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
  • 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
• • 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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid 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
  • C11D3/37—Polymers

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 Finally a readily water-soluble organic film-forming polymer (for example, polyvinyl alcohol) provides a coating to make the detergent tablet resistant to abrasion and accidental breakage
• 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
• W09518215 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
• EP-A-0 846 754 published on the 10' ' of June 1998, provides a tablet having a coating comprising a dicarboxylic acid, the coating material typically having a melting point of from 40°C to 200°C
• EP-A-0 846 755 published on the 10 ,r of June 1998, provides a tablet having a coating comprising a material insoluble in water at 25°C, such as C12-C22 fatty acids, adipic acid or C8-C13 dicarboxylic acids
• the present invention provides a means by which coated tablets can be provided with a coating so that they can be stored, shipped and handled without damage, the coating being easily broken when the tablet is in the washing machine, releasing the active ingredients into the wash solution
• the object of the present invention is to provide a tablet having a coating which is sufficiently hard to protect the tablet from mechanical forces when stored, shipped and handled, and provides sufficient flexibility to the coating to avoid splitting due to mechanical stresses
• the object of the invention is achieved by providing a coated detergent tablet, characterised in that the coating comprises reinforcing fibres
• Solidity of a tablet may be improved by making a coated tablet, the coating covering a non-coated tablet thereby further improving the mechanical characteristics of the tablet while maintaining or further improving dissolution
• the tablets may then be coated 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 quickly when subjected to stronger mechanical shock
• the coating material is dissolved under alkaline conditions, or is readily emulsified by surfactants This contributes to avoiding the problem of visible residue in the window of a front-loading washing machine during the wash cycle and also avoids deposition of undissolved particles or lumps of coating material on the laundry load
• the coating material has 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
• the coating material is applied at a temperature above its melting point, and solidifies on the tablet
• 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
• the rapid cooling again causes rapid solidification of the coating material
• the coating undergoes some internal stress (e.g shrinkage upon cooling) and external stress (e.g tablet relaxation) This will likely cause some cracks in the structure such as edge splitting if the coating material is too b ⁇ ttle to withstand these mechanical stress
• the addition of reinforcing fibres allows to reinforce the structure of the coating, so that it can withstand mechanical stress better
• the coating comprises a component which is liquid at 25°C It is believed that this liquid component will allow the coating to better withstand and absorb mechanical stress by
• the coating comprises a crystallised structure.
• crystallised it should be understood that the coating comprises a material which is solid at ambient temperature (25°C) and has a structure exhibiting some order. This can be detected typically by usual crystallography techniques e.g. X-ray analysis, on the material itself.
• the material forming the crystallised structure does not co-crystallise or co-crystallises only partially with the optional component which is liquid at 25°C mentioned above. Indeed, it is preferred that the optional component remains in the liquid state at 25°C in the coating crystalline structure in order to provide flexibility to the structure and resistance to mechanical stress.
• the optional component which is liquid at 25°C may advantageously have a functionality in the washing of laundry, for example silicone oil which provides suds suppression benefits or perfume oil..
• the coating comprises materials other than the optional component which is liquid at 25°C.
• Suitable coating materials are for example 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.
• adipic acid Most preferred is adipic acid.
• 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.
• an acid having a melting point of more than 90°C such as azelaic, sebacic acid, dodecanedioic acid and more preferably an acid having a melting point of more than 145°C such as adipic was found particularly suitable.
