Fiber-laminated structures and waterproof and breathable clothing

Abstract

The present invention provides a fiber laminated structure and waterproof and breathable clothing that offer excellent breathability, waterproofing, and long-term waterproofing (moisture and heat resistance). [Solution] A fiber laminated structure having a woven or knitted fabric and a non-porous resin layer on the woven or knitted fabric, wherein the resin layer contains polyamide and polyvinylpyrrolidone.

Description

[Technical Field]

[0001] This invention relates to a fiber-laminated structure and waterproof, breathable clothing. [Background technology]

[0002] Conventionally, a fiber laminated structure with excellent breathability and waterproofing properties is known to be one in which a microporous polytetrafluoroethylene membrane is bonded to a woven fabric.

[0003] However, in recent years, with regulations being implemented in various countries regarding products containing fluorine compounds from an environmental protection standpoint, there has been a growing need for waterproof and breathable membranes other than those containing fluorine. Examples of waterproof and breathable membranes other than fluorine include polyurethane membranes, polyester membranes, and polyamide membranes. Among these, polyamide membranes have the advantage of excellent durability and less degradation from ultraviolet rays. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2011-37101 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, it is known that membranes using polyamide alone without copolymer components have poor breathability as waterproof and breathable clothing. In contrast, it is conceivable to use a polyamide-based elastomer membrane with breathability as disclosed in Patent Document 1, but it has been found that although it has a certain degree of breathability and waterproofness, it has low resistance to humid heat and its waterproofness deteriorates significantly over time.

[0006] The present invention aims to solve the above problems and provide a fiber laminated structure and waterproof and breathable clothing that are excellent in breathability, waterproofness, and waterproofness (moisture and heat resistance) even after a long period of time. [Means for solving the problem]

[0007] To solve the aforementioned problems, the present invention has the following configuration. [1] A woven or knitted fabric and a non-porous resin layer on the woven or knitted fabric, The aforementioned resin layer is a fiber laminated structure containing polyamide and polyvinylpyrrolidone. [2] The polyvinylpyrrolidone content in the resin layer is 5 to 35% by mass, The fiber laminated structure according to [1], wherein the pyrrolidone content in the resin layer is 0.035% by mass or less. [3] The fiber laminated structure according to [1] or [2], wherein the polyamide is polyamide 6 or polyamide 66. [4] A fiber laminated structure according to any one of [1] to [3], further comprising inorganic particles in the resin layer. [5] The fiber laminated structure according to any one of [1] to [4], wherein the resin layer comprises a polyether ester amide. [6] The fiber laminated structure according to any one of [1] to [5], wherein the fibers constituting the woven or knitted fabric are polyamide fibers. [7] The fiber laminated structure according to [6], wherein both the polyamide in the resin layer and the polyamide in the fibers constituting the woven fabric are polyamide 6. [8] The resin layer has a second woven fabric on the surface opposite to the woven fabric, The second woven or knitted fabric is a fiber laminated structure as described in any of [1] to [7], wherein the pH of the fabric according to JIS L1096:2021 Method A is 3.5 to 6.5. Waterproof and breathable clothing containing a fiber-laminated structure as described in any of [9][1] to [8]. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a fiber laminated structure and waterproof and breathable clothing that are excellent in breathability, waterproofness, and waterproofness (moisture and heat resistance) even after a long period of time. [Modes for carrying out the invention]

[0009] Hereinafter, the present invention will be described in detail.

[0010] The fiber laminate of the present invention is a fiber laminate having a woven or knitted fabric and a porous resin layer on the woven or knitted fabric. The above fiber laminate is preferably used for clothing such as sports clothing, uniform clothing, and raincoats. In that case, it is preferable to use the woven or knitted fabric side as the outer fabric.

[0011] [Woven or knitted fabric] The fiber laminate of the present invention has a woven or knitted fabric.

[0012] Examples of the 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. From the viewpoints of wear resistance and recyclability, polyamide fibers are preferable, and further, the polymer constituting the polyamide fibers preferably contains the same constituent components as the resin layer described later.

[0013] The polymer constituting the polyamide fiber is a polymer having an amide bond. Specifically, aliphatic polyamides such as polyamide 6, polyamide 11, polyamide 12, polyamide 66, polyamide 46, polyamide 610, polyamide 56, polyamide 510, aromatic polyamides such as polyamide 6T and polyamide 9T using diamine and terephthalic acid as raw materials, and polyamide 6I using hexamethylenediamine and isophthalic acid as raw materials, and further aramids obtained by co-condensation polymerization reaction of aromatic diamine and dicarboxylic acid can be mentioned.

[0014] Among the above polyamide fibers, polyamide 6 fibers and polyamide 66 fibers are preferable in terms of cost and versatility, and polyamide 6 fibers are more preferable from the viewpoints of moisture permeability and chemical recyclability.

[0015] As the fiber form, multifilaments are preferred, and there is no problem even if it is a single yarn of multifilaments, or a multifilament having a side-by-side or core-sheath composite single yarn cross-sectional structure (hereinafter sometimes referred to as "composite multifilament"). The single yarn referred to here means a fiber composed of a single material as a material constituting the fiber (which may be a single polymer or a composition containing two or more components).

[0016] The core-sheath composite type described above may be an eccentric core-sheath composite type or a concentric core-sheath composite type.

