WO1996028056A1 - Structures adaptables - Google Patents

Structures adaptables Download PDF

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Publication number
WO1996028056A1
WO1996028056A1 PCT/US1996/003470 US9603470W WO9628056A1 WO 1996028056 A1 WO1996028056 A1 WO 1996028056A1 US 9603470 W US9603470 W US 9603470W WO 9628056 A1 WO9628056 A1 WO 9628056A1
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WO
WIPO (PCT)
Prior art keywords
gel
responsive
incorporated
responsive gel
temperature
Prior art date
Application number
PCT/US1996/003470
Other languages
English (en)
Other versions
WO1996028056A9 (fr
Inventor
George W. Mckinney
James Tanenbaum
Rhonda Levy
Harris Gold
Stephen Jens
M. J. Timm
E. C. Lupton
Michael Orkisz
Matthew Schiller
Barry Hand
Lev Bromberg
Neil Goldman
Original Assignee
Gel Sciences, Inc.
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
Priority claimed from US08/580,986 external-priority patent/US5939485A/en
Application filed by Gel Sciences, Inc. filed Critical Gel Sciences, Inc.
Priority to AU58501/96A priority Critical patent/AU5850196A/en
Priority to EP96920098A priority patent/EP0759710A1/fr
Publication of WO1996028056A1 publication Critical patent/WO1996028056A1/fr
Publication of WO1996028056A9 publication Critical patent/WO1996028056A9/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B7/00—Footwear with health or hygienic arrangements
    • A43B7/14—Footwear with health or hygienic arrangements with foot-supporting parts
    • A43B7/1405—Footwear with health or hygienic arrangements with foot-supporting parts with pads or holes on one or more locations, or having an anatomical or curved form
    • A43B7/1415—Footwear with health or hygienic arrangements with foot-supporting parts with pads or holes on one or more locations, or having an anatomical or curved form characterised by the location under the foot
    • A43B7/142—Footwear with health or hygienic arrangements with foot-supporting parts with pads or holes on one or more locations, or having an anatomical or curved form characterised by the location under the foot situated under the medial arch, i.e. under the navicular or cuneiform bones
    • A—HUMAN NECESSITIES
    • A42—HEADWEAR
    • A42B—HATS; HEAD COVERINGS
    • A42B3/00—Helmets; Helmet covers ; Other protective head coverings
    • A42B3/04—Parts, details or accessories of helmets
    • A42B3/10—Linings
    • A42B3/12—Cushioning devices
    • A42B3/121—Cushioning devices with at least one layer or pad containing a fluid
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B1/00—Footwear characterised by the material
    • A43B1/0027—Footwear characterised by the material made at least partially from a material having special colours
    • A43B1/0036—Footwear characterised by the material made at least partially from a material having special colours with fluorescent or phosphorescent parts
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B1/00—Footwear characterised by the material
    • A43B1/0054—Footwear characterised by the material provided with magnets, magnetic parts or magnetic substances
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/14—Soles; Sole-and-heel integral units characterised by the constructive form
    • A43B13/18—Resilient soles
    • A43B13/189—Resilient soles filled with a non-compressible fluid, e.g. gel, water
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
    • A43B17/16—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined with heel or toe caps
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/26—Tongues for shoes
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B7/00—Footwear with health or hygienic arrangements
    • A43B7/02—Footwear with health or hygienic arrangements with heating arrangements 
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B7/00—Footwear with health or hygienic arrangements
    • A43B7/14—Footwear with health or hygienic arrangements with foot-supporting parts
    • A43B7/1405—Footwear with health or hygienic arrangements with foot-supporting parts with pads or holes on one or more locations, or having an anatomical or curved form
    • A43B7/1415—Footwear with health or hygienic arrangements with foot-supporting parts with pads or holes on one or more locations, or having an anatomical or curved form characterised by the location under the foot
    • A43B7/144—Footwear with health or hygienic arrangements with foot-supporting parts with pads or holes on one or more locations, or having an anatomical or curved form characterised by the location under the foot situated under the heel, i.e. the calcaneus bone
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B7/00—Footwear with health or hygienic arrangements
    • A43B7/14—Footwear with health or hygienic arrangements with foot-supporting parts
    • A43B7/1495—Footwear with health or hygienic arrangements with foot-supporting parts with arch-supports of the bracelet type
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B7/00—Footwear with health or hygienic arrangements
    • A43B7/14—Footwear with health or hygienic arrangements with foot-supporting parts
    • A43B7/16—Footwear with health or hygienic arrangements with foot-supporting parts with elevated heel parts inside
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B7/00—Footwear with health or hygienic arrangements
    • A43B7/14—Footwear with health or hygienic arrangements with foot-supporting parts
    • A43B7/18—Joint supports, e.g. instep supports
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B7/00—Footwear with health or hygienic arrangements
    • A43B7/14—Footwear with health or hygienic arrangements with foot-supporting parts
    • A43B7/28—Adapting the inner sole or the side of the upper of the shoe to the sole of the foot
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47C—CHAIRS; SOFAS; BEDS
    • A47C27/00—Spring, stuffed or fluid mattresses or cushions specially adapted for chairs, beds or sofas
    • A47C27/08—Fluid mattresses or cushions
    • A47C27/085—Fluid mattresses or cushions of liquid type, e.g. filled with water or gel
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B71/00—Games or sports accessories not covered in groups A63B1/00 - A63B69/00
    • A63B71/08—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions
    • A63B71/14—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the hands, e.g. baseball, boxing or golfing gloves
    • A63B71/141—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the hands, e.g. baseball, boxing or golfing gloves in the form of gloves
    • A63B71/143—Baseball or hockey gloves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D35/00—Producing footwear
    • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
    • B29D35/126—Uppers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D35/00—Producing footwear
    • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
    • B29D35/14—Multilayered parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D35/00—Producing footwear
    • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
    • B29D35/14—Multilayered parts
    • B29D35/142—Soles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D35/00—Producing footwear
    • B29D35/12—Producing parts thereof, e.g. soles, heels, uppers, by a moulding technique
    • B29D35/14—Multilayered parts
    • B29D35/146—Uppers
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41C—CORSETS; BRASSIERES
    • A41C3/00—Brassieres
    • A41C3/12—Component parts
    • A41C3/14—Stiffening or bust-forming inserts
    • A41C3/144—Pads
    • A41C3/146—Pads containing liquid or gel filling
    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B71/00—Games or sports accessories not covered in groups A63B1/00 - A63B69/00
    • A63B71/08—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions
    • A63B71/081—Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions fluid-filled, e.g. air-filled

