Fiber laminate structure and waterproof and breathable fabric

Abstract

The objective is to provide a highly practical fiber laminate structure and waterproof and breathable fabric that not only exhibits excellent moisture permeability and waterproofness, but also maintains excellent waterproofness (damp heat resistance) after prolonged use, and boasts excellent recycling efficiency. The fiber laminate structure of this invention comprises a woven knitted fabric with a non-porous resin layer on the fabric. The resin layer includes resin A and elastomer B, wherein resin A and elastomer B are any combination of polyamide and polyamide-based elastomers, or polyester and polyester-based elastomers. The phases of resin A and elastomer B are either co-continuous or island-continuous.

Description

Technical Field

[0001] This invention relates to fiber laminate structures and waterproof and breathable clothing. Background Technology

[0002] In the past, to obtain fiber laminate structures with excellent moisture permeability and waterproofness, the following methods have been used: dissolving polyurethane in a solvent such as dimethylformamide, laminating it onto a fabric through coating or other means, and then introducing it into water to solidify it, thus forming a microporous membrane and creating a membrane with both moisture permeability and waterproofness, a method known as wet coating of polyurethane; laminating a resin membrane mixed with a highly moisture-permeable hydrophilic resin onto a fabric, wherein the highly moisture-permeable hydrophilic resin is a polymer in which hydrophilic portions are introduced into the polymer chain; or, bonding a stretched and expanded microporous polytetrafluoroethylene membrane to a fabric; and so on.

[0003] However, in recent years, due to the depletion of petroleum resources and the conservation of resources for environmental protection, the recycling of clothing materials has received increasing attention. In the past, the materials used for the surface and inner layers of waterproof and breathable materials were often different from the materials used for the aforementioned waterproof and breathable membranes. For example, some used polyamide or polyester woven fabrics as the surface layer, and layered polyurethane or polytetrafluoroethylene membranes for the waterproof and breathable membrane. Others used three-layered products with polyamide knitted fabric as the inner layer. For these materials, when chemical recycling is required after use and disposal, the surface layer, waterproof and breathable membrane, and inner layer need to be separately classified and collected.

[0004] As an attempt to reduce the cost of sorting and collecting such materials and make them easier to recycle, a scheme was proposed to use polyamide copolymers, which are polyamide-based elastomers, as membranes with waterproof and breathable functions (Patent Document 1).

[0005] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2011-37101 Summary of the Invention

[0006] The problem that the invention aims to solve However, while the membrane made of a single polyamide elastomer with moisture permeability disclosed in Patent Document 1 has a certain degree of moisture permeability and water resistance, it has low resistance to damp heat, and its water resistance decreases significantly after a long period of time. In addition, membranes made of polyamides such as polyamide 6 and polyamide 66 alone can suppress the decrease in water resistance after a long period of time, but their moisture permeability is poor as a waterproof and breathable fabric.

[0007] The purpose of this invention is to solve the above-mentioned problems and provide a highly practical fiber laminate structure and waterproof and breathable clothing with excellent moisture permeability, waterproofness, and waterproofness (damp heat resistance) after a long period of time, as well as excellent recycling efficiency.

[0008] Methods for solving problems To address the aforementioned issues, the present invention has the following configuration.

[0009] [1] A fiber laminate structure having a woven or knitted fabric and a non-porous resin layer on the woven or knitted fabric. The resin layer comprises resin A and elastomer B. The resin A and the elastomer B are any combination of polyamide and polyamide-based elastomers, or polyester and polyester-based elastomers. The phase of resin A and the phase of elastomer B are either a co-continuous structure or an island-island structure with continuous island phases.

[0010] [2] The fiber laminate structure as described in [1], wherein the resin A and the elastomer B are a combination of the polyamide and the polyamide-based elastomer.

[0011] [3] The fiber laminate structure as described in [2], wherein the polyamide elastomer is a polyether ester amide comprising a dioxyethylene ether having a bisphenol A backbone as represented by the following structural formula (1) as a copolymer component. [Chemical Formula 1] .

[0012] [4] The fiber laminate structure as described in [2] or [3], wherein the phase of resin A and the phase of elastomer B are island-island structures with continuous island phases. The island phase is formed from the polyamide, and the sea phase is formed from the polyamide-based elastomer. The average diameter of the island phase is 5–200 nm.

[0013] [5] The fiber laminate structure as described in any one of [2] to [4], wherein the woven fabric is formed from polyamide.

[0014] [6] As described in [5], the fiber laminate structure wherein the fiber constituting the woven fabric is a fiber with polyamide 6 as the main component, the resin A is polyamide 6, and the elastomer B is a polyamide 6-based elastomer.

[0015] [7] The fiber laminate structure as described in any one of [1] to [6], wherein the moisture permeability of the fiber laminate structure according to JIS L1099:2021 (A-1 method) is 3500 g / m³.2 • For more than 24 hours, and the moisture permeability according to JIS L1099:2021 (B-1 method) is 10000 g / m³. 2 ·More than 24h.

[0016] [8] The fiber laminate structure as described in any one of [1] to [7], wherein the elongation of at least one of the warp and weft directions of the woven fabric is 10% or more according to the JIS L1096:2010 elongation rate A method (constant speed elongation method).

[0017] [9] A waterproof and breathable fabric comprising any one of [1] to [8] a fiber laminate structure.

[0018] The effects of the invention According to the present invention, a fiber laminate structure and waterproof and breathable clothing with excellent moisture permeability, waterproofness, and long-term waterproofness (damp heat resistance) are provided, along with excellent recycling efficiency and high practicality. The fiber laminate structure and waterproof and breathable clothing of the present invention can be practically and suitable for use in sportswear, uniforms, raincoats, etc., and also have excellent reuse efficiency after use. Attached Figure Description

[0019] [ Figure 1 This is a schematic diagram illustrating an example of a continuous island phase structure within a resin layer.

[0020] [ Figure 2 This is a schematic diagram illustrating an example of a discontinuous island phase structure within a resin layer.

[0021] [ Figure 3 This is a schematic diagram illustrating a method for calculating the maximum diameter of an island phase when island phases overlap. Detailed Implementation

[0022] The present invention will now be described in detail.

[0023] The fiber laminate structure of the present invention is a fiber laminate structure having a woven or knitted fabric and a non-porous resin layer on the woven or knitted fabric. The fiber laminate structure of the present invention is suitable for use in clothing such as sportswear, uniforms, and raincoats. In this case, it is preferable to use the woven or knitted fabric side as the surface material.

[0024] [Machine-knitted fabrics] The fiber laminate structure of the present invention has a woven or knitted fabric.

[0025] Examples of fibers constituting woven or knitted fabrics include polyester fibers, polyamide fibers, polyethylene fibers, polypropylene fibers, polyurethane fibers, cotton, linen, regenerated cellulose fibers, acrylic fibers, wool, and acetate fibers. From a recycling perspective, it is preferable that the resin is the same as resin A and elastomer B in the resin layer described later. If resin A in the resin layer is polyamide and elastomer B is a polyamide-based elastomer, it is even more preferable that the fibers constituting the woven or knitted fabric are also formed from polyamide.

[0026] Polymers constituting polyamide fibers are polymers containing amide bonds. Specifically, examples include: aliphatic polyamides such as polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 46, polyamide 610, polyamide 56, and polyamide 510; polyamide 6T and polyamide 9T made from diamine and terephthalic acid; semi-aromatic polyamides such as polyamide 6I made from hexamethylene diamine and isophthalic acid; and fully aromatic polyamides such as aromatic polyamides obtained through the co-condensation reaction of aromatic diamines and dicarboxylic acids.

[0027] Among the aforementioned polyamide fibers, polyamide 6 fibers and polyamide 66 fibers are preferred from the viewpoints of cost and versatility, and polyamide 6 fibers are more preferred from the viewpoints of moisture permeability and chemical recyclability.