[0017] In the case of composite multifilaments, potential crimp yarns of a side-by-side type or an eccentric core-sheath composite type, which are composite forms in which three-dimensional coiled (helical) crimps are exhibited in the fiber depending on the polymer combination, are preferred. When the side-by-side type or the eccentric core-sheath composite type is used as the composite form, examples of the polymer combination include combinations of the same type of polymers having different viscosities, and combinations of different types of polyamide-based polymers such as polyamide 6 and polyamide 66, which are preferably used.

[0018] Specific two-component combinations of the materials constituting the composite multifilaments include polyamide 6 and polyamide 66, polyamide 6 and polyamide 610, polyamide 66 and polyamide 610, etc.

[0019] By making the fiber used for the woven or knitted fabric have the same monomer components as the resin contained in the resin layer described later, it is excellent in recyclability such as material recycling and chemical recycling. Also, the fewer the types of resins used, the better the material recyclability, and the fewer the types of monomer components, the better the chemical recyclability. However, considering the functions required in practical use and the recyclability, the materials to be used may be appropriately selected.

[0020] In the present invention, in order to increase recycling efficiency, it is preferable that the main repeating unit constituting the fibers in the woven or knitted fabric be of one type, and that the common same resin component be 100% by mass. When different types of elastic yarns such as polyurethane fibers are used, it is desirable that the content of a single resin component in the fibers constituting the woven or knitted fabric be high, and it is preferable that the ratio of a single resin component be at least 80% by mass, more preferably 85% by mass or more, and even more preferably 90% by mass or more. Here, "different types" refers to those that do not contain the same components as monomer components constituting each other's resins, and "single resin" refers to those with the same basic polymer structure, without polymer blending or the like.

[0021] The cross-sectional shape of the fiber is not particularly limited, and round, triangular, hollow, and other shapes can be widely used. Furthermore, there is no problem in including additives or inorganic particles that impart antistatic properties to the yarn.

[0022] The total fineness of the yarn used in woven or knitted fabrics is preferably 150 dtex or less. Reducing the thickness of the woven or knitted fabric improves its breathability. If the yarn is too fine, the tear strength and burst strength will decrease, so it is preferably 11 dtex or more. More preferably, it is 20 dtex or more and 75 dtex or less.

[0023] Furthermore, while it is preferable to reduce the density of the woven or knitted fabric as much as possible to improve moisture permeability, reducing the density of the woven or knitted fabric by making the fibers finer tends to decrease the UV shielding rate. For example, when a woven or knitted fabric is used as the outer fabric and exposed to ultraviolet rays outdoors, the ultraviolet rays will be irradiated to the resin layer through the woven or knitted fabric. Generally, if the amount of ultraviolet rays irradiated to the resin layer through the woven or knitted fabric increases, the resin layer will be more susceptible to degradation due to ultraviolet irradiation, so the density of the woven or knitted fabric should be appropriately determined taking these factors into consideration.

[0024] The fabric is not particularly limited in form, but plain, twill, satin and ripstop weaves, double weaves, oxford, and tussah fabrics are preferred.

[0025] The form of the knitted fabric is not particularly limited, but high-gauge, high-density circular knit or warp knit fabrics are preferred.

[0026] [Resin layer] Next, the non-porous resin layer on the woven or knitted 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 connecting pores between the front and back surfaces. 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.

[0027] In the present invention, the resin layer contains polyamide and polyvinylpyrrolidone (hereinafter sometimes referred to as PVP). Since sufficient moisture permeability cannot be obtained if the resin layer is made of polyamide alone, the inventors considered incorporating a moisture-absorbing component into the resin layer. They found that by incorporating PVP together with polyamide into the resin layer, moisture permeability can be imparted to the resin layer without impairing the aforementioned moisture and heat resistance.

[0028] The polyamide content in the resin layer is preferably 50 to 95% by mass. A polyamide content of 50% by mass or more further improves water resistance. A polyamide content of 70% by mass or more is more preferable. On the other hand, by including other components such as PVP in a polyamide content of 95% by mass or less, moisture permeability and heat resistance can be further improved. A polyamide content of 90% by mass or less is more preferable.

[0029] As the polyamide, those polymers described for the polyamide fibers can be used. Among these, polyamide 6 or polyamide 66 is preferred from the viewpoint of increasing the mechanical strength and heat and humidity resistance of the resin layer. Furthermore, since materials used in waterproof and breathable clothing used in harsh environments are composites with woven or knitted fabrics made of polyamide 6 or polyamide 66 from the viewpoint of durability, cost, and versatility, it is preferable that the resin layer is also made of polyamide 6 or polyamide 66 from the viewpoint of recyclability. Moreover, it is preferable that both the polyamide in the resin layer and the polyamide in the fibers constituting the woven or knitted fabric are polyamide 6.

[0030] The PVP content in the resin layer is preferably 5 to 35% by mass. A PVP content of 5% by mass or more further improves moisture permeability. A PVP content of 15% by mass or more is more preferable. On the other hand, a PVP content of 35% by mass or less improves the mechanical strength of the resin layer and further improves waterproofness. A PVP content of 30% by mass or less is more preferable.

