Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/60—Deposition of organic layers from vapour phase
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
  • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
  • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
  • A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
  • D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
  • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
  • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
  • D06M15/353—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes containing fluorine
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/53—Polyethers
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/10—Coatings without pigments
  • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
  • D21H19/16—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising curable or polymerisable compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
  • B05D3/068—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using ionising radiations (gamma, X, electrons)
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
  • B05D3/141—Plasma treatment
  • B05D3/142—Pretreatment
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/10—Repellency against liquids
  • D06M2200/12—Hydrophobic properties

Definitions

• the present invention relates to a process, preferably a continuous process, of coating a substrate, which allows water vapour and preferably air permeation, with a hydrophobic coating.
• the process preferably uses a thin film vacuum condensation step to create a monomer coating which is cured in situ after the coating.
• the process has the benefit of allowing continuous operation and providing a alternative to existing processes for hydrophobic coating.
• the substrates are coated such that the water vapour permeation sites are not blocked by the coating to maintain the desired breathabiiity.
• the static water contact angle on the surface of such substrates is more than 95°.
• Such substrates are preferably employed in absorbent articles such as diapers, incontinence products, underarm sweat pads, sanitary napkins, catamenials, pantiliners, breast pads, shoe inserts or bandages or alternatively in protective garments such as gloves or rain coats for which water vapour transmission in particular from the inside to the outside is highly desirable.
• U.S. Pat. No. 3,498,527 teaches that paper board containers for liquids can be waterproofed by application of a waterproofing coating such as wax or polyethylene, and a similar method is shown in U.S. Pat. No. 2,708,645 for waterproofing paper drinking cups and in U.S. Pat. No. 3,212,697 for paper grocery sacks.
• a waterproofing coating such as wax or polyethylene
• temporary wet strength is imparted to paper by coating it with a polymeric alcohol- polymeric aldehyde reaction product. Coating processes, by themselves, have been used to produce disposable articles of sanitary clothing.
• a disposable sanitary napkin which consists of an adsorbent layer having a liquid-repellent backing of polyvinyl alcohol or similar material capable of initially repelling water but eventually solubilizing.
• the degree of water-repellency, therefore the lifetime of the napkin, is controlled by varying the thickness of the backing. Because the necessary life of the napkin cannot be predicted by manufacturer or user, the backing must be sufficiently thick to take account of all normal contingencies.
• U.S. Pat. No. 3,542,028 is directed to a flushable sanitary napkin consisting of a cellulosic sheet treated with a fluoropolymer coating.
• U.S. Pat. No. 3,559,650 teaches the preparation of a sanitary napkin having two flush- disposable sides separated by a waterproof film too thin to support itself once both faces of the napkin have disintegrated upon disposal.
• Analogous to the process of coating a surface with a waterproofing substance is the concept of reacting a surface with another material so as to form a reaction product on the surface which has water-repellent properties.
• U.S. Pat. Nos. 2,130,212 and 3,137,540 teach that materials such as polymeric alcohols may be reacted with other materials to increase their water-repellent properties.
• the latter patent teaches treating polyvinyl alcohol articles with an aqueous emulsion of an aldehyde to impart water- repellency thereto.
• U.S. Pat. No. 3,626,943 teaches that disposable diapers can be made from polyvinyl alcohol and waterproofed on one side by reaction with formaldehyde.
• 4,188,426 includes treatment in a glow discharge of per-fluoro-cyclo-butane or hexafluoroethane to reduce the friction coefficient and to improve the surface hydrophobia of organic and inorganic substrates (e.g. polyethylene films, metals).
• organic and inorganic substrates e.g. polyethylene films, metals.
• these disclosures do not achieve a level of water repellency as the present invention when employing the coating process disclosed herein.
