EP1781768B2 - Beschichteter wasch- oder reinigungsmittelformkörper - Google Patents

Beschichteter wasch- oder reinigungsmittelformkörper Download PDF

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Publication number
EP1781768B2
EP1781768B2 EP05769966.2A EP05769966A EP1781768B2 EP 1781768 B2 EP1781768 B2 EP 1781768B2 EP 05769966 A EP05769966 A EP 05769966A EP 1781768 B2 EP1781768 B2 EP 1781768B2
Authority
EP
European Patent Office
Prior art keywords
coated
shaped
water
coating
coating agent
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.)
Active
Application number
EP05769966.2A
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German (de)
English (en)
French (fr)
Other versions
EP1781768A1 (de
EP1781768B1 (de
Inventor
Thomas Holderbaum
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PL05769966T priority Critical patent/PL1781768T5/pl
Publication of EP1781768A1 publication Critical patent/EP1781768A1/de
Application granted granted Critical
Publication of EP1781768B1 publication Critical patent/EP1781768B1/de
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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
    • 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
    • C11D17/0082—Coated 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
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y10T428/277—Cellulosic substrate

Definitions

  • the present invention relates to coated detergent tablets and to processes for their production.
  • the present application relates to shaped bodies which have a cavity in the form of a depression or a through hole and whose surface coverage of the coated molding surface with the coating agent is between 0.2 and 50 mg / cm 2 .
  • Detergents or cleaners are now available to the consumer in a variety of forms.
  • this offer also includes, for example, detergent concentrates in the form of extruded or tabletted compositions.
  • These fixed, concentrated or compressed forms of supply are characterized by a reduced volume per dosing unit and thus reduce the costs for packaging and transport.
  • the washing or cleaning agent tablets additionally meet the consumer's desire for simple dosing. The corresponding means are comprehensively described in the prior art.
  • tableted detergents or cleaners are more difficult to dissolve than conventional powdered or liquid detergents or cleaners due to the high densification of their constituents. This can cause problems. Delayed disintegration / dissolution of the ingredients can result in reduced cleaning performance, incomplete flushing of the media through the dispenser compartment, and the formation of stains and encrustations.
  • This object has been achieved by a coating method for detergent tablets, in which the tablet surface is coated with a surface coverage of between 0.2 and 50 mg / cm 2 .
  • the coating compositions can be used as pure substances, for example in the form of their melts, but also as dispersions or solutions.
  • organic solvents are also suitable as dispersants, with aqueous dispersions or aqueous solutions being particularly preferred.
  • These dispersions or solutions, in particular the aqueous dispersions or solutions preferably have a weight fraction of the coating agent below 80% by weight, preferably below 65% by weight, more preferably below 50% by weight and in particular below 40% by weight, in each case based on the total weight of the dispersion or solution.
  • the application of the molding with the coating agent is carried out by spraying.
  • spraying all known to those skilled in the art for this purpose are suitable.
  • the spraying is preferably carried out by means of single-fluid or high-pressure spray nozzles, two-component spray nozzles or three-component spray nozzles.
  • a high melt pressure 5-15 MPa
  • spraying in dual-fluid spray nozzles takes place by means of a stream of compressed air (at 0.15-0.3 MPa).
  • the spraying with two-component spray nozzles is more favorable, especially with regard to possible blockages of the nozzle, but more expensive due to the high consumption of compressed air.
  • three-component spray nozzles which, in addition to the stream of compressed air for atomization, are intended to prevent a further air-guiding system which prevents blockages and droplet formation at the nozzle.
  • the use of two-component spray nozzles preferably two-component spray nozzles with a fluid bore of between 1 and 6 mm, in particular between 3 and 5 mm, is particularly preferred.
  • the droplet diameter of the sprayed-on coating material or of the sprayed coating dispersion or solution is preferably between 1 and 100 ⁇ m, particularly preferably between 2 and 80 ⁇ m, very particularly preferably between 4 and 70 ⁇ m and in particular between 8 and 60 ⁇ m.
  • the temperature of the sprayed coating material is preferably between 20 and 90 ° C, preferably between 25 and 60 ° C, more preferably between 30 and 55 ° C and in particular between 40 and 50 ° C.
