WO2003083189A1 - Polymeric fiber composition and method - Google Patents

Polymeric fiber composition and method Download PDF

Info

Publication number
WO2003083189A1
WO2003083189A1 PCT/US2003/008910 US0308910W WO03083189A1 WO 2003083189 A1 WO2003083189 A1 WO 2003083189A1 US 0308910 W US0308910 W US 0308910W WO 03083189 A1 WO03083189 A1 WO 03083189A1
Authority
WO
WIPO (PCT)
Prior art keywords
use according
light
minutes
particles
filament
Prior art date
Application number
PCT/US2003/008910
Other languages
English (en)
French (fr)
Inventor
John H. Schnurer
Robert M. Klein
David D. Horinek
Original Assignee
Schnurer John H
Klein Robert M
Horinek David D
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Schnurer John H, Klein Robert M, Horinek David D filed Critical Schnurer John H
Priority to KR1020047015048A priority Critical patent/KR100740730B1/ko
Priority to AU2003220481A priority patent/AU2003220481B2/en
Priority to EP03716790A priority patent/EP1488026B1/de
Priority to AT03716790T priority patent/ATE460514T1/de
Priority to CA002479958A priority patent/CA2479958C/en
Priority to DE60331636T priority patent/DE60331636D1/de
Priority to JP2003580616A priority patent/JP4489439B2/ja
Publication of WO2003083189A1 publication Critical patent/WO2003083189A1/en

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • D01F1/106Radiation shielding agents, e.g. absorbing, reflecting agents
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1362Textile, fabric, cloth, or pile containing [e.g., web, net, woven, knitted, mesh, nonwoven, matted, etc.]

