EP1562740A1 - Moisture transpiration composite and products therefrom - Google Patents

Abstract

A formed hydrophilic urethane polymer foam composite HF with particles 3 up to 0.1% by weight of superabsorbent polymer and selectively other additives to enable collected moisture to move from an area of high humidity to an area of lower humidity, having a urethane polymer foam layer formed into a sized and shaped matrix, having interconnected strands 4 and filaments 1 of the urethane polymer and sized and shaped interstitial gaps and spaces 2, said particles 3 of superabsorbent polymer dispersed in, on and through said interconnected strands and filaments in spaced relationship and the sized and shaped interstitial air gaps 2 to provide improved capillarity in the formed foam matrix enhance transpiration and also multi-layered embodiments including at least one of said formed foam composites 5 to transpire collected moisture and enable evaporation of the transpired moisture.

Description

MOISTURE TRANSPIRATION COMPOSITE AND PRODUCTS THEREFROM CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Application No. 10/146,237 filed May 15, 2002 which is based on a provisional application for a United States patent entitled Footwear with Hydrophilic Foam Lining to Enhance Breathability under Application No. 60/293,335 filed on May 24, 2001, and this continuation-in-part will rely on these prior applications for all the benefits of the corresponding invention as shown, disclosed and claimed herein. BACKGROUND OF THE INVENTION

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 .

Manufacturers of body coverings such as apparel, shoes and the like strive to improve the comfort of their products to encourage the use of such products. It is a known fact that the human body responds negatively to high humidity in conjunction with elevated temperatures. ASHRAE provides a comfort index chart comparing temperature and humidity in relation to human comfort. The U.S. NAVAL FLIGHT SURGEONS MANUAL provides many papers on the effect of excessive heat in relation to physiological body changes for protective apparel, garments, shoes and other clothing. In most cases the problem is created by not allowing the human thermoregulatory system to function .

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. The more efficient the textiles, fabric or other material covering the human body is at allowing this water vapor to reach the ambient air, the more breathable the textiles, fabrics or other materials are considered to be. Thus, 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 . Breathability of conventional textiles and other materials designed specifically for the purposes intended in the present invention is regarded as acceptable when tests of the Moisture Vapor Transmission Rate (MVTR) is in the approximate range of 600 to 4,000 gms/sq. meter/24 hrs . @ 40°C.

Prior art in this water vapor aspect of the field of the present invention is plentiful, and a good compilation can be found in the patents teaching absorbency, water vapor transmission, wicking to remove condensed vapor, membranes and the technology to improve the comfort zone in clothing and footwear. For example, reference is made to U.S. Patent Nos. 5,128,082; 5,260,345 and 5,331,728.

However, one of the continuing problems attaching to body coverings such as suits, dresses, shoes, helmets and other apparel or appliances, accessories, backpacks etc. is providing devices and methods to overcome heat-generated moisture, namely, the above-mentioned condensed water droplets and stagnant air which collect in the microenvironment created by the enumerated body coverings. These problems cause both discomfort and act as a breeding ground for bacteria and create various physical ailments. Thus, many devices, methods and technology for body coverings such as suits, dresses, shoes, helmets and other apparel, appliances and accessories have been tried to improve breathability, namely, to establish sufficient circulation, transpiration or migration to enable the entrapped moisture, i.e., the condensed droplets of moisture, the water vapor and stagnant air to move from the interior microenvironment formed by such body coverings, appliances and accessories to the ambient air exterior of the body covering and to enable the ambient air to move from the exterior into the microenvironment at the interior formed by such body coverings to replace the moisture, water vapor and stagnant air so as to cool and improve the comfort and increase the durability of such body coverings .

For example, 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 . In the present invention, 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.

