CN100371163C - 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

The rising composite of moisture and by the product of its production

The mutual reference of related application

The application is that the part of the U. S. application 10/146237 of application on May 15th, 2002 continues; this U. S. application 10/146237 is " have the hydrophilic foam lining to improve the footwear boots (Footwear with Hydrophilic Foam Lining to Enhance Breathability) of gas permeability " with title; application number is 60/293335; the applying date is that the United States Patent (USP) provisional application in May 24 calendar year 2001 is the basis; and for shown here; the ownership equity of disclosed and corresponding invention required for protection, this part continuation application will depend on these existing applications.

Background technology

The present invention briefly relates to and is used to improve the materials and methods that moves that textile and other products are passed in the water vapour migration, with the moisture in the confined space that relates more specifically to come free body cover (body covering) to form as coat, clothes, footwear, the helmet, cap, other clothes, utensil and accessory, especially laterally moving or rising (transpiration) and remove of body fluid, wherein the removing the humidity that provides lower, lower temperature and improve the zone of comfort of this body cover inside of the moisture that generates such as sweat.

The manufacturer of body cover such as clothes, footwear etc. makes great efforts to improve its product comfort level, to encourage to use these products.The known fact is the human body pair high humility negative response relevant with high temperature.ASHRAE provides comfort index figure, and it has compared the temperature and humidity relevant with the human comfort degree.It is many about change the paper to the influence of excessive heat because of physiology health that protective garment, coat, footwear and other cloth produced that U.S.NAVAL FLIGHT SURGEONS MANUAL provides.As a rule, working has problems because of not allowing human humidity control system (thermoregulatory system).

The normal temperature control method of human body is realized with perspiring when feeling that temperature raises.Then, normal evaporation makes sweat change into water vapour, and this conversion is consumption of calorie and make the health cooling conversely.Minimizing of evaporation makes this method lose effect, and outside above-mentioned thermal comfort exponent data, most of people feel uncomfortable.By relatively among the hot day that causes because of the environment temperature that raises and high humility and have the sensation of human body in uniform temp and low humidity one day, can understand the operation of the normal temperature control method of human body best.

Under the situation that the somatosensory temperature raises, any body cover such as coat, clothes, footwear, the helmet or other clothes or utensil can influence the generation and the evaporation of sweat.The domestic perspiration of any finite ring that reaches dew point within it will reduce.As understood by one of ordinary skill in the art, dew point be the domestic air of finite ring by water vapour the saturated and point of moisture when this finite ring condenses from the air with the water droplet form within the border.Cover health and skin at the restrictive material with body cover and limited or minimized and perspire and evaporation, same situation can be in clothes, footwear or the helmet of generation confined space or microenvironment that link to each other with health, occur in knapsack or the utensil.Minimizing uncomfortable effort in the microenvironment comprises and improves air-flow, makes the film that water vapour passes through, siphon, phase-transition material and other technology of accumulation moisture.

The ability that can make the water vapour (this condensing drip with moisture is different) that overflows from health arrive the employed textile of ambient air, fabric or other material is to assess the key factor of comfort levels such as above-mentioned body cover such as coat, footwear, the helmet, utensil, accessory.The textile, fabric or other material that cover human body allow the efficient of this water vapour arrival surrounding air high more, think that then the gas permeability of textile, fabric or other material is good more.Therefore, the term in textile " gas permeability " is that measuring of textile, fabric or other material passed in water vapour migration, rather than the measuring of its air permeability or windproof feature.When under 40 ℃, (Moisture Vapor Transmission Rate, MVTR) test is at 600-4000g/m for the moisture vapour transmission rate ²In the time of in the approximate range of/24h, the gas permeability of specially designed conventional textile and other material is considered to and can accepts for the desired purpose of the present invention.

Aspect this water vapour in field of the present invention a large amount of prior aries are being arranged, and can collect well in patent about following instruction: trap, steam breathability, siphon are to remove the technology of condensed steam, film and the improvement zone of comfort in clothes and footwear boots (footwear).For example, can be with reference to United States Patent(USP) Nos. 5128082,5260345 and 5331728.

Yet, one of lasting problem that is associated with body cover such as coat, clothes, footwear, the helmet and other clothes or utensil, accessory, knapsack etc. provides apparatus and method to overcome the moisture that generates because of heat, that is, water droplet with above-mentioned condensation (condesend water) and the air entrapment in the microenvironment that produces by cited body cover, collected.These problems all cause uncomfortable and serve as the breeding base of bacterium and produce various physical infirmities.

Therefore, many devices have been attempted, method and technology, improve body cover such as coat, clothes, footwear, the helmet and other clothes, the gas permeability of utensil and accessory, that is, set up circulation fully, transpiration or migration, can make the moisture of holding back, it is the condensing drip of moisture, water vapour and air entrapment are from by this body cover, move in the surrounding air of body cover outside in the inside microenvironment that utensil and accessory form and surrounding air is moved to from the outside the inside microenvironment that is formed by this body cover to replace moisture, the air of water vapour and delay is so that cooling and improve comfort level and increase the durability of this body cover.

For example, United States Patent (USP) 5763335 and 6025287 discloses the Hdyrophilic polyurethane foamed polymer with 0.6% super-absorbent polymer composite (superabsorbentpolymer) that is used to form stratiform lining material (layered lining material), and manufacture method, for collecting and rising water or moisture from microenvironment.Composite that discloses in these patents and stratiform lining material absorb moisture and convert it into gel in the stratiform lining materials, removing or opening body cover, utensil or accessory then, after under the environment around this microenvironment is exposed to, can make or allow the moisture evaporation of collecting in the gel.

In the present invention, the new prescription and the method for preparation hydrophilic polyurethane polymer foamed composite are disclosed, this hydrophilic polyurethane polymer foamed composite has limited amount super-absorbent polymer particles, surfactant and other additive optional and that select, and it is eliminated and prevents that the gel of described prior art patent `335 and `287 from forming or gel adhesion (gel blocking) and evaporation mechanism.Newly prescription and method are by modification like this and optimize the single thread (strand) of super-absorbent polymer particles in interconnection, on the long filament (filament), within and among orientation and the size and dimension of the air gap is realized between the crack of random distribution in shaping foam hydrophilic polyurethane polymer matrices of composite material, so that strengthen significantly on the length of shaping foam base plate or x direction and width or y direction moisture and/or water vapour transversely absorptivity and physics moves or rising, so that moisture and/or water vapour can move to the low humidity zone from high humidity regions, in described low humidity zone, can eliminate moisture and moist steam and institute satisfactorily by introducing colder atmospheric air displacement moisture and moist steam by evaporation.

According to the present invention, shaping hydrophilic polyurethane polymer foamed composite (formed hydrophiclicurethane polymer foam composite) and product are except having improved absorption and rising feature, when comparing with the material of the prior art of developing for same purpose, the surface condition of each layer of formed product and this material also keeps relatively dry.

According to the present invention, the conventionally test of the MVTR of improved shaping hydrophilic polyurethane polymer foamed composite and product is higher 5 times than the above-mentioned acceptable MVTR of this prior art material of developing for same purpose.Effectively, this means shaping foamed material of the present invention and product will be for example in footwear, the helmet, overcoat, gloves or under the braces of shoulder pad, kneepad or knapsack from the moisture that shifts out 5 times of amounts in the confined space or the microenvironment to zone than low humidity for evaporation, thereby overcome because of cause uncomfortable of this situation and improved the comfort level and the use of these body covers.In addition, find that this improved shaping foamed composite reduces or eliminate accumulation and the odour nuisance of bacterium significantly.

Summary of the invention

So, one aspect of the present invention contains shaping hydrophilic polyurethane polymer foamed composite and product, it has at least a super-absorbent polymer particles, the surfactant of capacity and selection and other optional additive, so that can make moisture from the zone of high humility move to than the zone of low humidity as around environment in, described composite and product comprise at least a polyether polyols with reduced unsaturation froth bed that forms the matrix of making by certain size and shape, described matrix has gap (interstitial gap) or space between the single thread of interconnection and long filament and crack in the polyether polyols with reduced unsaturation that is shaped, the usually abundant compartment of terrain of particle is dispersed in described interconnection single thread in maximum 0.1% the described at least a super-absorbent polymer, long filament and pressing between the crack of certain size manufacturing and random distribution within the gap and space, on and among, also rising in zone to improve collected moisture than low humidity from the zone absorption of high humility, so be connected in the described zone with described formed polyurethane froth bed, so that the moisture that can make institute absorb and collect is evaporated to the environment on every side from described matrix than low humidity.