Definitions

  • the present invention generally relates to specific combinations of active particles, forming a powder, that may be combined with carrier materials such as resins to produce fibers or filaments for textiles, films, coatings, and/or protective or insulating materials.
  • carrier materials such as resins to produce fibers or filaments for textiles, films, coatings, and/or protective or insulating materials.
  • the specific mixture of particles and materials may be engineered to impart unique and valuable properties to end products, including integration with optical energies, heat, and other electromagnetic energies. Resultant compositions may interact with light in the visible spectrum, as well as optical and electromagnetic energy beyond the visible spectrum.
  • the powder may be added to a carrier material, such as, for example, a polymer, which may then be extruded to form a fiber or filament or formed into a membrane, or film, which may be used to create a fabric or coating useful in a variety of applications.
  • a carrier material such as, for example, a polymer
  • Such applications may include hosiery, footwear, active wear, sports wear, sports wraps, base layer, gloves, and bandages. These items may also have certain properties such as controlling odor, regulating heat, providing protection from fire, providing protection from harmful light, insulation, wound healing, and preserving food.
  • the powder may be designed to interact in a benign manner with the human body, its needs, requirements, and homeostatic stabilization.
  • This invention seeks to correct the problems and meet the needs of the industry as detailed above. Therefore, it is a specific objective of the present invention to provide methods and compositions that will provide a biologically benign composition that is optically responsive.
  • One embodiment of the invention relates to a composition
  • a composition comprising titanium dioxide, quartz, aluminum oxide, and a resin.
  • the resin composition is a polymer.
  • the aluminum oxide, titanium dioxide, and quartz may be dispersed within the resin.
  • the titanium dioxide, quartz, and aluminum oxide may be present in a dry weight ratio of 10:10:2, respectively.
  • the titanium dioxide, quartz, and aluminum oxide may comprise about 1 to about 2 percent of the total weight of the composition, and the composition may be biologically benign.
  • the titanium dioxide within the composition may comprise an average grain size of about 2.0 microns or less and the grains may be substantially triangular.
  • the aluminum oxide within the composition may comprise an average grain size of about 1.4 microns or less and the grains may be scalloped-shaped.
  • the quartz within the composition may comprise an average grain size of about 1.5 microns or less and the grains may be rounded in shape.
  • the titanium dioxide, aluminum oxide, and quartz composition may be homogenized within this embodiment of the present invention.
  • the composition may shift the wavelength of incident light, by both shortening and lengthening the wavelength of the incident light that is exposed to the composition.
  • the invention herein also relates to methods for creating an optically responsive yarn comprising the steps of extruding the composition of the above mentioned embodiments into a plurality of fibers and spinning those fibers into yarn.
  • the present invention may consist of woven fibers comprising the aforementioned composition.
  • the composition may also be woven with fibers comprising one or more additional natural fibers such as wool, cotton, silk, linen, hemp, ramie, and jute.
  • the composition may also include woven fibers comprising one or more synthetic fibers such as acrylic, acetate, lycra, spandex, polyester, nylon, and rayon.
  • the present invention may also consist of non- woven fibers comprising the aforementioned composition.
  • the non- woven fibers may be spun with woven natural fibers such as wool, cotton, silk, linen, hemp, ramie, and jute, or synthetic fibers such as acrylic, acetate, lycra, spandex, polyester, nylon, and rayon.
  • the optically responsive yarn can be produced by these methods to create a fabric comprising either the woven or non- woven fibers of the aforementioned composition, spun together with a plurality of natural, synthetic or both natural and synthetic fibers.
  • Yet another embodiment of the present invention herein also relates to methods of retaining source radiation emitted from a subject or object comprising covering or surrounding an object bodily area with one of the above mentioned fabrics.
  • the fabric may be comprised of woven fibers consisting of the aforementioned composition.
  • the composition spun with the woven fibers may be either natural or synthetic.
  • the radiation may also be infrared radiation.
  • the present invention also relates to methods of retaining source radiation emitted from an object and may be achieved by covering or surrounding the object with one of the above mentioned fabrics.
  • Fig. 1 is a graph of hand data from transcutaneous oxygen measurements.
  • Fig. 2 is a graph of foot data from transcutaneous oxygen measurements.
  • Fig. 3 is a graph of a spectral distribution pattern of alumina.
  • Fig. 4 is a graph of a spectral distribution pattern of titanium dioxide.
  • Fig. 5 is a flow chart of a process for making filaments with particles added.
  • the present invention focuses on the creation of and methods of use of a biologically benign powder in a resin that has certain beneficial properties such as retaining source infrared radiation and changing the wavelength of light reflected by the powder or passing through the powder.
  • This powder may be combined with a carrier material, such as a resin, specifically a polymer, and/or implemented into a textile fiber, a non-woven membrane, or a similar product.
  • Products that incorporate this powder may provide additional beneficial properties to a subject wearing such a product such as, for example, wound healing, skin fibroblast stimulation, fibroblast growth and proliferation, increased DNA synthesis, increased protein synthesis, increased cell proliferation by changing the optical properties in and around the human system interacting with light, and changing the wavelength, reflecting, or absorbing light in the electromagnetic spectrum.
  • the compositions and fibers of the present invention represent a combination of substances that work together with electromagnetic radiation to provide such beneficial properties.
  • compositions of the present invention may be used in a variety of settings to trap source infrared radiation, to provide heat to an object, or to prevent the escape of infrared light.
  • Some uses may include, but are not limited to, insulation of heating and cooling systems, thermal insulation for outdoor recreation, retention of infrared light by military forces to prevent detection, and insulation of perishable items.
  • Other uses of a fabric made from such a composition include hosiery, footwear, active wear, sports wear, sports wraps, base layer, gloves, and bandages. These items may also have certain properties such as controlling odor, regulating heat, providing protection from fire, providing protection from harmful light, insulation, wound healing, and preserving food.
  • Electromagnetic light spans a very large spectrum from 10 nm to 1060 nm of wavelength and spans ultraviolet light, visible light, and infrared light.
  • Ultraviolet (“UV") light has wavelengths from 10 nm to 390 nm and is divided in to near (390 to 300 nm), mid (300 to 200 nm), and far (200 to 10 nm) spectra regions.
  • Visible light is a small band in the electromagnetic spectrum with wavelengths between 390 and 770 nm and is divided into violet, blue, green, yellow, orange, and red light.
  • Infrared (“IR”) light spans from 770 nm to 1060 nm and includes near (770 to 1.5 X 10 3 ), mid (1.5X 10 3 to 6 X 10 3 ), and far (6 X 10 3 to 10 6 ) regions.