• 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 For most purposes, the coating forms from 1 % to 10%, preferably from 1 5% to 7%, of the tablet weight
• Tablet coatings are very hard and provide extra strength to the tablet
• optional components which are liquid at 25° are including PolyEthylene Glycols, thermal oil, silicon oil, esters of dicarboxylic acids, mono carboxylic acids, parafin, tnacetin, perfumes or alkaline solutions
• the structure of the components which is liquid at 25°C is close to the material forming the crystallised structure, so that the structure is not excessively disrupted
• the crystallised structure is made of adipic acid, the component which is liquid at 25°C being available under the name CoasolTM from Chemoxy International, being a blend of the di-isobutyl esters of the glutaric, succinic and adipic acid
• CoasolTM from Chemoxy International
• dismtegrant in the coating melt at a level of up to 30%, preferably between 5% and 20%, most preferably between 5 and 10% by weight
• suitable disintegrants include starch natural, modified or pregelatmized 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 algmate, silicone dioxide, clay, polyvmylpyrrolidone, soy polysacha ⁇ des, ion exchange resins, polymers containing
• the coating further comprises reinforcing fibres
• Such fibres have been found to improve the resistance of the coating to mechanical stress and minimize the splitting defect occurence
• Such fibres are preferably having a length of at least 100 ⁇ m, more preferably of at least 200 ⁇ m and most preferably of at least 250 ⁇ m to allow structure reinforcement.
• Such fibres are preferably having a length of at less than 500 ⁇ m, more preferably of less than 400 ⁇ m and most preferably of less than 350 ⁇ m in order not to impact onto dispersion of the coating in an aqueous medium.
• a preferred process for making a tablet according to the invention comprises the steps of
• Another preferred process for making a tablet according to the invention comprises the steps of :
• the tablets may comprise components such as fragrance, surfactants, enzymes, detergent etc....
• Typical tablet compositions for the preferred embodiment of the present invention are disclosed in the pending European applications of the Applicant n° 96203471.6, 96203462.5, 96203473.2 and 96203464.1 for example.
• Elements typically entering in the composition of detergent tablets or of other forms of detergents such as liquids or granules are detailed in the following paragraphs.
• the tablet may comprise a highly soluble compound.
• a highly soluble compound is defined as follow:
• a solution is prepared as follows comprising de-iomseo water as well as 20 grams per litre of a specific compound:
• Step 3 is repeated after 20, 30, 40, 50, 1 m ⁇ n, 2 mm, 5 mm and 10 mm after step 2
• the measurement taken at 10 mm is used as the plateau value or maximum value.
• the specific compound is highly soluble according to the invention when the conductivity of the solution reaches 80% of its maximum value in less than 10 seconds, starting from the complete addition of the de-ionised water to the compound Indeed, when monitoring the conductivity in such a manner, the conductivity reaches a plateau after a certain period of time, this plateau being considered as the maximum value
• Such a compound is preferably in the form of a flowable material constituted of solid particles at temperatures comprised between 10 and 80°Cels ⁇ us for ease of handling, but other forms may be used such as a paste or a liquid
• Example of highly soluble compounds include Sodium di isoalkylbenzene sulphonate (DIBS) or Sodium toluene sulphonate
• the tablet may comprise a compound having a Cohesive Effect on the particulate material of a detergent matrix forming the tablet.
• the Cohesive Effect on the particulate material of a detergent matrix forming the tablet or a layer of the tablet is characterised by the force required to break a tablet or layer based on the examined detergent matrix pressed under controlled compression conditions For a given compression force a high tablet or layer strength indicates that the granules stuck highly together when they were compressed, so that a strong cohesive effect is taking place
• Means to assess tablet or layer strength also refer to diametrical fracture stress
• the cohesive effect is measured by comparing the tablet or layer strength of the original base powder without compound having a cohesive effect with the tablet or layer strength of a powder mix which comprises 97 parts of the original base powder and 3 parts of the compound having a cohesive effect
• the compound having a cohesive effect is preferably added to the matrix in a form in which it is substantially free of water (water content below 10%
• a compound is defined as having a cohesive effect on the particulate material according to the invention when at a given compacting force of 3000N, tablets with a weight of 50g of detergent particulate material and a diameter of 55mm have their tablet tensile strength increased by over 30% (preferably 60 and more preferably 100%) by means of the presence of 3% of the compound having a cohesive effect in the base particulate material
• An example of a compound having a cohesive effect is Sodium di isoalkylbenzene sulphonate
• the dissolution of the tablet or layer in an aqueous solution is significantly increased
• at least 1 % per weight of a tablet or layer is formed from the highly soluble compound, more preferably at least 2%, even more preferably at lest 3% and most preferably at least 5% per weight of the tablet or layer being formed from the highly soluble compound having a cohesive effect on the particulate material
• a composition comprising a highly soluble compound as well as a surfactant is disclosed in EP-A-0 524 075. this composition being a liquid composition.