Definitions

  • This invention relates to conformable structures and more particularly to structures which conform to the body part of a human or animal in response to body heat.
  • Products which conform to a body pan or parts would provide added levels of comfort, support, efficiency and perhaps performance enhancement. Because everyone's body is different, mass produced consumer goods don't fit perfectly. Not only is this the case for wearing apparel and products gripped in the hand, but also objects which come into contact with the body, such as chairs, beds, sofas and other products which support the body. Bladder-based products that conform or provide cushioning are described in United States Patent Nos. 4,144,658 and 5,313,717.
  • Conformable structures according to the invention include an environmentally-responsive gel forming a part of the structure, the gel responsive to an environmental condition to change state reversibly.
  • the gel may be sealed within an enclosure such as a bladder.
  • the gel may be a crosslinked gel obtainable from a polymeric precursor which is in a gelled state at lower temperatures and contracts to disgorge a liquid at body temperatures.
  • the gel may be a reverse thermal gel which is liquid at lower temperatures and becomes more viscous at body temperatures.
  • the reverse thermal gels include interpenetrating polymer networks containing a responsive component capable of aggregating in response to a change in an environmental stimulus such as temperature, a structural component which supports and interacts with the responsive component, and an aqueous-based solvent.
  • the responsive and structural components may be oligomers or polymers.
  • the responsive component will respond to a stimulus to change its degree of association and/or agglomeration.
  • the stimulus may be temperature, pH, ionic concentration, solvent concentration, light, magnetic field, electric field, pressure or other triggers commonly used to trigger a responsive gel material.
  • temperature is the preferred trigger.
  • the aggregation may be in the form of micelle formation, precipitation, labile crosslinking or other factors.
  • the structural component is an oligomer or polymer which supports and interacts with the responsive component so that a multi-material, responsive polymer network is formed. The structural component is not required to be responsive.
  • a typical reversibly gelling polymer network may contain less than about 4 weight percent of total polymer solids of which less than about 2 weight percent is the responsive component and less than about 2 weight percent is the structural component. The rest is made of the aqueous-based solvent.
  • An exemplary responsive component is a triblock polyol having the formula (EO)(PO)(EO).
  • An exemplary structural component is sodium acrylate which is manufactured by polymerization of acrylic acid in the presence of triblock polyol followed by hydration and neutralization of the polyacrylic acid.
  • the viscosity of the gel increases at least ten-fold with an increase in temperature of about 5° C.
  • Yet another suitable reverse thermal gel is poly(ethylene oxide)- poly(propylene oxide)-poly(ethylene oxide) triblock copolymers (trade name Pluronics, Poloxomers) in aqueous solutions.
  • Pluronics poly(ethylene oxide)- poly(propylene oxide)-poly(ethylene oxide) triblock copolymers
  • Pluronics Poloxomers
  • aqueous Pluronics solution As an aqueous Pluronics solution is heated up, and the temperature exceeds a certain value called a lower transition temperature, the viscosity changes by several orders of magnitude. The consistency of the solution changes from that of a liquid to that of a solid gel (like butter).
  • the particular concentration needed to achieve such a transition depends on the kind of Pluronic polymer. For example, F127 will not show the gelation properties at concentrations lower than about 16%, whereas other Pluronics may need an even higher concentration.
  • the materials useful for the inventions disclosed herein may be encapsulated into bladders made of materials suitably impervious to water loss, such as mono- or multi-layered sealable structure of sufficiently low moisture vapor transmission rate to ensure appropriate performance.
  • Suitable materials include, but are not limited to, hydrocarbon-based films, modified hydrocarbon-based films, multi-layered or composite films with both hydrocarbon and metallic-based layers.
  • materials such as foams may be adhered to the bladder film for the purpose of making a more effective and stronger material after the gel material undergoes a phase transition.
  • the bladder films may be sealable using heat, pressure, sonic welding, RF and pressure sealing techniques.
  • the conformable structures of the invention provide improved fit, comfort, mechanical support and shock resistance. Applications may be broken down into the following exemplary categories.
  • the structures may be used for mouthpieces, helmets, head gear (e.g., wrestling), specialty gloves (e.g., baseball, boxing, biking, golf, lacrosse, equestrian, hockey, etc.), masks (e.g., scuba, hockey, soccer, lacrosse, baseball catcher, etc.), goggles (e.g., swimming, skiing, scuba, etc.), lacrosse head stops, sports bras, socks, grips for athletic equipment, ear and nose plugs.
