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EP0846754A1 - Comprimé détergent sous forme de tablette enrobée - Google Patents

Comprimé détergent sous forme de tablette enrobée Download PDF

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Publication number
EP0846754A1
EP0846754A1 EP96203464A EP96203464A EP0846754A1 EP 0846754 A1 EP0846754 A1 EP 0846754A1 EP 96203464 A EP96203464 A EP 96203464A EP 96203464 A EP96203464 A EP 96203464A EP 0846754 A1 EP0846754 A1 EP 0846754A1
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.)
Ceased
Application number
EP96203464A
Other languages
German (de)
English (en)
Inventor
Paul Irma Albertus Van Dijk
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
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP96203464A priority Critical patent/EP0846754A1/fr
Priority to US09/319,473 priority patent/US6087311A/en
Priority to CA002272642A priority patent/CA2272642C/fr
Priority to JP52560398A priority patent/JP2001505603A/ja
Priority to PCT/US1997/021042 priority patent/WO1998024874A1/fr
Priority to BR9713992-0A priority patent/BR9713992A/pt
Priority to AU76250/98A priority patent/AU7625098A/en
Priority to HU0000220A priority patent/HUP0000220A3/hu
Priority to CN97181565.8A priority patent/CN1245528A/zh
Priority to TR1999/01225T priority patent/TR199901225T2/xx
Priority to ZA9710698A priority patent/ZA9710698B/xx
Priority to EG129697A priority patent/EG20970A/xx
Priority to ARP970105745A priority patent/AR012290A1/es
Priority to MA24889A priority patent/MA24417A1/fr
Publication of EP0846754A1 publication Critical patent/EP0846754A1/fr
Ceased 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0052—Gas evolving or heat producing compositions
    • 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

