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EP0846755B1 - Beschichtetes Reinigungsmittel in Tablettenform - Google Patents

Beschichtetes Reinigungsmittel in Tablettenform Download PDF

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Publication number
EP0846755B1
EP0846755B1 EP96203471A EP96203471A EP0846755B1 EP 0846755 B1 EP0846755 B1 EP 0846755B1 EP 96203471 A EP96203471 A EP 96203471A EP 96203471 A EP96203471 A EP 96203471A EP 0846755 B1 EP0846755 B1 EP 0846755B1
Authority
EP
European Patent Office
Prior art keywords
coating
tablet
tablets
acid
detergent
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
EP96203471A
Other languages
English (en)
French (fr)
Other versions
EP0846755A1 (de
Inventor
Paul Irma Albertus Van Dijk
Jose Luis Vega
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
Priority to EP96203471A priority Critical patent/EP0846755B1/de
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to ES96203471T priority patent/ES2294784T3/es
Priority to DE69637355T priority patent/DE69637355T2/de
Priority to AT96203471T priority patent/ATE380235T1/de
Priority to HU0000257A priority patent/HUP0000257A3/hu
Priority to US09/319,474 priority patent/US6232284B1/en
Priority to CA002273325A priority patent/CA2273325C/en
Priority to JP52560498A priority patent/JP2001505604A/ja
Priority to TR1999/01239T priority patent/TR199901239T2/xx
Priority to AU54438/98A priority patent/AU5443898A/en
Priority to CN97181566.6A priority patent/CN1245529A/zh
Priority to PCT/US1997/021044 priority patent/WO1998024875A1/en
Priority to BR9714379A priority patent/BR9714379A/pt
Priority to ZA9710696A priority patent/ZA9710696B/xx
Priority to EG129597A priority patent/EG20924A/xx
Priority to MA24888A priority patent/MA24416A1/fr
Priority to ARP970105746A priority patent/AR010746A1/es
Publication of EP0846755A1 publication Critical patent/EP0846755A1/de
Application granted granted Critical
Publication of EP0846755B1 publication Critical patent/EP0846755B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof

