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
  • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial 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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
• • 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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
  • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
• • 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
  • C11D17/0034—Fixed on a solid conventional detergent ingredient
• • 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
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
• • 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
  • C11D3/0031—Carpet, upholstery, fur or leather cleansers
• • 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
  • C11D3/04—Water-soluble compounds
  • C11D3/10—Carbonates ; Bicarbonates
• • 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
• • 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
  • C11D3/43—Solvents

Definitions

• the present invention relates to methods of reducing fines in powdered products, and more particularly to a method of reducing fines in powdered textile treating compositions, and powdered textile treating compositions prepared by the method.
• Household cleaning compositions are often supplied in a liquid or a powdered form.
• carpet cleaning compositions have been widely available for some time in both liquid and powdered form.
• Liquid carpet cleaning compositions have typically been the first choice of many consumers.
• dry powdered carpet cleaning compositions have become quite popular. Examples of dry powdered carpet cleaning compositions can be found in U.S. Patent Nos. 4,666,940, 4,552,777, 4,493,781, 4,395,347 and 4,161,449.
• dry carpet cleaners and certain other powdered household products have a tendency to lose their free flowing properties during storage.
• powdered products may become compacted or "caked” due to settling and/or their tendency for absorbing moisture from the ambient air.
• Caked product is difficult to fill as well as dispense from containers. Therefore, flow agents (also known as anti-caking agents) are often added to powdered compositions in order to keep the powder free flowing.
• Flow agents typically contain particles of small size and low density known as "fines" that can readily become airborne. Fines can be very irritating to nasal passages.
• fines can be very irritating to nasal passages.
• a large number of fines in the ambient air can build up a static charge.
• fines may be difficult to vacuum.
• the fines that are removed may not remain trapped inside a typical paper vacuum cleaner bag.
• a dust cloud of fines may develop during vacuuming that can be irritating to the nasal passages.
• the fines may leave an unsightly residue on shoes, clothing and surfaces in the home .
• U.S. Patent Nos. 4,161,449 and 4,552,777 disclose a conventional process for preparing a dry carpet cleaning composition from dry powdered components.
• a typical dry powdered carpet cleaning composition may include a dry powder inorganic salt carrier, a dry powder anti-caking agent, a liquid fragrance and a liquid dedusting agent.
• Typical inorganic salt carriers include sodium sulfate, sodium chloride, sodium carbonate, sodium bicarbonate, sodium borate, sodium citrate, sodium tripolyphosphate and sodium nitrate; suitable anti-caking agents include starch, silica powders, grain flours, wood flour, talc, pumice, clays, and calcium phosphates; conventional fragrances are liquid volatile odorous agents including essential oils and aromatic chemicals; and typical liquid dedusting agents may be alkyl phthalates, mineral oil, glycols, ethoxylated alcohols, alcohols, glycol ethers, vegetable oils, naphtha, mineral spirits and naphthalene sulfonates.
• improved methods of blending and agglomerating powdered products can be used to reduce fines in a final powdered product without the need for dedusting agents or screening techniques. Accordingly, these improved methods can be used to produce a particulate textile fiber or fabric cleaning composition that satisfies the need for a dry textile cleaning composition that has a minimal level of fines .
• Agglomeration is the process of bringing together fine powders or particulates into larger masses with pressure, agitation and/or other mechanisms. Agglomerating techniques include: (1) pressure compacting, such as briquetting, tableting and using a pellet mill; (2) tumbling or granulation; and (3) spray congealing. In the context of dry powdered or particulate household cleaning chemicals, tumbling or granulation is typically the process of choice.
• a method for producing a particulate textile fiber or fabric cleaning composition that includes the steps of introducing at least one particulate material into a mixing vessel, introducing at least one liquid material into the mixing vessel to form a mixture, blending the mixture for a first time period, chopping the mixture for at least a portion of the first time period, and thereafter blending the mixture without chopping for a second time period.
