HK1169902A - Lightweight, durable apparel and laminates for making the same - Google Patents

Description

Lightweight durable garments and laminates for making same

Cross Reference to Related Applications

This application is a continuation-in-part application of U.S. application serial No. 12/465383 filed on 13/5/2009.

Technical Field

A breathable, lightweight, durable laminate having an outer film surface is described, along with lightweight, durable garments having an outer film surface produced from the laminate.

Background

Garments having both breathable and waterproof or liquidproof film layers are known. Laminates and garments are designed to provide protection to the film layer against tearing or damage caused by poking or grinding or similar actions. Inner and outer fabric layers are most often added to both sides of the membrane to avoid damage to the surface of the membrane.

In addition, garments in which the membrane surface is not covered by a protective inner or outer fabric layer are often used in conjunction with garments in which the fabric surface is capable of protecting the membrane layer from damage. For example, an undergarment made from a composite film lacking an outer protective textile layer is typically worn under a separate outer garment that is not susceptible to direct damage.

The addition of inner and outer fabric layers to protect the film layers from damage increases the weight of the garment, resulting in a higher water absorbency of the outer surface of the material. In addition, wearing outer garments to protect the undergarment with the film layer can be bulky.

Summary of The Invention

A lightweight laminate having an outer film surface is described. The light weight laminate has sufficient durable abrasion resistance, and the outer film surface can maintain waterproofness under abrasion, and can be used for preparing clothes or other articles, such as outerwear and covering. The lightweight laminate has a porous polymeric surface and can be dyed, e.g. printed. The laminate outer membrane surface may be coated with a hydrophobic and oleophobic coating composition to provide oleophobicity and to help maintain water impermeability or water repellency.

A method of making a lightweight laminate having an abrasion resistant outer film surface is also described. The method comprises the steps of selecting a fabric layer; selecting a pleated porous fluoropolymer membrane; coating and dyeing a porous fluoropolymer membrane to form a hydrophobic and oleophobic fluoropolymer membrane having an outer membrane surface; the fabric and porous fluoropolymer membrane are laminated to form a laminate, optionally before or after the coating or dyeing step, to form a laminate having an outer film surface and an inner fabric surface. In one embodiment, a composition having a viscosity of greater than 1000g/m is obtained²24 h water vapour transmission laminate having a mass per unit area of less than 200g/m²The laminate of (1), the outer film surface of the laminate being abrasion resistant, forming a durable water resistant laminate.

A method of making a garment, such as a lightweight outerwear, having a durable wear-resistant waterproof outer membrane surface is also described. The method comprises the steps of selecting a woven, knitted or nonwoven fabric layer laminated to a porous fluoropolymer membrane; coating and dyeing a porous fluoropolymer membrane with an oleophobic polymer composition, optionally before or after a lamination step, such that a laminate having an outer membrane surface and an inner fabric surface is formed; the laminate is assembled into a garment such that the dyed outer membrane surface is the outer membrane surface of the garment and the inner surface of the fabric is on the side opposite the outer membrane surface.

Drawings

The operation of the present invention is explained in detail by the following description and the attached drawings, in which:

figure 1a is a perspective view of the front surface of a garment in one embodiment.

Figure 1b is a perspective view of the rear surface of the garment in one embodiment.

FIG. 2 is a perspective view of a laminate in one embodiment.

Fig. 3a is a photomicrograph of a cross-section of a sample of hooke's (Hook) material used in the hooke's Modified Abrasion Test (Hook Modified Abrasion Test).

Fig. 3b is a photomicrograph of the top surface (top-down surface) of a sample of hooke's material used in the hooke's modified wear test.

Detailed Description

Described herein is a breathable, lightweight, durable laminate for use in the manufacture of low water absorbency (water pick up) waterproof garments, such as outerwear. The laminate is designed to have a durable dyed outer film surface. The breathable lightweight outerwear described in the present invention comprises an exterior film surface that is abrasion resistant and therefore durably waterproof, and a printable, non-woven exterior surface.

One embodiment, a perspective view of a jacket (1) as shown in fig. 1a and 1b, has a non-woven outer surface on the front (20) and back (21) surfaces of the jacket. The garment comprises a non-woven outer surface (2) and a woven inner surface (3) facing the body of the wearer. The jacket (1) comprises a front seal (4), sleeves (5) with cuffs (6) and a waistband (7). The garment is made from a laminate as shown in the cross-sectional view of figure 2. In one embodiment, the garment is comprised of a laminate (10) comprising an outer film surface (11) and an inner fabric surface (12). The laminate (10) includes a porous membrane (13) formed attached to a fabric layer (14). The porous membrane (13) may be dyed with a coloring agent (16) or coated with an oil-repellent composition that is also hydrophobic at the same time, thereby forming the outer film surface (11) of the laminate (10). The fabric layer (14) is attached to the opposite side of the outer membrane surface (11) of the porous membrane (13) and is attached to the porous membrane by a linker (15), shown as a discrete joint in fig. 2.

It is desirable to have a laminate with a membrane surface that is continuously durably coated, such as with a stain or oleophobic coating. For lower surface energy membrane layers, such as many fluoropolymer materials, the porosity of the membrane facilitates the formation of a sustained, durable mechanical bond of the coating composition in the membrane structure. However, it is well known that many porous membranes are easily abraded and it is difficult to obtain a continuous water repellency when the porous membrane is applied under abrasion conditions. The laminates described herein have a film surface formed from a film having sufficient porosity to provide a durable coating that is abrasion resistant and remains water resistant.

The outer porous membrane surface (11) of the laminate (10) may be made of a porous membrane of a polymeric material, such as fluoropolymers, polyolefins, polyurethanes and polyesters. Suitable polymers include resins that can be processed into porous or microporous structures. For example, Polytetrafluoroethylene (PTFE) resin that can be processed to form an elongated porous material is suitable for use herein. For example, according to the processes of U.S. patent nos. 3,953,566, 5,814,405, or 7,306,729, PTFE resin may be stretched to form a microporous membrane structure characterized by nodes of interconnected fibrils when expanded. In some embodiments, expanded PTFE fluoropolymer membranes are prepared from PTFE resins according to patent us patent No.6,541,589, containing the comonomer Perfluorobutene (PFBE). For example, microporous expanded PTFE (eptfe) can be made from PTFE containing about 0.05 to 0.5 weight percent comonomer PFBE relative to the total weight of the polymer.