• a highly soluble compound having a cohesive effect on the particulate material allows to obtain a tablet having a higher tensile strength at constant compacting force or an equal tensile strength at lower compacting force when compared to traditional tablets
• a whole tablet will have a tensile strength of more than 5kPa, preferably of more than 10kPa, more preferably, in particular for use in laundry applications, of more than 15kPa, even more preferably of more than 30 kPa and most preferably of more than 50 kPa, in particular for use in dish washing or auto dish washing applications, and a tensile strength of less than 300 kPa, preferably of less than 200 kPa, more preferably of less than 100 kPa, even more preferably of less than 80 kPa and most preferably of less than 60 kPa
• the tablets should be less compressed than in case of auto dish washing applications for example, whereby the dissolution is more readily achieved, so that in a laundry application, the
• the tablet may comprise several layers.
• the layer may be considered as a tablet itself.
• Detergent tablets 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
• the principal ingredients in particular gelling surfactants, 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 tablets according to the invention are compressed using a force of less than 100000N, more preferably of less than 50000N, even more preferably of less than 5000N and most preferably of less than 3000 N
• the most preferred embodiment is a tablet suitable for laundry compressed using a force of less than 2500N, but tablets for auto dish washing may also be considered for example, whereby such auto dish washing tablets are usually more compressed than laundry tablets
• the particulate material used for making a tablet 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 sentenng, etc
• Individual particles can also be any other particle, granule, sphere or gram
• the components of the particulate material 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 m ⁇ xer(s)
• Non-gelling binder can be sprayed on to the mix of some, or all of, the components of the particulate material
• Other liquid ingredients may also be sprayed on to the mix of components either separately or premixed
• perfume and slurries of optical b ⁇ ghteners may be sprayed.
• a finely divided flow aid dustting 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 20mm and 60mm, preferably of at least 35 and up to 55 mm, and a weight between 25 and 100 g.
• the ratio of height to diameter (or width) of the tablets is preferably greater than 1 :3, more preferably greater than 1 :2.
• the compaction pressure used for preparing these tablets need not exceed 100000 kN/m 2 , preferably not exceed 30000 kN/m ⁇ , more preferably not exceed 5000 kN/nr, even more preferably not exceed 3000kN/m 2 and most preferably not exceed 1000kN/m 2 .
• the tablet has a density of at least 0.9 g/cc, more preferably of at least 1.0 g/cc. and preferably of less than 2.0 g/cc, more preferably of less than 1.5 g/cc, even more preferably of less than 1.25 g/cc and most preferably of less than 1.1 g/cc.
• Multi layered tablets are typically formed in rotating presses by placing the matrices of each layer, one after the other in matrix force feeding flasks. As the process continues, the matrix layers are then pressed together in the pre- compression and compression stages stations to form the multilayer layer tablet. With some rotating presses it is also possible to compress the first feed layer before compressing the whole tablet.
• a highly soluble compound having a cohesive effect may be integrated to a detergent tablet, whereby this compound is also a hydrotrope compound.
• Such hydrotrope compound may be generally used to favour surfactant dissolution by avoiding gelling.