• the method produces a particulate fabric cleaning composition having acceptable flow characteristics yet results in a reduced level of fines without the need for a screening step to remove fines.
• fabric includes natural and/or synthetic fiber products such as carpets, upholstery, drapes, and even clothing.
• chopping creates greater surface area (which is otherwise lessened by mixing liquid with solids) and that the greater area permits fine particles of the particulate materials (such as silica fines in a dry carpet cleaning composition) to become attached to the larger particles in the mix by agglomeration.
• the inclusion of a time period of blending and chopping the mixture serves to agglomerate particles and at the same time break up any large agglomerated particles that might clog the container.
• the blending serves to agglomerate smaller particles while the chopping serves to breakup larger oversized agglomerations.
• the chopping process is a high shear mixing that generally shears large agglomerated particles at the liquid interface between particles. However, individual particles may shear through the particle body. Therefore, as used herein, the term " chopping" refers to an action that can shear particle agglomerations at a liquid-solid interface or a solid-solid interface.
• the step of introducing liquid material into the mixing vessel and the step of blending and chopping the mixture for a first period of time may all be performed simultaneously.
• the liquid material may be added to the mixing vessel in any manner, it is preferred that the liquid materials be introduced into the mixing vessel at a uniform flow rate, most preferably by a sprayer that provides a spray in order to produce a uniform powder.
• acceptable flow characteristics for a fabric cleaner means that the composition may be dispensed without clogging from conventional shaker-type containers that are widely used for packaging household cleaning compositions and have outlets of about 5 millimeters in diameter.
• One version of a particulate textile fiber or fabric cleaning composition produced in accordance with the invention includes at least 80% by weight of inorganic salt carrier particulates, 1-10% by weight of flow agent particulates, and 0.1-15% by weight of a liquid active material, such as a fragrance and/or a pesticide.
• a liquid active material such as a fragrance and/or a pesticide.
• Other standard fabric cleaner additives may also be included such as surfactants and solvents.
• At least 90% of the composition particulates have a particle size greater than 0.105 millimeters.
• the composition may be applied without dusting to natural or synthetic textile fibers or fabric and removed by vacuuming.
• compositions of the invention are particularly and beneficially adapted for use in the cleansing of pile fabrics of the type knitted or woven principally into yarns or fibers.
• the compositions are believed most useful in the treatment of rugs and carpets.
• the formed textile fabric may be of vegetable, synthetic or animal origin, including mixtures thereof.
• Typical synthetic fabrics which may be beneficially treated by the present composition include viscose rayon, acetate rayon, polyamide, polyester polyolefin and acrylic.
• Other fibers of a vegetable or animal origin which can be treated include cotton, jute, ramie, wool and the like.
• the compositions of the present invention may also be designed for maintaining textile fabrics by including vacuuming aids.
• the cleaning composition is applied to the surface, allowed to stand (e.g. a few minutes to a few hours) and thereafter removed by vacuuming or the like.
• the composition may be applied to the carpet by sprinkling from a shaker type container or through the use of any conventional particulate dispensing means.
• liquid active material preferably designates a material that provides active properties to a particulate textile fiber or fabric cleaning composition.
• the liquid active material used in the textile fiber or fabric cleaning composition may be a fragrance for odor control, a surfactant for cleaning, a solvent for cleaning, or a pesticide for pest control, such as an acaricide for control of mites and ticks.
• the liquid active materials may be: (1) a fragrance, such as a liquid volatile odorous agent including essential oils and aromatic chemicals; (2) a solvent suitable for cleaning textile fibers, such as an ether alcohol (e.g., ethylene glycol monomethyl ether); (3) a surfactant or surfactant mixture suitable for cleaning textile fibers selected from any of the four basic groups of surface active agents including anionic (such as alkali metal salts of sulfate esters or sulfonates containing higher aliphatic hydrocarbon radicals of 8 or more carbon atoms) , non-ionic (such as polyethylene oxide condensates of aliphatic alcohols having 8 or more carbon atoms) , cationic (such as quaternary ammonium compounds) , and amphoteric (such as tertiary amine oxide salts having a hydrophobic radical attached to the nitrogen atom) ; (4) an acaricide, such as benzyl benzoate; or (5) mixtures of any of the above listed liquid active materials
• suitable particulate carriers are inorganic salt carriers such as sodium sulfate, sodium chloride, sodium carbonate, sodium bicarbonate, sodium borate, sodium citrate, sodium tripolyphosphate, sodium nitrate and mixtures thereof .
