WO2003097345A1 - Composite d'humidite et de transpiration et produits issus dudit composite - Google Patents

Composite d'humidite et de transpiration et produits issus dudit composite Download PDF

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Publication number
WO2003097345A1
WO2003097345A1 PCT/US2003/013997 US0313997W WO03097345A1 WO 2003097345 A1 WO2003097345 A1 WO 2003097345A1 US 0313997 W US0313997 W US 0313997W WO 03097345 A1 WO03097345 A1 WO 03097345A1
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WO
WIPO (PCT)
Prior art keywords
moisture
footwear
urethane polymer
hydrophilic urethane
foam composite
Prior art date
Application number
PCT/US2003/013997
Other languages
English (en)
Inventor
James E. Issler
Wayne Celia
Paul F. Hermann
Original Assignee
H. H. Brown Shoe Technologies, 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
Application filed by H. H. Brown Shoe Technologies, Inc. filed Critical H. H. Brown Shoe Technologies, Inc.
Priority to AU2003243198A priority Critical patent/AU2003243198A1/en
Priority to JP2004504718A priority patent/JP4163682B2/ja
Priority to EP03752997A priority patent/EP1562740A4/fr
Publication of WO2003097345A1 publication Critical patent/WO2003097345A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/14—Water soluble or water swellable polymers, e.g. aqueous gels

Definitions

  • the invention relates generally to materials and methods for improving the movement of water vapor migration through textiles and other products and more particularly to the lateral movement or transpiration and removal of moisture, particularly body fluids, from confined spaces formed by body coverings such as suits, dresses, shoes, helmets, hats, other apparel, appliances and accessories wherein the removal of the generated moisture such as perspiration provides a lower humidity, lower temperature and improves the comfort zone inside such body coverings .
  • the normal thermoregulatory process of the human body is by the production of perspiration when a temperature increase is sensed. Normal evaporation then converts the perspiration into water vapor, which in turn consumes heat and cools the body. Minimizing evaporation defeats this process, and most people feel uncomfortable outside the heat comfort index data as mentioned above.
  • This operation of the normal thermoregulatory process of the human body is best understood by comparing the body's sensation during a hot day generated by elevated ambient temperature with high humidity versus a day with the same temperature with low humidity.
  • Any body covering such as suits, dresses, shoes, a helmet or other apparel or appliances effects the production and evaporation of perspiration where the body senses a temperature increase. Perspiration will be reduced in any restricted environment in which the dew point is being reached. Dew point, as will be understood by those skilled in the art, being the point at which the air in the restricted environment is saturated with water vapor and moisture condenses out of the air in such restricted environment as water droplets. Covering over the body and the skin with the restrictive materials of body coverings limits or minimizes perspiration and evaporation, as occurs with apparel, in a shoe or helmet, a backpack or appliance attached to the body which creates a closed space or microenvironment . Efforts to minimize the discomfort in microenvironments have included improvements in airflow, membranes for passing the water vapor away, wicking of accumulated moisture, phase change materials and other technologies .
  • the ability of the textiles, fabrics or other material used to enable water vapor emitted from the body, as distinguished from the condensed droplets of moisture, to pass to the ambient atmosphere is an important factor in assessing the comfort of body coverings such as apparel, shoes, helmets, appliances, accessories and the like as above described.
  • body coverings such as apparel, shoes, helmets, appliances, accessories and the like as above described.
  • breathability in textile terms is a measure of the water vapor migration through the textiles, fabrics or other materials and not a measure of its air permeability or windproof characteristics .
  • U.S. Patents 5,763,335 and 6,025,287 disclose a hydrophilic urethane foam polymer with 0.6% superabsorbent polymer composite for forming a layered lining material and a process for making the same for the collection and transpiration of water or moisture vapor from a microenvironment.
  • the composite and layered lining material as disclosed in these patents absorbs and converts the moisture into a gel in the layered lining material and then enables or allows the collected moisture in the gel to evaporate after the body covering, appliance or accessory is removed or opened to expose the microenvironment to the surrounding ambient atmosphere .
  • a new formulation and method of making a hydrophilic urethane polymer foam composite with limited particles of superabsorbent polymer, a surfactant and optionally and selectively other additives is disclosed which eliminates and prevents the gel formation or gel blocking and evaporation mechanism of the said prior art Pats '335 and '287.
  • This new formulation and method is achieved by so modifying and optimizing the orientation of the particles of superabsorbent polymer on, in and through the interconnected strands, filaments and the size and shape of the randomly disposed interstitial air gaps in the matrix of the formed foam hydrophilic urethane polymer composite that the absorbency and physical movement or transpiration of moisture and/or water vapor laterally both in the length or x direction and width or y direction of the formed foam matrix is materially enhanced to enable the moisture and/or water vapor to move from an area of high humidity to an area of low humidity where the moisture and moisture vapor can be eliminated by evaporation and desirably replaced by incoming cooler atmospheric air.
  • the surface condition of the formed products and layers of this material remains relatively dry when compared with the prior art materials developed for this same purpose .
  • the conventional testing of the MVTR of the improved formed hydrophilic urethane polymer foam composites and products in accordance with the present invention surpassed the above entioned acceptable MVTR for such prior art materials developed for the same purposes by a factor of over five (5) times.
