Fabric laminate structure and waterproof / breathable garment

Abstract

The present invention addresses the problem of providing: a fabric laminate structure which is highly practical, which has breathability and waterproofing properties, which exhibits excellent waterproofing properties after a long period of time (moisture and heat resistance), and which exhibits excellent recycling efficiency; and a waterproof / breathable garment.　This fabric laminate structure has: a woven or knitted fabric; and a non-porous resin layer on the woven or knitted fabric. The resin layer contains a resin A and an elastomer B. The resin A and the elastomer B are formed by combining a polyamide and a polyamide-based elastomer, or by combining a polyester and a polyester-based elastomer. The phase of the resin A and the phase of the elastomer B are either co-continuous or have a sea-island structure having continuous island phases.

Description

Fiber laminated structure and waterproof and breathable clothing

[0001] The present invention relates to a textile laminate structure and a waterproof and breathable garment.

[0002] Conventionally, in order to obtain a fiber laminated structure having excellent moisture permeability and waterproofness, there have been used methods such as a wet polyurethane coating method in which polyurethane is dissolved in a solvent such as dimethylformamide, laminated onto a woven fabric by coating or the like, and then introduced into water to solidify, forming a microporous film that has both moisture permeability and waterproofness; a method in which a resin film is laminated onto a woven fabric, the resin film being a blend of a hydrophilic resin having high moisture permeability, using a polymer in which a hydrophilic moiety has been introduced into the polymer chain; or a method in which a stretched and expanded microporous polytetrafluoroethylene film is attached to a woven fabric.

[0003] However, in recent years, the depletion of petroleum resources and the need to conserve resources for environmental conservation have led to an emphasis on recycling clothing. In conventional waterproof and breathable materials, the textile materials used for the outer and inner layers were typically different from the materials used for the waterproof and breathable membrane. For example, there was a three-layer laminate product in which a polyamide or polyester woven fabric was used for the outer layer, a polyurethane or polytetrafluoroethylene membrane was laminated on the waterproof and breathable membrane, and a polyamide knit fabric was further laminated on the inner layer. When these materials were chemically recycled after use and disposal, the outer layer, waterproof and breathable membrane, and inner layer had to be separately sorted and collected.

[0004] In an attempt to reduce the costs of sorting and collecting the above-mentioned materials and to make them easier to recycle, a membrane using only a polyamide copolymer, which is a polyamide-based elastomer, as a waterproof and breathable membrane has been proposed (Patent Document 1).

[0005] JP 2011-37101 A

[0006] However, it has been found that while films made solely of a moisture-permeable polyamide elastomer as disclosed in Patent Document 1 have a certain level of moisture permeability and waterproofness, they have low resistance to moist heat and their waterproofness deteriorates significantly over time. Also, films made solely of polyamides such as polyamide 6 and polyamide 66 can prevent deterioration in waterproofness over time, but their moisture permeability is poor when used as waterproof and moisture-permeable clothing.

[0007] The present invention aims to solve the above problems and provide a textile laminated structure and waterproof / breathable clothing that have excellent moisture permeability, waterproofness, and waterproofness (moisture and heat resistance) even after a long period of time, as well as a waterproof / breathable function with excellent recycling efficiency and high practicality.

[0008] In order to solve the above-mentioned problems, 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, wherein the resin layer contains a resin A and an elastomer B, the resin A and the elastomer B being a combination of either a polyamide and a polyamide-based elastomer or a polyester and a polyester-based elastomer, and wherein the resin A phase and the elastomer B phase have a co-continuous structure or a sea-island structure in which island phases are continuous.

[0010] [2] The fiber laminated structure according to [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 according to [2], wherein the polyamide elastomer is a polyether ester amide containing, as a copolymerization component, a dioxyethylene ether having a bisphenol A skeleton represented by the following structural formula (1):

[0012]

[0013] [4] The fiber laminated structure according to [2] or [3], wherein the resin A phase and the elastomer B phase have a sea-island structure with continuous island phases, the island phases are made of the polyamide, and the sea phase is made of the polyamide-based elastomer, and the average diameter of the island phases is 5 to 200 nm.

[0014] [5] The fiber laminated structure according to any one of claims [2] to [4], wherein the woven or knitted fabric is made of polyamide.

[0015] [6] The fiber laminated structure according to [5], wherein the fibers constituting the woven or knitted fabric are fibers mainly composed of polyamide 6, the resin A is polyamide 6, and the elastomer B is a polyamide 6-based elastomer.

[0016] [7] JIS L1099:2021 (A-1 method) moisture permeability is 3500 g / m ２ ・24h or more, and the moisture permeability according to JIS L1099:2021 (B-1 method) is 10,000g / m ２ - The fiber laminated structure according to any one of [1] to [6], which has a hardness of 24 hours or more.

[0017] [8] The woven or knitted fabric has an elongation of 10% or more in at least one of the warp and weft directions according to JIS L1096:2010 elongation method A (constant rate elongation method).

[0040] The fiber laminate structure according to any one of [1] to [7].

[0018] [9] Waterproof and breathable clothing comprising the fiber laminate structure according to any one of [1] to [8].

[0019] According to the present invention, it is possible to provide a textile laminated structure and waterproof / breathable clothing that have excellent moisture permeability, waterproofness, and even long-term waterproofness (moisture and heat resistance), and that have a waterproof / breathable function and are highly practical with excellent recycling efficiency. The textile laminated structure and waterproof / breathable clothing of the present invention can be practically and suitably used in sportswear, uniforms, raincoats, and the like, and are also highly recyclable after use.

[0020] 1 is a schematic diagram showing an example of a case where island phases of a sea-island structure are continuous in a resin layer, FIG. 2 is a schematic diagram showing an example of a case where island phases of a sea-island structure are discontinuous in a resin layer, and FIG. 3 is a schematic diagram showing a method of calculating the maximum diameter of island phases when island phases are overlapping.

[0021] The present invention will be described in detail below.

[0022] The textile laminate structure of the present invention is a textile laminate structure having a woven or knitted fabric and a nonporous resin layer on the woven or knitted fabric. The textile laminate structure of the present invention is suitably used for clothing such as sportswear, uniforms, and raincoats, and in such cases, it is preferable to use the woven or knitted fabric side as the outer surface.

[0023] [Woven / Knitted Fabric] The fiber laminated structure of the present invention has a woven / knitted fabric.

[0024] Examples of fibers constituting the woven or knitted fabric include polyester fibers, polyamide fibers, polyethylene fibers, polypropylene fibers, polyurethane fibers, cotton, hemp, regenerated cellulose fibers, acrylic fibers, wool, acetate fibers, etc. Among these, from the viewpoint of recyclability, it is preferable that the resin is the same type as the resin A and elastomer B of the resin layer described below, and when the resin A of the resin layer is polyamide and the elastomer B is a polyamide-based elastomer, it is preferable that the fibers constituting the woven or knitted fabric are also made of polyamide.

[0025] The polymer constituting the polyamide fiber is a polymer having an amide bond, and specific examples include aliphatic polyamides such as polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 46, polyamide 610, polyamide 56, and polyamide 510; semi-aromatic polyamides such as polyamide 6T and polyamide 9T made from diamine and terephthalic acid; and polyamide 6I made from hexamethylenediamine and isophthalic acid; and fully aromatic polyamides such as aramid obtained by a co-condensation polymerization reaction between an aromatic diamine and a dicarboxylic acid.

[0026] Among the above polyamide fibers, polyamide 6 fiber and polyamide 66 fiber are preferred in terms of cost and versatility, and polyamide 6 fiber is more preferred in terms of moisture permeability and chemical recyclability.

