Laminated fiber structure and waterproof moisture-permeable garment

Abstract

In order to provide a fiber laminate structure and a waterproof and moisture-permeable garment having excellent light resistance, excellent recycling efficiency, and high utility, this fiber laminate structure is obtained by laminating a non-porous film having a thickness of 10-30 [mu] m and comprising a polyester film on one surface of a woven fabric comprising polyester fibers, the polyester film contains 0.05-1.0% by mass of each of an ultraviolet absorber and a light stabilizer, and 0.1-1.0% by mass of titanium oxide having a band gap of 3.1 (eV) or more. The fiber laminate structure can be suitably used in waterproof and moisture-permeable clothing.

Description

Technical Field

[0001] The present invention relates to a fiber stack structure and waterproof and moisture-permeable clothing. Background Art

[0002] Conventionally, the following methods have been used to obtain fiber laminate structures having excellent moisture permeability and waterproof properties: a method of so-called wet coating of polyurethane, in which a film having both moisture permeability and waterproof properties is formed by dissolving polyurethane in a dimethylformamide solvent or the like, laminating the film on a woven fabric by coating or the like, and then introducing the film into water to solidify the film to form a microporous film; or a method of laminating a resin film having high moisture permeability, which is a mixture of a polymer having a hydrophilic portion introduced into a polymer chain, on a woven fabric; or a method of laminating a stretched and expanded microporous polytetrafluoroethylene film to a woven fabric.

[0003] However, in recent years, due to the depletion of petroleum resources and the conservation of resources for environmental protection, the recycling of clothing items has received attention. As for the previous waterproof and breathable materials, the materials of the fiber products generally used for the surface fabrics and linings are different from the materials of the above-mentioned membranes with waterproof and breathable functions. For example, there are three-layer laminates that use nylon or polyester woven fabrics as surface fabrics and laminate polyurethane and polytetrafluoroethylene membranes as waterproof and breathable functional membranes, and then laminate polyester knitted fabrics as linings, etc. In the case of chemical recycling of these materials after use and disposal, it is necessary to classify and collect the surface fabrics, waterproof and breathable functional membranes, and linings separately.

[0004] As an attempt to reduce the cost of material sorting and facilitate recycling, a method of using a polyester material as a film having a waterproof and moisture-permeable function has been proposed (Patent Documents 1 and 2).

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 11-170461

[0008] Patent Document 2: Japanese Patent Application Publication No. 2007-296797 Summary of the invention

[0009] Problems to be solved by the invention

[0010] However, the moisture-permeable polyester resin films disclosed in Patent Documents 1 and 2 have low light resistance and are not satisfactory for use as clothing materials.

[0011] An object of the present invention is to solve the above-mentioned problems and to provide a fiber laminate structure having waterproof and moisture-permeable functions and waterproof and moisture-permeable clothing which are excellent in light resistance and recycling efficiency and highly practical.

[0012] Means for solving problems

[0013] In order to solve the above-mentioned problems, the present invention has the following configurations.

[0014] (1) A fiber stack structure, which is a fiber stack structure in which a non-porous membrane with a thickness of 10 to 30 μm composed of a polyester film is laminated on one side of a woven knitted fabric composed of polyester fibers, wherein the polyester film contains 0.05 to 1.0 mass % of an ultraviolet absorber and a light stabilizer, respectively, and contains 0.1 to 1.0 mass % of titanium oxide having a band gap of 3.1 (eV) or more.

[0015] (2) A fiber stacking structure, which is a fiber stacking structure in which a non-porous membrane with a thickness of 10 to 30 μm comprising a polyester film is laminated on one side of a woven knitted fabric comprising polyester fibers, wherein the polyester film contains 0.05 to 1.0 mass % of an ultraviolet absorber and a light stabilizer each, and 0.1 to 1.0 mass % of anatase-type titanium oxide.

[0016] (3) The fiber stack structure according to (1) or (2), wherein the polyester film comprises a polyester block copolymer having a hard segment comprising a crystalline polyester unit and a soft segment comprising an aliphatic polyether unit and / or an aliphatic polyester unit as constituent components.

[0017] (4) The fiber stack structure according to any one of (1) to (3), wherein the woven knitted fabric is a woven fabric.

[0018] (5) The fiber stack structure according to any one of (1) to (4), further comprising a knitted fabric containing polyester filaments on the nonporous film containing the polyester film.

[0019] (6) The fiber stack structure according to any one of (1) to (5), wherein the woven knitted fabric containing the polyester fiber has an ultraviolet shielding rate of 80% or more.

[0020] (7) The fiber stacked structure according to any one of (1) to (6), wherein the moisture permeability of JIS L-1099A-1 is 4000 g / m 2 ·More than 24h, and JIS L-1099B-1 moisture permeability is 10000g / m 2 ·More than 24h.

[0021] (8) A fiber stack structure according to any one of (1) to (7), wherein the woven knitted fabric has stretchability in at least one of the warp and weft directions, and the elongation in the JIS L1096-2010 elongation A method (constant rate elongation method) is 10% or more.

[0022] (9) A waterproof and moisture-permeable garment comprising the fiber laminate structure according to any one of (1) to (8).

[0023] Effects of the Invention

[0024] According to the present invention, a fiber layered structure and waterproof and breathable clothing having excellent light resistance and recycling efficiency and high practicality can be provided. The fiber layered structure and waterproof and breathable clothing of the present invention are practical and can be appropriately used in sportswear, uniforms, raincoats, etc., and have excellent recycling efficiency after use. DETAILED DESCRIPTION

[0025] Hereinafter, the present invention will be described in detail.

[0026] The fiber laminate structure of the present invention is a fiber laminate structure in which a nonporous film having a thickness of 10 to 30 μm and comprising a polyester film is laminated on one side of a woven knitted fabric comprising polyester fibers. The fiber laminate structure of the present invention is suitable for use in clothing such as sportswear, uniforms, and raincoats, and in this case, the woven knitted fabric side is preferably used as the surface material.

[0027] [Woven fabrics containing polyester fibers]

[0028] The polymer constituting the polyester fiber is a polymer having an ester bond, and specifically, preferably polyalkylene terephthalates such as polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate. In addition, in order to modify these polyalkylene terephthalates, copolymers with 5-sodium sulfonate of isophthalic acid and other copolymer components may also be used.

[0029] As the fiber form, multifilament is preferred, and it can also be a single yarn of multifilament, or a parallel or core-sheath composite multifilament. The so-called single yarn here refers to a fiber composed of a single material (which can be a polymer monomer or a composition containing two or more components) as a material constituting the fiber.

[0030] In the above, the core-sheath type may be an eccentric core-sheath or a concentric core-sheath.

[0031] In the case of parallel and core-sheath type composite multifilaments, it is preferred to use a parallel type or eccentric core-sheath type composite form in which the fiber presents a three-dimensional coil (helical) curl by combining polymers. When using a parallel type or eccentric core-sheath as a composite form, examples of polymer combinations are suitable: a combination of polyester polymers of the same type with different viscosities; a combination of polyester polymers of different types such as polyethylene terephthalate and polybutylene terephthalate, etc.

[0032] Specific examples of the combination of two components constituting the parallel core-sheath composite multifilament include polytrimethylene terephthalate and polytrimethylene terephthalate, polytrimethylene terephthalate and polyethylene terephthalate, polyethylene terephthalate and polyethylene terephthalate, polyethylene terephthalate and polybutylene terephthalate, and the like.