[0028] As for the fiber form, multifilament is preferred, but individual filaments of multifilament or multifilaments with a parallel or core-sheath composite cross-sectional structure (hereinafter sometimes referred to as "composite multifilament") are also acceptable. Individual filaments, as referred to here, are fibers whose constituent materials are composed of a single material (which can be a polymer alone or a composition containing two or more components).

[0029] The aforementioned core-sheath composite can be either an eccentric core-sheath composite or a concentric core-sheath composite.

[0030] In the case of composite multifilaments, it is preferable to have a potential crimped filament of the side-by-side or eccentric core-sheath composite type, which exhibits a three-dimensional coiled (spiral) crimp within the fiber through the combination of polymers. When using a side-by-side or eccentric core-sheath composite type as the composite form, examples of polymer combinations can be combinations of the same polymers with different viscosities, combinations of different types of polymers, preferably combinations of the same polyester polymers with different viscosities, or combinations of different types of polyamide polymers such as polyamide 6 and polyamide 66.

[0031] Examples of specific combinations of two components constituting composite multifilaments include polyamide 6 and polyamide 66, polyamide 6 and polyamide 610, and polyamide 66 and polyamide 610.

[0032] By using the same resin as resin A and elastomer B in the resin layer (described later) in woven and knitted fabrics, excellent recyclability, including material recycling and chemical recycling, is achieved. Furthermore, the fewer types of resin used, the better the material recycling performance; the fewer types of monomer components, the better the chemical recycling performance. Therefore, the appropriate materials should be selected based on the required functionality and recyclability for practical applications.

[0033] Stretchability can be achieved by using potentially crimped filaments, such as false-twisted yarns or parallel filaments of polymers with different heat shrinkage rates, as fibers. Alternatively, covering yarns using elastic filaments such as polyurethane (Spandex) fibers can also be used. However, when recycling products containing fiber-laminated structures, if the proportion of polyurethane fibers mixed with other materials increases, the mixing rate (incorporation rate, i.e., the proportion blended in) of other materials increases, and consequently, the content of the material to be recycled decreases. As a result, recycling efficiency decreases, which is something to be aware of.

[0034] In this invention, to improve recycling efficiency, it is preferable to have fewer types of structural units in the polymer components constituting the fibers of the woven or knitted fabric. For example, in the case of polyamide 6, hexamethylenediamine units are included as structural units, and these structural units are also repeating units. Additionally, in the case of polyamide 66, adipamide units are repeating units, and these repeating units contain hexamethylenediamine residues and adipic acid residues as structural units. When the fibers contained in the woven or knitted fabric are polyamide 6 fibers and polyamide 66 fibers and / or composite multifilaments formed from polyamide 6 and polyamide 66, the structural units include hexamethylenediamine units, hexamethylenediamine residues, and adipic acid residues. When the fibers contained in the woven or knitted fabric are polyamide 66 fibers and polyamide 610 fibers, the structural units include hexamethylenediamine residues, adipic acid residues, and sebacic acid residues. Preferably, the polymer constituting the fibers of the woven or knitted fabric has only one main repeating unit. For example, in woven and knitted fabrics containing polyamide copolymer fibers with hexamethylenediamine units (polyamide 6 units) as the main constituent unit and polyamide 6 fibers formed from polyhexamethylenediamine homopolymers, the main repeating unit is the polyamide 6 unit. Similarly, in woven and knitted fabrics containing polyamide 6 fibers formed from polyhexamethylenediamine homopolymers and a small amount of polyurethane fibers, the main repeating unit is also the polyamide 6 unit. Furthermore, in woven and knitted fabrics containing polyamide 6 fibers and composite multifilaments of polyamide 6 and polyamide 66, the woven and knitted fabric contains both polyamide 6 units and hexamethylenediamine units (polyamide 66 units) in all its repeating units, but the one with the higher proportion of repeating units is considered the main repeating unit. From the viewpoint of chemical recycling, the higher the proportion of the main repeating unit among all repeating units in the woven and knitted fabric's woven and knitted fabric, the more desirable it is, with 100% by mass being the most preferred. As described above, when using different types of elastic yarns such as polyurethane fibers or composite multifilaments formed from different types of polymers, the higher the content of the main repeating unit in the polymer constituting the fibers in the woven or knitted fabric, the better, preferably at least 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more.

[0035] There are no particular limitations on the cross-sectional shape of the fiber; circular, triangular, hollow, and other shapes can be widely used. In addition, the fiber may contain additives that impart antistatic properties, as well as matting agents such as titanium dioxide.

[0036] The total fineness of the yarn used for woven or knitted fabrics is preferably 150 dtex or less. By reducing the thickness of the woven or knitted fabric, the moisture permeability increases. If the yarn is too fine, the tear strength and bursting strength decrease; therefore, 11 dtex or more is preferred. More preferably, it is 20 dtex or more and 75 dtex or less.

[0037] Furthermore, from the perspective of improving moisture permeability, it is preferable to keep the density of woven fabrics as low as possible. When the fineness is the same or lower, reducing the density of woven fabrics tends to decrease the UV shading rate. For example, when using woven fabrics as surface materials, UV rays can penetrate the fabric and reach the resin layer when exposed to UV light outdoors. If the amount of UV rays penetrating the fabric and reaching the resin layer increases, the resin layer is more prone to deterioration due to UV exposure. Therefore, it is essential to consider these factors and appropriately determine the density of the woven fabric and the fineness of the fibers used.

[0038] Furthermore, in this invention, the woven fabric preferably has an elongation rate of 10% or more in at least one of the warp and weft directions according to the JIS L1096:2010 elongation rate A method (constant speed elongation method). It should be noted that, in order to produce the woven fabric described above, to further improve the elongation rate, elastic fibers such as polyamide fibers can be used. It should be noted that, in the case of knitted fabrics, the warp direction refers to the longitudinal direction, and the weft direction refers to the transverse direction. In addition, by achieving an elongation rate of 10% or more for the woven fabric, the wearing comfort is improved, the applicability is increased, and the freedom of sewing patterns is further increased. The elongation rate is more preferably 15% or more and 100% or less. If the elongation rate is greater than 100%, misalignment may easily occur during the bonding process with the waterproof and breathable membrane, reducing productivity.

[0039] As for the form of woven fabric, there are no particular restrictions, but plain weave, twill weave, satin weave, as well as rib weave, double weave, Oxford cloth, Taslon and other woven fabrics are preferred.

[0040] There are no particular limitations on the form of knitted fabric, but circular knitted fabrics and warp knitted fabrics with fine gauge and high density are preferred.

[0041] [Resin Layer] Next, the non-porous resin layer on the woven fabric will be described. Here, "non-porous" means that when the cross-section of the resin layer is observed with an electron microscope using the method described in the examples, there are no interconnecting pores on the surface and back. In addition, the resin layer can be formed directly on the woven fabric, or other layers can be formed between the resin layer and the woven fabric.

[0042] In this invention, the resin layer comprises resin A and elastomer B. By configuring it as described above, it is possible to combine the mechanical strength and water resistance of resin A with the softness and breathability of elastomer B. It should be noted that the elastomer referred to here is an object as defined in JIS K 6200 (2019) that exhibits the property of deforming under a weak force and rapidly returning to approximately its initial shape and size after the force is removed. As a standard, it is an object that, after being stretched to twice its original length and held for one minute, shrinks to less than 1.5 times its original length within five minutes. Furthermore, the elastomer also includes thermoplastic elastomers as defined in JIS K 6418:2017.

[0043] Furthermore, the aforementioned resin A and elastomer B are any combination of polyamide and polyamide-based elastomers, or polyester and polyester-based elastomers. From the viewpoints of durability, cost, and versatility, materials used in waterproof and breathable clothing are typically composites with woven or knitted fabrics formed from polyamide or polyester. Therefore, having the resin layer in this configuration is advantageous for recycling, as it easily improves recycling efficiency. From the viewpoint of further improving recyclability, when the composite woven or knitted fabric is formed from polyamide, it is preferable that the aforementioned resin layer is a fiber laminate structure formed from polyamide and polyamide-based elastomers; when the composite woven or knitted fabric is formed from polyester, it is preferable that the aforementioned resin layer is a fiber laminate structure formed from polyester and polyester-based elastomers. From the viewpoints of weather resistance and mechanical strength, it is more preferable that the woven or knitted fabric composited with the aforementioned fiber structure is formed from polyamide, and that resin A and elastomer B are a combination of polyamide and polyamide-based elastomers.