• a specific compound is defined as being hydrotrope as follows (see S.E. Friberg and M Chiu, J Dispersion Science and Technology, 9(5&6), pages 443 to 457, (1988-1989)):
• a solution is prepared comprising 25% by weight of the specific compound and 75% by weight of water 2 Octanoic Acid is thereafter added to the solution in a proportion of 1.6 times the weight of the specific compound in solution, the solution being at a temperature of 20°Cels ⁇ us
• the solution is mixed in a Sotax beaker with a stirrer with a marine propeller, the propeller being situated at about 5mm above the bottom of the beaker, the mixer being set at a rotation speed of 200 rounds per minute
• the specific compound is hydrotrope if the the Octanoic Acid is completely solubi sed, i.e . if the solution comprises only one phase, the phase being a liquid phase It should be noted that in a preferred embodiment of the invention, the hydrotrope compound is a flowable material made of solid particles at operating conditions between 15 and 60° Celsius.
• Hydrotrope compounds include the compounds listed thereafter: A list of commercial hydrotropes could be found in McCutcheon's Emulsifiers and Detergents published by the McCutcheon division of Manufacturing Confectioners Company. Compounds of interest also include.
• Nonionic hydrotrope with the following structure: where R is a C8-C10 alkyl chain, x ranges from 1 to 15, y from 3 to 10.
• Anionic hydrotropes such as alkali metal aryl sulfonates. This includes alkali metal salts of benzoic acid, salicylic acid, bezenesulfonic acid and its many derivatives, naphthoic acid and various hydroaromatic acids.
• sodium, potassium and ammonium benzene sulfonate salts derived from toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, tetralin sulfonic acid, naphtalene sulfonic acid, methyl- naphtalene sulfonic acid, dimethyl naphtalene sulfonic acid, trimethyl naphtalene sulfonic acid
• Other examples include salts of dialkyl benzene sulfonic acid such as salts of di- isopropyl benzene sulfonic acid, ethyl methyl benzene sulfonic acid, alkyl benzene sulfonic acid with an alkyl chain length with 3 to 10, (pref.
• alkoxylated glycerines and alkoxylated glycerides, esters slakoxylated glycerines, alkoxylated fatty acids, esters of glycerin, polyglycerol esters.
• Preferred alkoxylated glycerines have the following structure:
• Preferred alkoxylated glycerides have the following struture
• Polymeric hydrotropes such as those described in EP636687:
• R is H or a C1-C10 alkyl group or is a hydrophilic functional group; R1 is H a lower alkyl group or an aromatic group, R2 is H or a cyclic alkyl or aromatic group.
• the polymer typically has s molecular weight of between about 1000 and
• Such compound would further increase the dissolution rate of the tablet, as a hydrotrope compound facilitates dissolution of surfactants, for example.
• a hydrotrope compound facilitates dissolution of surfactants, for example.
• Such a compound could be formed from a mixture or from a single compound.
• the layer may be considered as a tablet itself.
• the used compacting force may be adjusted to not affect the tensile strength, 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 or layer, and t the thickness of the tablet or layer. For a non round tablet, ⁇ D may simply be replaced by the perimeter of the tablet.
• a tablet having a diametral fracture stress of less than 20 kPa is considered to be fragile and is likely to result in some broken tablets being delivered to the consumer.
• a diametral fracture stress of at least 25 kPa is preferred. This applies similarly to non cylindrical tablets, to define the tensile strength, whereby the cross section normal to the height of the tablet is non round, and whereby the force is applied along a direction perpendicular to the direction of the height of the tablet and normal to the side of the tablet, the side being perpendicular to the non round cross section.
• the rate of dispensing of a detergent tablet can be determined in the following way:
• Effervescent Detergent tablets may further comprise 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 0 7 + 3NaHCO3 « * • Na 3 C6H 5 O 7 + 3C02 + 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
• the addition of this effervescent to the detergent tablet 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 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
• dissolution aid could be provided by using compounds such as sodium acetate or urea
• suitable dissolution aid may also be found in Pharmaceutical Dosage Forms Tablets, Volume 1 , Second edition, Edited by H.A Lieberman et all, ISBN 0-8247-8044-2
• Surfactant are typically comprised in a detergent composition.