The present invention provides above-mentioned shaping hydrophilic polyurethane polymer foamed composite and product on the other hand, sheet material blank (sheet stock) as all thickness, it has the particle that is evenly distributed in it and has at least a super-absorbent polymer with certain proportion, to avoid in formed composite material and the adhesion of product inner gel, but by using following one or more additives, adopt described formed composite material and product to allow maximum moisture transpiration, additive therefor is: anion, cation, both sexes and amphiphilic surfactant; Wetting agent such as glycerine; Solid packing such as wollastonite, feldspar, calcium carbonate, sodium acid carbonate; Fiber such as cellulose, polyester, glass fibre and optional and selectively micro-colouring agent, bactericide and spices.

The present invention provides multi-layered product on the other hand, it has the various combinations of fabric, film and other matrix, so that be connected to shaping hydrophilic polyurethane polymer foamed composite, on the sheet material blank as all thickness, described composite has the particle that is evenly distributed in it and has at least a super-absorbent polymer with certain proportion, avoiding the gel adhesion, but adopt described composite to allow along formed composite material and to comprise that the vertical x axle and the width y axle of the multi-layered product of above-mentioned this shaping Hdyrophilic polyurethane foamed composite have maximum moisture transpiration.

The present invention provides multi-layered product on the other hand, it has the various combinations of fabric, film and other matrix, so that be connected to above-mentioned shaping hydrophilic polyurethane polymer foamed composite, on the sheet material blank as all thickness, wherein by impermeable damp-proof membrane is bonding or be adhesively secured on the side of multi-layered product, prevent moisture with the vertical line of multi-layered product perpendicular laterally or z direction upper reaches cross multi-layered product.

The present invention provides multi-layered product on the other hand, it has the various combinations of fabric, film and other matrix, so that be connected to above-mentioned shaping hydrophilic polyurethane polymer foamed composite, on the sheet material blank as all thickness, wherein by impermeable damp-proof membrane is bonding or be adhesively secured on the side of multi-layered product, optional or selectively allow or prevent moisture with the vertical line of multi-layered product perpendicular laterally or on the z direction, flow through multi-layered product.

On the other hand, the invention still further relates to the footwear boots, described footwear boots comprise upper part and sole (sole) part, and wherein upper part and sole portion link together.Thereby determine the space of microenvironment for user's lower margin.Preferably, the upper part has one of above-mentioned multiple layer combination on inner surface, described multiple layer combination comprises one deck at least of one of the present invention ground shaping hydrophilic polyurethane polymer foamed composite of containing maximum 0.1% super-absorbent polymer particles, wherein the described shaping of one deck at least froth bed of liner (liner) or multi-layer gasket with than the zone of low humidity, as environment intercommunication in footwear boots outside.

The present invention provides the footwear boots on the other hand, described footwear boots have one of above-mentioned liner or multiple layer combination, one of described liner or multiple layer combination have be shaped one deck at least of hydrophilic polyurethane polymer foamed composite of the present invention who contains maximum 0.1% super-absorbent polymer particles, one of described liner or multiple layer combination so connect in the footwear boots, so that allow the moisture of collection, water vapour exchanges with the surrounding air of footwear boots outside mutually with the microenvironment of air entrapment from footwear boots inside, to produce lower humidity in the gas permeability that improves the footwear boots and the microenvironment in the footwear boots, lower heat, and provide bigger overall comfort level for the user of footwear boots.

The present invention provides the footwear boots of being made by the waterproof material of the film with moisture permeable in it on the other hand, described footwear boots have one of above-mentioned liner or multiple layer combination, one of described liner or multiple layer combination have one deck at least of the shaping hydrophilic polyurethane polymer foamed composite of the present invention that contains maximum 0.1% super-absorbent polymer particles, one of described liner or multiple layer combination so connect in the footwear boots, so that allow the moisture of collection, water vapour exchanges with the surrounding air of footwear boots outside mutually with the microenvironment of air entrapment from footwear boots inside, to produce lower humidity in the gas permeability that improves the footwear boots and the microenvironment in the footwear boots, lower heat, and provide bigger overall comfort level for the user of footwear boots.

The present invention provides the footwear boots on the other hand, described footwear boots have one of above-mentioned liner or multiple layer combination, one of described liner or multiple layer combination are made by the shaping hydrophilic polyurethane polymer foamed composite that contains maximum 0.1% super-absorbent polymer particles, one of described liner or multiple layer combination so connect in the footwear boots, so that allow the moisture of collection, water vapour exchanges with the surrounding air of footwear boots outside mutually with the microenvironment of air entrapment from footwear boots inside, to improve the gas permeability of the footwear boots of making by routine techniques, and when liner or multi-layered product were applied on the footwear boots, it did not require the shape that changes the footwear boots, style and may be used on the footwear boots of all types of daily exercises and dress.

Further aspect of the present invention provides the footwear boots, it has the film of the moisture permeable of waterproof within it, with above-mentioned liner or multilayer in conjunction with one of product, described liner or multilayer are made by the shaping hydrophilic foam composite that contains maximum 0.1% super-absorbent polymer particles in conjunction with one of product, wherein said liner or multiple layer combination product so connect in the footwear boots, so that improve intrinsic moisture vapour transmission rate (MVTR), to allow significantly to increase collected moisture, water vapour and air entrapment are from the microenvironment of footwear boots inside and exchange at the surrounding air of footwear boots outside, thereby lower humidity and lower heat are provided in the microenvironment that forms in the footwear boots, and for the user being provided bigger overall comfort level.

Description of drawings

Fig. 1 showed before compacting or drying, the partial view in the matrix cross section in the shaping hydrophilic polyurethane polymer froth bed of the present invention, it shows gap or space between interconnection single thread in the polyether polyols with reduced unsaturation matrix and long filament and crack, wherein be dispersed in usually between single thread, long filament and crack within gap or the space at super-absorbent polymer particles, on and among.

Fig. 2 is the cross sectional view of the amplification that obtains of one of interconnection single thread shown in Figure 1 and long filament 2-2 along the line, the super-absorbent polymer particles that it shows some dispersions within the interconnection single thread and long filament of shaping hydrophilic polymer froth bed, on and among.

Fig. 3 shows the illustrated section of outward appearance of the layer of shaping hydrophilic polyurethane polymer froth pulp of the present invention, the layer of described hydrophilic polyurethane polymer froth pulp comprises super-absorbent polymer particles and non woven fibre additive, wherein is filled with maximum 0.1% super-absorbent polymer particles between the crack between non woven fibre in gap and the space.

Fig. 4 shows the illustrated section of another embodiment of formed product of the present invention, described product has shaping hydrophilic polyurethane polymer foamed composite of the present invention shown in Figure 3, and described product has the adhesive of the using moisture permeable hydrophilic covering fabric on it.

Fig. 5 shows the illustrated section of another embodiment of shaping multi-layered product of the present invention, described product has hydrophilic polyurethane polymer foamed composite shown in Figure 3, described product has the hydrophilic covering fabric that is fixed on the inner surface, and fixing on the outer surface hydrophobic waterproof covering fabric, and preferably make and operate material relevant or that be correlated with by leather or hide-like material.

Fig. 6 shows the illustrated section of the another embodiment of shaping multi-layered product of the present invention, described product has the hydrophilic polyurethane polymer foamed composite of the present invention shown in Figure 3 and cladding material such as the fabric or the film of independence and unique forms, so that on arbitrary surface of formed composite material, acquisition maybe can obtain variable functional character aspect moisture control and collected moisture rising.

Fig. 7 shows the illustrated section of the part of shaping multi-layered product, described product has hydrophilic polyurethane polymer foamed composite of the present invention shown in Figure 3, thereby explanation makes the permeable adhesive of water that the warp thread and the weft yarn of covering fabric are bonded on the formed composite material.

Fig. 8 shows the illustrated section of part of multi-layered product of the relative light weight of another form, and described product has shaping hydrophilic polyurethane polymer foamed composite of the present invention, without any non-woven fiber additive.It bonds on it to peeling paper and with woven fabric layer " on the spot " by scraper type coating foamed composite and prepares.