[0044] The polyamide used in resin A is a polymer with amide bonds. Specifically, examples include nylon 6 (polyamide 6), nylon 11 (polyamide 11), nylon 12 (polyamide 12), nylon 66 (polyamide 66), nylon 46 (polyamide 46), nylon 610 (polyamide 610), nylon 56 (polyamide 56), and nylon 510 (polyamide 510). Among these, from the perspective of cost and versatility, polyamide 6 and polyamide 66 are preferred. From the perspective of moisture permeability and chemical recyclability, polyamide 6 is more preferred.

[0045] The polyamide-based elastomer used in elastomer B can be any polyamide-based elastomer as long as it is formed from a polyamide copolymer and exhibits elastomer behavior. Specifically, examples include polyether ester amides formed from polyamide components such as polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 46, polyamide 610, polyamide 56, polyamide 510, polyamide 6T and polyamide 9T (based on diamine and terephthalic acid), and poly(epoxy) glycol and dicarboxylic acid components; and polyether ester amides formed from polyamide components, glycol components, poly(epoxy) glycol components, and dicarboxylic acid components. From the viewpoint of further improving moisture permeability, polyether ester amides formed from polyamide components with high moisture permeability, poly(epoxy) glycol components, and dicarboxylic acid components, or polyether ester amides formed from polyamide components, glycol components, poly(epoxy) glycol components, and dicarboxylic acid components, are preferred. Furthermore, elastomer B may also contain other copolymer components.

[0046] Furthermore, a polyether ester amide containing a bisphenol A backbone-containing vinyl ether (hereinafter sometimes also referred to as an ethylene oxide adduct of bisphenol A) as a copolymer component is more preferred. By adopting the above-described manner, when the waterproof and breathable fabric absorbs moisture such as rain and sweat, it can suppress water swelling caused by the poly(epoxy)diol contained in elastomer B, and can further improve the resistance to damp heat, that is, the waterproofness after a long period of time. In addition, in the above-described polyether ester amide, the number average molecular weight of the bisphenol A backbone-containing vinyl ether as a copolymer component is preferably 1000 to 3000, more preferably 1500 to 2500. Furthermore, from the viewpoint of further improving breathability and resistance to damp heat, the bisphenol A backbone-containing vinyl ether is preferably 15 to 70% by mass, more preferably 30 to 55% by mass, relative to the polyether ester amide as a whole.

[0047] [Chemical Formula 2] In the above structural formula (1), m and n represent the degree of polymerization of the dioxyethylene ether with a bisphenol A backbone. The independent values ​​cannot be determined, but the average value of m+n can be calculated from the structure of the compound and the number-average molecular weight. m+n is preferably 5 to 60, and more preferably 20 to 40.

[0048] It should be noted that, in this invention, in terms of number average molecular weight, when 1g of sample is heated with an excess of acetylation agent such as acetic anhydride to acetylate, and the amount of potassium hydroxide (mg) required to neutralize the generated acetylated product is set as A, and the amount of potassium hydroxide (mg) required to neutralize 1g of sample before acetylation is set as B, it can be calculated by the following formula.

[0049] Number average molecular weight = 11200 / {[A / (1 - 0.00075 × A)] - B} It should be noted that, among the above-mentioned polyether ester amides, polyamide 6 and polyamide 66 are preferred as copolymer components from the viewpoints of cost and versatility, and polyamide 6 is more preferred from the viewpoints of moisture permeability and chemical recyclability.

[0050] Furthermore, to improve recycling efficiency, it is preferable to use the same polymer in both the woven fabric and the resin layer. From the viewpoint of moisture permeability and chemical recyclability, it is more preferable that the fibers constituting the woven fabric are fibers with polyamide 6 as the main component, the resin A is polyamide 6, and the elastomer B is a polyamide 6-based elastomer. Here, "with polyamide 6 as the main component" means that the fiber composition contains 50% by mass or more of polyamide 6. Additionally, if elastomer B is a polyamide-based elastomer, and the main repeating unit of its polyamide component is the same as the main repeating unit in the polyamide constituting resin A and the fiber, it is considered that the same polymer was used.

[0051] For the resin layer, it is important that the phase of resin A and the phase of elastomer B have a co-continuous structure or an island-island structure with continuous island phases. The inventors of this application conducted research and found that simply mixing resin A and elastomer B results in a decrease in water resistance over a long period. This problem can be solved by having specific structures for resin A and elastomer B. Specifically, the phases of resin A and elastomer B are not completely miscible, but rather form the aforementioned structure, thereby further improving the resistance to damp heat from resin A and the permeability from elastomer B. If the phases of resin A and elastomer B are completely miscible, the degree of swelling when the membrane absorbs water increases, the membrane strength decreases, and thus the resistance to damp heat, i.e., the water resistance over a long period, decreases. Furthermore, in the case where the island phase is a discontinuous island structure in the phase of resin A and the phase of elastomer B, the difference in swelling behavior when the phase of resin A and the phase of elastomer B absorb water causes deformation in the film, making it prone to cracking and fissures, thereby reducing the resistance to damp heat, i.e., the waterproofing after a long period of time.

[0052] The co-continuous structure mentioned here generally refers to a three-dimensional continuous or interconnected structure (mesh structure). This is a known morphological structure exemplified in non-patent literature such as "Fundamentals and Applications of Polymer Alloys, 2nd Edition," edited by the Polymer Society, published by Tokyo Chemical Doji Co., Ltd., 1993. Additionally, the island-phase continuous island structure mentioned here refers to, for example... Figure 1As shown in the transmission electron microscope (TEM) at 5000x magnification, when observing ultrathin sections of resin layers appropriately stained with functional groups, island phases of 10 or more consecutive island phases accounted for more than 50% of the area of ​​island phases in the field of view. Here, "consecutive" means that the interfaces of the island components in the above image are close to each other within 20 nm. Furthermore, the number of consecutive island phases refers to the number of units that can be divided into near-circular sections in the above image, for example... Figure 2 In island phase example B, there is one island phase that is discontinuous, while in island phase example A, there are three continuous island phases (wherein, since island phase example A has three island phases, it is not determined to have the aforementioned "island structure with continuous island phases" based on the presence of this island phase). By setting the phase structure as described above, the island components form a network, taking into account the characteristics of each phase, and the mechanical strength from the island components can be further improved, thus improving the resistance to damp heat, i.e., the water resistance after a long period of time. In order to form the phase structure as described above, it is effective to reduce the difference in melt viscosity between the resin A and the elastomer B, preferably 200 poise (20 Pa·s) or less, more preferably 0 to 100 poise (0 to 10 Pa·s). In addition, in order to stabilize the phase structure as described above, it is also effective to set the content of the resin A or the elastomer B, based on the mass of the resin layer, to 5 to 50%, more preferably 10 to 40%.

[0053] Furthermore, from the viewpoint of improving moisture permeability and resistance to damp heat, it is preferable that the phase of resin A and the phase of elastomer B are a continuous island-island structure, with the island phase formed from polyamide and the sea phase formed from polyamide-based elastomer. By forming the above structure, deformation of the resin layer caused by water swelling of the polyamide-based elastomer, which is the sea phase, can be suppressed, thus further improving the resistance to damp heat, i.e., the water resistance after a long period of time. In order to form the above structure, it is effective to make the melt viscosity of the polyamide-based elastomer lower than that of polyamide. Specifically, it is preferable that the melt viscosity of the polyamide-based elastomer is 1 to 200 poise (0.1 to 20 Pa·s) lower than that of polyamide, more preferably 10 to 100 poise (1 to 10 Pa·s).