• Plasma coating processes of metals, polymers, and other substrates, with fluorocarbon films are also known in the art. As an example, it is known from
• U.S. Pat No 5,328,576 discloses a method for imparting water and oil repellent surface properties to fabrics or paper that includes pretreatment in a low pressure oxygen plasma in the presence of water vapor followed by plasma polymerization of methane in a high frequency glow discharge carried out in the same treatment chamber. This method doesn't deliver durable, permanent coatings with a WCA higher than about 120°.
• U.S. Pat. No. 5,262,208 discloses an gas plasma treatment for archival preservation of paper manuscripts by a thin film protective polymer film. The treatment time is ranging from 30-3600 seconds. Other methods have been used to obtain thin coatings on the web materials with short treatment periods. Providing surface treatment is disclosed in US Patent No.
• the method of using a high speed vacuum coating process for producing durable and thin water- repellent coatings on a substrate uses a movable support such as rotating drum in a vacuum chamber.
• the surface of the support is maintained at a temperature sufficient to permit condensation of a vaporized material deposited in the chamber.
• the material is a curable monomer with a relatively low molecular weight.
• the monomer vapor is created using a flash vaporizer.
• the desired amount of curable monomer is metered to a heated flash vaporizer system where the material is vaporized. It is then transported e.g. by it's inherent pressure, to the substrate resting on the rotating drum and condensed on the surface of the substrate.
• the substrate is then transported to a curing means such as an energy source which emits an electron beam, UV-light radiation or exposure to an electro magnetic field.
• a curing means such as an energy source which emits an electron beam, UV-light radiation or exposure to an electro magnetic field.
• the curable monomer can also be transferred into radicals by passing through a plasma zone (zone of high voltage discharge).
• the curing of the monomer by the curing means then provides a coating on the substrate surface which has a static water contact angle of more than 95°.
• the method for delivering the curable monomer to the substrate for minimizing the amount of monomers can use an ultrasonic atomizer producing micro droplets of curable monomer. They are released into a vaporization tube heated by band heaters. The atomized droplets impinge on the inner wall of the vaporization tube and are instantaneously vaporized, i.e., flash vaporized. This reduces the opportunity for polymerization prior to being deposited on the substrate.
• the substrate can be one side water-repellent and capable of absorbing and storing fluids from the other side, or alternatively be repellent on both sides.
• a preferred embodiment of the present invention relates to a method of providing a durable water-repellent coating to a substrate material, using a high speed electron beam radiation process.
• the terms "hydrophobic” and “water-repellent” are used interchangeably and refer to surfaces that are repellent to aqueous liquids (e.g., body liquids) deposited on these surfaces. Hydrophobicity and wettability are defined in terms of static water contact angle and alternative the surface tension of the liquids and solids involved. This is discussed in detail in the American Chemical Society publication entitled Contact Angle, Wettability and Adhesion, edited by Robert F. Gould (Copyright 1964). A surface is hydrophobic if the static water contact angle is greater than 90° and the liquid does not spread spontaneously across the surface of the web. In general, the higher the contact angle between the surface and the liquid, the more hydrophobic the surface.
• the coatings of the present invention are "durably hydrophobic", insofar as the hydrophobic character engendered to the substrate is maintained after exposure to liquids and humid air.
• the coating formed by the method of the present invention has a thickness of less than 5 microns, and preferably less than 2 microns and most preferably in the range of 0.001 to 1 microns.
• the coatings are formed by depositing a vapor of curable monomer, under vacuum, on a movable substrate which is mounted in thermal contact with a support, for continuos processing preferably a rotating drum, which is maintained at a temperature below the boiling point of the vaporized monomer under the environmental conditions in vacuum chamber . As a result of this temperature differential, the monomer vapor condenses on the surface of the substrate.
• the monomer materials utilized in the present invention are relatively low in molecular weight, between 150 and 1000 Atomic Mass Units (AMU) , and preferably in the range 200 to 300 AMU.
• AMU Atomic Mass Unit
• Polyfunctional flurocarbons and especially fluoroacrylates pr mixtures of monofunctional fluoroacrylates and polyfunctional fluoroacrylates are preferred.