Fig. 9 shows the partial illustration cross section of multi-layered product of the relative light weight of another form, and described product has shaping hydrophilic polyurethane polymer foamed composite of the present invention, without any non-woven fiber additive.It is by scraper type coating foamed composite between the lower floor of peeling paper and upper strata, and go up and preparation at least one surface bonding with the moisture permeable adhesive " on the spot " of preferably weaving covering fabric or that be fixed to formed composite material.

Figure 10 A is vertical lateral plan of making class footwear boots of lining with the multilevel shaping product with Woven fabric, described Woven fabric is set up or is fixed on the inner surface of leather upper part of footwear boots and the long part of the opening of pin and the ligulate (flap of top edge and footwear boots by suitable impermeable adhesive, tongue) part on and edge, for and the environment intercommunication.

Figure 10 B is along amplification cross section that the 10B-10B line of Figure 10 A obtains.

Figure 11 is the longitudinal cross-section view of the footwear boots shown in Figure 10 B.

Figure 12 is the cross section that the line 12-12 along Figure 11 obtains.

Figure 13 is the amplification cross section that the line 13-13 along Figure 12 obtains.

Figure 14 is collected moisture drops from the shaping multi-layered product of zone through having hydrophilic polyurethane polymer foamed composite of the present invention of high humility to the schematic diagram that flows than the theoretical differential in the zone of low humidity.

The specific embodiment

In order to realize favourable outcome of the present invention, the aqueous mixture that needs the preparation polymerization, so that shaping froth bed or formed composite material to be provided, the foamed composite matrix that wherein is shaped will have high moisture vapour transmission rate, can make generation moisture (that is, the water vapour drop of the condensation of in the microenvironment that produces by the body cover that exemplifies, collecting) from wet place (that is, high humidity regions in the microenvironment that is produced) physically moves to the low humidity zone, arrive the permission evaporation then to eliminate the place of described moisture.

The method of preparing this improvement and shaping froth pulp is in conjunction with comprising enough water; maximum 0.1% finite quantity super-absorbent polymer particles; the surfactant that the size of the air gap is used between the crack of adjusting open cells or random distribution; the aqueous formulation and at least a suitable polyurethane prepolymer of other additive of choosing wantonly and selecting; form polyblend; this polyblend of deposition on the strippable bottom paper on mobile vehicle or the transmission system; and cover upper surface with strippable top sheet; move the polyblend on carrier or transmission system; and simultaneously independent normal annular abscess starching (sizing) is become to be mainly elliptical shape; final polyether polyols with reduced unsaturation single thread and the fiber that generates more x-y direction of described elliptical shape; be used to improve the transpiration of collected moisture; remove top and bottom releasable paper; pass through such as the shaping sheet material with shaping layer material the polyether polyols with reduced unsaturation foamed composite; the die-cut secondary additional step that waits is used for various application such as clothes; footwear; the product that the lining of the helmet etc. is used.

United States Patent (USP) 5763335 and 6025287 and other patent in this method or the technology of making shaping foamed polyurethane polymer material layer has been described, and this is well known to a person skilled in the art, therefore will can describe more fully.

Yet, the difference of shaping foamed composite of the present invention is in the matrix of shaping foams, shape, size and the orientation in space and gap are optimised between interconnection single thread and long filament and crack, on the x-y direction, that is rising in the fore-and-aft plane identical with width for collected moisture with the length of shaping foamed composite.

In addition, yet, the ratio of the chemicals in the prescription of shaping foamed composite of the present invention has been designed to also prevent that gel from forming and adhesion, as described in United States Patent (USP) 5331728 and patent `335 and the `287, make absorptivity, transpiration and the gas permeability maximum of this shaping foamed composite simultaneously.Therefore, improved shaping foamed composite of the present invention will be from the place of high humility such as microenvironment absorb moisture and be transferred to it than the zone of low humidity and can evaporate the place of eliminating moisture.

By improvement shaping foamed composite of the present invention, except obtaining improved transpiration and evaporation,, find that also the surface appearance of improved foamed composite still keeps relatively dry if compare with the absorbing material of the prior art of routine.If water droplet is placed on any surface of improved shaping foamed composite, as described below, and allow the water droplet impermeable surface, then when paper handkerchief is pressed into this surperficial same area, it will can not siphon away any water, even on applying pressure to this paper handkerchief the time.

In the conventional batch mixed technology of preparation shaping hydrophilic polyurethane polymer foamed composite of the present invention, aqueous mixture uses the water of about 15%-85% weight, at least a super-absorbent polymer of 0.05%-0.1% weight, and select and optional additive, with the Hdyrophilic polyurethane prepolymer of 1%-50% weight, form the polyblend that foamed composite is used to provide.

The super-absorbent polymer that is used for this prescription is preferably Sodium Polyacrylate/polyhydric alcohol polymer and copolymer absorbent, these can obtain easily with liquid, fibers form in the commercial market, and be preferred for herein, have for the object of the invention and application and the composite of the particle size that adopts.This super-absorbent polymer has been described in United States Patent (USP) 5763335 and 4914170.

Super-absorbent polymer is commonly defined as to have spontaneous absorption aqueous fluid and keeps the ability of integrality separately simultaneously.In this super-absorbent polymer, when contacting with aqueous fluid, the carboxyl on the polymer chain is by solvation.As a result, these groups partly are dissociated into electronegative carboxylate anion.Polymer chain contains a large amount of similar charged ionic groups now, and these groups repel each other.The volume of chain becomes big and will absorb also that the quantity of liquid hold-up constantly increases.

Opposite with superabsorbents, comprise the conventional absorbent of wetting agent, mainly absorb liquid by physics mode and under the lightest stress or pressure with reinstatement.Therefore, the optimization formula of Shi Yonging is the combination of limited superabsorbent polymer and wetting agent in the present invention, and this binding energy makes the moisture of collecting and absorbing move to the zone of low humidity from the zone of high humility because of pressure reduction.

Yet for the functional character this of the present invention that obtains improved shaping foamed composite and favourable result, importantly, the consumption of the super-absorbent polymer that uses in aqueous mixture in process for preparation as mentioned above must be restricted.About this point, preferred consumption will be 0.1% of a mixture weight.Too many super-absorbent polymer tends to cause the moisture gelling of collection, as in the prescription of prior art, take place and in this will slow down the required transpiration of collected moisture effectively and prevent to move to zone than low humidity from the zone of high humility.

Because surfactant plays the size effect of gap between the crack of control abscess or random distribution or the air gap in shaping foamed composite matrix, so in process for preparation, surfactant is joined in the aqueous mixture.This influences capillarity conversely, and capillarity is within the interconnection single thread and long filament of moisture in being distributed in any shaping foamed composite of the present invention matrix of improve collecting, on and among super-absorbent polymer particles between the principal element that moves.It is well known in the art using surfactant to change surface appearance.Typically, oxirane and the expoxy propane surfactant that is called PLURONIC available from the trade mark of BASF or name can obtain on the commercial market.Under the situation of wishing small gap or open cells, in aqueous mixture, use the PLURONIC L 62 of 2% weight.Under the situation of wishing large scale gap or open cells, in aqueous mixture, use the PLURONIC F88 of 5% weight.

Similarly, the Hdyrophilic polyurethane prepolymer also can obtain on the commercial market, and according to United States Patent(USP) Nos. 5763335,4209605,4160076,4137200,3805532 and 2999013, is known to one skilled in the art; With can be at John Wiley ﹠amp; Sons, New York, N.Y. publish, the Polyurethane`s Chemistry and Technology of J.H.Saunders and K.C.Frisch, Vol.XVI Part 2, High Polymer Series, " Foam Systems ", 7-26 page or leaf and " Procedure for thePreparation of Polymers " the 26th page and following or the like in find the universal method of preparation and this polymer of preparation.A kind of preferred Hdyrophilic polyurethane prepolymer of Shi Yonging is sold with trade name BIPOL 6 by MaceAdhesives and Coatings in the present invention, another kind is sold with trade name HYPOL by Dow ChemicalCompany and another kind is sold with trade name PREPOL by Lendall ManufacturingIncorporated.These prepolymers because their strong hydrophilic features, reasonably cost and under the relative humidity of 50%-90% the equilibrium moisture content of 5-45%, therefore be suitable for using in the present invention.

In the shaping of multi-layered product, described multi-layered product has basic unit and cover layer and other material layer of hydrophilic polyurethane polymer foamed composite; This covering or other layer can be weave, non-woven, water is permeable, waterproof, natural or synthetic textiles and fiber and will maybe should be used for according to the function for given multi-layered product selecting.Influence this function of cover layer or other layer selection or application have no restrictedly to satisfy for example abrasion, hot strength, percentage elongation, fire-retardant, moisture sees through, insulation, aesthetics, sense of touch, density, thickness and be used for the further feature of various application and purposes.