  • the refractive index (“RI”) is a measure of a substance's ability to bend light. Light and optical energy that the body is exposed to extends throughout the electromagnetic spectrum. The adult human body, at rest, emits about 100 watts of IR in the mid and far wavelengths. During exercise this level rises sharply and the distribution of wavelengths changes.
  • the present invention relates to a material, such as a resin, film, polymer or fiber, for example, that is optically responsive to light and electromagnetic spectrums.
  • the end materials created may be used to interact with living or non-living systems.
  • the end material may be created by adding various active materials together to form a powder.
  • the powder may then be combined or mixed with carrier materials that may have their own unique optical properties and may also act as a matrix for the powder and its particles.
  • the active materials selected to form the powder are selected based upon several characteristics.
  • One characteristic is that the active materials, in particle form, may be biologically benign, or inert.
  • the material preferably exhibits one of two optical properties: being transparent or having a different refractive index than the carrier material.
  • Specific active materials that may be used in the present invention include silicon, carbon, and various vitreous glasses including oxides of aluminum, titanium, silicon, boron, calcium, sodium, and lithium.
  • the active materials are titanium dioxide, quartz, and aluminum oxide.
  • the choice of materials and their optical properties can be selected to effect a certain result, such as, for example, a biological excitation for a range of wavelengths from 1.015 microns to 0.601 microns (601 nm).
  • a biological excitation for a range of wavelengths from 1.015 microns to 0.601 microns (601 nm).
  • an overlapping series of pass-bands that promote excitation and emission in the ranges that bracket the desired wavelength may be created by the materials.
  • These pass bands may be created by using particles of staggered refractive indices with respect to the host, creating a known transparency and if possible concentrating normally blocked or attenuated wavelengths by using particles with high transparency and moderate refractive indices.
  • a material that is transparent to UN light with a high refractive index that is not transmissive at short wave, or harmful, UN regions may be used.
  • Specific carrier materials that may be used in the present invention include resins such as rayon, polyester (PET), nylon, acrylic, polyamide, and polyimide.
  • resins such as rayon, polyester (PET), nylon, acrylic, polyamide, and polyimide.
  • solid transparent materials with a transmission in the range, of about 0.5 to about 11 microns is preferable, such as, for example, polyethylene and many of its derivatives, polypropylene and many of its derivatives, polymethylpentene, and polystyrene and many of its derivatives. These materials may also exhibit useful transparencies in the ultraviolet.
  • the addition of active particles with varying refractive indices may yield a wide range of filtering effects in the IR and UV ranges.
  • resin may serve as a medium to encase and act as a lensing medium for active materials.
  • the materials may be ground or processed to comprise various properties.
  • the grinding or processing helps to determine the particle size of the active material, the concentration of each type of active material, and the physical characteristics of the active material, and is known in the art.
  • the physical characteristics may include the smoothness or shape of the particles.
  • the particles may be smooth, round, triangular, or scalloped.
  • the end material may achieve one of two results with respect to wavelength: it may shorten or lengthen wavelength depending the desired effect.
  • IR light excites atomic and/or molecular structure. The excitation may frequently result in stresses on either atomic or molecular levels. When the stress is released, the electron energy level may change and release energy as photons.
  • particular wavelengths may be selected by the ease that a given wavelength may be absorbed and/or emitted. If the active particles are suspended in a matrix that performs a filtering action, i.e., passing optical energy, the active particles may be closer to the wavelength of the carrier material. Conversely, if shorter or longer wavelengths are to be passed, the size of the active particles may be closer to the size of the wavelength of the light passed. For example, in applications in which the desired wavelength is 1 micron, the particle size may be the same, i.e., 1 micron. If carrier material, such as resinfor example, is capable of passing 14 micron to 4 microns it may be desirable to have some particles slightly larger than or equal to those wavelengths. Desired particles sizes may range from about 2 microns to about 0.5 micron and are preferably related to the targeted wavelength.
  • the powder may comprise aluminum oxide (Al 2 O 3 ), quartz (SiO 2 ), and titanium dioxide (TiO 2 - in rutile form).
  • Titanium dioxide may be obtained from any commercially available source, such as from Millennium Chemicals, Inc., Hunt Valley, MD. Quartz may be obtained from any commercially available source, such as Barbera Co., Alameda, CA.
  • Aluminum oxide may be obtained from any commercially available source, such as from Industrial Supply, Loveland, CO.
  • Aluminum oxide has a unique property that promotes infrared light bandshifts under certain conditions.
  • interaction with IR light occurs.
  • the IR light emission of the human body is absorbed and excites electron energy levels in the atoms and molecules of the components of the compositions of the present invention.
  • the electrons return to their previous energy levels they release energy in the IR range but at a different wavelength, i.e., a longer wavelength.
  • the compositions of the present application when used in a body covering, such as a compression wrap or sleeve, utilize these bandshifting properties of aluminum oxide to reflect longer infrared wavelengths back into the human body.
  • the longer infrared wavelength allows capillaries to relax and be less constricted, resulting in greater blood flow where required, which results in improved body circulation.
  • Quartz or silicon dioxide, is biologically benign if it is incorporated into a carrier material in solid bulk form. Quartz is also capable of non-linear frequency multiplication, and, in proper combination with a particular wavelength and a carrier, may emit ultraviolet (UV) light. UV light is known to inhibit bacterial growth and the creation of ozone. UV that has a wavelength that is too short can be detrimental to the human system. Quartz may be used to absorb the shorter wavelength UV light if its physical particle size is close to the wavelength of light that should be excluded. In the present invention, quartz may be used to increase frequency or shorten wavelength.
  • UV ultraviolet
  • quartz may exhibit piezoelectric properties. When quartz is stressed, the distribution of charges may become unequal and an electric field may be established along one face and an opposite field may be established along the other face. If the stressing effect, such as pressure, for example, is constant, the charges may redistribute themselves in an equal and neutral manner. If the stress is removed once the charges are redistributed, a charge of opposite polarity and equal magnitude to the initial charge may be established. This charge redistribution results in nonlinear behavior, which may be manifested as frequency doubling.
  • Titanium dioxide is unique because it has a high refractive index and also has a high degree of transparency in the visible region of the spectrum.