[0054] Furthermore, the average diameter of the island phases is preferably 5 to 200 nm. By making the average diameter of the island phases 5 nm or more, it is possible to prevent the island phases from becoming too fine, fully utilize the mechanical strength from the island phases, and further improve the resistance to damp heat, i.e., the water resistance after a long period of time. The average diameter of the island phases is more preferably 50 nm or more. On the other hand, by making the average diameter of the island phases 200 nm or less, it is possible to suppress the coarsening of the island phases and the resulting local unevenness in the mechanical strength of the resin layer, thereby preventing the reduction of resistance to damp heat, i.e., the water resistance after a long period of time. The average diameter of the island phases is more preferably 150 nm or less. To achieve the above-mentioned method, it is effective to melt-blend resin A and elastomer B using a twin-screw extruder or similar method. It should be noted that the average diameter of the island phases in this invention is the value obtained by observing the resin layer with a transmission electron microscope (TEM) and randomly selecting 20 island phases, and calculating the number average of the maximum diameters of each island phase. It should be noted that when the island phases are not circular, the length of the longer side is taken as the maximum diameter, such as... Figure 3 When the islands shown in (a) overlap, as Figure 3 (b) The ellipse is separated using the least squares method described in the Papers of the Institute of Electronics and Information Communications, DVol.J70-D No.6 PP.1173-1180 (June 1987), thereby creating an approximate interface for each island phase, which is taken as the maximum diameter D of the island phase with the largest diameter. max .

[0055] Considering the physical strength of the resin layer and the feel when making waterproof and breathable fabric, the thickness of the resin layer is preferably 10–30 μm. When the resin layer thickness is less than 10 μm, the waterproofness decreases. Furthermore, when the thickness is greater than 30 μm, the moisture permeability decreases. A thickness of 15–25 μm is preferred.

[0056] The elongation of the resin layer is preferably 100% or more and less than 800%, more preferably 200% or more and less than 600%. Setting the elongation of the resin layer to 100% or more maintains the flexibility of the film after lamination and suppresses the decrease in moisture permeability and water resistance during deformation of the laminate, thus it is preferred. Furthermore, setting the elongation of the resin layer to less than 800% suppresses excessive elongation and deformation of the film during laminate deformation, thus suppressing the decrease in moisture permeability and water resistance, thus it is preferred.

[0057] In addition to the elongation rate mentioned above, excellent elongation recovery rate is also preferred for the elasticity of the resin layer. The elongation recovery rate of the resin layer is preferably 80% or more, and more preferably 90% or more. By making the elongation recovery rate of the film as described above, when worn as clothing, the laminated structure follows the body's movements and has excellent fit, thereby providing the effect of easy movement and less fatigue.

[0058] In addition, the resin layer exhibits elasticity based on the proportion of elastomers. Considering both moisture permeability and water swelling, the copolymerization rate can be selected based on practicality and application, or it can be chosen from commercially available products.

[0059] [Antioxidants] In this invention, an antioxidant is preferably used to improve the heat resistance of the resin layer. Examples of antioxidants include phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants, with hindered phenolic antioxidants being particularly preferred. The resin layer preferably contains 0.05 to 5.0% by mass of the antioxidant, and as a further preferred amount, it is 0.5 to 4.0% by mass, more preferably 0.2 to 0.5% by mass.

[0060] [Hydrolysis resistance improver] In this invention, to improve the hydrolysis resistance of the resin layer used, a hydrolysis resistance improver is preferably used. Examples of hydrolysis resistance improvers include carbodiimide compounds, epoxy compounds, and chelating agents (metal catalyst deactivators). From the viewpoint of suppressing process contamination caused by tackification and gases, epoxy compounds and chelating agents are particularly preferred. Furthermore, when using metals such as titanium as the polymerization catalyst for ester-based resins, adding an octadecyl phosphate chelating agent to suppress the reverse reaction of transesterification is a more preferred method to further improve hydrolysis resistance. The resin layer preferably contains 0.05 to 3.0% by mass of the hydrolysis resistance improver, and a further preferred addition amount is 0.1 to 2.0% by mass.

[0061] [UV absorber] In this invention, an ultraviolet absorber can be used to improve the lightfastness of the resin layer. Examples of ultraviolet absorbers include benzotriazoles and benzophenones. Examples of benzotriazoles include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, and 2-[5-chloro-(2H)-benzotriazole-2-yl]-4-methyl-6-(tert-butyl)phenol; examples of benzophenones include 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octyloxybenzophenone. The resin layer preferably contains 0.05 to 1.0% by mass of the ultraviolet absorber, and more preferably 0.1 to 0.5% by mass.

[0062] [Light stabilizer] In this invention, a light stabilizer can be further used to improve the lightfastness of the resin layer. Examples of light stabilizers include NR-type hindered amines. Examples of NR-type hindered amines include bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, and 2,4-bis[N-butyl-N-(1-cyclohexanoyl-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-tetraazine, an N-OR type amine. The resin layer preferably contains 0.05 to 1.0% by mass of the light stabilizer, and more preferably 0.1 to 0.5% by mass.

[0063] [pigment] In this invention, pigments are preferably used to improve the coloring of the resin layer and the color development of the fiber laminate structure. Examples of pigments include calcium carbonate, barium sulfate, clays such as kaolin or talc, titanium dioxide, and zinc oxide. From the viewpoint of stability and dispersibility, titanium dioxide is preferred, and rutile titanium dioxide with low photocatalytic activity is even more preferred. The titanium dioxide content in the resin layer is preferably 0.1 to 3.0% by mass, and more preferably 0.5 to 2.0% by mass. By making the titanium dioxide content 0.1% by mass or more, the color development of the fiber laminate structure can be improved; on the other hand, by making it 3.0% by mass or less, the flexibility of the resin layer is improved.

[0064] [Other Additives] In this invention, lubricants, flame retardants, heat stabilizers, weather resistant agents, etc., can be appropriately added to the resin layer as needed.

[0065] [other] The fiber laminate structure of the present invention is a fiber laminate structure in which a resin layer is laminated on one side of a woven or knitted fabric (hereinafter, for convenience, it is sometimes referred to as a 2-layer fiber laminate structure). However, for example, when the resin A and the elastomer B are a combination of polyamide and polyamide-based elastomer, and the woven or knitted fabric is formed from polyamide, it is also possible to further have a knitted fabric formed from polyamide filaments on the resin of the fiber laminate structure (hereinafter, it is sometimes referred to as a third layer of knitted fabric).

[0066] When using a fiber-layered structure with the aforementioned third layer of knitted fabric for clothing or similar items, it is preferable to use the knitted fabric side of the third layer as the inner layer (the side closest to the skin) and the woven knitted fabric side as the outer layer.

[0067] The fiber layered structure of the present invention can also be used as a two-layer product consisting of woven knitted fabric and resin layer without installing the third layer of knitted fabric. However, from the perspective of preventing damage caused by friction of the resin layer and giving it a high-end feel, it is preferable to install the third layer of knitted fabric so that it functions as an inner layer.

[0068] In the third layer of knitted fabric, a knitted fabric formed from 100% by weight of polyamide multifilament is suitable. As such polyamide multifilament, multifilament composed of polyamide 6, polyamide 66, and polyamide 610 is preferred.

[0069] As a fiber form, even individual filaments or composite multifilaments are acceptable. The terms "individual filament" and "composite multifilament" used here are the same as those mentioned above.

[0070] When composite multifilaments are core-sheath composites, they can be either eccentric core-sheath composites or concentric core-sheath composites.

[0071] In the case of composite multifilaments, the same potential crimped yarns as described above are preferred. When using parallel type or eccentric core-sheath composite as the composite form, examples of polymer combinations can be combinations of the same polymers with different viscosities, combinations of different types of polymers, preferably combinations of the same polyester polymers with different viscosities, or combinations of different types of polyamide polymers such as polyamide 6 and polyamide 66.

[0072] Examples of specific combinations of two components constituting composite multifilaments include polyamide 6 and polyamide 66, polyamide 6 and polyamide 610, and polyamide 66 and polyamide 610.

