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EP0846756A1 - Comprimé détergent sous forme de tablette enrobée - Google Patents

Comprimé détergent sous forme de tablette enrobée Download PDF

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Publication number
EP0846756A1
EP0846756A1 EP96203473A EP96203473A EP0846756A1 EP 0846756 A1 EP0846756 A1 EP 0846756A1 EP 96203473 A EP96203473 A EP 96203473A EP 96203473 A EP96203473 A EP 96203473A EP 0846756 A1 EP0846756 A1 EP 0846756A1
Authority
EP
European Patent Office
Prior art keywords
tablet
coating
coating material
tablets
core
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.)
Granted
Application number
EP96203473A
Other languages
German (de)
English (en)
Other versions
EP0846756B1 (fr
Inventor
Serge Salager
Paul Irma Albertus Van Dijk
Jeroen Van Poucke
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 ES96203473T priority Critical patent/ES2284164T3/es
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AT96203473T priority patent/ATE360056T1/de
Priority to EP96203473A priority patent/EP0846756B1/fr
Priority to DE69637030T priority patent/DE69637030T2/de
Priority to PCT/US1997/021041 priority patent/WO1998024873A1/fr
Priority to TR1999/01233T priority patent/TR199901233T2/xx
Priority to US09/319,475 priority patent/US6169062B1/en
Priority to JP52560298A priority patent/JP2001506682A/ja
Priority to HU0000221A priority patent/HUP0000221A3/hu
Priority to CN97181564.XA priority patent/CN1245527A/zh
Priority to BR9713871-1A priority patent/BR9713871A/pt
Priority to AU54436/98A priority patent/AU5443698A/en
Priority to CA002272537A priority patent/CA2272537C/fr
Priority to ZA9710697A priority patent/ZA9710697B/xx
Priority to EG129797A priority patent/EG21191A/xx
Priority to ARP970105747A priority patent/AR010747A1/es
Priority to MA24890A priority patent/MA24418A1/fr
Publication of EP0846756A1 publication Critical patent/EP0846756A1/fr
Application granted granted Critical
Publication of EP0846756B1 publication Critical patent/EP0846756B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0052—Gas evolving or heat producing compositions