• the dissolution of surfactants is favoured by the addition of the highly soluble compound.
• Nonlimitmg examples of surfactants useful herein typically at levels from about 1 % to about 55%, by weight, include the conventional C-J -
• the N-propyl through N-hexyl C12- 18 glucamides can be used for low sudsing C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-cham C-jo-Ci 6 soaps may be used Mixtures of anionic and nonionic surfactants are especially useful Other conventional useful surfactants are listed in standard texts.
• the tablet comprises at least 5% per weight of surfactant, more preferably at least 15% per weight, even more preferably at least 25% per weight, and most preferably between 35% and 45% per weight of surfactant
• Non gelling binders can be integrated in detergent compositions to further facilitate dissolution.
• suitable non-gelling binders include synthetic organic polymers such as polyethylene glycols, polyvinyipyrrolidones, polyacrylates and water-soluble acrylate copolymers.
• the handbook of Pharmaceutical Excipients second edition has the following binders classification. Acacia, Alginic Acid, Carbomer, Carboxymethylcellulose sodium, Dextrin, Ethylcellulose, Gelatin, Guar gum, Hydrogenated vegetable oil type I, Hydroxyethyl cellulose, Hydroxypropyl methylcellulose, Liquid glucose.
• binders also have an active cleaning function in the laundry wash such as cationic polymers, i.e. ethoxylated hexamethylene diamme quaternary compounds, bishexamethylene tnammes, or others such as pentaammes, ethoxylated polyethylene amines, maleic acrylic polymers.
• cationic polymers i.e. ethoxylated hexamethylene diamme quaternary compounds, bishexamethylene tnammes, or others such as pentaammes, ethoxylated polyethylene amines, maleic acrylic polymers.
• Non-gelling binder materials are preferably sprayed on and hence have an appropriate melting point temperature below 90°C, preferably below 70°C and even more preferably below 50°C so as not to damage or degrade the other active ingredients in the matrix
• non-aqueous liquid binders i.e. not in aqueous solution
• Non-gelling binder materials are preferably used in an amount within the range from 0.1 to 15% of the composition, more preferably below 5% and especially if it is a non laundry active material below 2% by weight of the tablet.
• gelling binders such as nonionic surfactants are avoided in their liquid or molten form
• Nonionic surfactants and other gelling binders are not excluded from the compositions, but it is preferred that they be processed into the detergent tablets as components of particulate materials, and not as liquids. Builders
• 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
• Inorganic or P-contammg detergent builders include, but are not limited to, the alkali metal, ammonium and aikanolammonium salts of polyphosphates (exemplified by the tnpolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and alummosilicates
• 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 S ⁇ 2'Na2 ⁇ ratio in the range 1 6 1 to 3 2
• Alummosilicate 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
• Alummosilicate builders include those having the empirical formula M z (zAl ⁇ 2) y ] xH 2 0 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 alummosilicate 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 alummosilicate ion exchange materials is disclosed in U.S Patent 3,985,669,
• the alummosilicate 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
• polycarboxylate builders include a variety of categories of useful materials
• One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisucc ate, 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 alicyc c 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
• Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 , 3, 5- tnhydroxy benzene-2, 4, 6-tr ⁇ sulphon
• 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 biodegradabi ty Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders Oxydisucc ates are also especially useful in such compositions and combinations Also suitable in the detergent compositions of the present invention are the 3,3- d ⁇ carboxy-4-oxa-1 ,6-hexaned ⁇ oates and the related compounds disclosed in U.S Patent 4,566,984, Bush, issued January 28, 1986
• Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof A particularly preferred compound of this type is dodecenylsuccinic acid.
• succmate builders include: lauryisuccinate, my ⁇ stylsuccinate, palmitylsuccinate, 2-dodecenylsucc ⁇ nate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccmates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
• Fatty acids e.g., C-12-C18 monocarboxyhc acids
• the aforesaid builders especially citrate and/or the succmate builders, to provide additional builder activity.