  • the optical properties of titanium are used in conjunction with quartz and an appropriate carrier material, such as PET, for example, a greenhouse effect may be created. Infrared wavelengths of one size may pass back through the resinand may be reflected. This reflection creates longer wavelengths that prevent passage back through the PET. In a specific embodiment of the present invention this property may be used to reflect longer wavelengths into the human system while directing shorter, more harmful wavelengths away from the human system.
  • an appropriate carrier material such as PET
  • Particle size and shape of the active materials in the powder may also affect the end product by controlling the wavelength of light that is allowed to pass through the particles.
  • a particle size of about 1.4 microns or smaller is used for aluminum oxide.
  • the particle shape may be scalloped.
  • the particle size of quartz may be about 1.5 microns or smaller.
  • the quartz particles may be spherical or substantially spherical.
  • the titanium dioxide particles may be about 2 microns or smaller and triangular with rounded edges.
  • the specific properties and characteristics of the active particles and carrier materials may be combined to produce a specific effect such as wound healing, skin fibroblast stimulation, fibroblast growth and proliferation, increased DNA synthesis, increased protein synthesis, and increased cell proliferation by changing the optical properties in and around the human system. These properties are related to specific wavelengths of light and the interaction of that light with the compositions of the present invention.
  • wavelengths may be selected to provoke melanin excitement, which occurs at about 15 nm.
  • melanin excitement an energy range from a band about 10 nm to about 2.5 microns from the human metabolic action may be used.
  • Daylight from either an outdoor broadband or an indoor lamp ranges from about 1.1 microns, with a "hump" around 900 nm and a broad general peak around 700-800 nm, and also includes lesser wavelengths such as 400 to 700 nm.
  • Some of the general properties and desirable filtering and changes include but are not limited to having band pass in the 600 to 900 nm band range.
  • a carrier material may be selected to have a transparency from 200- 900 nm. resinhas a known transparency in the 8 to 14 micron range.
  • An active particle may also be selected to have a wavelength between about 950 and 550 nm. This may be accomplished by using particles with a general size distribution of 2 microns and lower.
  • Tissues stimulate the basic energy processes in the mitochondria (energy compartments) of each cell, particularly when near-infrared light is used to activate the color sensitive chemicals (chromophores, cytochrome systems) inside each cell.
  • Optimal LED wavelengths may include 680, 730, and 880 nm. Whelan et al., 552 SPACE TECH. & APP. INT'L FORUM 35-35 (2001). Whelan et al., 458 SPACE TECH. & APP. INT'L FORUM 3-15 (1999). Whelan et al., 504 SPACE TECH. & APP. INT'L FORUM 37-43 (2000).
  • the particle size of the compositions of the present invention may be selected to provide reflective or pass through beneficial wavelengths of light.
  • the active particles of the present invention may be ground to reach an approximate particle size of about 0.5 to about 2.0 microns.
  • titanium dioxide may be ground to a grain size of between 1 and 2 microns and may be triangular with rounded edges.
  • Aluminum oxide may be ground to a grain size of between 1.4 and 1 microns and may be scalloped-shaped.
  • Quartz is preferably ground to a grain size of about 1.5 to 1 microns and is generally rounded. All particles are reduced in size and shaped by processes known in the art, such as grinding, polishing, or tumbling, for example.
  • the dry weight ratio of the active materials titanium dioxide, quartz, and aluminum oxide in the powder is 10:10:2, respectively.
  • the compositions may further comprise a resin, such as a polymer made into a film or fiber.
  • a resin such as a polymer made into a film or fiber.
  • the polymer may initially be in pellet form and dried to remove moisture by using, for example, a desiccant dryer.
  • the powder may then be dispersed into the resin by methods known in the art, such as for example in a rotating drum with paddle-type mixers.
  • the polymer used may be polyester.
  • the powder may comprise from about 0.5 to about 20 percent of the mixture.
  • the powder may comprise from about 1 to about 10 percent of the mixture.
  • the powder may comprise from about 1 to about 2 percent of the total weight of the resin/powder mixture.
  • about 100 pounds of the powder may be combined with about 1000 pounds of PET.
  • the powder may be introduced to the resin by other processes known in the art such as compounding, for example.
  • 100 pounds of the powder may be combined with about 250 to about 300 pounds of PET.
  • the resulting liquid may be extruded into fiber that maybe drawn into staple fibers of various lengths.
  • This process of grinding, combining, and extrusion is known in the art, as described in, for example, U.S. Patent Nos. 6,204,317; 6,214,264; and 6,218,007, which are expressly incorporated by reference in their entirety herein.
  • the step of spinning the fibers of the present invention into yam comprises spinning staple having a denier per fiber of between about 1 and about 3; accordingly, the prior step of spinning the melted polyester into fiber likewise comprises forming a fiber of those dimensions.
  • the fiber is typically heat set before being cut into staple with conventional techniques. While the extruded fibers are solidifying, they may be drawn by methods known in the art to impart strength.
  • the method can further comprise forming fabrics, typically woven or knitted fabrics from the spun yam in combination with both natural and synthetic fibers.
  • Typical natural fibers may include cotton, wool, hemp, silk, ramie, and jute.
  • typical synthetic fibers may include acrylic, acetate, Lycra, spandex, polyester, nylon, and rayon.
  • the present invention also includes spinning a blend of cotton into yam in which the polyester may include between about 0.5 and 4% by weight of polyethylene glycol into yam in a rotor spinning machine.
  • the method can further comprise spinning the fibers of the present invention.
  • the fibers of the present invention may include a woven or knitted fabric from the blended yam with the yam being either dyed as spun yam, or after incorporation into the fabric in which case it is dyed as a fabric.
  • the cotton and polyester can be blended in any appropriate proportion, but in the specific embodiments the blend includes between about 35 and 65% by weight of cotton with the remainder polyester. Blends of 50% cotton and 50% polyester ("50/50") are also used.
  • the yam formed according to this embodiment can likewise be incorporated into blends with cotton, and is known to those familiar with such blending processes, the cotton is typically blended with polyester staple fiber before spinning the blend into yarn.
  • the blend may contain between about 35% and 65% by weight cotton with 50/50 blends being typical.
  • Other methods of production of fibers are equally suitable such as those described in U.S. Patent Nos.
  • the polyester mixture may be used to create a staple fiber.
  • the staple fiber may then be used to create a non-woven membrane.
  • This membrane may be bonded to another fabric, membrane or material.
  • the non-woven membrane may be used as a lining by being bonded to the inside of a pair of leather gloves or, for example, being bonded to another fabric such as ThinsulateTM by 3M by methods known to those skilled in the art.
  • WBl woven with fibers comprising the powder composition of the present invention
  • WB2 woven with fibers lacking the powder composition of the present invention