[0031] Furthermore, in order to enhance the color development of the fiber laminated structure in the present invention, the pyrrolidone content in the resin layer is preferably 0.035% by mass or less, and more preferably 0.025% by mass or less. Here, pyrrolidone is a by-product of PVP polymerization, and if the pyrrolidone content is high, the color development of the resin layer decreases. In order to reduce the pyrrolidone content to 0.035% by mass or less, isopropyl alcohol can be used as the solvent during PVP polymerization. Generally, water or the like is used as the solvent during PVP polymerization, but by using isopropyl alcohol, the solvent polarity is reduced, and the interaction between PVP and pyrrolidone can be reduced, thus reducing the pyrrolidone content. In addition, it is preferable not to include a hydrogen peroxide-based catalyst as the polymerization initiator in order to further suppress the generation of pyrrolidone, a by-product that causes yellowness. Preferred polymerization initiators include azo-based initiators. Other conditions can be handled using a normal polymerization method. The pyrrolidone content in the resin layer can be measured by the method described in the examples.

[0032] From the viewpoint of obtaining moisture permeability by including a certain amount of polyvinylpyrrolidone while improving color development, it is preferable that the polyvinylpyrrolidone content in the resin layer is 5 to 35% by mass, and the pyrrolidone content in the resin layer is 0.035% by mass or less.

[0033] The resin layer preferably contains polyether ester amide. The inclusion of polyether ester amide further improves moisture permeability and imparts flexibility to the resin layer. A preferred polyether ester amide content in the resin layer is 5 to 40% by mass. A polyether ester amide content of 5% by mass or more further improves moisture permeability and flexibility. A more preferable polyether ester amide content is 10% by mass or more. On the other hand, a polyether ester amide content of 40% by mass or less further improves heat and humidity resistance. A more preferable polyether ester amide content is 25% by mass or less.

[0034] Here, polyether ester amide can be a block copolymer of a polyether block and a polyamide block. Polyether ester amide may be contained throughout the resin layer, but as will be described later, when the resin layer is a three-layer laminate, it is preferable to contain polyether ester amide only in both surface layers or the center layer, as this improves moisture permeability while suppressing the decrease in moisture and heat resistance due to deterioration of the entire resin laminate.

[0035] A resin layer thickness of 5 to 35 μm is preferable in terms of the physical strength of the resin layer and the texture when used in waterproof and breathable clothing. A resin layer thickness of 5 μm or more further improves waterproofing. Furthermore, a thickness of 35 μm or less further improves breathability. A resin layer thickness of 10 to 20 μm is preferable.

[0036] The resin layer may be further laminated with other resin layers to form a resin laminate. When used as a resin laminate, each laminated resin layer contains at least one of the resin layers described above. The number of layers in the resin laminate is not particularly limited, but three layers are preferred. The ratio of the thicknesses of each layer can be adjusted as appropriate depending on the purpose.

[0037] [Antioxidant] It is preferable to use antioxidants to improve the heat resistance of the resin layer. Examples of preferred antioxidants include phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants, but hindered phenolic antioxidants are particularly preferred. The resin layer preferably contains 0.1 to 5.0% by mass of antioxidant, a more preferable content is 0.5 to 4.0% by mass, and even more preferable is 0.2 to 0.5% by mass.

[0038] [Light stabilizer] To further improve the light resistance of the resin layer, a light stabilizer may be used. 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 the N-OR type amine 2,4-bis[N-butyl-N-(1-cyclohexylloyl-2,2,6,6-tetramethylpiperidic-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-tetrazine. The resin layer preferably contains 0.1 to 1.0% by mass of the light stabilizer, and a more preferable content is 0.1 to 0.5% by mass.

[0039] [Inorganic particles] To improve the light reflectivity of the resin layer and enhance the color development of the laminated surface fabric, it is preferable to further include inorganic particles in the resin layer. Examples of inorganic particles include calcium carbonate, barium sulfate, clay such as kaolin and talc, titanium dioxide, and zinc oxide. From the viewpoint of whiteness, light reflectivity, stability, and dispersibility, titanium dioxide or zinc oxide are preferred, and among these, titanium dioxide is more preferred because it has a high refractive index and therefore a high light reflectivity. In addition, titanium dioxide has crystalline forms such as anatase, rutile, and brookite, but rutile is the most preferred from the viewpoint of refractive index and stability.

[0040] The inorganic particles are preferably present in the resin layer in an amount of 0.1 to 10.0% by mass, and more preferably in an amount of 0.5 to 4.0% by mass. A inorganic particle content of 0.1% by mass or more further improves the color development of the fiber laminated structure, while a content of 10.0% by mass or less improves the mechanical strength of the resin layer and further improves its water pressure resistance.

[0041] [Other additives] In the present invention, lubricants, flame retardants, heat stabilizers, weather-resistant agents, etc., may be appropriately blended into the resin layer as needed.

[0042] [others] The fiber laminated structure of the present invention may have a second woven or knitted fabric on the surface of the resin layer opposite to the woven or knitted fabric. That is, it is also possible to have a woven or knitted fabric (hereinafter sometimes referred to as a third woven or knitted fabric) on the other surface of the resin layer. In this embodiment, by having the second woven or knitted fabric function as a lining, damage to the resin layer due to friction and other factors can be prevented, and a high-quality feel can be added. Furthermore, it is preferable that the pH of the fabric of the second woven or knitted fabric is 3.5 to 6.5 according to JIS L1096:2021 Method A. The resin layer containing polyamide may yellow due to the evaporation of antioxidants such as BHT (butylhydroxytoluene) contained in packaging materials and hangers, which react with nitrogen oxides, potentially worsening the appearance of the back surface. However, by setting the pH of the fabric of the second woven or knitted fabric within the above range, the reaction between BHT and nitrogen oxides can be suppressed, and the generation of yellowing substances can be suppressed. A pH of 3.5 or higher can reduce skin irritation, and a pH of 6.5 or lower enhances the effect of suppressing yellowing. A pH of 4.0 to 5.5 is more preferable for the fabric. To achieve a pH within this range, organic acids such as citric acid, malic acid, and fumaric acid can be applied to the woven or knitted fabric. Conventional processing methods such as pad-drying can be used. Any processing method can be applied at any time, such as before or after lamination of the resin layer. The pH of the fabric can be measured by the method described in the examples.