In addition to the improved absorbency and transpiration characteristic of the formed hydrophilic urethane polymer foam composites and products in accordance with the present invention, 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. Effectively, this means that the formed foam materials and products in accordance with the present invention will remove five (5) times the amount of moisture from a confined space or microenvironment to an area of lower humidity for evaporation such as in a shoe, helmet, jacket, glove or under a shoulder pad, kneepad or strap of a backpack, thus overcoming the discomfort caused by this condition and improving the comfort and use of these body coverings. In addition, it has been found that this improved formed foam composite materially reduces or eliminates bacterial build-up and obnoxious odors SUMMARY OF THE INVENTION

Thus, in one aspect 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 comprising, at least one urethane polymer foam layer formed into a sized and shaped matrix, said matrix having interconnected strands, and filaments and interstitial gaps or spaces in the formed urethane polymer, particles of up to 0.1% of said at least one superabsorbent polymer generally dispersed in sufficient spaced relationship in, on and through said interconnected strands, filaments, and interstitial gaps and spaces, sized and randomly spaced, to enhance absorbency and transpiration of the collected moisture from an area of high humidity to an area of lower humidity, and said formed urethane foam layer so connected to said area of lower humidity to enable the absorbed and collected moisture to evaporate from said matrix to the surrounding ambient atmosphere.

It is another aspect of the present invention to provide a formed hydrophilic urethane polymer foam composite and products such as sheet stock of varying thicknesses as above described with particles of at least one super absorbent polymer homogenously distributed therein and ratioed to avoid gel blocking in the formed composite and products but adapted to permit maximum moisture transpiration by utilizing one or more additives from the following group: 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 selectively minor quantities of a color, bactericide and fragrance.

It is another aspect of the present invention to provide multi-layered products having various combinations of fabrics, films and other substrates for attachment to the formed hydrophilic urethane polymer foam composites such as sheet stock of varying thicknesses with particles of at least one super absorbent polymer homogenously distributed therein and ratioed to avoid get blocking, but adapted to permit maximum moisture transpiration along the longitudinal length x axis and width y axis of the formed composite and multi-layer products including such formed hydrophilic urethane foam composite as above described.

It is another aspect of the present invention to provide multi-layered products having various combinations of fabrics, films and other substrates for attachment to the formed hydrophilic urethane polymer foam composites such as sheet stocks of varying thicknesses as above described in which moisture is prevented from passing through the multi-layered product in the transverse or z direction, at right angles, to the longitudinal line of the multi-layered product by bonding or adhesively affixing a non-permeable moisture-proof film to one side of the multi-layered product.

It is another aspect of the present invention to provide multi-layered products having various combinations of fabrics, films and other substrates for attachment to the formed hydrophilic urethane polymer foam composites such as sheet stocks of varying thicknesses as above described in which moisture is optionally and selectively allowed or prevented from passing through the multi-layered product in the transverse or z direction, at right angles, to the longitudinal line of the multi-layered product by bonding or adhesively affixing a non-permeable moisture-proof film to one side of the multi-layered product.

In another aspect, 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.

It is another aspect of the present invention to provide footwear which has a liner or one of the multi-layered combinations as above described having at least one layer of formed hydrophilic urethane polymer foam composite in accordance with the present invention containing particles of up to 0.1% of superabsorbent polymer which is so connected in the footwear that it allows the exchange of collected moisture, water vapor and stagnant air from the microenvironment of the interior of the footwear with ambient air exterior of the footwear to enhance the breathability of the footwear and results in lower humidity, lower heat in the microenvironment in the footwear and provides greater overall comfort for the user of the footwear.

It is another aspect of the present invention to provide footwear made of waterproof materials with moisture- permeable membranes therein which has a liner or one of the multi-layered combinations as above described having at least one layer of formed hydrophilic urethane polymer foam composite in accordance with the present invention containing particles of up to 0.1% of superabsorbent polymer which is so connected in the footwear that it allows the exchange of collected moisture, water vapor and stagnant air from the microenvironment of the interior of the footwear with ambient air exterior of the footwear to enhance the breathability of the footwear and results in lower humidity, lower heat in the microenvironment in the footwear and provides greater overall comfort for the user of the footwear.

It is another aspect of the present invention to provide footwear which has a liner or one of the multi-layered combinations as above described made of a formed hydrophilic urethane polymer foam composite having particles of up to 0.1% of superabsorbent polymer which is so connected in the footwear that it allows the exchange of collected moisture, water vapor and stagnant air from the microenvironment of the interior of the footwear with ambient air exterior of the footwear to enhance the breathability of the footwear that can be manufactured by conventional techniques, and when the liner or multi-layer product is applied to the footwear, it does not require changes in shapes, styles of the footwear and can be applied to all types of everyday sports and dress footwear.