In one embodiment, the porous outer membrane (13) comprises ePTFE having a microstructure characterized by nodes of small fiber interconnections, wherein the pores of the porous membrane are sufficiently tight to provide water resistance and sufficiently open to provide properties such as water vapor permeability and penetration of stains and oleophobic coatings. For example, in some embodiments, the pores of the porous membrane have an average size of less than or equal to about 400nm to provide water resistance and greater than about 50nm for coloration. This can be accomplished by blending a PTFE resin suitable for creating node and fibril microstructures upon elongation. The resin may be blended with an aliphatic hydrocarbon lubricating oil, such as mineral spirits, for extrusion. The mixed resin may be formed into cylindrical pellets and paste by known procedures and extruded into the desired extrudable shape, preferably ribbon and film. The article may be calendered between rolls to a desired thickness and then dried by heating to remove the lubricating oil, and the dried product is stretched to expand in the machine and/or transverse directions, for example, to produce an expanded PTFE structure characterized by a series of nodes of interconnected fibrils, as described in U.S. patent nos. 3,953,566, 5,814,405, or 7,406,729. The ePTFE product is then fixed in the amorphous state by heating the product above the crystalline melting point of PTFE, e.g., between 343 ℃ and 375 ℃ or between 320 ℃ and 390 ℃.

The mass per unit area and thickness of the porous polymer membrane may be selected according to the application, for example, a mass per unit area of less than about 80g/m may be selected²While the porous membrane also preferably has a mass per unit area greater than about 10g/m²Or 18g/m². In some embodiments, it is desirable to select a mass per unit area of less than about 60g/m²Or about 50g/m²Or about 30g/m²The porous membrane of (1). It may also be desirable to select a mass per unit area of about 19g/m²And 60g/m²With a porous membrane in between. However, in applications such as footwear, it may be necessary to use a membrane having a greater mass per unit area. Various thicknesses of porous polymer film may be selected, and in some embodiments, a thickness of less than about 120 μm may be desired. It may further be required that the thickness of the porous polymer film is below 35 μm.

The laminates described herein have durable water repellency, which means that the laminates retain water repellency After Abrasion according to the post Abrasion water repellency test method described herein. In some embodiments, a laminate having durable water repellency includes a fabric attached to a porous membrane having a ball burst strength greater than 17 pounds force (lb) according to the ball burst strength (ballburst load) test described herein_f) Or greater than about 19 lbf. In some embodiments, a laminate having good durable water repellency comprises a fabric attached to a porous film having properties according to the tenacity described hereinMaximum Load (Maximum Load), MTS and modulus test. For example, in some embodiments, the average maximum load (average maximum load in the machine and cross directions) of a fabric fit on a porous membrane to form a laminate having durable water repellency is greater than 10N, or greater than 12N, or greater than 20N. Suitable porous membranes have an average modulus in the machine and transverse directions of greater than about 40MPa or greater than about 50MPa or greater than about 60 MPa. In some embodiments, the laminate having durable water repellency comprises a porous film having an average substrate tensile strength in the machine direction and the transverse direction of greater than 90MPa, or greater than 95MPa, or greater than 100MPa, or greater than 150 MPa.

The porous nodes and fibril structure of the expanded polytetrafluoroethylene membrane allow the coating material and/or printing material to penetrate into the porous nodes or fibril structure and thereby remain in or on the expanded polytetrafluoroethylene membrane. It is well known that the lower surface energy of fluoropolymers such as ePTFE is detrimental to most surface treatments, which provides difficulties in using durable coatings, such as stains. However, in one embodiment, the coating composition includes a binder and a colorant for coloring the surface of the film, which is used as the outer film surface of the laminate. The coating composition coats and encapsulates the nodes and/or fibrils of the expanded fluoropolymer structure to form a durable aesthetic appearance.

Films suitable for use on the surface of an exterior film, which when printed provides a durable aesthetic surface. In some embodiments, a colorant coating composition comprising a pigment having a particle size sufficiently small to enter the pores of the porous substrate provides a durable aesthetic appearance. Pigment particles having an average diameter of less than about 250nm are effective for forming durable colors. The coating composition further comprises a binder capable of wetting the porous substrate and attaching the pigment to the walls of the channels.

Multiple colors may be used or the concentration of one or more pigments may be varied, or both methods may be used to obtain multiple colors. In one embodiment, a laminate comprising an outer film surface, more than 90% of the outer film surface is dyed by printing or other techniques while preserving porosity and water vapor permeability. In one embodiment, the surface of the film is dyed with a coloring agent to form a solid color or pattern (engineered). Coating compositions containing colorants can be used to provide a range of colors and designs, such as solid colors, camouflage colors, and printed patterns. Coating compositions suitable for printing camouflage patterns, such as forest or desert patterns, comprise one or more colorants. In one embodiment, a coating composition for printing a forest camouflage pattern on a surface of a porous membrane includes black, brown, green, and aqua colorants. In another embodiment, the coating composition comprising brown, khaki and brown colorants is suitable for printing desert camouflage designs. Other embodiments include compositions comprising a gradient colorant in both of these examples.

The coating composition can be applied to the porous membrane to form a porous outer membrane by a variety of methods. Application methods of dyeing include, but are not limited to, transfer coating (transfer coating), screen printing (screen printing), gravure printing (gravure printing), ink-jet printing (ink-jet printing), and knife coating (knifecoating). In addition, topical treatments may also be applied to the porous film to provide sufficient porosity to the laminate to maintain water vapor transmission. Other treatments may provide functionality such as, but not limited to, oleophobicity and hydrophobicity when the membrane surface lacks a desired degree of oleophilicity and hydrophilicity. Examples of oleophobic coatings are the following, fluoropolymers such as fluorinated acrylates and other materials as disclosed in U.S. patent application 11/440,870. Oleophobicity can also be achieved by coating at least one surface of a porous membrane with a continuous oleophobic water vapor permeable polymer coating to form an outer porous membrane. Several examples of water vapor permeable polyurethanes are disclosed in U.S. patent 4,969,998. Some polymers form an outer membrane surface with the desired high degree of oleophobicity, while others are not sufficiently oleophobic. The oleophobicity of these membranes can be increased by the addition of an oleophobic coating. This resulted in a laminate having an outer membrane surface oleophobic rating of greater than about 2 according to the oil repellency Test described herein. In other embodiments, the laminate is formed with an outer film surface of greater than or equal to about 4, or greater than or equal to about 5, or greater than or equal to about 6. Additionally, the outer porous membrane comprises a discontinuous coating, for example in the form of particles or discrete units to provide further abrasion resistance. A coating of discrete material, which may comprise, for example, polyurethane, epoxy, silicone, fluoropolymer, and the like, is sprayed or otherwise applied to the outer film surface to provide abrasion resistance to the laminate.