[0043] For the second type of woven or knitted fabric, a knitted fabric made of 100% polyamide multifilament by mass is suitable because it offers good recyclability, breathability, and a comfortable feel against the skin. Preferably, such polyamide multifilaments are composed of polyamide 6 or polyamide 66, with polyamide 6 being particularly preferred. Stretchability can be achieved by using false-twisted yarn or side-by-side yarns of different polymers as the polyamide multifilament.

[0044] In terms of fiber morphology, it is acceptable to use single multifilament threads or composite multifilaments with side-by-side or core-sheath composite single-fiber cross-sectional structures.

[0045] In the present invention, in order to increase recycling efficiency, it is preferable that the fiber component in the second woven or knitted fabric is 100% by mass of polyamide fibers containing polyamide multifilaments. A higher content of polyamide fibers in the fibers constituting the knitted fabric is desirable, and it is preferable that the ratio of polyamide fibers be at least 80% by mass, more preferably 85% by mass or more, and even more preferably 90% by mass or more.

[0046] Similar to the woven and knitted fabrics described above, the second type of woven or knitted fabric also exhibits excellent recyclability, including material recycling and chemical recycling, by using fibers containing polyamide. The fewer types of polyamide used in the fibers constituting the fiber laminate structure, the better the material recyclability, and the fewer types of monomer components, the better the chemical recyclability. However, the materials used should be appropriately selected considering the practically required functions and recyclability.

[0047] Furthermore, woven or knitted fabrics may be treated with water-repellent, antistatic, antibacterial, ultraviolet-absorbing, or near-infrared-absorbing finishes as needed.

[0048] When using seam sealing tape to maintain the waterproofness of the seams, the seam sealing tape is adhered to the lining with molten resin. To allow this molten resin to easily penetrate the lining and reach the waterproof and breathable film, it is preferable to use a low-density knit fabric for the second woven or knitted material. From the standpoint of being thin and low-density, tricot or circular knit fabrics are preferred.

[0049] The second knitted fabric described above is preferably laminated onto the resin layer of the fiber laminated structure using an adhesive.

[0050] As the adhesive for laminating the second woven or knitted fabric, a hot-melt type adhesive that does not use organic solvents is preferred, similar to the adhesive for woven or knitted fabrics described later. Examples of resins with hot-melt adhesive properties include polyurethane, polyester, polyether, and polyamide resins, but polyurethane or polyamide resins are preferred considering adhesiveness, flexibility, texture, and stretchability. Solvent-based adhesives can also be suitably used. Furthermore, the adhesive application method and lamination conditions can be carried out in the same way as the bonding conditions for woven or knitted fabrics described later.

[0051] The fiber laminated structure of the present invention preferably has excellent moisture permeability. The moisture permeability according to JIS L1099:2021 (A-1 method) is 3500 g / m². 2 • The moisture permeability must be 24 hours or more, and the moisture permeability according to JIS L1099:2021 (B-1 method) must be 10,000 g / m². 2 It is preferable that it be 24 hours or more. Here, the moisture permeability in JIS L1099:2021 (A-1 method) is an index representing the rate of water vapor transmission, and the moisture permeability in JIS L1099:2021 (B-1 method) is an index representing the rate of liquid phase moisture transmission. The moisture permeability in JIS L1099:2021 (A-1 method) is 6000 g / m 2 ・More preferably 24 hours or longer, 8000g / m² 2 • A humidity level of 24 hours or higher is even more preferable. While a higher humidity level is preferable according to JIS L1099:2021 (A-1 method), in reality, 20,000 g / m² is acceptable. 2 • It is less than 24 hours. Also, the moisture permeability according to JIS L1099:2021 (B-1 method) is 20,000 g / m². 2 It is more preferable that it be 24 hours or longer, and 30,000 g / m² 2 • A humidity level of 24 hours or more is even more preferable. While a higher humidity level is preferable according to JIS L1099:2021 (B-1 method), in reality, 100,000 g / m² is preferable. 2 • Less than 24 hours

[0052] The fiber laminated structure of the present invention preferably has excellent performance, such as high waterproofness, preventing rainwater from penetrating, i.e., a water resistance of at least 150 kPa or higher. More preferably 200 kPa or higher. Being within this range also suppresses the penetration of rainwater into clothing when worn. A higher water resistance is preferable, but in reality, it is 300 kPa or lower.

[0053] Furthermore, from the perspective of ensuring durability in actual wear, it is preferable that the water resistance after accelerated degradation testing under high temperature and constant humidity conditions is 150 kPa or higher. More preferably, it is 200 kPa or higher. Being within the above range provides excellent resistance to humidity and heat, and enhances waterproofness even after a long period of time. The accelerated degradation testing under high temperature and constant humidity conditions referred to here means treatment for 35 days in a constant temperature and humidity chamber or similar under a 70°C, 95% RH environment. While a higher water resistance after accelerated degradation testing under high temperature and constant humidity conditions is preferable, in reality, it is 500 kPa or lower.