  • this improved formed foam composite material ly reduces or eliminates bacterial build-up and obnoxious odors SUMMARY OF THE INVENTION
  • the present invention covers formed hydrophilic urethane polymer foam composites and products with particles of at least one superabsorbent polymer, sufficient surfactant and selectively and optionally other additives to enable moisture to move from an area of high humidity to an area of lower humidity such as the surrounding ambient atmosphere
  • anionic, cationic, amphoteric and swittering surfactants humectants such as glycerin, solid fillers such as wollastonite, feldspar, calcium carbonate, sodium bicarbonate, fiber such as cellulose, polyester, glass and optionally and selective
  • the present invention also relates to footwear comprising an upper section and a sole section wherein the upper section and the sole section are connected to define a space for a user's foot forming a microenvironment, preferably, the upper section has one of the multi-layered combinations as above described on the inner surface including at least one layer of one of the formed hydrophilic urethane polymer foam composites in accordance with the present invention containing particles of up to 0.1% of superabsorbent polymer, wherein said at least one formed foam layer of the liner or multi-layered liner communicates with an area of lower humidity such as the ambient atmosphere at the exterior of the footwear.
  • MVTR Moisture Vapor Transmission Rate
  • FIGURE 1 shows a fragmentary view of a section of the matrix in a formed hydrophilic urethane polymer foam layer in accordance with the present invention prior to compression or drying showing the interconnected strands and filaments and interstitial gaps or spaces in the matrix of the urethane polymer, with the particles of superabsorbent polymer generally uniformly dispersed in, on and throughout the strands, filaments and the interstitial gaps or spaces.
  • FIGURE 2 is an enlarged cross-sectional view taken on line 2-2 of one of the interconnected strands and filaments shown in FIGURE 1 showing that some of the dispersed particles of the superabsorbent polymer are in, on and through the interconnected strands and filaments of the formed hydrophilic polymer foam layer.
  • FIGURE 3 shows a pictorial cross-section through a garment of a layer of formed hydrophilic urethane polymer foam product in accordance with the present invention including particles of superabsorbent polymer and non-woven fiber additive in which the interstitial gaps and spaces between the non-woven fibers are filled with particles of up to 0.1% of superabsorbent polymer.
  • FIGURE 4 shows a pictorial cross-section of another embodiment of a formed product in accordance with the present invention with the formed hydrophilic urethane polymer foam composites in accordance with the present invention as shown in FIGURE 3 having a hydrophilic covering fabric affixed thereto using a moisture-permeable adhesive.
  • FIGURE 5 shows a pictorial cross-section of another embodiment of a formed multi-layered product with the hydrophilic urethane polymer foam composite as shown in FIGURE 3 in accordance with the present invention having hydrophilic covering fabric affixed on the inner face, hydrophobic waterproof covering fabric affixed on the outer face and an operatively associated or connected material made preferably of leather or leather-like material.
  • FIGURE 6 shows a pictorial cross-section of still another embodiment of a formed multi-layered product with the hydrophilic urethane polymer foam composite in accordance with the present invention as shown in FIGURE 3 with separate and distinctive forms of covering material such as fabrics or films to obtain or enable obtaining variable functional characteristics in regard to moisture management and transpiration of collected moisture on either of the surfaces of the formed composite.
  • FIGURE 7 shows a pictorial cross-sectional view of a fragment of a formed multi-layered product with the hydrophilic urethane polymer foam composite in accordance with the present invention as shown in FIGURE 3 illustrating the use of a water- permeable adhesive for bonding of the warp and weave of a covering fabric to the formed composite.
  • FIGURE 8 shows a pictorial cross-sectional view of a fragment of another form of relatively lightweight multi- layered product with the formed hydrophilic urethane foam composite in accordance with the present invention without any non-woven fiber additive prepared by knife blade coating of the foam composite onto a release paper and bonding of a woven fabric layer thereto, "in situ . "
  • FIGURE 9 shows a pictorial cross-sectional view of a fragment of still another form of a relatively lightweight multi-layered product with the hydrophilic urethane foam composite in accordance with the present invention; without any non-woven fiber additive prepared by knife blade coating of the foam composite between a lower layer and an upper layer of réelle_-_---,
  • release paper for "in situ” bonding or affixing by a preferred moisture-permeable adhesive of a woven cover fabric to at least one surface of the formed composite.
  • FIGURE 10A is a longitudinal side view of one type of footwear lined with a multi-layered formed product with a woven cover fabric based or affixed as by a suitable non-permeable adhesive to the inner face of the leather upper section of the footwear and over and about the longer section and upper edges of the foot opening and the tongue section of the footwear for communication with the ambient atmosphere.
  • FIGURE 10B is an enlarged cross-section taken on line 10B-10B of FIGURE 10A.
  • FIGURE 11 is a longitudinal cross-sectional view of the footwear shown in FIGURE 10B.
  • FIGURE 12 is a cross-section taken on line 12-12 of
  • FIGURE 13 is an enlarged cross-section taken on line 13-13 of FIGURE 12.
  • FIGURE 14 is a diagrammatic illustration of the theoretical differential flow of a droplet of the collected moisture from an area of high humidity to an area of lower humidity through a formed multi-layered product with the hydrophilic urethane polymer foam composite in accordance with the present invention.