[0027] The fiber form is preferably a multifilament, and it may be a single multifilament yarn, or a multifilament having a side-by-side or core-sheath composite single yarn cross-sectional structure (hereinafter sometimes referred to as a "composite multifilament"). The single yarn referred to here refers to a fiber composed of a single material (which may be a polymer alone or a composition containing two or more components) as the material that constitutes the fiber.

[0028] The core-sheath composite type mentioned above may be either an eccentric core-sheath composite type or a concentric core-sheath composite type.

[0029] In the case of composite multifilaments, side-by-side or eccentric sheath-core composite latent crimped yarns are preferred, which are composite forms in which a three-dimensional coil-like (spiral) crimp is generated in the fiber depending on the combination of polymers. When a side-by-side or eccentric sheath-core composite is used as the composite form, examples of the polymer combination may be a combination of the same type of polymers with different viscosities or a combination of different types of polymers, and preferred are a combination of the same type of polyester polymers with different viscosities and a combination of different types of polyamide polymers, such as polyamide 6 and polyamide 66.

[0030] Specific examples of combinations of two components of the materials constituting the composite multifilament include polyamide 6 and polyamide 66, polyamide 6 and polyamide 610, and polyamide 66 and polyamide 610.

[0031] By using the same type of resin for the fibers used in the woven or knitted fabric and for the resin A and elastomer B of the resin layer described below, excellent recyclability is achieved in terms of material recycling, chemical recycling, etc. Furthermore, the fewer the types of resins used, the better the material recycling property, and the fewer the types of monomer components used, the better the chemical recycling property. However, the materials to be used may be selected appropriately in consideration of the practically required functions and recyclability.

[0032] Stretchability can be achieved by using latent crimped yarns, such as false-twisted yarns or side-by-side yarns made of polymers with different thermal shrinkage rates. Covering yarns made of elastic yarns, such as polyurethane (spandex) fibers, can also be used. However, when recycling products containing fiber laminate structures, if the polyurethane fiber content, which is classified as a secondary material, increases, the content of other materials (i.e., the contamination rate) also increases, resulting in a relative decrease in the content of the material desired to be recycled. It is important to note that this results in a decrease in recycling efficiency.

[0033] In the present invention, to increase recycling efficiency, it is preferable to have a small number of structural units in the polymer components constituting the fibers in the woven or knitted fabric. For example, polyamide 6 has a caproamide unit as a structural unit, which is also a repeating unit. Furthermore, polyamide 66 has a hexamethylene adipamide unit as a repeating unit, which contains a hexamethylene diamine residue and an adipic acid residue as structural units. When the fibers contained in the woven or knitted fabric are polyamide 6 fibers and polyamide 66 fibers and / or a composite multifilament composed of polyamide 6 and polyamide 66, the structural units contain three types of units: caproamide units, hexamethylene diamine 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 contain three types of units: hexamethylene diamine residues, adipic acid residues, and sebacic acid residues. It is particularly preferable that the polymer constituting the fibers contained in the woven or knitted fabric has a single main repeating unit. For example, in a fiber-constituting polymer in a woven or knitted fabric containing a polyamide copolymer fiber having caproamide units (polyamide 6 units) as the main constituent unit and a polyamide 6 fiber made of polycaproamide homopolymer, the main repeating unit is a single type of polyamide 6 unit. Similarly, in a fiber-constituting polymer in a woven or knitted fabric containing a polyamide 6 fiber made of polycaproamide homopolymer and a small amount of polyurethane fiber, the main repeating unit is also a single type of polyamide 6 unit. Furthermore, in a fiber-constituting polymer in a woven or knitted fabric containing a polyamide 6 fiber and a bicomponent multifilament of polyamide 6 and polyamide 66, the total repeating units contain polyamide 6 units and hexamethylene adipamide units (polyamide 66 units), with the repeating unit with the greater proportion being the main repeating unit. From the viewpoint of chemical recycling, the higher the proportion of the main repeating unit among all repeating units contained in the fiber-constituting polymer in the woven or knitted fabric, the more preferable, with 100% by mass being the most preferable.As described above, when using different elastic yarns such as polyurethane fibers or composite multifilaments made of different polymers, it is desirable that the content of the main repeating unit in the polymer that constitutes the fiber in the woven or knitted fabric is high, and it is preferably at least 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more.

[0034] The cross-sectional shape of the fiber is not particularly limited, and a wide variety of shapes can be used, such as round, triangular, hollow, etc. In addition, there is no problem if the yarn contains additives that impart antistatic properties or a matting agent such as titanium oxide.

[0035] The total fineness of the yarn used in the woven or knitted fabric is preferably 150 dtex or less. Reducing the thickness of the woven or knitted fabric increases moisture permeability. If the yarn is too thin, tear strength and burst strength decrease, so it is preferably 11 dtex or more. More preferably, it is 20 dtex or more and 75 dtex or less.

[0036] Furthermore, it is preferable to make the density of the woven or knitted fabric as small as possible from the viewpoint of improving moisture permeability, but if the fineness is kept the same or smaller and the density of the woven or knitted fabric is reduced, the ultraviolet ray shielding rate tends to decrease. For example, when a woven or knitted fabric is used as a surface and exposed to ultraviolet rays outdoors, the ultraviolet rays will pass through the woven or knitted fabric and irradiate the resin layer. If the amount of ultraviolet rays that pass through the woven or knitted fabric and irradiate the resin layer increases, the resin layer will generally be more susceptible to deterioration due to ultraviolet ray irradiation, so the density of the woven or knitted fabric and the fineness of the fibers used can be appropriately determined taking these factors into consideration.

[0037] In addition, in the present invention, the woven / knitted fabric preferably has an elongation of 10% or more in at least one of the warp and weft directions according to JIS L1096:2010 Elongation A Method (constant speed elongation method). To achieve a higher elongation, stretchable fibers, such as polyamide fibers, can be used as the fibers. In the case of knitted fabrics, the warp direction refers to the wale direction, and the weft direction refers to the course direction. Furthermore, a woven / knitted fabric with an elongation of 10% or more improves comfort, expands its range of applications, and further increases the flexibility of sewing patterns. A more preferred elongation is 15% or more and 100% or less. If the elongation exceeds 100%, misalignment is more likely to occur during the lamination process with the waterproof / breathable membrane, potentially reducing productivity.

[0038] The form of the woven fabric is not particularly limited, but plain, twill, satin, ripstop, double woven, oxford, tussah, and other woven fabrics are preferred.

[0039] The knitted fabric is not particularly limited in form, but high-gauge, high-density circular knitted fabrics and warp knitted fabrics are preferred.

[0040] [Resin Layer] Next, the non-porous resin layer on the woven or knitted fabric will be described. Here, "non-porous" means that there are no interconnecting pores on the front and back surfaces when the cross section of the resin layer is observed under an electron microscope using the method described in the Examples. The resin layer may be formed directly on the woven or knitted fabric, or another layer may be formed between the resin layer and the woven or knitted fabric.

[0041] In the present invention, the resin layer contains resin A and elastomer B. This configuration allows for both the mechanical strength and waterproofness inherent in resin A and the flexibility and moisture permeability inherent in elastomer B. The term "elastomer" as used herein refers to a material defined in JIS K 6200 (2019) that exhibits the property of being deformed by a weak force and rapidly returning to approximately its original shape and dimensions after the force is removed. As a guideline, it is a material that can be stretched to twice its original length, held for one minute, and then shrinks to 1.5 times or less of its original length within five minutes. Elastomers also include thermoplastic elastomers defined in JIS K 6418:2017.