[0073] Stretchability can be achieved by using potentially crimped filaments such as false-twisted filaments and parallel filaments of different polymers as polyamide multifilaments. Alternatively, covering filaments using elastic filaments such as polyurethane fibers can also be used. However, when recycling products containing fiber-laminated structures, if the polyurethane fiber blending rate among other materials increases, the blending rate of other materials also increases, resulting in a relatively lower content of the material to be recycled. Consequently, recycling efficiency decreases, which is something to be aware of.

[0074] In this invention, in order to improve recycling efficiency, the fiber component in the knitted fabric used as the inner layer preferably includes 100% by mass of polyamide fibers, which are polyamide multifilaments. As described above, when using non-polyamide elastic yarns or the like, it is preferable that the content of polyamide fibers in the fibers constituting the knitted fabric is high, and the proportion of polyamide fibers is preferably at least 80% by mass, more preferably at least 85% by mass, and even more preferably at least 90% by mass.

[0075] As for the third layer of knitted fabric, similar to the woven knitted fabrics mentioned above, it exhibits excellent recyclability, including material recycling and chemical recycling, through the use of polyamide multifilament. The fewer types of polyamides used in the fibers constituting the fiber laminate structure, the better the material recycling performance; the fewer types of monomer components, the better the chemical recycling performance. Appropriate selection of materials is sufficient, considering the required functionality and recyclability for practical applications.

[0076] The higher the content of the main repeating units in the polymer constituting the fiber laminate structure, the better; preferably at least 80% by mass, more preferably at least 85% by mass, further preferably at least 90% by mass, and most preferably at 100% by mass. It should be noted that the fibers in the fiber laminate structure referred to here not only refer to the fibers contained in woven or knitted fabrics, but also, in the case of knitted fabrics using an inner layer, to the fibers contained in the fiber laminate structure including the knitted fabric of the inner layer.

[0077] In addition, knitted fabrics can also undergo water-repellent processing, antistatic processing, antibacterial processing, ultraviolet absorption processing, near-infrared absorption processing, and other processing as needed.

[0078] When seam sealant is used to maintain the waterproofness of the seams, the sealant is typically bonded to the inner layer with molten resin. To allow the molten resin to easily penetrate the inner layer and reach the waterproof and breathable membrane, the inner layer is preferably made of a low-density knitted fabric. From the viewpoint of being thin and low-density, tricot warp-knitted fabrics and circular knitted fabrics are preferred.

[0079] The knitted fabric of the third layer is preferably laminated onto the resin layer of the two-layer fiber laminate structure by means of an adhesive.

[0080] As for the adhesive used in the third layer of the laminated knitted fabric, similar to the adhesive used in the woven knitted fabric described later, a hot-melt adhesive that does not use organic solvents is preferred. Examples of resins with hot-melt adhesive properties include polyurethane-based, polyester-based, polyether-based, and polyamide-based resins, but polyurethane-based or polyamide-based resins are preferred considering adhesion, flexibility, hand feel, and stretchability. Solvent-based adhesives can also be preferred. Furthermore, the adhesive coating method and lamination conditions can be the same as those for the woven knitted fabric adhesive described later.

[0081] The fiber laminate structure of the present invention preferably has excellent moisture permeability. Preferably, the moisture permeability according to JIS L1099:2021 (A-1 method) is 3500 g / m³. 2 • For more than 24 hours, and the moisture permeability according to JIS L1099:2021 (B-1 method) is 10000 g / m³. 2• 24 hours or more. Specifically, the water permeability in JIS L1099:2021 (A-1 method) is an indicator of the rate of water vapor transmission, while the water permeability in JIS L1099:2021 (B-1 method) is an indicator of the rate of water vapor transmission in the liquid phase. A more preferred water permeability in JIS L1099:2021 (A-1 method) is 6000 g / m³. 2 • After 24 hours or more, further optimization is needed for 8000g / m 2 • More than 24 hours. According to JIS L1099:2021 (A-1 method), higher moisture permeability is better, but in reality, it's around 20000 g / m². 2 • Less than 24 hours. Furthermore, according to JIS L1099:2021 (B-1 method), a more preferred moisture permeability is 20000 g / m³. 2 • More than 24 hours, preferably 30000g / m 2 • More than 24 hours. According to JIS L1099:2021 (B-1 method), higher moisture permeability is better, but in reality, it's 100,000 g / m³. 2 • Less than 24 hours.

[0082] The fiber laminate structure of the present invention has high water resistance, and therefore preferably possesses excellent properties that prevent rainwater intrusion, i.e., a water resistance of at least 150 kPa or higher. More preferably, it has a water resistance of 200 kPa or higher. Within the above range, it can also suppress rainwater intrusion into clothing during wear. Higher water resistance is more preferred, but in practice, it is below 300 kPa.

[0083] Furthermore, from the perspective of ensuring durability during actual wear, a water resistance of 150 kPa or higher after the accelerated degradation test under high temperature and humidity is preferred. More preferably, it should be 200 kPa or higher. Within this range, excellent resistance to damp heat improves water resistance over extended periods. The accelerated degradation test under high temperature and humidity refers to treatment for 7 days in a constant temperature and humidity bath at 70°C and 95% RH. Higher water resistance after the accelerated degradation test under high temperature and humidity is preferable, but in practice, it is below 300 kPa.

[0084] It is preferable to apply a water-repellent treatment to the fiber laminate structure of the present invention. By applying the water-repellent treatment, it becomes a more practical product as a waterproof and breathable material; water-repellent treatment with high wash durability and friction durability is preferred. As the water-repellent agent, known water-repellent agents such as fluorine-based, silicone-based, and paraffin-based agents can be used. As the processing method, conventional processing methods such as padding-drying-curing can be used. During processing, any processing method can be applied at any time, such as before or after the resin layer is laminated.

[0085] In addition, antistatic processing, antibacterial processing, ultraviolet absorption processing, near-infrared absorption processing, and other processing can be carried out as needed.

[0086] [Waterproof and breathable clothing] Waterproof and breathable clothing containing the fiber laminate structure of the present invention has a good effect of preventing stuffiness due to its high waterproofness and breathability, and excellent wearing comfort. At the same time, its waterproofness is also excellent after a long time, making it suitable for waterproof and breathable clothing such as outdoor clothing, windproof clothing, and raincoats for mountaineering and skiing.

[0087] [Method for manufacturing the resin layer] The resin layer used in this invention can be manufactured using conventional film-forming methods such as the T-die method and blow molding. For example, the aforementioned polyamide, polyamide-based elastomer, and optional components such as antioxidants and titanium dioxide are supplied to a single-screw extruder or a twin-screw extruder. Next, the resin in the extruder is heated above its melting point, and in the T-die method, it is extruded as a film from the nozzle, melting and coating it onto a support material such as lightweight polyester or release paper, and then wound and stored for later use. It should be noted that, in order to improve the dispersibility of the resin and additives, it is also preferable to use a material obtained by pre-mixing and mastering the resins together or the resin and additives in a twin-screw extruder, combining them in a manner that includes the remaining components to form the desired composition, and then using the above-described method to form a film.

[0088] [Manufacturing Method of Fiber Laminated Structures] In the method of manufacturing the fiber laminate structure of the present invention, the relevant resin layer is laminated onto a base fabric formed from a woven or knitted fabric.

[0089] The above-mentioned lamination process can employ the following methods, but there are no limitations.

[0090] That is, a lamination method using an adhesive. Preferred adhesives include conventional hot-melt adhesives and hot-melt adhesives such as those for heat-bonding fibers. Solvent-based adhesives can also be used. When using a hot-melt adhesive, hot pressing can be performed using a heating device. However, when using conventional hot-melt adhesives, if the actual application area is large, it often reduces the fabric's moisture permeability; therefore, it is preferable to use an adhesive formed from a moisture-permeable resin.