Definitions

  • the present invention relates to coated detergent tablets, especially those adapted for use in washing machines, and to processes for making the coated detergent tablets.
  • coating of tablets is often desired for aesthetic reasons, to improve the outer appearance of the tablet or to achieve some particular aesthetic effect.
  • 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.
  • EP-A-0 716 144 published on 12th June 1996, also discloses laundry detergent tablets with water-soluble coatings which may be organic polymers including acrylic/maleic co-polymer, polyethylene glycol, PVPVA, and sugar.
  • WO9518215 published on 6th July 1995, provides water-insoluble coatings for solid cast tablets.
  • the tablets are provided with hydrophobic coatings including wax, fatty acid, fatty acid amides, and polyethylene glycol.
  • a disadvantage of the prior art disclosures is that a coating which is thick enough and strong enough to withstand abrasion, also tends to be slow to break up or dissolve in use.
  • 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 particular in alkaline or surfactant-rich solutions such as the wash liquor.
  • the object of the present invention is achieved by providing a tablet which further comprises a disintegrant, at least some of the disintegrant being in the coating. It is preferred that the tablet further comprises an effervescent, for example a soluble acid source and an alkali metal carbonate.
  • 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 detergent tablets can be made in any size or shape and can, if desired, be surface treated before coating, according to the present invention.
  • a surfactant and a builder which normally provides a substantial part of the cleaning power of the tablet.
  • builder is intended to mean all materials which tend to remove calcium ion from solution, either by ion exchange, complexation, sequestration or precipitation.
  • 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 Courtoy®, 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 , preferably not exceed 3000 kN/m , and most preferably not exceed 1000 kN/m .
  • the tablets are then coated with a coating 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".
  • Suitable coating materials are fatty acids, C2-C13 dicarboxylic acids, fatty alcohols, diols, esters and ethers.
  • Preferred fatty acids are those having a carbon chain length of from C12 to C22 and most preferably from C18 to C22.
  • Preferred dicarboxylic acids are oxalic acid (C2), malonic acid (C3), succinic acid (C4), glutaric acid (C5), adipic acid (C6), pimelic acid (C7), suberic acid (C8), azelaic acid (C9), sebacic acid (C10), undecanedioic acid (C11), dodecanedioic acid (C12) and tridecanedioic acid (C13).
  • Preferred fatty alcohols are those having a carbon chain length of from C12 to C22 and most preferably from C14 to C18.
  • Preferred diols are 1,2-octadecanediol and 1,2-hexadecanediol.
  • Preferred esters are tristearin, tripalmitin, methylbehenate, ethylstearate.
  • Preferred ethers are diethyleneglycol mono hexadecylether, diethyleneglycol mono octadecylether, diethyleneglycol mono 0tetradecylether, phenylether, ethyl naphtyl ether, 2 methoxynaphtalene, beta naphtyl methyl ether and glycerol monooctadecylether.
  • Other preferred coating materials include dimethyl 2,2 propanol, 2 hexadecanol, 2 octadecanone, 2 hexadecanone, 2, 15 hexadecanedione and 2 hydroxybenzyl alcohol.
  • the detergent tablets are prepared and in whatever from they are, they are then coated according to the present invention with a coating material having a melting point preferably of from 40 °C to 200 °C.
  • the coating can be applied in a number of ways. Two preferred coating methods are a) coating with a molten material and b) coating with a solution of the material. In a), the coating material is applied at a temperature above its melting point, and solidifies on the tablet. In b), the coating is applied as a solution, the solvent being dried to leave a coherent coating.
  • the substantially insoluble material can be applied to the tablet by, for example, spraying or dipping. Normally when the molten material is sprayed on to the tablet, it will rapidly solidify to form a coherent coating.
  • 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 200 °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 tablet coatings of the present invention are very hard and provide extra strength to the tablet.
  • the fracture of the coating in the wash is improved by adding a disintegrant in the coating.
  • This disintegrant will swell once in contact with water and break the coating in small pieces. This will improve the dissolution of the coating in the wash solution.
  • the disintegrant is suspended in the coating melt at a level of up to 30%, preferably between 5 and 20%, and most preferably between 5 and 10% by weight. Possible disintegrants are described in Handbook of Pharmaceutical Excipients (1986).
  • Suitable disintegrants include starch: natural, modified or pregelatinized starch, sodium starch gluconate; gum: agar gum, guar gum, locust bean gum, karaya gum, pectin gum, tragacanth gum; croscarmylose Sodium, crospovidone, cellulose, carboxymethyl cellulose, algenic acid and its salts including sodium alginate, silicone dioxide, clay, polyvinylpyrrolidone, soy polysacharides, ion exchange resins and mixtures thereof.
  • the used compaction force will be adjusted to not affect the strength (Diametral Fracture Stress), and the disintegration time in the washing machine.
  • This process may be used to prepare homogenous or layered tablets of any size or shape.
  • the rate of disintegration of a detergent tablet can be determined in two ways :
  • 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.
  • this effervescent improves the disintegration time of the tablet.
  • the amount will preferably be between 5 and 20 % and most preferably between 10 and 20% by weight of the tablet.
  • the effervescent should be added as an agglomerate of the different particles or as a compact, and not as separated particles. Due to the gas created by the effervescency in the tablet, the tablet can have a higher D.F.S. and still have the same disintegration time as a tablet without effervescency. When the D.F.S. of the tablet with effervescency is kept the same as a tablet without, the disintegration of the tablet with effervescency will be faster.
  • 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 EO 1-5
  • 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.
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C 12 -C 18 glucamides can be used for low sudsing.
  • C 10 -C 20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C 10 -C 16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness.
  • Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils. The level of builder can vary widely depending upon the end use of the composition.
  • Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • 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.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na 2 SiO 5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x O 2x+1 ⁇ yH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na 2 SiO 5 (NaSKS-6 form) is most preferred for use herein.
  • Other 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.
  • 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.
  • Examples of 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. Aluminosilicate builders include those having the empirical formula: M z (zAlO 2 ) y ] ⁇ xH 2 O
  • the detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
  • bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering.
  • the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S.
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.
  • a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. Mixtures of bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
  • bleach activators Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • Highly preferred amido-derived bleach activators are those of the formulae: R 1 N(R 5 )C(O)R 2 C(O)L or R 1 C(O)N(R 5 )R 2 C(O)L
  • Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of refugee dye transfer, and for fabric restoration.
  • the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof.
  • Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on.
  • bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition.
  • the compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation.
  • Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms.
  • protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
  • Proteolytic enzymes suitable for removing protein-based stains include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
  • Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No.
  • Amylases include, for example, ⁇ -amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
  • the cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander).
  • suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) is especially useful.
  • 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.
  • Lipase P Lipase 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. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
  • a wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al.
  • Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both.
  • Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations are disclosed in U.S. Patent 4,261,868, Hora et al, issued April 14, 1981.
  • Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent 3,519,570.
  • 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.
  • Nonionic agglomerates comprise 26% nonionic surfactant, 48% zeolite and 26% carbonate.
  • Bleach activator agglomerates comprise 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.
  • Zinc Phthalocyanine sulphonate encapsulates are 10% active.
  • Suds suppressor comprises 11.5% silicone oil (ex Dow Corning), and 88.5% starch.
  • Layered silicate comprises 78% SKS-6, ex Hoechst, 22% citric acid.
  • Dye transfer inhibitor agglomerates comprise 21% PVNO/PVPVI, 61% zeolite and 18% carbonate.
  • Perfume encapsulates comprise 50% perfume and 50% starch.
  • Nonionic paste spray-on comprises 67% C12-C15 AE5 (alcohol with an average of 5 ethoxy groups per molecule), 24% N-methyl glucose amide and 9% water.
  • Effervescent compact comprises 54.5% sodium bicarbonate and 45.5% citric acid.
  • 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.
  • Comparative Example 3 the process of example 1 was repeated but without the disintegrant.
  • the final tensile strength of the three series of tablets was 6.5 kPa, 15.5 kPa and 19.5 kPa respectively.
  • Comparative Example 4 the process of example 4 was repeated but without the disintegrant.
  • the final tensile strength of the three series of tablets was 10.4 kPa, 14.5 kPa and 21.3 kPa respectively.