[0042] Furthermore, the resin A and the elastomer B are a combination of either polyamide and a polyamide-based elastomer, or polyester and a polyester-based elastomer. From the viewpoints of durability, cost, and versatility, composites of woven and knitted fabrics made of polyamide or polyester are commonly used as materials for waterproof and breathable clothing. Therefore, this configuration of the resin layer is advantageous for recycling and facilitates increased recycling efficiency. From the viewpoint of further improving recyclability, it is preferable that when the woven and knitted fabric to be composited is made of polyamide, the resin layer be a fiber laminate structure made of polyamide and a polyamide-based elastomer, and when the woven and knitted fabric to be composited is made of polyester, the resin layer be a fiber laminate structure made of polyester and a polyester-based elastomer. Among these, from the viewpoints of weather resistance and mechanical strength, it is more preferable that the woven and knitted fabric to be composited with the fiber structure is made of polyamide, and that the resin A and the elastomer B be a combination of polyamide and a polyamide-based elastomer.

[0043] The polyamide used in Resin A is a polymer having an amide bond, and specific examples thereof 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). Of these, polyamide 6 and polyamide 66 are preferred in terms of cost and versatility, and polyamide 6 is more preferred in terms of moisture permeability and chemical recyclability.

[0044] The polyamide-based elastomer used for elastomer B can be any polyamide-based copolymer that exhibits elastomeric behavior. Specific examples include polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 46, polyamide 610, polyamide 56, polyamide 510, polyamide 6T and polyamide 9T, which are derived from diamines and terephthalic acid, polyetheresteramides composed of a polyamide component, a poly(alkylene oxide) glycol component, and a dicarboxylic acid component, and polyetheresteramides composed of a polyamide component, a diol component, a poly(alkylene oxide) glycol component, and a dicarboxylic acid component. Among these, polyetheresteramides composed of a polyamide component, a poly(alkylene oxide) glycol component, and a dicarboxylic acid component, which have high moisture permeability, are preferred from the perspective of further improving moisture permeability. Elastomer B may also contain other copolymer components.

[0045] Furthermore, polyetheresteramides containing a dioxyethylene ether having a bisphenol A skeleton represented by the following structural formula (1) (hereinafter sometimes referred to as an ethylene oxide adduct of bisphenol A) as a copolymerization component are more preferred. By adopting this embodiment, when a waterproof / breathable garment absorbs moisture such as rain or sweat, swelling due to the poly(alkylene oxide) glycol contained in elastomer B can be suppressed, thereby further improving moist heat resistance, i.e., waterproofness over an extended period of time. Furthermore, in the above polyetheresteramides, the number-average molecular weight of the dioxyethylene ether having a bisphenol A skeleton, which is a copolymer component, is preferably 1,000 to 3,000, more preferably 1,500 to 2,500. Furthermore, the dioxyethylene ether having a bisphenol A skeleton preferably accounts for 15 to 70 mass% of the total polyetheresteramide, more preferably 30 to 55 mass%, from the viewpoint of further improving moisture permeability and moist heat resistance.

[0046]

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

[0048] In the present invention, the number average molecular weight can be calculated by the following formula, where A is the amount (in mg) of potassium hydroxide required to neutralize 1 g of the sample by heating it with an excess of an acetylating agent, for example, acetic anhydride, and B is the amount (in mg) of potassium hydroxide required to neutralize 1 g of the sample before acetylation: Number average molecular weight = 11,200 / [[A / (1 - 0.00075 x A)] - B]. In the above polyetheresteramide, the polyamide component to be copolymerized is preferably polyamide 6 or polyamide 66 from the viewpoints of cost and versatility, and more preferably polyamide 6 from the viewpoints of moisture permeability and chemical recyclability.

[0049] In order to improve recycling efficiency, it is preferable to use the same polymer in the woven or knitted fabric and the resin layer, and it is more preferable from the viewpoint of moisture permeability and chemical recyclability that the fibers constituting the woven or knitted fabric be fibers containing polyamide 6 as the main component, the resin A be polyamide 6, and the elastomer B be a polyamide 6-based elastomer. Here, "containing polyamide 6 as the main component" refers to a fiber containing 50% by mass or more of polyamide 6 as its constituent components. Furthermore, when elastomer B is a polyamide-based elastomer, it is considered that the same polymer is used if the main repeating unit of the polyamide component is the same as the main repeating unit in the polyamide constituting resin A or the fiber.

[0050] It is important that the resin layer has a co-continuous structure of the resin A phase and the elastomer B phase or a sea-island structure in which the island phases are continuous. After investigation, the inventors found that simply mixing the resin A and the elastomer B reduces waterproofness over a long period of time, and that the above problem can be solved by having a specific resin A and elastomer B have a specific structure. That is, by forming the above structure without the resin A phase and the elastomer B phase being completely miscible with each other, the moisture resistance derived from the resin A and the moisture permeability derived from the elastomer B can be further improved. When the resin A phase and the elastomer B phase are completely miscible with each other, the degree of swelling when the film absorbs water increases, reducing the strength of the film and thereby reducing the moisture and heat resistance, i.e., the waterproofness over a long period of time. Furthermore, if the resin A phase and the elastomer B phase have a sea-island structure in which the island phases are not continuous, the difference in swelling behavior between the resin A phase and the elastomer B phase when they absorb water will cause distortion in the membrane, making it more likely to develop cracks and other problems, and thereby reducing the moist heat resistance, i.e., waterproofing after a long period of time.

[0051] The term "cocontinuous structure" as used herein generally refers to a three-dimensionally continuous or connected structure (network structure). This is a well-known structure exemplified in, for example, the non-patent document "Polymer Alloys: Fundamentals and Applications, 2nd Edition," edited by the Society of Polymer Science, Inc., published by Tokyo Kagaku Dojin Co., Ltd. in 1993. The term "sea-island structure" as used herein refers to a structure in which island phases are continuous, as shown in FIG. 1. When an ultrathin section of a resin layer, in which functional groups have been appropriately stained, is observed at 5000x magnification using a transmission electron microscope (TEM), a continuous island phase consisting of 10 or more continuous island phases accounts for 50% or more of the area ratio of the island phases in the observed field. The term "continuous" as used herein refers to the fact that the interfaces of the island components are in contact with each other or that the interfaces are close to each other, with a distance of 20 nm or less, in the image. The number of continuous island phases is the number of units that can be divided into quasi-circular shapes in the image. For example, Island Phase Example B in Figure 2 has one discontinuous island phase, while Island Phase Example A has three continuous island phases (however, because Island Phase Example A has three island phases, the presence of these island phases is not considered to be the "sea-island structure with continuous island phases"). By achieving this phase structure, the island phases form a network, which balances the properties of each phase and further improves the mechanical strength derived from the island phases, thereby improving moist heat resistance, i.e., waterproofness over long periods of time. To achieve this phase structure, it is effective to reduce the difference in melt viscosity between the resin A phase and the elastomer B. A minimum of 200 poise (20 Pa s) is preferred, and a value of 0 to 100 poise (0 to 10 Pa s) is even more preferred. In addition, it is also effective to stabilize the phase structure by adjusting the content of the resin A or the elastomer B to 5 to 50% by mass in the resin layer, and it is more preferable to adjust it to 10 to 40%.

[0052] Furthermore, from the viewpoint of improving moisture permeability and moist heat resistance, it is preferable that the resin A phase and the elastomer B phase have a sea-island structure with continuous island phases, with the island phase consisting of polyamide and the sea phase consisting of a polyamide-based elastomer. This structure can suppress distortion of the resin layer due to swelling of the polyamide-based elastomer in water, thereby further improving moist heat resistance, i.e., waterproofness over long periods of time. To achieve this structure, it is effective to make the melt viscosity of the polyamide-based elastomer lower than that of the polyamide. Specifically, it is preferable to make the melt viscosity of the polyamide-based elastomer 1 to 200 poise (0.1 to 20 Pa s) lower than that of the polyamide, and more preferably 10 to 100 poise (1 to 10 Pa s) lower.