• suitable flow agents include silica, metal oxides such as alumina, and metal titanates .
• One version of a particulate fabric cleaning composition made in accordance with the present invention includes at least 80% by weight of inorganic salt carrier particulates, 1-10% by weight of flow agent particulates, and 0.1-15% by weight of liquids selected from the group consisting of fragrances, surfactants, solvents, pesticides, and mixtures thereof, wherein at least 90% of the composition particulates have a particle size greater than 0.105 millimeters.
• One version of the method of the invention is a method for producing a fabric cleaning composition that includes the steps of introducing at least one particulate material into a mixing vessel, introducing at least one liquid material into the mixing vessel to form a mixture, blending the mixture for a first time period, chopping the mixture for at least a portion of the first time period, and thereafter blending the mixture without chopping for a second time period, wherein at least 90% of the resulting composition is particulates having a particle size greater than 0.105 millimeters.
• An exemplary embodiment of the most preferred version of the composition is produced by: (1) adding 71 wt% sodium sulfate, 20 wt% sodium bicarbonate and 4 wt% hydrated amorphous silica to a ribbon blender having chopper blades; (2) adding a combination of 4.6 wt% liquid benzyl benzoate and 0.4 wt% liquid fragrance to the blender while mixing; (3) mixing with ribbons for a total of 2 minutes (or longer if needed to complete the transfer of liquid to the product) ; (4) mixing with ribbons and high speed chopper blades for 2.5 minutes; (5) turning off the chopper blades and continuing to mix with ribbons for 5.5 more minutes; (6) mixing with chopper blades and ribbons for 0.5 minutes; and (7) turning off the chopper blades and continuing to mix with ribbons for 5 minutes. In certain circumstances, mix times may be extended to accommodate raw materials with more fines .
• a mix and chop step may be run for 1 minute, and then a mix step may be run for two minutes. These extra steps may be repeated as needed. However, it is preferred that every mix and chop step be followed by a blending step without chopping so that any fines generated by the chopping process can be allowed to agglomerate in the further mixing step. It is should noted that this specific embodiment and the Examples that follow are illustrative in nature and should not be used to limit the scope of the invention.
• the process can be facilitated by use of a paddle mixer equipped with high speed flat or tulip chopper blades or a ribbon blender equipped with high speed flat or tulip chopper blades.
• a paddle mixer equipped with high speed flat or tulip chopper blades or a ribbon blender equipped with high speed flat or tulip chopper blades.
• One suitable paddle-type mixer is a
• the American Process Systems Gurnee, Illinois, USA.
• the inner and outer ribbons operate in opposite directions to provide an even movement of material and effect a homogeneous blend.
• the paddle mixer or ribbon blender motors should be sized appropriately for the density of the final dry carpet cleaning formulation.
• Suitable mixers or blenders include: (1) a 60 cubic foot capacity unit with a 75 horsepower main motor and four 20 horsepower chopper blades; and (2) a 100 cubic foot unit with a 100 horsepower main motor and four 20 horsepower chopper blades. All process equipment (including blender, chopping blades and filling equipment) are preferably clean and dry before starting the process, as water as may adversely affect the product.
• the level of particle agglomeration was evaluated using a " Shake and Smoke” test and a sieve test.
• a Shake and Smoke test approximately 4 ounces of material were placed in an 8 ounce glass jar and the jar is sealed. The jar is then shaken vigorously by hand. The jar is opened immediately and observed to determine whether any dust particles rise out of the container (i.e., the material " smokes” ) .