[0033] By using polyester fibers, material recycling, chemical recycling, and other recyclability are excellent. The fewer the types of polyester used, the better the material recyclability; the fewer the types of monomer components, the better the chemical recyclability. The materials used can be appropriately selected in view of the functions and recyclability required for practical use.

[0034] By using false twisted yarns or parallel yarns of different polymers as polyester fibers, stretchability can be obtained. In addition, core-spun yarns using elastic yarns such as spandex yarns can also be used. However, it should be noted that if the blending rate of spandex yarns increases, the blending rate of other materials increases, and the recycling efficiency decreases.

[0035] In the present invention, in order to improve recycling efficiency, the fiber component in the woven fabric is preferably 100% by mass of polyester fiber. As described above, in the case of using non-polyester elastic yarn, the content of polyester fiber in the fiber constituting the woven fabric is preferably higher, and the ratio of polyester fiber is preferably at least 80% by mass, more preferably 85% by mass, and further preferably 90% by mass.

[0036] The cross-sectional shape of the fiber is not particularly limited, and a wide range of cross-sectional shapes such as round, triangular, and hollow can be used. In addition, the yarn may contain additives that impart antistatic properties, or matting agents such as titanium oxide.

[0037] The form of the woven fabric is not particularly limited, but woven fabrics such as plain weave, twill weave, satin weave, alternating double weave, double weave, oxford weave, and tussah weave are preferred.

[0038] The total fineness of the yarn used in the woven fabric is preferably 150 dtex or less. By reducing the thickness of the woven fabric, the moisture permeability becomes higher. If it is too thin, the tear strength and burst strength are reduced, so it is preferably 11 dtex or more. More preferably, it is 20 dtex or more and 75 dtex or less.

[0039] Furthermore, from the viewpoint of improving moisture permeability, it is preferred that the density of the woven fabric is as thick as possible. If the fineness is reduced and the density of the woven fabric is reduced, there is a tendency for the ultraviolet shielding rate to decrease. For example, when the woven fabric is used as the surface material and exposed to ultraviolet rays outdoors, the ultraviolet rays will pass through the woven fabric and irradiate the polyester film. If the amount of ultraviolet rays passing through the woven fabric and irradiating the polyester film increases, the polyester film is generally prone to deterioration due to ultraviolet irradiation.

[0040] When the function of preventing strength degradation due to ultraviolet irradiation is required at a higher level, it is preferable to increase the cover factor of the woven fabric to an extent that does not cause a problem at a practical level.

[0041] Regarding the method of improving the ultraviolet shielding rate by the cover factor of the woven fabric, a woven fabric having a cover factor of about 1600 to 3200 as shown in the following formula can be preferably used.

[0042] The smaller the cover factor, the higher the JIS L1099 (B-1 method) moisture permeability becomes. Therefore, from the perspective of moisture permeability, the smaller the cover factor, the more preferred. On the other hand, if the cover factor is too small, the gaps between the filaments become larger and the waterproof and moisture-permeable film is exposed, which is damaged by friction and the like, and the waterproof property is reduced. In addition, if the texture of the fiber laminate structure is also considered, it is preferably in the range of 1600 to 2800, and more preferably in the range of 2000 to 2600.

[0043] CF={(D1) 1 / 2 ×M}+{(D2) 1 / 2 ×N}

[0044] Where, CF: Coverage Factor;

[0045] D1: warp yarn fineness (dtex);

[0046] M: warp density (root / 2.54cm);

[0047] D2: weft yarn fineness (dtex);

[0048] N: Weft density (root / 2.54cm)

[0049] It should be noted that the cover factor is calculated based on the fineness and density of the final finished product after lamination.

[0050] Furthermore, by making the color of the surface material dark or mixing ultraviolet absorbers, titanium oxide and other additives with ultraviolet shielding effects into the fibers to make it difficult for ultraviolet rays to reach the polyester film, a higher function of preventing strength degradation caused by ultraviolet irradiation can be obtained.

[0051] The ultraviolet shielding rate brought by the woven fabric of the surface side material is preferably 80% or more, more preferably 85% or more. The lower the ultraviolet shielding rate, the greater the degree of freedom for the fineness, weaving structure and density of the woven fabric, and the color, the titanium oxide content in the fiber, and the amount of ultraviolet absorber added are no longer limited. When the woven fabric side is used as the surface side material, the selection range of the woven fabric is increased. However, as a result, ultraviolet rays easily penetrate the woven fabric to reach the polyester film. Therefore, there is a tendency for the water resistance after irradiation of the blue standard 4 level obtained by a fade meter according to the JISL0842 light fastness test to become lower.

[0052] In order to make the ultraviolet shielding rate of the woven fabric of the front side fabric 80% or more, it is particularly effective to increase the cover factor of the woven fabric or to make the front side fabric dark in color.

[0053] In addition, as a method for improving the ultraviolet shielding rate by dyeing woven fabrics, dyeing processing using dyes is generally used. Such dyes can be disperse dyes, cationic dyes, fluorescent whitening agents, etc., without particular limitation, but since cationic dyes need to select fibers that can be dyed by cationic dyes, it is more appropriate to use disperse dyes with higher versatility for dyeing.

[0054] In addition, it is more preferable to use a woven fabric having stretchability in at least one of the warp and weft directions in the present invention, wherein the elongation in the elongation method A (constant rate elongation method) of JIS L1096-2010 is preferably 10% or more. It should be noted that when making a woven fabric having stretchability, it is sufficient to use a stretchable fiber as the polyester fiber.

[0055] By having stretchability, the wearing comfort is improved, the application range is increased, and the freedom of sewing patterns is further increased, which is preferred.

[0056] [Knitted fabrics containing polyester fibers]

[0057] Preferred fiber embodiments such as the polymer constituting the polyester fiber, the fiber form, the cross-sectional shape, the additives, the content of the polyester fiber, etc. are the same as those described in the above section [woven fabric comprising polyester fiber].

[0058] The form of the knitted fabric is not particularly limited, but a knitted fabric having a fine gauge and a high density is preferred.

[0059] The total fineness of the yarn used in the knitted fabric is preferably 150 dtex or less. By reducing the thickness of the knitted fabric, the moisture permeability becomes higher. If the fineness is too fine, the tear strength and burst strength are reduced, so it is preferably 11 dtex or more. More preferably, it is 20 dtex or more and 75 dtex or less.

[0060] Furthermore, regarding the consideration of the ultraviolet shielding rate of knitted fabrics, from the perspective of improving moisture permeability, it is preferred that the density is as thick as possible. However, if the fineness is reduced and the density of the knitted fabric is reduced, there is a tendency for the ultraviolet shielding rate to decrease, which is the same as for woven fabrics.

[0061] The ultraviolet shielding rate brought by the knitted fabric of the surface side material is preferably 80% or more, more preferably 85% or more. The lower the ultraviolet shielding rate, the greater the degree of freedom for the fineness, knitting structure and density of the knitted fabric, and the color, titanium oxide content in the fiber, and the amount of ultraviolet absorber added are no longer limited. When the knitted fabric side is used as the surface side material, the range of choices for knitted fabrics is expanded. However, as a result, ultraviolet rays easily penetrate the knitted fabric and reach the polyester film. Therefore, there is a tendency for the water resistance after irradiation of the blue standard 4 level obtained by the fading tester according to the JISL0842 light fastness test to become lower.

[0062] In order to make the ultraviolet shielding rate of the knitted fabric of the front side fabric 80% or more, it is particularly effective to increase the density of the knitted fabric and to make the front side fabric dark in color.