  • the process for formulating this improved and formed foam composite is to combine an aqueous formulation including, adequate water, a limited amount of up to 0.1% of superabsorbent polymer particles, surfactant for adjusting the size of the open cells or randomly spaced interstitial air gaps, optionally and selectively other additives with at least one suitable urethane prepolymer to form a polymerizing mixture, depositing the polymerizing mixture on a releasable bottom paper on a moving carrier or conveying system and covering the upper surface with releasable top paper, moving the polymerizing mixture on the carrier or conveying system and simultaneously sizing the individually normally circular-shaped cells into predominantly oval shapes which ultimately create more x-y directional strands and fibers of urethane polymer for enhancing transpiration of collected moisture, removing the top and bottom releasable paper, and passing the formed layer of urethane polymer foam composite to such secondary steps as forming sheets, die cutting etc. to prepare products for various applications such as lining for apparel, shoes
  • the formed foam composite in accordance with the present invention differs in that the shape, size and orientation of the interconnected strands and filaments and of the interstitial spaces and gaps in the matrix of the formed foam has been optimized for lateral transpiration of collected moisture in the x-y direction, namely, in the same longitudinal plane as the length and width of the formed foam composites.
  • the ratio of chemicals in the formulation of the formed foam composite in accordance with the present invention has also been designed to prevent gel formation and blocking as described in U.S. Patent 5,331,728 and Pats '335 and '287 while maximizing the absorbency, transpiration and breathability of such formed foam composite.
  • the improved formed foam composite in accordance with the present invention will absorb and transport moisture from a high humidity location such as a microenvironment to a lower humidity region and where the moisture can be evaporatively eliminated.
  • the surface condition of the improved foam composite remains relatively dry if compared to conventional prior art absorbent materials. If a drop of water is placed on the surface of any of the improved formed foam composite, as hereinafter described, and allowed to permeate the surface, when a paper towel is pressed to the same area of the surface, it will not blot away any water even when pressure is applied to the paper towel .
  • the aqueous mixture utilizes about 15% to 85% by weight of water, .05% to 0.1% by weight of at least one superabsorbent polymer, selectively and optional additives with 1% to 50% by weight of hydrophilic urethane prepolymer to provide the polymerizing mixture for forming the foam composite.
  • Superabsorbent polymers for such formulations are preferably sodium polyacrylate/polyalchohol polymers and copolymer sorbents which are readily available in the commercial marketplace in liquid, fibrous and, preferably for the composites herein, in particle sizes adapted for the purposes and applications of the present inventions.
  • Such superabsorbent polymers are described in U.S. Patents 5,763,335 and 4,914,170.
  • the superabsorbent polymers are defined generally as having the capability of spontaneously absorbing aqueous fluids while maintaining individual integrity.
  • the carboxylic groups along the polymer chains are solvated when brought into contact with aqueous fluid. As a result, these groups partially dissociate into negatively charged carboxylic ions.
  • the polymer chains now contain large numbers of similarly charged ionic groups, which repel each other. The chains become bulky and will absorb and retain increasing amounts of liquid.
  • the preferred formulation for use in the present invention is a combination of limited superabsorbent polymer and humectant which enables the collected and absorbed moisture to move by differential pressure from an area of high humidity to an area of low humidity.
  • the quantity of superabsorbent polymer used in the aqueous mixture during formulation must, as above indicated, be limited.
  • a preferred quantity would be one tenth of one percent (0.1%) by weight of the mixture. Too much superabsorbent polymer tends to cause the collected moisture to gel as occurs in the prior art formulations, and this will effectively slow down the desired transpiration of the collected moisture and prevent it from moving from an area of high humidity to an area of lower humidity.
  • Surfactants are added to the aqueous mixture during formulation because they act to control the size of the cells or randomly disposed interstitial gap or air spaces in the matrix of the formed foam composite. This in turn affects capillarity, which is a major factor for enhancing the movement of the collected moisture from particle to particle of superabsorbent polymer disposed in, on and through the interconnected strands and filaments of the matrix of any formed foam composite in accordance with the present invention.
  • the use of surfactant for altering surface conditions is well known in the art. Typically ethylene oxide and propylene oxide surfactants from BASF under the mark or name PLURONIC are available in the commercial marketplace.
  • hydrophilic urethane prepolymers are also available in the commercial marketplace and are known to those skilled in the art from U.S. Patents Nos. 5,763,335; 4,209,605; 4,160,076; 4,137,200; 3,805,532 and 2,999,013; and the general procedures for the preparation and formulations of such polymers can be found in Polyurethane ' s Chemistry and Technology by J.H. Saunders and K.C.
  • cover or other layer may be woven, non-woven, water-permeable, waterproof, natural or synthetic fabrics and fiber and will be selected by the function or application for the given multi- layered product.
  • function or application which affect the selection of the cover or other layers and are without limitation to satisfy for example abrasion, tensile strength, elongation, flame retardance, moisture transmission, insulation, aesthetics, feel, density, thickness and other characteristics for various applications and uses.
  • cover and other layers may be connected or disposed on opposite surfaces of the base layer of a formed foam composite in accordance with the present invention and where required or preferred can be bonded, laminated or adhered to the base layer of the formed foam composite. Bonding can be accomplished "in situ” by attachment to the polymerizing moisture during formation of the formed foam composite .
  • Adhesive bonding is well known in the art.
  • the adhesive being used to attach a cover or a layer to a surface of the base layer of formed foam composite is also required to pass moisture through the adhesive, the preferred adhesive would include heat-activated web adhesives such as those sold in the commercial marketplace under the mark or words SPA 111 by Bostic, Middleton, MA and other equivalent hot melt dot matrix applied materials.