It is still another aspect of the present invention to provide footwear having waterproof moisture-permeable membranes therein and a liner or one of the multi-layered combination products as above described made of formed hydrophilic foam composite with particles of up to 0.1% of superabsorbent polymer, which liner or multi-layered combination product is so connected in the footwear that it enhances the inherent Moisture Vapor Transmission Rate (MVTR) to allow a substantial increase in the exchange of collected moisture, water vapor and stagnant air from the microenvironment of the interior of the footwear with the air in the ambient atmosphere exterior of the footwear to provide lower humidity and lower heat in the microenvironment formed in the footwear and greater overall comfort for the user. BRIEF DESCRIPTION OF THE DRAWINGS 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 „_-_---,

PCT/US03/13997

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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 11.

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. DETAILED DESCRIPTION

In order to achieve the advantageous results of the present invention, it is necessary to formulate an aqueous mixture polymerized to provide a formed foam layer or shaped composite in which the matrix of the formed foam composite will have a high moisture vapor transmission rate to enable generated moisture, that is, droplets of condensed water vapor that collect in the microenvironment created by the enumerated body coverings, to move physically from a wet location namely, the area of high humidity in the created microenvironment to an area of lower humidity and then to a location to allow for evaporation to eliminate said moisture. 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, helmets, etc.

This method or process for making formed foam urethane polymer layers of material is described in U.S. Patents 5,763,335 and 6,025,287 and other patents, and is well known to those skilled in the art and accordingly will not be more fully described.

However, 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.

Further, however, 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. Thus, 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.

In addition to the improved transpiration and evaporation obtained by the improved formed foam composite in accordance with the present invention, it has been found that 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 .

In the conventional batch mixing process for the formulation of the formed hydrophilic urethane polymer foam composites in accordance with the present invention, 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. In such superabsorbent polymers, 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.

Conventional sorbents including humectants in contrast to the superabsorbents take up liquids by mainly physical means and will give it back with the slightest stress or pressure. Consequently, 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.

Important, however, to obtaining this functional aspect and advantageous result of the present invention for the improved formed foam composites is that the quantity of superabsorbent polymer used in the aqueous mixture during formulation must, as above indicated, be limited. In this regard 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. Where a small size gap or open cell is desired, two percent (2%) by weight of PLURONIC L 62 was used in the aqueous mixture. Where a large size gap or open cell was desired, five percent (5%) by weight of PLURONIC F88 was used in the aqueous mixture. Similarly, 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. Frisch published by John Wiley & Sons, New York, N.Y. at Vol. XVI Part 2. High Polymer Series. "Foam Systems" pages 7-26 and "Procedures for the Preparation of Polymers" pages 26 et seq. One preferred hydrophilic urethane prepolymer for use in the present invention is sold under the trademark BIPOL 6 by Mace Adhesives and Coatings, another under the trademark HYPOL sold by the Dow Chemical Company, and another under the trademark PREPOL sold by Lendall Manufacturing Incorporated. These prepolymers are suitable for use in the present invention because of their strong hydrophilic characteristics, reasonable cost and equilibrius moisture content of 5-45% moisture at 50% to 90% relative humidity.

In the formation of multi-layered products having a base layer of hydrophilic urethane polymer foam composite with a cover layer and others layers of material; such 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. Such 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. Further, the 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. When 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.

Referring to the drawings, 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. Thus, as shown, 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. Those skilled in the art would consider such formed foam composite HF as an open-celled foam material. Further, and significant to the present invention, these figure show that there are bonded to or within the strands and filaments 1 particles of up to 0.1% of superabsorbent polymer generally designated 3.

The superabsorbent polymer particles 3 as shown in FIGURES 1 and 2 of the drawings, during formulation and processing of the ingredients as above described to provide the improved formed foam composite HF, are disposed in spaced relation to each other. 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.

Conventional urethane polymer prior art foam also suffers from migration, non-homogeneity and collapse when wetted. The instant invention, wherein the superabsorbent polymer is immobilized within the interconnected strands, filaments and interstitial gaps or air spaces in the matrix of the formed hydrophilic urethane foam composite, as shown in FIGURES 1 and 2 allows moisture transpiration along the strands and filaments from one particle to the next particle of superabsorbent polymer and prevents the collapse of the matrix of the formed foam composite.