[0063] As another method of improving the ultraviolet shielding rate by dyeing the knitted fabric, the same consideration as described in the above-mentioned item [woven fabric containing polyester fiber] and other woven fabrics can be applied.

[0064] In addition, it is more preferable to use a knitted fabric having stretchability in at least one of the warp direction and the weft direction in the present invention, wherein the elongation in the elongation method A (constant rate elongation method) of JIS L1096-2010 is preferably 10% or more. It should be noted that as an example of making a knitted fabric having stretchability, a polyester fiber can be used as a stretchable fiber. It should be noted that the warp direction here refers to the wale direction of the coils, and the weft direction refers to the course direction of the coils.

[0065] By having stretchability, the wearing comfort is improved, the application range is increased, and the freedom of sewing patterns is further increased, which is preferred.

[0066] [Non-porous membrane]

[0067] Hereinafter, the above-mentioned nonporous membrane will be described.

[0068] Waterproof and breathable materials are mostly used for outdoor purposes. When worn outdoors, they are often exposed to sunlight. In addition, clothing is often washed and dried in the sun. In order to improve practical durability, light resistance must be improved.

[0069] To this end, as described above, woven knitted fabrics are used for the front and side fabrics and the ultraviolet shielding rate of the woven knitted fabrics is increased so that ultraviolet rays do not reach the polyester film as the waterproof and moisture-permeable film.

[0070] However, when the fiber laminate structure of the present invention is used for clothing, the material of the surface material is selected in order to give the function of preventing ultraviolet rays from reaching the polyester film, which means that the texture, touch, and even the color and pattern are specially specified. Such special provisions become an obstacle to the expansion of the use of clothing. Therefore, it is ideal to increase the freedom of choice of the surface material as much as possible. In order to increase the freedom of choice of the surface material, it is ideal to give the polyester film as much as possible the function of preventing strength degradation caused by ultraviolet irradiation.

[0071] Therefore, in the present invention, the polyester film constituting the nonporous film having a thickness of 10 to 30 μm needs to contain an ultraviolet absorber, a light stabilizer, and titanium oxide. In the present invention, the nonporous film can function as a waterproof and moisture permeable functional film. In addition, the ultraviolet absorber, the light stabilizer, and the titanium oxide can function as a light resistance improver.

[0072] As a result of the addition of the above three components, the polyester film can be suppressed from being deteriorated even when exposed to ultraviolet rays, and as a result, the decrease in water resistance after ultraviolet irradiation can be suppressed, resulting in a white and highly durable waterproof and moisture-permeable functional film.

[0073] It should be noted that the non-porous in the present invention means that when the cross section of the film is observed by an electron microscope, there are no continuous pores on the surface and the back surface, and in the JIS L1096-2010 A method (Frazier method) air permeability test, no air permeability is confirmed when the film is measured, that is, the air permeability is 0 cm 3 / (cm 2 ·s).

[0074] [Ultraviolet light absorber]

[0075] In the present invention, an ultraviolet absorber is used to improve the light resistance of the polyester film used. If the ultraviolet absorber is exemplified, benzotriazoles, benzophenones, etc. can be preferably cited. As benzotriazoles, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-[5-chloro-(2H)-benzotriazole-2-yl]-4-methyl-6-(tert-butyl)phenol, etc. can be cited, and as benzophenones, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, etc. can be cited. In the polyester film, it is necessary to contain 0.05 to 1.0% by mass of ultraviolet absorber, preferably 0.1 to 0.5% by mass, more preferably 0.2 to 0.5% by mass.

[0076] [Light stabilizer]

[0077] In the present invention, in order to improve the light resistance of the polyester film used, a light stabilizer is further used. If the light stabilizer is exemplified, NR-type hindered amines are preferred. As NR-type hindered amines, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, 2,4-bis[N-butyl-N-(1-cyclohexanoyl-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-tetrazine of N-OR type amine, etc. The polyester film needs to contain 0.05 to 1.0% by mass of the light stabilizer, and the preferred addition amount is 0.1 to 0.5% by mass, and more preferably 0.2 to 0.5% by mass.

[0078] [Titanium oxide]

[0079] The titanium oxide used in the present invention has a band gap of 3.1 (eV) or more.

[0080] The absorption wavelength of the titanium oxide in the present invention can be obtained by diffuse reflectance spectrum using an ultraviolet visible spectrophotometer. The band gap of the titanium oxide used in the present invention is 3.1 (eV) or more, and its absorption wavelength is equivalent to a wavelength of 400nm or less in the ultraviolet region. The band gap of the titanium oxide is preferably 3.2 (eV) or more. It is equivalent to a wavelength of 388nm or less in terms of absorption wavelength. As such titanium oxide, anatase-type titanium oxide belongs to this category and can be preferably used.

[0081] The calculation formula for converting wavelength and light energy can be converted as shown below, assuming that the band gap is E (eV) and the absorption wavelength (excitation wavelength) during excitation is λ (nm).

[0082] E[eV]=1240 / λ[nm]

[0083] The absorption wavelength of titanium oxide in the present invention can be determined using UV-2600 and ISR-2600Plus ultraviolet visible spectrophotometers manufactured by Shimadzu Corporation.

[0084] Generally speaking, the crystal structure of titanium oxide can be anatase type (tetragonal crystal), rutile type (tetragonal crystal), or brookite type (orthorhombic crystal). In the present invention, titanium oxide within the above range needs to be used.

[0085] From the viewpoint of general light resistance, it is generally preferred to use titanium oxide with a rutile crystal structure having low photocatalytic activity. However, even if titanium oxide with a rutile crystal structure is used, it is still difficult to suppress degradation caused by exposure to ultraviolet rays. In the present invention, from the viewpoint of suppressing strength degradation of the polyester film due to ultraviolet rays, the above-mentioned specific titanium oxide is used. The mechanism has not yet been determined, but it is speculated that the excitation wavelength of titanium oxide with a band gap of 3.1 (eV) or more is a wavelength of 400nm or less. By making the ultraviolet absorber and the light stabilizer coexist, the ultraviolet absorber absorbs ultraviolet rays to suppress the light excitation of titanium oxide, and at the same time, the reaction based on the activated titanium oxide is stabilized by the light stabilizer, thereby suppressing degradation caused by ultraviolet rays.

[0086] The average particle size of the titanium oxide used is preferably 0.01 to 1 μm, more preferably 0.1 to 0.5 μm, and particularly preferably 0.1 to 0.3 μm. This is because the average particle size of the titanium oxide in the dispersion is 0.18 to 0.24 μm, which has large light scattering and is the most excellent in color rendering and concealment as a white pigment, so it is preferred. It should be noted that the above average particle size refers to the average particle size determined by converting the light intensity distribution of scattered light based on laser light into a particle size distribution using a laser diffraction particle size distribution measuring device SALD-2300 manufactured by Shimadzu Corporation.

[0087] By making the average particle size of titanium oxide less than 1 μm, the aggregation caused by poor dispersion of titanium oxide on the film surface is suppressed, and the unevenness of the film surface caused by aggregation is also suppressed, so that an excellent appearance can be obtained. In addition, it is preferred because it does not deteriorate the moisture permeability and waterproofness. In addition, by making the average particle size more than 0.1 μm, the workability during film making becomes good and it is preferred. Depending on the application, ultraviolet absorbers and light stabilizers, as well as two or more titanium oxides with different crystal structures and average particle sizes can also be used.

