EP0846755B1 - Comprimé détergent sous forme de tablette enrobée - Google Patents
Comprimé détergent sous forme de tablette enrobée Download PDFInfo
- 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
Links
- HTTLBYITFHMYFK-UHFFFAOYSA-N O=C1OC(c2ccccc2)=Nc2c1cccc2 Chemical compound O=C1OC(c2ccccc2)=Nc2c1cccc2 HTTLBYITFHMYFK-UHFFFAOYSA-N 0.000 description 1
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)
- Tablette comprenant un noyau et un enrobage, le noyau étant formé en comprimant un matériau particulaire, le matériau particulaire comprenant un agent tensioactif et un adjuvant de détergence, caractérisée en ce que l'enrobage comprend de l'acide adipique, des acides dicarboxyliques en C8 à C13, ou leurs mélanges, qui a une solubilité dans l'eau à 25 °C de moins de 20 g/L.
- Tablette selon la revendication 1, comprenant un enrobage de matériaux sensiblement insolubles dans l'eau ayant un point de fusion dans la gamme allant de 40 °C à 180 °C.
- Procédé de fabrication d'un tablette comprenant les étapes consistant à :(a) former un noyau en comprimant un matériau particulaire, le matériau particulaire comprenant un agent tensioactif et un adjuvant de détergence ;(b) appliquer un matériau d'enrobage sur le noyau, le matériau d'enrobage étant sous la forme d'une fonte ;(c) laisser le matériau d'enrobage fondu se solidifier ;caractérisé en ce que le matériau d'enrobage comprend de l'acide adipique, des acides dicarboxyliques en C8 à C13, ou leurs mélanges, qui a une solubilité dans l'eau à 25 °C de moins de 20 g/L.
- Procédé selon la revendication 3, dans lequel le matériau d'enrobage, ou le mélange de matériaux, a un point de fusion allant de 40 °C à 180 °C.
- Procédé de fabrication d'une tablette comprenant les étapes consistant à:(a) former un noyau en comprimant un matériau particulaire, le matériau particulaire comprenant un agent tensioactif et un adjuvant de détergence;(b) appliquer un matériau d'enrobage sur le noyau, le matériau d'enrobage étant dissous dans un solvant;(c) laisser le solvant s'évaporer;caractérisé en ce que le matériau d'enrobage comprend de l'acide adipique, des acides dicarboxyliques en C8 à C13, ou leurs mélanges, qui a une solubilité dans l'eau à 25 °C de moins de 20 g/L.
Priority Applications (17)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96203471A EP0846755B1 (fr) | 1996-12-06 | 1996-12-06 | Comprimé détergent sous forme de tablette enrobée |
AT96203471T ATE380235T1 (de) | 1996-12-06 | 1996-12-06 | Beschichtetes reinigungsmittel in tablettenform |
DE69637355T DE69637355T2 (de) | 1996-12-06 | 1996-12-06 | Beschichtetes Reinigungsmittel in Tablettenform |
ES96203471T ES2294784T3 (es) | 1996-12-06 | 1996-12-06 | Pastilla de detergente recubierta. |
HU0000257A HUP0000257A3 (en) | 1996-12-06 | 1997-11-19 | Coated detergent tablet |
US09/319,474 US6232284B1 (en) | 1996-12-06 | 1997-11-19 | Coated detergent tablet with disintegration means |
CA002273325A CA2273325C (fr) | 1996-12-06 | 1997-11-19 | Pain de detergent a enrobage |
CN97181566.6A CN1245529A (zh) | 1996-12-06 | 1997-11-19 | 涂覆的洗涤剂片 |
TR1999/01239T TR199901239T2 (xx) | 1996-12-06 | 1997-11-19 | Kaplanm�� deterjan tableti. |
JP52560498A JP2001505604A (ja) | 1996-12-06 | 1997-11-19 | 被覆洗浄剤タブレット |
AU54438/98A AU5443898A (en) | 1996-12-06 | 1997-11-19 | Coated detergent tablet |
PCT/US1997/021044 WO1998024875A1 (fr) | 1996-12-06 | 1997-11-19 | Pain de detergent a enrobage |
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 |
MA24888A MA24416A1 (fr) | 1996-12-06 | 1997-12-05 | Comprime detergent enrobe |
