Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
  • A61F13/00—Bandages or dressings; Absorbent pads
  • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
  • A61F13/56—Supporting or fastening means
  • A61F13/66—Garments, holders or supports not integral with absorbent pads
  • A61F13/82—Garments, holders or supports not integral with absorbent pads with means for attaching to the body
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/20—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself
  • C09J2301/204—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive itself the adhesive coating being discontinuous

Definitions

• the invention relates to a method for producing discrete patterns of adhesive coatings on a substrate.
• hydrogels In connection with hygiene articles that are attached to the human body, adhesive materials based on so-called hydrogels are often used. These are water-containing gels based on hydrophilic, water-insoluble polymers that form a three-dimensional network.
• the adhesive layers contain hydrocolloids such as starch, modified starch, cellulose esters, vegetable gums or carboxypolymethylene and / or prepolymers, partially crosslinked polymers, polymer mixtures, branched polymers and graft (co) polymers thereof.
• Adhesive layers made of hydrogels are obtained by photopolymerizing solutions of suitable precursor compounds, such as solutions of suitable hydrophilic monomers or suitable uncrosslinked hydrophilic polymers or mixtures thereof, in the presence of crosslinking agents.
• a substrate is coated with a solution of the precursor compounds and the layer is photopolymerized or photocrosslinked by irradiation with high-energy radiation or polymerized or crosslinked by other suitable processes. From the substrate obtained in this way, coated with an adhesive layer, patterns are punched out in the desired shape and used, for example, in the manufacture of the hygiene articles mentioned.
• the process is cumbersome and has the disadvantage that large amounts of waste are produced which are generated as waste.
• the object of the invention is to provide a method for producing discrete patterns of an adhesive coating on a substrate which is economical and does not have the disadvantages of the prior art.
• the object is achieved by a process for producing discrete patterns of an adhesive coating on a substrate with the following process steps:
• a low-viscosity, polymerizable and / or crosslinkable precursor material of an adhesive material is applied flatly to the substrate through at least one essentially slit-shaped opening of at least one movable application device, a pattern being generated by moving the application device relative to the substrate,
• the applied precursor material is polymerized and / or crosslinked.
• the polymerized and / or crosslinked material is aftertreated, refined and / or made up.
• the low-viscosity precursor material is generally applied to the substrate in a layer thickness of 0.3 to 5 mm, preferably 0.5 to 2 mm.
• the substrate is moved continuously or discontinuously in a conveying direction.
• the substrate passes through an application zone and a polymerization and / or Crosslinking zone.
• the substrate is usually in the form of a substrate tape which is rolled up from a tape roll upstream of the application zone and is rolled up again to form a tape roll downstream of the polymerization and crosslinking zone, if appropriate after being connected to a protective film.
• the method according to the invention preferably comprises coating the substrate, polymerizing and / or crosslinking the coating, optionally aftertreatment by applying one or more further components, covering with a protective film and rolling up the film composite formed.
• garlands festooning
• sheets sheets
• other suitable methods for storing, transporting and distributing flat (sheet-like) material.
• the at least one application device is moved in the substrate plane by means of a robot arm, which can move freely at least in the substrate plane, but usually in all three spatial directions, and are moved by the movement of the robot arm relative to the substrate during the application of the low-viscosity precursor material created the pattern.
• the substrate can be moved further in the conveying direction, since the robot arm can be programmed so that its movement compensates for the movement of the substrate.
• the at least one application device is moved along a translation device at an angle to the conveying direction of the substrate.
• the coating patterns are thus generated by the movement of the substrate in the conveying direction and the transverse movement of the application device.
• the translation device is expediently arranged perpendicular to the conveying direction and the movement of the at least one application device takes place perpendicular to the conveying direction of the substrate, but it is also readily possible to arrange the translation device at an angle other than 90 °.
• Two application devices are particularly preferably provided on the translation device and can be moved separately along the translation device.
• closed patterns can be produced, for example by moving the application devices apart and together, such as circular or oval patterns that are closed in a ring. It is also possible to produce ring-shaped closed patterns with only one application device movable along a translation device, by first moving the substrate in the conveying direction during the application process, part of the pattern being generated, and then briefly moving the substrate in order to complete the pattern reverses.
• the polymerizable and / or crosslinkable low-viscosity precursor material is applied to the substrate over a large area, that is to say that the thickness of the layer is small compared to the width of the layer.
• the application width can be varied by inclining the slot-shaped opening of the application device.