[0054] The fiber laminated structure of the present invention is preferably treated with a water-repellent finish. By applying a water-repellent finish, the material becomes a more practical product as a waterproof and breathable material, and a water-repellent finish with high wash durability and abrasion durability is desirable. 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 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.

[0055] Furthermore, additional processing such as antistatic treatment, antibacterial treatment, ultraviolet absorption treatment, and near-infrared absorption treatment may be applied as needed.

[0056] [Waterproof and breathable clothing] The waterproof and breathable garments containing the fiber laminated structure of the present invention have a high waterproof and breathable effect, effectively preventing stuffiness, offering excellent wearing comfort, and also maintaining excellent waterproofness even after long periods of time. They are therefore suitable for use in waterproof and breathable garments such as outdoor wear for mountaineering and skiing, windbreakers, and raincoats.

[0057] [Method for manufacturing resin layers] The resin layer described above can be manufactured using conventional film-forming methods such as the T-die method and the inflation method.

[0058] For example, the polyamide, polyvinylpyrrolidone, inorganic particles, and antioxidants mentioned above are supplied to a single-screw or twin-screw extruder. Next, the resin in the extruder is heated above its melting point, and extruded as a film from the die using the T-die method. This film is then melt-coated onto a support, such as polyester film or release paper, wound up, and stored for use. In addition, a method of forming a film using the above-described method, which involves pre-mixing resins together or resins with additives such as inorganic particles in a twin-screw process to create a masterbatch, is also preferably used to improve the dispersibility of the resins and additives.

[0059] Furthermore, in order to laminate resin layers to form a three-layer resin laminate, a preferred method is to melt each resin component separately by extrusion, laminate them in a molten state in a confluence device provided between the extruder and the die, guide them to the die, and extrude them from the die onto a casting drum to process them into a sheet. However, other known techniques may be used as appropriate.

[0060] [Method for manufacturing fiber laminated structures] The fiber laminated structure of the present invention can be manufactured by laminating such resin layer onto a base fabric made of a woven or knitted material. The lamination method can be the following, but is not limited to them.

[0061] In other words, this method involves lamination using an adhesive. Preferred adhesives include conventional hot-melt adhesives and heat-bondable fiber adhesives. Solvent-based adhesives can also be used. When using a heat-bonding adhesive, the process can be carried out by using a heating device and applying heat pressure. When using a conventional hot-melt adhesive, if the actual surface area covered is large, it can often reduce the breathability of the fabric, so it is preferable to use an adhesive made of a breathable resin.

[0062] It is preferable that the adhesive be provided in a proportion of 70% or less in terms of area ratio with respect to the woven or knitted fabric in the plane direction in order to improve the accuracy of controlling the peel strength and to stabilize the moisture permeability, air permeability, and water resistance of the fiber laminate structure at a high level. The area ratio is more preferably 10 to 70%, and even more preferably 30 to 70%. In order to achieve the above area ratio, it is preferable to provide the adhesive in the form of dots or lines in the plane direction. Here, the area ratio refers to the coverage rate by the adhesive.

[0063] It is preferable to reduce the area of the dots or lines of the adhesive and also reduce the area ratio of the adhesive, but the peel strength will decrease. On the other hand, in order to improve the peel strength, it is preferable to increase the area of the dots or lines of the adhesive and also increase the area ratio. Most preferably, it is preferable to form a full-surface adhesive layer, but the moisture permeability may decrease in some cases. In order to moderately maintain this contradictory functionality, it is preferable to apply the adhesive in the form of dots with an area of 0.1 to 100.0 mm 2 or in the form of lines or grids with a thickness of 0.1 to 10.0 mm, in an area ratio of 10 to 70%.

[0064] The dots may be in any shape such as circular, square, rhombus, oval, triangle, etc., or they may be arranged in combination, formed into patterns or letters, or arranged in the shape of a trademark logo. Also, they may be arranged to form a continuous pattern or arranged randomly. Also, the lines may be straight or curved.

[0065] As the adhesive, a hot-melt type adhesive that does not use an organic solvent is preferable. Examples of resins having hot-melt adhesiveness include polyurethane-based, polyester-based, polyether-based, polyamide-based, etc. Considering adhesiveness, flexibility, texture, stretchability, etc., polyurethane-based resins and polyamide-based resins are preferable. Also, solvent-based adhesives can also be suitably used.

[0066] Methods for applying the adhesive include knife coaters, bar coaters, and gravure coaters. Gravure coaters are particularly preferable because they allow for relatively easy application in dot, linear, or grid patterns, and are beneficial in terms of moisture permeability, but the method is not limited to these.

[0067] Furthermore, the bonding method can be selected from wet lamination, dry lamination, etc., depending on the desired characteristics, but preferably, from the viewpoint of texture and adhesion, it is preferable to apply the adhesive to the woven fabric and use the dry lamination method. [Examples]

[0068] The present invention will now be specifically described with reference to examples, but the present invention is not limited in any way to these examples. The various measurement methods in the present invention are as follows.

[0069] (1) Thickness of the resin layer The resin layer, in a free state without any load applied, was cut at 10 arbitrary points using a single-edged razor blade. The cross-sections were observed with an electron microscope to measure the thickness, and the average value was taken as the thickness.

[0070] (2) Accelerated degradation test The samples were left to stand for 35 days in a constant temperature and humidity chamber maintained at 70°C and 95% RH.

[0071] (3) Water resistance The water resistance was measured according to JIS L1092:2009 Method B (high water pressure method).