  • FIGURES 1 and 2 of the drawings show pictorial illustrations of a fragment of the interconnected strands and filaments generally designated 1 in a section of formed hydrophilic urethane foam composite HF in accordance with the present invention.
  • the strands and filaments 1 in the formed foam composite are in part so interconnected that there will be interstitial gaps defining randomly disposed air spaces generally designated 2 throughout the formed foam.
  • each strand and filament 1 is not segregated from the others by an individual air space 2. Therefore, in this type of foam material, some of the strands or filaments 1 may be interconnected with each other by means of a thin-walled membrane of hydrophilic urethane polymer.
  • This spacing between individual particles of superabsorbent polymer limits or effectively eliminates gel formation or gel blocking as defined in the prior art. It has been found that if the particles of superabsorbent polymer are not in contact with each other, as they swell when absorbing moisture, they will prevent gel formation and will not gel block transpiration of condensed water vapor and droplets of the collected moisture through the formed foam composite. Further, such spacing also reduces the individual particle absorption capacity or rate of absorption. Spacing is controlled by the ratio of the amount of particles of the superabsorbent polymer added to the mixture versus the amount of the hydrophilic prepolymer.
  • Transpiration is enhanced by changing the cell size, shape and dimensions of the randomly established interstitial gaps and air spaces between the interconnected strands and filaments to provide capillarity differentials required to satisfy different viscosities of the droplets of the collected moisture absorbed by the superabsorbent polymers in the matrix of the formed foam composite.
  • Capillarity is a function of the size and shape of the interstitial gaps and air spaces in the matrix of the formed urethane polymer foam composite. Those skilled in the art will recognize and know that the smaller the size of the gaps or air spaces, the better capillarity that will be established to enhance transpiration of the collected moisture form the area of high humidity. Capillarity changes are obtained by adding surfactants when formulating the aqueous mixture and by compression in the formation of the layer of the polymerizing foam during processing of the hydrophilic urethane polymer foam composite and/or by modifying the temperature during processing of the hydrophilic polymer foam composite. Those skilled in the art will recognize that capillarity affects both the absorption of and the rate of transpiration of the condensed droplets of the collected moisture.
  • a further embodiment of the formed urethane polymer foam composite is obtained by the addition of a fibrous web or cut fiber materials .
  • Fibrous webs and cut fiber materials can be natural or synthetic fibers, and either hydrophilic or hydrophobic. Examples of such fibers are cellulose, polyester and glass. This embodiment of the present invention is shown at
  • FIGURE 3 of the drawings serves to establish a formed hydrophilic urethane polymer foam composite sheet stock material which serves many purposes and can be used as at least one of the layers of other multi-layered products in accordance with the present invention.
  • natural or synthetic non-woven fiber web or material is added in a ratio of .5% to 5% by weight of the aqueous mixture during formulation.
  • the woven or non-woven fiber web or material 4 has its interstices completely filled with hydrophilic urethane foam and superabsorbent polymer in the same manner as shown at FIGURES 1 and 2 of the drawings .
  • the fibrous material may either be natural or a manmade synthetic and enhances the transpiration activity of the composite as well as the tensile strength of the formed foam composite and therefor is ideal for forming a base sheet stock material generally designated 5 which can also serve as a layer in the multi-layered products in accordance with the present invention as is hereinafter shown and described.
  • a base sheet stock material generally designated 5 which can also serve as a layer in the multi-layered products in accordance with the present invention as is hereinafter shown and described.
  • the second layer of a covering fabric 6 will be affixed by any permeable-type adhesive means to the opposite surface of the stock sheet 5.
  • the adhesive may be permeable or non-permeable as a function of or depending on the application or use of the particular layered product.
  • the covering fabric is affixed to the surface of the sheet stock 5 that will be in contact with the collected moisture, the covering fabric must be able to pass the collected moisture through to the formed hydrophilic urethane polymer foam composite defined by the sheet stock 5 to which the covering material is attached.
  • Adhesives for affixing or bonding such covering fabric 6 to the formed foam composite sheet stock 5 are open web hot melt or dot matrix deposition types, all of which is shown in FIGURE 7 of the drawings.
  • FIGURE 5 of the drawings another product is shown in FIGURE 5 of the drawings.
  • This is obtained from varying ratios of hydrophilic urethane prepolymer, water, humectant, up to 0.1% superabsorbent polymer and a fibrous web or cut fiber materials.
  • affixed by a permeable-type adhesive to the moisture contacting surface of the formed foam composite layer 5 is a first hydrophilic covering fabric 8.
  • affixed by any suitable means to another of the surfaces of the formed foam composite layer 5 is a waterproof hydrophobic covering fabric 9.
  • the basic formed foam composite layer of sheet stock 5 is operatively connected and so disposed about a leather or leather-like material as at 10 that the formed foam composite layer extends about the end as at 10a of the leather or leather-like layer of material to allow at least one end of the formed foam composite layer 5 to communicate with the ambient environment surrounding the embodiment.
  • This will facilitate the transpiration along the x-y length and width plane of the sheet stock layer 5 of collected moisture from an area of high humidity to an area of lower humidity, namely, to the ambient atmosphere.
  • the leather or leather like material is waterproof, the waterproof covering fabric layer may be eliminated.
  • a formed foam composite layer of the sheet stock material 5 as shown in FIGURES 3, 4 and 5 is provided.