  • Twenty panelists are selected from the general population, and no specific demographic parameters are utilized in recruiting the panelists. Panelists are placed within a climate-controlled area of standard room temperature, standard humidity, and sea-level atmospheric pressure. A measurement of each panelist's middle finger temperature is taken prior to the panelists' donning of any band. Panelists are asked to don a band from WB2. Five minutes later, a measurement of each panelist's middle finger temperature is taken. Panelists are then asked to remove the band from WB2, wait five minutes, and don a band from WBl. Five minutes later, measurements of each panelist's middle finger temperature are taken. Thermographic instruments are used to record the temperatures of the fingers of the panelists throughout the trials. All temperature measurements are averaged.
  • WBl woven with fibers comprising the powder composition of the present invention
  • WB2 woven with fibers lacking the powder composition of the present invention
  • Panelists are selected from the general population, and no specific demographic parameters are utilized in recruiting the panelists. Panelists are placed within a climate- controlled area of standard room temperature, standard humidity, and sea-level atmospheric pressure. A measurement of each panelist's grip strength is taken prior to the panelists' donning of any band. Panelists are asked to don a band from WB2. Five minutes later, a measurement of each panelist's grip strength is taken. Panelists are then asked to remove the band from WB2, wait five minutes, and don a band from WBl. Five minutes later, measurements of each panelist's grip strength are taken. Grip dynamometers are used to record the grip strengths of the panelists throughout the trials. All grip strength measurements are averaged.
  • the powder composition of the present invention is prepared by the processes of the present invention. Two batches of insoles are prepared: INI (woven with fibers comprising the powder composition of the present invention) and IN2 (woven with fibers lacking the powder composition of the present invention).
  • Panelists are selected from the general population, and no specific demographic parameters are utilized in recmiting the panelists. Samples, are presented to panelists in a blinded manner (samples are identified only by a random digit label). Each panelist receives two insoles to wear, one within each shoe, and panelists are instructed to randomly place one insole within each shoe. Thus, the shoe (right or left) in which each insole is worn is completely random. In each pair of insoles, one sample is from INI and one sample is from IN2. Panelists are asked to record any differences between the two insoles that they notice after wearing them for an eight hour period.
  • a number of the panelists note a difference between the insoles.
  • a statistically significant number of those panelists noting a difference between the two insoles regard the insole comprising the powder composition of the present invention as providing greater comfort than the insole lacking the powder composition of the present invention.
  • the ability of the insoles woven with the fibers comprising the powder composition of the present invention to provide comfort is demonstrated.
  • proximal means close to, abutting, next to, or underneath a material used in the examples. Instances of "proximal” include a wrist to a hand, an elbow to a hand, a wrist to a finger, an ankle to a foot, and an ankle to a toe.
  • Subjects were evaluated for baseline blood flow status. They then had transcutaneous oxygen (Perimed Inc. North Royalton, Ohio, PF5040 transcutaneous module) and laser Doppler flowometry measurements (PF5010 Laser Doppler Perfusion module) with stockings and gloves made with and without the test material. Measurements were made prior to wearing the garments and continuously over a one hour period while wearing the garments. Data was analyzed at ten minute intervals. The tester and subject were blinded to the study garment. Garments were randomly selected and tested from a computer generated randomization list. Measurements were taken of both the hand and foot with the study subjects wearing the test material versus standard fiber gloves and stockings.
  • diabetes mellitus was based on World Health Organization criteria.
  • diagnosis of peripheral vascular disease was a transcutaneous oxygen measurement > 30mm Hg taken at the transmetatarsal level on the day of enrollment. Patients varied in age from 18 to 80 years old.
  • the dynamic non-invasive vascular assessment consisted of transcutaneous oxygen pressure (TcPO 2 ) measurement, and laser Doppler flowmetric measurement.
  • TcPO 2 transcutaneous oxygen pressure
  • laser Doppler flowmetric measurement The PeriFlux 5000 System was used. It is a multifunctional system that incorporates four functional units that combine transcutansous oxygen and laser Doppler function units.
  • the transcutaneous oxygen electrodes were warmed to 44°C and allowed to equilibrate on the skin for 5 minutes (until stable values were achieved). The resultant values were measured in mmHg.
  • the laser Doppler monitor was used to continuously measure tissue blood perfusion (PF5010 Laser Doppler Perfusion module). The application was non-invasive. Two stick-on probes similar to standard EKG probes were applied to the skin. In the tissue, the laser light was scattered and Doppler shifted by interaction with the moving blood cells according to the well-known Doppler principle. The sampling depth was on the order of 200-500 micrometers. A fraction of the backscattered light was detected by a remotely positioned photo detector.
  • TCOM transcutaneous oxygen
  • LD laser Doppler
  • FIG. 1 shows that with the use of gloves comprising the test material, transcutaneous oxygen in the patients' hands increased more than twelve percent over that when placebo gloves were used.
  • figure 2 shows that transcutaneous oxygen in feet wearing socks comprising the test material was approximately 8 percent higher than in those with the placebo socks.
  • EXAMPLE 5 Subjects were analyzed for the effects of a material of the invention (the test material) on strength of proximal muscles. Wrist bands made either with the test material or without it were used. Subjects ranged in age between 20 and 80 years old. Each subject was asked to stand in a relaxed position and to squeeze a dynamometer having an analog readout with his or her preferred hand. The device used is also used to test patients with carpal tunnel syndrome.
  • a second wrist band was placed on the other wrist. The subjects were then allowed to rest their wrists and hands for between two and ten minutes, after which their strength was again measured on the dynamometer.
  • test material successfully caused an increase in strength in muscles proximal to the location of the wrist bands comprising the test material. It is believed that this increased strength is due to increased blood flow to those muscles, caused by the presence of the test material.
  • EXAMPLE 6 Subjects were analyzed for the temperature effects of test material on skin and subdermal tissue. An Agema 5500 thermo vision camera was employed. Temperature of a location can be read as a number readout on the camera, as well as by a color change. The camera was calibrated regularly to maintain accuracy. Wrist bands made either with the test material or without it were used. All studies were performed in a climate-controlled area at standard room temperature, standard humidity, and sea-level atmospheric pressure.
  • a subject was seated at a table that was approximately waist high, with his or her hands on the table in a resting position.
  • the camera was used to scan a hand, including the fingers, for approximately ten minutes, to locate the coldest spot.
  • the temperature of this spot was used as the baseline.
  • the subject then put on a wrist band next to the hand being monitored. The temperature of that hand was continuously monitored, and data were recorded at 0 minutes, 3 minutes, 8 minutes and 10 minutes.
  • the temperature at the coldest spot on the subject's hand increased a degree centigrade within the first 3 minutes, another 6 degrees in the next 5 minutes, and another 3 degrees in the following 2 minutes, for a total of a 10 degrees C increase.
