Breathable waterproof material and method for manufacturing breathable waterproof material

Abstract

The present invention aims to provide a non-fluorine waterproof breathable fiber product with excellent wear durability, which does not use fluorine compounds, possesses high water resistance and wash durability, and also obtains sufficient adhesion when bonding films or materials to waterproof surfaces. The present invention is a breathable waterproof material comprising a laminated fabric and a porous polyurethane layer, wherein a silicone-based water-repellent agent is attached to the inner surface of the pores of the porous polyurethane layer.

Description

Technology Field

[0001] The present invention relates to a breathable waterproof processed fabric suitable for use in sportswear and the like, and a method for manufacturing the same. Background Technology

[0002] Conventional wet-coating breathable waterproof materials are manufactured by a method in which a polyurethane resin is dissolved in a water-soluble solvent, a fluorine-based water-repellent agent is mixed and applied to a fabric, and then wet-gelled. The porous polyurethane film containing the fluorine-based water-repellent agent formed on the fabric when the solvent is replaced by water does not allow rain or other water to pass through, but allows moisture (water vapor) to pass through. Such breathable waterproof processed fabrics are described, for example, in Patent Documents 1 and 2. Prior art literature

[0003] Japanese Patent Publication No. Sho 60-47954 Japanese Patent Publication No. Hei 11-131373 The problem to be solved

[0004] Although recent regulatory trends require the non-use of fluorine compounds, simply replacing fluorine-based water repellents with non-fluorine-based ones has not been able to achieve an equivalent level of performance.

[0005] The present invention is made in consideration of the above, and aims to provide a non-fluorine waterproof breathable fiber product with excellent wear durability, which possesses high water resistance and washing durability, and also obtains sufficient adhesion when bonding a film or backing material to a waterproof surface. means of solving the problem

[0006] As a result of careful consideration to solve the above problem, the inventors have come to make the present invention. The present invention has the following configuration.

[0007] (1) A breathable waterproof material formed by laminating a fabric and a porous polyurethane layer, wherein a silicone-based water-repellent agent is attached to the inner surface of the holes of the porous polyurethane layer.

[0008] (2) The above silicone-based water-repellent agent is a modified silicone, and the breathable waterproof material described in (1).

[0009] (3) A breathable waterproof material as described in (1) or (2), having a water pressure resistance of 5,000 mmH2O or more after 10 washes and not getting wet in a water test held at 2,000 mmH2O pressure for 10 minutes.

[0010] (4) A breathable waterproof material described in any one of (1) to (3), wherein the peel strength of the porous polyurethane layer and the fabric is 200 cN / cm or more.

[0011] (5) A moisture-permeable waterproof material described in any one of (1) to (4), wherein a non-porous hydrophilic resin layer and / or a second fabric layer are further laminated on the side opposite to the side of the porous polyurethane layer laminated with the fabric layer.

[0012] (6) A moisture-permeable waterproof material described in (5) that does not have peeling between the porous polyurethane layer and the non-porous hydrophilic resin layer.

[0013] (7) A breathable waterproof material as described in (5) having a water pressure resistance of 10,000 mmH2O or more after 10 washes.

[0014] (8) A method for manufacturing a moisture-permeable waterproof material having a porous polyurethane layer and a fabric layer laminated thereon, comprising the step of attaching a silicone-based water-repellent agent to the side opposite to the laminated surface of the porous polyurethane layer and the fabric layer of the laminated sheet formed by laminating the porous polyurethane layer and the fabric layer.

[0015] (9) A method for manufacturing a breathable waterproof material as described in (8), using a coating method in the process of attaching the above silicone-based water-repellent agent. Effects of the invention

[0016] The fiber product according to the present invention, despite not using fluorine compounds, possesses water pressure resistance performance with high washing durability, and also has sufficient peel strength to withstand wear even when a non-porous resin layer or other materials are bonded to the porous membrane surface. Brief explanation of the drawing

[0017] FIG. 1 is a cross-sectional view showing the composition of a breathable waterproof fiber material according to one embodiment of the present invention. FIG. 2 is a cross-sectional view showing the composition of a breathable waterproof fiber material according to one embodiment of the present invention. FIG. 3 is a cross-sectional view showing the composition of a breathable waterproof fiber material according to one embodiment of the present invention. FIG. 4 is a cross-sectional view showing the composition of a breathable waterproof fiber material according to one embodiment of the present invention. Specific details for implementing the invention

[0018] The present invention will be described in more detail below.