  • head gear e.g., wrestling
  • specialty gloves e.g., baseball, boxing, biking, golf, lacrosse, equestrian, hockey, etc.
  • masks e.g., scuba, hockey, soccer, lacrosse, baseball catcher, etc.
  • goggles e.g., swimming, skiing, scuba, etc.
  • lacrosse head stops sports bras, socks, grips for athletic equipment, ear and nose plugs.
  • Other athletics applications includes grips for oars, tennis, squash and cricket rackets, baseball bats, shoulder pads, knee pads, elbow pads, bicycle handlebars and seats, padding for sleds, saddles and undersaddles, joint support (e.g., elbow, wrist, knee, hip, neck, shoulder and ankle), muscle and bone support, sports clothing including wet suits, dry suits, padded garments (e.g., biking shorts, etc.), conformable garments and socks.
  • Other uses are for motorcycle grips and gun handles.
  • the conformable structures of the invention may also find application in orthopedic devices, prosthetic appliances, ostomy bag fittings, molding material (dental, etc.), casting, bandaging, joint braces (e.g., elbow, wrist, knee, hip, neck, shoulder and ankle), splints, eyeglass pads and tennis elbow braces.
  • Other health care applications include bedding, bed pads and sheets, whirlpool bath rests, pillows, crutch padding, x-ray boards, walkers, cervical pillows, wheelchair padding, general padding, lumbar supports and electrocardiogram pads.
  • the conformable structures have application in ergodynamic chairs, beds, sofas, shoulder rests and telephone receiver cushioning pads, palm rests for ergonomic keyboards, and other ergonomic computer accessories and cushioning for writing instruments.
  • Other applications are for chairs, seating for vehicles of transport such as automobiles, airplanes, boats, etc., and vibration damping control.
  • conformable structures include vibration control shock absorbers, socks, shimming, padding for instrumentation, padding for shipping pressure equipment, sealing thermal imaging equipment and oven mitts. Wearing Apparel
  • Conformable structures of the invention also have application in brassieres, sports bras, formal dress wear and bathing suits.
  • the materials also may be incorporated into men's jock straps, undershorts or bathing shorts.
  • the material may also be incorporated into an article of eyewear.
  • Figure 1 is a graph of viscosity versus temperature for a Pluronic material
  • Figure 2 is a graph of viscosity versus temperature for another Pluronic material
  • Figure 3 is a graph of viscosity versus temperature illustrating the effect of NaCl on transition temperature
  • Figure 4(a)-(c) are schematic illustrations of bladders encompassing the conformable structures of the invention.
  • Figure 5 is a schematic illustration of a conventional baseball fielder's glove including a gel bladder.
  • the gel is a microporous, fast response, crosslinked gel obtainable from a polymeric precursor, the gel being reversibly responsive to a change in an environmental condition, preferably temperature.
  • the gel can be made from any responsive polymer with side groups that can react with di- or multi-functional crosslinking molecules.
  • the polymers can have hydroxyl, acid or amine side groups which have lower critical solution temperatures in aqueous solutions together with water-soluble crosslinkers.
  • the precursor is preferably a linear polymer or cellulose ether such as hydroxypropyl acrylate, hydroxyethyl acrylate copolymer.
  • the water- based fluid used to make the gel can include sucrose in the range of 30-60% to vary the reaction temperature.
  • a temperature-responsive gel suitable for use in the invention is a crosslinked, three-dimensional polymeric network that contains a substantial quantity of liquid so that the properties of the gel are determined by both the polymeric network and the liquid. If the liquid is water, the gel is commonly called a hydrogel. The volume of this type of reactive gel may contract by a factor of up to several hundred percent when the gel undergoes a change in external conditions such as temperature.
  • the network material of a responsive hydrogel may include a number of polymeric materials that possess a lower critical solution temperature (LCST). The term LCST is the temperature below which the polymer is substantially soluble in liquid and above which the polymer is substantially insoluble.
  • the responsive gel forms a two phase system.
  • suitable hydrogels are set forth in U.S. Patent No. 5,183,879, the teachings of which are hereby incorporated by reference.
  • the preferred temperature-responsive gel contracts upon application of heat from contact with the body, thereby causing water to be disgorged from the gel. Therefore, the temperature responsive hydrogel can be enclosed within a bladder to contain water that is expelled from a contracted gel and located in an article of apparel or other structure. The water may then flow around and conform to the portion of the body with which it is in contact.