  • a surface load of the shaped body surface by spraying the sprayed liquid between 0.1 and 200 mg / (cm 2 s), preferably between 0.2 and 100 mg when spraying the molded body / (cm 2 s), more preferably between 0.4 and 50 mg / (m 2 s), and in particular between 0.8 and 20 mg / (cm 2 s).
  • a surface load of the shaped body surface by spraying the sprayed liquid between 0.1 and 200 mg / (cm 2 s), preferably between 0.2 and 100 mg when spraying the molded body / (cm 2 s), more preferably between 0.4 and 50 mg / (m 2 s), and in particular between 0.8 and 20 mg / (cm 2 s).
  • the coating composition to the molding is preferably completed in less than 10 minutes, preferably less than 5 minutes, more preferably less than 2 minutes, most preferably less than 1 minute, and most preferably less than 0.5 minutes.
  • the sprayed washing or cleaning agent shaped body is preferably dried after spraying.
  • the drying can be carried out, for example, thermally and / or by the action of a vacuum. In the case of thermal drying, methods using hot air or heat radiation are preferred. Drying temperatures are preferably between 35 and 90 ° C, preferably between 40 and 80 ° C and in particular between 50 and 70 ° C.
  • the drying of the moldings is usually not complete, that is, not all of the amount of solvent applied by the spraying is removed by the drying.
  • Polyvinyl alcohols of a certain molecular weight range are preferably used as the coating material, it being preferred according to the invention that the film material comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol -1 , preferably from 11,000 to 90,000 gmol -1 , particularly preferably from 12,000 to 80,000 gmol -1 and in particular from 13,000 to 70,000 gmol -1 .
  • Coating materials which comprise a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof, are preferred within the scope of the process according to the invention.
  • the inventive method is suitable for simple as well as repeated coating of the shaped body.
  • a method characterized in that the coating agent is applied to the molding by the moldings is sprayed several times with a solution or a dispersion of the coating composition, according to the invention are preferred.
  • a "multiple" or “repeated” coating of the shaped body takes place in such a way that the shaped body is dried at least superficially between the individual coating steps.
  • the coating steps are consequently interrupted by a drying step but at least by a waiting time, which preferably exceeds at least one minute, preferably at least two minutes and in particular at least three minutes. Drying steps which are carried out under more severe conditions, that is to say at elevated temperature and / or higher vacuum, can preferably be reduced to at least 10 seconds, particularly preferably at least 30 seconds, preferably at least 40 seconds and in particular to at least 50 seconds.
  • the surface coverage of the moldings after this repeated coating is preferably between 0.2 and 100 mg / cm 2 , preferably between 1 and 80 mg / cm 2 , more preferably between 10 and 70 mg / cm 2 and in particular between 20 and 60 mg / cm 2 .
  • LCST substances are substances that have better solubility at low temperatures than at higher temperatures. They are also referred to as substances with lower critical demixing temperature. These substances are usually polymers. Depending on the conditions of use, the lower critical demixing temperature should be between room temperature and the temperature of the heat treatment, for example between 20 ° C, preferably 30 ° C and 100 ° C, in particular between 30 ° C and 50 ° C.
  • the LCST substances are preferably selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and blends of these substances.
  • LCST substances are cellulose ethers and mixtures of cellulose ethers with carboxymethylcellulose (CMC).
  • CMC carboxymethylcellulose
  • Other polymers which exhibit a lower critical demixing temperature in water and which are also suitable are polymers of mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylates and / or acrylic acids or mixtures of interconnected networks of the above (co) polymers.
  • polyethylene oxide or copolymers thereof such as ethylene oxide / propylene oxide copolymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain proteins such as poly (VATGVV), a repeating unit in the natural protein elastin, and certain alginates.
  • LCST low critical demixing temperature
  • waxing is meant a number of natural or artificially derived substances which generally melt above 35 ° C without decomposition and are already slightly above the melting point, relatively low viscosity and non-stringy. They show a strong temperature-dependent consistency and solubility. According to their origin, the waxes are divided into three groups, the natural waxes, chemically modified waxes and the synthetic waxes.