• 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 tnpolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
• Phosphonate builders such as ethane-1-hydroxy-1 ,1-d ⁇ phosphonate 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 comDnsing 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 percarboxyiic 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-nonyiamino- 4-oxoperoxybutyr ⁇ c 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-nonylam ⁇ no-6-oxoperoxycapro ⁇ c 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. 26
• 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-denved bleach activators are those of the formulae R1 N(R 5 )C(0)R2C(0)L or R 1 C(0)N(R5)R2C(O)L wherein R 1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 IS an alkylene containing from 1 to about 6 carbon atoms, R ⁇ 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 nucleophi c attack on the bleach activator by the perhydrolysis anion
• a preferred leaving group is phenyl sulfonate
• Preferred examples of bleach activators of the above formulae include (6- octanam ⁇ do-caproyl)oxybenzenesulfonate, (6-nonanam ⁇ docaproyl)oxybenzene- sulfonate, (6
• Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
• R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
• Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-tr ⁇ methylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-tr ⁇ methylhexanoyl valerolactam and mixtures thereof.
• 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 phthalocyanmes 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 phthalocyanme.
• 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. 5,1 14,606; and European Pat. App. Pub. Nos. 549,271 A1 , 549.272A1 , 544.440A2, and 544.490A1 ; Preferred examples of these catalysts include ,4,7-trimethyM ,4,7- triazacyclononane)2(PF6)2.
• 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 tnglyceride-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 In this respect 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 Stated otherwise, 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.
• AU Anson units
• proteases are the subtilisins which are obtained from particular strains of B. subtiiis and B. licheniforms. Another suitable 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 that are commercially available include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
• proteases include Protease A (see European Patent Application 130.756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).
• Amylases include, for example, u-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 iipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
• lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
• the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
• Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e.
• 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.
• 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.
• Other components which are commonly used in detergent compositions and which may be incorporated into detergent tablets include chelating agents, soil release agents, soil antiredeposition agents, dispersing agents, suds suppressors, fabric softeners, dye transfer inhibition agents and perfumes.
• the compounds disclosed above for a product are advantageously packed in a packaging system.
• a packaging system may be formed from a sheet of flexible material.
• Materials suitable for use as a flexible sheet include mono-layer, co-extruded or laminated films.
• Such films may comprise various components, such as poly-ethylene, polypropylene, poly-styrene, poly-ethylene-terephtalate.
• the packaging system is composed of a poly-ethylene and bi-oriented-poly-propylene co- extruded film with an MVTR of less than 5 g/day/m 2 .
• the MVTR of the packaging system is preferably of less than 10 g/day/m 2 , more preferably of less than 5 g/day/nr.
• the film (2) may have various thicknesses.
• the thickness should typically be between 10 and 150 ⁇ m, preferably between 15 and 120 ⁇ m, more preferably between 20 and 100 ⁇ m, even more preferably between 25 and 80 ⁇ m and most preferably between 30 and 40 ⁇ m.
• a packaging material preferably comprises a barrier layer typically found with packaging materials having a low oxygen transmission rate, typically of less than 300 cm 3 /m 2 /day, preferably of less than 150 cm 3 /m 2 /day, more preferably of less than 100 cm 3 /m 2 /day, even more preferably of less than 50 cm 3 /m 2 /day and most preferably of less than 10 cm 3 /m 2 /day.
• Typical materials having such barrier properties include bi oriented polypropylene, poly ethylene terephthalate, Nylon, poly(ethylene vinyl alcohol) , or laminated materials comprising one of these, as well as SiOx (Silicium oxydes), or metallic foils such as aluminium foils for example.
• Such packaging material may have a beneficial influence on the stability of the product during storage for example.
• the packing method used are typically the wrapping methods disclosed in WO92/20593, including flow wrapping or over wrapping.