  • a degree centigrade within the first 3 minutes, another 6 degrees in the next 5 minutes, and another 3 degrees in the following 2 minutes, for a total of a 10 degrees C increase.
  • an overall increase of 8 degrees C was observed.
  • a wearable fabric or material is woven from resin filaments, such as polymers and, preferably from resinfilaments or fibers, including uniformly distributed 0.5 to 1.5 micron, biologically benign particles of titanium dioxide, alumina and silicon oxides.
  • the material may also be formed from non woven filaments.
  • the material may also be used between a user and a source of light, for example, the material may be used for bedding, tents, umbrellas, shades and awnings. Particles having substantially intact crystal lattice structures, and minimal contamination, have improved optical performance when uniformly distributed within the resin filaments beyond what is achievable with substantially or partially amorphous particles and are therefore preferred.
  • the particles may be added in substantially equal weight for a .25% to 15% loading of the PET. A range of 1% to 2% loading of the resinis presently preferred.
  • Crystalline particles of titanium dioxide, alumina and silicon oxides, with the desirable properties, may be obtained from the following suppliers.
  • Silicon oxide Alibab.com., 39899 Balentine Dr., Ste 325, Newark, CA 94560
  • Alumina PACE Technologies, 200 Larkin Dr., Wheeling, IL 60090
  • Titanium Dioxide Goodfellow Corporation, 800 Lancaster Ave, Berwyn, PA 19312
  • Ambient light incident on the woven material typically includes visible light as well as some infrared (IR) and ultraviolet (UN) radiation.
  • the crystalline particles within the resinfilaments have pass bands in or overlapping the visible spectrum and also translates or converts some portions of UV and IR light into light in specific pass bands in or overlapping the visible light spectrum including the near IR.
  • the light applied to the skin of the wearer of the material therefore has a substantially modified distribution of light in pass bands in or overlapping the visible spectrum.
  • Fig. 3 is a graph of the intensities of light emerging from a suspension of alumina particles, from about .25 to 1.75 micron in a fluid having a refractive index of 1.51, similar to the resincarrier.
  • the fluid may be prepared by mixing Agar-Agar, water, propylene glycol and amyl alcohol to form a gel to suspend the particles.
  • a generally broadband relatively flat spectrum of light is applied to the gel suspension and a scanning spectrophotometer is used to detect and measure the light emerging from the gel with suspended particles.
  • the graph shows the results, normalized to a peak intensity of 1.00 at a wavelength of about 300 nm.
  • the emerging light has substantial peaks and valleys, for example, valley "A" occurring just below about 400 nm and twin peaks "B" at just above 400 nm.
  • a similar graph of the light emerging from a suspension of titanium dioxide particles in a similar gel is shown for a similar flat spectrum input.
  • the graph shows the results, normalized to a peak intensity of 1.00 at a wavelength of about 425 nm.
  • the emerging light has substantial peaks and valleys, for example, valley "C” occurring just below about 400 nm and peak "D" occurring at about 425 nm.
  • the spectral distribution of light emerging from Quartz particles also has peak amplitudes at certain wavelengths and minima or valleys at other wavelengths.
  • the spectral altering characteristics of the particles shown in Fig.s 1 and 2 for titanium dioxide and alumina, respectively, interact to further alter the spectral distribution of the light emerging from the filament material, that is, the spectral distribution pattern.
  • the resultant pattern becomes quite complex and provides wide and narrow peaks and valleys at many different spectral lines.
  • the characteristics of the PET, and temperature, particle size distribution and other effects may shift or further vary the spectral density pattern.
  • the variations in the spectral density pattern from the ambient that is, the pattern of peaks and valleys is not random but rather intentional and permits selective illumination of the wearer's skin with a somewhat higher intensity light at certain specific wavelengths and ranges of wavelengths su ⁇ ounded by light at lower intensity at other specific wavelengths and ranges of wavelengths.
  • the selective spectral distribution pattern of illumination can cause various beneficial effects in the wearer by selectively energizing some components of the human body, such as mitochondria.
  • the spectral distribution pattern of the wearable fiber having titanium dioxide, alumina and quartz particles may include spectral lines, 35 nm wide on each side, for the following sets of spectra, and ranges of spectra (all in nm):
  • Distributed harmonic outputs may also be present, 45 nm wide, on either side of (all in nm): 950, 975, 1050, 1070, 1100, 1150, 1190, 1205, 1250, 1285, 1290, 1310, 1350 1370 and 1390.
  • the resultant spectral distribution pattern provides selective illumination of the wearer which has been shown to be advantageous to the wearer.
  • the human body is known to radiate heat and also, at very low levels, to radiate light in various pass bands.
  • the wearable fiber material will therefore also receive light and heat from wearer's body, which is also subject to the effects of the particles in the PET, the resultant radiation may also be applied to the wearer's skin.
  • Polarization of the light in the fiber may be caused by the resinmaterial as well as the particles and further enhances the ability of the resinand particulate system to modify the distribution of wavelengths in the visible and near IR light applied to the wearer .
  • the increase in applied visible and near IR radiation may be on the order of 0.01 to .03 percent using wearable materials made from the fiber and particulate system.
  • step 10 the sizes of one or more the types of the particles may be adjusted by pre-processing if the particles are not within the desired range of particles sizes.
  • step 20 the particles may be physically combined by mechanical mixing to provide a powder or other particle mixture.
  • the particle mixture may be prepared by compounding or fluid suspension or other known mechanisms to permit introduction into the filament forming process in step 40.
  • Conventional compounding techniques include forming a high concentration of the particles in pellets, typically on the order of 1/8 inch diameter rods about 1" long. In the filament forming process step 40, these pellets are combined with additional pellets or chips of resinin order to achieve the desired loading or concentration of particles in the final filament.
  • Conventional fluid suspension techniques include suspending the particles in a liquid, such a propylene glycol, which is compatible with the resinused in filament forming step 40.
  • the filament forming process in step 50 is conventional thermal extrusion. Thereafter, depending up the final use of the filaments, end process steps 60 may be applied.
PCT/US2003/008910 2002-03-22 2003-03-24 Polymeric fiber composition and method WO2003083189A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
KR1020047015048A KR100740730B1 (ko) 2002-03-22 2003-03-24 중합체 섬유 조성물 및 방법
AU2003220481A AU2003220481B2 (en) 2002-03-22 2003-03-24 Polymeric fiber composition and method
EP03716790A EP1488026B1 (de) 2002-03-22 2003-03-24 Verfahren zur steigerung der muskelleistung
AT03716790T ATE460514T1 (de) 2002-03-22 2003-03-24 Verfahren zur steigerung der muskelleistung
CA002479958A CA2479958C (en) 2002-03-22 2003-03-24 Polymeric fiber composition and method
DE60331636T DE60331636D1 (de) 2002-03-22 2003-03-24 Verfahren zur steigerung der muskelleistung
JP2003580616A JP4489439B2 (ja) 2002-03-22 2003-03-24 ポリマー繊維組成物および方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US36623702P 2002-03-22 2002-03-22
US60/366,237 2002-03-22
US41553202P 2002-10-02 2002-10-02
US60/415,532 2002-10-02