• the monomers or monomer mixtures employed have an average of about two or more double bonds (i.e., a plurality of olefinic groups) and have a vapor pressure such that they condense on the substrate surface.
• Such vapor pressures are for example pressure between about 1.33 10 "6 mbar and 1.33 10 "1 mbar, most preferably a vapor pressure of approximately 1.33 10 "2 mbar at standard temperature and pressure, (i.e., relatively low boiling materials) are selected.
• high-vapor-pressure monomers can be flash vaporized already at low temperatures and thus are not degraded (cracked) by the heating process.
• the absence or low amount of unreactive degradation products results in coatings with a reduced levels of volatile components in which substantially all of the deposited monomer is reactive and will cure to form an integral film when exposed to a source of radiation.
• These properties make it possible to provide a substantially continuous coating despite the fact that the deposited film is very thin.
• the cured films exhibit excellent adhesion and are resistant to chemical attack by organic solvents and inorganic salts.
• the process according to the present invention can continuously create substrate surfaces having a hydrophobic characteristic such that the static water contact angle is more than 95°, preferably more than about 120°, more preferably higher than about 130° and most preferably between about 150° and about 165°.
• the static water contact angle value can be measured with a water contact angle goniometer. The measurement is done on a flat, i.e. plane, and smooth surface of a substrate after coating.
• smooth as used herein for water contact angle measurements refers to a roughness of no more than 5 microns in accordance with standard roughness measurements on continuous surfaces.
• the high speed vacuum coating process for producing water vapour permeable substrates with exceptional water repellent properties or on either one side or both sides requires a curable monomer component.
• the curable monomer for obtaining water-repellent coatings comprises fluoro-containing group.
• any suitable fluoromonomer may be used, including, but not limited to, fluoroacrylate monomers, fluoro olefin monomers, fluorostyrene monomers, fluoroalkylene oxide monomers (e.g., perfluoropropylene oxide, perfluorocyclohexene oxide), fluorinated vinyl alkyl ether monomers, and the copolymers thereof with suitable comonomers, wherein the comonomers are fluorinated or unfluorinated. Fluoromonomers which are polymerized by a free radical polymerization process are preferred.
• fluorostyrenes and fluorinated vinyl alkyl ether monomers which may be used in the method of the present invention include, but are not limited to, ⁇ -fluorostyrene; ⁇ -fluorostyrene; ⁇ , ⁇ - difluorostyrene; ⁇ , ⁇ -difluorostyrene; ⁇ , ⁇ , ⁇ -trifluorostyrene; ⁇ - trifluoromethylstyrene; 2,4,6-Tris (trifluoromethyl)styrene; 2,3,4,5,6- pentafluorostyrene; 2,3,4,5,6-pentafluoro- ⁇ -methylstyrene; and 2,3,4,5,6- pentafluoro- ⁇ -methylstyrene.
• tetrafluoroethylene can also be used in the method of the present invention and include, but are not limited to, tetrafluoroethylene-hexafluoropropylene copolymers, tetrafiuoroethylene- perfluorovinyl ether copolymers (e.g., copolymers of tetrafluoroethylene with perfluoropropyl vinyl ether), tetrafluoroethylene-ethylene copolymers, and perfluorinated ionomers (e.g., perfluorosulfonate ionomers; perfluorocarboxylate ionomers).
• fluorocarbon elastomers see, e.g., 7
• fluoro olefin polymers which can also be used in the process of the present invention and include, but are not limited to, poly(vinylidene fluoride-co- hexafluoropropylene); poly(vinylidene fluoride-co-hexafluoropropylene-co- tetrafluoroethylene); poly[vinylidene fluoride-co-tetrafluoroethylene-co- perfluoro(methyl vinyl ether)]; poly[tetrafluoroethylene-co-perfluoro(methyl vinyl ether)]; poly(tetrafluoroethylene-co-propylene; and poly(vinylidene fluoride-co-chlorotrifluoroethylene).