• a longitudinal seal which may be a fin seal or an overlapping seal, after which a firsi end of the packaging system is closed with a first end seal, followed by closure of the second end with a second end seal
• the packaging system may comprise re-closing means as described in WO92/20593
• a cold seal or an adhesive is particularly suited Indeed, a band of cold seal or a band of adhesive may be applied to the surface of the packaging system at a position adjacent to the second end of the packaging system, so that this band may provide both the initial sea!
• the adhesive or cold seal band may correspond to a region having a cohesive surface, i.e a surface which will adhere only to another cohesive surface
• Such re-closing means may also comprise spacers which will prevent unwanted adhesion
• spacers are described in WO 95/13225, published on the 18 th of May 1995
• There may also be a plurality of spacers and a plurality of strips of adhesive material The mam requirement is that the communication between the exterior and the interior of the package should be minimal, even after first opening of the packaging system
• a cold seal may be used, and in particular a grid of cold seal, whereby the cold seal is adapted so as to facilitate opening of the packaging system
• a detergent base powder of composition A was prepared as follows: all the particulate material of base composition were mixed together in a mixing drum or spray drum to form a homogenous particulate mixture, apart from the binder spray-on system, the fluorescer or brightener, and the photobleach Zinc Phthalocyanme sulphonate The particulate mixture was thereafter divided in two equal parts, one part for making a white layer, another part for making a green layer
• the white layer material is obtained by spraying the brightener or fluorescer together with half of the binder
• the green layer material is obtained by spraying the photobleach Zinc Phthalocyanme sulphonate together with the rest of the binder
• the layer where then processed independently in a Loedige KM 600* n) Using a Bonals 6 rotary press both matrices were filled in two independent force feeding flasks Both layers are compressed together in the pre- compression and compression stations to form a dual layer tablet.
• the tablets have a square cross section of 45 mm side, a height of 24 mm and a weight of 45 gr
• the height of the green bottom layer corresponded to 50% of the total height of the tablet.
• the tensile strength of the uncoated tablets was 13 kpa ⁇ v)
• the tablet was thereafter coated with 2.5 g of coating formed from 90% by weight of sebacic acid and 10% by weight of Nymcel-ZSB16TM by Metsa
• Anionic agglomerates 1 comprise of 40% anionic surfactant, 27% zeolite and 33% carbonate
• Anionic agglomerates 2 comprise of 40% anionic surfactant, 28% zeolite and 32% carbonate
• Nonionic agglomerate comprise 26% nonionic surfactant, 6% Lutensit K-HD 96, 40% Sodium acetate anhydrous, 20% carbonate and 8% zeolite.
• Cationic agglomerates comprise of 20% cationic surfactant, 56% zeolite and 24% sulphate
• Layered silicate comprises of 95% SKS 6 and 5% silicate
• Bleach activator agglomerates comprise of 81 % TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.
• Ethylene diamine N,N-disuccinic acid sodium salt/Sulphate particle comprise of 58% of Ethylene diamine N,N-d ⁇ succinic acid sodium salt, 23% of sulphate and 19% water.
• Suds suppressor comprises of 1 1.5% silicone oil (ex Dow Corning); 59% of zeolite and 29.5% of water.