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  • 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)
EP96203473A 1996-12-06 1996-12-06 Comprimé détergent sous forme de tablette enrobée et procédé de fabrication Expired - Lifetime EP0846756B1 (fr)

Priority Applications (17)

Application Number Priority Date Filing Date Title
AT96203473T ATE360056T1 (de) 1996-12-06 1996-12-06 Beschichtetes reinigungsmittels in tablettenform und herstellungsverfahren dafür
EP96203473A EP0846756B1 (fr) 1996-12-06 1996-12-06 Comprimé détergent sous forme de tablette enrobée et procédé de fabrication
DE69637030T DE69637030T2 (de) 1996-12-06 1996-12-06 Beschichtetes Reinigungsmittel in Tablettenform und Herstellungsverfahren dafür
ES96203473T ES2284164T3 (es) 1996-12-06 1996-12-06 Pastilla de detergente recubierta y procedimiento para producir la misma.
HU0000221A HUP0000221A3 (en) 1996-12-06 1997-11-19 Coated detergent tablet
TR1999/01233T TR199901233T2 (xx) 1996-12-06 1997-11-19 Kaplanm�� deterjan tableti.
US09/319,475 US6169062B1 (en) 1996-12-06 1997-11-19 Coated detergent tablet
JP52560298A JP2001506682A (ja) 1996-12-06 1997-11-19 被覆洗浄剤タブレット
PCT/US1997/021041 WO1998024873A1 (fr) 1996-12-06 1997-11-19 Detergent en pain a enrobage
CN97181564.XA CN1245527A (zh) 1996-12-06 1997-11-19 涂覆的洗涤剂片
BR9713871-1A BR9713871A (pt) 1996-12-06 1997-11-19 Tablete detergente revestido
AU54436/98A AU5443698A (en) 1996-12-06 1997-11-19 Coated detergent tablet
CA002272537A CA2272537C (fr) 1996-12-06 1997-11-19 Detergent en pain a enrobage
ZA9710697A ZA9710697B (en) 1996-12-06 1997-11-27 Coated detergent tablet.
EG129797A EG21191A (en) 1996-12-06 1997-12-04 Cooted detergent tablet
MA24890A MA24418A1 (fr) 1996-12-06 1997-12-05 Comprime detergent enrobe
ARP970105747A AR010747A1 (es) 1996-12-06 1997-12-05 Tableta de detergente recubierta y proceso para fabricar dicha tableta

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP96203473A EP0846756B1 (fr) 1996-12-06 1996-12-06 Comprimé détergent sous forme de tablette enrobée et procédé de fabrication

Publications (2)

Publication Number Publication Date
EP0846756A1 true EP0846756A1 (fr) 1998-06-10
EP0846756B1 EP0846756B1 (fr) 2007-04-18