Publications (1)

Publication Number Publication Date
WO2003083189A1 true WO2003083189A1 (en) 2003-10-09

Family

ID=28678165

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/008910 WO2003083189A1 (en) 2002-03-22 2003-03-24 Polymeric fiber composition and method

Country Status (11)

Country Link
US (1) US20040043174A1 (de)
EP (1) EP1488026B1 (de)
JP (2) JP4489439B2 (de)
KR (1) KR100740730B1 (de)
AT (1) ATE460514T1 (de)
AU (1) AU2003220481B2 (de)
CA (1) CA2479958C (de)
DE (1) DE60331636D1 (de)
ES (1) ES2341765T3 (de)
PT (1) PT1488026E (de)
WO (1) WO2003083189A1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7100352B2 (en) 2004-01-21 2006-09-05 Robins Steven D Protective composite yarn
WO2011059937A3 (en) * 2009-11-12 2011-09-09 Saucony, Inc. Training and recovery clothing and related methods
WO2014163574A1 (en) * 2013-04-05 2014-10-09 Ten Medical Design Ab Radiation protective material
ITMI20131095A1 (it) * 2013-06-28 2014-12-29 Allergosystem S R L Tessuto e filato con proprieta' ossigenanti

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008092227A1 (en) * 2007-01-31 2008-08-07 Innovision Headwear Inc. Optically active headgear
US20090291108A1 (en) * 2008-05-25 2009-11-26 Tsai-Chin Chen Fabric with health care component
JP5597021B2 (ja) * 2010-04-15 2014-10-01 オリンパス株式会社 画像処理装置及びプログラム
US20110277216A1 (en) * 2010-05-13 2011-11-17 Alan Norman Higgins Fiber material
KR101345694B1 (ko) 2011-03-11 2013-12-30 옵토팩 주식회사 파이버, 파이버 집합체 및 이를 포함하는 접착제
US10252945B2 (en) 2012-09-26 2019-04-09 Multiple Energy Technologies Llc Bioceramic compositions
ES2492215B1 (es) 2013-02-06 2015-06-29 Jesús CANDEL FABREGAS Polvo cerámico fotocatalítico y de emisión infrarroja, aplicable a fibras textiles y procedimiento de obtención de dicho polvo
CN111840319A (zh) 2014-05-05 2020-10-30 复合能源技术有限公司 生物陶瓷组合物及其生物调节用途
CA2961956C (en) * 2014-09-24 2019-01-08 Kai-Li Huang Environment-controlling fibers, method manufacturing the same and fabrics using the same
JPWO2017018470A1 (ja) * 2015-07-27 2018-05-17 国立研究開発法人理化学研究所 発光装置、発光システム、及び、発光装置の製造方法
US10337124B2 (en) * 2015-08-26 2019-07-02 Teague Egan Textile graphene component thermal fiber
US20220218115A1 (en) * 2017-08-27 2022-07-14 Under Armour, Inc. Bedding for a mattress
WO2020150493A1 (en) * 2019-01-16 2020-07-23 Hologenix, Llc Cellulose and semi-cellulose based fibers and yarns embedded with mineral particles and methods of making the same
WO2022268368A1 (de) * 2021-06-23 2022-12-29 Beiersdorf Ag Wundabdeckung, zur erhöhung der no konzentration in wunden

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0462275A1 (de) * 1989-12-20 1991-12-27 KOMURO, Toshio Pulver das schwach-energie infrarot strahlen ausstrahlt; kunstfaser die dieses enthaelt sowie daraus hergestellte textilerzeugnisse.
US5466526A (en) * 1992-07-16 1995-11-14 Magata; Katsumi Far infrared radiant composite fiber containing metal
WO2001088054A1 (fr) * 2000-05-19 2001-11-22 Toshio Komuro Composition pour rayonnement infrarouge lointain presentant une excellente propriete antistatique et fibre et produit textile la contenant
US20020035755A1 (en) * 2000-06-14 2002-03-28 Widdemer John D. Interactive leather for gloves, shoes, garments and upholstery

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1415313A (en) * 1918-10-15 1922-05-09 William M Cavanaugh Method of making leather yarn and article
US1713113A (en) * 1927-10-01 1929-05-14 William M Cavanaugh Leather manufacture
FR2384836A1 (fr) * 1977-03-25 1978-10-20 Bric Textiles photoluminescents par enduction
DE4142240A1 (de) * 1991-12-20 1993-06-24 Basf Ag Verwendung von pigmentpraeparationen zum pigmentieren oder mattieren von zurichtmitteln fuer leder und lederimitate
US5851668A (en) * 1992-11-24 1998-12-22 Hoechst Celanese Corp Cut-resistant fiber containing a hard filler
IL109236A (en) * 1993-04-13 1998-01-04 Sumitomo Chemical Co A-alumina powder and its production
WO1996039032A1 (en) * 1995-06-06 1996-12-12 Kimberly-Clark Worldwide, Inc. Microporous fabric containing a microbial adsorbent
DE19647038B4 (de) * 1996-11-14 2007-02-22 Ferro Gmbh Kugelförmige Pigmente, Verfahren zu ihrer Herstellung und deren Verwendung
US5779950A (en) * 1996-12-02 1998-07-14 Kang; Dong Soon Method of making a synthetic fiber containing infrared energy powder
TWI285671B (en) * 1998-10-13 2007-08-21 Orion 21 A D Pty Ltd Luminescent gel coats and moldable resins
US6332993B1 (en) * 1999-09-16 2001-12-25 Nan Ya Plastics Corporation Process of making heat-retaining fibers
JP4175558B2 (ja) * 2002-07-23 2008-11-05 株式会社ファーベスト 遠赤外線放射材料