  • Synthetic waxes are generally understood as meaning polyalkylene waxes or polyalkylene glycol waxes. Also suitable as coating materials are compounds from other classes of substances which fulfill the stated requirements with regard to the softening point. Suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which is commercially available under the name Unimoll ® 66 (Bayer AG), proved. Also suitable are synthetic waxes made of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea) is available. Conversely, synthetic or partially synthetic esters of lower alcohols can be used with fatty acids from natural sources. This class of substances includes, for example, Tegin® 90 (Goldschmidt), a glycerol monostearate palmitate. Shellac, for example shellac KPS three-ring SP (Kalkhoff GmbH) can be used as further substance.
  • Wax alcohols are higher molecular weight, water-insoluble fatty alcohols having generally about 22 to 40 carbon atoms.
  • the wax alcohols are present, for example, in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent of many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • Paraffin is the term for a solid or liquid mixture of purified, saturated aliphatic hydrocarbons (paraffins). This is readily soluble in ether and chloroform but not soluble in water. Both liquid paraffins and paraffin melts can be used in the context of the present invention.
  • paraffin waxes have the advantage over the other natural waxes mentioned that the use of preferred washing or cleaning agent shaped bodies coated with paraffin waxes in an alkaline cleaning agent environment does not result in hydrolysis of the waxes (as for example in the case of wax esters), since paraffin wax contains no hydrolyzable groups.
  • Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes.
  • the paraffin to be used according to the invention preferably has substantially no constituents with a melting point of more than 70 ° C., more preferably of more than 60 ° C.
  • Preferred coating materials contain at least one paraffin wax with a melting range from 40 ° C to 60 ° C.
  • Paraffin waxes applied in the form of their melts preferably solidify within 10 minutes, preferably within 5 minutes and especially within 2 minutes.
  • hydrophobic substances as a coating material is preferred in the present invention, since these substances improve the storage behavior of the laundry detergent or cleaner moldings according to the invention at high humidities.
  • the increased moisture resistance of the coated body makes it possible to dispense after application of a hydrophobic substance to a seal with a water-soluble or water-dispersible film.
  • this is only a preferred embodiment of the method according to the invention.
  • it may be preferable to apply a film to the hydrophobic-coated molded body.
  • the film can be fused at least proportionately with the coating, loosely, that enclose the body, or contain an air cushion, so that the molded body is additionally protected from mechanical effects.
  • the shaped bodies are coated twice, three times or four times, it being possible in each case for the coating processes to use the same or different coating materials.
  • coating materials from the group of water-soluble polymers (for example PVA, PVP, gelatin or LCST polymers) and the water-insoluble waxes and the paraffins.
  • the table below gives an overview of a number of particularly preferred sequences of these coating materials.
  • the coating marked as the first layer corresponds to the layer first applied to the shaped body.
  • the slash (I) takes on the meaning of a "and / or" -link.
  • the coating materials can be mixed with active ingredients and active ingredients. Dyes, fragrances or bitter substances are preferably added to the coating materials.
  • the spatial form of the detergent tablets is not subject to any restriction.
  • Examples are room bodies with a polygonal base area, whereby the body represents a continuation of the polygonal floor space in the room.
  • Preferred examples of the polygonal body are prismatic bodies.
  • Examples of the prismatic body are trigonal prisms, rhombic prisms, orthorhombic prisms, tetragonal prisms, pentagonal prisms, hexagonal prisms, or octagonal prisms. Particularly preferred is a cuboid shape.
  • Examples of other suitable polygonal bodies are trigonal, tetragonal, rhombic, orthorhombic, hexagonal or octagonal pyramids and dipyramids.
  • the body may also be a hybrid of various geometric bodies. Preference is furthermore given to moldings with an oval or round base surface, wherein the body preferably again represents a continuation of the base surface in the room.
  • the volume of the detergent tablets is preferably between 12 and 30 ml, preferably between 15 and 25 ml and in particular between 17 and 22 ml.
  • the weight of the tablets is preferably between 10 and 25 g.
  • Such detergent tablets are particularly suitable as dosing units for single use.
  • the dosage of these moldings is usually done via the metering chambers of washing machines or dishwashers.
  • the spatial form of the molding can therefore of course be adapted to any irregular shapes of dosing / Ein Hughesschitzn different washing machines and dishwashers.
  • a cuboid shape of the washing or cleaning agent shaped body is preferred insofar as this makes it possible to fill in the usual cuboid insufflation chambers or dishwashers best in terms of volume.
