatz zu kompakten, teilchenförmigen Wasch- und Reinigungsmitteln zur Erhöhung ihrer Zerfallsgeschwindigkeit beim Zusammenbringen mit Wasser, dadurch gekennzeichnet, daß die Partikel des quervernetzten Polyvinylpyrrolidons eine Korngröße von 50 bis 400 µm aufweisen.Use of cross-linked polyvinylpyrrolidone as an additive to compact, particulate detergents and cleaning agents to increase their rate of decay when brought together with water, characterized in that the particles of the crosslinked polyvinylpyrrolidone has a grain size of Have 50 to 400 microns. Verwendung nach Anspruch 1, dadurch gekennzeichnet, daß mindestens 10 Gew.-% der Partikel des quervernetzten Polyvinylpyrrolidons eine Korngröße kleiner 200 µm aufweisen.Use according to claim 1, characterized in that at least 10% by weight of the particles of the crosslinked polyvinylpyrrolidone have a grain size less than 200 microns. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Partikel direkt durch Klassiern der aus der Polymerisation und Trocknung erhaltenen Polyvinylpyrrolidonfestkörper erhalten werden.Use according to claim 1 or 2, characterized in that that the particles directly by classifying the from the polymerization and drying obtained polyvinylpyrrolidone solids be preserved. Kompakte, teilchenförmige Wasch- und Reinigungsmittel, dadurch gekennzeichnet, daß sie quervernetztes Polyvinylpyrrolidon in Mengen von 0,5 bis 20 Gew.-% zur Erhöhung ihrer Zerfallsgeschwindigkeit beim Zusammenbringen mit Wasser enthalten, wobei die Partikel des quervernetzten Polyvinylpyrrolidons eine Korngröße von 50 bis 400 µm und mindestens 10 Gew.-% der Partikel eine Korngröße kleiner 200 µm aufweisen.Compact, particulate detergents and cleaning agents, characterized in that they cross-linked polyvinylpyrrolidone in amounts of 0.5 to 20 wt .-% to increase their rate of decay when contacted with water included, the particles of the cross-linked polyvinylpyrrolidone a grain size of 50 to 400 microns and at least 10% by weight of the particles have a grain size of less than 200 μm. Verfahren zur Herstellung von kompakten, teilchenförmige Wasch- und Reinigungsmittel, enthaltend quervernetztes Polyvinylpyrrolidon als Sprengmittel, dadurch gekennzeichnet, daß man quervernetztes Polyvinylpyrrolidon in Mengen von 0,5 bis 20 Gew.-%, wobei die Partikel des quervernetzten Polyvinylpyrrolidons eine Korngröße von 50 bis 400 µm und mindestens 10 Gew.-% der Partikel eine Korngröße kleiner 200 µm aufweisen mit den pulverförmigen Inhaltsstoffen von Waschmitteln vermischt und anschließend das Gemisch durch Verdichten in eine kompakte Form überführt.Process for the production of compact, particulate Detergents and cleaning agents containing cross-linked polyvinylpyrrolidone as an explosive, characterized in that cross-linked polyvinylpyrrolidone in amounts from 0.5 to 20 wt .-%, the particles of the cross-linked polyvinylpyrrolidone a grain size of 50 to 400 microns and at least 10% by weight of the particles have a grain size of less than 200 μm with the powdery ingredients of detergents mixed and then the mixture by compression in transferred a compact form.
EP00103131A 1999-03-17 2000-02-16 Tablets and particulate detergents comprising cross-linked polyvinylpyrrolidone and its use Withdrawn EP1036839A3 (en)

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US11268045B2 (en) 2015-12-08 2022-03-08 Ecolab Usa Inc. Pressed manual dish detergent
US11746304B2 (en) 2015-12-08 2023-09-05 Ecolab Usa Inc. Pressed manual dish detergent
WO2023117494A1 (en) 2021-12-20 2023-06-29 Basf Se Polypropylene imine polymers (ppi), their preparation, uses, and compositions comprising such ppi
WO2024175409A1 (en) 2023-02-21 2024-08-29 Basf Se Modified hyperbranched alkoxylated polyalkylene imines
WO2024175407A1 (en) 2023-02-21 2024-08-29 Basf Se Modified alkoxylated polyalkylene imines or modified alkoxylated polyamines
WO2024175401A1 (en) 2023-02-21 2024-08-29 Basf Se Modified alkoxylated polyalkylene imines or modified alkoxylated polyamines
WO2024188713A1 (en) 2023-03-13 2024-09-19 Basf Se Alkoxylated nitrogen containing polymers and their use

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US6329334B1 (en) 2001-12-11
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CN1267715A (en) 2000-09-27
CN1165605C (en) 2004-09-08
EP1036839A3 (en) 2001-04-18

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