[0053] The average diameter of the island phases is preferably 5 to 200 nm. Having an average diameter of the island phases of 5 nm or more prevents the island phases from becoming too fine, fully utilizing the mechanical strength inherent in the island phases and further improving moist heat resistance, i.e., waterproofness after prolonged use. The average diameter of the island phases is more preferably 50 nm or more. On the other hand, having an average diameter of the island phases of 200 nm or less prevents the island phases from becoming coarse and causing local unevenness in the mechanical strength of the resin layer, thereby preventing a decrease in moist heat resistance, i.e., waterproofness after prolonged use. The average diameter of the island phases is more preferably 150 nm or less. To achieve the above aspect, it is effective to melt-knead the resin A phase and the elastomer B by kneading using a twin-screw extruder, for example. The average diameter of the island phases in the present invention is a value obtained by observing the resin layer with a transmission electron microscope (TEM), randomly selecting 20 island phases, and calculating the number average of the maximum diameters of each island phase. If the island phase is not circular, the length of the long side is taken as the maximum diameter. If the island phases are overlapping as shown in Figure 3(a), an ellipse is separated by the least squares method described in the Transactions of the Institute of Electronics, Information and Communication Engineers, Vol. J70-D, No. 6, pp. 1173-1180 (June 1987), as shown in Figure 3(b). The maximum diameter D of the island phase with the largest diameter is taken as the maximum diameter D of the island phase with the largest diameter. ｍａｘ Let's say.

[0054] The thickness of the resin layer is preferably 10 to 30 μm in terms of the physical strength of the resin layer and the texture when made into waterproof and breathable clothing. If the thickness of the resin layer is less than 10 μm, the waterproofness decreases. If the thickness is more than 30 μm, the breathability decreases. The thickness is preferably 15 to 25 μm.

[0055] The elongation percentage of the resin layer is preferably 100% or more and less than 800%, and more preferably 200% or more and less than 600%. By making the elongation percentage of the resin layer 100% or more, flexibility after lamination of the membrane can be maintained and a decrease in moisture permeability and waterproofness can be suppressed when the laminate is deformed. Furthermore, by making the elongation percentage of the resin layer less than 800%, excessive elongation deformation of the membrane can be suppressed when the laminate is deformed, and a decrease in moisture permeability and waterproofness can be suppressed.

[0056] The stretchability of the resin layer is preferably excellent not only in the elongation percentage mentioned above but also in elongation recovery percentage. The elongation recovery percentage of the resin layer is preferably 80% or more, and more preferably 90% or more. When the elongation recovery percentage of the film is within the above range, the laminated structure follows the movement of the body when worn as clothing, providing excellent fit and facilitating movement and reducing fatigue.

[0057] The resin layer exhibits stretchability according to the proportion of elastomer. The copolymerization ratio can be selected based on practicality and application, taking into account the balance between moisture permeability and water swelling, or it can be selected from commercially available products.

[0058] [Antioxidant] In the present invention, an antioxidant is preferably used to improve the heat resistance of the resin layer used. Preferred examples of the antioxidant include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants, with hindered phenol-based antioxidants being particularly preferred. The resin layer preferably contains 0.05 to 5.0% by mass of the antioxidant, more preferably 0.5 to 4.0% by mass, and even more preferably 0.2 to 0.5% by mass.

[0059] [Hydrolysis Resistance Improver] In the present invention, a hydrolysis resistance improver is preferably used to improve the hydrolysis resistance of the resin layer used. Preferred examples of hydrolysis resistance improvers include carbodiimide compounds, epoxy compounds, and chelating agents (metal catalyst deactivators). Epoxy compounds and chelating agents are particularly preferred from the viewpoint of suppressing thickening and process contamination due to gases. Furthermore, when a metal such as titanium is used as an ester-based resin polymerization catalyst, the addition of an octadecyl phosphate-based chelating agent is even more preferred, as it suppresses the reverse transesterification reaction and further improves hydrolysis resistance. The resin layer preferably contains 0.05 to 3.0% by mass of the hydrolysis resistance improver, and the more preferred amount is 0.1 to 2.0% by mass.

[0060] [UV Absorber] In the present invention, an UV absorber may be used to improve the light resistance of the resin layer used. Preferred examples of UV 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)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol. Examples of benzophenones include 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone. The resin layer preferably contains 0.05 to 1.0% by mass of the UV absorber, and more preferably 0.1 to 0.5% by mass.

[0061] [Light Stabilizer] In the present invention, a light stabilizer may be further used to improve the light resistance of the resin layer used. Examples of light stabilizers include N-R hindered amines. Examples of N-R hindered amines include bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate and the N-OR amine 2,4-bis[N-butyl-N-(1-cyclohexyloyl-2,2,6,6-tetramethylpiperidic-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-tetrazine. 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.

[0062] [Pigment] In the present invention, a pigment is preferably used to color the resin layer used and to improve the color development of the fiber laminate structure. Examples of pigments that can be used include calcium carbonate, barium sulfate, clays such as kaolin and talc, titanium oxide, and zinc oxide. Among these, titanium oxide is preferred from the viewpoint of stability and dispersibility, and rutile-type titanium oxide, which has low photocatalytic activity, is even more preferred. The titanium oxide content in the resin layer is preferably 0.1 to 3.0% by mass, and more preferably 0.5 to 2.0% by mass. A titanium oxide content of 0.1% by mass or more can improve the color development of the fiber laminate structure, while a titanium oxide content of 3.0% by mass or less can improve the flexibility of the resin layer.

[0063] [Other Additives] In the present invention, lubricants, flame retardants, heat stabilizers, weather resistance agents, etc. may be appropriately blended into the resin layer used as needed.

[0064] [Others] 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, this may be referred to as a two-layer fiber laminate structure). For example, when the resin A and the elastomer B are a combination of polyamide and a polyamide-based elastomer, and the woven or knitted fabric is made of polyamide, it is also possible to further have a knitted fabric made of polyamide filaments on the resin of this fiber laminate structure (hereinafter, this may be referred to as a third-layer knitted fabric).

[0065] When the fiber laminated structure having the third layer of knitted fabric is used in clothing or the like, it is preferable to use the third layer of knitted fabric as the lining (the side closest to the skin) and the woven / knitted fabric side as the outer fabric.

[0066] The fiber laminated structure of the present invention can be used as a two-layer product consisting of a woven or knitted fabric and a resin layer without attaching a third layer of knitted fabric, but it is desirable to attach a third layer of knitted fabric to function as a lining in order to prevent damage to the resin layer due to friction and to impart a luxurious feel.

[0067] The third layer of knitted fabric is preferably made of 100% polyamide multifilament by weight, preferably polyamide 6, polyamide 66, or polyamide 610.

[0068] The fiber form may be a multifilament single yarn or a composite multifilament, and the single yarn and composite multifilament mentioned here are the same as those mentioned above.

[0069] When the composite multifilament is a sheath-core composite type, it may be an eccentric sheath-core composite type or a concentric sheath-core composite type.

[0070] In the case of a composite multifilament, the same latent crimped yarn as described above is preferred. When a side-by-side type or an eccentric core-sheath type composite is used as the composite form, examples of the polymer combination may be a combination of the same type of polymer but different viscosities, or a combination of different types of polymers. A combination of the same type of polyester polymer but different viscosities, or a combination of different types of polyamide polymers such as polyamide 6 and polyamide 66, is preferably used.

[0071] Specific examples of combinations of two components of the materials constituting the composite multifilament include polyamide 6 and polyamide 66, polyamide 6 and polyamide 610, and polyamide 66 and polyamide 610.

[0072] Stretchability can be achieved by using latent crimped yarns, such as false-twisted yarns or side-by-side yarns of different polymers, as polyamide multifilaments. Covering yarns made of elastic yarns, such as polyurethane fibers, can also be used. However, when recycling products containing fiber laminate structures, if the blending ratio of polyurethane fibers, which are classified as other materials, is high, the blending ratio of other materials also increases, resulting in a relative decrease in the content of the material to be recycled. It is important to note that this results in a decrease in recycling efficiency.