• the application width of the layer is preferably 3 to 50 mm.
• the movable application device used in the method according to the invention can be largely miniaturized. Their dimensions are only limited by the size of the technology available.
• the polymerizable and / or crosslinkable precursor material applied in the form of a pattern is polymerized and / or crosslinked, and finally a patterned, adhesive coating is thus obtained.
• the precursor material is preferably photopolymerizable and / or radiation-crosslinkable.
• the photopolymerization and / or radiation crosslinking can be effected by irradiation with high-energy radiation, for example with electron radiation, preferably with UV radiation, suitable initiators being able to be present in the precursor material.
• the photopolymerization and / or radiation crosslinking can be carried out in a special crosslinking atmosphere, for example in a simple container with an inlet slot and an outlet slot for the substrate and radiation-permeable windows which are gassed with a suitable gas mixture.
• gases are, for example, noble gases, nitrogen, carbon dioxide or oxygen-containing gas mixtures which contain less oxygen than air (lean air).
• the adhesive coating is made from
• Hydrogel-forming polymers are formed.
• Hydrogel-forming polymers are in particular polymers of (co) polymerized hydrophilic monomers, graft (co) polymers of one or more hydrophilic monomers on a suitable graft base, Comb polymers and polymer networks, crosslinked cellulose or starch ethers, crosslinked carboxymethyl cellulose, partially crosslinked polyalkylene oxide or natural products that swell in aqueous liquids, such as guar derivatives, alginates and carrageenans.
• the low-viscosity, polymerizable or crosslinkable precursor material contains corresponding polymerizable and / or crosslinkable monomers and / or polymers and crosslinkers which form crosslinked polymers which form hydrogels when crosslinked, and suitable initiators.
• the crosslinkable precursor material can include hydrocoids, plasticizers, polyols, carbohydrates, polyethers, polysaccharides, stabilizers, thickeners, rheology modifiers, antioxidants, UV stabilizers, skin care agents, antibacterial or bacteriostatic agents, fillers such as inorganic or organic colloids, pigments, water-soluble solvents , Silicates, titanium dioxide, nanoparticles, surfactants, preservatives, dyes, fragrances and water.
• Suitable polymers can be of natural or synthetic origin. Examples are starch, cellulose or cellulose derivatives and further polysaccharides and oligosaccharides, polyvinyl alcohol, polyalkylene oxides, in particular polyethylene oxides and polypropylene oxides, polyelectrolytes, polyethers, polyamines, polyamides and hydrophilic polyesters.
• Suitable polyalkylene oxides have, for example, the formula
• R 1 and R 2 independently of one another are hydrogen, alkyl, alkenyl or acyl, X is hydrogen or methyl and n is an integer from 1 to 10,000
• R 1 and R 2 are preferably hydrogen, (C 1 -C 4 ) alkyl, (C 2 -C 6 ) alkenyl or phenyl.
• Preferred hydrogel-forming polymers are polymers with acid groups, which are present in the form of their salts, generally the alkali, alkaline earth or ammonium salts. Such polymers swell particularly strongly into gels on contact with aqueous liquids.
• Polymers obtained by crosslinking polymerization or copolymerization of monoethylenically unsaturated monomers bearing acid groups or salts thereof are preferred. It is also possible to (co) polymerize monomers without crosslinking agents and to crosslink them subsequently.
• Monomers carrying acid group are, for example, monoethylenically unsaturated C 3 to C 25 carboxylic acids or anhydrides such as acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid.
• monoethylenically unsaturated C 3 to C 25 carboxylic acids or anhydrides such as acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid and fumaric acid.
• monoethylenically unsaturated sulfonic or phosphonic acids and their salts for example vinylsulfonic acid, allylsulfonic acid, sulfoethyl (meth) acrylate, sulfomethacrylate, sulfopropylacrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, vinylphosphonic acid , Allylphosphonic acid, styrene sulfonic acid and 2-acrylamido-2-methyl propane sulfonic acid.
• the monomers can be used alone or as a mixture with one another.
• Preferred monomers which can be contained in the low-viscosity precursor material are acrylic acid, methacrylic acid, vinylsulfonic acid, acrylamidopropanesulfonic acid and their derivatives and salts. Mixtures of these acids and their salts, e.g. B. mixtures of acrylic acid and methacrylic acid, mixtures of acrylic acid and acrylamidopropanesulfonic acid or mixtures of acrylic acid and vinylsulfonic acid.