The Color Change of the stained outer membrane surface of the Color durable laminate is less than 20Delta-E (dE) After Abrasion as measured by Color Change After Abrasion (Color Change After Abrasion). The dyed outer film of the color durable laminate may also have a dE value of less than 15, alternatively less than 10.

Further, the laminate includes a fabric (14), such as a woven, knitted or non-woven fabric, attached to the outer porous membrane (13) on the side opposite the outer membrane surface (11) of the laminate (10). The fabric (14) may be selected to provide dimensional stability to the outer porous membrane (13) when forming the laminate. In the case of an outer garment, the fabric (14) may also be selected so that the side of the laminate facing the wearer provides a pleasant tactile sensation thereto. Suitable lightweight fabrics include cotton, rayon, nylon, polyester, and mixtures thereof. In some applications it may be desirable for the fabric to be flame resistant, such that the fabric comprises, for example, aramid (e.g., sold under the trade name Nomex or Defender), modacrylic (modacrylic), glass fiber, and the like. In some applications it may be desirable for the fabric to weigh less than about 10 ounces per square yard, or less than about 8 ounces per square yard, or less than about 6 ounces per square yard (oz/yd)²) Or less than about 5 ounces per square yard, or less than about 3 ounces per square yard.

Coatings may also be applied to the fabric (14) layer to provide multiple properties to the laminate. For example, the coloring agent may color the fabric layer into a solid color or a color of one or more colors. The fabric and film that make up the outer film surface may be dyed by the same or different techniques as the outer film, as well as being dyed the same or different colors or patterns as the outer film.

The layer of porous membrane (13) forming the outer membrane surface (11) is joined to the fabric (14) in a manner that maintains the desired high water vapor transmission rate. In some embodiments, discrete bonds are used to join the layers in order to maximize breathability and water vapor transmission. In other embodiments, the porous film (13) and the fabric (14) are attached together using a continuous adhesive, but require a continuous tie layer that allows water vapor transmission, such as disclosed in U.S. patent 4,925,732, where the laminate has a water vapor transmission rate greater than 2000g/m²And/24 hours. The adhesive composition includes a thermosetting adhesive such as polyurethane and silicone. The thermoplastic adhesive comprises a thermoplastic polyurethane. The porous membrane layer and the fabric are adhesively bonded together by a lamination process, such as gravure lamination, spray bonding, and melt bonding, to a thermoplastic scrim to form a lightweight laminate.

The durable water repellent laminate is abrasion resistant and does not leak after more than 1400 abrasion movement tests on the outer film surface of the laminate according to the Water repellency after abrasion (Suter) test described herein for hooke Hook. In other embodiments, the resulting laminate is water resistant after 3000 abrasion movements of the outer film surface, may be water resistant after 4000 abrasion movements of the outer film surface, or may be water resistant after 6000 abrasion movements of the outer film surface.

Water vapor permeability or breathability is important to provide cooling to the wearer who wears garments made from the laminate. The laminate of the present invention is breathable and has a water vapor transmission rate (MVTR) greater than 1000g/m²24 hours, or more than 2000g/m²24 hours, or more than 4000g/m²24 hours, or more than 5000g/m²24 hours, or more than 10000g/m²24 hours, or more than 15000g/m²24 hours, or more than 20000g/m²And/24 hours. Lightweight laminates as described hereinMay be less than about 400g/m²Or less than about 350g/m²Or less than about 200g/m²Or less than about 150g/m²Or less than about 145g/m²Or less than about 125g/m²Or less than about 100g/m²。

The laminate outer film surface described herein has low water adsorption compared to the water resistant laminate of the outer fabric surface. In some embodiments, the laminates have a water absorbency of less than or equal to 10g/m as tested by the Water absorbency test described herein (WaterPickup)². In other embodiments, a water adsorption of less than or equal to about 8g/m is formed²Or less than or equal to about 6g/m²Or less than or equal to about 4g/m²Or less than or equal to about 3g/m²A laminate of (a).

A method of producing a lightweight laminate having an abrasion resistant outer film surface comprising the steps of: selecting a fabric layer; selecting a porous fluoropolymer membrane having an average maximum load in the transverse and longitudinal directions of greater than 10N; coating and/or dyeing the porous fluoropolymer membrane with an oleophobic polymer composition and/or stain to yield a porous fluoropolymer membrane having a dyed outer membrane surface with an oleophobicity rating of greater than 2. The method further comprises laminating the fabric and the porous fluoropolymer membrane to form a laminate having an outer membrane surface and an inner fabric surface, optionally before or after the coating and/or dyeing step. In one embodiment, the laminate has a water vapor of greater than 1000g/m²24 hours, mass per unit area less than 150g/m²The outer film surface of the laminate is abrasion resistant and remains water resistant after abrasion.

A method of producing a lightweight garment, such as an outer garment, having a wear resistant outer film surface comprising the steps of: selecting a fabric layer and a porous fluoropolymer membrane; the porous fluoropolymer layer is coated and/or dyed with an oleophobic polymer composition and/or a dyeing agent to yield a porous fluoropolymer membrane having a dyed outer membrane surface with an oleophobicity rating of greater than 2. TheThe method further comprises laminating the fabric and the porous fluoropolymer membrane to form a laminate having an outer membrane surface and an inner fabric surface, optionally before or after the coating and/or dyeing step, the laminate having a water vapor of greater than 1000g/m²The outer film surface of the laminate was abrasion resistant and remained water resistant after abrasion testing for 24 hours. The method further comprises the step of assembling the laminate into a garment such that the outer membrane surface of the laminate that is dyed is the outer membrane surface of the garment.