• Binder spray-on system comprises 16% by weight of polymer of the following kind:
• DIBS Sodium di isoalkylbenzene sulphonate or Sodium toluene sulphonate
• composition which may have been used is as follows:
• Anionic agglomerates 1 comprise of 40% anionic surfactant, 27% zeolite and 33% carbonate
• Anionic agglomerates 2 comprise of 40% anionic surfactant, 28% zeolite and
• Nonionic agglomerate comprise 26% nonionic surfactant 6% Lutensit K-HD 96,
• zeolite Cationic agglomerates comprise of 20% cationic surfactant, 56% zeolite and 24% sulphate
• Layered silicate comprises of 95% SKS 6 and 5% silicate
• Bleach activator agglomerates comprise of 81 % TAED, 17% acrylic/maleic copolymer (acid form) and 2% water Ethylene diamine N,N-d ⁇ succ ⁇ n ⁇ c acid sodium salt/Sulphate particle comprise of
• Suds suppressor comprises of 11.5% silicone oil (ex Dow Corning), 59% of zeolite and 29.5% of water
• Binder spray-on system comprises 16% by weight of polymer of the following
• DIBS Sodium di isoalkylbenzene sulphonate or Sodium toluene sulphonate
• a detergent base powder of composition A was prepared as follows: all the particulate material of base composition were mixed together in a mixing drum or spray drum to form a homogenous particulate mixture, apart from the binder spray-on system, the fluorescer or brightener, and the photobleach Zinc Phthalocyanme sulphonate.
• the particulate mixture was thereafter divided in two equal parts, one part for making a white layer, another part for making a green layer
• the white layer material is obtained bv spraying the brightener or fiuoresce'- together with half of the binder
• the green lave- material is obtained by spraying the photobleach Zinc Phthalocyanme sulphonate together with the rest of the binder
• the layer where then processed independently in a Loedige KM 600 ® .
• both matrices were filled in two independent force feeding flasks Both layers are compressed together in the pre- compression and compression stations to form a dual layer tablet.
• the tablets have a square cross section of 45 mm side, a height of 24 mm and a weight of 45 gr.
• the height of the green bottom layer corresponded to 50% of the total height of the tablet
• the tensile strength of the uncoated tablets was 13 kpa ⁇ v)
• the tablet was thereafter coated with 2.5 g of coating formed from 90% by weight of sebacic acid, 8% by weight of Nymcel-ZSB16TM by Metsa Serla, and 2% by weight of Solka-FlocTM1016
• a detergent base powder of composition A was prepared as follows: all the particulate material of base composition were mixed together in a mixing drum or spray drum to form a homogenous particulate mixture The binder system was then sprayed on The powder where then processed in a Loedige
• a detergent base powder of composition A was prepared as follows all the particulate material of base composition were mixed together in a mixing drum or spray drum to form a homogenous particulate mixture The binder system was then sprayed on The powder where then processed in a Loedige
• a detergent base powder of composition A was prepared as follows: all the particulate material of base composition were mixed together in a mixing drum or spray drum to form a homogenous particulate mixture. The binder system was then sprayed on The powder where then processed in a Loedige
• the tablets made according to example 1 exhibit a splitting occurence more than 5 times higher than for the tablets made according to example 2 once the coating has crystallised

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• 1999
  • 1999-02-03 AT AT99870018T patent/ATE257856T1/de not_active IP Right Cessation
  • 1999-02-03 DE DE69914172T patent/DE69914172T2/de not_active Expired - Fee Related
  • 1999-02-03 EP EP99870018A patent/EP1026228B1/de not_active Expired - Lifetime
  • 1999-02-03 ES ES99870018T patent/ES2212513T3/es not_active Expired - Lifetime
• 2000
  • 2000-01-27 AU AU27371/00A patent/AU2737100A/en not_active Abandoned
  • 2000-01-27 CA CA002360662A patent/CA2360662A1/en not_active Abandoned
  • 2000-01-27 MX MXPA01007839A patent/MXPA01007839A/es not_active Application Discontinuation
  • 2000-01-27 CN CN00805464.9A patent/CN1345367A/zh active Pending
  • 2000-01-27 WO PCT/US2000/001870 patent/WO2000046339A1/en not_active Application Discontinuation
  • 2000-01-27 BR BR0007960-0A patent/BR0007960A/pt not_active IP Right Cessation
  • 2000-01-27 EP EP00905731A patent/EP1149152A1/de not_active Withdrawn
  • 2000-02-02 AR ARP000100444A patent/AR022479A1/es not_active Application Discontinuation

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