• the crosslinkable, low-viscosity precursor material can contain water-soluble or water-dispersible monomers and additional monoethylenically unsaturated compounds which do not carry acid groups but can be copolymerized with the monomers bearing acid groups.
• additional monoethylenically unsaturated compounds which do not carry acid groups but can be copolymerized with the monomers bearing acid groups.
• these include, for example, the amides and nitriles of monoethylenically unsaturated carboxylic acid, e.g. B. acrylamide, methacrylamide and N-vinylformamide, N-vinyl acetamide, N-methyl vinyl acetamide, acrylonitrile and methacrylonitrile.
• Suitable compounds are, for example, vinyl esters from saturated - to C 4 -carboxylic acids such as vinyl formate, vinyl acetate or vinyl propionate, alkyl vinyl ether with at least 2 carbon atoms in the alkyl group, such as. B. ethyl vinyl ether or butyl vinyl ether, esters of monoethylenically unsaturated C 3 - to C 6 -carboxylic acids, for. B. esters of monohydric - to C 18 alcohols and acrylic acid, methacrylic acid or maleic acid, half-ester of maleic acid, for. B.
• N-vinyl lactams such as N-vinyl pyrrolidone or N-vinyl caprolactam
• acrylic acid and methacrylic acid esters of alkoxylated monohydric, saturated alcohols e.g. B. of alcohols with 10 to 25 carbon atoms which have been reacted with 2 to 200 moles of ethylene oxide and / or propylene oxide per mole of alcohol
• Other suitable monomers are styrene and alkyl-substituted styrenes such as ethylstyrene or tert-butylstyrene.
• These monomers bearing no acid groups can also be used in a mixture with other monomers, for.
• Preferred hydrogel-forming, crosslinked polymers are composed of 60-100% by weight of monoethylenically unsaturated monomers bearing acid groups, which have optionally been converted into their alkali metal, alkaline earth metal or ammonium salts, and from 0-40% by weight, based on the total weight of the monomers, composed of monoethylenically unsaturated monomers bearing no acid groups.
• Crosslinked polymers of monoethylenically unsaturated C 3 to C 1 carboxylic acids and / or their alkali metal, alkaline earth metal or ammonium salts are particularly preferred.
• crosslinked polyacrylic acids are preferred, the acid groups of which are 10-100% in the form of alkali or ammonium salts.
• Compounds which have at least two ethylenically unsaturated double bonds can function as crosslinkers.
• Examples of compounds of this type are N, N'-methylenebisacrylamide, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate, which are each derived from polyethylene glycols with a molecular weight of 106 to 8500, preferably 400 to 2000, trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate propylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, allyl methacrylate, diacrylates and dimethacrylate of block copolymers of ethylene oxide and propylene oxide, doubly or multiply with acrylic acid or methacrylic
• water-soluble crosslinking agents are used, e.g. B. N, N'-methylene bisacrylamide, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate, which are derived from addition products of 2 to 400 moles of ethylene oxide to 1 mole of a diol or polyol, vinyl ethers of addition products of 2 to 400 moles of ethylene oxide to 1 mole of a diol or polyol, ethylene glycol diacrylate , Ethylene glycol dimethacrylate or triacrylates and trimethacrylates of addition products of 6 to 20 moles of ethylene oxide with 1 mole of glycerol, pentaerythritol triallyl ether and / or divinyl urea.
• B. N, N'-methylene bisacrylamide, polyethylene glycol diacrylate and polyethylene glycol dimethacrylate which are derived from addition products of 2 to 400 moles of ethylene oxide to 1 mole of a diol or polyol, vinyl
• crosslinkers are compounds which contain at least one polymerizable ethylenically unsaturated group and at least one further functional group.
• the functional group of these crosslinkers must be able to react with the functional groups, essentially the acid groups, of the monomers. Suitable functional groups are, for example, hydroxyl, amino, epoxy and aziridino groups. Can be used for.
• N-vinylimidazole, l-vinyl-2-methylimidazole and N-vinylimidazolines such as N-vinylimidazoline, l-vinyl-2-methylimidazoline, l-vinyl-2-ethylimidazoline or 1-vinyl-2-propylimidazoline, which are in the form of free bases, in quaternized form or as a salt can be used in the polymerization.
• Dialkylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate are also suitable.
• the basic esters are preferably quaternized Form or used as salt.
• Glycidyl (meth) acrylate can also be used.
• crosslinkers are compounds which contain at least two functional groups which are capable of reacting with the functional groups, essentially the acid groups of the monomers.