  • 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.
  • 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.
  • 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 object 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.
  • the object of the invention is acheived by providing a coating comprising a dicarboxylic acid, preferably wherein the length of the carbon chain of the dicarboxylic acid is from C2 to C13.
  • the coating consists essentially of dicarboxylic acid.
  • 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 2 , preferably not exceed 3000 kN/m 2 , and most preferably not exceed 1000 kN/m 2 .
  • the tablets are then coated with dicarboxylic acid 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 more water-insoluble dicarboxylic acids are used.
  • 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 C2-C13 dicarboxylic acids.
  • Particularly suitable dicarboxylic acids are selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and mixtures thereof.
  • 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.
  • F is the maximum force (Newton) to cause tensile failure (fracture) measured by a VK 200 tablet hardness tester supplied by Van Kell industries, Inc.
  • D is the diameter of the tablet, and t the thickness of the tablet.
  • 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.
  • the tablet 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.
  • 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 al
  • 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.
  • Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10 -C 18 N-(3-methoxypropyl) glucamide.
  • 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.
  • 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.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na 2 SiO 5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043.
  • 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 ⁇ H 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. As noted above, the delta-Na 2 SiO 5 (NaSKS-6 form) is most preferred for use herein.
  • 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.
  • Aluminosilicate builders include those having the empirical formula: M z (zAlO 2 ) y ] ⁇ xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived.
  • a method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of categories of useful materials.
  • 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.
  • ether hydroxypolycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986.
  • 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.
  • Fatty acids e.g., C 12 -C 18 monocarboxylic acids
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
  • 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.
  • 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. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
  • 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
  • OXONE manufactured commercially by DuPont
  • 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
  • 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 wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R 5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group.
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenyl sulfonate.
  • bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference.
  • a highly preferred activator of the benzoxazin-type is: Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae: wherein R 6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
  • lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S.
  • Patent 4,545,784 issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • the bleaching compounds can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos.
  • Preferred examples of these catalysts include Mn IV 2 (u-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (PF 6 ) 2 , Mn III 2 (u-O) 1 (u-OAc) 2 (1,4,7-trimethyl-1,4,7-triazacyclononane) 2- (ClO 4 ) 2 , Mn IV 4 (u-O) 6 (1,4,7-triazacyclononane) 4 (ClO 4 ) 4 , Mn III Mn IV 4 (u-O) 1 (u-OAc) 2- (1,4,7-trimethyl-1,4,7-triazacyclononane) 2 (ClO 4 ) 3 , Mn IV- (1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH 3 ) 3 (PF 6 ), and mixtures thereof.
  • metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
  • 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.
  • Anionic agglomerates comprise 38% anionic surfactant, 22% zeolite and 40% carbonate.
  • 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.
  • a first series of tablets were made the following way, about 37.5 g. of the mixture was introduced into a mould of circular shape with a diameter of 4.5 cm, and compressed with a force of 0.5 kN. or about 30 Newton/cm 2 , to give tablets of about 2.2 cm height and a density of about 1.1 g./cc.
  • the tensile strength of the tablet was 3.5 kPa.
  • Adipic acid was heated in a thermostatic bath till 170 °C with gentle stirring until molten. The molten product was clear liquid.
  • the tablets prepared as above were then dipped into the liquid to give the final coated tablet, this tablet had a total weight of 40.2 g, and a tensile strength of 6.5 kPa.
  • An second series of tablets was made with a compaction force of 1kN. or about 63 N/cm 2 to give tablets of about 2.0 cm height, a density of about 1.2 g./cc, and a tensile strength of 9.0 kPa. After coating with Adipic Acid the tablets had a weight of 40.2 g, and the tensile strength was 15.5 kPa.
  • 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 Adipic Acid the tablets had a weight of 40.2 g, and the tensile strength was 19.5 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 gr./cc, and a tensile strength of 4.5 kPa. After coating with Adipic acid the tablets had a weight of 40.2 g, and the tensile strength was 10.4 kPa.
  • a second series of tablets was made with a compaction force of 1.5 kN. or about 95 N/cm 2 to give tablets of about 2.1 cm height, a density of about 1.2 gr./cc, and a tensile strength of 8.5 kPa. After coating with Adipic Acid the tablets had a weight of 40.2 g, and a tensile strength was 14.5 kPa.
  • An third series of tablets was made with a compaction force of 2.5 kN. or about 160 N/cm 2 to give tablets of about 2.0 cm height, a density of about 1.2 g./cc, and a tensile strength of 15.7 kPa. After coating with Adipic Acid the tablets had a weight of 40.2 g, and the tensile strength increased to 21.3 kPa.
  • Example 1 was repeated replacing the adipic acid by glutaric acid.
  • the glutaric acid was heated in a thermostatic bath to 120°C with gentle stirring until molten.
  • the final tensile strength of the three series of tablets was 10.4 kPa, 17.3 kPa and 22.5 kPa respectively.
  • Example 2 was repeated replacing the adipic acid by glutaric acid.
  • the glutaric acid was heated in a thermostatic bath to 120°C with gentle stirring until molten.
  • the final tensile strength of the three series of tablets was 11.3 kPa, 16.9 kPa and 23.0 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)
  • Health & Medical Sciences (AREA)
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  • Medicinal Preparation (AREA)
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EP96203464A 1996-12-06 1996-12-06 Comprimé détergent sous forme de tablette enrobée Ceased EP0846754A1 (fr)

Priority Applications (14)

Application Number Priority Date Filing Date Title
EP96203464A EP0846754A1 (fr) 1996-12-06 1996-12-06 Comprimé détergent sous forme de tablette enrobée
US09/319,473 US6087311A (en) 1996-12-06 1997-11-19 Coated detergent tablet
CA002272642A CA2272642C (fr) 1996-12-06 1997-11-19 Detergent en tablette a enrobage
JP52560398A JP2001505603A (ja) 1996-12-06 1997-11-19 被覆洗浄剤タブレット
PCT/US1997/021042 WO1998024874A1 (fr) 1996-12-06 1997-11-19 Detergent en tablette a enrobage
BR9713992-0A BR9713992A (pt) 1996-12-06 1997-11-19 Tablete detergente revestido
AU76250/98A AU7625098A (en) 1996-12-06 1997-11-19 Coated detergent tablet
HU0000220A HUP0000220A3 (en) 1996-12-06 1997-11-19 Coated detergent tablet
CN97181565.8A CN1245528A (zh) 1996-12-06 1997-11-19 涂覆的洗涤剂片
TR1999/01225T TR199901225T2 (xx) 1996-12-06 1997-11-19 Kaplanm�� deterjan tableti.
ZA9710698A ZA9710698B (en) 1996-12-06 1997-11-27 Coated detergent tablet.
EG129697A EG20970A (en) 1996-12-06 1997-12-04 Coated detergent tablet
ARP970105745A AR012290A1 (es) 1996-12-06 1997-12-05 Tableta que comprende un nucleo formado por un surfactante y un mejorador detergente y proceso para fabricarla
MA24889A MA24417A1 (fr) 1996-12-06 1997-12-05 Comprime detrgent enrobe