In addition, cover layer or other layer can be connected or be arranged on the apparent surface of basic unit of shaping foamed composite of the present invention and optionally or preferably can be bonding, lamination or be adhered in the basic unit of shaping foamed composite.

Can be by in the forming process of shaping foamed composite, being connected on the polymerization moisture, bonding thereby " on the spot " realizes.

Adhesive is bonding to be well known in the art.When using adhesive cover layer or other layer to be connected on the surface of basic unit of shaping foamed composite, also require to make moisture can pass adhesive, the netted adhesive (web adhensive) that preferred adhesive will comprise thermal activation is as by Bostic, Middleton, those and other hot melt dot matrix (dot matrix) coating material of equal value that MA sells in the commercial market with trade mark or wording SPA 111.

With reference to the accompanying drawings, Fig. 1 and 2 shows in the cross section of shaping Hdyrophilic polyurethane foamed composite HF of the present invention the partial illustration of interconnection single thread and long filament (being labeled as 1 usually) in the accompanying drawing.Single thread in the shaping foamed composite and long filament 1 be so interconnection partly, so that between the crack of the air gap of existence qualification random distribution gap (being labeled as 2 usually) in whole shaping foams.Therefore, as shown in, each single thread and long filament 1 is not separated from each other because of single the air gap 2.Therefore, in this class A foam A material, some single thread or long filament 1 can the interconnection each other by the thin-walled film of hydrophilic polyurethane polymer.Those skilled in the art can think that this shaping foamed composite is an open-cell foam materials.In addition, to the present invention importantly, these illustrate maximum 0.1% super-absorbent polymer particles (being labeled as 3 usually) and bond to or be present in single thread and the long filament 1.

The preparation of above-mentioned each composition and processing with the process that improved shaping foamed composite HF is provided in, the super-absorbent polymer particles 3 in the accompanying drawing shown in Fig. 1 and 2 distributes with discrete each other relation.This interval constraint between single super-absorbent polymer particles or eliminated the defined gel of prior art effectively and form or the gel adhesion.Find that if super-absorbent polymer particles do not contact each other, when their absorb moisture swelling, then they will prevent that gel from forming, and the drop of the moisture of the water vapour of condensation and collection is through the transpiration of shaping foamed composite, can the gel adhesion.In addition, this interval also reduces the absorptive capacity or the absorptivity of individual particle.By adding super-absorbent polymer particles amount in the mixture to the hydrophilic prepolymer amount recently controlled this interval.

Conventional prior art polyether polyols with reduced unsaturation foams also stand to move when wetting, inhomogeneous and cave in.Super-absorbent polymer is fixed between interconnection single thread, long filament and crack in the shaping Hdyrophilic polyurethane foamed composite matrix in gap or the airspace among the present invention, as illustrated in fig. 1 and 2, the present invention allows moisture to cave in to next particle and the foamed composite matrix that prevents to be shaped from a particle transpiration of super-absorbent polymer along single thread and long filament.

Although this does not improve transpiration, it increases the saturation degree of absorbed collection moisture, and owing to collect the saturation degree of the drop of moisture increase in the shaping foam base plate, cause take place by pressure reduction rising or flow to zone from high humidity regions than low humidity.

The size in gap and the air gap improves transpiration between abscess-size, shape and the crack set up at random between interconnection single thread and the long filament by changing, so that the capillarity difference to be provided, the different viscosities of the drop of the collection moisture that super-absorbent polymer absorbed in the shaping foamed composite is satisfied in this capillarity requirement.

Capillarity is the function of the size and dimension of gap and the air gap between crack in the formed polyurethane foam of polymers matrices of composite material.Those skilled in the art can realize and know that the size of gap or airspace is more little, and it is good more with the capillarity of setting up from the high humidity regions transpiration to improve collected moisture.

Capillary variation is by following acquisition: when the preparation aqueous mixture by adding surfactant, with in processing hydrophilic polyurethane polymer foamed composite process, in forming the polymeric foam layer, pass through compression, and/or in processing hydrophilic polymer foamed composite process, by changing temperature.Persons skilled in the art will recognize that capillarity had both influenced the absorption of drop of condensation of the moisture of collection, also influenced its transpiration rate.

The further embodiment of formed polyurethane foam of polymers composite obtains by adding fiber mesh material or chopped strand material (cut fiber material).Fiber mesh material and chopped strand material can be natural or synthetic fibers and or hydrophilic or hydrophobic.The example of this fiber is cellulose, polyester and glass fibre.

Fig. 3 shows this embodiment of the present invention and is used for setting up the sheet material blank of shaping hydrophilic polyurethane polymer foamed composite in the accompanying drawing, and this sheet material blank can be used for many purposes and can be used as one deck at least of other multi-layered product of the present invention.In preparation and this embodiment of processing, the ratio with the 0.5%-5% of aqueous mixture weight in process for preparation is added natural or synthetic netted thing of non woven fibre or material.Therefore, when making shaping hydrophilic polyurethane polymer foamed composite, weave or the netted thing of non woven fibre or material 4 have with accompanying drawing in the gap of filling with Hdyrophilic polyurethane foam and super-absorbent polymer fully of the same way as shown in Fig. 1 and 2.

Fibrous material can be or natural or artificial synthetic materials and improve the rising activity of composite and the hot strength of shaping foamed composite, therefore be desirable for forming matrix sheet material blank (being labeled as 5 usually), shown in this base sheet blank also serves as hereinafter and the one deck in the multi-layered product of describing of the present invention.

Therefore, in the of the present invention two-layer embodiment shown in Figure 4 in the accompanying drawings, has the shaping layer of hydrophilic polyurethane polymer foamed composite, i.e. the sheet material blank 5 of described variable thickness of the embodiment of the present invention shown in the partial cross section of Fig. 3 and density.This can be by being function with required application and fiber mesh material or chopped strand material, changes Hdyrophilic polyurethane prepolymer, water, maximum 0.1% super-absorbent polymer, maximum 70% wetting agent, the ratio of adequate surface activating agent and obtain.In order to satisfy friction, aesthstic and use or use other condition that may require, the adhesive means by any permeable type fixedly the second layer 6 of covering fabric to the apparent surface of blank sheet material 5.As the function of the application of specific laminar product or purposes or depend on the application or the purposes of specific laminar product, adhesive can be permeable or impermeable.

Be fixed at covering fabric under the lip-deep situation of the sheet material blank 5 that contacts with the moisture of collecting, covering fabric must be able to make the moisture of collection pass shaping hydrophilic polyurethane polymer foamed composite, and the sheet material blank 5 that this shaping hydrophilic polyurethane polymer foamed composite is connected with cladding material limits.Fixing or bonding this covering fabric 6 is the netted hot melt type or the dot matrix sedimentation type of opening to the adhesive of sheet material blank 5 usefulness of shaping foamed composite, and all these are in the accompanying drawings shown in Fig. 7.

In multilayer embodiment of the present invention, Fig. 5 shows another product in the accompanying drawing.Again, the formed composite material layer of hydrophilic polyurethane polymer foam, i.e. the sheet material blank 5 of described variable thickness of the embodiment of the present invention shown in the partial cross section of Fig. 3 and density.This can obtain by changing Hdyrophilic polyurethane prepolymer, water, wetting agent, maximum 0.1% super-absorbent polymer and the ratio of fiber mesh material or chopped strand material.Then, the first hydrophilic covering fabric 8 is to be fixed on the moisture contact surface of shaping foamed composite layer 5 by permeable type adhesive.Similarly, the hydrophobic covering fabric 9 of waterproof is fixed on another surface of shaping foamed composite layer 5 by any suitable manner.

In this embodiment, the basic formed composite material layer of sheet material blank 5 is arranged by being operatively connected with like this as 10 places around leather or hide-like material, so that shaping foamed composite layer extends at the leather of material or an end such as the 10a of hide-like layer material, thereby allow at least one end and the surrounding environment intercommunication that centers on this embodiment of shaping foamed composite layer 5 on every side.This will promote collected moisture rising to the zone than low humidity from the zone of high humility along the x-y length and the width in-plane of sheet material blank layer 5, that is in the surrounding air.If leather or hide-like material waterproofing then can be saved waterproof covering fabric layer.