  • This layer is formulated in the same manner to provide a layer of the sheet stock 5 of varying thickness and density as a function of the application and use.
  • the respective opposite surfaces of the formed foam composite can be covered by any combination and variation of separate and distinct fabrics and films to provide varying characteristics for the respective opposite sides of the layer of sheet stock 5.
  • a covering fabric 11 is provided, and on the side remote from the moisture contacting surface of the layer of sheet stock, another covering fabric 12 is provided.
  • the application or use does not want the transpiration of the condensed droplets of the collected moisture to pass through the formed foam sheet stock ' composite in the "z" direction that is perpendicular to the thickness of the sheet stock composite.
  • a non-permeable moisture-proof film 9 is bonded to the side of composite opposite the cover fabric, as is shown at FIGURE 5 of the drawings .
  • the formed foam composite can be affixed or bonded to "leather" or leather-like materials to add the characteristics of absorption, transpiration and evaporation to, for example, shoes made with such formed foam composite.
  • the component foam roll goods such as the sheet stock 5 and cover layer 6 in FIGURE 4, with a bonded waterproof film, was die stamped into a larger profile than the size and shape of a leather shoe upper.
  • the excess foam composite could then be rolled over the outer edges of the shoe upper, exposing the foam material to the outside or ambient atmosphere while still in communication with the shoe interior.
  • moisture from the shoe interior will then be transpired along the "x-y" length and width plane of the formed urethane polymer foam composite and when exposed to the ambient atmosphere will evaporate through the open end of the sheet stock 5, all as shown in FIGURE 5 of the drawings .
  • FIGURE 6 another shaped, sized and multi-layered product in accordance with the present invention has a first cover fabric 11 which has its outer face 11a in communication with the denser and higher pressure area where the condensed droplets of the collected moisture is located.
  • the cover fabric 12 On the opposite or inner face lib the cover fabric 12 is bonded, connected, laminated or adhered to a second layer of formed urethane polymer foam composite 5, of sheet stock as above described.
  • the inner face 12a of a second layer of woven, non-woven, natural or synthetic material is bonded, connected, laminated or adhered to the said side 5a.
  • the outer face 12b of the natural or synthetic material 12 will be in communication with a lower density and lower pressure area of humidity such as the ambient atmosphere .
  • the first cover fabric layer 11 is in communication with the area where the condensed droplets of collected moisture and water vapor are the greatest.
  • the strands and filaments of the matrix of the layer of formed urethane polymer foam composite having the superabsorbent polymer integrally and generally uniformly dispersed therethrough being hydrophilic acts to draw and absorb the droplets of collected moisture and water vapor and cause them to transpire through the cover fabric 11 from the area of denser and high humidity to the area of less dense and lower humidity represented by the layer of formed foaming composite 5 and the third layer of natural and synthetic materials.
  • FIGURE 7 is a cross-section through a fragment of a hydrophilic urethane polymer foam composite with a covering fabric bonded thereto, showing a more detailed means of bonding the covering fabrics as at 6, 8, 9, 10 and 11, respectively at FIGURES 3, 4 and 6, to the sheet stock base 5. It shows the warp and weave fibers at 13 and 14 of the covering woven fabric in communication with a water-permeable adhesive 15 and connected to the sheet stock base 5.
  • the functional operation in using the technology taught herein is to physically use the high moisture vapor transmission rate afforded by the sheet stock base 5 to move unwanted collected moisture from one location to another.
  • the sheet stock base 5 may or may not require a cover material. If cover material is required, the composite needs a means to bond, connect, laminate or adhere the cover material to the sheet stock base 5, as is shown in FIGURES 4, 5, 6 and 7 of the drawing .
  • the cover materials include at least water-permeable, waterproof manmade, synthetic, fabric membranes or film.
  • the cover material chosen is predicated by the function it is to perform. That is, as an example, the cover material characteristic to satisfy abrasion, tensile strength, elongation, flame retardance, moisture transmission, insulation, aesthetics, feel, density, thickness, etc.
  • FIGURES 4, 5, 6 and 7 Combinations of cover materials on opposite sides of the sheet stock base is shown in FIGURES 4, 5, 6 and 7 as above described, including a plurality of different cover materials on one or both sides of the sheet stock base 5.
  • Bonding by integral "in situ” formation or by connecting or adhering of the cover sheet or other layer of material to the layer of the formed urethane polymer form composite is done by conventional techniques which are known to those skilled in the art.
  • Adhesive bonding to the sheet stock base may be accomplished by conventional bonding methods known by those skilled in the trade.
  • preferred adhesives would include heat-activated web adhesives similar to SPA 111 from BOSTIC, Middleton, MA and the equivalent hot melt and dot matrix applied adhesives.
  • the hydrophilic urethane prepolymer is a liquid system which, when reacted with water, forms carbon dioxide and an amine .
  • the amine creates a polymerization of the urethane prepolymer, forming a solid foam polymer, while the carbon dioxide produces bubbles within the forming polymer.
  • process controls including temperature and surfactants which change surface tension within the reaction, and adjusting volume fractions of the formulation, we have been able to create a combination of cell size, pore volume, hydrophilicity, moisture absorption and evaporation to maximize the transpiration of moisture, as shown in the examples and tables which follow below.
  • the hydrophilic urethane prepolymer chemistry in the present invention differs from conventional urethane by means of its hydrophilic urethane polymer component.