  • a preferred gel precursor is a linear polymer or cellulose ether, and more particularly, hydroxypropyl acrylate/hydroxyethyl acrylate copolymer.
  • the hydroxypropyl acrylate/hydroxyethyl acrylate copolymer gel includes between 50 to 100 percent hydroxypropyl acrylate and between 50 and 0 percent hyroxyethyl acrylate.
  • glycerine or glycerol can be added to reduce the freezing temperature of the solution.
  • the gel material be a reverse thermal gel which is substantially liquid at lower temperatures and whose viscosity increases at body temperatures.
  • One suitable class of materials are interpenetrating networks of a responsive component such as an oligomer or polymer which will respond to a stimulus to change its degree of association and/or agglomeration.
  • a preferred stimulus is temperature.
  • the aggregation may be in the form of micelle formation, precipitation, labile crosslinking or other factors.
  • the responsive and structural components are dissolved in an aqueous-based solvent. Since a gel comprises three-dimensional polymeric networks dissolved in the solvent, the liquid component makes up a responsive polymer network.
  • Suitable materials are disclosed in detail in pending U.S. Application Serial No. 08/580,986, filed January 3, 1996, the teachings of which are incorporated herein by reference. The following examples are representative of suitable interpenetrating network gels.
  • This example describes the synthesis of a responsive polymer network and an aqueous responsive polymer network solution prepared using a triblock polymer of ethylene oxide and propylene oxide (Pluronic ® F27) and poly (acrylic acid). This example also characterizes the gelation and the physical properties of the resultant responsive polymer network.
  • Block copolymer of propylene oxide (PO) and ethylene oxide (EO) having sandwich structure (EO) A (PO) B (EO) A (Pluronic F127 NF, Poloxamer 407 NF, where "F” means Flakes, "12” means 12X300 3600 - MW of the poly (propylene oxide) section of the block copolymer, "7” ethylene oxide in the copolymer is 70 wt%, and nominal molecular weight is 12,600) from BASF (3.0 g) was dissolved in 3.0 g acrylic acid (Aldrich). This represents a substantially 1:1 molar ratio of Pluronic ® F127 and polyacrylic acid.
  • a known amount of the resultant polymer was suspended in 100 ml deionized water into which NaOH was added. Following swelling for 3 days while stirring, the pH of the resulting fine suspension was adjusted to 7. Samples of 15 ml each were taken, and pH in each vial was adjusted to desired value by addition of 1 M HC1 or NaOH. Samples were then kept overnight and their viscosities were measured at different temperatures using Brookfield viscometer using either an SC4-18 or an SC4-25 spindle.
  • Responsive polymer network structure Solutions (1 wt% each) of responsive polymer network composition, a polyacrylic acid (alone) polymerized without Pluronic ® and Pluronic ® F127 (alone) were subjected to gel permeation chromatography analysis using triple detector system (light scattering, viscometer, and refractive index detection, Viscotek). The results of molecular weight determination are outlined in Table 1. Table 1. Results of molecular weight determination of polyacrylic acid in responsive polymer network, polyacrylic acid itself (PAA), and Pluronic ® F127.
  • PAA polyacrylic acid itself
  • polyacrylic acid of the responsive polymer network composition and polyacrylic acid synthesized alone are substantially different in molecular weights and polydispersity.
  • the presence of the triblock (EO)(PO)(EO) polymer and its interaction with the developing polyacrylic acid chains had a measurable effect on the final responsive polymer network composition.
  • polyacrylic acid synthesized in presence of the triblock (EO)(PO)(EO) polymer is of lower molecular weight and is much more monodisperse than the polyacrylic acid prepared alone.
  • Pluronic ® was very monodisperse and it ' s molecular weight corresponded to the data provided by the supplier.
  • the responsive polymer network compositions of the present invention are more than the sum of two individual polymers. Further information on the structure of the responsive polymer network may be gained using the Mark-Houwink equation. Analysis using Mark-Houwink equation
  • the constituent polymers experience a much stronger degree of interaction than physically mixed polymers. These structures interact even more strongly because of the tendency of responsive components, such as the triblock (EO)(PO)(EO) polymers to form aggregates in solution. No covalent bonds, i.e., crosslinks, are even required for either of the constituent polymers.
  • the insoluble portion of the responsive polymer network was analyzed by FTIR and compared to a sample of pure polyacrylic acid (MW 450,000, from Aldrich).
  • the polyacrylic acid extracted from responsive polymer network and the one available commercially were spectroscopically identical.
  • the individual components of the responsive polymer network may be separated by solvent extraction, indicating the lack of covalent bonding.