Constructions made from the above laminates include garments such as jackets, ponchos, raincoats, hats, headscarfs, gloves, pants, coveralls, shoes, and other items such as covers, tents, covers, and the like.

Test method

Mass per unit area

The mass per unit area of the samples was tested according to ASTM D3776 (standard test method for mass per unit area of fabric (weight)) method (option C) using a mettler-toledo balance model 1060. The balance is recalibrated before weighing the sample. The weight is recorded in ounces, with a minimum scale of 0.5 ounces. The units are then converted to grams per square meter.

Film Density

Performance data of the samples to be tested were collected to test the density of the membrane materials of the examples and comparative examples of the present invention. The mass of the 165mm x 15mm sample (using a Mettler-Torido analytical balance AB 104) and the thickness of the sample (using a Kafer FZ1000/30 caliper) were tested as described above. Using these data, the density can be calculated by the following formula:

wherein: rho ═ density (g/cc)

mass (g)

w is width (1.5cm)

length (16.5cm)

thickness (cm)

Film thickness

The thickness of the film material of the examples of the present invention was measured using calipers (Kafer FZ 1000/30). At least four regions of each sample were tested and the average of these data was taken as the thickness value for each film.

Gurley (Gurley) Air Flow (Gurley Air Flow)

The air permeability of each sample was characterized by the time it took 50cc of air to pass through the sample, with the following exceptions, according to FED-STD-191A method 5452. This was done except that the samples were well sealed before testing and no edge leakage occurred during testing.

Average pore diameter test

The average pore size (MFP) of the porous membrane samples was tested according to ASTM F316-03 test method B, except that silicone oil (Dow Corning 200(R) fluid, 10cs) was used as the wetting fluid instead of mineral oil. A silicone oil with a surface pressure of about 20.1 dynes/cm was used when the sample contained Polytetrafluoroethylene (PTFE). MFPs were tested according to this test method using a PMI capillary stomatometer model CFP-1500-A.

Steel ball type bursting strength

The Test method and associated sample assembly apparatus used in conjunction with the Chatillon Test Stand was developed by w.l. gore and partnership, Inc. Ball burst strength tests were performed on materials including fabrics (woven, knit, nonwoven, etc.), porous or non-porous plastic films, sheets, etc., and laminates thereof, as well as other planar materials.

The sample was mounted taut on two annular jaws with an opening of 7.62 cm in diameter, but could not be stretched. The end of the metal rod was a polished steel ball 2.54cm in diameter, providing force in the Z direction (the direction normal to the X-Y plane) against the center of the sample. The other end of the wand is attached to a suitable Chatillon dynamometer mounted on a Chatillon Materials Test station (Chatillon Materials Test Stand) model TCD-200. A force was applied at a rate of 25.4 cm/min until the sample broke. Fractures (tears, ruptures, etc.) may occur anywhere in the fixation area. The average of the maximum force before fracture of the three tests was taken as the test result.

The test is carried out under room temperature and humidity conditions, typically at a temperature of 21 ℃ to 24 ℃ and a relative humidity of 35% to 55%. The data of the steel ball type bursting strength can be expressed as a function of the steel ball type bursting strength to the mass of the sample in unit area; the mass per unit area can be derived from the density and thickness of the sample.

Tenacity, maximum load, MTS and modulus test methods

A rectangular sample of 165mm long by 15mm wide was cut out of the ePTFE membrane as a sample using a die punch, and the membrane was placed on a cutting bed to avoid wrinkles at the cut. A165 mm by 15mm former was then placed on the film (typically 200mm at the center of the web) so that the long axis was parallel to the test direction. The directions referred to herein are measured along the longitudinal axis (parallel to the machine direction) and the transverse direction (perpendicular to the machine direction). Once the dies are aligned, pressure is applied to cut through the film web. After the pressure was removed, the rectangular samples used for testing were inspected to ensure that there were no edge defects that could affect the tensile testing.

The film web was characterized by cutting at least 3 samples in the machine (L) and cross (T) directions. Once the sample was prepared, it was tested for mass (using a Mettler-Toledo analytical balance model AB 104) and thickness (using a Kafer FZ1000/30 caliper). The samples were then tested for tensile properties using an Instron 5500 tensile machine running the Merlin (Merlin) IX series software (version 7.51). The sample was inserted into a tensile machine and held using Instron catalog 2702-. The pressure applied by the splint is about 50 psi. The measured length between the clamps was 50mm and the carriage speed (draw rate) was set at 508 mm/min. The test was performed using a 0.1kN load cell, and data was recorded at a rate of 50 points/second. The laboratory temperature was between 68 ° f and 72 ° f to ensure that the results were comparable. Finally, if the sample breaks at the clip interface, the data is discarded.

At least 3 samples (no slippage or breakage at the nip) were successfully stretched in the machine and cross directions to characterize the film web. Data analysis and calculations were performed using mellin (Merlin) software or other data analysis packages. First, the maximum load that the L and T direction samples can support in the tensile test is determined. The maximum loads of L and T are then normalized to the sample physical properties (thickness and density) and the matrix tensile strength in the L and T directions is calculated by the following equation.

Wherein MTS is Matrix Tensile Strength (MTS) in MPa

F_maxMaximum load in the test (newton)

ρ_oTheoretical density of PTFE (2.2 g/cc)

length of sample (cm)

Sample mass (g)

Then, the average maximum load is calculated by averaging the maximum load of L and the maximum load of T. The average matrix tensile strength was calculated from the average L matrix tensile strength and T matrix tensile strength.

The toughness of each sample was determined by integrating the stress-strain curve of the sample, calculating the area under the curve, and averaging 3 measurements in each of the L and T directions. This data reflects the energy required to fracture the sample and is reported as the sample toughness. The average toughness is then calculated by averaging the toughness of L and T.

The modulus of the sample is obtained by taking the slope of the linear elastic portion of the stress-strain curve. First, the modulus in the machine direction and the transverse direction was calculated by averaging three tests. The average modulus is then calculated by averaging the moduli of L and T.

Oil Repellency Test (Oil repellancy Test)

In this test, the laminate samples were tested for oleophobic rating (oil rating) using AATCC test method 118-. Add 3 drops of test oil to the sample surface. A glass plate was placed directly on the oil droplets. After 3 minutes, the glass plate and the surface were degreased unnecessarily. One side of the sample film was visually inspected and a change in appearance indicated the test oil penetration and staining. The oleophobic rating corresponds to the highest amount of oil for which no visible staining of the sample test membrane was present.