[0088] As the above-mentioned preferred titanium oxide, commercial products can also be used. Specific examples of commercial products having a band gap of 3.1 (eV) or more include anatase-type titanium oxide SA-1L manufactured by Sakai Chemical Co., Ltd., anatase-type titanium oxide JA-C manufactured by TAYCA Co., Ltd., anatase-type titanium oxide TA100 manufactured by Fuji Titanium Industries Co., Ltd. It should be noted that rutile-type titanium oxide CR-63 manufactured by Ishihara Sangyo Co., Ltd. has a band gap of less than 3.1 (eV) and is not suitable for use in the present invention.

[0089] The titanium oxide also functions as a white pigment. The inclusion of the titanium oxide is preferred in terms of improving the color development and hiding properties of the polyester film compared to other white pigments.

[0090] The polyester film needs to contain 0.1 to 1.0% by mass of titanium oxide, preferably 0.3 to 1.0% by mass, and more preferably 0.5 to 0.8% by mass. When the amount of titanium oxide added is less than 0.1% by mass, the deterioration caused by exposure to ultraviolet rays cannot be suppressed, and a film surface showing a good white color cannot be obtained. On the other hand, when the amount exceeds 1.0% by mass, the softness and water resistance of the polyester film are reduced.

[0091] [Polyester constituting polyester film]

[0092] In order to improve the moisture permeability of the fiber laminate structure, as the polyester constituting the polyester film, a polyester block copolymer is preferably used, wherein the polyester block copolymer has a hard segment comprising a crystalline polyester unit and a soft segment comprising an aliphatic polyether unit and / or an aliphatic polyester unit as constituent components. Compared with the case where a hard segment comprising a crystalline polyester unit is used alone, the strength degradation of the copolymer due to ultraviolet irradiation is greater due to copolymerization of the soft segment. That is, the more the moisture permeability is improved, the greater the strength degradation due to ultraviolet irradiation.

[0093] The hard segment of the polyester block copolymer used in the present invention is a polyester formed from an aromatic dicarboxylic acid or its ester-forming derivative and an aliphatic diol, preferably polybutylene terephthalate derived from terephthalic acid and / or dimethyl terephthalate and 1,4-butanediol, but in addition thereto, it may be a polyester formed from a dicarboxylic acid component such as isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, diphenoxyethane dicarboxylic acid, 5-sulfoisophthalic acid, or their ester-forming derivatives and a diol having a molecular weight of 300 or less (for example, ethylene glycol, trimethylene glycol, pentamethylene glycol). The present invention can be a polyester derived from an aromatic diol such as bis(p-hydroxy)biphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxy)phenyl]sulfone, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, 4,4'-dihydroxy-p-terphenyl, 4,4'-dihydroxy-p-quaterphenyl, or a copolyester obtained by using two or more of these dicarboxylic acid components and diol components. In addition, a trifunctional or higher polyfunctional carboxylic acid component, a polyfunctional oxyacid component, and a polyfunctional hydroxyl component can be copolymerized in an amount of 5 mol% or less.

[0094] The soft segment of the polyester block copolymer used in the present invention is an aliphatic polyether and / or an aliphatic polyester. As the aliphatic polyether, poly(ethylene oxide) glycol, poly(propylene oxide) glycol, poly(butylene oxide) glycol, poly(hexylene oxide) glycol, copolymers of ethylene oxide and propylene oxide, addition polymers of ethylene oxide and poly(propylene oxide) glycol, copolymers of ethylene oxide and butylene oxide, etc. can be cited. In addition, as aliphatic polyesters, poly(ε-caprolactone), polyheptanolactone, polyoctalactone, polybutylene adipate, polyethylene adipate, etc. can be cited. Among these aliphatic polyethers and / or aliphatic polyesters, poly(butylene oxide) glycol, ethylene oxide adducts of poly(propylene oxide) glycol, poly(ε-caprolactone), polybutylene adipate, polyethylene adipate, etc. are preferred from the elastic properties of the obtained polyester block copolymer.

[0095] Furthermore, in order to increase the moisture permeability, the polyester film is preferably a copolymer of polybutylene terephthalate and polyether.

[0096] In the present invention, the polyester block copolymer preferably used in the polyester film can be manufactured by a common method. For example, any method such as the following method can be used: a method of subjecting a lower alcohol diester of a dicarboxylic acid, an excess of a low molecular weight diol, and a soft segment component to an ester exchange reaction in the presence of a catalyst, and polycondensing the obtained reaction product; or a method of subjecting a dicarboxylic acid to an ester exchange reaction with an excess of a diol and a soft segment component in the presence of a catalyst, and polycondensing the obtained reaction product; or a method of preparing a hard segment in advance, adding a soft segment component thereto, and randomizing it by an ester exchange reaction; a method of connecting a hard segment to a soft segment by a chain linker; and further, when poly(ε-caprolactone) is used for the soft segment, an ε-caprolactone monomer is subjected to an addition reaction with the hard segment.

[0097] As the above-mentioned preferred polyether ester block copolymer, commercially available products can be used, and specific preferred examples include "HYTREL (registered trademark)" HTR8206 and "HYTREL (registered trademark)" G3548 from DuPont.

[0098] [Polyester film]

[0099] In addition, in the present invention, from the viewpoint of waterproofness (water resistance) and moisture permeability, the thickness of the polyester film is set to 10 to 30 μm as described above. If the thickness is thinner than 10 μm, the required waterproofness cannot be obtained. In addition, if the thickness is thicker than 30 μm, the moisture permeability becomes low. The thickness is preferably 15 to 20 μm.

[0100] From the viewpoint of moisture permeability, the polyester film used in the present invention preferably has a D hardness of 55D or less as determined in accordance with JIS K6253-3:2012. The lower the D hardness is than 55D, the higher the moisture permeability and softness are. However, if the D hardness is too low, the production stability and swelling property of the film during film production increase, and thus the problem of laminated film peeling during wearing is likely to occur. Therefore, from the viewpoint of moisture permeability and film peeling strength, it is particularly preferred that the D hardness is more preferably 30D or more and 50D or less.

[0101] The elongation of the polyester film used in the present invention is preferably 100% or more and less than 800% regardless of the stretching treatment after film formation, and more preferably 200% or more and less than 600%. By setting the elongation of the polyester film to 100% or more, the flexibility of the film after lamination can be maintained, and the decrease in moisture permeability and water resistance when the laminate is deformed can be suppressed, which is preferred. In addition, by setting the elongation of the polyester film to less than 800%, the excessive elongation deformation of the film when the laminate is deformed can be suppressed, and the decrease in moisture permeability and water resistance can be suppressed, which is preferred.

[0102] As for the stretchability of the polyester film in the present invention, it is desirable that in addition to the aforementioned elongation, the elongation recovery rate is also excellent. The elongation recovery rate of the polyester film is preferably 80% or more, and more preferably 90% or more. By setting the elongation recovery rate of the film to the aforementioned value, when worn as clothing, the fiber laminate structure follows the movement of the body and has excellent fit, thereby achieving the effect of easy movement and low fatigue.

[0103] The polyester film exhibits stretchability depending on the ratio of the copolymerized soft segments. The copolymerization ratio can be selected in accordance with the practicality and purpose from the balance with the moisture permeability and the water swelling property, or can be selected from commercially available products.