[0091] To improve the control precision of peel strength and ensure that the moisture permeability, air permeability, and water resistance of the fiber laminate structure remain stable at a high level, it is preferable to apply the adhesive in the surface direction at a proportion of 70% or less relative to the area ratio of the woven or knitted fabric. More preferably, it is 10% to 70%, and even more preferably, it is 30% to 70%. To achieve the above-mentioned area ratio, it is preferable to apply the adhesive in the surface direction in the shape of dots or lines.

[0092] It is preferable to reduce the area of ​​the adhesive dots and lines, and to reduce the area ratio of the adhesive, but this will reduce the peel strength. On the other hand, to improve peel strength, it is preferable to increase the area of ​​the adhesive dots and lines, and to increase the area ratio, most preferably forming a full-surface adhesive layer, but sometimes this reduces moisture permeability. To maintain this opposite functionality well, it is preferable to use the adhesive at an area ratio of 10-70% in a layer of 0.1-100.0 mm. 2 The area is given by dots or lines or grids of thickness 0.1 to 10.0 mm.

[0093] Dots can be any shape, such as circles, quadrilaterals, rhombuses, ellipses, and triangles. They can also be combined and arranged to form patterns, text, or even trademarks. Furthermore, they can be arranged in a continuous pattern or randomly. Lines can be straight or curved. Area ratio refers to the coverage rate of the adhesive.

[0094] As an adhesive, a hot-melt adhesive that does not use organic solvents is preferred. Examples of resins with hot-melt adhesive properties include polyurethane-based, polyester-based, polyether-based, and polyamide-based resins, but polyurethane-based resins and polyamide-based resins are preferred considering adhesion, flexibility, feel, and extensibility. Alternatively, solvent-based adhesives may also be preferred.

[0095] As an adhesive, coating methods such as blade coating, rod coating, and gravure coating can be used. Gravure coating, in particular, can be applied more easily in dots, lines, or grids, and is preferred from the viewpoint of moisture permeability, but it is not limited to these methods.

[0096] In addition, the bonding method can be wet lamination, dry lamination, etc., and can be used according to the desired characteristics. From the point of view of feel and adhesion, it is preferable to apply the adhesive to the fabric and set it to dry lamination.

[0097] Example The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples in any way. It should be noted that the various measurement methods in the present invention are as follows.

[0098] (1) Membrane thickness The membrane in its free state without any applied load is cut at any 10 points with a single-edged razor, and its cross-section is observed with an electron microscope to determine the thickness. The average value is taken as the thickness.

[0099] (2) Accelerated Deterioration Test The samples were treated for 7 and 14 days in a constant temperature and humidity bath maintained at 70°C and 95%RH.

[0100] (3) Water resistance The water resistance was determined according to JIS L1092:2009 Method B (high water pressure method).

[0101] In this method, non-stretchable taffeta was overlapped on the back side (the side not in contact with water), and the sample was tested without stretching. Five samples were set as one level, and the average value was set as the water resistance.

[0102] In addition, the water resistance was determined by measuring the samples after the above-mentioned accelerated degradation test.

[0103] (4) Moisture permeability The determination was based on the JIS L1099:2021 calcium chloride method (A-1 method) and the JIS L1099:2021 potassium acetate method (B-1 method).

[0104] Specifically, the test was conducted by contacting water vapor (Method A-1) or water (Method B-1) with the fabric surface opposite to the fiber laminate structure. Both test methods were converted to moisture permeability per 24 hours. It should be noted that measurements were performed on three samples per level, and the average value was taken as the moisture permeability.

[0105] (6) Elongation The elongation was determined according to JIS L1096:2010, Method A (Constant Elongation Method). Specifically, the fabric sample was subjected to a strip method with a clamping interval of 200 mm and a width of 50 mm, and the elongation at a stress of 14.7 N was used as the stretch rate. The stretch rates in the warp and weft directions were measured. Three samples were measured at each level, and the average value was taken as the elongation rate.

[0106] (7) Observation of the resin layer (7-1) Observation of phase state A 100 nm thick slice was cut from a randomly selected part of the resin layer along the thickness direction. The polyamide resin was selectively stained using phosphotungstic acid staining to clarify the dispersion state of the polyamide resin. Then, it was observed by magnification up to 5000x using a transmission electron microscope.

[0107] (7-2) Average diameter of island phases After magnifying the observation using the same method as described in (7-1), the average diameter of the island phases is calculated from the maximum diameter of 20 randomly selected island phases from the obtained observation image. It should be noted that when the number of island phases in the field of view is less than 20, the average diameter is calculated from the maximum diameter of all island phases whose diameter can be calculated.

[0108] (8) Confirmation of non-porous membrane The presence or absence of connecting holes was determined on the surface and back side by observing five randomly selected resin layer cross-sections using an electron microscope (Hitachi High Technology Co., Ltd. SU3800, magnification: 2000x).

[0109] (9) Melt viscosity Using a vacuum dryer, the polymer flakes were dried to a moisture content of less than 200 ppm. The melt viscosity was measured using a Toyo Seiki Capilograp (L / D=40) machine with progressively varying strain rates. It should be noted that the measurement temperature was set to the same as the melt processing temperature, and the time from sample placement in the heating furnace under a nitrogen atmosphere to the start of the measurement was set to 5 minutes, with a shear rate of 1216 s⁻¹. -1 The value is used to evaluate the melt viscosity of the polymer.

[0110] (10) Movement comfort A mountaineering jacket was made using the obtained fiber laminate structure. After wearing the jacket, the following assessment was conducted: from 10 randomly selected individuals, the assessment with the most frequent rating was taken as the result. If multiple assessments had the most frequent rating, the median rating was selected. It should be noted that the jacket sizes worn by each individual were based on JIS L4004:20019, and were set to sizes suitable for their respective body types (S, M, L).

[0111] A: I can hardly feel any pressure or tightness from the fabric, and my movements are very comfortable.

[0112] B: Although I felt a sense of pressure and tightness from the fabric to some extent, I can't say that the comfort of movement was poor.

[0113] C: I could clearly feel the pressure and tightness from the fabric, and my movements were not comfortable.

[0114] [Example 1] The polyamide 6 semi-dull circular cross-section multifilament, with a warp yarn of 56 dtex-42 filament and a weft yarn of 78 dtex-34 filament, was false-twisted in a stretchable manner. This processed yarn was then used for both warp and weft yarns and woven on a water-jet loom with a warp × weft density of 111 yarns / 2.54 cm × 77 yarns / 2.54 cm. After refining and relaxation treatment, the fabric is pre-set and dyed using a liquid flow dyeing machine according to conventional methods. Then, a 5% aqueous solution of "Asahi Guard" (registered trademark) AG710 (fluorine-based water repellent, manufactured by Asahi Glass Co., Ltd.) is applied to the surface of the woven fabric using a pad-dry-curing method to achieve an adhesion rate of 60%. After drying at 120°C for 1 minute, it is heat-treated at 170°C for 40 seconds. Finally, the fabric is finished by processing it with a warp and weft density of 154 threads / 2.54cm × 122 threads / 2.54cm to obtain the woven fabric.

[0115] On the other hand, as a method for preparing a polyamide-based elastomer for forming a resin layer film, 45 parts of caprolactam, 45 parts of ethylene oxide adduct of bisphenol A with a number average molecular weight of 1,500 as represented by the above formula (1), 5 parts of polyethylene glycol with a number average molecular weight of 1,500, and 5.82 parts of terephthalic acid with a carboxyl group amount [COOH] such that [OH] / [COOH] = 0.95 relative to the amount of hydroxyl group [OH] from the poly(epoxy) glycol, and 0.5 parts of antioxidant ("IRGANOX" (registered trademark) 1098: manufactured by Ciba Specialty Chemicals Co., Ltd.) are loaded into a reaction vessel, purged with N2, heated and stirred at 260°C for 60 minutes to prepare a transparent homogeneous solution, and then the pressure is reduced to below 0.07 kPa. Add 0.1 parts of tetrabutyl titanate, and stop the reaction when the stirring torque reaches 11 kg·m (11 r / min) under conditions of pressure below 0.07 kPa and temperature of 260 °C. The reaction time was 2.1 hours, yielding a product with a crystallization temperature of 115.0 °C, an unreacted lactam content of 0.24%, and an amino content of 0.48 × 10⁻⁶. -5 Polyether ester amide (A) with eq / g and melt viscosity of 920 poise (92 Pa·s).