Definitions

  • GB-A-0 989 683 published on 22nd April 1965, discloses a process for preparing a particulate detergent from surfactants and inorganic salts; spraying on water-soluble silicate; and pressing the detergent particles into a solid form-retaining tablet.
  • a readily water-soluble organic film-forming polymer for example, polyvinyl alcohol
  • EP-A-0 002 293 published on 13th June 1979, discloses a tablet coating comprising hydrated salt such as acetate, metaborate, orthophosphate, tartrate, and sulphate.
  • the present invention provides a means by which tablets with a core which is formed by compressing a particulate material, the particulate material comprising surfactant and detergent builder, can be provided with a hard, thin, coating so that they can be stored, shipped and handled, but the coating is broken when the tablet is in the washing machine exposing the soft core which breaks up easily and rapidly, releasing the active ingredients into the wash solution.
  • the objective of the present invention is to provide a tablet which completely disintegrates and disperses in alkaline or surfactant-rich solutions such as the wash liquor.
  • Tablets to be coated in the present invention can be prepared simply by mixing the solid ingredients together and compressing the mixture in a conventional tablet press as used, for example, in the pharmaceutical industry.
  • Any liquid ingredients for example the surfactant or suds suppressor, can be incorporated in a conventional manner into the solid particulate ingredients.
  • the principal ingredients are used in particulate form.
  • the ingredients such as builder and surfactant can be spray-dried in a conventional manner and then compacted at a suitable pressure.
  • the particulate material used for making the tablet of this invention can be made by any particulation or granulation process.
  • An example of such a process is spray drying (in a co-current or counter current spray drying tower) which typically gives low bulk densities 600g/l or lower.
  • Particulate materials of higher density can be prepared by granulation and densification in a high shear batch mixer/granulator or by a continuous granulation and densification process (e.g. using Lodige ® CB and/or Lodige ® KM mixers).
  • Other suitable processes include fluid bed processes, compaction processes (e.g. roll compaction), extrusion, as well as any particulate material made by any chemical process like flocculation, crystallisation sentering, etc.
  • Individual particles can also be any other particle, granule, sphere or grain.
  • the particulate materials may be mixed together by any conventional means. Batch is suitable in, for example, a concrete mixer, Nauta mixer, ribbon mixer or any other. Alternatively the mixing process may be carried out continuously by metering each component by weight on to a moving belt, and blending them in one or more drum(s) or mixer(s). A liquid spray-on to the mix of particulate materials (e.g. non-ionic surfactants) may be carried out. Other liquid ingredients may also be sprayed on to the mix of particulate materials either separately or premixed. For example perfume and slurries of optical brighteners may be sprayed. A finely divided flow aid (dusting agent such as zeolites, carbonates, silicas) can be added to the particulate materials after spraying the non-ionic, preferably towards the end of the process, to make the mix less sticky.
  • a finely divided flow aid dusting agent such as zeolites, carbonates, silicas
  • the tablets may be manufactured by using any compacting process, such as tabletting, briquetting, or extrusion, preferably tabletting.
  • Suitable equipment includes a standard single stroke or a rotary press (such as Courtly ® , Korch ® , Manesty ® , or Bonals ® ).
  • the tablets prepared according to this invention preferably have a diameter of between 40mm and 50mm, and a weight between 25 and 60 g.
  • the compaction pressure used for preparing these tablets need not exceed 5000 kN/m 2 , preferably not exceed 3000 kN/m 2 , and most preferably not exceed 1000 kN/m 2 .
  • the tablets are then coated with a coating that is substantially insoluble so that the tablet does not absorb moisture, or absorbs moisture at only a very slow rate.
  • the coating is also strong so that moderate mechanical shocks to which the tablets are subjected during handling, packing and shipping result in no more than very low levels of breakage or attrition.
  • the coating is preferably brittle so that the tablet breaks up when subjected to stronger mechanical shock.
  • the coating material is dissolved under alkaline conditions, or is readily emulsified by surfactants. This avoids the deposition of undissolved particles or lumps of coating material on the laundry load. This may be important when the coating material is completely insoluble (for example less than 1 g/l) in water.
  • substantially insoluble means having a very low solubility in water. This should be understood to mean having a solubility in water at 25°C of less than 20 g/L, preferably less than 5 g/l, and more preferably less than 1 g/l. Water solubility is measured following the test protocol of ASTM E1148-87 entitled, "Standard Test Method for Measurements of Aqueous Solubility".
  • the used coating materials are adipic acid and C8-C13 dicarboxylic acids.
  • Preferred dicarboxylic acids are suberic acid (C8), azelaic acid (C3), sebacic acid (C10), undecanedioic acid (C11), dodecanedioic acid (C12) and tridecanedioic acid (C13).
  • substantially insoluble materials having a melting point below 40 °C are not sufficiently solid at ambient temperatures and it has been found that materials having a melting point above about 180 °C are not practicable to use.
  • the materials melt in the range from 60 °C to 160 °C, more preferably from 70 °C to 120 °C.
  • melting point is meant the temperature at which the material when heated slowly in, for example, a capillary tube becomes a clear liquid.
  • a coating of any desired thickness can be applied according to the present invention.
  • the coating forms from 1% to 10%, preferably from 1.5% to 5%, of the tablet weight.
  • the tablets further comprises an effervescent.
  • Effervescency as defined herein means the evolution of bubbles of gas from a liquid, as the result of a chemical reaction between a soluble acid source and an alkali metal carbonate, to produce carbon dioxide gas, i.e. C 6 H 8 O 7 + 3NaHCO 3 ⁇ Na 3 C 6 H 5 O 7 + 3CO 2 ⁇ + 3H 2 O
  • acid and carbonate sources and other effervescent systems may be found in : ( Pharmaceutical Dosage Forms : Tablets Volume 1 Page 287 to 291 ) An effervescent may be added to the tablet mix in addition to the detergent ingredients.
  • Nonlimiting examples of surfactants useful herein typically at levels from about 1% to about 55%, by weight include the conventional C 11- C 18 alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C 10- C 20 alkyl sulfates (“AS”), the C 10- C 18 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOSO 3 -M + ) CH 3 and CH 3 (CH 2 ) y (CHOSO 3 -M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C 10- C 18 alkyl alkoxy sulfates (“AE x S”; especially EO 1-7 ethoxy sulfates), C 10- C 18 alkyl alkoxy carboxylates (especially the
  • the conventional nonionic and amphoteric surfactants such as the C 12- C 18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C 6 -C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C 12- C 18 betaines and sulfobetaines ("sultaines"), C 10- C 18 amine oxides, and the like, can also be included in the overall compositions.
  • the C 10 -C 18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 12 -C 18 N-methylglucamides. See WO 9,206,154 .
  • non-phosphate builders are required in some locales.
  • the compositions herein function surprisingly well even in the presence of the so-called "weak” builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the alkali metal silicates, particularly those having a SiO 2 :Na 2 O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck .
  • silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973 .
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations.
  • polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964 , and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972 . See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987 .
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679 ; 3,835,163 ; 4,158,635 ; 4,120,874 and 4,102,903 .
  • succinic acid builders include the C 5 -C 20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986 . Other suitable polycarboxylates are disclosed in U.S.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034 . See also lipases in Japanese Patent Application 53,20487 , laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e.
  • compositions which are comonly used in detergent compositions and which may be incorpoated into the detergent tablets of the present invention include chelating agents, soil release agents, soil antiredeposition agents, dispersing agents, brighteners, suds suppressors, fabric softeners, dye transfer inhibition agents and perfumes.
  • Example 2 All the particulate materials of Example 1, except for the dried zeolite, were mixed together in a mixing drum to form a homogeneous particulate mixture, during this mixing the spray-ons were carried out. After the spray-ons the dusting was carried out with the dried zeolite.
  • a third series of tablets was made with a compaction force of 1.5 kN. or about 95N/cm 2 to give tablets of about 1.9 cm height, a density of about 1.3 g./cc, and a tensile strength of 12.9 kPa. After coating with Lauric Acid the tablets had a weight of 38.5 g, and the tensile strength was 23.4 kPa.
  • Example 2 Mixing according to the method described in Example 1, after the dusting the effervescency granules were added to the mix drum, and a final mix was made. Tabletting and coating was carried out according to the method described in Example 1. A first series of tablets was made with a Compaction Force of 1 kN. or about 63 Newton/cm 2 , to give tablets of about 2.2 cm height, a density of about 1.1 g./cc, and a tensile strength of 4.5 kPa. After coating with Lauric acid the tablets had a weight of 38.5 g, and the tensile strength was 13.1 kPa.
  • Example 2 was repeated replacing the Lauric acid by hexadecanol.
  • the hexadecanol was heated in a thermostatic bath to 80°C with gentle stirring until molten.
  • the final tensile strength of the three series of tablets was 12.1 kPa, 13.6 kPa and 22.1 kPa respectively.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Claims (5)