While this does not enhance transpiration, it increases the saturation of the collected moisture being absorbed, and due to the increased saturation of the droplets of the collected moisture in the formed foam matrix, transpiration or flow from the area of high humidity to an area of lower humidity occurs by differential pressure. 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 and 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. In the formulation and processing of this embodiment, 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. Thus, when the formed hydrophilic urethane polymer foam composite is made, 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. Thus, in the two layer embodiment of the present invention shown in FIGURE 4 of the drawings, there is the formed layer of hydrophilic urethane polymer foam composite, sheet stock 5 of varying thicknesses and densities as described for the embodiment of the invention shown in the fragmentary cross-section at FIGURE 3. This is obtained from varying ratios of hydrophilic urethane prepolymer, water, up to 0.1% of superabsorbent polymer, up to 70% of humectant, sufficient surfactant as a function of the desired application and a fibrous web or cut fiber materials . In order to meet the frictional, aesthetic and other conditions that applications or usage may require, 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.

Where 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.

In the multi-layer embodiments of the present invention another product is shown in FIGURE 5 of the drawings. Once again, the formed composite layer of hydrophilic urethane polymer foam, sheet stock 5 of varying thicknesses and densities described for the embodiment of the invention shown in the fragmentary cross-section at FIGURE 3. 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. Then, 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. Similarly affixed by any suitable means to another of the surfaces of the formed foam composite layer 5 is a waterproof hydrophobic covering fabric 9.

In this embodiment, 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. If the leather or leather like material is waterproof, the waterproof covering fabric layer may be eliminated.

Similarly, in the embodiment shown at FIGURE 6 of the drawings, 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. Thus, on the moisture contacting surface, 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.

In some cases, 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. In this case, 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 .

Various combinations of fabrics, films and other substrates can be attached to the formed urethane polymer foam composite 5. For example, another embodiment of the invention may require that the formed foam composite 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 leather upper 10, as shown in FIGURE 5, was then bonded to the waterproof film side of the leather upper 10. 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. In operations, 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 .

In 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. 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. On the side 5a of the formed foam composite remote from the cover fabric layer 11, 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 .

In operation and use, 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.

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.

Similarly, flame lamination to connect the cover sheet or other layer of material to the layer of the base stock sheet 5 of the formed urethane polymer foam components is also well 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. In cases where the adhesive wants to bond to a cover material and to also pass moisture through the adhesive, it has been found that 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. With 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.

Conventional urethane strands and fibers described as hydrophilic allow water transpiration only along the surface of such strands and fibers or by means of capillarity.

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%. Another multi-shaped embodiment of the present invention at 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.

Thus, 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.

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.

Another embodiment of the present invention is shown at 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. When the footwear is in use, this enables the collected moisture in the foam layer of the liner or multi-layered liner 26 to move or transpire from the interior of the footwear 20 through both the open side edge 5a and the sock lining layer into the ambient air exterior of the shoe. Thus, a more efficient mechanism is provided for the Moisture Vapor Transmission Rate (MVTR) not only along the x-y axis or the longitudinal line of the foam layer, but also transversely through the sock-lining layer of the liner 66. Further, 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.

Testing of the above described shoe lined with multi- layered products or liners with the formed foam composite as shown in FIGURES 3, 4, 5, 6 and 7 and above described was done against a conventional shoe of the same type, utilizing a male subject thirty (30) years of age walking on a treadmill for two (2) forty-five (45) minute sessions with a fifteen (15) minute rest between sessions. Air temperature and humidity readings were monitored inside the shoes simultaneously, and the Perceived Comfort Index (PCI) was determined by means of ASHRE data. The results are provided below in TABLE 1.

TABLE 1

Shoe with Formed Foam Conventional Shoe Composite Liner Test Temp. Deg. F 80 79.2

Cycle 1 Rel. Humidity 74 62

PCI 83 81

Test Temp. Deg. F 81.91 78.2 Cycle 2 Rel. Humidity 77 73

PCI 88 80

It was concluded from this test that a shoe construction having such multi-layered products or liners with a formed foam composite in accordance with the present invention reduces relative humidity in the microenvironment of the foot space in the shoe and significantly effects the Perceived Comfort Index (PCI) . The reduction of the PCI is more significant with higher temperatures, as seen by comparing Test Cycle 1 and Test Cycle 2. Perceived Comfort Index is how a person interprets the combination of heat with elevated humidity. In the temperature ranges within a shoe, the lower the PCI, the more comfortable the person feels . 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. Thus, 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. In order to better understand the improved moisture transpiration by the formed foam composite in accordance with the present invention, 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. In particular, 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.