• the functional groups suitable for this have already been mentioned above, i. H. Hydroxyl, amino, epoxy, isocyanate, ester, amido and aziridino groups.
• crosslinkers examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, polyglycerol, triethanolamine, propylene glycol, polypropylene glycol, block copolymers of ethylene oxide and propylene oxide, ethanolamine, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid, pentanediol fatty acid, penta-adenol fatty acid, penta-adenol fatty acid, penta-adenol fatty acid, penta-adenol fatty acid, penta-ethane-1-propanol, penta-ethylenediol, penta-adenol fatty acid, penta-ethane-1-propanol, penta-ethylenediol, penta-adenol fatty acid, penta-ethane-1-propanol, penta
• Polyaziridine compounds such as 2,2-bishydroxymethylbutanol-tris [3- (l-aziridinyl) propionate], 1,6-hexamethylene-diethyleneurea, diphenylmethane-bis-4,4'-N, N'-diethylene urea, haloepoxy compounds such as epichlorohydrin and ⁇ -methylepifluorohydrin , Polyisocyanates such as 2,4-tolylene diisocyanate and hexamethylene diisocyanate, alkylene carbonates such as 1,3-dioxolan-2-one and 4-methyl-1,3-dioxolan-2-one, further bisoxazolines and oxazolidones, polyamidoamines and their reaction products with epichlorohydrin, furthermore polyquaternary amines such as condensation products of dimethylamine with epichlorohydrin, homopolymers and copolymers of diallyldimethylammonium chloride and homo
• crosslinkers are polyvalent metal ions, which are able to form ionic crosslinks.
• crosslinkers are magnesium, calcium, barium, aluminum, chromium, titanium and zirconium ions. These crosslinkers are used, for example, as hydroxides, carbonates or hydrogen carbonates.
• suitable crosslinkers are multifunctional bases which are also able to form ionic crosslinks, for example polyamines or their quaternized salts. Examples of polyamines are ethylenediamine, diethylenetriamine, triethylenetetramine, Tetraethylene penta in, pentaethylene hexamine and polyethylene imines as well as polyamines with molecular weights of up to 4000000 each.
• crosslinking agents are usually contained in the polymerizable and / or crosslinkable, low-viscosity precursor material in amounts of 0.001 to 20 and preferably of 0.01 to 5% by weight.
• the photopolymerization and / or radiation crosslinking of the low-viscosity precursor material applied in a pattern to the substrate to form the adhesive coatings can take place in the presence of a suitable initiator.
• a suitable initiator All compounds which break down into free radicals when irradiated with UV light or electron radiation can be used as initiators. These can be, for example, so-called ⁇ -splitters, H-abstracting systems or also azides.
• initiators examples include benzophenone derivatives such as Michlers ketone, phenanthrene derivatives, fluorene derivatives, anthraquinone derivatives, thioxanone derivatives, coumarin derivatives, benzoin ethers and their derivatives, azo compounds such as the radical formers mentioned above, substituted hexaarylbisimidazoles or acylphosphine oxides.
• azides examples include 2- (N, N-dimethylamino) ethyl 4-azidocinnamate, 2- (N, N-dimethylamino) ethyl 4-azidonaphthyl ketone, 2- (N, N-dimethylamino) ethyl 4-azidobenzoate, 5-azido-1-naphthyl-2 '- (N, N-dimethylamino) ethyl sulfone, N- (4-sulfonyl azidophenyl) maleimide,
• the photoinitiators are usually used in amounts of 0.001 to 5% by weight, based on the monomers to be polymerized.
• Suitable UV crosslinkers are generally all molecules which initiate a crosslinking reaction when irradiated with UV light. Further examples are vinyl ether, vinyl caprolactam, Laromer® brands such as Laromer® TMPTA, Laromer®BDDA, Laromer® HDDA, Laromer® TPGDA, Laromer®DPGDA, Laromer® UR8837 and Laromer® TBCH.
• the polymerizable and / or crosslinkable, low-viscosity precursor material usually also contains one or more plasticizers.
• Suitable plasticizers are water, alcohols, polyols such as glycerol or sorbitol, glycols and glycol ethers such as polyalkylene glycol mono- or diether, polyalkylene glycol mono- or diesters, glycolates, glycerol and sorbitan esters, tartaric acid or citric acid esters, of imidazolines derived amphoteric surfactants, lactams, amides, polyamides, quaternary ammonium compounds, condensation products of polyethyleneimine and epichlorohydrin, phthalates, adipates, stearates, palmitates, sebacates and myristates as well as natural or synthetic oils such as vegetable oils or mineral oils.