  1. Tablette, umfassend einen Kern und eine Beschichtung, wobei der Kern durch Verdichtung eines teilchenförmigen Materials gebildet wird, wobei das teilchenförmige Material Tensid und Reinigungsmittelbuilder umfasst, dadurch gekennzeichnet, dass die Beschichtung Adipinsäure, C8-C 13-Dicarbonsäuren oder Mischungen davon umfasst, mit einer Wasserlöslichkeit bei 25 °C von weniger als 20 g/l.
  2. Tablette nach Anspruch 1, umfassend eine Beschichtung aus im Wesentlichen wasserunlöslichen Materialien mit einem Schmelzpunkt im Bereich von 40 °C bis 180°C.
  3. Verfahren zum Herstellen einer Tablette, umfassend die Schritte:
    (a) Bilden eines Kerns durch Verdichtung eines teilchenförmigen Materials, wobei das teilchenförmige Material Tensid und Reinigungsmittelbuilder umfasst;
    (b) Auftragen eines Beschichtungsmaterials auf den Kern, wobei das Beschichtungsmaterial die Form einer Schmelze aufweist;
    (c) Verfestigenlassen des geschmolzenen Beschichtungsmaterials;
    dadurch gekennzeichnet, dass das Beschichtungsmaterial Adipinsäure, C8-C13-Dicarbonsäuren oder Mischungen davon umfasst, mit einer Wasserlöslichkeit bei 25 °C von weniger als 20 g/l.
  4. Verfahren nach Anspruch 3, wobei das Beschichtungsmaterial, oder die Mischung von Materialien, einen Schmelzpunkt von 40 °C bis 180 °C aufweist.
  5. Verfahren zum Herstellen einer Tablette, umfassend die Schritte:
    (a) Bilden eines Kerns durch Verdichtung eines teilchenförmigen Materials, wobei das teilchenförmige Material Tensid und Reinigungsmittelbuilder umfasst;
    (b) Auftragen eines Beschichtungsmaterials auf den Kern, wobei das Beschichtungsmaterial in einem Lösungsmittel gelöst ist;
    (c) Verdampfenlassen des Lösungsmittels;
    dadurch gekennzeichnet, dass das Beschichtungsmaterial Adipinsäure, C8-C 13-Dicarbonsäuren oder Mischungen davon umfasst, mit einer Wasserlöslichkeit bei 25 °C von weniger als 20 g/l.
EP96203471A 1996-12-06 1996-12-06 Beschichtetes Reinigungsmittel in Tablettenform Expired - Lifetime EP0846755B1 (de)