[0072] However, the measurements were taken with a non-stretchable taffeta layered on the reverse side (the side not exposed to water) to prevent the sample from stretching. Five samples were used for each level, and the average value was defined as the water resistance. Furthermore, water resistance was determined in the same manner using the samples after the accelerated degradation test described above, and this was used to evaluate the resistance to humidity and heat.

[0073] (4) Moisture permeability Measurements were taken according to JIS L1099:2021 Calcium Chloride Method (Method A-1) and JIS L1099:2021 Potassium Acetate Method (Method B-1). Specifically, the fiber laminated structure was set up so that water vapor (Method A-1) or water (Method B-1) was applied from the side opposite to the woven surface, and measurements were taken. However, both test methods converted the values ​​to the amount of moisture permeability per 24 hours. Three samples were measured for each level, and the average value was used as the moisture permeability.

[0074] (5) Observation of the resin layer (confirmation of non-porous material) The presence or absence of connecting pores on the front and back surfaces was measured when five randomly selected cross-sections of the resin layer were observed using an electron microscope (Hitachi High-Tech SU3800, magnification: 1500x, observation field: 64μm × 85μm).

[0075] (6) Pyrrolidone content 100 mg of a sample taken from the resin layer was dissolved in 3 ml of hexafluoroisopropanol and 1 ml of chloroform. Ethanol was added to the resulting solution to reprecipitate the polymer components, which were then dissolved in 20 ml of solution. The solution components were analyzed by gas chromatography using a standard method. A GC14A instrument (Shimadzu Corporation) and an NB-1 column (15 m) were used. A calibration curve for valerolactam was prepared in advance and used for the quantification of pyrrolidone. The pyrrolidone content relative to the resin layer was determined using the following formula. Pyrrolidone content (relative to resin layer) (mass%) = [(GC peak area / calibration curve coefficient) (mg / ml) × solution volume (ml) / sample volume (mg)] × 100.

[0076] (7) Degree of yellowing on the reverse side The degree of yellowing on the back surface of the fiber laminated structure was evaluated based on the ISO 105-X18 yellowing test. A lower yellowing grade indicates a greater susceptibility to yellowing due to BHT.

[0077] (8) pH of the second woven or knitted fabric For the second woven / knitted fabric, the pH of the fabric was measured according to JIS L1096:2021 Method A.

[0078] (9) Color development of the fabric The color development of the fiber laminated structure was visually evaluated by 10 participants (5 healthy adult men and 5 healthy adult women). Specifically, the surface appearance of the fiber laminated structure was visually assessed using the following three-level evaluation system, and the most frequent evaluation was used as the color development of the fiber laminated structure. However, in the case of a tie in evaluations, the higher evaluation was adopted. ○: Good color development. △: The color is somewhat dull and not very vibrant. ×: The color is dull and the color payoff is poor.

[0079] [Example 1] Polyamide 6 semi-dull round cross-section multifilaments, consisting of 56dtex-42 filaments for the warp and 78dtex-34 filaments for the weft, were subjected to a false twist process to give them stretchability. Subsequently, these processed yarns were used as both warp and weft threads and woven in a waterjet loom to achieve a warp x weft density of 111 threads / 2.54cm x 77 threads / 2.54cm. Next, after scouring and relaxing, the fabric was pre-set and dyed blue using a conventional method with an acid dye (manufactured by Nippon Kayaku Co., Ltd., Kayanol Blue NR) 0.5% owf in a liquid flow dyeing machine. Then, using the pad-dry-cure method, a 5% aqueous solution of "Asahi Guard" (registered trademark) AG710 (fluorine-based water repellent, manufactured by Asahi Glass Co., Ltd.) was applied to the fabric surface to an adhesion rate of 60%, dried at 120°C for 1 minute, then heat-treated at 170°C for 40 seconds, and finally set to a final setting with a finished warp x weft density of 154 threads / 2.54cm x 122 threads / 2.54cm to obtain the fabric.

[0080] 100.0 parts by mass of polyamide 6 (72.7 parts by mass), polyvinylpyrrolidone polymerized using an azo polymerization initiator and isopropyl alcohol as the polymerization solvent (25.0 parts by mass), rutile-type titanium dioxide with a particle size of 0.6 μm (2.0 parts by mass), and hindered phenol antioxidant (0.3 parts by mass) were melt-kneaded using a twin-screw extruder with a 45 mm diameter and three-threaded screw, with the cylinder temperature (melt processing temperature) set to 255°C. The mixture was then extruded in strand form and cooled in a water bath, followed by pelletization in a pelletizer to a size of 3 mm in diameter and 3 mm in length. The resulting pellets were dried under reduced pressure at 110°C for 14 hours to reduce the moisture content to 300 ppm or less. Finally, they were melt-extruded through a T-slit die using a single-screw extruder at a cylinder temperature of 255°C to a thickness of 15 μm (basis weight 14 g / m²). 2 An unoriented film (resin layer) was prepared. The resulting resin layer had no interconnected pores and was non-porous.

[0081] A moisture-curing polyurethane hot-melt adhesive was heated and melted at 110°C. This adhesive was then applied to the fabric using a gravure coater equipped with a gravure roll engraved with 40 mesh, creating 0.40 mm × 0.40 mm squares (20 μm deep) at a 45° angle to the direction of fabric movement. The adhesive was dried at 120°C for 1 minute. As a result, the adhesive was applied to the fabric in a dotted pattern, with each dot being a 0.40 mm square positioned at a 45° angle to the length. The area ratio (coverage rate) of the adhesive to the fabric was 40%, and the adhesive application amount was 15 g / m². 2 That was the case.