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0462275A1 (de) * 1989-12-20 1991-12-27 KOMURO, Toshio Pulver das schwach-energie infrarot strahlen ausstrahlt; kunstfaser die dieses enthaelt sowie daraus hergestellte textilerzeugnisse.
US5466526A (en) * 1992-07-16 1995-11-14 Magata; Katsumi Far infrared radiant composite fiber containing metal
WO2001088054A1 (fr) * 2000-05-19 2001-11-22 Toshio Komuro Composition pour rayonnement infrarouge lointain presentant une excellente propriete antistatique et fibre et produit textile la contenant
EP1291405A1 (de) * 2000-05-19 2003-03-12 Toshio Komuro Zusammensetzung für ferninfrarotbestrahlung mit excellenten antistatischen eigenschaften und faser- sowie textilprodukt beides dieses enthaltend
US20020035755A1 (en) * 2000-06-14 2002-03-28 Widdemer John D. Interactive leather for gloves, shoes, garments and upholstery

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ANON.: "Breakthrough Double Blind Clinical Study Proves. Holofiber Claims to be Compelling and Significant", WELLMAN, 31 January 2003 (2003-01-31), XP002248567, Retrieved from the Internet <URL:http://www.wellmaninc.com/Fibers/Holofiber/default.asp> [retrieved on 20030722] *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7100352B2 (en) 2004-01-21 2006-09-05 Robins Steven D Protective composite yarn
WO2011059937A3 (en) * 2009-11-12 2011-09-09 Saucony, Inc. Training and recovery clothing and related methods
WO2014163574A1 (en) * 2013-04-05 2014-10-09 Ten Medical Design Ab Radiation protective material
US10364513B2 (en) 2013-04-05 2019-07-30 Ten Medical Design Ab Radiation protective material
ITMI20131095A1 (it) * 2013-06-28 2014-12-29 Allergosystem S R L Tessuto e filato con proprieta' ossigenanti
EP2818588A2 (de) 2013-06-28 2014-12-31 Allergosystem S.r.l. Gewebe und Garn mit sauerstofffördernden Eigenschaften
EP2818588A3 (de) * 2013-06-28 2015-04-15 Allergosystem S.r.l. Gewebe und Garn mit sauerstofffördernden Eigenschaften

Also Published As

Publication number Publication date
JP4489439B2 (ja) 2010-06-23
AU2003220481B2 (en) 2007-11-22
KR20040104539A (ko) 2004-12-10
JP2005520950A (ja) 2005-07-14
KR100740730B1 (ko) 2007-07-19
PT1488026E (pt) 2010-05-31
AU2003220481A1 (en) 2003-10-13
ATE460514T1 (de) 2010-03-15
CA2479958A1 (en) 2003-10-09
ES2341765T3 (es) 2010-06-28
EP1488026B1 (de) 2010-03-10
DE60331636D1 (de) 2010-04-22
US20040043174A1 (en) 2004-03-04
JP2008231657A (ja) 2008-10-02
CA2479958C (en) 2009-11-03
EP1488026A1 (de) 2004-12-22

Similar Documents

Publication Publication Date Title
JP2008231657A (ja) ポリマー繊維組成物および方法
US7074499B2 (en) Polymeric fiber composition and method
US10682257B2 (en) Biological fiber composite dressing
US20110107502A1 (en) Training and recovery clothing and related methods
HUE031249T2 (hu) Mézet és különösen nagy elnyelõképességû anyagot tartalmazó összeállítás
CA2556402A1 (en) Method of chemiluminescence-utilizing makeup and beautification, luminant for skin irradiation beautification and makeup/ beautification equipment
JP2021534334A (ja) 電気的に受動的な低レベル光線療法システムおよびそれを組み込む方法
Washington et al. Randomized controlled trial comparing the effects of far-infrared emitting ceramic fabric shirts and control polyester shirts on transcutaneous PO2
JP2021525778A (ja) 吸収性バイオフォトニック繊維システム
Osti Skin ph variations from the acute phase to re-epithelialization in burn patients treated with new materials (burnshield®, semipermeable adhesive film, dermasilk®, and hyalomatrix®). Non-invasive preliminary experimental clinical trial
KR20170045822A (ko) 미용용 마스크 팩
KR20170045823A (ko) 미용용 마스크 팩
EP3910105A1 (de) Industrielles verfahren zur synthese von metallnanopartikeln mit anpassbarer grösse
Yüce Yarns Emitting Far Infrared Rays
AU2016421086B2 (en) Polymer material comprising at least one different doping element, uses and production method
KR20140134983A (ko) 생체활성 에너지를 방사하는 의류용 섬유시트
Gordon et al. Effect of Celliant® armbands on grip strength in subjects with chronic wrist and elbow pain: Randomized double-blind placebo-controlled trial
JP2004316005A (ja) 繊維構造物
KR20200081646A (ko) 원적외선 발산물질을 포함하는 기능성 스포츠 테이프
Gao et al. A diester to protect hair from color fade and sun damage
Lavery et al. Randomized Placebo-Controlled Clinical Trial of Gloves and Stockings Made from Infrared-Emitting Fabric (Celliant®) for Transcutaneous Oxygen and Peripheral Blood Flow in Diabet-ic Patients with Vascular Impairment
KR100836491B1 (ko) 생체광자의 측정을 통한 기능성 화장품의 제조방법 및효능검증방법 및 그 방법에 의해 제조되거나 검증된화장품 조성물
ElNashar Effect the design and materials of eyesswathe dressing and diapers clothes for Infant’s Incubator
WAGEEH THE EFFECT OF DIFFERENT STRUCTURES ON THE PROPERTIES OF FABRICS USED IN THE TREATMENT OF DIABETIC FOOT THAT IS TREATING BY NANOTECHNOLOGY
Yao et al. Preparation and Research of Iatric Fiber with Far Infrared Ray Radiation Function

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PH PL PT RO RU SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2479958

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2003580616

Country of ref document: JP

Ref document number: 1020047015048

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 2003716790

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2003220481

Country of ref document: AU

WWP Wipo information: published in national office

Ref document number: 1020047015048

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 2003716790

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2003220481

Country of ref document: AU

Date of ref document: 20030324

Kind code of ref document: B