  • This hydrophilic urethane polymer component renders the urethane polymer strands and filaments of the foam matrix capable of absorbing water into the backbone of each strand and fiber for contact with the surfactants, absorbents, humectants or cut fiber materials dispersed in the foam matrix.
  • the transpiration rate is therefor increased by means of the hydrophilic urethane prepolymer used in the formulations of the formed foam composite in accordance with the present invention.
  • the embodiment of the invention shown at FIGURE 5 regarding the exposure of the sheet stock base material 5 indicates that the sheet stock material is a thin substrate wrapped around the leather item 10 with a small surface area exposed to the outside environment. This design construction could be altered to increase the volume ratio of exposed sheet stock base 5 in relation to the inside surface area.
  • the moisture transpiration volume in the "x-y" length and width plane or direction is related to the density of the sheet stock base 5. For example, a .061 inch thickness of sheet stock base material 5 tested with a standard MVTR cup test transpires 1.61 grams of moisture per hour. The same product compressed during processing to .049 inch thickness transpires .335 grams of moisture per hour. This shows that a 20% reduction in thickness reduced the transpiration rate approximately 80%.
  • FIGURE 8 shows a lightweight sheet stock of formed urethane polymer foam composite 50 prepared during formulation of the formed urethane polymer foam composition by knife coating the polymerizing mixture onto the bottom release paper and " in si tu" bonding of the cover fabric to the polymerizing mixture to provide the formed product.
  • the lightweight sheet stock of formed urethane polymer foam composite 50 has generally uniformly dispersed through the strands 51 and filament 52 of the material for the formed foam composite 50 particles of superabsorbent polymer as at 53.
  • the cover fabric 54 is bonded or connected to the upper face of the formed foam composite 50 during the formulation and polymerization as above described.
  • Another layer of woven or non-woven material or synthetic material 55 may be bonded, connected, laminated or adhered to the lower face of the formed foam composite 50.
  • FIGURE 9 A still further embodiment of the present invention is shown at FIGURE 9 which differs from FIGURE 8 only to the extent that the cover fabric 54 is adhesively bonded to the upper face of the formed foam composite 50 by any suitable types of adhesive generally designated 56 as may be required for a given application and use.
  • FIGURES 10A and 10B for footwear generally designated 60, made of any conventional natural or synthetic materials having an upper section 61 and a sole section 62 connected to each other to define a foot receiving space 63.
  • An access opening 63a communicates with the foot receiving space 63, and a collar 64 is formed about the access opening.
  • the upper section 61 is split by a tongue member 65 so that when the upper section 61 is folded into assembled position over the tongue section 65, the side edge as at 61a of the upper section communicates with the ambient atmosphere at the exterior of the shoe 60.
  • the multi-layered liner 66 including at least one layer of the sheet stock base 5 as above described and shown at FIGURES 3, 4, 5, 6 and 7, is affixed to the inner surface of the upper section 61 by any suitable means such as the permeable adhesive as above described and/or by stitching not shown.
  • the multi-layered product with the formed hydrophilic urethane foam composite such as that shown at FIGURE 8B, includes the layer of formed foam composite 5, which has an open side edge 5a, and a suitable sock lining layer as at 67 which is in contact with the foot of the user when the footwear is in use.
  • the multi-layered liner 66 is so affixed or adhered by the adhesive 68 to the interior surface 61a of the leather or leather-like material of the upper section 61 that it extends over the tongue section 65 and collar 64 of the footwear 60 so that the side edge 5a and the sock lining layer 67 communicate with the ambient air exterior of the footwear 60.
  • the ambient air will also enter the footwear through the side edge of the formed foam composite layer or liner 66 and the sock lining layer 67 to replace the evaporating moisture, thus acting to enhance the MVTR and the breathability of the footwear, transporting the collected moisture and stagnant air from the interior of the footwear and replacing it with ambient air to cool the interior of the footwear and make it more comfortable for the user.
  • FIGURES 11, 12 and 13 are further diagrammatic sketches of another type of footwear showing the upper section 71 made of leather and a sole section 72 which define the foot receiving space 73 having a foot entry edge 73a and a tongue area 71a.
  • Attached, or lining the inner face of the upper section 71 is a multi-layered formed urethane polymer foam product generally designated 74 in accordance with the present invention which includes the formed urethane polymer foam composite 75 formulated as above described.
  • the multi-layered formed foam product 74 is affixed utilizing a suitable adhesive and so disposed relative the inner surface of the shoe that it forms a first collar generally designated 74a about 'the tongue area and a second collar 74b about the foot entry edge 73a on the footwear 70.
  • the multi-layered formed foam product 74 in accordance with the present invention enables the microenvironment in the denser and higher humidity section of the shoe having droplets of collected moisture and moisture vapor to communicate with a less dense and lower humidity area at the exterior of the footwear 70, and for the reasons above set forth with respect to the formed hydrophilic urethane polymer foam composite, moisture transpiration occurs therethrough to improve the comfort conditions in the microenvironment in the foot receiving space 73 of the footwear 70.
  • FIGURE 14 shows a cross-section through a fragment of a shaped, sized and multi-layered embodiment of a product generally designated 80 which has a woven cover fabric layer 81 having its outer face 81a in communication with the denser high humidity area of the collected moisture and water vapor in the microenvironment of, for example, a shoe, as shown in FIGURES 10A and 11.