[0073] In the present invention, in order to increase recycling efficiency, it is preferable that the fiber component of the lining knitted fabric is 100% by mass of polyamide fiber including polyamide multifilament. As described above, when a non-polyamide elastic yarn is used, it is desirable that the content of polyamide fiber in the fibers constituting the knitted fabric is high, and the ratio of polyamide fiber is preferably at least 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more.

[0074] Similarly to the above-described woven and knitted fabrics, the third layer knitted fabric also uses polyamide multifilaments, which results in excellent recyclability in terms of material recycling, chemical recycling, etc. The fewer the types of polyamides used in the fibers constituting the fiber laminate structure, the better the material recycling, and the fewer the types of monomer components used, the better the chemical recycling; however, the materials to be used may be appropriately selected in consideration of the practically required functions and recyclability.

[0075] The content of the main repeating unit in the polymer constituting the fiber in the fiber laminate structure is desirably high, and is preferably at least 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, and most preferably 100% by mass. Note that the fiber in the fiber laminate structure referred to here refers not only to woven or knitted fabrics, but also to the fibers contained in the fiber laminate structure including the knitted lining fabric when a knitted lining fabric is used.

[0076] The knitted fabric may be subjected to water-repellent treatment, antistatic treatment, antibacterial treatment, ultraviolet absorbing treatment, near-infrared absorbing treatment, or the like, as required.

[0077] When sealing tape is used to maintain the waterproofness of seams, the sealing tape is usually adhered to the lining with molten resin, but it is preferable to use a low-density knit fabric for the lining so that this molten resin can easily pass through the lining and reach the waterproof / breathable film. Tricot and circular knit fabrics are preferred because they are thin and have a low density.

[0078] The third layer of knitted fabric is preferably laminated onto the resin layer of the two-layered fiber laminate structure with an adhesive.

[0079] The adhesive used to laminate the third layer of knitted fabric is preferably a hot-melt adhesive that does not use an organic solvent, similar to the adhesive for woven and knitted fabrics described below. Examples of resins with hot-melt adhesive properties include polyurethane, polyester, polyether, and polyamide resins, but polyurethane or polyamide resins are preferred in terms of adhesion, flexibility, texture, stretchability, etc. Solvent-based adhesives can also be used suitably. The adhesive application method and lamination conditions can be the same as the adhesive conditions for woven and knitted fabrics described below.

[0080] The fiber laminated structure of the present invention preferably has excellent moisture permeability. ２ ・24h or more, and the moisture permeability according to JIS L1099:2021 (B-1 method) is 10,000g / m ２ Preferably, the moisture permeability is 24 hours or more. Here, the moisture permeability in JIS L1099:2021 (A-1 method) is an index representing the transmission rate of water vapor, and the moisture permeability in JIS L1099:2021 (B-1 method) is an index representing the transmission rate of liquid-phase moisture. The moisture permeability in JIS L1099:2021 (A-1 method) is 6000 g / m ２ 24 hours or more is more preferable, 8000 g / m ２ It is more preferable that the moisture permeability according to JIS L1099:2021 (A-1 method) is higher, but in reality, it is 20,000 g / m ２ ・24 hours or less. Also, the moisture permeability according to JIS L1099:2021 (B-1 method) is 20,000 g / m ２ 24 hours or more is more preferable, and 30,000 g / m ２ It is more preferable that the moisture permeability according to JIS L1099:2021 (B-1 method) is higher, but in reality, it is 100,000 g / m ２ ・24 hours or less.

[0081] The fiber laminated structure of the present invention has high waterproofing properties, and therefore has the property of preventing the intrusion of rainwater, i.e., it preferably has excellent performance with a water resistance of at least 150 kPa or more. More preferably, it is 200 kPa or more. By keeping the water resistance in this range, it is possible to prevent rainwater from invading the garment when worn. The higher the water resistance, the better, but in reality, it is 300 kPa or less.

[0082] Furthermore, from the viewpoint of ensuring durability during actual wear, the water resistance after an accelerated degradation test under high temperature and constant humidity is preferably 150 kPa or more. More preferably, it is 200 kPa or more. By being in the above range, it is possible to achieve excellent resistance to moist heat and improve waterproofness even after a long period of time has passed. The accelerated degradation test under high temperature and constant humidity referred to here refers to treatment for 7 days in an environment of 70°C and 95% RH in a constant temperature and humidity chamber or the like. The higher the water resistance after the accelerated degradation test under high temperature and constant humidity, the better, but in reality it is 300 kPa or less.

[0083] The laminated fiber structure of the present invention is preferably subjected to a water-repellent treatment. By applying a water-repellent treatment, the product becomes more practical as a waterproof and breathable material, and a water-repellent treatment that has high washing durability and friction durability is desirable. As the water repellent agent, known water-repellent agents such as fluorine-based, silicone-based, and paraffin-based water-repellent agents can be used. As the processing method, a conventional processing method such as pad-dry-cure can be used. During processing, any processing method can be applied at any timing, such as before or after lamination of the resin layer.

[0084] Furthermore, the fabric may be subjected to processing such as antistatic processing, antibacterial processing, ultraviolet absorbing processing, near infrared absorbing processing, etc., as required.

[0085] [Waterproof and breathable clothing] Waterproof and breathable clothing containing the fiber laminated structure of the present invention is highly effective in preventing stuffiness due to its high waterproofness and breathability, and is comfortable to wear while also maintaining excellent waterproofness even after long periods of time. Therefore, it can be suitably used for waterproof and breathable clothing such as outdoor wear for mountain climbing and skiing, windbreakers, and raincoats.

[0086] [Method for Producing Resin Layer] The resin layer used in the present invention can be produced by conventional film-forming methods such as the T-die method and inflation method. For example, the above-mentioned polyamide and polyamide-based elastomer, along with optional components such as an antioxidant and titanium oxide, are fed into a single-screw extruder or twin-screw extruder. The resin in the extruder is then heated above its melting point and extruded as a film from a die using the T-die method. This film is then melt-coated onto a support material, such as lightweight polyester or release paper, wound up, and stored for use. It is also preferable to use a masterbatch prepared by twin-screw kneading resins or resins and additives in advance, and blending the remaining components to obtain the desired composition, followed by film formation using the above-mentioned method, in order to improve the dispersibility of the resin and additives.

[0087] [Method for producing a fiber laminated structure] The fiber laminated structure of the present invention is produced by laminating the resin layer on a base fabric made of a woven or knitted fabric. The laminating method may be any of the following methods, but is not limited thereto.

[0088] That is, it is a method of laminating using an adhesive. Preferred examples of adhesives include ordinary hot melt adhesives and hot melt adhesives such as thermal adhesive fibers. Solvent-based adhesives can also be used. When a hot melt adhesive is used, it can be performed by thermocompression bonding using a heating device. When an ordinary hot melt adhesive is used, if the actual area used is large, it often reduces the moisture permeability of the fabric, so it is preferable to use an adhesive made of a moisture-permeable resin.

[0089] The adhesive is preferably provided in an area ratio of 70% or less of the woven or knitted fabric in the surface direction in order to increase the precision of control of peel strength and to stabilize the moisture permeability, air permeability, and water resistance of the fiber laminated structure at a high level. 10 to 70% is more preferable, and 30 to 70% is even more preferable. To achieve the above area ratio, the adhesive is preferably provided in the form of dots or lines in the surface direction.