[0104] [Method for producing polyester film]

[0105] The polyester film used in the present invention can be manufactured by a conventionally known film-making method such as a T-die method or a blow molding method. For example, in the T-die method, the polyester block copolymer containing an ultraviolet absorber, a light stabilizer, and a specific titanium oxide is supplied to an extruder. Then, the polymer in the extruder is heated to a temperature above its melting point, extruded from a spinneret in the form of a film, melted and coated on a support material (e.g., a lightweight polyester, a release paper, etc.), and wound and stored for use.

[0106] [Method for producing fiber stacked structure]

[0107] The fiber laminate structure of the present invention is manufactured by laminating the polyester film on a base fabric including a woven knitted fabric. The lamination process may be the following method, but is not limited thereto.

[0108] That is, a method of laminating using an adhesive. As the adhesive, preferably, a conventional hot melt adhesive, a hot melt adhesive such as a heat-adhesive fiber, etc. can be cited. In addition, a solvent-based adhesive can also be used. When a hot melt adhesive is used, a heating device can be used to perform thermal compression bonding. If a conventional hot melt adhesive is used and its actual use area is large, there is often a situation where the moisture permeability of the fabric is reduced, so it is preferred to use an adhesive itself or an adhesive containing a moisture permeable resin.

[0109] In the present invention, the adhesive between the woven knitted fabric and the polyester film is preferably 0.1 to 100.0 mm thick in the surface direction. 2 The larger the area, the higher the peel strength, but the texture becomes rougher, so 0.5 to 50.0 mm is preferred. 2 , more preferably 1.0 to 25.0 mm 2In addition, it can also be a linear adhesive in the surface direction, preferably a linear or lattice adhesive with a thickness of 0.1 to 10.0 mm. As mentioned above, it is further preferably in the range of 1.0 to 10.0 mm, and most preferably in the range of 1.0 to 5.0 mm. It should be noted that the so-called "surface direction" refers to the surface direction of the fiber stack structure. Therefore, the area and thickness of the adhesive A here refer to the area and thickness of the projection surface of the adhesive A on the horizontal plane when the fiber stack structure is arranged in the horizontal direction.

[0110] In addition, the adhesive is preferably provided at a ratio of 70% or less in terms of area ratio relative to the woven fabric in the plane direction, because the control accuracy of the peel strength can be improved and the moisture permeability, air permeability and water resistance of the fiber laminate structure can be stabilized at a high level. It is more preferably 10 to 70%, and even more preferably 30 to 70%.

[0111] It is preferred to reduce the area of ​​the adhesive dots and lines and reduce the area ratio of the adhesive, but the peel strength and water resistance will be reduced. On the other hand, in order to improve the peel strength and water resistance, it is preferred to increase the area of ​​the adhesive dots and lines and increase the area ratio. It is most preferred to set it as a full-surface adhesive layer, but the moisture permeability will decrease. In order to appropriately maintain this opposite functionality, it is preferred to set the adhesive to 10 to 70% in area ratio and 0.1 to 100.0 mm 2 It can be applied in the form of dots with an area of ​​0.1 to 10.0 mm, or in the form of lines or grids with a thickness of 0.1 to 10.0 mm.

[0112] The so-called point shape can be any shape such as a circle, a quadrilateral, a rhombus, an ellipse, a triangle, etc., and they can also be combined and arranged to form a pattern, a text shape, or arranged in a logo shape of a trademark. In addition, they can be arranged in a manner to form a continuous pattern, or they can be arranged randomly. In addition, the so-called line shape can be a straight line or a curve. The so-called area ratio refers to the coverage of the adhesive.

[0113] When the adhesive A is applied in dots, if the application area of ​​each dot is less than 0.1 mm 2 , the adhesion is low; if it is greater than 100.0mm 2 If the thickness of the line and grid pattern is less than 0.1 mm, the adhesion is low; if the thickness is greater than 10.0 mm, the binding points of the woven fabric become larger, so the texture may become rough. Furthermore, if the coating area ratio of the adhesive is less than 10%, the adhesion is low; if it is greater than 70%, the binding points of the woven fabric may increase and the texture may become rough.

[0114] In the present invention, as the adhesive, a hot melt adhesive that does not use an organic solvent is preferred. Examples of resins having hot melt adhesive properties include polyurethane resins, polyester resins, polyether resins, polyamide resins, etc. Considering adhesiveness, flexibility, texture, elasticity, etc., polyurethane resins are preferred. In addition, solvent-based adhesives may also be used appropriately.

[0115] As a method for applying the adhesive, a knife coater, a bar coater, a gravure coater, etc. can be used. In particular, a gravure coater can relatively easily apply in a dot, line, or grid pattern and is preferred from the viewpoint of moisture permeability, but the coating method is not limited to these.

[0116] The bonding method may be a wet lamination method, a dry lamination method, or the like, and may be selected and used according to the desired characteristics. From the viewpoint of texture and adhesiveness, it is preferred to apply an adhesive to the woven fabric and adopt a dry lamination method.

[0117] [Fiber laminate structure]

[0118] The fiber stack structure of the present invention is a fiber stack structure in which a non-porous membrane is laminated on one side of a woven knitted fabric containing polyester fibers as described above (hereinafter sometimes referred to as a two-layer fiber stack structure for convenience), but it is also possible to further have a knitted fabric containing polyester filaments on the non-porous membrane of the fiber stack structure (hereinafter sometimes referred to as a third-layer knitted fabric).

[0119] When the fiber laminate structure having the third layer of knitted fabric is used in clothing or the like, the knitted fabric side of the third layer is preferably used as a lining material (the side close to the skin) and the woven knitted fabric side is used as a surface material.

[0120] The fiber stack structure of the present invention can also be used in the form of a two-layer product of a woven knitted fabric and a non-porous film without providing a third layer of knitted fabric. However, from the perspective of preventing damage to the non-porous film due to friction, etc. and imparting a sense of luxury, it is ideal to provide a third layer of knitted fabric so that it functions as a lining.

[0121] The knitted fabric of the third layer is preferably a knitted fabric composed of 100% by mass polyester multifilament.

[0122] As such a polyester multifilament, a multifilament composed of polyethylene terephthalate, polytrimethylene terephthalate, or polybutylene terephthalate is preferred. The filament may be in the form of a single multifilament or a multifilament in which filaments are arranged in parallel or in a core-sheath composite.

[0123] By using false twisted yarns or parallel yarns of different polymers as polyester multifilaments, stretchability can be obtained. In addition, core-spun yarns using spandex-based elastic yarns can also be used. However, it should be noted that if the spandex yarn mixing ratio increases, the mixing ratio of other materials increases, and the recycling efficiency decreases.

[0124] In the present invention, in order to improve the recycling efficiency, the fiber component in the knitted fabric is preferably 100% by mass of polyester fibers including polyester multifilaments. As described above, in the case of using non-polyester elastic yarns, it is desirable that the content of polyester fibers in the fibers constituting the knitted fabric is high, and the ratio of polyester fibers is preferably at least 80% by mass, more preferably 85% by mass, and further preferably 90% by mass.

[0125] By using polyester multifilaments in knitted fabrics as in woven fabrics, the material recycling and chemical recycling are excellent. The fewer the types of polyester used in the fibers constituting the fiber laminate structure, the better the material recycling; the fewer the types of monomer components, the better the chemical recycling. The materials used can be appropriately selected in consideration of the functions and recyclability required for practical use.

[0126] Furthermore, the knitted fabric may be subjected to processing as required, such as water repellent processing, antistatic processing, antibacterial processing, ultraviolet ray absorption processing, near infrared ray absorption processing, etc.