[0116] Granules of polyether ester amide (A) and granules of polyamide 6 with a melt viscosity of 960 poise (96 Pa·s) were dried under reduced pressure at 110°C for 14 hours to reduce the moisture content to below 300 ppm. A total of 100 parts were prepared, consisting of 80 parts of polyether ester amide (A), 17 parts of polyamide 6, 2 parts of rutile titanium dioxide, and 1 part of hindered phenolic antioxidant. A 45mm diameter... A twin-screw extruder with three threaded screws sets the barrel temperature (melt processing temperature) to 255°C for melt mixing. The product is then discharged in strands, cooled in a water bath, and subsequently granulated using a granulator. The pellets were 3mm in diameter and 3mm in length. The resulting pellets were dried under reduced pressure at 110℃ for 14 hours to reduce the moisture content to below 300ppm. Then, using a single-screw extruder, the pellets were melt-extruded using a T-slot die at a barrel temperature set to 255℃ to produce pellets with a thickness of 20μm (18g / m²). 2 The resulting non-stretchable membrane (resin layer) has no interconnected pores and is non-porous.

[0117] A moisture-curing polyurethane hot-melt adhesive was melted at 110°C and applied to the woven fabric using a gravure coating machine equipped with a gravure roller engraved with square grooves (0.40mm x 0.40mm, 20μm deep) at a 40-mesh angle relative to the fabric's direction of travel. The coating was dried at 120°C for 1 minute. As a result, the adhesive was applied to the fabric in a dotted pattern, each dot being a square with sides of 0.40mm, arranged at a 45° angle relative to the length direction. The area ratio (coverage) of the adhesive relative to the fabric was 40%, and the adhesive application rate was 15g / m². 2 .

[0118] Next, the obtained non-stretch film is overlapped on the adhesive side of the woven fabric coated with the above adhesive, and then subjected to a linear pressure of 49 N / cm by passing it between a metal roller and a rubber roller at a temperature of 110°C. After aging at room temperature for 48 hours, a two-layer fiber laminate structure is obtained by laminating the woven fabric and the film (resin layer).

[0119] Next, on the sinking surface of a semi-trico warp-knitted fabric made of 22dtex-16 filament polyamide 6 semi-dull circular cross-section multifilament dyed gray, a moisture-curing polyurethane hot melt adhesive is applied in the same manner as the adhesive applied to the aforementioned woven fabric, with an area ratio of 40% and an adhesive amount of 10 g / m². 2 A three-layer fiber laminate structure is made by laminating the knitted fabric with the film (resin layer) side of the two-layer fiber laminate structure.

[0120] The composition and evaluation results of the obtained surface material, resin layer, and fiber laminate structure are shown in Table 1. It exhibits excellent waterproof and breathable properties, as well as comfortable movement. In the accelerated degradation test (7 days), its water resistance is 230 kPa, and it demonstrates excellent resistance to damp heat. Furthermore, the phase state of the obtained resin layer is as follows: Figure 1The diagram shows a continuous island-island structure. Furthermore, the island phase is polyamide 6, and the sea phase is polyether ester amide (A). The fibers in the fiber laminate structure are 100% polyamide 6 fibers by mass, and the main repeating unit in the polymer constituting the fibers is also 100% polyamide 6 units by mass.

[0121] [Example 2] Except for not bonding the inner layer material in Example 1 and making a two-layer fiber laminate structure, the fiber laminate structure was obtained using the same method as in Example 1.

[0122] The composition and various evaluation results of the obtained surface material, resin layer, and fiber laminate structure are shown in Table 1. It has excellent waterproof and breathable properties and movement comfort. The water resistance in the accelerated degradation test (7 days) is 230 kPa, and it has excellent hygrothermal properties.

[0123] [Example 3] As a method for preparing a polyamide-based elastomer for forming a resin layer film of Example 1, without using a bisphenol A ethylene oxide adduct, 45 parts of caprolactam, 50 parts of polyethylene glycol with a number average molecular weight of 1,500, and 5.82 parts of terephthalic acid with a carboxyl group content [COOH] such that [OH] / [COOH] = 0.95 relative to the amount of hydroxyl groups [OH] from the poly(epoxy) glycol are added together with 0.5 parts of an antioxidant ("IRGANOX" (registered trademark) 1098: manufactured by Ciba Specialty Chemicals Co., Ltd.) into a reaction vessel. The mixture was purged with N2, heated and stirred at 260°C for 60 minutes to form a transparent homogeneous solution, and then the pressure was reduced to below 0.07 kPa. 0.1 parts of tetrabutyl titanate were added, and the reaction was stopped when the stirring torque reached 11 kg·m (11 r / min) under conditions of pressure below 0.07 kPa and temperature of 260°C. The reaction time was 2.1 hours, yielding a crystal with a crystallization temperature of 115.0℃, an unreacted lactam content of 0.24%, and an amino content of 0.48 × 10⁻⁶. -5 A polyether ester amide with a melt viscosity of 920 poise (92 Pa·s) was used, and a fiber laminate structure was obtained using the same method as in Example 1. The resulting resin layer was non-porous, without interconnected pores. Furthermore, the island phase was polyamide 6, and the sea phase was polyether ester amide.

[0124] The composition of the obtained surface material, resin layer, and fiber laminate structure, along with various evaluation results, are shown in Table 1. It exhibits excellent waterproof and breathable properties and comfortable movement. The water resistance in the accelerated degradation test (7 days) is 165 kPa, slightly worse than Example 1, but it demonstrates sufficient resistance to damp heat.

[0125] [Example 4] Except that the warp yarns of the woven fabric of Example 1 are not falsely twisted, the fiber laminate structure is obtained using the same method as in Example 1.

[0126] The composition of the obtained surface material, resin layer, and fiber laminate structure, along with various evaluation results, are shown in Table 1. The comfort of movement is slightly worse than in Example 1, but it exhibits excellent waterproof and breathable properties, with a water resistance of 230 kPa in the accelerated degradation test (7 days), and excellent resistance to damp heat.

[0127] [Example 5] The filaments used in the woven fabrics and semi-trico warp-knitted fabrics of Example 1 were made of polyamide 66. The polymers used in the resin layer were polyamide 66, an ethylene oxide adduct of polyamide 66 and bisphenol A, and a copolymer of polyethylene glycol and terephthalic acid. The melt viscosity was set to 920 poise (92 Pa·s), and the melt processing temperature was set to 280°C. Otherwise, the fiber laminate structure was obtained using the same method as in Example 1. The resulting resin layer had no interconnected pores and was non-porous. Furthermore, the island phase was polyamide 6, and the sea phase was polyether ester amide. The fibers in the fiber laminate structure were 100% by mass of polyamide 66 fibers, and the main repeating units in the polymer constituting the fibers were also 100% by mass of polyamide 66 units.

[0128] The composition of the obtained surface material, resin layer, and fiber laminate structure, along with various evaluation results, are shown in Table 1. It exhibits excellent waterproof and breathable properties, with a water resistance of 230 kPa in the accelerated degradation test (7 days), and excellent resistance to damp heat.

[0129] [Example 6] Before forming the resin layer of Example 1, polyamide 6 with a melt viscosity of 960 poise (96 Pa·s), rutile titanium dioxide, and a hindered phenolic antioxidant were granulated. The various formulations of the resulting granules and polyether ester amide (A) granules were made in the same ratios as those used in the resin layer of Example 1. The mixture was melt-extruded using a single-screw extruder and a T-slit die to produce a non-stretchable film (resin layer). Otherwise, a fiber laminate structure was obtained using the same method as in Example 1. The resulting resin layer was non-porous, without interconnected pores. Furthermore, the island phase was polyamide 6, and the sea phase was polyether ester amide (A).