ARP970105746A AR010746A1 (es) | 1996-12-06 | 1997-12-05 | Tableta que comprende un nucleo y un recubrimiento y proceso para fabricar dicha tableta |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96203471A EP0846755B1 (fr) | 1996-12-06 | 1996-12-06 | Comprimé détergent sous forme de tablette enrobée |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0846755A1 EP0846755A1 (fr) | 1998-06-10 |
EP0846755B1 true EP0846755B1 (fr) | 2007-12-05 |
Family
ID=8224673
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96203471A Expired - Lifetime EP0846755B1 (fr) | 1996-12-06 | 1996-12-06 | Comprimé détergent sous forme de tablette enrobée |
Country Status (16)
Country | Link |
---|---|
EP (1) | EP0846755B1 (fr) |
JP (1) | JP2001505604A (fr) |
CN (1) | CN1245529A (fr) |
AR (1) | AR010746A1 (fr) |
AT (1) | ATE380235T1 (fr) |
AU (1) | AU5443898A (fr) |
BR (1) | BR9714379A (fr) |
CA (1) | CA2273325C (fr) |
DE (1) | DE69637355T2 (fr) |
EG (1) | EG20924A (fr) |
ES (1) | ES2294784T3 (fr) |
HU (1) | HUP0000257A3 (fr) |
MA (1) | MA24416A1 (fr) |
TR (1) | TR199901239T2 (fr) |
WO (1) | WO1998024875A1 (fr) |
ZA (1) | ZA9710696B (fr) |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0896053B1 (fr) * | 1997-08-08 | 2004-09-08 | The Procter & Gamble Company | Tablette détergente |
EP0997387A1 (fr) | 1998-10-28 | 2000-05-03 | The Procter & Gamble Company | Matériaux d'emballage exhalant un parfum ou autre substance odorifère |
GB9826097D0 (en) * | 1998-11-27 | 1999-01-20 | Unilever Plc | Detergent compositions |
EP1026227A1 (fr) * | 1999-02-03 | 2000-08-09 | The Procter & Gamble Company | Comprimé détergent sous forme de tablette enrobée |
ES2212513T3 (es) * | 1999-02-03 | 2004-07-16 | THE PROCTER & GAMBLE COMPANY | Pastilla detergente revestida. |
EP1026229A1 (fr) * | 1999-02-03 | 2000-08-09 | The Procter & Gamble Company | Comprimé détergent sous forme de tablette enrobée |
EP1035198B1 (fr) * | 1999-03-12 | 2008-08-27 | The Procter & Gamble Company | Comprimé détergent parfumé |
ATE387486T1 (de) * | 1999-03-12 | 2008-03-15 | Procter & Gamble | Parfümierte waschmitteltablette |
US7084102B1 (en) | 1999-03-12 | 2006-08-01 | The Procter & Gamble Company | Perfumed detergent tablet |
US6630438B1 (en) | 1999-03-12 | 2003-10-07 | The Procter & Gamble Company | Perfumed detergent tablet |
EP1072715A1 (fr) | 1999-07-19 | 2001-01-31 | The Procter & Gamble Company | Distributeur de détergent en pastilles |
EP1072674A1 (fr) * | 1999-07-27 | 2001-01-31 | The Procter & Gamble Company | Comprimé détergent sous forme de tablette enrobée |
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 |
PL199102B1 (pl) * | 2001-05-03 | 2008-08-29 | Unilever Nv | Ukształtowana detergentowa kompozycja i sposób jej wytwarzania |
DE10125441A1 (de) * | 2001-05-25 | 2002-12-05 | Henkel Kgaa | Verfahren und benötigte Zusätze zur Erhöhung der Stabilität von Tabletten |
EP1293556A1 (fr) * | 2001-09-14 | 2003-03-19 | Rent-a-Scientist GmbH | Détergent sous forme de tablette ayant un revêtement comprenant de l'urée |
DE102004040330A1 (de) | 2004-08-20 | 2006-03-02 | Henkel Kgaa | Beschichteter Wasch- oder Reinigungsmittelformkörper |
CN103154230B (zh) | 2010-10-14 | 2015-01-21 | 荷兰联合利华有限公司 | 洗衣用洗涤剂颗粒 |
MY164216A (en) | 2010-10-14 | 2017-11-30 | Unilever Nv | Laundry detergent particles |
AU2011315792B2 (en) | 2010-10-14 | 2014-03-13 | Unilever Plc | Laundry detergent particle |
IN2013MN00622A (fr) | 2010-10-14 | 2015-06-12 | Unilever Plc | |
CA2813697C (fr) | 2010-10-14 | 2018-08-28 | Unilever Plc | Fabrication de detergents particulaires enrobes |