[0082] 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. After that, it was aged at room temperature for 48 hours to obtain a two-layer fiber laminated structure in which the fabric and the film (resin layer) were laminated.

[0083] Next, a half-tricot knitted fabric was prepared using 22dtex-16 polyamide 6 semi-dull round cross-section multifilament, which was dyed gray and then acid-treated with malic acid. A moisture-curing polyurethane hot-melt adhesive was applied to the sinker surface of this fabric in the same way as the adhesive was applied to the aforementioned woven fabric (area ratio 40%, amount of adhesive resin 10g / m²). 2 Furthermore, a knitted fabric was laminated on top of the above two fiber laminated structures so that the film (resin layer) side of the two fiber laminated structures would adhere to it, thereby creating a three-layer fiber laminated structure.

[0084] The composition of the obtained fiber laminated structure and the results of various evaluations are shown in Tables 1 and 2. The fabric exhibited excellent color development, as well as superior breathability, waterproofing, and heat and humidity resistance (waterproofing after accelerated degradation testing).

[0085] [Example 2] A fiber laminated structure was obtained in the same manner as in Example 1, except that the lining was not bonded and a two-layer fiber laminated structure was used.

[0086] The composition of the obtained fiber laminated structure and the results of various evaluations are shown in Tables 1 and 2. The fabric exhibited excellent color development, breathability, waterproofing, and heat resistance (waterproofing after accelerated degradation testing), but the reverse side was somewhat prone to yellowing.

[0087] [Example 3] The outer fabric was obtained in the same manner as in Example 1, except that the warp threads were made of 56 dtex-42 filaments and the weft threads were made of polyamide 66 semi-dull round cross-section multifilament with 78 dtex-34 filaments.

[0088] Furthermore, the resin layer consisted of 72.7 parts by mass of polyamide 66, 25.0 parts by mass of polyvinylpyrrolidone, 2.0 parts by mass of rutile-type titanium dioxide, and 0.3 parts by mass of a hindered phenol-based antioxidant, totaling 100.0 parts by mass. Using a twin-screw extruder with a 45 mm diameter and a three-threaded screw, the mixture was melt-kneaded with a cylinder temperature (melting temperature) set to 285°C, then extruded in strand form, cooled in a water bath, and subsequently pelletized into 3 mm diameter, 3 mm length pellets using a pelletizer. The resulting pellets were dried under reduced pressure at 110°C for 14 hours to reduce the moisture content to 300 ppm or less, and then melt-extruded through a T-slit die using a single-screw extruder with a cylinder temperature set to 285°C, to a thickness of 15 μm (basis weight 14 g / m²). 2 An unstretched film (resin layer) was fabricated.

[0089] For the lining, a half-tricot fabric was used, prepared in the same manner as in Example 1, except that a 22dtex-16 polyamide 66 semi-dull round cross-section multifilament was used.

[0090] Except as described above, a three-layer fiber laminate structure was fabricated using the same method as in Example 1. The composition of the obtained fiber laminate structure and the results of various evaluations are shown in Tables 1 and 2. The fabric exhibited excellent color development, as well as excellent breathability, waterproofing, and heat and humidity resistance (waterproofing after accelerated degradation testing).

[0091] [Examples 4, 6, 8] A three-layer fiber laminate structure was prepared in the same manner as in Example 1, except that the resin layer component ratio was as shown in Table 1. The composition of the obtained fiber laminate structure and various evaluation results are shown in Tables 1 and 2. The fabric exhibited excellent color development, as well as excellent breathability, waterproofing, and heat and humidity resistance (waterproofing after accelerated degradation testing).

[0092] [Example 5] A resin layer with a thickness of 10 μm (basis weight 9 g / m²) 2A three-layer fiber laminated structure was prepared in the same manner as in Example 1, except that it was made of an unoriented film (resin layer). The composition of the obtained fiber laminated structure and the results of various evaluations are shown in Tables 1 and 2. The fabric exhibited excellent color development, as well as excellent breathability, waterproofing, and heat and humidity resistance (waterproofing after accelerated degradation testing).

[0093] [Example 7] A three-layer fiber laminate structure was prepared in the same manner as in Example 1, except that barium sulfate with a particle size of 4.5 μm was used instead of titanium dioxide in the resin layer. The composition of the obtained fiber laminate structure and various evaluation results are shown in Tables 1 and 2. The color development of the fabric was excellent, although slightly inferior to that of Example 1, and it also exhibited excellent breathability, waterproofing, and heat and humidity resistance (waterproofing after accelerated degradation testing).

[0094] [Example 9] A three-layer fiber laminate structure was prepared in the same manner as in Example 1, except that the half-tricot used for the lining was not acid-treated. The composition of the obtained fiber laminate structure and the results of various evaluations are shown in Tables 1 and 2. The fabric had excellent color development, breathability, waterproofing, and heat resistance (waterproofing after accelerated degradation testing), but the reverse side was somewhat prone to yellowing.