  • the responsive polymer network composition described above is a unique composition of matter consisting of interacting and entangled polyacrylic acid and copolymers of ethylene oxide and propylene oxide (Pluronic ® ), without covalent bonding.
  • Example 2 This example describes the synthesis of a responsive polymer network and an aqueous responsive polymer network composition prepared using Pluronic ® F108 and poly(acrylic acid). This example also characterizes the gelation and the physical properties of the resultant responsive polymer network composition. Synthesis
  • Block copolymer of propylene oxide (PO) and ethylene oxide (EO) having sandwich structure (EO) A (PO) B (EO) A (Pluronic F108 NF, Poloxamer 338 NF, where "F” means Flakes, "10” means 10X300 3000 - MW of the poly (propylene oxide) section of the block copolymer, "8” means that the weight percentage of ethylene oxide in the copolymer is 80%, and nominal molecular weight is 14,600, 3.0 g) was dissolved in 3.0 g acrylic acid (Aldrich). The solution was prepared as described above for Example 1. Viscosity measurements A known amount of the resultant polymer was suspended in 100 ml deionized water into which NaOH was added.
  • the responsive polymer network composition was studied as described in Example 1. Responsive polymer network compositions of 1 wt% Pluronic ® F108 and polyacrylic acid (1:1) viscosified at temperatures of around 34 °C and higher at pH 7. Repeated heating and cooling of the responsive polymer network composition did not degrade the gelling effect.
  • the liquid to gel transition of 34 °C correlates well with the observed characteristic temperature of 33.7 °C of the endothermic peaks that are seen in the DSC endotherm. The peaks are measured to have enthalpy value of 1.504 cal/g. This also corresponds closely to a similar endotherm observed for Pluronic ® F108 alone. The observed correlation supports the conclusion that it is the formation of the triblock (EO)(PO)(EO) polymer aggregates that contribute to the gelation of the responsive polymer network compositions.
  • This example describes the synthesis of a responsive polymer network and an aqueous responsive polymer network composition prepared using Pluronic ® F88 Prill and poly(acrylic acid). This example also characterizes the gelation and the physical properties of the resultant responsive polymer network composition.
  • Block copolymer of propylene oxide (PO) and ethylene oxide (EO) having sandwich structure (EO) A (PO) B (EO) A (Pluronic F88 Prill, where "F” means Flakes, “8” means 8X300 2400 - MW of the poly(propylene oxide) section of the block copolymer, “8” means 80 wt% ethylene oxide in the copolymer is 80%, and the nominal molecular weight is 11,400, 3.0 g) was dissolved in 3.0 g acrylic acid (Aldrich). The solution was prepared as described above for Example 1. Viscosity measurements
  • a responsive polymer network composition was prepared and studied as described in Example 1. Responsive polymer network compositions of 1 wt% Pluronic ® F88 and polyacrylic acid (1:1) viscossified at temperatures of around 48 ° C and higher at pH 7. Repeated heating and cooling of responsive polymer network suspensions was not observed to cause deterioration of the gelation effect. This measurement correlates well with the observed characteristic temperature of 47 ° C of the endothermic peaks that are seen in the DSC endotherm. The peaks are measured to have enthalpy value of 0.9 cal/g.
  • Pluronic polyols are also suitable for use in the conformable structures of the invention.
  • Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers (trade name Pluronics, Poloxamers) in aqueous solutions show some remarkable reverse thermoviscossification properties.
  • Pluronics Poloxamers
  • the viscosity changes by several orders of magnitude.
  • the consistency of the solution changes from that of a liquid to that of a solid gel (like butter).
  • the particular concentration needed to achieve such a transition depends on the kind of Pluronic polymer.
  • Figure 1 illustrates the viscossification of 17% aqueous solution of F127. It also shows that the viscosity can be increased by adding a thickener, in this case 1% of hydroxyethylcellulose.
  • Another potentially desirable property of a Pluronic solution is that when the gel temperature is further increased, it can revert to a liquid state. This is useful, for example, in connection with conformable products, where there is a need to distinguish between the effect of contact with human body temperatures, when the materials should be a gel, and a potentially higher ambient temperature (e.g., in a car trunk on a hot day), when the material should be a liquid.
  • Figure 2 shows this effect for a 17% solution of F127, both for increasing and for decreasing temperature.
  • transition temperature For may potential uses of the material it is desirable to be able to control the exact transition temperature. This can be achieved by varying the Pluronic type, as well as the concentration of a given Pluronic solution. A straightforward way of controlling the temperature is by modifying a solution of given concentration through incorporation of additives, such as salts and polymers.