Similarly, in the embodiment shown in Figure 6, provide the shaping foamed composite layer of the sheet material blank material 5 shown in Fig. 3,4 and 5 in the accompanying drawing.Prepare this layer in an identical manner, the sheet material blank 5 of one deck variable thickness and density (is function with application and purposes) is provided.Available independence is come drape forming foamed composite facing surfaces separately with the different fabric and the combination and the variant of film, so that be the opposite side separately of the layer of sheet material blank 5, provides variable feature.Therefore, on the surface of moisture contact, provide covering fabric 11 and provide another covering fabric 12 in a side away from the moisture contact surface of sheet material blank layer.

In some cases, use or purposes do not wish collected moisture condensation drop with perpendicular " z " direction of the thickness of composite material of sheet material blank on through the composite transpiration of shaping foam sheet blank.In the case, impermeable damp-proof membrane 9 is bonded on the composite side opposite with covering fabric, as shown in Figure 5 in the accompanying drawing.

The various combinations of fabric, film and other matrix can be connected on the shaping polyether polyols with reduced unsaturation foamed composite 5.For example, another embodiment of the present invention requires shaping foamed composite should to fix or bond on " leather " or the hide-like material, with the absorption, transpiration that for example increase the footwear of being made by this shaping foamed composite with evaporate feature.Have the roll-in material (component foam roll goods) of the combination foam of bonding waterproof membrane,, be stamped into the curve shape bigger than the size and dimension on leather shoes top as sheet material blank 5 among Fig. 4 and cover layer 6.As shown in Figure 5, then with the top 10 of leather, bond on the waterproof membrane side on leather top 10.Then can be at the excessive foamed composite of external margin roll-in of footwear upper ends, thus make foamed material be exposed to the outside or on every side under the atmosphere, simultaneously still with the inner intercommunication of footwear.In operation, from the moisture of footwear inside then along " x-y " length and the transpiration of width in-plane of formed polyurethane foam of polymers composite, and when being exposed on every side atmosphere following time, will be through the openend evaporation of sheet material blank 5, all these are as shown in Figure 5 in the accompanying drawing.

In Fig. 6, another shaping of the present invention, have first covering fabric 11 by the multi-layered product of certain size manufacturing, the regional intercommunication of the residing fine and close and elevated pressures of its outer surface 11a and the drop of the condensation of the moisture of wherein collecting.Covering fabric 12 is at bonding on opposite face or the inner surface 11b, connection, lamination or be adhered on the second layer of formed polyurethane foam of polymers composite 5 of above-mentioned sheet material blank.On a side 5a, weave, the inner surface 12a of the second layer of non-woven, natural or synthetic material is bonding, connection, lamination or be adhered on the described 5a side away from the shaping foamed composite of covering fabric 11.The outer surface 12b of natural or synthetic material 12 with than the low humidity zone of low-density and lower pressure as around the atmosphere intercommunication.

In operation and use, the first covering fabric layer 11 and the drop of the condensation of the moisture of wherein collecting and the regional intercommunication of water vapour maximum.The super-absorbent polymer complete sum be dispersed in usually single thread in the matrix of formed polyurethane foam of polymers composite layer wherein and single thread play draw and absorb the effect of the drop of collected moisture and water vapour and cause they from the zone of high fine and close and high humility through covering fabric 11 transpirations to by the low densification of the 3rd layer of expression of the layer of the foam composite material 5 that is shaped and natural and synthetic material and the zone of low humidity.

Fig. 7 is the fragmentary sectional view that covering fabric bonds to the hydrophilic polyurethane polymer foamed composite on it, and it shows respectively in Fig. 3,4 and 6 covering fabric at 6,8,9,10 and 11 places and bonds to more detailed mode on the sheet material blank basis 5.It shows with permeable adhesive 15 intercommunications of water and is connected to warp thread and weft yarn fiber at the covering Woven fabric at 13 and 14 places on the sheet material blank basis 5.

Feature operation in the technology of using this place instruction is that the high wet steam transmitance that is provided by sheet material blank basis 5 physically is provided, not required collected moisture is moved to another place from a place.Sheet material blank basis 5 can maybe can not require cladding material.If require cladding material, then composite needs bonding, connection, lamination or the bonding cladding material mode to the sheet material blank basis 5, shown in Fig. 4,5,6 and 7 in the accompanying drawing.

Cladding material comprises that at least a water is permeable, artificial, synthetic, the fabric membrane of waterproof or film.By it the function of exercising is expected selected cladding material.That is to say that as an example, cladding material is characterised in that satisfied abrasion, hot strength, percentage elongation, fire-retardant, moisture vapour transmission, insulation, aesthetics, sense of touch, density, thickness etc.The combination of the cladding material on the opposite side on sheet material blank basis has been shown, comprising at a side on sheet material blank basis 5 or a plurality of different cladding material on the both sides in above-mentioned Fig. 4,5,6 and 7.

By well known to a person skilled in the art that routine techniques carries out forming or by connecting or bonding to the formed polyurethane foam of polymers composite of other layer of bonding cover sheets or material by complete " on the spot ".

Similarly, other layer that connects cover sheets or material presses (flame lamination) also to well known to a person skilled in the art to the flame crucible zone on the layer material of the basic blank sheet material 5 of formed polyurethane foam of polymers assembly.

Can finish the adhesive on sheet material blank basis bonding by well known to a person skilled in the art conventional adhering method.Want to bond to cladding material and moisture is passed under the situation of adhesive at adhesive, find that preferred adhesive will comprise the netted adhesive of the thermal activation that is similar to SPA 111, it is available from BOSTIC, Middleton, MA and hotmelt and dot matrix application of adhesive of equal value.

The Hdyrophilic polyurethane prepolymer is when reacting with water, forms the liquid system of carbon dioxide and amine.Amine produces the polymerization of polyurethane prepolymer, thereby forms the solid foam polymer, and carbon dioxide produces bubble in the polymer that forms.Adopting process control, comprising temperature and the surfactant that changes at reaction inner surface tension force, and the volume fraction of regulating prescription, the combination that we can set up abscess-size, pore volume, hydrophily, moisture absorbs and evaporate is with the transpiration of maximization moisture, shown in the embodiment and Biao of the following stated.

Being described to hydrophilic conventional polyurethanes single thread and fiber allows water only along the surface of this single thread and fiber or with the capillarity transpiration.

Hdyrophilic polyurethane prepolymer chemistry in the present invention is different from conventional polyurethane because of the component of its hydrophilic polyurethane polymer.This hydrophilic polyurethane polymer component makes the polyether polyols with reduced unsaturation single thread of foam base plate and long filament water can be absorbed in the trunk of every single thread and fiber, for contacting with surfactant, absorbent, wetting agent or the chopped strand material that is dispersed in the foam base plate.

Therefore, increase transpiration rate by the Hdyrophilic polyurethane prepolymer that uses in the shaping foamed composite prescription of the present invention.

Invention embodiment (shown in Figure 5) about the exposure of sheet material blank basic material 5 shows that the sheet material blank material is that it has little surface area exposure in external environment condition around the thin matrix of leather object 10 parcels.Can change this project organization,, expose the volume ratio on sheet material blank basis 5 to increase with respect to internal surface area.Relevant with the density on sheet material blank basis 5 in " x-y " length with the rising volume of the moisture on width plane or the direction.For example, with the rising 1.61g moisture of 0.061 inch thick sheet material blank basic material of the MVTR cup test of standard test/hour.In process, be compressed to the rising 0.335g moisture of 0.049 inch thick identical product/hour.This shows that thickness reduces by 20% and causes transpiration rate to descend about 80%.

In Fig. 8, the embodiment of another multiform shape of the present invention shows the lightweight sheet material blank of formed polyurethane foam of polymers composite 50, this polyether polyols with reduced unsaturation foamed composite 50 is by be coated with polyblend with scraper type on the peeling paper of bottom, and " on the spot " bonding covering fabric is to polyblend, so that formed product to be provided, thereby preparation shaping polyether polyols with reduced unsaturation foam compositions process of preparing.

Therefore, the lightweight sheet material blank of formed polyurethane foam of polymers composite has the material single thread 51 that is dispersed in shaping foamed composite 50 and the super-absorbent polymer particles among the long filament 52 usually, as 53 places.In above-mentioned preparation and polymerization process, covering fabric 54 is bonding or be connected on the upper surface of shaping foamed composite 50.Another layer weave or non-woven material or synthetic material 55 can be bonding, connection, lamination or be adhered on the lower surface of shaping foamed composite 50.