[0090] It is preferable to reduce the area of ​​the adhesive dots or lines and to reduce the adhesive area ratio, but this reduces the peel strength. On the other hand, in order to improve the peel strength, it is preferable to increase the area of ​​the adhesive dots or lines and to increase the area ratio, and the most preferable is to make the entire surface an adhesive layer, but this may result in a decrease in moisture permeability. In order to maintain these contradictory functions at a moderate level, the adhesive should be applied to a thickness of 0.1 to 100.0 mm. ２ It is preferable to apply the pigment in the form of dots having an area of ​​0.1 to 10.0 mm, or in the form of lines or lattices having a thickness of 0.1 to 10.0 mm, with an area ratio of 10 to 70%.

[0091] The dots may be any shape, such as circles, squares, diamonds, ellipses, or triangles, and may be combined and arranged to form patterns, letters, or trademark logos. They may also be arranged to form a continuous pattern or randomly. The lines may be straight or curved. The area ratio refers to the coverage rate of the adhesive.

[0092] The adhesive is preferably a hot-melt adhesive that does not use an organic solvent. Examples of resins having hot-melt adhesive properties include polyurethanes, polyesters, polyethers, and polyamides. In consideration of adhesiveness, flexibility, texture, stretchability, etc., polyurethane resins and polyamide resins are preferred. Solvent-based adhesives can also be used.

[0093] The adhesive can be applied using a knife coater, a bar coater, a gravure coater, or the like. In particular, a gravure coater can be used to apply the adhesive in a dotted, linear, or grid pattern relatively easily, and is preferred from the viewpoint of moisture permeability, but the adhesive can be applied using other methods without being limited to these.

[0094] The adhesive method may be a wet lamination method, a dry lamination method, or the like, which may be selected depending on the desired properties. However, from the viewpoint of texture and adhesiveness, it is preferable to use a dry lamination method in which an adhesive is applied to the woven fabric.

[0095] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. Various measurement methods used in the present invention are as follows.

[0096] (1) Film Thickness A film in a free state without any load was cut with a single-edged razor at 10 random locations, and the cross sections were observed under an electron microscope to measure the thickness, and the average value was taken as the thickness.

[0097] (2) Accelerated Deterioration Test Samples were treated in a thermo-hygrostat maintained at 70° C. and 95% RH for 7 days and 14 days.

[0098] (3) Water Resistance: Measured in accordance with JIS L1092:2009 Water Resistance Method B (high water pressure method).

[0099] However, a non-stretchable taffeta was placed on the reverse side (the side not exposed to water) to prevent the sample from stretching. Five samples were assigned to each level, and the average value was used as the water resistance. Furthermore, measurements were taken using samples after the accelerated aging test, and the water resistance was determined in the same manner.

[0100] (4) Moisture permeability Measured based on JIS L1099:2021 calcium chloride method (method A-1) and JIS L1099:2021 potassium acetate method (method B-1).

[0101] Specifically, the fiber laminated structure was set so that water vapor (method A-1) or water (method B-1) was applied to the surface opposite the woven fabric surface, and the measurement was performed. In both test methods, the moisture permeability was converted into the amount of moisture permeation per 24 hours. Three samples were measured for each level, and the average value was taken as the moisture permeability.

[0102] (6) Elongation: Measured in accordance with JIS L1096:2010 Elongation Method A (constant speed elongation method). Specifically, the elongation of a woven fabric sample was measured in the warp and weft directions using a strip method with a grip distance of 200 mm and a width of 50 mm, with the elongation measured at a stress of 14.7 N as the stretch rate. Measurements were performed on three samples per level, and the elongation rates were measured, and the average value was taken as the elongation rate.

[0103] (7) Observation of Resin Layer (7-1) Observation of Phase State A 100 nm thick slice was cut in the thickness direction from a randomly selected location of the resin layer, and the polyamide resin was stained differently using a phosphotungstic acid staining method to clarify the dispersion state of the polyamide resin. The slice was then observed at 5000x magnification using a transmission electron microscope.

[0104] (7-2) Average diameter of island phases After magnification observation using the same method as in (7-1) above, the average diameter of the island phases was calculated from the number average of the maximum diameters of 20 island phases randomly selected from the obtained observation image. When the number of island phases in the observation field was less than 20, the average diameter was calculated from the number average of the maximum diameters of all island phases whose diameters could be calculated.

[0105] (8) Confirmation of non-porous film The cross section of the resin layer at five randomly selected locations was observed using an electron microscope (SU3800 manufactured by Hitachi High-Technologies Corporation, magnification: 2000 times), and the presence or absence of communicating holes was measured on the front and back surfaces.

[0106] (9) Melt Viscosity The chip-shaped polymer was dried to a moisture content of 200 ppm or less using a vacuum dryer, and the melt viscosity was measured using a Toyo Seiki Capillograph (L / D = 40) by changing the strain rate stepwise. The measurement temperature was the same as the melt processing temperature, and the time from when the sample was placed in a heating furnace under a nitrogen atmosphere to when the measurement started was 5 minutes. The shear rate was 1216 s －１ The value was evaluated as the melt viscosity of the polymer.

[0107] (10) Movement Comfort An outer jacket for mountain climbing was produced using the obtained fiber laminated structure. The outer jacket was worn and judged as follows, and the most common judgement among the evaluations by 10 randomly selected people was recorded as the result. If there were multiple most common judgements, the intermediate judgement was recorded. The size of the outer jacket worn by each person was the size (S, M, L) that suited their physique based on JIS L4004:2001 9. A: Almost no feeling of pressure or tension from the fabric, and movement comfort is good. B: Some feeling of pressure or tension from the fabric is felt, but movement comfort cannot be said to be bad. C: A great deal of feeling of pressure or tension from the fabric is felt, and movement comfort is poor.

[0108] Example 1: A polyamide 6 semi-dull round cross section multifilament yarn with a warp of 56 dtex-42 filaments and a weft of 78 dtex-34 filaments was false-twisted to impart stretchability. The textured yarn was then used as the warp and weft yarns, and woven in a water jet loom to a warp x weft density of 111 threads / 2.54 cm x 77 threads / 2.54 cm. The fabric was then scoured and relaxed, and then preset and dyed in a liquid jet dyeing machine in the usual manner. A 5% aqueous solution of "Asahi Guard" (registered trademark) AG710 (a fluorine-based water repellent, manufactured by Asahi Glass Co., Ltd.) was applied to the woven surface by the pad-dry-cure method to a deposition rate of 60%, dried at 120°C for 1 minute, heat-treated at 170°C for 40 seconds, and then final set to a finished warp x weft density of 154 threads / 2.54 cm x 122 threads / 2.54 cm, yielding a woven fabric.

[0109] On the other hand, a polyamide-based elastomer for forming a resin layer was prepared by charging 45 parts of caprolactam, 45 parts of an ethylene oxide adduct of bisphenol A represented by the formula (1) and having a number-average molecular weight of 1,500, 5 parts of polyethylene glycol having a number-average molecular weight of 1,500, and 5.82 parts of terephthalic acid so that the amount of carboxyl groups [COOH] relative to the amount of hydroxyl groups [OH] derived from the poly(alkylene oxide) glycol was [OH] / [COOH]=0.95, together with 0.5 parts of an antioxidant ("Irganox" (registered trademark) 1098: manufactured by Ciba Specialty Chemicals Co., Ltd.), into a reaction vessel, and then heating under reduced pressure. ２ The mixture was purged and heated and stirred at 260°C for 60 minutes to obtain a transparent homogeneous solution, after which the pressure was reduced to 0.07 kPa or less. 0.1 parts of tetrabutyl titanate was added, and the reaction was terminated when the stirring torque reached 11 kg m (11 r / min) under the conditions of a pressure of 0.07 kPa or less and a temperature of 260°C. The reaction time was 2.1 hours, the crystallization temperature was 115.0°C, the unreacted lactam content was 0.24%, and the amino group amount was 0.48 x 10 －５ A polyether ester amide (A) having a viscosity of 920 poise (92 Pa·s) was obtained.