Priority Applications (17)

Application Number Priority Date Filing Date Title
ES96203471T ES2294784T3 (es) 1996-12-06 1996-12-06 Pastilla de detergente recubierta.
DE69637355T DE69637355T2 (de) 1996-12-06 1996-12-06 Beschichtetes Reinigungsmittel in Tablettenform
AT96203471T ATE380235T1 (de) 1996-12-06 1996-12-06 Beschichtetes reinigungsmittel in tablettenform
EP96203471A EP0846755B1 (de) 1996-12-06 1996-12-06 Beschichtetes Reinigungsmittel in Tablettenform
TR1999/01239T TR199901239T2 (xx) 1996-12-06 1997-11-19 Kaplanm�� deterjan tableti.
US09/319,474 US6232284B1 (en) 1996-12-06 1997-11-19 Coated detergent tablet with disintegration means
CA002273325A CA2273325C (en) 1996-12-06 1997-11-19 Coated detergent tablet
JP52560498A JP2001505604A (ja) 1996-12-06 1997-11-19 被覆洗浄剤タブレット
HU0000257A HUP0000257A3 (en) 1996-12-06 1997-11-19 Coated detergent tablet
AU54438/98A AU5443898A (en) 1996-12-06 1997-11-19 Coated detergent tablet
CN97181566.6A CN1245529A (zh) 1996-12-06 1997-11-19 涂覆的洗涤剂片
PCT/US1997/021044 WO1998024875A1 (en) 1996-12-06 1997-11-19 Coated detergent tablet
BR9714379A BR9714379A (pt) 1996-12-06 1997-11-19 Tablete detergente revestido
ZA9710696A ZA9710696B (en) 1996-12-06 1997-11-27 Coated detergent tablet.
EG129597A EG20924A (en) 1996-12-06 1997-12-04 Coated detergent tablet
ARP970105746A AR010746A1 (es) 1996-12-06 1997-12-05 Tableta que comprende un nucleo y un recubrimiento y proceso para fabricar dicha tableta
MA24888A MA24416A1 (fr) 1996-12-06 1997-12-05 Comprime detergent enrobe

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP96203471A EP0846755B1 (de) 1996-12-06 1996-12-06 Beschichtetes Reinigungsmittel in Tablettenform

Publications (2)

Publication Number Publication Date
EP0846755A1 EP0846755A1 (de) 1998-06-10
EP0846755B1 true EP0846755B1 (de) 2007-12-05

Family

ID=8224673

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96203471A Expired - Lifetime EP0846755B1 (de) 1996-12-06 1996-12-06 Beschichtetes Reinigungsmittel in Tablettenform

Country Status (16)

Country Link
EP (1) EP0846755B1 (de)
JP (1) JP2001505604A (de)
CN (1) CN1245529A (de)
AR (1) AR010746A1 (de)
AT (1) ATE380235T1 (de)
AU (1) AU5443898A (de)
BR (1) BR9714379A (de)
CA (1) CA2273325C (de)
DE (1) DE69637355T2 (de)
EG (1) EG20924A (de)
ES (1) ES2294784T3 (de)
HU (1) HUP0000257A3 (de)
MA (1) MA24416A1 (de)
TR (1) TR199901239T2 (de)
WO (1) WO1998024875A1 (de)
ZA (1) ZA9710696B (de)