[0127] When a sealing tape is used to maintain the waterproofness of the seam, the sealing tape is bonded to the lining by molten resin, and it is preferred to use a knitted fabric with a large mesh size for the lining so that the molten resin can pass through the lining and easily reach the waterproof and breathable membrane. From the perspective of being thin and having a large mesh size, tricot warp knitting and circular knitting fabrics are preferred.

[0128] The knitted fabric of the third layer is preferably laminated on the nonporous film of the two-layer fiber stack structure via an adhesive.

[0129] As the adhesive for laminating the knitted fabric of the third layer, a hot-melt adhesive without using an organic solvent is preferred, similarly to the adhesive for the woven fabric. Examples of resins having hot-melt adhesive properties include polyurethane resins, polyester resins, polyether resins, polyamide resins, etc., and polyurethane resins are preferred in consideration of adhesiveness, flexibility, texture, elasticity, etc. In addition, solvent-based adhesives may also be used appropriately. In addition, the coating method and lamination conditions of the adhesive may be carried out similarly to the bonding conditions for the woven fabric.

[0130] The fiber stack structure of the present invention preferably has excellent moisture permeability. Preferably, the moisture permeability of JIS L-1099A-1 is 4000 g / m 2·24h or more, and JIS L-1099B-1 moisture permeability is 10000g / m 2 ·More than 24h.

[0131] The fiber stack structure of the present invention has high water resistance, and therefore preferably has the property of preventing rainwater from penetrating, that is, has excellent performance of having a water resistance of at least 150 kPa or more. The water resistance is more preferably 200 kPa or more. By being within the above range, it is also possible to suppress rainwater from penetrating into the clothes when they are worn.

[0132] In addition, from the perspective of ensuring durability during actual wearing, the water resistance after irradiation with a UV fading tester at level 4 is preferably 150 kPa or more. More preferably, it is 200 kPa or more. By being within the above range, the durability to sunlight exposure is excellent, and it is also possible to suppress rainwater from penetrating into the clothes when worn.

[0133] The term "after 4-level irradiation with an ultraviolet fading tester" means after 4-level irradiation with a blue standard using a fading tester in accordance with JIS L0842-2004 light fastness test. Generally speaking, for clothing applications, for light fastness after 4-level irradiation, fading of 4 or more levels in grayscale judgment is judged as a pass value without problems. That is, after 4-level irradiation with an ultraviolet fading tester, it is ideal that the water fastness does not change significantly.

[0134] On the other hand, in terms of the durability of water resistance, which is one of the most important functionalities in waterproof and breathable functional processed products, washing durability is mostly confirmed as a representative characteristic for judging durability. However, in terms of outdoor use in particular, it has been confirmed that the reduction of water resistance due to ultraviolet irradiation under sunlight exposure is also an important factor. If the water resistance after 4-level irradiation according to the above-mentioned light fastness test is 150kPa or more, general practical durability can be obtained, which is preferred. In addition, under more severe conditions, such as high mountains, snowy mountains, or seas with high ultraviolet irradiation energy, the water resistance after 4-level irradiation is ideally 200kPa or more.

[0135] In order to improve the water resistance after irradiation with the UV fading tester level 4, it can be achieved by using a UV absorber, a light stabilizer and titanium oxide in combination in a preferred embodiment in the polyester film as described above.

[0136] In addition, for the fiber laminated structure of the present invention, it is preferred to implement water repellent processing. By implementing water repellent processing, it becomes a more practical commodity as a waterproof and breathable material, and it is desirable to use water repellent processing with high washing durability and friction durability. As a water repellent, known water repellent processing agents such as fluorine, silicone, and paraffin can be used. As a processing method, a common processing method such as pad-dry-cure can be used. During processing, any processing technique can be applied at any time before and after lamination of the polyester film.

[0137] Furthermore, it is also possible to perform processing as needed, such as antistatic processing, antibacterial processing, ultraviolet absorption processing, and near infrared absorption processing.

[0138] The waterproof and breathable clothing made using the fiber stack structure of the present invention has a high effect of preventing stuffiness and excellent wearing comfort due to its high waterproofness and breathability, and has high durability against ultraviolet radiation caused by exposure to sunlight. Therefore, it can be suitable for outdoor clothing for mountaineering and skiing, windbreakers for intense sports, raincoats for intense work, etc.

[0139] Example

[0140] The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. It should be noted that various measuring methods in the present invention are as follows.

[0141] (1) Film thickness

[0142] The film was cut at random at 10 locations in a free state without applying a load with a single-edged razor, and the cross section was observed with an electron microscope to measure the thickness, and the average value was taken as the thickness.

[0143] (2) UV fading test machine irradiation

[0144] The woven fabric surface of a 15 cm×15 cm fiber laminate structure sample was irradiated with ultraviolet rays in accordance with JIS L0842-2021 Color Fastness Test Method for Ultraviolet Carbon Arc Light Method, Level 4 (20 hours) of the 5th Exposure Method.

[0145] (3)Water resistance

[0146] The water resistance was measured according to JIS L1092-2009, method B (high water pressure method).

[0147] When the film is measured alone or when a sample with stretchability is measured, non-stretchable taffeta is placed on the back side (the side not in contact with water) to prevent the sample from stretching. The number of samples per level is set to 5 points, and the average value is taken as the water resistance.

[0148] In addition, the sample was irradiated with 4 levels of irradiation using the above-mentioned ultraviolet fading tester and measured, and the water resistance was determined in the same manner.

[0149] (4) Ultraviolet shielding rate

[0150] The ultraviolet shielding rate is measured according to JIS L1925-2019.

[0151] That is, an arbitrary portion (randomly selected portion) of the woven fabric was cut and sampled, and the transmittance to ultraviolet rays in the wavelength range of 290 to 400 nm was measured and calculated by the following formula.

[0152] UV shielding rate (%) = 100 - average transmittance to UV rays (%)

[0153] The number of samples set at one level was 4 points (2 points in the longitude direction and 2 points in the latitude direction), and the average value was taken as the average transmittance.

[0154] When the fiber stacked structure is used for measurement, the measurement object is prepared by removing as many layers other than the woven fabric as possible.

[0155] (5) Moisture permeability

[0156] According to JIS L1099-2021 calcium chloride method (A-1 method), and

[0157] The measurement was carried out according to the JIS L1099-2021 potassium acetate method (B-1 method).

[0158] Specifically, the fiber stack structure was set and measured so that water vapor came into contact with the surface opposite to the woven fabric surface.

[0159] However, both test methods are converted into moisture permeability per 24 hours. It should be noted that the measurement was performed at 3 points, with the number of samples being 1 level, and the average value was taken as the moisture permeability.

[0160] (6) Elongation

[0161] The elongation was measured according to JIS L1096-2010, method A (constant rate elongation method).

[0162] The weft expansion and contraction rate of the woven fabric sample was measured by the spline method with a clamping interval of 200 mm and a width of 50 mm, and the elongation rate at a stress of 14.7 N was used as the expansion and contraction rate. The elongation rate was measured at 3 points per level of the sample, and the average value was used as the elongation rate.

[0163] (7) Brightness

[0164] The brightness (L* value) of the woven fabric was measured using CM-3700A manufactured by Konica Minolta Co., Ltd. on the side opposite to the side on which the nonporous film was laminated.

[0165] The number of samples was set at 1 level and the measurement was performed at 3 points, and the average value was defined as the L* value.