Family

ID=8224675

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96203473A Expired - Lifetime EP0846756B1 (fr) 1996-12-06 1996-12-06 Comprimé détergent sous forme de tablette enrobée et procédé de fabrication

Country Status (16)

Country Link
EP (1) EP0846756B1 (fr)
JP (1) JP2001506682A (fr)
CN (1) CN1245527A (fr)
AR (1) AR010747A1 (fr)
AT (1) ATE360056T1 (fr)
AU (1) AU5443698A (fr)
BR (1) BR9713871A (fr)
CA (1) CA2272537C (fr)
DE (1) DE69637030T2 (fr)
EG (1) EG21191A (fr)
ES (1) ES2284164T3 (fr)
HU (1) HUP0000221A3 (fr)
MA (1) MA24418A1 (fr)
TR (1) TR199901233T2 (fr)
WO (1) WO1998024873A1 (fr)
ZA (1) ZA9710697B (fr)

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999013042A1 (fr) * 1997-09-09 1999-03-18 Henkel Kommanditgesellschaft Auf Aktien Corps moules de produit detergent et nettoyant a solubilite amelioree
WO1999024547A1 (fr) * 1997-11-10 1999-05-20 The Procter & Gamble Company Composition de detergent
EP0971028A1 (fr) * 1998-07-10 2000-01-12 The Procter & Gamble Company Comprimé détergent à caractéristiques de dissolution et mécaniques améliorées
EP0971029A1 (fr) * 1998-07-10 2000-01-12 The Procter & Gamble Company Comprimé détergent ayant des caractéristiques mécaniques et des propriétés de dissolution élevées
GB2339574A (en) * 1998-07-15 2000-02-02 Procter & Gamble Disintegrating components
EP0997387A1 (fr) 1998-10-28 2000-05-03 The Procter & Gamble Company Matériaux d'emballage exhalant un parfum ou autre substance odorifère
EP1026227A1 (fr) * 1999-02-03 2000-08-09 The Procter & Gamble Company Comprimé détergent sous forme de tablette enrobée
EP1026229A1 (fr) * 1999-02-03 2000-08-09 The Procter & Gamble Company Comprimé détergent sous forme de tablette enrobée
EP1026228A1 (fr) * 1999-02-03 2000-08-09 The Procter & Gamble Company Comprimé détergent sous forme de tablette enrobée
EP1043389A1 (fr) * 1999-03-29 2000-10-11 DALLI-WERKE WÄSCHE-UND KÖRPERPFLEGE GmbH & Co.KG. Comprimés détergents contenant un desintégrant granulaire
EP1043388A1 (fr) * 1999-03-29 2000-10-11 DALLI-WERKE WÄSCHE-UND KÖRPERPFLEGE GmbH & Co.KG. Comprimés détergents pour le lavage de vaisselle en machine contenant un desintégrant granulaire
WO2000066688A1 (fr) * 1999-04-30 2000-11-09 The Procter & Gamble Company Pastilles et compositions de nettoyage
EP1035199A3 (fr) * 1999-03-12 2000-12-20 The Procter & Gamble Company Comprimé détergent parfumé
EP1035198A3 (fr) * 1999-03-12 2001-01-03 The Procter & Gamble Company Comprimé détergent parfumé
EP1072674A1 (fr) * 1999-07-27 2001-01-31 The Procter & Gamble Company Comprimé détergent sous forme de tablette enrobée
WO2001025391A1 (fr) * 1999-10-06 2001-04-12 The Procter & Gamble Company Comprime detergent presentant des caracteristiques dissolvantes et mecaniques puissantes
US6221832B1 (en) 1998-11-11 2001-04-24 Stockhausen Gmbh & Co. Kg Compacted granulate, process for making same and use as disintegrating agent for pressed detergent tablets, cleaning agent tablets for dishwashers, water softening tablets or scouring salt tablets
US6232285B1 (en) 1998-11-11 2001-05-15 Stockhausen Gmbh & Co. Kg Compacted granulate, process for making same and use as disintegrating agent for pressed detergent tablets, cleaning agent tablets for dishwashers, water softening tablets and scouring salt tablets
EP1099751A3 (fr) * 1999-11-02 2001-08-01 Smiths Industries Public Limited Company Moyens de rebut
US6274538B1 (en) 1997-11-10 2001-08-14 The Procter & Gamble Company Detergent compositions
US6340664B1 (en) 1999-08-26 2002-01-22 Henkel Kommanditgesellschaft Auf Aktien (Kgaa) Laundry detergent or cleaning product tablets with partial coating
WO2002042404A1 (fr) * 2000-11-24 2002-05-30 Unilever N.V. Comprimes de nettoyage
EP1293556A1 (fr) * 2001-09-14 2003-03-19 Rent-a-Scientist GmbH Détergent sous forme de tablette ayant un revêtement comprenant de l'urée
US6559115B1 (en) * 1998-07-10 2003-05-06 The Procter & Gamble Company Detergent tablet with high mechanical and dissolution characteristics
EP1113071A3 (fr) * 1997-12-02 2003-08-20 The Procter & Gamble Company Compositions détergentes
US6630438B1 (en) 1999-03-12 2003-10-07 The Procter & Gamble Company Perfumed detergent tablet
US6812200B2 (en) 2000-12-23 2004-11-02 Henkel Kommanditgesellschaft Auf Aktien Process for coating detergent tablets
US7084102B1 (en) 1999-03-12 2006-08-01 The Procter & Gamble Company Perfumed detergent tablet
DE19920118B4 (de) * 1999-05-03 2016-08-11 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittelformkörper mit Beschichtung und Verfahren zu seiner Herstellung
US9493731B2 (en) 2010-11-12 2016-11-15 Dental Care Innovation Gmbh Soluble tablet, containing abrasive media
US10959931B2 (en) 2017-02-02 2021-03-30 Water Pik, Inc. Tablet including abrasive for dental cleaning