[0019] The breathable waterproof material of the present invention is formed by laminating a porous polyurethane layer and a fabric bag.

[0020] Useful fiber materials constituting the above-mentioned fabric include polyester, nylon, acrylic, polyurethane, or rayon such as acetate or viscose. In addition to these, chemical fibers such as polylactic acid, aromatic polyamide, polyimide, or polyphenylene sulfide, natural fibers such as cotton, linen, silk, or wool, or blended, woven, or knitted products of these materials may be used. Among these, it is preferable to include polyester or nylon as the fiber material. From the perspective of dye transfer sublimation into the polyurethane resin being coated, nylon-based materials dyed with acid dyes are preferred. From the perspective of performance such as water pressure resistance or moisture permeability, polyester-based or olefin-based synthetic fibers, or blended or woven products with natural fibers may be used.

[0021] In addition, the fibers constituting the above-mentioned fabric may be either long fibers or short fibers. Furthermore, the yarn made from these fibers may be any of raw yarn (flat yarn), twisted yarn, or processed yarn. The processed yarn is not specifically limited and may be a twisted processed yarn (woolly processed yarn, DTY, modified twisted processed yarn, etc.), press-fit processed yarn, shaping processed yarn, abrasion processed yarn, Taslan processed yarn, yarn length difference alignment processed yarn, composite processed yarn, napped processed yarn, entangled bundled yarn, entangled blended yarn, etc. It is desirable to use processed yarn from the perspective of increasing water repellency by attaching a large amount of silicone-based water repellent to the fiber surface and from the perspective of improving tear strength.

[0022] In the drawing, the above-mentioned fabric (outer fabric) schematically represents a cross-sectional view of a fabric, but it may be a knitted fabric or a non-woven fabric instead of a woven fabric.

[0023] The breathable waterproof material of the present invention may also have a water-repellent agent attached to the above-mentioned fabric, for example, a silicone-based water-repellent agent, which does not contain a fluorine compound.

[0024] Regarding the timing for applying a water-repellent treatment to the above fabric (outer fabric), it is preferable to perform it before laminating the porous polyurethane layer. Specifically, for example, the water-repellent treatment can be performed by using a water-repellent agent that does not contain fluorine compounds, such as a silicone-based water-repellent agent, and at least one of a crosslinking agent, a penetrating agent, and a pH adjuster, and then treating, drying, and curing using a pad method, a spray method, etc. Furthermore, it is desirable to achieve a performance of Grade 4 or higher before washing and Grade 3 or higher after 20 washes in the JIS L1092 spray test.

[0025] The breathable waterproof material shown in Fig. 1 is formed by laminating a porous polyurethane layer that does not contain fluorine compounds onto an outer layer.

[0026] In addition, regarding the pores within the polyurethane resin shown in the drawings, they are merely schematic representations, and the shape and size are not limited to these embodiments.

[0027] As a polyurethane forming a porous polyurethane layer, it is preferable to have a polyurethane obtained by reacting a polyol compound (A) having at least two hydroxyl groups reactive to an isocyanate group, an isocyanate compound (B) having an isocyanate structure and at least two isocyanate groups, and a chain extender (C) added as needed in a reaction solution containing a polar solvent (D) soluble in water, and stopping the polymerization with a reaction stopping agent (E).

[0028] The above polyurethane may be a polyurethane consisting solely of simple urethane bonds, or a polyurethane-polyurea resin containing urea bonds.

[0029] Examples of the above polyol compound (A) include polyester polyols having ester bonds, polyether polyols having ether bonds, and polycarbonate polyols having carbonate groups.

[0030] Examples of the above isocyanate compounds (B) include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, hexamethylene diisocyanate (HMDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), hydrogenated MDI, etc.

[0031] Examples of the above chain extender (C) include aliphatic diols such as ethylene glycol, 1,4-butanediol, 1,3-butanediol (1,3-butylene glycol), neopentyl glycol, 1,5-pentanediol, methylpentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol, alicyclic diols such as 1,4-cyclohexanediol and hydrogenated xylylene glycol, and aromatic diols such as xylylene glycol.

[0032] The above polar solvent (D) is not particularly limited, but it is preferable that it dissolves easily with the isocyanate compound (B), and examples include dimethylformamide (DMF) or dimethyl sulfoxide (DMSO).