[0110] Pellets of polyether ester amide (A) and pellets of polyamide 6 having a melt viscosity of 960 poise (96 Pa s) were dried under reduced pressure at 110 ° C. for 14 hours to a moisture content of 300 ppm or less, and a total of 100 parts of 80 parts of polyether ester amide (A), 17 parts of polyamide 6, 2 parts of rutile titanium oxide, and 1 part of a hindered phenolic antioxidant were melt-kneaded using a twin-screw extruder having a 45 mmφ triple-thread screw, with a cylinder temperature (melt processing temperature) set to 255 ° C., and then discharged in a strand shape and cooled in a water bath. The pellets were then pelletized to a diameter of 3 mm and a length of 3 mm using a pelletizer. The resulting pellets were dried under reduced pressure at 110 ° C. for 14 hours to a moisture content of 300 ppm or less, and then melt-extruded from a T-slit die using a single-screw extruder at a cylinder set temperature of 255 ° C. to a thickness of 20 μm (basis weight 18 g / m ２ The obtained resin layer was non-porous and had no continuous pores.

[0111] A moisture-curing polyurethane hot melt adhesive was heated to 110°C and melted. The adhesive was applied to the fabric using a gravure coater equipped with a gravure roll engraved with 40 mesh and 0.40mm x 0.40mm square depressions (20µm deep) at a 45° angle to the direction of fabric travel, and then dried at 120°C for 1 minute. As a result, the adhesive was applied to the fabric in dots, each dot being a 0.40mm square and arranged at a 45° angle to the longitudinal direction. The adhesive area ratio (coverage) to the fabric was 40%, and the adhesive application amount was 15g / m. ２ It was.

[0112] Next, the unstretched film obtained above was placed on the adhesive side of the fabric to which the adhesive had been applied, and a linear pressure of 49 N / cm was applied by passing it between a metal roll and a rubber roll at a temperature of 110°C, and then aging was carried out at room temperature for 48 hours to obtain a two-layer fiber laminate structure in which the fabric and the film (resin layer) were laminated.

[0113] Next, a moisture-curing polyurethane hot melt adhesive was applied to the sinker surface of a half tricot dyed gray using 22 dtex-16 filament polyamide 6 semi-dull round cross section multifilament in the same manner as the adhesive was applied to the woven fabric, and then a 40% area ratio, 10 g / m adhesive resin was applied thereon. ２ ) A knitted fabric was laminated onto the two-layered fiber laminate structure so that the film (resin layer) side surfaces of the two-layered fiber laminate structure were bonded to each other, thereby producing a three-layered fiber laminate structure.

[0114] The configurations of the obtained outer fabric, resin layer, and fiber laminate structure, as well as the results of various evaluations, are shown in Table 1. The structure exhibited excellent waterproof and breathable properties and operational comfort. The water resistance in an accelerated aging test (7 days) was 230 kPa, demonstrating excellent moist heat resistance. The phase state of the obtained resin layer was a sea-island structure with continuous island phases, as shown in Figure 1. The island phase was polyamide 6, and the sea phase was polyetheresteramide (A). The fiber in the fiber laminate structure was 100% by mass of polyamide 6 fiber, and the main repeating unit in the polymer constituting the fiber was also 100% by mass of polyamide 6 units.

[0115] Example 2 A fiber laminate structure was obtained in the same manner as in Example 1, except that the backing was not bonded and a two-layer fiber laminate structure was used.

[0116] The configurations of the obtained outer fabric, resin layer, and fiber laminated structure, as well as the results of various evaluations, are shown in Table 1. The fabric had excellent waterproof and breathable properties and was comfortable to wear, and the water resistance in an accelerated degradation test (7 days) was 230 kPa, demonstrating excellent heat and humidity resistance.

[0117] Example 3 In a method for preparing a polyamide-based elastomer for forming the resin layer of Example 1, without using an ethylene oxide adduct of bisphenol A, 45 parts of caprolactam, 50 parts of polyethylene glycol having a number average molecular weight of 1,500, and 5.82 parts of terephthalic acid were added to a reaction vessel together with 0.5 parts of an antioxidant (Irganox (registered trademark) 1098: manufactured by Ciba Specialty Chemicals Co., Ltd.) in an amount of 0.95 to 5.82 parts of terephthalic acid, so that the amount of carboxyl groups [COOH] relative to the amount of hydroxyl groups [OH] derived from the poly(alkylene oxide) glycol was [OH] / [COOH]=0.95, and the mixture was heated at 2000°C for 1 hour. ２The mixture was purged and heated and stirred at 260°C for 60 minutes to obtain a transparent homogeneous solution, after which the pressure was reduced to 0.07 kPa or less. 0.1 parts of tetrabutyl titanate was added, and the reaction was terminated when the stirring torque reached 11 kg m (11 r / min) under the conditions of a pressure of 0.07 kPa or less and a temperature of 260°C. The reaction time was 2.1 hours, the crystallization temperature was 115.0°C, the unreacted lactam content was 0.24%, and the amino group amount was 0.48 x 10 －５ A fiber laminated structure was obtained in the same manner as in Example 1, except that a polyether ester amide having a viscosity of 920 poise (92 Pa s) and a viscosity of 1000 sq ft / g was obtained. The obtained resin layer was non-porous, with no continuous pores. The island phase was polyamide 6, and the sea phase was polyether ester amide.

[0118] The configurations of the obtained outer fabric, resin layer, and fiber laminated structure, as well as the results of various evaluations, are shown in Table 1. The fabric had excellent waterproof and breathable properties and was comfortable to wear. The water resistance in an accelerated degradation test (7 days) was 165 kPa, which was slightly inferior to that of Example 1, but the fabric had sufficient moist heat resistance.

[0119] Example 4 A fiber laminated structure was obtained in the same manner as in Example 1, except that the warp yarns of the woven fabric of Example 1 were used without being false twisted.

[0120] The configurations of the obtained outer fabric, resin layer, and fiber laminated structure, as well as the results of various evaluations, are shown in Table 1. Although the operational comfort was slightly inferior to that of Example 1, it had excellent waterproof and breathable properties, and the water resistance in an accelerated degradation test (7 days) was 230 kPa, indicating excellent moist heat resistance.

[0121] Example 5 A fiber laminate structure was obtained in the same manner as in Example 1, except that the filaments used in the woven fabric and half tricot of Example 1 were polyamide 66, the polymer used in the resin layer was polyamide 66, a copolymer of polyamide 66, an ethylene oxide adduct of bisphenol A, and polyethylene glycol and terephthalic acid, with a melt viscosity of 920 poise (92 Pa·s), and the melt processing temperature was 280°C. The resulting resin layer was nonporous and had no interconnected pores. The island phase was polyamide 6, and the sea phase was polyetheresteramide. The fiber laminate structure consisted of 100% polyamide 66 fiber by mass, and the main repeating unit in the polymer constituting the fiber was also 100% polyamide 66 by mass.

[0122] The configurations of the obtained outer fabric, resin layer, and fiber laminated structure, as well as the results of various evaluations, are shown in Table 1. The fabric had excellent waterproof and breathable properties, and the water resistance in an accelerated degradation test (7 days) was 230 kPa, demonstrating excellent resistance to moist heat and moisture.

[0123] Example 6 A fiber laminate structure was obtained in the same manner as in Example 1, except that polyamide 6 having a melt viscosity of 960 poise (96 Pa s), rutile-type titanium oxide, and a hindered phenol-based antioxidant were pelletized before the resin layer of Example 1 was formed, and the resulting pellets and pellets of polyether ester amide (A) were melt-extruded using a single-screw extruder and a T-slit die to produce an unstretched film (resin layer) in a ratio similar to that of the resin layer of Example 1. The resulting resin layer was nonporous and had no continuous pores. The island phase was polyamide 6, and the sea phase was polyether ester amide (A).