Water vapor Transmission Rate test (MVTR)

The water vapor transmission rate of each sample was tested according to ISO 15496 standard, except that the sample water vapor transmission was converted to water vapor transmission rate (MVTR) based on the device water vapor transmission (WVPapp) and using the following conversion equation.

MVTR (Δ P value 24)/((1/WVP) + (1+ WVPapp value))

Air transmission rate

The air transmission of each laminate sample was tested according to ASTM D737 using a standard pressure drop of 125Pa, but with the following modifications to the equipment. The using area is 20cm²Alternative test heads of (3). The test apparatus is FX3300-20 from Advanced Testing Instruments, Schwerzenbach, Switzerland. The data are reported in cubic feet per minute and are shown in Table 3.

Water adsorption test

An 8 "x 8" square sample was weighed using a calibrated balance with an accuracy of 0.1mg, the balance being a product of the AG104 series from Mettler Toledo, columbu, ohio. The samples were then placed in a hydrostatic tester of the type described in ASTM D751, "Standard test method for coated fabrics" sections 41 to 49, circular force area with a diameter of 4.25, "hydrostatic resistance method B". The sample was placed so that the surface of the laminate labeled outer surface was subjected to 0.7psi of water for 5 minutes. Care was taken to ensure that no water adhered or adsorbed to the back of the sample when placed or removed, otherwise the readings would change. After uncovering, the sample was removed from the tester and weighed again on a balance as described previously, assuming all added mass was from water adsorbed on a circular force-bearing area of 4.25 "diameter, since a very high clamping force was used to hold the sample. The water absorbency of this region is calculated by converting to grams per square meter by the following equation.

Water adsorption (sample final weight-sample initial weight)/((4.25 inch × 0.0254 m/inch/2)²*π)

Water resistance test (Suter)

The waterproof test was conducted as follows. The laminates were tested for water repellency using a processed suter test apparatus with water as the representative test liquid. In the fixture, a sample area of approximately 17/4 inches in diameter sealed between two rubber gaskets was subjected to forced compression by water. When the sample is tested, the sample is oriented in such a way that the outer membrane surface of the sample is the surface which is subjected to the action of water. The water pressure on the sample was increased to about 1psi by a pump connected to a reservoir, which was controlled by appropriate gauge indication and tube built-in valving. The test specimen is placed at an angle and the water is circulated to ensure contact of the water without air contacting the lower surface of the specimen. The reverse side of the outer membrane surface of the sample was observed for 3 minutes to see if any water penetrated the sample. Seemingly visible liquid water is interpreted as a leak. The sample surface reached an acceptable (water-proof) level with no visible liquid water within three minutes. As used herein, a sample is "water resistant" in the sense that it passes the test. Samples with any visible liquid water leakage, e.g. in the form of droplets, air hole leakage, etc., are not waterproof and fail the test.

Resistance to hydrostatic pressure-initiation

The initial hydrostatic pressure resistance of each sample was tested according to ASTM D751 "Standard Test Methods for coated Fabrics". The pressure was increased until the sample broke. The hydrostatic resistance recorded is the water pressure at which the sample breaks. This value is expressed in pounds per square inch (psi).

Hooke improved Abrasion (Hook Modified Abrasion)

Abrasion testing was according to ASTM D4966: "Standard Test Method for Abrasion Resistance of Textile Fabrics (Martindale Abrasion Test Method)" A Martindale Abrasion Test apparatus modified as described below was used for the Test. A circular sample of diameter 6.25 "was placed on a standard felt on a test table and the sample film surface was subjected to abrasion. The sample on the sample holder was replaced with a 1.5 "diameter circular hook with the loop fastener facing downward to apply the action to the sample. This material is a nylon Hook available from Norman Shatz Co, 3570, Town, Bensalem, part number 1509000075, PA 19020 as a "two foot wide Black Hook and Loop". Fig. 3a and 3b are scanning electron micrographs of examples of hook materials suitable for use in this test.

The time interval over which the wear movement is controlled is typically tested for color change and/or hydrostatic pressure resistance at the end of the movement interval. Initially, the time interval for movement is 400 movements until 2400 movements are reached. After that the movement time interval jumps to 800 movements until 9600 movements are reached. After this, the remaining test movement time interval jumps to 1600 movements. All samples were stopped at 16000 moves.

Hooke improved color change after wear

After each wear movement interval, the samples were removed from the Martindale test station described previously and evaluated for performance. An X-Rite i1 basic spectrophotometer (X-Rite world headquarters, waterfall, michigan, usa or www.xrite.com) was used to take L a b readings from the middle of the sample. The difference between the "worn" reading at the same slot and the initial reading without any wear was calculated. The color change was tested at intervals of each wear movement and the root mean square of the difference was calculated using the following equation.

Color change ((shift L reading-initial L reading)²Plus (move a reading-initial a reading)²Plus (shift b reading-initial b reading)²)^1/2

The root mean square of the color change values is reported in units of delta e (de).

Water resistance (suter) -after-hook improvement

After any given interval of abrasion movement, each sample was tested for water repellency using the "Water repellency test (Sutt)" as previously described. When any visible water leakage, such as water drops, air hole leakage, etc., is observed, the sample is no longer waterproof. No further abrasion or water resistance tests were performed on the samples.

Huke improved resistance to hydrostatic pressure after abrasion

Hydrostatic pressure resistance after abrasion was tested according to ASTM D751 "Standard Test Methods for Coated Fabrics". Each test specimen was abraded according to the Hook Modified Abrasion Method (Hook Modified Abrasion Method) mentioned previously, but the specimen was subjected to 1000 Abrasion movements using the Hook side of the fixed Hook as an abrasive. Each sample was then tested for hydrostatic pressure resistance according to astm d751, with the sample outer film surface facing the water. These values are in units of pounds per square inch (psi).

Examples

A two-layer laminate having an outer film surface and an inner fabric surface was prepared according to the following examples.