• fluoroacrylates are particularly useful monomeric materials.
• R is hydrogen or methyl; and R 2 is a perfluorinated aliphatic or perfluorinated aromatic group, such as a perfluorinated linear or branched, saturated or unsaturated Ci to C 10 alkyl, phenyl, or naphthyl.
• R 2 is a Ci to C 8 perfluoroalkyl or - CH 2 - NR 3 - SO 2 - R 4 , wherein R 3 is C C 2 alkyl and R is C-i to C 8 perfluoroalkyl.
• perfluorinated as used herein, means that all or essentially all hydrogen atoms on an organic group are replaced with fluorine.
• EtFOSEA 2-(N-ethylperfluorooctanesulfonamido) ethyl acrylate
• EtFOSEMA 2-(N-ethylperflooctanesulfonamido) ethyl methacrylate
• MeFOSEA 2-(N-methylperfluorooctanesulfonamido) ethyl acrylate
• MeFOSEMA 2-(N-methylperflooctanesulfonamido) ethyl methacrylate
• MeFOSEMA 2-(N-methylperflooctanesulfonamido) ethyl methacrylate
• FOA 1 ,1-Dihydroperfluorooctyl acrylate
• FOMA 1 ,1-Dihydroperfluorooctyl methacrylate
• the curable monomer component can also include polyfunctional acrylates, which are set forth in U.S. Patent 4,842,893, incorporated herein by reference.
• the substrate for coating according to the process of the present invention can be any substrate which supports water vapour transport through it.
• the substrate can for example be an apertured film which allows free air circulation through the apertures or a woven or non-woven which also allows free air circulation through the pores of the woven or non-woven.
• the substrates can however also be impermeable to air passage such as microporous substrates (usually Ca filled films which are stretched) or vapour transmitting monolithic films.
• Particularly preferred are substrates which can be employed in garments or absorbent articles such as those listed above.
• Substrates can be coated from one or both sides and the coating can be identical or different depending on the desired final use of such substrates.
• the substrates are useful in disposable articles such as diapers, sanitary napkins, pantiliners, adult incontinence products, under arm sweat pads, breast pads, shoe inserts, and so for.
• the substrate can either be used in a position in these articles where it supports the containment function of an impermeable sheet in which case the substrate needs to provide water vapour transport without allowing liquid transport under the usual usage conditions of the article.
• such substrates can also be used as liquid permeable substrates on the liquid receiving sides of such articles so that liquid deposited on the surface of the substrate is transported quickly through the substrate towards an absorbent structure from which liquid cannot or only under extreme conditions be moved back towards the user of such an article (rewet prevention).
• Substrates coated according to the present invention also can find utility in protective garments such as raincoats or gloves or hats or generally apparel which is beneficially provided with water vapour permeability.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Textile Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Epidemiology (AREA)
• Hematology (AREA)
• Materials Engineering (AREA)
• Toxicology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• General Health & Medical Sciences (AREA)
• Public Health (AREA)
• Veterinary Medicine (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Laminated Bodies (AREA)
• Treatments Of Macromolecular Shaped Articles (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

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• 1999
  • 1999-09-07 BR BR9917480-4A patent/BR9917480A/pt not_active IP Right Cessation
  • 1999-09-07 CN CN99816892.0A patent/CN1367721A/zh active Pending
  • 1999-09-07 CA CA002383168A patent/CA2383168A1/en not_active Abandoned
  • 1999-09-07 EP EP99946764A patent/EP1363747A1/en not_active Withdrawn
  • 1999-09-07 WO PCT/US1999/020422 patent/WO2001017696A1/en not_active Application Discontinuation
  • 1999-09-07 AU AU59097/99A patent/AU5909799A/en not_active Abandoned
  • 1999-09-07 JP JP2001521475A patent/JP2003508219A/ja not_active Withdrawn
  • 1999-09-07 MX MXPA02002451A patent/MXPA02002451A/es not_active Application Discontinuation

Non-Patent Citations (1)

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