US9273271B2 (en) | 2010-10-14 | 2016-03-01 | Conopco Inc. | Laundry detergent particles |
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 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0716144A2 (fr) * | 1994-11-14 | 1996-06-12 | Unilever Plc | Détergent sous forme de tablette ayant un revêtement soluble dans l'eau |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1183960A (fr) * | 1957-10-05 | 1959-07-16 | Belge Produits Chimiques Sa | Compositions détergentes solides |
US4253842A (en) * | 1974-05-15 | 1981-03-03 | Colgate-Palmolive Company | Detergent compositions and washing methods including and utilizing separate tablets of components |
US4219436A (en) * | 1977-06-01 | 1980-08-26 | The Procter & Gamble Company | High density, high alkalinity dishwashing detergent tablet |
NL7815064A (nl) * | 1977-11-29 | 1980-05-30 | Procter & Gamble | Wasmiddeltablet met een bekleding van gehydrateerd zout en werkwijze voor het vervaardigen van dit tablet. |
GB2041966A (en) * | 1977-11-29 | 1980-09-17 | Procter & Gamble | Detergent tablet having a hydrated salt coating and process for preparing the tablet |
JPH0674440B2 (ja) * | 1986-03-27 | 1994-09-21 | ライオン株式会社 | 錠剤型洗剤 |
IE61651B1 (en) * | 1990-07-04 | 1994-11-16 | Zambon Spa | Programmed release oral solid pharmaceutical dosage form |
US5133892A (en) * | 1990-10-17 | 1992-07-28 | Lever Brothers Company, Division Of Conopco, Inc. | Machine dishwashing detergent tablets |
CA2171616C (fr) * | 1993-12-30 | 2005-07-26 | Bernard Joseph Heile | Article detergent hygroscopique stable |
-
1996
- 1996-12-06 ES ES96203471T patent/ES2294784T3/es not_active Expired - Lifetime
- 1996-12-06 DE DE69637355T patent/DE69637355T2/de not_active Expired - Fee Related
- 1996-12-06 AT AT96203471T patent/ATE380235T1/de not_active IP Right Cessation
- 1996-12-06 EP EP96203471A patent/EP0846755B1/fr not_active Expired - Lifetime
-
1997
- 1997-11-19 WO PCT/US1997/021044 patent/WO1998024875A1/fr not_active Application Discontinuation
- 1997-11-19 CA CA002273325A patent/CA2273325C/fr not_active Expired - Fee Related
- 1997-11-19 CN CN97181566.6A patent/CN1245529A/zh active Pending
- 1997-11-19 TR TR1999/01239T patent/TR199901239T2/xx unknown
- 1997-11-19 BR BR9714379A patent/BR9714379A/pt not_active IP Right Cessation
- 1997-11-19 AU AU54438/98A patent/AU5443898A/en not_active Abandoned
- 1997-11-19 HU HU0000257A patent/HUP0000257A3/hu unknown
- 1997-11-19 JP JP52560498A patent/JP2001505604A/ja not_active Ceased
- 1997-11-27 ZA ZA9710696A patent/ZA9710696B/xx unknown
- 1997-12-04 EG EG129597A patent/EG20924A/xx active
- 1997-12-05 MA MA24888A patent/MA24416A1/fr unknown
- 1997-12-05 AR ARP970105746A patent/AR010746A1/es unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0716144A2 (fr) * | 1994-11-14 | 1996-06-12 | Unilever Plc | Détergent sous forme de tablette ayant un revêtement soluble dans l'eau |
Also Published As
Publication number | Publication date |
---|---|
CN1245529A (zh) | 2000-02-23 |
BR9714379A (pt) | 2000-03-21 |
TR199901239T2 (xx) | 1999-08-23 |
JP2001505604A (ja) | 2001-04-24 |
WO1998024875A1 (fr) | 1998-06-11 |
EP0846755A1 (fr) | 1998-06-10 |
HUP0000257A3 (en) | 2001-11-28 |
DE69637355D1 (de) | 2008-01-17 |
DE69637355T2 (de) | 2008-10-23 |
ATE380235T1 (de) | 2007-12-15 |
ES2294784T3 (es) | 2008-04-01 |
ZA9710696B (en) | 1998-08-26 |
CA2273325A1 (fr) | 1998-06-11 |
MA24416A1 (fr) | 1998-07-01 |
AU5443898A (en) | 1998-06-29 |
HUP0000257A2 (hu) | 2000-06-28 |
CA2273325C (fr) | 2002-12-24 |
EG20924A (en) | 2000-06-28 |
AR010746A1 (es) | 2000-07-12 |
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