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0896053B1 (fr) * 1997-08-08 2004-09-08 The Procter & Gamble Company Tablette détergente
WO2000043488A1 (fr) * 1999-01-23 2000-07-27 The Procter & Gamble Company Comprime detergent
GB9901688D0 (en) 1999-01-26 1999-03-17 Unilever Plc Detergent compositions
JP3352977B2 (ja) 1999-06-15 2002-12-03 花王株式会社 固形状洗剤
JP4424605B2 (ja) * 2004-12-09 2010-03-03 花王株式会社 洗浄剤
DE102006029793A1 (de) * 2006-06-27 2008-01-03 Licciardi, Natale, Dipl.-Ing. Verfahren zur Herstellung eines Schiebenreinigerkonzentrats in Tablettenform, Scheibenreinigerkonzentrat selbst und entsprechende Aufmachung
WO2008040152A1 (fr) * 2006-09-01 2008-04-10 Tao Wang Détergent solide et son procédé de préparation
JP5917964B2 (ja) * 2012-03-19 2016-05-18 富士ゼロックス株式会社 錠剤、錠剤の製造方法、錠剤管理装置、錠剤照合装置及びプログラム
JP5985547B2 (ja) * 2013-07-25 2016-09-06 四国化成工業株式会社 浮上性発泡錠剤
RU2017123523A (ru) 2014-12-05 2019-01-11 Далли-Верке Гмбх Унд Ко. Кг Шипучие композиции, содержащие пектин
ES2586461B1 (es) * 2015-03-12 2017-12-01 Lorena MARTÍ COMA Composición detergente en forma de pastilla efervescente
CN106381236A (zh) * 2016-08-27 2017-02-08 朱耀灯 一种洗衣片及其制备方法
CN106381235A (zh) * 2016-08-27 2017-02-08 朱耀灯 一种超浓缩多功能洗衣片及其制备方法
CN106367222A (zh) * 2016-08-27 2017-02-01 朱耀灯 一种多功能洗衣片及其制备方法
EP3825392A1 (fr) 2019-11-21 2021-05-26 Dalli-Werke GmbH & Co. KG Pastille de détergent comprenant un système effervescent
EP4166638A1 (fr) 2021-10-13 2023-04-19 CLARO Products GmbH Pastille de nettoyage destinée au nettoyage des lunettes

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US3487021A (en) * 1966-08-11 1969-12-30 Katz Jacob M One-use hand-cleaning tablets
DE2406455A1 (de) * 1974-02-11 1975-08-21 Henkel & Cie Gmbh Lagerbestaendiger, leichtloeslicher waschmittelzusatz und verfahren zu dessen herstellung
CA2040307A1 (fr) * 1991-04-12 1992-10-13 Yogesh Sennik Comprimes de detergent efferverscent
EP0522766A2 (fr) * 1991-07-01 1993-01-13 Unilever Plc Compositions détergentes sous forme de tablettes
EP0711828A2 (fr) * 1994-11-14 1996-05-15 Unilever Plc Compositions détergentes