[0033] The above reaction stopping agent (E) is used to stop polymerization to a target viscosity by reacting with the end of the chemical structure in a polyurethane polymerization reaction. Monovalent and polyvalent alcohols, monovalent amines, etc. may be used as the reaction stopping agent (E). Examples include monovalent and polyvalent alcohols (methanol, ethanol, butanol, propylene glycol, higher alcohols, higher fatty acid esters having hydroxyl groups, etc.) and monovalent amines (methylamine, butylamine, etc.).

[0034] The above components (A) to (E) may each be used individually, but two or more types may also be used in combination.

[0035] When polymerizing the above polyurethane, the reaction temperature may be the same as the temperature typically used for urethane reaction, and when using a polar solvent (D), it is typically 30 to 90°C.

[0036] As a method for laminating the porous polyurethane layer onto the fabric bag, a polyurethane solution containing the polyurethane may be directly applied to the surface of the fabric bag and wet-solidified, or a sheet of the porous polyurethane layer may be produced by applying it to a substrate other than the fabric bag and then wet-solidifying it, and then bonding the sheet to the surface of the fabric bag.

[0037] As a method for applying the polyurethane solution to the above-mentioned fabric or substrate, it is preferable to use a method generally referred to as a direct coating method, and various coating methods such as knife coating, knife overall coating, and reverse roll coating may be used.

[0038] When producing the above-mentioned porous polyurethane layer sheet, the substrate may be one from which the sheet can be peeled off; for example, a fabric bag or release paper separate from the above-mentioned fabric bag may be used. After forming the above-mentioned sheet, an adhesive may be applied to the surface layer of the above-mentioned sheet to bond it to the above-mentioned fabric bag. A waterproof fabric bag can be obtained by peeling off the substrate after the adhesive has solidified.

[0039] The breathable waterproof material of the present invention is formed by attaching a silicone-based water-repellent agent to the inner surface of the holes of the porous polyurethane layer.

[0040] Straight silicone oil and modified silicone oil can be used as the above silicone-based water repellent.

[0041] Examples of straight silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil.

[0042] Examples of modified silicone oils include straight silicone oil modified with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc.

[0043] Among modified silicone oils, reactive silicone oil having reactive groups within the molecule is preferred, and among them, carboxyl-modified silicone oil is preferred from the perspective of imparting adhesion and water repellency.

[0044] Examples of silicone compounds used as the above silicone-based water-repellent agents include those disclosed in Japanese Patent Publication No. 2017-218713, Japanese Patent Publication No. 2017-226946, Japanese Patent Publication No. 2017-155095, Japanese Patent Publication No. 2017-218713, etc.

[0045] In addition, commercially available silicone compounds used as the above silicone-based water repellents include, for example, Geranex (registered trademark) SH (Matsumoto Yushi Co., Ltd.), Dryfon (registered trademark) 600E (manufactured by Nika Kagaku Co., Ltd.), Rikenparan SG-54 (Miki Riken Co., Ltd.), Light Silicone P-290E (Kitahiro Chemical Co., Ltd.), Poron (registered trademark) MR (Shinetsu Kagaku Co., Ltd.), Poron (registered trademark) MF-49 (Shinetsu Kagaku Co., Ltd.), Neoseed (registered trademark) NR8000 (Nika Kagaku Co., Ltd.), KF-96 series (Shinetsu Kagaku Co., Ltd.), KF8005 (Shinetsu Kagaku Co., Ltd.), KF8010 (Shinetsu Kagaku Co., Ltd.), and KF4003 (Shinetsu Examples include the Kagaku High School (Shin-Etsu Kagaku High School), X-22-3701E (Shin-Etsu Kagaku High School), SF-8417 (Dow Toray Corporation), BY16-880 (Dow Toray Corporation), MQ-1600 (Dow Toray Corporation), etc.

[0046] The breathable waterproof material of the present invention can be efficiently obtained, for example, by attaching a silicone-based water-repellent agent to the side opposite to the laminated surface of the porous polyurethane layer with the fabric bag of a laminated sheet formed by laminating the porous polyurethane layer and the fabric bag. That is, the method for manufacturing the breathable waterproof material of the present invention is a method for manufacturing a breathable waterproof material comprising a porous polyurethane layer and a fabric bag, and includes a process of attaching a silicone-based water-repellent agent to the side opposite to the laminated surface of the porous polyurethane layer with the fabric bag of a laminated sheet formed by laminating the porous polyurethane layer and the fabric bag.