  • Figure 3 shows the effect of addition of sodium chloride to a 30% solution of Pluronic F68.
  • the transition temperature can be brought down from 45°C to 10°C by addition of 10% (by weight) of NaCl.
  • Figure 4a illustrates a cross-section of a bladder filled with a Pluronic solution.
  • the material thermoviscosifies becomes harder.
  • the resistance to flow in this design is not very great. It can be improved by incorporation of a foam into the bladder, as illustrated in Figure 4b.
  • the foam is impregnated with the Pluronic solution and provides a resistance to flow.
  • the material thermoviscosifies the resistance becomes much greater, and the foam becomes very hard and rigid.
  • Figure 4c Another structural design improving the strength of the viscosified material is presented in Figure 4c.
  • the bladder is divided into a number of chambers (two are depicted here) separated by narrow channels, through which the Pluronic solution must flow in order to redistribute itself when pressed or squeezed.
  • the resistance to flow offered by these narrow channels is much greater than that in the case of an open bladder, as in Figure 4a. Therefore the overall stiffness of the systems is enhanced.
  • thermochromatic dye can be incorporated into the solution and/or the bladder or container.
  • the user's perception of a radical change in the material properties is then enhanced by a change in the material's color.
  • thermochromatic material is commercially available from 2nd Story Concepts, Inc. When suspended in an aqueous solution, it is capable of changing color from its original hue at low temperatures to white at body temperature.
  • the thermochromatic powder may be incorporated either directly into the bulk of the gel or into the structure of the container holding the gel. Further colors can be achieved by mixing the thermochromatic powder with a dye of desired color to the effect that at high temperatures the color is that of the dye and at low temperature the color is determined by the composition of the dye color with the basic hue of the thermochromatic powder.
  • a 50/50 mixture of 10% gel solution in 1% suspension of the thermochromatic powder was prepared. A blue to white change in color accompanied the reverse thermal gelation of the systems. Different color changes were achieved by incorporating dyes into the system, for example, purple to red, green to yellow.
  • the gel materials of the invention be encapsulated within bladders.
  • Bladder materials will consist of a mono or multilayered sealable structure of sufficient MVTR (Moisture Vapor Transmission Rate) to ensure product performance over the lifetime of the product.
  • Some examples include, but are not limited to, hydrocarbon based films, modified hydrocarbon based films, multilayered or composite films with both hydrocarbon and metallic based layers.
  • materials such as foams and the like may be adhered to the film for the purpose of making a more effective (i.e., stronger) material after the phase transition.
  • Films may be sealable using heat/pressure, sonic welding, RF and pressure adhesive sealing techniques. Additionally, vacuum and heat forming of the package may be required.
  • the bladder may be manufactured using one of three basic techniques. 1) form, fill and seal, and 2) vacuum form, fill and seal, and 3) pouch prefabrication, fill and seal.
  • Form, fill and seal utilizes the formation of the pouch while at the same time the pouch is filled with the responsive polymer network material.
  • Vacuum form, fill and seal utilizes a vacuum forming step prior to the filling and sealing operations.
  • the bladder material must be somewhat thicker than the form fill and seal case in that the material will thin out and weaken at the corners being formed.
  • the hollow that has been formed can be filled with a liquid, or a combination of liquids and solids in one or sequential steps.
  • Pouch prefabrication, fill and seal utilizes a premade pouch that is filled with liquids and/or solids in a subsequent filling step and then sealed. Variations of this technique may include filling a premade rigid or soft pouch and then sealing or filling a soft pouch utilizing one way valves that are subsequently cut off and sealed.
  • a baseball fielder's glove 10 includes a gel bladder 12 disposed as shown in the figure. It is preferred that the gel within the gel bladder 12 be either the interpenetrating network gel or the Pluronic gel described above.
  • the gel When a hand is inserted into the glove 10, the gel is in the liquid state and conforms to the hand of the wearer (not shown). As the gel warms to body temperature, it becomes viscous, thereby retaining its shape and conforming to the hand of the wearer.
  • the gel bladders of the invention may be incorporated into any of the articles of clothing or other articles of manufacture set forth earlier in this specification. In all of these applications the gel undergoes a phase change or transition from a first state at a lower temperature to a second state at body temperature. In the case of reverse thermal gels, the gel at the lower temperature is liquid and becomes viscous upon contact with the body.