Although the outer face 81a of the cover layer of fabric 81 is located in an area where the collected moisture and water vapor is the greatest and at the higher humidity, 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.

Referring further to FIGURE 14, the flow through the first cover layer 81 of a droplet DW of the collected moisture is relatively high. Thus, 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 .

The mere abundance of collected moisture does not enhance the transpiration of the droplet DW of water because collected moisture does not add energy to the existing ambient conditions .

The movement of the droplet through the matrix of the formed form composite layer 82 reduces slightly and then increases materially as it transpires through the third layer

83 of the natural and synthetic material and evaporates into the less dense and lower humidity of the adjacent atmosphere.

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.

The following examples are given as specific illustrations of the invention. It should be understood, however, that the invention is not limited to the specific details set forth in the examples . All parts and percentages in the examples, as well as in the remainder of the specification, are by weight unless otherwise specified. EXAMPLE 1

An aqueous phase was prepared by admixing in order of addition:

Pluronic (BASF) F88 .3% solution 93.36%

Foley Fluff (Buckeye Cellulose) 1.54 Glycerine (Emery 916) 3.07

Pluronic (BASF) L62 1.29 Superabsorbent (Stockhausen AP 80-HS) 0.10

Guar Gum (Alpha-Chem) 0.64

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. EXAMPLE 2

An aqueous phase was prepared as in EXAMPLE 1 above comprising: Pluronic (BASF) F88 1% solution 37.88%

Calcium Carbonate (Noah Technologies) 54.43

Glycerine (Emery 916) 7.59

Superabsorbent (Stockhausen AP 80-HS) 0.1

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 :

Surfactants Absorbents Fillers Non-Ionic Polyethylene Oxide Cut Man-Made Fibers

Ionic Polyvinylpyrrolidone Minerals

Amphoteric Clays Cellulosic Fiber TESTING Prior art shoe liner material described as Cambrelle liner on Duratex Foam was subjected to Moisture Vapor Transmission Rate (MVTR) test per recognized Quality Assurance Procedure. Product made in accordance with the present invention surpassed the industry standard of 600 to 4,000 grams of water per sq. meter per 24 hours @ 40°C. Results shown in Table 1 represent the lengthwise x direction and widthwise y direction along the longitudinal plane of the layer of formed hydrophilic urethane polymer foam composite, and Table 2 shows the transverse or z direction perpendicular to this longitudinal plane. It was discovered that lower density and thinner samples exemplified in the preferred formulation, EXAMPLE 2, also surpassed the prior art MVTR. TABLE 1 x-y Direction Cambrelle/Duratex Invention % Improved

MVTR G/m. sq./24 hr . 5056 10696 112

TABLE 2 z Direction 4018 5897 47 EXAMPLE 3

To lower the density of foam composite described in EXAMPLE 2, a variation in formula was prepared comprising:

Pluronic (BASF) F88 1% solution 89.11%

Sodium Bicarbonate (Arm-Hammer) .90 Glycerine (Emery 916) 9.99

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%. EXAMPLE 4

The formula as in EXAMPLE 3 was prepared and dispensed onto release paper. The paper was then drawn through a knife opening of .005-.375 leaving a continuous film thickness of foam superabsorbent on paper. The paper was further advanced until the foaming reaction had risen, yet was still tacky. A cover fabric K2 Hub Fabric was then laid onto the tacking surface wherein it bonded to the urethane without bleeding through. EXAMPLE 5

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.

Claims

1. Formed hydrophilic urethane polymer foam composite comprising limited amounts of at least one absorbent from the group of polyethylene oxide, polyvinyl pirrolidone, superabsorbent polymers and humectants, at least one surfactant, and optionally and selectively additives to enhance moisture transpiration from an environment of dense and high humidity to an area of less dense and lower humidity.