[0166] (8) Confirmation of non-porous membrane

[0167] (8-1) Confirmation of membrane cross section

[0168] The presence or absence of communicating pores on the front and back surfaces was measured by observing the cross section of the film using an electron microscope (SU3800 manufactured by Hitachi High-Tech Corporation, magnification: 2000 times).

[0169] (8-2) Air permeability

[0170] The air permeability of the film not bonded to the woven knitted fabric was measured at 5 locations according to JIS L1096-2010, Method A (Frazier type method), and the average value was determined.

[0171] When measuring air permeability using a fiber stacked structure, gas leaks from between layers of the fiber stacked structure sample during measurement, resulting in a high air permeability measurement result. Therefore, the measurement may be performed with measures taken to prevent gas leakage between layers.

[0172] (9) Band gap of titanium oxide

[0173] The relationship between the absorption wavelength and the band gap was measured using an integrating sphere spectrophotometer UV-2600 manufactured by Shimadzu Corporation, using titanium oxide powder as the measurement sample. The diffuse reflection spectrum of the titanium oxide powder was measured using an integrating sphere and a standard white plate of barium sulfate as the standard sample, and the absorption spectrum of titanium oxide was obtained using the Kubelka-Munk representation. The calculation formula for converting the absorption wavelength and the band gap is as follows, with the band gap set to E (eV) and the absorption wavelength set to λ (nm).

[0174] E[eV]=1240 / λ[nm]

[0175] The excitation wavelength λ used here is the absorption wavelength between energy bands in indirect transition. When the band gap is calculated from the absorption spectrum, the spectrum obtained from the indirect transition is also used for calculation. When the band gap is calculated from the absorption spectrum of titanium oxide obtained by the above-mentioned instrument measurement, the following formula is used.

[0176] (hνα) 1 / n =A(hν-E g )

[0177] hν: photon energy, α: absorption coefficient, Eg: band gap, A: constant

[0178] In the case of direct transition, n = 1 / 2, and in the case of indirect transition, n = 2. In the present invention, n = 2 is used for indirect transition. The energy unit is expressed in eV, which is expressed relative to hν as (hνα) 1 / 2 It is plotted and used to calculate the band gap. It should be noted that the absorption coefficient α uses the value of Kubelka-Munk as a value approximately proportional to it. In order to find the band gap, a tangent is drawn at the inflection point of the curve corresponding to the absorption rise believed to be from the transition between energy bands, and the value of the intersection of the above tangent and the approximate straight line near 1.5 to 2.3 eV is taken as the band gap. It should be noted that in the case where there is no absorption from other additives in titanium oxide, the approximate straight line near 1.5 to 2.3 eV usually becomes the x-intercept (intersection with the vertical axis = 0).

[0179] (10) Hardness of non-porous membrane

[0180] An injection molded plate having a thickness of 6 mm was prepared with the same composition as the nonporous film, and the hardness was measured at 5 locations according to JIS K6253-3:2012 durometer hardness (type D), and the average value was determined.

[0181] [Example 1]

[0182] The polyethylene terephthalate semi-bright circular cross-section multifilament yarn with 56 dtex-42 filaments in the warp and 94 dtex-48 filaments in the weft was subjected to false twisting to make it stretchable. Then, the processed yarn was used for the warp and weft, and woven by a water jet loom in a manner that the density was warp×weft: 111 filaments×77 filaments / 2.54 cm. Then, after scouring and relaxation treatment, it was pre-shaped and dyed to white by a liquid jet dyeing machine by a conventional method, and then a 5% aqueous solution of "AsahiGuard (registered trademark)" AG710 (fluorine-based water repellent, manufactured by Asahi Glass Co., Ltd.) was applied to the woven fabric surface in a manner that the adhesion rate was 60% by a pad-dry-curing method, and after drying at 120°C for 1 minute, it was heat-treated at 170°C for 40 seconds, and then finally shaped, and finished with a finishing density of warp×weft: 154 filaments×122 filaments / 2.54 cm to obtain a white woven fabric.

[0183] On the other hand, as a method for preparing a polyester block copolymer composition for forming the polyester film in the examples and comparative examples, a polyester block copolymer ("HYTREL (registered trademark)" HTR8206 manufactured by DuPont), an ultraviolet absorber (benzotriazole ultraviolet absorber "TinuVin (registered trademark)" 326 manufactured by BASF) in a ratio shown in Table 1, a light stabilizer (hindered amine light stabilizer "TinuVin (registered trademark)" 144 manufactured by BASF) and titanium oxide (anatase-type titanium oxide SA-1L manufactured by Sakai Chemical Co., Ltd., average particle size 0.18 μm) were dry-blended, melt-kneaded using a twin-screw extruder having a 45 mm φ, three-flight screw, with the barrel temperature set to 210° C., and then discharged in a strand shape and cooled in a water bath, and then pelletized into a size of 3 mm φ and 3 mm long using a pelletizer.

[0184] The pellets of the polyester block copolymer composition were dried at 80°C for 4 hours and then melt-extruded from a T-slit die at a resin temperature of 230°C through an extruder to produce a 20 μm thick (unit area weight 19 g / m 2 ) of an unstretched polyester film (white).

[0185] The moisture-curing polyurethane hot-melt adhesive was heated and melted at 110°C, and applied to the above-mentioned woven fabric finished in white by a gravure coater, and dried at 120°C for 1 minute, wherein the gravure coater has a 0.40mm×0.40mm square (depth 20μm) engraved with a 40-mesh gravure roller at an angle of 45° relative to the running direction of the woven fabric. As a result, the adhesive was applied to the fabric in the form of dots, each dot was a square with a side length of 0.40mm, and was arranged at an angle of 45° relative to the longitudinal direction. In addition, the area ratio (coverage rate) of the adhesive relative to the fabric was 40%, and the amount of adhesive applied was 15g / m 2 .

[0186] Next, the above-obtained unstretched polyester film is overlapped on the adhesive surface side of the woven fabric coated with the above-mentioned adhesive, and is passed between a metal roller and a rubber roller at a temperature of 110°C while applying a linear pressure of 49 N / cm. It is then aged at room temperature for 48 hours to obtain a two-layer fiber stack structure of laminated organic fabric and polyester film.

[0187] Next, a moisture-curable polyurethane hot melt adhesive was applied to the sinker side of a half tricot made of 22 dtex-20 filament polyethylene terephthalate semi-glossy cross-section multifilament and dyed gray, in the same manner as the adhesive was applied to the above woven fabric, and a 40% area ratio, 10 g / m2 of adhesive resin was applied thereto. 2) A knitted fabric is laminated in such a manner as to bond the two-layer fiber laminate structure to the polyester film side surface, thereby producing a three-layer fiber laminate structure.

[0188] The obtained fiber stack structure has an A-1 method moisture permeability of 4500 g / m 2 ·24 hours, B-1 method moisture permeability: 25000g / m 2 · 24 hours, water resistance of 250kPa, weft elongation of 15%, excellent moisture permeability and waterproof performance. In addition, the water resistance after irradiation with the UV fading tester level 4 is 230kPa, which has excellent light resistance.

[0189] The ultraviolet shielding rate of the woven fabric finished in white before lamination was 83%.

[0190] The obtained measured values ​​are shown in Table 1.

[0191] [Example 2]

[0192] The woven fabric of Example 1 was dyed black so as to have the L* value shown in Table 1. A woven fabric was manufactured by the same method as in Example 1 except that the amount of the ultraviolet absorber and the light stabilizer added during the polyester film formation was changed so that the amount of each added was 0.2% by mass as calculated on the content in the polyester film, and a fiber laminate structure laminated into three layers was obtained by the same method as in Example 1.