[0130] The composition and various evaluation results of the obtained surface material, resin layer, and fiber laminate structure are shown in Table 1. The average diameter of the island phase in the resin layer is 190 nm, and the water resistance in the accelerated degradation test (7 days) is 185 kPa, which is slightly worse than that in Example 1, but it has excellent resistance to damp heat.

[0131] [Example 7] Except for the use of polyamide 6 with a melt viscosity of 1030 poise (103 Pa·s) in the film formation of the resin layer in Example 1, the fiber laminate structure was obtained using the same method as in Example 1. The resulting resin layer had no interconnected pores and was non-porous. In addition, the island phase was polyamide 6 and the sea phase was polyether ester amide (A).

[0132] The composition and various evaluation results of the obtained surface material, resin layer, and fiber laminate structure are shown in Table 1. The average diameter of the island phase in the resin layer is 300 nm, and the water resistance in the accelerated degradation test (7 days) is 168 kPa, which is slightly worse than that in Example 1, but it has excellent resistance to damp heat.

[0133] [Example 8] The granules of polyether ester amide (A) from Example 1 and the granules of polyamide 6 with a melt viscosity of 960 poise (96 Pa·s) were dried under reduced pressure at 110°C for 14 hours to reduce the moisture content to below 300 ppm. A total of 100 parts were prepared, consisting of 80 parts of polyether ester amide (A), 17 parts of polyamide 6, 0.1 parts of an octadecyl phosphate chelating agent (“Adeka stab” (registered trademark) AX-71; manufactured by ADEKA Co., Ltd.), 1.9 parts of rutile titanium dioxide, and 1 part of a hindered phenolic antioxidant. A 45mm diameter... A twin-screw extruder with three threaded screws melts and mixes the material in a barrel at 255°C, then discharges it in strands. After cooling in a water bath, it is granulated using a granulator. The fiber laminate structure was obtained using the same method as in Example 1, except for the dimensions of 3mm in diameter and 3mm in length. The resulting resin layer had no interconnected pores and was non-porous. Furthermore, the island phase was polyamide 6, and the sea phase was polyether ester amide (A).

[0134] The composition of the obtained surface material, resin layer, and fiber laminate structure, along with various evaluation results, are shown in Table 1. The water resistance in the accelerated degradation test (14 days) was 220 kPa, demonstrating superior resistance to damp heat compared to Example 1.

[0135] [Comparative Example 1] Before forming the resin layer in Example 1, polyamide 6 with a melt viscosity of 500 poise (50 Pa·s), rutile titanium dioxide, and hindered phenolic antioxidant were granulated so that the various combinations of the resulting granules and polyether ester amide (A) granules when forming the resin layer were the same as those in Example 1. The unstretched film (resin layer) was produced by melt extrusion through a single screw extruder and a T-slit die. Otherwise, a fiber laminate structure was obtained by the same method as in Example 1.

[0136] The composition and evaluation results of the obtained surface material, resin layer, and fiber laminate structure are shown in Table 1. The island phase in the resin layer is polyamide 6, and the sea phase is polyether ester amide (A). However, the island phase is discontinuous (not a continuous island-sea structure), with an average diameter of 400 nm, an accelerated degradation test (7 days) water resistance of 109 kPa, and poor resistance to damp heat. Furthermore, the phase state of the obtained resin layer is... Figure 2 This indicates a discontinuous island structure.

[0137] [Comparative Example 2] In the preparation of the resin layer in Example 3, 97 parts of a polyamide-based elastomer were used, but polyamide 6 was not used. The resin layer was then prepared using the same method as in Example 3 to obtain the fiber laminate structure. The resulting resin layer was non-porous, with no interconnected pores.

[0138] The composition and evaluation results of the obtained surface material, resin layer, and fiber laminate structure are shown in Table 1. The resin layer is a single phase, neither a co-continuous layer nor containing island phases. The water resistance in the accelerated degradation test (7 days) is 30 kPa, indicating poor resistance to damp heat.

[0139] [Comparative Example 3] In the resin layer fabrication of Example 1, a polyamide-based elastomer was not used; instead, 97 parts of polyamide 6 were used to prepare the resin layer. Otherwise, the fiber laminate structure was obtained using the same method as in Example 1. The resulting resin layer had no interconnected pores and was non-porous. The resin layer was a single phase, neither a co-continuous layer nor containing island phases. Furthermore, the resulting fiber laminate structure had low moisture permeability and was unsuitable as a moisture-permeable material.

[0140] [Comparative Example 4] Except that the woven fabric of Comparative Example 2 was not false-twisted, the fiber laminate structure was obtained using the same method as Comparative Example 2.

[0141] The composition and evaluation results of the obtained surface material, resin layer, and fiber laminate structure are shown in Table 1. The resin layer is a single phase, neither a co-continuous layer nor containing island phases. The water resistance in the accelerated degradation test (7 days) is 30 kPa, indicating poor resistance to damp heat. In addition, the comfort of movement is also poor.

[0142] [Table 1] As shown above, the fiber laminate structures manufactured in Examples 1-8 exhibit excellent resistance to damp heat and moisture, high practicality, and high waterproof and breathable properties. Furthermore, these fiber laminate structures are essentially composed of polyamide, and most of the constituent monomers are common, resulting in high recycling efficiency in all aspects of material recycling and chemical recycling.

[0143] Industrial availability The fiber laminate structure of this invention possesses high moisture permeability and waterproofness, as well as excellent durability. Therefore, it is suitable for use in various fields, including outdoor clothing such as fishing and mountaineering apparel; ice skating and skiing clothing; windproof clothing; sportswear such as sportswear, golf apparel, and tennis apparel; uniforms; raincoats; casual wear; work clothes; and waterproof and breathable fabrics such as gloves, shoes, glove inserts, and boot inserts. Furthermore, after fulfilling its functions in the aforementioned applications, the fiber laminate structure of this invention can be appropriately recycled with excellent recycling efficiency.

[0144] Explanation of reference numerals in the attached figures A. Island Example B. Island phase example.

Claims

1. A fiber laminate structure having a woven or knitted fabric and a non-porous resin layer on the woven or knitted fabric, The resin layer comprises resin A and elastomer B. The resin A and the elastomer B are any combination of polyamide and polyamide-based elastomers, or polyester and polyester-based elastomers. The phase of resin A and the phase of elastomer B are either a co-continuous structure or an island-island structure with continuous island phases.

2. The fiber laminate structure as described in claim 1, wherein, The resin A and the elastomer B are a combination of polyamide and polyamide-based elastomers.

3. The fiber laminate structure as described in claim 2, wherein, The polyamide elastomer is a polyether ester amide containing a bisphenol A backbone dioxyethylene ether as a copolymer component, represented by the following structural formula (1). [Chemical Formula 1] 。 4. The fiber laminate structure as described in claim 2 or 3, wherein, The phase of resin A and the phase of elastomer B are island-island structures with continuous island phases. The island phase is formed from the polyamide, and the sea phase is formed from the polyamide-based elastomer. The average diameter of the island phase is 5–200 nm.

5. The fiber laminate structure as described in any one of claims 2 to 4, wherein, The woven fabric is formed from polyamide.

6. The fiber laminate structure as described in claim 5, wherein, The fibers constituting the woven fabric are fibers with polyamide 6 as the main component, the resin A is polyamide 6, and the elastomer B is a polyamide 6-based elastomer.

7. The fiber laminate structure according to any one of claims 1 to 6, wherein, The moisture permeability of the fiber laminate structure, according to JISL1099:2021 (A-1 method), is 3500 g / m³. 2 • For more than 24 hours, and the moisture permeability according to JIS L1099:2021 (B-1 method) is 10000 g / m³. 2 ·More than 24h.

8. The fiber laminate structure according to any one of claims 1 to 7, wherein, The elongation of at least one of the warp and weft directions of the woven or knitted fabric, according to JIS L1096:2010 Elongation A Method (Constant Elongation Method), is 10% or more.

9. A waterproof and breathable fabric comprising the fiber laminate structure according to any one of claims 1 to 8.

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