  • the inner face 81b of the cover fabric 81 is bonded, laminated or adhered to the adjacent face 82a matrix of the second layer of formed hydrophilic urethane polymer foam composite 82 formulated in accordance with the various formulations as described herein and as illustrated in the examples which follow below.
  • this second layer 82 of formed foam composite illustrated has been formulated with a humectant additive such as glycerin to enhance moisture transpiration.
  • FIGURE 14 shows that on the opposite face or side 82b of the matrix layer of formed foam composite 82 a third non- woven or woven layer 83 of natural or synthetic material also has its inner face 83a bonded, laminated or adhered to said opposite face or side 82b of the matrix of the formed foam composite 82.
  • the opposite or outer faces 83b of said third layer 83 of material is in communication with an area of less dense or lower humidity such as the atmosphere.
  • the matrix layer of the formed hydrophilic urethane polymer foam composite acts to draw and absorb the collected water so that it moves transversely through the first fabric cover layer 80 from the area of denser and higher humidity or collected water to the area of less dense or lower humidity of the matrix layer of formed foam composite 82 and the third layer 83 of natural or synthetic material.
  • the flow through the first cover layer 81 of a droplet DW of the collected moisture is relatively high.
  • the diameter of a droplet expands to almost twice its diameter as the droplet moves into the adjacent face 82a of the second layer of formed foam composite in accordance with the present invention.
  • the strands and filaments in the matrix layer 82 of the formed hydrophilic urethane polymer foam composite, having the superabsorbent polymer integrally and generally uniformed dispersed in, on and through the strands and filaments being hydrophilic act to draw and absorb the droplet DW of water and cause it to transpire through this first fabric cover layer from the area of denser and higher humidity to the area of lower humidity represented by the matrix layer of the formed foam composite 82 and the third layer 83 of natural or synthetic material .
  • Transpiration namely movement, occurs either due to differential pressure or capillarity.
  • Capillarity is a function of the size and shape of the interstitial gaps and air spaces in the matrix of the formed foam composite.
  • the size and shape of the interstitial gaps and air spaces in the matrix of the formed foam composite is adjusted by the volume of surfactant in the aqueous mixtures used during polymerization in the formation of the hydrophilic urethane polymer foam composites in accordance with the present invention, as above described.
  • An aqueous phase was prepared by admixing in order of addition:
  • the aqueous phase was then added to and mixed with 33% by weight of Dow Chemical Hypol Prepolymer.
  • the mixed composition was cast onto a silicone release paper and covered with a second piece of same.
  • the thickness of the resultant foam reaction was controlled by shims and a top cover plate clamped to the table. After rise and cure approximately 8 minutes, the foam composite was removed and dried in an oven. The foam component was then laminated to K2 fabric supplied by Hub Fabric with heat-activated web adhesive from Bostic.
  • aqueous phase was prepared as in EXAMPLE 1 above comprising: Pluronic (BASF) F88 1% solution 37.88%
  • the aqueous phase was added to and mixed with 27.5% Prepolymer as above.
  • the mix was poured between shims onto release paper as in EXAMPLE 1, and prior to foam rise a 2.5 oz./sq. yd. polyester non-woven fiber from Carr-Lee 1/4 thick was placed onto the liquid mix.
  • a piece of release paper was then added to the top of the rising foam, non-woven, combination.
  • the shim's thickness, in this example were 1/8 in thickness which compressed the 1/4 non-woven fiber, conforming it to the 1/8 thickness desired of the final composite during the clamping and curing. This composite is shown in FIGURES 3, 4, 5, 6 and 7. It is well known to those skilled in the art that variations of cell size, hydrophilicity, water retention and water wicking can be adjusted by means of varied surfactants, absorbents and/or fillers added to the aqueous phase such as :
  • the aqueous phase was mixed with Dow Chemical Hypol at a ratio of 1:1 parts by weight.
  • the mix was cast onto a leather skin, covered with a release paper, and thickness was sized by shims. After curing and drying, a fabric layer was heat laminated with a web adhesive.
  • This process differs from the product as shown in FIGURE 5 by the elimination of covering fabric 9.
  • This process defines another embodiment showing the versatility of the invention.
  • the formulation change of EXAMPLE 3 versus EXAMPLE 2 lowered the foam density from 15.61 lb./cu. ft. to 10.91 lb./cu. ft., a reduction of over 9%.
  • a formulation as in EXAMPLE 3 was prepared and processed as in EXAMPLE 4.
  • the cover fabric was replaced with a second layer of release paper, allowing the foam only to be cured within the top and bottom paper. Upon full cure the top paper was removed and residual water was driven off in oven.
  • the resultant foam sheet of the invention could then be further processed by adhesively bonding it to the fabric, film or substrate of choice. See FIGURE 9.
  • the formulations, processes, products, materials and applications described above are shown to exemplify the major embodiments .
  • the present invention is a formed urethane polymer foam composite of lightweight flexible, moisture- retentive material adapted for use in multi-layered products, which will transpire moisture from a wet area to a dry area.
  • the principles, preferred embodiments, and modes of operation of the present invention have been described in the foregoing specification.