Film 1(M1)

A water vapor permeable, microporous Polytetrafluoroethylene (PTFE) membrane was prepared from a PTFE resin according to the teachings of U.S. patent No.6,541,589. The PTFE resin consists of 0.5 weight percent Perfluorobutene (PTFE) based on the total mass of the resin and is processed into an expanded PTFE (ePTFE) membrane as taught in U.S. Pat. No.3,953,566. The properties of the film are detailed in table 1.

Film 2(M2)

A water vapor permeable, microporous PTFE membrane was prepared from PTFE resin and processed into an expanded PTFE (eptfe) membrane as taught in U.S. patent No.5,814,405. The properties of the film are detailed in table 1.

Film 3(M3)

A water vapor permeable, microporous PTFE membrane is prepared from PTFE resin and processed into an expanded PTFE (eptfe) membrane as taught in U.S. patent No.3,953,566. The properties of the film are detailed in table 1.

Membrane 4(M4)

A water vapor permeable, microporous membrane was prepared from PTFE resin and processed into an expanded PTFE (eptfe) microporous membrane as taught in U.S. patent No.3,953,566. The properties of the film are detailed in table 1.

Film 5(M5)

A microporous membrane was prepared from PTFE resin and processed into an expanded PTFE (ePTFE) microporous membrane as taught in U.S. Pat. No.3,953,566. The properties of the film are detailed in table 1.

TABLE 1 Properties of porous membranes

Fabric 1(T1)

A spun polyester fabric is provided comprising yarns weighing about 80g/m²From Milliken, Inc. (Milliken)&Company) (scada burgh, south carolina, usa; type 141125.)

Fabric 2(T2)

A spun nylon 6, 6 fabric is provided comprising yarns weighing about 50g/m²From Milliken corporation (Sbadabje, south Carolina, USA; model 131907.)

Fabric 3(T3)

A woven fabric is provided comprising polyester in plain weave warp weave, weighing about 38g/m²From Glen Raven, Inc. (part number A1012.) of Glen Raven, Inc., Greenwich, N.C.

Dyeing method 1 (blue)

After lamination, the ePTFE membrane surface of the bilayer laminate was printed with a blue, solvent-based pigment-containing ink that wetted the ePTFE. The laminate was printed using a solvent-based ink jet printer from Epson, Japan, to form a dyed outer film surface.

Dyeing method 2 (Red)

After lamination, the ePTFE membrane surface of the bilayer laminate was printed with a red, solvent-based pigment-containing ink that wetted the ePTFE. The laminates were printed using a solvent-based ink jet printer from Epson technologies, Japan, to form a dyed outer film surface.

Oleophobic coating (C1)

The laminate dyed ePTFE outer membrane surface was coated with 2-propanol (Sigma-Aldrich, st louis, missouri) to completely wet the laminate. Immediately after wetting, the fluoropolymer solution was applied (within 30 seconds) and about 6.0g of fluorocarbon (AG8025, Asahi Glass, Japan) was mixed into about 14.0g of deionized water in the formulation the dyed film surface was hand-coated with a roller to form about 3g/m of the mixture²Coating of (2). The coated film was cured at 180 ℃ for 2 minutes.

Oleophobic coating (C2)

About 2.5% Teflon by coatingAF (Fluorinert of Dupont Fluoropolymers, Wilmington, Del., USA)FC-40 (3M Corporation, Minneapolis, Minn., USA) solution renders oleophobic the outer membrane surface of laminate dyed ePTFE the dyed membrane surface was formed with a roller hand-coating mixture to about 3g/M²Coating of (2). The coated film was dried at 180 ℃ for about 2 minutes.

Examples 1 to 14

A laminate comprising an outwardly-facing dyed outer film surface and a textile is prepared.

The laminate samples of examples 1-14 were prepared using the specific porous films and fabrics shown in table 2. The porous film and fabric are bonded together by gravure printing a moisture-curable polyurethane adhesive in a dot pattern onto the surface of the film. The adhesive was prepared as taught in U.S. Pat. No.4,532,316, covering approximately 35% of the film surface. The adhesive coated side of the ePTFE membrane was pressed against the woven fabric side on a nip roll and then transferred to a hot roll to form a bi-laminate. The moisture-curable adhesive was cured for 48 hours.

The laminates were dyed according to the specific dyeing and oleophobic coating methods in table 2.

TABLE 2 description of the example laminates

Example number	Film	Fabric	Dyeing process	Coating layer
					1	M1	T1	Blue color	C2
2	M2	T1	Red colour	C1
					3	M1	T2	Blue color	C1
4	M2	T3	Blue color	C1
					5	M2	T3	Blue color	C2
6	M3	T1	Blue color	C1
					7	M3	T1	Blue color	C2
8	M2	T2	Blue color	C1
					9	M2	T1	Blue color	C1
10	M2	T1	Blue color	C2
					11	M4	T1	Blue color	C1
12	M4	T1	Blue color	C2
					13	M5	T1	Blue color	C1
14	M5	T1	Blue color	C2
					16	M4	T2	Blue color	C1

The resulting laminate is lightweight, water vapor permeable, air permeable, has an oleophobicity rating of 5 or greater, and has low water absorption. The results of the tests performed according to the methods described herein are listed in table 3.

To compare a low water-adsorption laminate having an outer film surface with a water repellent material having a textile outer surface, comparative material samples were obtained. Comparative example 1 is a commercially available fabric comprising nylon with a microcellular polyurethane (tightly woven) on one side and a Durable Water Repellent (DWR) coating on the other side. The DWR side of the comparative example 1 sample was tested for water absorption up to about 11 grams per square meter (gsm), which is significantly higher than the water absorption of the example 1-11 examples shown in table 3.

TABLE 3 laminate Properties

The laminates were tested according to the test methods described herein to determine the number of abrasion movements made before water repellency was lost, and the hydrostatic pressure before and after abrasion. The results are shown in Table 4.

TABLE 4 laminate Water repellency and hydrostatic pressure results

^*Examples16 no leakage occurred after 16000 wear movements.

The durability of the aesthetic appearance of the example 1 laminate was tested as described herein for color change after abrasion. The color change value after abrasion of the outer film surface of the laminate was about 8 dE.

Example 15

An outerwear jacket with an adventitial surface made using a simple outerwear style without a pocket or hook, with a full length front zipper (4) is shown in figures 1a and 1 b.