  • cuboid-shaped detergents or cleaning agents can be stored very well in a space-saving manner.
  • the detergent tablets may have a cavity in the form of a through hole.
  • the openings of this hole may be located in adjacent side surfaces and / or in opposite side surfaces of the shaped body. If the openings of the hole are located on mutually opposite sides of the shaped body, the corresponding shaped bodies are also referred to as ring shaped bodies or ring tablets.
  • the tablets in the context of the present invention also multi-phase, in particular multi-layered, ausgestalten.
  • the moldings can be made in a predetermined spatial form and predetermined size.
  • the training as a blackboard the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
  • This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article
  • D is the molded article diameter in meters and t the height of the moldings.
  • the stability and hardness of the processed shaped bodies can be improved by the method according to the invention without impairing their decay and dissolution properties.
  • the molded body after coating with constant dissolution behavior characterized by an increased breaking strength.
  • preferred processes according to the invention are characterized in that the coating in step b) takes place on the outer surfaces of the molded body with the cavity, but not within the cavity.
  • the coating of the molding is repeated in this process variant, preferably twice, three or four times.
  • the substances or mixtures of substances filled in the cavity can be fixed in the cavity in different ways.
  • the substances or substance mixtures are present in a water-soluble or water-dispersible packaging, for example a deep-drawn bag or an injection-molded container, which at least partially fills the cavity and in turn with the molding by adhesion or a mechanical connection, for example a detent, Snap, plug or clamp connection is connected.
  • the cavity is preferably filled to at least 70% by volume, preferably at least 80% by volume, more preferably at least 90% by volume and in particular at least 95% by volume of its volume.
  • a water-soluble or water-dispersible film is sealed onto the coated surface of the shaped body, the sealing being effected by heat sealing.
  • the sealed foil can perform a number of different functions.
  • such a film is suitable for fixing the substances or substance mixtures filled in the cavity of the shaped body in this cavity.
  • the breaking strength and / or storage stability of the shaped body can be further increased by means of these films.
  • Preferred film materials used are, in particular, the water-soluble polymers mentioned above from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and derivatives thereof and mixtures thereof.
  • a further subject of the present application is a coated washing or cleaning agent shaped article, characterized in that the surface coverage of the coated molding surface with the coating agent is between 0.2 and 50 mg / cm 2 and the water-soluble or water-dispersible film is sealed onto the coated surface, characterized in that the shaped body comprises a coated surface and a water-soluble or water-dispersible film, wherein the coating and the water-soluble or water-dispersible film are at least partially fused together and the coating agent was sprayed onto the shaped body.
  • preferred coated detergent tablets have a surface coverage of the coated shaped body surface with the coating agent between 0.4 and 40 mg / cm 2 , preferably between 0.8 and 30 mg / cm 2 and in particular between 1 and 20 mg / cm 2 ,
  • the coating agent is preferably a water-soluble organic polymer, preferably a polymer from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone and cellulose ethers.
  • the fracture hardness of the coated detergent tablets is preferably above 60 N, preferably above 80 N, particularly preferably above 100 N and in particular above 110 N.
  • the shaped bodies preferably have a cavity in the form of a depression or a through hole, wherein those shaped bodies which are coated on the outer surfaces but not within the cavity are particularly preferred.
  • the cavity of the shaped bodies according to the invention is preferably filled.
  • compositions according to the invention or the compositions prepared by the process according to the invention described above contain washing and cleaning substances, preferably washing and cleaning substances from the group of builders, surfactants, polymers, bleaches, bleach activators, enzymes, glass corrosion inhibitors, corrosion inhibitors, disintegration aids , Fragrances and perfume carriers.
  • the agents are therefore usually water-soluble or water-dispersible.
  • the detergents and cleaners can contain further ingredients which further improve the performance and / or aesthetic properties of these compositions.
  • Preferred agents contain one or more of the group of electrolytes, pH adjusters, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , Phobic and impregnating agents, swelling and anti-slip agents and UV absorbers.