  • the invention which is intended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art, ' without departing from the spirit and scope of the invention as set forth in the appended claims which follow.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne un composite de mousse de polymère d'uréthanne hydrophile formée HF comprenant des particules (3) représentant jusqu'au 0,1 % en poids d'un polymère superabsorbant et sélectivement d'autres additifs. Ledit composite permet de déplacer l'humidité collectée dans une zone à humidité élevée vers une zone à humidité moins élevée comprenant une couche de mousse de polymère d'uréthanne formée dans une matrice dimensionnée et mise en forme. Ladite matrice comprend des brins (4) et des filaments (1) de polymère d'uréthanne interconnectés et des interstices et des espaces (2) dimensionnés et mis en forme, lesdites particules (3) de polymère superabsorbant étant dispersées dans les brins (4) et les filaments (1) interconnectés, sur ceux-ci ou à travers ceux-ci en une relation espacée et dans les interstices (2) dimensionnés en mis en forme afin de fournir une capillarité améliorée dans la matrice de mousse formée améliorant la transpiration. Des modes de réalisation multicouche comprennent au moins l'un des composites de mousse formée (5) enfin d'éliminer l'humidité collectée et de permettre l'évaporation de l'humidité provenant de la transpiration.
PCT/US2003/013997 2002-05-15 2003-05-05 Composite d'humidite et de transpiration et produits issus dudit composite WO2003097345A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2003243198A AU2003243198A1 (en) 2002-05-15 2003-05-05 Moisture transpiration composite and products therefrom
JP2004504718A JP4163682B2 (ja) 2002-05-15 2003-05-05 水分蒸散複合材料およびその製品
EP03752997A EP1562740A4 (fr) 2002-05-15 2003-05-05 Composite d'humidite et de transpiration et produits issus dudit composite

Applications Claiming Priority (2)

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US14623702A 2002-05-15 2002-05-15
US10/146,237 2002-05-15

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JP (1) JP4163682B2 (fr)
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WO2010083547A2 (fr) 2009-01-22 2010-07-29 Eurofoam Gmbh Élément alvéolaire contenant des matières hydrophiles
GB2468556A (en) * 2009-01-22 2010-09-15 Eurofoam Gmbh Foam element containing cellulose-II
CN106257468A (zh) * 2015-06-22 2016-12-28 波音公司 用于确定复合结构中的允许含水量的方法和系统
CN107130444A (zh) * 2017-06-12 2017-09-05 江苏豪赛科技股份有限公司 一种红外隐身仿生材料及其制备方法

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EP2027210A1 (fr) * 2006-05-22 2009-02-25 Basf Se Semelles de chaussure avec des propriétés absorbant l'eau
US8932678B2 (en) * 2012-06-18 2015-01-13 United States Gypsum Company Composition comprising superabsorbent polymer

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DE102010000116B4 (de) * 2009-01-22 2013-04-04 Eurofoam Gmbh Schaumstoffelement mit darin eingelagerter Zellulose und Verwendung desselben
GB2468556A (en) * 2009-01-22 2010-09-15 Eurofoam Gmbh Foam element containing cellulose-II
RU2480489C2 (ru) * 2009-01-22 2013-04-27 Юрофоум Гмбх Вспененный элемент с включенным в него гидрофильным агентом
GB2467225B (en) * 2009-01-22 2013-08-28 Eurofoam Gmbh Foam element with hydrophilic substances incorporated in it
GB2468556B (en) * 2009-01-22 2011-05-25 Eurofoam Gmbh Foam element with cellulose incorporated in it
ES2378806A1 (es) * 2009-01-22 2012-04-18 Eurofoam Gmbh Elemento de espuma con sustancias hidrófilas incorporadas en el mismo.
BE1019498A5 (fr) * 2009-01-22 2012-08-07 Eurofoam Gmbh Element en mousse dans lequel sont incorporees des substances hydrophiles.
GB2493099A (en) * 2009-01-22 2013-01-23 Eurofoam Gmbh Foam element with hydrophilic substances incorporated in it
WO2010083547A2 (fr) 2009-01-22 2010-07-29 Eurofoam Gmbh Élément alvéolaire contenant des matières hydrophiles
CN101791179A (zh) * 2009-01-22 2010-08-04 优若福姆有限公司 其中结合有亲水物质的泡沫元件
WO2010083547A3 (fr) * 2009-01-22 2011-01-27 Eurofoam Gmbh Élément alvéolaire contenant des matières hydrophiles
GB2493099B (en) * 2009-01-22 2013-09-25 Eurofoam Gmbh Foam element with hydrophilic substances incorporated in it
US8906497B2 (en) 2009-01-22 2014-12-09 Eurofoam Gmbh Foam element with hydrophilic substances incorporated in it
CN106257468A (zh) * 2015-06-22 2016-12-28 波音公司 用于确定复合结构中的允许含水量的方法和系统
US10983078B2 (en) 2015-06-22 2021-04-20 The Boeing Company Methods and systems for designing a composite structure
CN106257468B (zh) * 2015-06-22 2021-06-29 波音公司 用于确定复合结构中的允许含水量的方法和系统
CN107130444A (zh) * 2017-06-12 2017-09-05 江苏豪赛科技股份有限公司 一种红外隐身仿生材料及其制备方法
CN107130444B (zh) * 2017-06-12 2019-11-12 江苏豪赛科技股份有限公司 一种红外隐身仿生材料及其制备方法

Also Published As

Publication number Publication date
CN1665677A (zh) 2005-09-07
CN100371163C (zh) 2008-02-27
EP1562740A4 (fr) 2009-07-15
EP1562740A1 (fr) 2005-08-17
JP4163682B2 (ja) 2008-10-08
AU2003243198A1 (en) 2003-12-02
JP2005525455A (ja) 2005-08-25

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