[0124] The configurations of the obtained outer fabric, resin layer, and fiber laminated structure, as well as the results of various evaluations, are shown in Table 1. The average diameter of the island phases in the resin layer was 190 nm, and the water resistance in an accelerated degradation test (7 days) was 185 kPa, which was slightly inferior to that of Example 1, but the structure had excellent moist heat resistance.

[0125] [Example 7] A fiber laminated structure was obtained in the same manner as in Example 1, except that polyamide 6 having a melt viscosity of 1030 poise (103 Pa s) was used in the film formation of the resin layer in Example 1. The obtained resin layer had no continuous pores and was non-porous. The island phase was polyamide 6, and the sea phase was polyether ester amide (A).

[0126] The configurations of the obtained outer fabric, resin layer, and fiber laminated structure, as well as the results of various evaluations, are shown in Table 1. The average diameter of the island phases in the resin layer was 300 nm, and the water resistance in an accelerated degradation test (7 days) was 168 kPa, which was slightly inferior to that of Example 1, but the structure had excellent moist heat resistance.

[0127] [Example 8] In Example 1, pellets of polyetheresteramide (A) and pellets of polyamide 6 having 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 300 ppm or less. A total of 100 parts of 80 parts of polyetheresteramide (A), 17 parts of polyamide 6, 0.1 parts of an octadecyl phosphate chelating agent ("ADK STAB" (registered trademark) AX-71; manufactured by ADEKA Corporation), 1.9 parts of rutile titanium oxide, and 1 part of a hindered phenol-based antioxidant were melt-kneaded using a twin-screw extruder having a 45 mm diameter and a three-thread screw, with the cylinder temperature set to 255 ° C., and then extruded in the form of a strand, cooled in a water bath, and subsequently pelletized to a diameter of 3 mm and a length of 3 mm using a pelletizer. A fiber laminate structure was obtained in the same manner as in Example 1, except that the resulting resin layer had no communicating holes and was non-porous. The island phase was made of polyamide 6, and the sea phase was made of polyetheresteramide (A).

[0128] The configurations of the obtained outer fabric, resin layer, and fiber laminated structure, as well as the results of various evaluations, are shown in Table 1. The water resistance in an accelerated degradation test (14 days) was 220 kPa, which was even better than that of Example 1 in terms of moist heat resistance.

[0129] Comparative Example 1 A fiber laminate structure was obtained in the same manner as in Example 1, except that polyamide 6 having a melt viscosity of 500 poise (50 Pa s), rutile-type titanium oxide, and a hindered phenol-based antioxidant were pelletized before the resin layer of Example 1 was formed, and a melt-extruded unstretched film (resin layer) was produced using a single-screw extruder and a T-slit die in such a ratio that the various components when the resulting pellets and pellets of polyether ester amide (A) were used to form a resin layer were the same as those in Example 1.

[0130] The configurations of the obtained outer fabric, resin layer, and fiber laminate structure, as well as the results of various evaluations, are shown in Table 1. The island phase in the resin layer was polyamide 6, and the sea phase was polyetheresteramide (A). However, the island phases were discontinuous (not a sea-island structure in which the island phases are continuous), had an average diameter of 400 nm, and the water resistance in an accelerated degradation test (7 days) was 109 kPa, indicating poor moist heat resistance. In addition, the phase state of the obtained resin layer was a sea-island structure in which the island phases were discontinuous, as shown in Figure 2.

[0131] Comparative Example 2 A fiber laminated structure was obtained in the same manner as in Example 3, except that in preparing the resin layer in Example 3, 97 parts of a polyamide elastomer was used and no polyamide 6 was used. The obtained resin layer had no communicating pores and was non-porous.

[0132] The configurations of the obtained outer fabric, resin layer, and fiber laminate structure, as well as the results of various evaluations, are shown in Table 1. The resin layer was a single phase, and neither a co-continuous layer nor an island phase was present. In an accelerated degradation test (7 days), the water resistance was 30 kPa, indicating poor moist heat resistance.

[0133] Comparative Example 3 A fiber laminated structure was obtained in the same manner as in Example 1, except that the resin layer was prepared using 97 parts of polyamide 6 instead of the polyamide-based elastomer. 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 an island phase. Furthermore, the resulting fiber laminated structure had low moisture permeability and was not suitable as a moisture-permeable material.

[0134] Comparative Example 4 A fiber laminated structure was obtained in the same manner as in Comparative Example 2, except that the woven fabric of Comparative Example 2 was used without being false-twisted.

[0135] The configurations of the resulting outer fabric, resin layer, and fiber laminate structure, as well as the results of various evaluations, are shown in Table 1. The resin layer was a single phase, neither a co-continuous layer nor an island phase. The water resistance in an accelerated degradation test (7 days) was 30 kPa, indicating poor resistance to moist heat and moisture, and the operating comfort was also poor.

[0136]

[0137] As described above, the fiber laminate structures produced in Examples 1 to 8 had excellent wet heat resistance and highly practical waterproof and moisture permeable functions. Furthermore, these fiber laminate structures were essentially composed of polyamide, and many of the constituent monomers were common, so they had high recycling efficiency in terms of both material recycling and chemical recycling.

[0138] The fiber laminated structure of the present invention has high breathability and waterproofness and is excellent in durability, and therefore can be suitably used in the fields of outdoor wear such as fishing and mountain climbing wear, sportswear such as ski and snowboard wear, windbreakers, athletic wear, golf wear, tennis wear, etc., waterproof and breathable clothing such as uniforms, rainwear, casual wear, workwear, etc., and waterproof and breathable clothing materials such as gloves, shoes, glove inserts, boot inserts, etc. Furthermore, the fiber laminated structure of the present invention can be suitably recycled after functioning in the above-mentioned applications, and has excellent recycling efficiency.

[0139] A. Examples of island fauna B. Examples of island fauna

Claims

1. A fiber laminated structure having a woven or knitted fabric and a non-porous resin layer on the woven or knitted fabric, the resin layer containing resin A and elastomer B, the resin A and the elastomer B being a combination of either polyamide and a polyamide-based elastomer or polyester and a polyester-based elastomer, the resin A phase and the elastomer B phase being a co-continuous structure or a sea-island structure in which the island phases are continuous.

2. The fiber laminated structure according to claim 1, wherein said resin A and said elastomer B are a combination of said polyamide and a polyamide-based elastomer.

3. The fiber laminate structure according to claim 2, wherein the polyamide elastomer is a polyether ester amide containing, as a copolymerization component, a dioxyethylene ether having a bisphenol A skeleton represented by the following structural formula (1):

4. The fiber laminate structure according to claim 2 or 3, wherein the resin A phase and the elastomer B phase have a sea-island structure with continuous island phases, the island phases are made of the polyamide and the sea phase is made of the polyamide-based elastomer, and the average diameter of the island phases is 5 to 200 nm.

5. The fiber laminated structure according to any one of claims 2 to 4, wherein the woven or knitted fabric is made of polyamide.

6. The fiber laminate structure according to claim 5, wherein the fibers constituting the woven or knitted fabric are fibers whose main component is polyamide 6, the resin A is polyamide 6, and the elastomer B is a polyamide 6-based elastomer.

7. JIS L1099:2021 (A-1 method) moisture permeability is 3500g / m ２ ・24h or more, and JIS L1099:2021 (B-1 method) moisture permeability is 10,000g / m ２ The fiber laminated structure according to any one of claims 1 to 6, having a hardness of 24 hours or more.

8. The fiber laminate structure according to any one of claims 1 to 7, wherein the woven or knitted fabric has an elongation of 10% or more in at least one of the warp and weft directions as measured by JIS L1096:2010 elongation method A (constant speed elongation method).

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

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