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BR (1) BR9713992A (fr)
CA (1) CA2272642C (fr)
EG (1) EG20970A (fr)
HU (1) HUP0000220A3 (fr)
MA (1) MA24417A1 (fr)
TR (1) TR199901225T2 (fr)
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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0997387A1 (fr) 1998-10-28 2000-05-03 The Procter & Gamble Company Matériaux d'emballage exhalant un parfum ou autre substance odorifère
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
EP1026228A1 (fr) * 1999-02-03 2000-08-09 The Procter & Gamble Company Comprimé détergent sous forme de tablette enrobée
EP1035198A2 (fr) * 1999-03-12 2000-09-13 The Procter & Gamble Company Comprimé détergent parfumé
EP1035199A2 (fr) * 1999-03-12 2000-09-13 The Procter & Gamble Company Comprimé détergent parfumé
WO2000066699A1 (fr) * 1999-04-29 2000-11-09 Henkel Kommanditgesellschaft Auf Aktien Comprimes effervescents comprenant des auxiliaires de pastillage et procede permettant de les produire
EP1072674A1 (fr) * 1999-07-27 2001-01-31 The Procter & Gamble Company Comprimé détergent sous forme de tablette enrobée
EP1099751A2 (fr) * 1999-11-02 2001-05-16 Smiths Industries Public Limited Company Moyens de rebut
EP1149896A1 (fr) * 2000-04-27 2001-10-31 The Procter & Gamble Company Composition d' enrobage de corps solides
EP1172352A1 (fr) * 2000-07-10 2002-01-16 The Procter & Gamble Company Retardation de la décoloration d'acides dicarboxyliques
EP1172353A1 (fr) * 2000-07-10 2002-01-16 The Procter & Gamble Company Retardation de la décoloration d'acides dicarboxyliques
US6340664B1 (en) 1999-08-26 2002-01-22 Henkel Kommanditgesellschaft Auf Aktien (Kgaa) Laundry detergent or cleaning product tablets with partial coating
EP1188820A1 (fr) * 2000-09-13 2002-03-20 Henkel KGaA Pièces détergentes avec un revêtement de polyuréthane
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
EP1348017B2 (fr) † 2001-01-05 2009-11-11 Henkel AG & Co. KGaA Portion d'agent de lavage, d'agent de rincage ou d'agent de nettoyage contenant des tensioactifs
EP3543326A1 (fr) * 2018-03-21 2019-09-25 Miele & Cie. KG Corps de produit de nettoyage destiné à être utilisé dans un appareil de nettoyage conçue sous forme de lave-linge ou de lave-vaisselle

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WO2002090475A2 (fr) * 2001-05-03 2002-11-14 Unilever N.V. Compositions de detergents solides moules
CN104233328A (zh) * 2014-09-25 2014-12-24 无锡康柏斯机械科技有限公司 用于金属表面清洗的粉状组合物及其制备方法

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EP0716144A2 (fr) * 1994-11-14 1996-06-12 Unilever Plc Détergent sous forme de tablette ayant un revêtement soluble dans l'eau

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EP0716144A2 (fr) * 1994-11-14 1996-06-12 Unilever Plc Détergent sous forme de tablette ayant un revêtement soluble dans l'eau