[0193] The obtained fiber laminate structure maintained good water resistance after irradiation with an ultraviolet fading tester. In addition, the ultraviolet shielding rate of the woven fabric finished in black before lamination was 93%.

[0194] The obtained measured values ​​are shown in Table 1.

[0195] [Example 3]

[0196] The woven fabric of Example 1 was manufactured by the same method as in Example 1 except that the woven fabric was dyed yellow so as to have the L* value shown in Table 1. The woven fabric was manufactured in the same manner as in Example 1 except that the amounts of the ultraviolet absorber and the light stabilizer added during the polyester film formation were changed so that the contents in the polyester film were each 0.4% by mass. A fiber laminate structure laminated into three layers was obtained by the same method as in Example 1.

[0197] The obtained fiber laminate structure still maintained good water resistance after irradiation with an ultraviolet fading tester. In addition, the ultraviolet shielding rate of the woven fabric finished in yellow before lamination was 85%. The obtained measured values ​​are shown in Table 1.

[0198] [Example 4]

[0199] The woven fabric of Example 1 was dyed blue so as to have the L* value shown in Table 1. A woven fabric was manufactured by the same method as in Example 1 except that the woven fabric was dyed blue so as to have the L* value shown in Table 1. Using the woven fabric, the amounts of the ultraviolet absorber and the light stabilizer added during the polyester film formation were changed so that the amounts each became 0.3% by mass in the polyester film. A fiber laminate structure laminated into three layers was obtained by the same method as in Example 1.

[0200] The obtained fiber laminate structure maintained good water resistance after irradiation with an ultraviolet fading tester. In addition, the ultraviolet shielding rate of the woven fabric finished in blue before lamination was 89%. The obtained measured values ​​are shown in Table 1.

[0201] [Comparative Example 1]

[0202] A fiber laminate structure was obtained and evaluated in the same manner as in Example 1 except that the following points were changed. That is, when no ultraviolet absorber was added to the polyester film, the water resistance after irradiation with a UV fading tester at level 4 was 120 kPa, and the water resistance was reduced by ultraviolet rays. The measured values ​​are shown in Table 1.

[0203] [Comparative Example 2]

[0204] A fiber laminate structure was obtained and evaluated in the same manner as in Example 1 except that the following points were changed. That is, when no light stabilizer was added to the polyester film, the water resistance after irradiation with a UV fading tester at level 4 was 105 kPa, and the water resistance was reduced by ultraviolet rays. The measured values ​​are shown in Table 1.

[0205] [Comparative Example 3]

[0206] A fiber laminate structure was obtained and evaluated in the same manner as in Example 1 except that the following points were changed. That is, when no ultraviolet absorber and light stabilizer were added to the polyester film, the water resistance after irradiation with a UV fading tester at level 4 was 60 kPa, and the water resistance was reduced by ultraviolet rays. The measured values ​​are shown in Table 1.

[0207] [Comparative Example 4]

[0208] A fiber laminate structure was obtained and evaluated in the same manner as in Example 1 except that the following points were changed. That is, when no ultraviolet absorber, light stabilizer, or white pigment was added to the polyester film, the water resistance after irradiation with a UV fading tester at level 4 was 20 kPa, indicating that the water resistance was reduced by ultraviolet rays. The measured values ​​are shown in Table 1.

[0209] [Comparative Example 5]

[0210] A fiber laminate structure was obtained and evaluated in the same manner as in Example 1 except for the following changes: In other words, no ultraviolet absorber or light stabilizer was added to the polyester film, but rutile titanium oxide CR-63 (average particle size 0.21 μm) manufactured by Ishihara Sangyo Co., Ltd. was added as titanium oxide.

[0211] The water resistance after irradiation with the UV fading tester at level 4 was 40 kPa, and the water resistance was reduced by the UV rays. The measured values ​​are shown in Table 1.

[0212] [Comparative Example 6]

[0213] A fiber laminate structure was obtained and evaluated in the same manner as in Example 1 except for the following changes: Specifically, rutile titanium oxide CR-63 (average particle size: 0.21 μm) manufactured by Ishihara Sangyo Co., Ltd. was added to the polyester film as titanium oxide.

[0214] The water resistance after irradiation with the UV fading tester at level 4 was 50 kPa, and the water resistance was reduced by the UV rays. The measured values ​​are shown in Table 1.

[0215] [Table 1]

[0216]

[0217] As shown above, the fiber stacked structures produced in Examples 1 to 4 have excellent light resistance, high practicality, and high waterproof and moisture permeability. In addition, the fiber stacked structures are substantially composed of polyester, and the monomers of the dicarboxylic acid component and diol component are also mostly common, and have high recycling efficiency in all aspects of material recycling and chemical recycling.

[0218] Industrial Applicability

[0219] The fiber stack structure of the present invention has high moisture permeability and waterproofness, and excellent durability, and therefore can be applied to outdoor clothing such as fishing and mountaineering clothing, skating / snowboard clothing, windbreakers, sportswear, golf clothing, tennis clothing, raincoats, casual clothing, work clothes, gloves, shoes, glove liners, boot liners and other clothing material fields. In addition, the fiber stack structure of the present invention can be suitably provided for recycling after functioning as the above-mentioned uses, and the recycling efficiency is also excellent.

Claims

1. A fiber laminate structure comprising a woven knitted fabric comprising polyester fibers and a nonporous film having a thickness of 10 to 30 μm laminated on one side of the woven knitted fabric comprising polyester fibers, in, The polyester film contains 0.05 to 1.0 mass % of each of an ultraviolet absorber and a light stabilizer, and 0.1 to 1.0 mass % of titanium oxide having a band gap of 3.1 (eV) or more.

2. A fiber laminate structure comprising a woven knitted fabric comprising polyester fibers and a nonporous film having a thickness of 10 to 30 μm laminated on one side of the woven knitted fabric comprising polyester fibers, in, The polyester film contains 0.05 to 1.0 mass % of each of an ultraviolet absorber and light stabilizer, and 0.1 to 1.0 mass % of anatase-type titanium oxide.

3. The fiber stack structure according to claim 1 or 2, in, The polyester film includes a polyester block copolymer having a hard segment including a crystalline polyester unit and a soft segment including an aliphatic polyether unit and / or an aliphatic polyester unit as constituent components.

4. The fiber stack structure according to claim 1 or 2, in, The woven knitted fabric is a woven fabric.

5. The fiber stacked structure according to claim 1 or 2, in, A knitted fabric including polyester filaments is further provided on the nonporous film including the polyester film.

6. The fiber stacked structure according to claim 1 or 2, in, The ultraviolet shielding rate of the woven knitted fabric containing polyester fibers is greater than 80%.

7. The fiber stacked structure according to claim 1 or 2, in, JIS L-1099A-1 moisture permeability: 4000g / m 2 ·More than 24h, and JIS L-1099B-1 moisture permeability is 10000g / m 2 ·More than 24h.

8. The fiber stacked structure according to claim 1 or 2, in, The woven knitted fabric has stretchability in at least one of a warp direction and a weft direction, and has an elongation of 10% or more in JIS L1096-2010 elongation method A (constant rate elongation method).

9. Waterproof and moisture-permeable clothing, which is obtained by using the fiber stack structure according to claim 1 or 2.

Images