2. Formed hydrophilic urethane foam composite having a defined matrix of interconnected strands, filaments and interstitial gaps and spaces formulated to optimize moisture retention and transpiration therethrough from an environment of denser and higher humidity to an area of less dense and lower humidity from the reaction products comprising: a. an aqueous phase including the required water, a limited amount of at least one absorbent from the group polyethylene oxide, polyvinyl pirrolidone, superabsorbent polymers and humectants with a hydrophilic urethane prepolymer; b. said aqueous phase also including optionally and selectively at least one anionic, cationic, amphoteric and swittering surfactant; and c. optionally and selectively additives from the group of fillers, woven, non-woven cut fiber materials, coloring, antibacterials and fragrances.

3. The formed hydrophilic urethane polymer foam composite as in claims 1 or 2 wherein the filler material is from the group of wollastonite, feldspar, calcium carbonate and sodium bicarbonate.

4. The formed hydrophilic urethane polymer foam composite as in claims 1 or 2 wherein the fiber material is from the group of cellulose, polyester and glass.

5. The formed hydrophilic urethane polymer foam composite as in claims 1 or 2 wherein the filler materials are from the group of wallastonite, feldspar, calcium carbonate and sodium bicarbonate, and the fiber materials are from the group of celluloses, polyesters and glass.

6. The hydrophilic urethane polymer composite as in claim 1 wherein the moisture vapor transmission rate is in a range from 600 to 20,000 gms/sq. meter/24 hrs . @ 40°C.

7. The formed hydrophilic urethane polymer as in claim 2, wherein: a. the absorbent is in particle form up to 0.1% by weight and is integrally and generally uniformly dispersed in, on and through the strands, filaments and interstitial gaps and spaces of the matrix; and b. said interstitial gaps and spaces sized and shaped to enhance moisture absorption and transpiration in said formed foam composite.

8. The formed hydrophilic urethane polymer foam composite as in claims 1 or 2 having a covering fabric material bonded on at least one surface of the matrix to readily pass moisture therethrough without absorbing said moisture.

9. The formed hydrophilic urethane polymer foam composite and covering fabric material as in claim 8 wherein the covering fabric material is bonded using a moisture- permeable adhesive and said adhesive from the group of heat- activated web adhesives, dot matrix adhesives and flame lamination adhesives.

10. The formed hydrophilic urethane foam composite and covering fabric material as in claim 9 having at least one further surface remote from the covering fabric bonded to another layer of material from the group films and membrane fabrics to impede the transpiration of collected moisture to the side of the formed foam composite adjacent to an area of low humidity.

11. The multi-layer hydrophilic urethane foam product as in claim 8 wherein the at least one formed urethane foam layer has a moisture vapor transmission rate in a range from 600 to 20,000 gms/sq. meter/24 hrs. @ 40°C.

12. 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 for collected moisture, said upper section having a multi-layered hydrophilic urethane polymer foam product containing particles up to 0.1% by weight of at least one absorbent and wherein the multi-layered product communicates with ambient air outside the footwear to enhance breathability and lower humidity in the footwear.

13. The footwear of claim 12, wherein the formed hydrophilic urethane polymer foam multi-layered product on the upper section comprises at least one hydrophilic urethane polymer foam composite through which the multi-layered product communicates between the microenvironment in the footwear and the ambient atmosphere at the exterior of said footwear, and said multi-layered product includes a cover in communication with said microenvironment in said footwear which is moisture- permeable.

14. The footwear of claim 13, wherein the multi- layered product is so affixed to the upper section that the collected moisture and the ambient air both travel longitudinally along the composite layer and transversely through the moisture-permeable area of the cover fabric so that the collected moisture is replaced by ambient air.

15. The footwear of claim 13, wherein the upper section has an upper edge about the space for the user's foot disposed for communication with the ambient atmosphere exterior of the footwear, and the multi-layered hydrophilic urethane polymer product is connected alternatively and selectively about said upper edge so that the open side edges of the at least one hydrophilic urethane polymer foam composite therein communicates between the microenvironment in the footwear and the ambient atmosphere at the exterior of said footwear, and said multi-layered product includes a cover fabric layer in communication with said microenvironment in said footwear which is moisture-permeable.

16. The footwear of claim 13, wherein the upper section has a tongue member formed integrally therewith and designed to communicate with the ambient atmosphere exterior of the footwear, and the multi-layered hydrophilic urethane polymer product is connected alternatively and selectively to at least the inner surface of the tongue member so that the open side edges communicate with the exterior of the footwear to permit collected moisture to flow from the microenvironment in said footwear and ambient air to enter the footwear through said foam material.