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Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0997387A1 (fr) 1998-10-28 2000-05-03 The Procter & Gamble Company Matériaux d'emballage exhalant un parfum ou autre substance odorifère
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
EP1026228A1 (fr) * 1999-02-03 2000-08-09 The Procter & Gamble Company Comprimé détergent sous forme de tablette enrobée
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
EP1035199A2 (fr) * 1999-03-12 2000-09-13 The Procter & Gamble Company Comprimé détergent parfumé
US6630438B1 (en) 1999-03-12 2003-10-07 The Procter & Gamble Company Perfumed detergent tablet
WO2000055287A2 (fr) * 1999-03-12 2000-09-21 The Procter & Gamble Company Pastilles de detergent parfumees
WO2000055294A2 (fr) * 1999-03-12 2000-09-21 The Procter & Gamble Company Pastilles de detergent parfumees
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
EP1035198A2 (fr) * 1999-03-12 2000-09-13 The Procter & Gamble Company Comprimé détergent parfumé
US7084102B1 (en) 1999-03-12 2006-08-01 The Procter & Gamble Company Perfumed detergent tablet
WO2000066699A1 (fr) * 1999-04-29 2000-11-09 Henkel Kommanditgesellschaft Auf Aktien Comprimes effervescents comprenant des auxiliaires de pastillage et procede permettant de les produire
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
EP1099751A3 (fr) * 1999-11-02 2001-08-01 Smiths Industries Public Limited Company Moyens de rebut
EP1099751A2 (fr) * 1999-11-02 2001-05-16 Smiths Industries Public Limited Company Moyens de rebut
EP1149896A1 (fr) * 2000-04-27 2001-10-31 The Procter & Gamble Company Composition d' enrobage de corps solides
WO2001081522A1 (fr) * 2000-04-27 2001-11-01 The Procter & Gamble Company Composition de revetement pour corps solides
EP1172352A1 (fr) * 2000-07-10 2002-01-16 The Procter & Gamble Company Retardation de la décoloration d'acides dicarboxyliques
WO2002004395A1 (fr) * 2000-07-10 2002-01-17 The Procter & Gamble Company Ralentissement de l'alteration de la couleur des acides dicarboxyliques
WO2002004396A1 (fr) * 2000-07-10 2002-01-17 The Procter & Gamble Company Retardement de la decoloration des acides dicarboxyliques
EP1172353A1 (fr) * 2000-07-10 2002-01-16 The Procter & Gamble Company Retardation de la décoloration d'acides dicarboxyliques
EP1188820A1 (fr) * 2000-09-13 2002-03-20 Henkel KGaA Pièces détergentes avec un revêtement de polyuréthane
US6812200B2 (en) 2000-12-23 2004-11-02 Henkel Kommanditgesellschaft Auf Aktien Process for coating detergent tablets
EP1348017B2 (fr) † 2001-01-05 2009-11-11 Henkel AG & Co. KGaA Portion d'agent de lavage, d'agent de rincage ou d'agent de nettoyage contenant des tensioactifs
EP3543326A1 (fr) * 2018-03-21 2019-09-25 Miele & Cie. KG Corps de produit de nettoyage destiné à être utilisé dans un appareil de nettoyage conçue sous forme de lave-linge ou de lave-vaisselle
DE102018106720A1 (de) * 2018-03-21 2019-09-26 Miele & Cie. Kg Reinigungsmittelkörper zur Verwendung in einem als Waschmaschine oder Geschirrspülmaschine ausgebildeten Reinigungsgerät und Reinigungsgerät

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CA2272642A1 (fr) 1998-06-11
BR9713992A (pt) 2000-02-08
TR199901225T2 (xx) 1999-08-23
WO1998024874A1 (fr) 1998-06-11
JP2001505603A (ja) 2001-04-24
CA2272642C (fr) 2002-12-17
HUP0000220A3 (en) 2001-02-28
HUP0000220A2 (hu) 2000-06-28
AR012290A1 (es) 2000-10-18
AU7625098A (en) 1998-06-29
MA24417A1 (fr) 1998-07-01
EG20970A (en) 2000-07-30

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