• Preferred plasticizers are polyols, polyethylene glycol, glycerin, sorbitol, polysaccharides, polyvinyl alcohol, water and mixtures thereof.
• the plasticizers are usually present in amounts of 5 to 75% by weight, based on the sum of all components contained in the radiation-crosslinkable, low-viscosity precursor material.
• the low-viscosity precursor material can contain hydrocoids such as starch, modified starch such as dextrin, cellulose esters such as carboxymethyl cellulose, vegetable gum such as pectin karaya, gelatin, guar gum, gum arabic, locust bean gum or carboxypolymethylene.
• hydrocoids such as starch, modified starch such as dextrin, cellulose esters such as carboxymethyl cellulose, vegetable gum such as pectin karaya, gelatin, guar gum, gum arabic, locust bean gum or carboxypolymethylene.
• the low-viscosity, polymerizable and / or crosslinkable precursor material usually has a viscosity between 50 and 10000 mPas, preferably between 50 and 1000 mPas.
• Suitable substrates to which the polymerizable and / or crosslinkable, low-viscosity precursor material is applied are PU foams, nonwoven materials such as polyethylene / polypropylene nonwoven materials, paper, textiles, nonwovens according to ISO 9092 / EN 29092, metal foils or plastic foils.
• FIG. 1 shows a sketch of a device for applying a low-viscosity, radiation-crosslinkable precursor material to a web-shaped substrate
• Figure 2 shows a half of an application device with a slot-shaped opening.
• the device 1 shown in FIG. 1 for applying a low-viscosity, radiation-crosslinkable precursor material to a web-like substrate essentially consists of a translation device 10 on a support 11 with first and second application devices 14 and 15 with funnels 17 and feed lines 16 that move along the translation device Funnels 17 of the application devices 14 and 15 are supplied with the low-viscosity, polymerizable and / or cross-linkable material during the operation of the device through the feed lines 16, the supply being regulated by valves (not shown).
• a substrate 2 is unwound from a substrate supply roll 4 which is rotatably mounted on an axis 7 below the application devices 14 and 15 and which can be rotated in a first and a second direction of rotation 12 and 13, respectively, and is thereby moved in the conveying direction 5.
• the substrate 2 with a substrate thickness 6 and a substrate width 9 has an upper side 1 and a lower side 3.
• a material application 19 of low-viscosity, radiation-crosslinkable precursor material is applied to the top 3 of the substrate 2.
• the material application takes place in freely selectable, discrete open or closed patterns 8 on the substrate 2.
• the application device shown in FIG. 2 has an inlet 19, a distribution chamber 20, a feed slot 21 and an outlet opening 22.

Landscapes

• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biomedical Technology (AREA)
• Animal Behavior & Ethology (AREA)
• Engineering & Computer Science (AREA)
• General Health & Medical Sciences (AREA)
• Heart & Thoracic Surgery (AREA)
• Vascular Medicine (AREA)
• Public Health (AREA)
• Epidemiology (AREA)
• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Veterinary Medicine (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Adhesive Tapes (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Materials For Medical Uses (AREA)
• Absorbent Articles And Supports Therefor (AREA)

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• 2002
  • 2002-07-04 DE DE10230121A patent/DE10230121A1/de not_active Withdrawn
• 2003
  • 2003-07-03 CA CA002490890A patent/CA2490890A1/en not_active Abandoned
  • 2003-07-03 US US10/520,021 patent/US20050233072A1/en not_active Abandoned
  • 2003-07-03 BR BR0312366-9A patent/BR0312366A/pt not_active Application Discontinuation
  • 2003-07-03 CN CN038156113A patent/CN1665898A/zh active Pending
  • 2003-07-03 EP EP03762607A patent/EP1523531A1/de not_active Withdrawn
  • 2003-07-03 JP JP2004518686A patent/JP2006511630A/ja not_active Withdrawn
  • 2003-07-03 PL PL03374819A patent/PL374819A1/xx unknown
  • 2003-07-03 AU AU2003257431A patent/AU2003257431A1/en not_active Abandoned
  • 2003-07-03 WO PCT/EP2003/007105 patent/WO2004005416A1/de not_active Application Discontinuation
  • 2003-07-03 MX MXPA05000036A patent/MXPA05000036A/es unknown

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