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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)
  • Moulds For Moulding Plastics Or The Like (AREA)
EP05769966.2A 2004-08-20 2005-07-28 Beschichteter wasch- oder reinigungsmittelformkörper Active EP1781768B2 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL05769966T PL1781768T5 (pl) 2004-08-20 2005-07-28 Powlekana kształtka środka piorącego lub czyszczącego

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004040330A DE102004040330A1 (de) 2004-08-20 2004-08-20 Beschichteter Wasch- oder Reinigungsmittelformkörper
PCT/EP2005/008180 WO2006021284A1 (de) 2004-08-20 2005-07-28 Beschichteter wasch- oder reinigungsmittelformkörper

Publications (3)

Publication Number Publication Date
EP1781768A1 EP1781768A1 (de) 2007-05-09
EP1781768B1 EP1781768B1 (de) 2010-02-10
EP1781768B2 true EP1781768B2 (de) 2014-10-08

Family

ID=34979903

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05769966.2A Active EP1781768B2 (de) 2004-08-20 2005-07-28 Beschichteter wasch- oder reinigungsmittelformkörper

Country Status (6)

Country Link
US (2) US20080255020A1 (pl)
EP (1) EP1781768B2 (pl)
AT (1) ATE457344T1 (pl)
DE (2) DE102004040330A1 (pl)
PL (1) PL1781768T5 (pl)
WO (1) WO2006021284A1 (pl)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005022786B4 (de) * 2005-05-12 2016-09-15 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmitteldosiereinheit
DE102008060470A1 (de) * 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa Reinigungsmittel
DE102008060471A1 (de) * 2008-12-05 2010-06-10 Henkel Ag & Co. Kgaa Maschinelles Geschirrspülmittel
ES2601906T3 (es) * 2010-05-17 2017-02-16 Dalli-Werke Gmbh & Co. Kg Pastillas de detergente que tienen más de cuatro superficies laterales
ES2725612T3 (es) 2013-03-14 2019-09-25 Ecolab Usa Inc Composición de detergente y prelavado que contiene enzima y métodos de uso
WO2016200673A1 (en) * 2015-06-09 2016-12-15 Dow Global Technologies Llc Support materials for 3d printing
DE102018106720A1 (de) * 2018-03-21 2019-09-26 Miele & Cie. Kg Reinigungsmittelkörper zur Verwendung in einem als Waschmaschine oder Geschirrspülmaschine ausgebildeten Reinigungsgerät und Reinigungsgerät

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CA2313875A1 (en) † 1999-07-14 2001-01-14 Henkel Kommanditgesellschaft Auf Aktien A filled detergent tablet
US20020006890A1 (en) † 2000-03-04 2002-01-17 Matthias Sunder Multiphase laundry detergent and cleaning product shaped bodies having noncompressed parts
US6548473B1 (en) † 1997-11-26 2003-04-15 The Procter & Gamble Company Multi-layer detergent tablet having both compressed and non-compressed portions
WO2004046297A1 (de) † 2002-11-21 2004-06-03 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung befüllter wasch- und reinigungsmittelformkörper

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DE19920118B4 (de) 1999-05-03 2016-08-11 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittelformkörper mit Beschichtung und Verfahren zu seiner Herstellung
DE19940547A1 (de) 1999-08-26 2001-03-01 Henkel Kgaa Wasch- oder Reinigungsmittelformkörper mit Partialcoating
DE19959875A1 (de) * 1999-12-10 2001-07-05 Henkel Kgaa Preßverfahren für mehrphasige Formkörper
DE10026334A1 (de) 2000-05-26 2001-12-06 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit Pfropfcopolymer-Beschichtung
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DE10064985A1 (de) * 2000-12-23 2002-07-11 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit Beschichtung
DE10233564A1 (de) * 2002-07-24 2003-10-16 Henkel Kgaa Wasch- und Reinigungsmittelportionen mit Umhüllung

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995018215A1 (en) † 1993-12-30 1995-07-06 Ecolab Inc. Stable hygroscopic detergent article
US6548473B1 (en) † 1997-11-26 2003-04-15 The Procter & Gamble Company Multi-layer detergent tablet having both compressed and non-compressed portions
CA2313875A1 (en) † 1999-07-14 2001-01-14 Henkel Kommanditgesellschaft Auf Aktien A filled detergent tablet
US20020006890A1 (en) † 2000-03-04 2002-01-17 Matthias Sunder Multiphase laundry detergent and cleaning product shaped bodies having noncompressed parts
WO2004046297A1 (de) † 2002-11-21 2004-06-03 Henkel Kommanditgesellschaft Auf Aktien Verfahren zur herstellung befüllter wasch- und reinigungsmittelformkörper

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ATE457344T1 (de) 2010-02-15
DE102004040330A1 (de) 2006-03-02
US20080255020A1 (en) 2008-10-16
PL1781768T5 (pl) 2015-05-29
PL1781768T3 (pl) 2010-07-30
US20090029055A1 (en) 2009-01-29
DE502005008999D1 (de) 2010-03-25
WO2006021284A1 (de) 2006-03-02
EP1781768A1 (de) 2007-05-09
EP1781768B1 (de) 2010-02-10

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