The resulting laminate contained an outer membrane surface of ePTFE similar to that of example 3, except that the membrane was attached to the woven fabric layer by discrete adhesive points, as in the woven fabric of example 3. The outer membrane surface is coated with an oleophobic coating. The sleeves of the outerwear are terminated with elastic cuffs having adjustable hook and loop tabs. The lower circular hem uses an elastic pull cord to fit a range of waist sizes.

The embossed laminate was sewn together to form a jacket using a single needle sewing machine with 65 gauge round head needles, with the laminate outer film surface oriented to conform to the outer surface of the jacket. The sewing machine includes a knife edge to cut the excess laminate so that the seam can be sealed with a narrow seam tape. Using a standard hot-melt seam sealer, a hot-melt type seam tape with a sufficiently low melt viscosity is sealed at the seams of the jacket so that the adhesive can contact the ePTFE membrane through the fabric to form a watertight seal. Seam seal tape is used on the woven fabric side of the jacket laminate.

The rear wing along the inner edge of the front zipper is reinforced with an adhesive sheet, thus avoiding being caught by the zipper. The total weight of the resulting male XL-sized garment was about 9.1 ounces.

Example 16

The laminate of this example was made in the same manner as examples 1-14 using the components shown in table 2 with the following exceptions. Prior to application, membrane M4 was coated with a single layer of partially permeable polyurethane according to us patent 4,969,998. The application of the polyurethane coated M4 was such that the uncoated ePTFE side was not facing the textile T2. The remaining processing was all as described in examples 1-14.

Example 17

A commercially available bi-layer laminate of microporous polypropylene film on polypropylene point-bonded nonwoven fabric, under the trade designation DriDucks, was used as a reference^TMFrom Frogg Toggs(Hill street 131 (131 Sundown Dr. NW, Arab, AL) zip 35016) in the northern Arrama, Alabama, part number DS 1204-04. This product was tested with a microporous polypropylene membrane as the outer surface. The laminates were tested for water repellency after abrasion and the results are listed in table 4.

While particular embodiments of the present invention have been illustrated and described, the present invention is not limited to such illustrations and descriptions. Variations and modifications within the scope of the claims are part of the invention.

Claims (52)

1. A method of making a garment having an abrasion resistant outer membrane surface comprising the steps of:

a) selecting a woven or knitted fabric layer and a porous fluoropolymer membrane;

b) dyeing the porous fluoropolymer membrane with a dyeing agent to obtain a dyed outer membrane surface;

c) laminating the fabric and the porous fluoropolymer membrane to form a laminate having an outer membrane surface and an inner fabric surface, optionally before or after dyeing;

d) assembling the laminate into a garment such that the dyed outer membrane surface is the outer membrane surface of the garment and the inner textile surface is on the side opposite the outer membrane surface of the garment;

wherein the laminate has a water vapor transmission rate of greater than 4000g/m²The laminates after the outer film surface abrasion test were abrasion resistant and durably waterproof 24 hours.

2. The method of claim 1, comprising assembling the laminate into a garment such that the inner fabric surface of the laminate fabric is a garment inner fabric surface.

3. The method of claim 1, comprising selecting a porous fluoropolymer membrane comprising expanded polytetrafluoroethylene (ePTFE).

4. The method of claim 1, comprising selecting a microporous PTFE membrane comprising Perfluorobutene (PFBE) comonomer.

5. The method of claim 1, comprising selecting a porous fluoropolymer membrane having an average maximum load in the transverse and longitudinal directions of greater than 10 newtons (N).

6. The method of claim 1, comprising selecting a porous fluoropolymer membrane having a ball burst strength of greater than 17 lbf.

7. The method of claim 1, comprising selecting a mass per unit area of less than 80g/m²The porous fluoropolymer membrane of (1).

8. The method of claim 1, comprising selecting a porous fluoropolymer membrane having a thickness of less than 35 μ ι η.

9. The method of claim 1, wherein the fabric used comprises a knit and the laminate is durably waterproof after more than 1400 abrasion movements on the outer membrane surface.

10. The method of claim 1, wherein the laminate is durably waterproof after more than 3000 abrasion movements of the outer membrane surface.

11. A method according to claim 1, wherein the fabric used comprises a textile fabric and the laminate is durably waterproof after more than 4000 abrasion movements on the outer membrane surface.

12. The method of claim 1, comprising printing with an ink jet printer to stain the laminate outer film surface.

13. The method of claim 1, wherein the laminate outer film surface has an oleophobicity rating of greater than 4.

14. The method of claim 1, comprising selecting a mass per unit area of less than 400g/m²A laminate of (a).

15. The method of claim 1, comprising selecting a porous fluoropolymer membrane having a thickness of less than 120 μ ι η.

16. The method of claim 1, further comprising coating the porous fluoropolymer membrane with an oleophobic coating.

17. The method of claim 1, further comprising applying a discrete material to the outer film surface to increase the abrasion resistance of the laminate.

18. The method of claim 17, wherein the discrete material coating comprises a material selected from the group consisting of polyurethane, epoxy, silicone, or fluoropolymer.

19. A method of preparing a garment having an abrasion resistant outer coating surface comprising the steps of

a) Selecting a composite fabric comprising an outer film surface dyed abrasion resistant laminate, wherein the laminate comprises:

(i) a porous fluoropolymer membrane having an average maximum loading of greater than 10N, and

(ii) a fabric attached to a side of the porous fluoropolymer membrane opposite the surface of the dyed outer membrane;

wherein the laminate has a water vapor transmission rate of greater than 4000g/m²24 hours and the laminate has abrasion resistance, is water resistant after 2000 abrasion movements;

b) forming a garment sheet comprising a composite fabric;

c) the garment is assembled with the garment piece comprising the composite fabric oriented such that the outer membrane surface is the outer membrane surface of the garment and the inner fabric surface is on the opposite side of the outer membrane surface.

20. A method of making a garment having an abrasion resistant, low water adhesion outer film surface comprising the steps of:

a) selecting a fabric layer and a porous membrane;

b) staining the porous membrane with a staining agent to obtain a stained outer membrane surface;

c) laminating the fabric and the porous film, optionally before or after dyeing, to form a laminate having an outer film surface and an inner fabric surface;

d) assembling the laminate into a garment such that the dyed outer film surface is the outer film surface of the garment and the inner fabric layer surface is on the opposite side of the outer film surface;

therein, a layerThe water adhesiveness of the pressed product is less than or equal to 10g/m²The water vapor permeability is higher than 4000g/m²24 hours, and the laminate has abrasion resistance, is durably waterproof after the outer film surface abrasion test.