• the " Shake and Smoke” test evaluates the dustiness of a product.
• a dry carpet cleaning composition was prepared using the following ingredients:
• the dry ingredients sodium sulfate, sodium bicarbonate and silica
• a ribbon blender such as the ribbon blender described above .
• the benzyl benzoate was inspected for visible evidence of crystallization, as it is preferred that the benzyl benzoate be completely liquid. If needed, the temperature of the benzyl benzoate may be raised to 75 ° ⁇ 5°F (23°+ 2°C) to reverse any crystallization.
• the liquid fragrance and the benzyl benzoate were then mixed together and poured over the dry ingredients in the ribbon blender.
• the sodium sulfate and sodium bicarbonate were charged to the ribbon blender and subjected to 4 minutes of ribbon blending.
• the liquid ingredients (benzyl benzoate and fragrance) were mixed together and applied to the sodium sulfate and sodium bicarbonate as a spray mist using a pressurized spray vessel with fine conical -style nozzles while all of the ingredients were subjected to 3 minutes of ribbon blending.
• the ingredients were then subjected to 1 minute of ribbon blending with chopper blades turned on.
• the silica was then added to the ribbon blender and the ingredients were subjected to 3 minutes of ribbon blending with chopper blades turned on.
• the ingredients in the ribbon blender were then subjected to 5 minutes of ribbon blending.
• a sample was obtained from the blender and it was discovered by visual inspection that adding the liquid ingredients through a spray device produced a more homogenous mixture than the mixture of Example 1.
• Example 3 A carpet cleaning composition was prepared using the ingredients listed in Example 1 and another method of blending and agglomerating the ingredients.
• the dry ingredients sodium sulfate, sodium bicarbonate and silica
• the liquid ingredients benzyl benzoate and fragrance
• the ingredients were mixed in the ribbon blender in the following sequence: (1) 2 minutes of ribbon blending during application of the liquid spray; (2) 2.5 minutes of ribbon blending with chopper blades turned on; (3) 5.5 minutes of ribbon blending; (4) 0.5 minutes of ribbon blending with chopper blades turned on; and (5) 5 minutes of ribbon blending.
• the dry powdered carpet composition produced by this method was evaluated using the " Shake and Smoke” test described above after 10, 10.5, 13.0 and 15.5 minutes of blending according to the blending sequence.
• the " Shake and Smoke” test produced the following results: (1) after 10 minutes of blending (which included 2.5 minutes of chopping beginning after two minutes) , the " smoking" of the composition began to disappear; (2) after 10.5 minutes of blending, the " smoking” of the composition reappeared as a result of the chopping process; and (3) after 13 and 15.5 minutes of blending, the " smoking" of the composition had disappeared. Agglomeration of the powder was acceptable after 10 minutes.
• Example 4 A batch of dry carpet cleaner was prepared using the ingredients of Example 1 and the following sequence of steps.
• the dry ingredients sodium sulfate, sodium bicarbonate and silica
• the liquid ingredients benzyl benzoate and fragrance
• the ingredients were mixed in the ribbon blender in the following sequence: (1) 2 minutes of ribbon blending during application of the liquid spray, which took 50 seconds at 15 psi; (2) 2.5 minutes of ribbon blending with chopper blades turned on; (3) 5.5 minutes of ribbon blending; (4) 0.5 minutes of ribbon blending with chopper blades turned on; and (5) 5 minutes of ribbon blending.
• Samples of the dry powdered carpet composition were taken from the blender after 10, 11, 11.5 and 15.5 minutes of blending according to the blending sequence. The samples were evaluated using the sieve test described above, i.e. 100 grams of each sample were placed into the sieve tester and separated by size using U.S. Standard Sieve sizes 20 (0.84 millimeter opening), 40 (0.42 mm.