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US3231506A (en) * 1961-04-03 1966-01-25 Colgate Palmolive Co Process for making detergent tablet
US3324038A (en) * 1964-04-17 1967-06-06 Procter & Gamble Detergent composition
US3751277A (en) * 1971-03-24 1973-08-07 Dow Chemical Co Tablet coating process and composition
CA1120819A (fr) * 1977-06-01 1982-03-30 Jurgen W.K. Gromer Comprime detersif
GB2041966A (en) * 1977-11-29 1980-09-17 Procter & Gamble Detergent tablet having a hydrated salt coating and process for preparing the tablet
DE3417820A1 (de) * 1984-05-14 1985-11-14 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung eines waschzusatzes in tablettenform
GB9015503D0 (en) * 1990-07-13 1990-08-29 Unilever Plc Detergent composition
GB9015504D0 (en) * 1990-07-13 1990-08-29 Unilever Plc Detergents composition
GB9422924D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions

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Publication number Priority date Publication date Assignee Title
US3487021A (en) * 1966-08-11 1969-12-30 Katz Jacob M One-use hand-cleaning tablets
DE2406455A1 (de) * 1974-02-11 1975-08-21 Henkel & Cie Gmbh Lagerbestaendiger, leichtloeslicher waschmittelzusatz und verfahren zu dessen herstellung
CA2040307A1 (fr) * 1991-04-12 1992-10-13 Yogesh Sennik Comprimes de detergent efferverscent
EP0522766A2 (fr) * 1991-07-01 1993-01-13 Unilever Plc Compositions détergentes sous forme de tablettes
EP0711828A2 (fr) * 1994-11-14 1996-05-15 Unilever Plc Compositions détergentes