The present invention's further embodiment again has been shown among Fig. 9, it only is the adhesive (being labeled as 56 usually) of any adequate types that may require by given application or purposes with Fig. 8 different, on the bonding upper surface that bonds to shaping foamed composite 50 of covering fabric 54.

For footwear boots (being labeled as 60 usually), Figure 10 A and 10B show another embodiment of the present invention, described footwear boots are by the natural of any routine or synthetic material manufacturing, described footwear boots have upper part 61 and the sole portion 62 that is connected to each other, to determine the receiving space (receiving space) 63 of pin.Receiving space 63 intercommunications of gateway (access opening) 63a and pin, and footwear neck (collar) 64 is formed on around the gateway.Upper part 61 is separated by tongue component 65, and when being folded into the assembling position that is higher than tongue-shaped member 65 with convenient upper part 61, the lateral edge of upper part such as 61a are in the outside of footwear 60 and atmosphere intercommunication on every side.

Multilayer lining 66, comprising as mentioned above and at least one synusia material blank basis 5 as shown in Fig. 3,4,5,6 and 7, by any suitable manner,, multilayer lining 66 is fixed on the inner surface of upper part 61 as above-mentioned permeable adhesive and/or by unshowned stitching.

Multi-layered product with shaping Hdyrophilic polyurethane foamed composite, as at shown in Fig. 8 B those, the layer material (this layer has open side edge 5a) that comprises shaping foamed composite 5, with as the suitable lining corrosion protection layer (socking layer) at 67 places (when using the footwear boots, it contacts with user's pin).Multilayer lining 66 by adhesive 68 by so fixing or be adhered on the inner surface 61a of the leather of upper part 61 or hide-like material, so that it extends above the tongue-shaped member 65 and the footwear neck 64 of footwear boots 60, the surrounding air intercommunication of lateral edges 5a and lining corrosion protection layer 67 and footwear boots 60 outsides as a result.When the footwear boots in use, this can make the moisture collected in the froth bed of lining or multilayer lining 26 these two moves or is rising to the surrounding air of footwear outside from the inside of footwear boots 20 through open side edge 5a and lining corrosion protection layer.Therefore,, provide more effective mechanism, and be horizontally through the lining corrosion protection layer transpiration of lining 66 not only along the x-y axle or the vertical line of froth bed for moisture vapour transmission rate (MVTR).In addition, surrounding air also will enter in the footwear boots through shaping foamed composite layer or lining 66 and lining corrosion protection layer 67, moisture with the displacement evaporation, thereby play following effects: the MVTR and the gas permeability that improve the footwear boots, transmission is from the moisture of the collection of footwear boots inside and the air of delay, and replace with surrounding air, inner and make the user more comfortable with cooling footwear boots.

The conventional footwear of contrast same type, testing appliance has shown in Fig. 3,4,5,6 and 7 and the multi-layered product of above-mentioned shaping foamed composite or lining are made the above-mentioned footwear of lining, and the male sex testee who wherein uses 30 years old age was once walking on the treadmill 2 hours 45 minutes and rest 15 minutes between each time walking.Monitor simultaneously in the air themperature of footwear inside and moisture readings and the comfort index (PCT) felt with the ASHRE data determination.The results are shown in following table 1.

Table 1

		Conventional footwear	Footwear with shaping foamed composite lining
				Test period
1	Temperature 	80	79.2
					Relative humidity	74	62
	PCT	83	81
Test period 2	Temperature 	81.91	78.2
					Relative humidity	77	73
	PCT	88	80

Draw to have from this test and contain the be shaped footwear structure of this multi-layered product of foamed composite or lining of the present invention and reduce relative humidity the microenvironment of the foot well in the footwear, and the comfort index that appreciable impact is felt (Perceived Comfort Index, PCT).Under higher temperature, the decline of PCT is more remarkable, and this can find out by comparative test cycle 1 and test period 2.

The comfort index of being felt is the combination how people separate heat release and high humility.In footwear temperature inside scope, PCT is low more, and it is more comfortable that people feel.

Figure 11,12 and 13 is the further schematic diagrames of another kind of footwear boots, and it shows upper part 71 of being made by leather and the sole portion 72 that limits the receiving space 73 of pin, and what described receiving space 73 had a pin enters edge 73a and the regional 71a of ligulate.Multilevel shaping polyether polyols with reduced unsaturation froth pulp of the present invention (being labeled as 74 usually) comprises the formed polyurethane foam of polymers composite 75 of preparation as mentioned above, and it is connected or is lining on the inner surface of upper part 71.

Use fixedly multilevel shaping froth pulp 74 of suitable bonding, and arrange with respect to the inner surface of footwear, so that form first footwear necks (being labeled as 74a usually) around the ligulate zone on footwear boots 70 and form second footwear neck 74b on every side at the edge 73a that enters of pin.Therefore, multilevel shaping froth pulp 74 of the present invention can make the drop of the moisture that in footwear, has collection and moist steam high fine and close and high humility part microenvironment and in the low densification of footwear boots 70 outsides and the regional intercommunication of low humidity, with the reason of listing owing to the above hydrophilic polyurethane polymer foamed composite that just is shaped, the transpiration that runs through of moisture takes place, the comfortable situation in the microenvironment of the receiving space 73 of the pin of result's improvement in footwear boots 70.

In order to understand the improvement moisture transpiration that causes by shaping foamed composite of the present invention better, Figure 14 shows the cross sectional view of the product (being labeled as 80 usually) of the multilayer embodiment of making by certain size and shape, this product has woven covering fabric layer 81, the fine and close high humidity regions intercommunication of its outer surface 81a and collected moisture in the microenvironment of for example footwear and water vapour is shown in Figure 10 A and 11.The inner surface 81b of covering fabric 81 is bonding, lamination or be adhered to according to described herein and on the adjacently situated surfaces 82a of the second layer matrix of the shaping hydrophilic polyurethane polymer foamed composite 82 that the various prescriptions described in the embodiment of the following stated are prepared.Especially, adopted wet agent additive such as glycerine to prepare the second layer 82 of described shaping foamed composite to improve the transpiration of moisture.

Figure 14 shows at the 3rd layer on the opposite face of the base layer of shaping foamed composite 82 or the side 82b natural or synthetic material non-woven or weaving layer 83 also to have bonding, lamination or is adhered to the described opposite face of matrix of shaping foamed composite 82 or the inner surface 83a on the side 82b.Described the 3rd layer 83 opposite face of material or the zone such as the atmosphere intercommunication of outer surface 83b and low densification or low humidity.

Although the tectal outer surface 81a of fabric 81 is positioned at wherein collected moisture and water vapour is maximum and the higher zone of humidity, but shaping hydrophilic polyurethane polymer foamed composite base layer plays the effect of drawing and absorbing collected water, so that it laterally moves to base layer and the 3rd layer 83 the low densification of natural or synthetic material or the zone of low humidity of reaching shape foamed composite 82 through first cover layer 80 from high the regional of water fine and close and high humility or collection.

Further with reference to Figure 14, the flow velocity that the drop DW of collected moisture flows through first cover layer 81 is high relatively.Almost 2 times of diameter when therefore, the diameter expansion of drop is to the adjacently situated surfaces 82a of the second layer that moves to shaping foamed composite of the present invention when drop.

Within the super-absorbent polymer complete sum is dispersed in single thread and long filament usually, on and among shaping hydrophilic polyurethane polymer foamed composite base layer 82 in single thread and long filament be hydrophilic, play draw and absorb the effect of water droplet DW and expect it from the zone first fabric cover layer transpiration of fine and close and higher levels of humidity to being the zone than low humidity of representative by the base layer of shaping foamed composite 82 and natural or synthetic material the 3rd layer 83.

The transpiration that pure a large amount of moisture of collecting does not improve water droplet DW, this is not give existing ambient conditions because of the moisture of collecting and with ability.

Drop descends slightly through the mobile meeting of the matrix of shaping foamed composite layer 82, then when it is rising and when being evaporated in the zone of the low densification of adjacent atmosphere and low humidity through the 3rd layer 83 of natural and synthetic material, and increase widely.

Owing to transpiration takes place for pressure reduction or capillarity, that is move.

Capillarity is the function of the size and dimension of gap and airspace between crack in shaping foamed composite matrix.