[0095] [Example 10] As a method for preparing polyether ester amide, 45.0 parts by mass of caprolactam, 45.0 parts by mass of ethylene oxide adduct of bisphenol A with a number average molecular weight of 1,500, 5.0 parts by mass of polyethylene glycol with a number average molecular weight of 1,500, and 5.8 parts by mass of terephthalic acid such that the amount of carboxyl groups [COOH] relative to the amount of hydroxyl groups [OH] derived from poly(alkylene oxide) glycol is [OH] / [COOH] = 0.95, were charged into a reaction vessel along with 0.5 parts by mass of an antioxidant ("Irganox" (registered trademark) 1098: manufactured by Ciba Specialty Chemicals Co., Ltd., hereafter the same), purged with N2, heated and stirred at 260°C for 60 minutes to obtain a clear homogeneous solution, and then the pressure was reduced to 0.07 kPa or less. 0.1 parts by mass of tetrabutyl titanate was added, and the reaction was terminated when the stirring torque reached 11 kg·m (11 r / min) under 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 content was 0.48 × 10⁶. -5 A polyether ester amide with eq / g and a melt viscosity of 920 poise (92 Pa·s) was obtained. Using this, a three-layer fiber laminate structure was prepared in the same manner as in Example 1, except that the resin layer component ratio was as shown in Table 1. The composition of the obtained fiber laminate structure and various evaluation results are shown in Tables 1 and 2. The fabric exhibited excellent color development, as well as excellent moisture permeability, waterproofing, and heat resistance (waterproofing after accelerated degradation testing).

[0096] [Example 11] Regarding the resin layer, the polyether ester amide from Example 10 was used, and the components of layers A and B, with the resin layer component ratios shown in Table 1, were melted in separate extruders. The molten layers were then laminated in a confluence device located between the extruder and the die, before being guided to the die. From the die, the three layers of A / B / A were extruded, and the laminated structure was obtained by forming a sheet with a layer thickness ratio of 1 / 8 / 1 for each layer. A three-layer (outer fabric / resin layer / lining) fiber laminate structure was produced in the same manner as in Example 1, except that the resin layer was prepared using the same method as in Example 1. The composition of the obtained fiber laminate structure and various evaluation results are shown in Tables 1 and 2. The fabric exhibited excellent color development, breathability, waterproofing, and heat and humidity resistance (waterproofing after accelerated degradation testing).

[0097] [Example 12] A three-layer fiber laminate structure was prepared in the same manner as in Example 11, except that the resin layer component ratio was as shown in Table 1. The composition of the obtained fiber laminate structure and various evaluation results are shown in Tables 1 and 2. The fabric exhibited excellent color development, as well as excellent breathability, waterproofing, and heat and humidity resistance (waterproofing after accelerated degradation testing).

[0098] [Example 13] A three-layer fiber laminate structure was prepared in the same manner as in Example 1, except that the resin layer component ratio was as shown in Table 1. The composition of the obtained fiber laminate structure and various evaluation results are shown in Tables 1 and 2. It did not contain inorganic particles and had poor color development, but it had excellent moisture permeability, waterproofing, and heat and humidity resistance (waterproofing after accelerated degradation testing).

[0099] [Comparative Example 1] A three-layer fiber laminate structure was prepared using the same method as in Example 1, except that the resin layer component ratios were as shown in Table 1. The composition of the obtained fiber laminate structure and various evaluation results are shown in Tables 1 and 2. It did not contain polyvinylpyrrolidone and had poor moisture permeability.

[0100] [Comparative Example 2] A three-layer fiber laminate structure was prepared in the same manner as in Example 1, except that the resin layer used the polyether ester amide from Example 10 and the resin layer component ratio was as shown in Table 1. The composition of the obtained fiber laminate structure and various evaluation results are shown in Tables 1 and 2. It had excellent moisture permeability but poor resistance to humid heat (waterproofing after accelerated degradation testing).

[0101] [Table 1]

[0102] [Table 2]

[0103] As shown above, the fiber laminated structures produced in Examples 1 to 13 exhibited excellent moisture permeability, waterproofing, and heat resistance. [Industrial applicability]

[0104] The fiber laminated structure of the present invention is excellent in moisture resistance, waterproofing, and heat resistance, making it suitable for use in waterproof and breathable clothing such as outdoor wear for fishing and mountaineering, ski and snowboard wear, windbreakers, athletic wear, golf wear, tennis wear, rainwear, casual wear, and work clothes, as well as in clothing materials such as gloves, shoes, glove inserts, and boot inserts.

Claims

1. The material comprises a woven or knitted fabric and a non-porous resin layer on the woven or knitted fabric. The aforementioned resin layer is a fiber laminated structure containing polyamide and polyvinylpyrrolidone.

2. The polyvinylpyrrolidone content in the resin layer is 5 to 35% by mass. The fiber laminated structure according to claim 1, wherein the pyrrolidone content in the resin layer is 0.035% by mass or less.

3. The fiber laminated structure according to claim 1 or 2, wherein the polyamide is polyamide 6 or polyamide 66.

4. The fiber laminated structure according to any one of claims 1 to 3, further comprising inorganic particles in the resin layer.

5. The fiber laminated structure according to any one of claims 1 to 4, wherein the resin layer comprises a polyether ester amide.

6. The fiber laminated structure according to any one of claims 1 to 5, wherein the fibers constituting the woven or knitted fabric are polyamide fibers.

7. The fiber laminated structure according to claim 6, wherein both the polyamide in the resin layer and the polyamide in the fibers constituting the woven fabric are polyamide 6.

8. A second woven fabric is provided on the surface of the resin layer opposite to the woven fabric, The fiber laminated structure according to any one of claims 1 to 7, wherein the second woven or knitted fabric has a pH of 3.5 to 6.5 based on JIS L1096:2021 Method A.

9. A waterproof and breathable garment comprising a fiber laminated structure according to any one of claims 1 to 8.

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