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999013042A1 (fr) * 1997-09-09 1999-03-18 Henkel Kommanditgesellschaft Auf Aktien Corps moules de produit detergent et nettoyant a solubilite amelioree
WO1999024547A1 (fr) * 1997-11-10 1999-05-20 The Procter & Gamble Company Composition de detergent
US6274538B1 (en) 1997-11-10 2001-08-14 The Procter & Gamble Company Detergent compositions
EP1113071A3 (fr) * 1997-12-02 2003-08-20 The Procter & Gamble Company Compositions détergentes
EP0971028A1 (fr) * 1998-07-10 2000-01-12 The Procter & Gamble Company Comprimé détergent à caractéristiques de dissolution et mécaniques améliorées
EP0971029A1 (fr) * 1998-07-10 2000-01-12 The Procter & Gamble Company Comprimé détergent ayant des caractéristiques mécaniques et des propriétés de dissolution élevées
WO2000002994A1 (fr) * 1998-07-10 2000-01-20 The Procter & Gamble Company Comprime detergent presentant des caracteristiques mecaniques et dissolvantes puissantes
US6559115B1 (en) * 1998-07-10 2003-05-06 The Procter & Gamble Company Detergent tablet with high mechanical and dissolution characteristics
GB2339574A (en) * 1998-07-15 2000-02-02 Procter & Gamble Disintegrating components
EP0997387A1 (fr) 1998-10-28 2000-05-03 The Procter & Gamble Company Matériaux d'emballage exhalant un parfum ou autre substance odorifère
US6232285B1 (en) 1998-11-11 2001-05-15 Stockhausen Gmbh & Co. Kg Compacted granulate, process for making same and use as disintegrating agent for pressed detergent tablets, cleaning agent tablets for dishwashers, water softening tablets and scouring salt tablets
US6221832B1 (en) 1998-11-11 2001-04-24 Stockhausen Gmbh & Co. Kg Compacted granulate, process for making same and use as disintegrating agent for pressed detergent tablets, cleaning agent tablets for dishwashers, water softening tablets or scouring salt tablets
WO2000046340A1 (fr) * 1999-02-03 2000-08-10 The Procter & Gamble Company Comprime detergent enrobe
WO2000046339A1 (fr) * 1999-02-03 2000-08-10 The Procter & Gamble Company Comprime detergent enrobe
WO2000046338A1 (fr) * 1999-02-03 2000-08-10 The Procter & Gamble Company Comprime detergent enrobe
EP1026228A1 (fr) * 1999-02-03 2000-08-09 The Procter & Gamble Company Comprimé détergent sous forme de tablette enrobée
EP1026229A1 (fr) * 1999-02-03 2000-08-09 The Procter & Gamble Company Comprimé détergent sous forme de tablette enrobée
EP1026227A1 (fr) * 1999-02-03 2000-08-09 The Procter & Gamble Company Comprimé détergent sous forme de tablette enrobée
EP1035199A3 (fr) * 1999-03-12 2000-12-20 The Procter & Gamble Company Comprimé détergent parfumé
EP1035198A3 (fr) * 1999-03-12 2001-01-03 The Procter & Gamble Company Comprimé détergent parfumé
WO2000055294A3 (fr) * 1999-03-12 2001-01-18 Procter & Gamble Pastilles de detergent parfumees
WO2000055287A3 (fr) * 1999-03-12 2001-01-25 Procter & Gamble Pastilles de detergent parfumees
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
EP1043388A1 (fr) * 1999-03-29 2000-10-11 DALLI-WERKE WÄSCHE-UND KÖRPERPFLEGE GmbH & Co.KG. Comprimés détergents pour le lavage de vaisselle en machine contenant un desintégrant granulaire
EP1043389A1 (fr) * 1999-03-29 2000-10-11 DALLI-WERKE WÄSCHE-UND KÖRPERPFLEGE GmbH & Co.KG. Comprimés détergents contenant un desintégrant granulaire
WO2000066688A1 (fr) * 1999-04-30 2000-11-09 The Procter & Gamble Company Pastilles et compositions de nettoyage
DE19920118B4 (de) * 1999-05-03 2016-08-11 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittelformkörper mit Beschichtung und Verfahren zu seiner Herstellung
EP1072674A1 (fr) * 1999-07-27 2001-01-31 The Procter & Gamble Company Comprimé détergent sous forme de tablette enrobée
WO2001007559A1 (fr) * 1999-07-27 2001-02-01 The Procter & Gamble Company Comprime detergent enrobe
US6340664B1 (en) 1999-08-26 2002-01-22 Henkel Kommanditgesellschaft Auf Aktien (Kgaa) Laundry detergent or cleaning product tablets with partial coating
WO2001025391A1 (fr) * 1999-10-06 2001-04-12 The Procter & Gamble Company Comprime detergent presentant des caracteristiques dissolvantes et mecaniques puissantes
EP1099751A3 (fr) * 1999-11-02 2001-08-01 Smiths Industries Public Limited Company Moyens de rebut
WO2002042406A1 (fr) * 2000-11-24 2002-05-30 Unilever N.V. Comprimes de nettoyage
WO2002042404A1 (fr) * 2000-11-24 2002-05-30 Unilever N.V. Comprimes de nettoyage
US6812200B2 (en) 2000-12-23 2004-11-02 Henkel Kommanditgesellschaft Auf Aktien Process for coating detergent tablets
EP1293556A1 (fr) * 2001-09-14 2003-03-19 Rent-a-Scientist GmbH Détergent sous forme de tablette ayant un revêtement comprenant de l'urée
US9493731B2 (en) 2010-11-12 2016-11-15 Dental Care Innovation Gmbh Soluble tablet, containing abrasive media
US10959931B2 (en) 2017-02-02 2021-03-30 Water Pik, Inc. Tablet including abrasive for dental cleaning
US11596587B2 (en) 2017-02-02 2023-03-07 Water Pik, Inc. Tablet including abrasive for dental cleaning

Also Published As

Publication number Publication date
CA2272537C (fr) 2002-12-17
ES2284164T3 (es) 2007-11-01
AU5443698A (en) 1998-06-29
HUP0000221A2 (hu) 2000-06-28
DE69637030D1 (de) 2007-05-31
AR010747A1 (es) 2000-07-12
ZA9710697B (en) 1998-06-12
TR199901233T2 (xx) 1999-10-21
CN1245527A (zh) 2000-02-23
JP2001506682A (ja) 2001-05-22
EG21191A (en) 2000-12-31
ATE360056T1 (de) 2007-05-15
WO1998024873A1 (fr) 1998-06-11
CA2272537A1 (fr) 1998-06-11
DE69637030T2 (de) 2007-12-27
HUP0000221A3 (en) 2001-11-28
MA24418A1 (fr) 1998-07-01
BR9713871A (pt) 2000-03-14
EP0846756B1 (fr) 2007-04-18

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