By the volume of the surfactant in the aqueous mixture that in the polymerization process that forms hydrophilic polyurethane polymer foamed composite of the present invention as mentioned above, uses, be adjusted in the size and dimension in gap and airspace between the crack in the shaping foamed composite matrix.

Providing following embodiment specifies as of the present invention.Yet, should be appreciated that the detail that the present invention is not limited to list in an embodiment.At embodiment, and all umbers in the specification remainder and percentage are by weight, except as otherwise noted.

Embodiment 1

Prepare water by mixing in proper order with following interpolation:

Pluronic (BASF) F88 .3% solution 93.36%

Foley Fluff(Buckeye Cellulose) 1.54

Glycerine (Emery 916) 3.07

Pluronic(BASF)L62 1.29

Superabsorbents (Stockhausen AP 80-HS) 0.10

Guar gum (Alpha-Chem) 0.64

Then water is added among the Dow Chemical Hypol Prepolymer of 33wt% and with it and mix.The composition that mixes curtain coating on silicone release paper also covers with same second (peeling paper).By being clamped to the thickness of partition on the workbench and top overlay control gained foam reactant.After occurring and solidifying about 8 minutes, take out foamed composite and dry in baking oven.Adopt netted adhesive then, foam component is laminated on the K2 fabric of being supplied by Hub Fabric available from the thermal activation of Bostic.

Embodiment 2

As embodiment 1, preparation comprises following water:

Pluronic (BASF) F88 1% solution 37.88%

Calcium carbonate (Noah Technologies) 54.43

Glycerine (Emery 916) 7.59

Superabsorbents (Stockhausen AP 80-HS) 0.1

Then water is added among above-mentioned 27.5% the Prepolymer and with it and mix.This mixture is poured between two partitions on the peeling paper, as embodiment 1 and before foam produces, 2.5 (oz/yd of 1/4 thickness ²) the polyester nonwoven fiber (available from Carr-Lee) of oz./sq.yd. is placed on the liquid mixture.Then with a peeling paper, add the foam non woven fibre that is rising, the top of combination to.In this embodiment, the thickness 1/8 of partition (non woven fibre of suppressing 1/4 thickness obtains), thereby 1/8 consistency of thickness required with final composite.In Fig. 3,4,5,6 and 7, this composite has been shown.To as well known to those skilled in the art, can regulate the siphon of various abscess-sizes, hydrophily, water retention and water with joining various surfactants, absorbent and/or filler in the water, as:

Surfactant	Absorbent	Filler
			Nonionic	PEO	Artificial chopped strand
Ion	PVP	Mineral
			Both sexes	Clay	Cellulose fibre

Test

The moisture vapour transmission rate (MVTR) of the described in the prior art shoe pad material (Cambrelle liner) of quality assurance program (Quality Assurance Procedure) test on the Duratex foam through generally acknowledging.The product of the present invention's preparation has surpassed 600-4000g water/m ²/ 24h@40 ℃ industrial standard.The result of table 1 shows along the length x direction of the fore-and-aft plane of shaping hydrophilic polyurethane polymer foamed composite layer and the result on the width y direction; Table 2 shows laterally or perpendicular to the result of the z direction of fore-and-aft plane.Test finds, example (embodiment 2) shown in the optimization formula also surpassed the MVTR of prior art than low-density and thin sample.

Table 1

The x-y direction	Cambrelle/Duratex	The present invention	Improve %
				MVTR g/m 2/24h	5056	10696	112
Table 2
				The Z direction	4018	5897	47

Embodiment 3

For reducing the density of the foamed composite described in the embodiment 2, change prescription, it comprises:

Pluronic (BASF) F881% solution 89.11%

Sodium acid carbonate (Arm-Hammer) .90

Glycerine (Emery 916) 9.99

This water is mixed with 1: 1 weight ratio with Dow Chemical Hypol.Composition curtain coating on leather surface of mixing covers with peeling paper, and adjusts size with pad.After curing and drying, with netted adhesive heat lamination tissue layer.This method is not used in product shown in Figure 5, is to have eliminated covering fabric 9.This method has defined another embodiment, and it has shown diversity of the present invention.Prescription between embodiment 3 and the embodiment 2 changes the density that has reduced foam, with density from 15.61lb./cu.ft. (pound/cubic feet) to 10.91lb./cu.ft., reduce about 9%.

Embodiment 4

The prescription of preparation as embodiment 3, and on peeling paper, disperse.By pocket knife paper is drawn back the opening of 0.005-0.375 then, thereby on paper, stay the continuous thickness of foam superabsorbents.Further make paper development, up to foam reactant occurring, but still be clamminess.Place covering fabric K2 (Hub Fabric) then on the surface of being clamminess, wherein do not having under the situation of leaking, it is bonded on the polyurethane.

Embodiment 5

Preparation is as prescription the embodiment 3 and processing as embodiment 4.With second layer peeling paper displacement covering fabric, thereby allow only cured foam in top and bottom paper.In case fully solidify, remove bottom paper and in baking oven, drive away residual water.Then can be by gained foam sheet of the present invention being bonded on fabric, film or the matrix of selection with adhesive, further processing.Referring to Fig. 9.

Above-mentioned prescription, technology, product, material and application are shown, so that exemplify main embodiment.The present invention is lightweight, flexible formed polyurethane foam of polymers composite, be in multi-layered product, to use the moisture reserved materials that adopts, it with moisture from the wet area transpiration to the arid region.

Principle of the present invention, preferred embodiment and embodiment have been described in aforementioned specification.Yet the present invention for required protection should not be considered limited to disclosed particular form herein, because think that these are to exemplify, rather than restriction.Under the present invention's spirit listed in not having the appended subsequently claim of disengaging and the situation of scope, those skilled in the art can make and change and change.

Claims (30)

1. shaping hydrophilic polyurethane polymer foamed composite, it has:

A. the shaping matrix of being made by single thread and long filament has the particle of at least a super-absorbent polymer of 0.1wt% at the most in described single thread and the long filament, so that the moisture of collecting moves also transpiration to the low humidity zone from high humidity regions,

B. described matrix limits one deck shaping hydrophilic polyurethane polymer froth bed at least, described shaping hydrophilic polyurethane polymer froth bed has the particle of described at least a super-absorbent polymer, described particle compartment of terrain is along the single thread of the matrix of shaping hydrophilic polyurethane polymer froth bed and long filament and disperse and be dispersed in the single thread and long filament of shaping hydrophilic polyurethane polymer froth bed matrix

The matrix of c. described shaping froth bed has certain size, shape and directed and air space between the crack of making, with the capillarity that improves the moisture of collecting and transpiration and

D. described shaping hydrophilic polyurethane polymer froth bed and the zone intercommunication of described low humidity are so that collection and rising moisture can be from described matrix transpirations.

2. the shaping hydrophilic polyurethane polymer foamed composite of claim 1, wherein said low humidity zone is a surrounding environment atmosphere.

3. the shaping hydrophilic polyurethane polymer foamed composite of claim 1, the moisture vapour transmission rate of the wherein said formed polyurethane of one deck at least froth bed in the time of 40 ℃ is at 600-20000g/m ²In the scope of/24h.

4. each shaping hydrophilic polyurethane polymer foamed composite among the claim 1-3, it has the covering fabric at least one outer surface that is fixed to the described shaping of one deck at least foam hydrophilic polyurethane polymer layer, described covering fabric be conditioned so that moisture by this covering material to the foam polyurethane layer that is shaped, and do not absorb described moisture.

5. the shaping hydrophilic polyurethane polymer foamed composite of claim 1, it comprises at least a absorbent, super-absorbent polymer and the wetting agent that is selected from PEO and the PVP, at least a surfactant and additive optional and selection, so that improve the moisture transpiration of the environment of fine and close from height in high humility to the zone of low densification and low humidity.

6. the shaping hydrophilic polyurethane polymer foamed composite of claim 5, wherein said additive is the filler material that is selected from wollastonite, feldspar, calcium carbonate and sodium acid carbonate.

7. the shaping hydrophilic polyurethane polymer foamed composite of claim 5, wherein said additive is the fibrous material that is selected from cellulose, polyester and glass fibre.

8. the shaping hydrophilic polyurethane polymer foamed composite of claim 5, wherein said additive is the filler material that is selected from wollastonite, feldspar, calcium carbonate and sodium acid carbonate, and the fibrous material that is selected from cellulose, polyester and glass fibre.