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Public Health (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

L'invention a pour objet des structures adaptables. Ces structures comprennent un gel réagissant à l'environnement, formant partie de la structure. Le gel répond à un état de l'environnement, comme la température, pour changer d'état de manière réversible. Il est préférable que le gel soit placé dans une enveloppe fermée. Dans un mode de réalisation, le gel est un gel thermique réversible, qui est liquide à basses températures et devient visqueux à la température corporelle. Des objets placés en contact avec le corps s'adaptent à la forme du corps et conservent cette forme en réponse à la température corporelle. Des structures représentatives sont des vêtements, tels que des chapeaux, des casques et des soutien-gorges. D'autres objets adaptables comprennent des chaises et des canapés.
PCT/US1996/003470 1995-03-15 1996-03-15 Structures adaptables WO1996028056A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU58501/96A AU5850196A (en) 1995-03-15 1996-03-15 Conformable structures
EP96920098A EP0759710A1 (fr) 1995-03-15 1996-03-15 Structures adaptables

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US40467595A 1995-03-15 1995-03-15
US08/404,675 1995-03-15
US805795P 1995-12-19 1995-12-19
US60/008,857 1995-12-19
US08/580,986 US5939485A (en) 1995-06-19 1996-01-03 Responsive polymer networks and methods of their use
US08/580,986 1996-01-03

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WO1996028056A1 true WO1996028056A1 (fr) 1996-09-19
WO1996028056A9 WO1996028056A9 (fr) 1996-12-05

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Cited By (13)

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WO1997000275A2 (fr) * 1995-06-16 1997-01-03 Gel Sciences, Inc. Reticulats polymeriques sensibles a des changements intervenus dans des stimulus environnementaux et leurs procedes d'utilisation
NL1003788C2 (nl) * 1996-08-13 1998-02-20 Stadtman B V Contactelement.
WO1998058572A3 (fr) * 1997-06-23 1999-04-22 Magna Reflex Holding Gmbh Partie de soutien d'un siege
US6012726A (en) * 1997-02-13 2000-01-11 K-2 Corporation In-line skate with temperature dependent support
WO2000032715A1 (fr) * 1998-12-03 2000-06-08 Bic Corporation Dispositif de prehension adapte a l'utilisateur forme d'une composition de gel thermoreversible
US6312667B1 (en) 1998-11-12 2001-11-06 3M Innovative Properties Company Methods of etching hard tissue in the oral environment
US6312666B1 (en) 1998-11-12 2001-11-06 3M Innovative Properties Company Methods of whitening teeth
US6620405B2 (en) 2001-11-01 2003-09-16 3M Innovative Properties Company Delivery of hydrogel compositions as a fine mist
US6669927B2 (en) 1998-11-12 2003-12-30 3M Innovative Properties Company Dental compositions
WO2010033329A1 (fr) * 2008-09-22 2010-03-25 Nike International, Ltd. Gant de sport avec système d'atténuation de force d'impact
US11484449B2 (en) 2019-08-13 2022-11-01 Stryker Corporation Support apparatus for bariatric person
WO2023003891A1 (fr) * 2021-07-19 2023-01-26 Carilion Clinic Dispositifs et systèmes pour fournir des forces de compression et/ou vibratoires à des tissus
US11737914B2 (en) 2017-11-17 2023-08-29 Stryker Corporation Thermal treatment devices