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EP0896053B1 (de) * 1997-08-08 2004-09-08 The Procter & Gamble Company Waschmitteltablette
EP0997387A1 (de) 1998-10-28 2000-05-03 The Procter & Gamble Company Parfüm- bzw. Duftstoffe abgebende Verpackungsmaterialien
GB9826097D0 (en) * 1998-11-27 1999-01-20 Unilever Plc Detergent compositions
ATE257856T1 (de) * 1999-02-03 2004-01-15 Procter & Gamble Beschichtetes reinigungsmittel in tablettenform
EP1026229A1 (de) * 1999-02-03 2000-08-09 The Procter & Gamble Company Beschichtetes Reinigungsmittel in Tablettenform
EP1026227A1 (de) * 1999-02-03 2000-08-09 The Procter & Gamble Company Beschichtetes Reinigungsmittel in Tablettenform
DE69938228T2 (de) * 1999-03-12 2009-02-19 The Procter & Gamble Company, Cincinnati Parfümierte Waschmitteltablette
US6630438B1 (en) 1999-03-12 2003-10-07 The Procter & Gamble Company Perfumed detergent tablet
US7084102B1 (en) 1999-03-12 2006-08-01 The Procter & Gamble Company Perfumed detergent tablet
DE69939424D1 (de) * 1999-03-12 2008-10-09 Procter & Gamble Parfümierte Waschmitteltablette
EP1072715A1 (de) 1999-07-19 2001-01-31 The Procter & Gamble Company Abgabevorrichtung für Waschmitteltabletten
EP1072674A1 (de) * 1999-07-27 2001-01-31 The Procter & Gamble Company Beschichtetes Reinigungsmittel in Tablettenform
DE19940547A1 (de) 1999-08-26 2001-03-01 Henkel Kgaa Wasch- oder Reinigungsmittelformkörper mit Partialcoating
DE10064985A1 (de) 2000-12-23 2002-07-11 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit Beschichtung
RU2303052C2 (ru) * 2001-05-03 2007-07-20 Унилевер Н.В. Формованное моющее средство и способ его производства
DE10125441A1 (de) * 2001-05-25 2002-12-05 Henkel Kgaa Verfahren und benötigte Zusätze zur Erhöhung der Stabilität von Tabletten
EP1293556A1 (de) * 2001-09-14 2003-03-19 Rent-a-Scientist GmbH Waschmitteltablette mit Harnstoff enthalter Umhüllung
DE102004040330A1 (de) 2004-08-20 2006-03-02 Henkel Kgaa Beschichteter Wasch- oder Reinigungsmittelformkörper
CN103201373B (zh) 2010-10-14 2016-06-08 荷兰联合利华有限公司 洗衣用洗涤剂颗粒
MY162810A (en) 2010-10-14 2017-07-14 Unilever Nv Laundry detergent particles
ES2542240T3 (es) 2010-10-14 2015-08-03 Unilever N.V. Fabricación de detergentes particulados revestidos
AU2011315793B2 (en) 2010-10-14 2014-03-06 Unilever Plc Laundry detergent particles
EP2627754B1 (de) 2010-10-14 2016-11-30 Unilever PLC Waschmittelteilchen
PH12013500623A1 (en) 2010-10-14 2017-07-28 Unilever Ip Holdings B V Laundry detergent particle
JP6504796B2 (ja) * 2014-11-20 2019-04-24 花王株式会社 機械練り石鹸の製造方法

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Publication number Publication date
AR010746A1 (es) 2000-07-12
CA2273325A1 (en) 1998-06-11
ATE380235T1 (de) 2007-12-15
BR9714379A (pt) 2000-03-21
JP2001505604A (ja) 2001-04-24
MA24416A1 (fr) 1998-07-01
CA2273325C (en) 2002-12-24
EP0846755A1 (de) 1998-06-10
HUP0000257A3 (en) 2001-11-28
DE69637355D1 (de) 2008-01-17
EG20924A (en) 2000-06-28
WO1998024875A1 (en) 1998-06-11
ES2294784T3 (es) 2008-04-01
AU5443898A (en) 1998-06-29
CN1245529A (zh) 2000-02-23
ZA9710696B (en) 1998-08-26
HUP0000257A2 (hu) 2000-06-28
TR199901239T2 (xx) 1999-08-23
DE69637355T2 (de) 2008-10-23

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