9. the shaping hydrophilic polyurethane polymer foamed composite of claim 5, wherein the moisture vapour transmission rate in the time of 40 ℃ is at 600-20000g/m ²In the scope of/24h.

10. the shaping hydrophilic polyurethane polymer foamed composite of claim 5, it has at least one the lip-deep covering fabric material that bonds to matrix, so that make moisture easily pass this covering fabric, and does not absorb described moisture.

11. the shaping hydrophilic polyurethane polymer foamed composite of claim 10 wherein uses the bonding covering fabric material of adhesive of moisture permeable, and netted adhesive, dot matrix adhesive and flame crucible zone that described adhesive is selected from thermal activation are pressed adhesive.

12. the shaping hydrophilic polyurethane polymer foamed composite of claim 11, it has at least one away from the surface that bonds to the covering fabric on another layer that is selected from the material in film and the film fabric, and collected moisture is rising to be arrived and the adjacent shaping foamed composite side in low humidity zone so that stop.

13. the shaping hydrophilic polyurethane polymer foamed composite of claim 10, wherein at least the moisture vapour transmission rate of one deck formed polyurethane froth bed in the time of 40 ℃ at 600-20000g/m ²In the scope of/24h.

14. comprise the footwear boots of upper part and sole portion, wherein connect this upper part and sole portion, so that be user's pin restriceted envelope, thereby form the microenvironment of collected moisture, described upper part has the multilevel shaping hydrophilic polyurethane polymer foamed composite of at least a absorbent that contains maximum 0.1wt%, and the wherein surrounding air intercommunication of multi-layered product and footwear boots outside, to improve the gas permeability in the footwear boots and to reduce humidity, wherein multilevel shaping hydrophilic polyurethane polymer foamed composite comprises the shaping hydrophilic polyurethane polymer foamed composite of claim 1 definition.

15. the footwear boots of claim 14, wherein the shaping hydrophilic polyurethane polymer foam multi-layered product in the upper part comprises at least a hydrophilic polyurethane polymer foamed composite, multi-layered product is through the microenvironment of described composite in the footwear boots and the intercommunication between the atmosphere on every side of described footwear boots outside, and described multi-layered product comprises and the cover layer of the described microenvironment intercommunication in described footwear boots, and this cover layer is a moisture permeable.

16. the footwear boots of claim 15, wherein multi-layered product so is fixed on the upper part, so that collected moisture and surrounding air are all along composite layer longitudinal propagation and the zone of laterally passing through the moisture permeable of covering fabric, so that collected moisture is replaced by surrounding air.

17. the footwear boots of claim 15, wherein the upper part has the space top edge on every side that is arranged in user's pin for the atmosphere intercommunication on every side with footwear boots outside, and multilayer hydrophilic polyurethane polymer product selectively and optionally is connected around the described top edge, so that the microenvironment of the open side edge of at least a hydrophilic polyurethane polymer foamed composite within it in the footwear boots and the intercommunication between the atmosphere on every side of described footwear boots outside, comprise and the covering fabric of described microenvironment intercommunication in described footwear boots that with described multi-layered product described covering fabric is a moisture permeable.

18. the footwear boots of claim 15, wherein the upper part has and its whole ligulate element that forms and design, so that with atmosphere intercommunication around the footwear boots outside, selectively and optionally be connected at least one inner surface of ligulate element with multilayer hydrophilic polyurethane polymer product, so that the outside intercommunication of open side edge and footwear boots, with allow collected moisture from the microenvironment of described footwear boots, to flow out and surrounding air in described foamed material enters the footwear boots.

19. comprise the footwear boots parts of upper part and sole portion, wherein this upper part and sole portion are connected so that be user's pin restriceted envelope, described upper part has the hydrophilic polyurethane polymer foam liner on the surface within it, described foam liner has the matrix of being made by single thread with hydrophilic polyurethane polymer and long filament, described matrix contains at least a super-absorbent polymer particles of 0.1wt% at the most, described super-absorbent polymer is distributed in described single thread and the long filament, distribute and distribute along described single thread and long filament by described single thread and long filament, described lining has the zone of at least one moisture permeable, surrounding air intercommunication by described lining in this zone and footwear boots parts outside, move to the outside of described footwear boots parts from the high humility space of user's pin with the moisture that improves collection, to remove the moisture of described collection, wherein the hydrophilic polyurethane polymer foam comprises the shaping hydrophilic polyurethane polymer foamed composite of claim 1 definition.

20. the footwear boots parts of claim 19, the zone of the moisture permeable in the wherein said upper part are the footwear necks with burr.

21. the footwear boots parts of claim 19 or 20, wherein said hydrophilic polyurethane polymer foamed material lining so is fixed on the upper part, so that collected moisture and surrounding air are all along lining longitudinal propagation and the zone of laterally passing through at least one moisture permeable of lining, so that collected moisture is replaced by surrounding air.

22. the footwear boots parts of claim 19 or 20, wherein the upper part further comprises ligulate element integrally formed with it and frenulum part, and they are arranged to the surrounding air intercommunication with footwear boots outside.

23. the footwear boots parts of claim 19 or 20, wherein the upper part further comprises:

(a) ligulate element integrally formed and frenulum part with it, they are arranged to the surrounding air intercommunication with footwear boots outside; With

(b) the hydrophilic polyurethane polymer foam liner of upper part is a multilayer hydrophilic polyurethane polymer foamed material, this material also selectively and optionally is connected at least one inner surface of ligulate element and the frenulum part, so that the outside intercommunication of open side edge and footwear boots, thereby allow collected moisture to flow out from described footwear boots parts, surrounding air is in described foamed material enters the footwear boots.

24. the footwear boots parts of claim 19, wherein said matrix comprise by space between the crack of certain size manufacturing and random distribution, to improve capillarity and the motion by described shaping foam liner of the moisture collected.

25. hydrophilic polyurethane polymer foamed composite, it is used to improve length and the width transpiration of the moisture of collection along this composite, and the moisture of described collection moved on to the low humidity zone from high humidity regions, remove moisture in described low humidity zone, described hydrophilic polyurethane polymer foamed composite comprises:

(a) one deck shaping foam base plate at least, it has the single thread of hydrophilic polyurethane polymer and long filament and by space between the crack of certain size manufacturing and random distribution,

(b) a large amount of absorbent granules of 0.05-0.1%, this absorbent fully are distributed within the single thread and long filament that forms foam base plate, on and among and

(c) at least a surfactant of scheduled volume, it is used to regulate the size and the shape of described clearance space, with moisture that improve to collect along the length and the capillarity between the absorbent granules on the width of one deck at least of shaping foam base plate with move.

26. the hydrophilic polyurethane polymer foamed composite of claim 25, it has gap between oval crack, the gap is used for generating more vertical and horizontal single thread and fiber at the shaping foam base plate of one deck at least between described oval crack, the transpiration of the moisture of collecting with further raising by described composite and mobile.

27. the hydrophilic polyurethane polymer foamed composite of claim 25 or 26, its moisture transmission in the time of 40 ℃ be at 600-20,000g/m ²In/24 hours the scope.

28. hydrophilic polyurethane polymer foamed composite, it is used to improve length and the width transpiration of the moisture of collection along this composite, and the moisture of described collection moved on to the low humidity zone from high humidity regions, remove moisture in described low humidity zone, described hydrophilic polyurethane polymer foamed composite comprises:

(a) one deck shaping foam base plate at least, it has the single thread of the hydrophilic polyurethane polymer on length of being oriented in and the width and long filament and by space between the crack of certain size manufacturing and random distribution,

(b) at least some described single thread and fiber interconnect,

(c) a large amount of particles, it be at least a super-absorbent polymer particles of 0.05-0.1%, this super-absorbent polymer fully the interval disperse and be oriented within the single thread and long filament of shaping foam base plate, on and among and

(d) gap has ellipse between described crack, and the gap is used for generating more vertical and horizontal single thread and fiber at the shaping foam base plate of one deck at least between described oval crack, the transpiration of the moisture of collecting with further raising by described composite and mobile.

29. the hydrophilic polyurethane polymer foamed composite of claim 28, its moisture transmission in the time of 40 ℃ be at 600-20,000g/m ²In/24 hours the scope.

30. the hydrophilic polyurethane polymer foamed composite of claim 28 or 29, it has at least a surfactant of scheduled volume, described surfactant is regulated the size in space between described crack, with moisture that improve to collect along the length and the capillarity between the absorbent granules on the width of one deck at least of shaping foam base plate with move.

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