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US4808469A (en) * 1985-05-09 1989-02-28 Maurice Hiles Energy absorbing polyurethane composite article
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US5083910A (en) * 1988-08-11 1992-01-28 Abshire Danny P Insole assembly base component molding pad
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US5334646A (en) * 1977-03-17 1994-08-02 Applied Elastomerics, Inc. Thermoplastic elastomer gelatinous articles
US5334646B1 (en) * 1977-03-17 1998-09-08 Applied Elastomerics Inc Thermoplastic elastomer gelatinous articles
US4454871A (en) * 1980-09-29 1984-06-19 Med-Con, Inc. Ankle-foot orthosis
EP0122035A1 (fr) * 1983-03-10 1984-10-17 Smith and Nephew Associated Companies p.l.c. Dispositif médical pour la prévention des escarres
US4808469A (en) * 1985-05-09 1989-02-28 Maurice Hiles Energy absorbing polyurethane composite article
US4961972A (en) * 1986-03-01 1990-10-09 Matsui Shikiso Chemical Co., Ltd. Process for producing linear material
US5027801A (en) * 1987-05-29 1991-07-02 Royce Medical Company Orthopaedic gel pad assembly
US5083910A (en) * 1988-08-11 1992-01-28 Abshire Danny P Insole assembly base component molding pad

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997000275A3 (fr) * 1995-06-16 1997-03-06 Gel Sciences Inc Reticulats polymeriques sensibles a des changements intervenus dans des stimulus environnementaux et leurs procedes d'utilisation
WO1997000275A2 (fr) * 1995-06-16 1997-01-03 Gel Sciences, Inc. Reticulats polymeriques sensibles a des changements intervenus dans des stimulus environnementaux et leurs procedes d'utilisation
NL1003788C2 (nl) * 1996-08-13 1998-02-20 Stadtman B V Contactelement.
US6012726A (en) * 1997-02-13 2000-01-11 K-2 Corporation In-line skate with temperature dependent support
US6378948B1 (en) * 1997-06-23 2002-04-30 Magna Reflex Holding Gmbh Supporting part for a seat
WO1998058572A3 (fr) * 1997-06-23 1999-04-22 Magna Reflex Holding Gmbh Partie de soutien d'un siege
US6312667B1 (en) 1998-11-12 2001-11-06 3M Innovative Properties Company Methods of etching hard tissue in the oral environment
US6312666B1 (en) 1998-11-12 2001-11-06 3M Innovative Properties Company Methods of whitening teeth
US6669927B2 (en) 1998-11-12 2003-12-30 3M Innovative Properties Company Dental compositions
USRE42024E1 (en) 1998-11-12 2011-01-11 3M Innovative Properties Company Dental compositions
WO2000032715A1 (fr) * 1998-12-03 2000-06-08 Bic Corporation Dispositif de prehension adapte a l'utilisateur forme d'une composition de gel thermoreversible
US6620405B2 (en) 2001-11-01 2003-09-16 3M Innovative Properties Company Delivery of hydrogel compositions as a fine mist
WO2010033329A1 (fr) * 2008-09-22 2010-03-25 Nike International, Ltd. Gant de sport avec système d'atténuation de force d'impact
US8656513B2 (en) 2008-09-22 2014-02-25 Nike, Inc. Sports glove with impact force attenuation system
US11737914B2 (en) 2017-11-17 2023-08-29 Stryker Corporation Thermal treatment devices
US11484449B2 (en) 2019-08-13 2022-11-01 Stryker Corporation Support apparatus for bariatric person
WO2023003891A1 (fr) * 2021-07-19 2023-01-26 Carilion Clinic Dispositifs et systèmes pour fournir des forces de compression et/ou vibratoires à des tissus

Also Published As

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EP0759710A1 (fr) 1997-03-05
CA2190255A1 (fr) 1996-09-19
AU5850196A (en) 1996-10-02

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