• the level of fines (as defined by particles passing through the 170 sieve) varies depending on the stage of the blending/chopping process. For example: (1) after 10 minutes of blending/chopping according to the blending sequence (i.e., 2 minutes of ribbon blending, 2.5 minutes of ribbon blending with chopping, and 5.5 minutes of ribbon blending) , 3.7 grams of the composition passed through the 170 sieve; (2) after 11 minutes of blending/chopping (i.e., 2 minutes of ribbon blending, 2.5 minutes of ribbon blending with chopping, 5.5 minutes of ribbon blending, 0.5 minutes of ribbon blending with chopping, and 0.5 minutes of ribbon blending), 5.1 grams of the composition passed through the 170 sieve; (3) after 11.5 minutes of blending/chopping (i.e., 2 minutes of ribbon blending, 2.5 minutes of ribbon blending with chopping, 5.5 minutes of ribbon blending, 0.5 minutes of ribbon blending with chopping, and 1 minute of ribbon blending), 2.0 grams of
• the variation in the level of fines throughout the blending/chopping process can likely be explained as follows. After 10 minutes of blending/chopping according to the blending sequence, the method of the present invention produces a composition having an acceptable level of fines as demonstrated by the " Shake and Smoke" test performed in Example 3 above. The level of fines (as defined by particles passing through the 170 sieve) was 3.7% (3.7 grams for a 100 gram sample) after 10 minutes. In the first 10 minutes of the blending sequence, the ingredients are subjected to blending, blending with chopping, and blending. After 11 minutes of blending/chopping according to the blending sequence, the level of fines (as defined by particles passing through the 170 sieve) rose to 5.1%.
• the data in the above table also indicates that the carpet cleaning powder produced in the examples will be free flowing powders that are acceptable for dispensing in shaker-type containers used in the carpet cleaning field. In addition, the carpet cleaning powder will have reduced level of fines.
• a batch of dry carpet cleaner was prepared using the ingredients of Example 1 and the following sequence of steps.
• the dry ingredients sodium sulfate, sodium bicarbonate and silica
• the liquid ingredients benzyl benzoate and fragrance
• the spray was a coarse spray from a planar fan-style nozzle.
• the ingredients were mixed in the ribbon blender in the following sequence: (1) 2 minutes of ribbon blending during application of the liquid spray; (2) 3.5 minutes of ribbon blending with chopper blades turned on; and (3) 20.5 minutes of ribbon blending. Samples of the dry powdered carpet composition were taken from the blender after blending and evaluated using " Shake and Smoke" test described above.
• the method of the present invention may be readily utilized with currently known filling techniques and production equipment for granular or powdered treating compositions.
• carpet cleaning compositions produced by the present method may be applied to a carpet by sprinkling from a shaker type container or through the use of any conventional particulate dispensing means.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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Citations (5)

• 1999
  • 1999-07-28 BR BR9912615-0A patent/BR9912615A/pt not_active Application Discontinuation
  • 1999-07-28 NZ NZ509527A patent/NZ509527A/en unknown
  • 1999-07-28 DE DE69903564T patent/DE69903564D1/de not_active Expired - Lifetime
  • 1999-07-28 EP EP99937518A patent/EP1102835B1/en not_active Expired - Lifetime
  • 1999-07-28 WO PCT/US1999/016960 patent/WO2000006681A1/en active IP Right Grant
  • 1999-07-28 AT AT99937518T patent/ATE226243T1/de not_active IP Right Cessation
  • 1999-07-28 JP JP2000562465A patent/JP2002521556A/ja active Pending
  • 1999-07-28 CA CA002339169A patent/CA2339169C/en not_active Expired - Fee Related
  • 1999-07-28 KR KR1020017001232A patent/KR20010071058A/ko active IP Right Grant
  • 1999-07-28 AU AU52333/99A patent/AU749030B2/en not_active Ceased
  • 1999-07-30 AR ARP990103821A patent/AR018961A1/es not_active Application Discontinuation
• 2001
  • 2001-02-07 ZA ZA200101049A patent/ZA200101049B/en unknown

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