21. The method of claim 20, further comprising coating the oleophobic polymer on the porous membrane.

22. The method of claim 20, wherein the porous membrane comprises Polytetrafluoroethylene (PTFE).

23. The method of claim 20, wherein the porous membrane comprises polyurethane.

24. A garment having an abrasion resistant outer membrane surface comprising a composite fabric consisting essentially of:

1) a first layer consisting essentially of a porous fluoropolymer membrane having an average ball burst strength of greater than 17 pounds-force, the porous fluoropolymer membrane having a dyed oleophobic outer membrane surface and an inner membrane surface opposite the outer membrane surface; and

2) a second layer consisting essentially of a woven layer bonded to the porous fluoropolymer membrane by adhesive bonds adjacent to the inner membrane surface;

wherein the garment is assembled such that the dyed oleophobic outer membrane surface is the outer membrane surface of the garment and the composite fabric has a water vapor transmission rate greater than 4000g/m²The composite fabric has abrasion resistance and is durable and waterproof after more than 1400 abrasion movements on the outer membrane surface for 24 hours.

25. The garment of claim 24, wherein the porous fluoropolymer membrane comprises a Polytetrafluoroethylene (PTFE) containing membrane.

26. A garment having a wear-resistant outer membrane surface, comprising:

an outer coating surface of the outer coat, and

a laminate, the laminate comprising:

1) a porous fluoropolymer membrane having an abrasion resistant dyed outer membrane surface and an inner membrane surface opposite the outer membrane surface, the porous fluoropolymer membrane having an oleophobic rating of greater than 2, the porous fluoropolymer membrane having an average maximum load in the transverse and longitudinal directions of greater than 10N; and

2) a woven or woven fabric layer bonded to the porous fluoropolymer membrane by adhesive bonds adjacent to the inner membrane surface;

wherein the mass per unit area of the laminate is less than 150g/m²The outer membrane surface of the garment thus assembled is the outer membrane surface of the laminate.

27. The garment of claim 26, wherein the porous fluoropolymer membrane comprises Polytetrafluoroethylene (PTFE).

28. The garment of claim 26, wherein said porous fluoropolymer membrane is microporous.

29. The garment of claim 26, wherein said porous fluoropolymer membrane comprises expanded polytetrafluoroethylene (ePTFE).

30. The garment of claim 26, wherein the porous fluoropolymer membrane comprises ePTFE comprising Perfluorobutene (PFBE) comonomer.

31. The garment of claim 26, wherein the porous fluoropolymer membrane has an average maximum load of greater than 12 newtons (N).

32. The garment of claim 26, wherein said porous fluoropolymer membrane has an average modulus in the machine and transverse directions of greater than 40 MPa.

33. The garment of claim 26, wherein said porous fluoropolymer membrane has an average modulus greater than 70 MPa.

34. The garment of claim 26, wherein the porous fluoropolymer membrane has a mass per unit area of less than 80g/m²。

35. The garment of claim 26, wherein the porous fluoropolymer membrane has a mass per unit area of less than 50g/m²。

36. The garment of claim 26, wherein said porous fluoropolymer membrane has a mass per unit area of 19g/m²And 60g/m²In the meantime.

37. The garment of claim 26, wherein said porous fluoropolymer membrane has a mass per unit area of greater than 10g/m²。

38. The garment of claim 26, wherein said porous fluoropolymer membrane has a thickness of less than 120 μm.

39. The garment of claim 26, wherein said porous fluoropolymer membrane has a thickness of less than 35 μm.

40. The garment of claim 26, wherein said porous fluoropolymer membrane is waterproof after abrasion of the outer membrane surface.

41. The garment of claim 26, wherein said textile is a knit and said laminate is waterproof after more than 1400 abrasion movements on the outer membrane surface.

42. The garment of claim 26, wherein said fabric is a textile and said laminate is waterproof after more than 2000 abrasion movements on the outer membrane surface.

43. The garment of claim 26, wherein said laminate has a water absorption value of less than or equal to 10g/m²。

44. The garment of claim 26, further comprising a discontinuous coating in the form of particles or discrete units to further provide abrasion resistance.

45. The garment of claim 44, wherein said discrete material coating comprises a material selected from the group consisting of polyurethane, epoxy, silicone, or fluoropolymer.

46. An outer garment having an abrasion resistant, low water adsorption outer film surface comprising:

an outer coating surface of the outer coat, and

a laminate comprising:

1) a porous polymeric membrane having an abrasion resistant dyed outer membrane surface and an inner membrane surface opposite the outer membrane surface, having an oleophobicity rating of greater than 2, the porous polymeric membrane having an average maximum load in the transverse and longitudinal directions of greater than 10N; and

2) a woven or knitted fabric layer bonded to the porous polymer membrane by a tie adjacent to the inner membrane surface; the MVTR of the laminate is higher than 4000g/m²24 hours, mass per unit area less than 150g/m²，

The outer film surface of the garment thus assembled is the outer film surface of the laminate, having a water absorption of less than 10g/m²。

47. A method of making a lightweight laminate having an abrasion resistant outer film surface comprising the steps of:

a) selecting a fabric layer;

b) selecting a porous membrane having an average maximum load greater than 10N;

c) dyeing the porous membrane with a dyeing agent to obtain the porous membrane with the dyed outer membrane surface; and is

d) Optionally laminating the fabric and porous film to form a surface having an outer film either before or after the dyeing step

And an inner fabric surface;

wherein the laminate has a water vapor transmission rate of greater than 4000g/m²24 hours, mass per unit area less than 400g/m²The outer film surface of the laminate is abrasion resistant and remains water resistant after abrasion.

48. The method of claim 47, further comprising coating the porous membrane with an oleophobic coating.

49. The method of claim 47, wherein the porous membrane is microporous.

50. The method of claim 47, wherein the porous membrane comprises polyurethane.

51. The method of claim 47, wherein the porous membrane comprises microporous Polytetrafluoroethylene (PTFE).

52. The method of claim 47, wherein the porous membrane comprises microporous expanded PTFE.