[0047] As a method for attaching the silicone-based water repellent, it may be applied directly to the porous polyurethane layer or applied from the fabric side. In order to efficiently penetrate the silicone-based water repellent, it is preferable to apply it directly to the porous polyurethane layer.

[0048] As a method for applying the above silicone-based water-repellent agent, various methods capable of single-sided treatment, such as gravure, cylinder roll, spray, and kiss coater, can be selected.

[0049] In order to improve water resistance, the breathable waterproof material of the present invention is also formed by further laminating a non-porous hydrophilic resin layer and / or a second fabric on the side opposite to the side laminated with the fabric of the porous polyurethane layer.

[0050] FIG. 2 shows an embodiment in which a non-porous hydrophilic resin layer is added for the purpose of further improving the water pressure resistance of the breathable waterproof material shown in FIG. 1.

[0051] In the above-mentioned non-porous hydrophilic resin layer, a hydrophilic polyurethane resin is preferably used in which 20 to 60 mol% of the polyol component is at least one of polyethylene glycol and polypropylene glycol. Particularly preferred is a polyurethane resin in which 20 to 60 mol% of the polyol component is polyethylene glycol. There are no particular limitations on other polyol components, but for example, polyester glycol, polycarbonate glycol, and other polyether glycols are used. As for the polyisocyanate component constituting the hydrophilic polyurethane resin, known aliphatic polyisocyanates and aromatic polyisocyanates may be used, and examples include hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate, isophorone diisocyanate, and 4,4'-diphenylmethane diisocyanate.

[0052] It is preferable that the above hydrophilic nonporous membrane possesses thermal fusion properties. By possessing thermal fusion properties, the hydrophilic nonporous membrane can be uniformly adhered without dissolving the microporous membrane. Thermal fusion properties are imparted by the use of a low-melting-point material or a crosslinking agent.

[0053] The thickness of the above hydrophilic nonporous membrane is preferably 1 to 10 μm.

[0054] The above-mentioned non-porous hydrophilic resin layer may be bonded with a highly moisture-permeable film using a moisture-curing polyurethane-based hot melt adhesive, or the entire surface may be coated with a highly moisture-permeable resin. Additionally, partial printing may be used to improve the design aesthetics or the surface texture of the porous resin layer.

[0055] Examples of methods for forming the above-mentioned non-porous hydrophilic resin layer include forming it by directly coating it onto the porous polyurethane layer, forming it by applying it to a release liner or the like in advance, and producing a film by extrusion.

[0056] FIG. 3 shows an embodiment in which a second fabric (other material) is further bonded for the purpose of protecting the porous polyurethane layer of the breathable waterproof material shown in FIG. 1. FIG. 4 also shows an embodiment in which a fabric layer is further bonded to the surface of the non-porous hydrophilic resin layer of the embodiment shown in FIG. 2.

[0057] In FIGS. 3 and 4, the second fabric is shown as a knitted fabric, but the use of woven or non-woven fabric is not limited.

[0058] For the second fabric mentioned above, special fabrics or knits made of various synthetic fibers, such as plain weaves (taffeta), twill weaves, and satin, as well as various fabrics and non-woven fabrics made of natural or semi-synthetic fibers, may be used. Among these, nylon tricot knits are more preferable in terms of texture and the like.

[0059] In the embodiment having the second fabric layer, regarding the timing for attaching the silicone-based water-repellent agent to the porous polyurethane layer, it may be done either before or after bonding the second fabric layer; however, from the perspective of efficiently applying the silicone-based water-repellent agent to the porous polyurethane layer, it is preferable to apply it before bonding.

[0060] In a moisture-permeable waterproof material of a form in which the above-mentioned non-porous hydrophilic resin layer and / or a second fabric bag are further laminated, it is preferable that there is no delamination between the porous polyurethane layer and the non-porous hydrophilic resin layer or the second fabric bag in contact with the porous polyurethane layer. In the present invention, delamination refers to a phenomenon in which the non-porous hydrophilic resin layer peels off or lifts from the porous polyurethane layer during washing.

[0061] The moisture-permeable waterproof material of the present invention preferably has a peel strength of 200 cN / cm or more between the porous polyurethane layer and the fabric. The peel strength is measured according to the measurement method of JIS L1086 (2020).

[0062] The breathable waterproof material of the present invention preferably has a water pressure resistance of 5,000 mmH2O or more after 10 washes and does not get wet in a water test where a water pressure of 2,000 mmH2O is maintained for 10 minutes. In the present invention, the water pressure resistance test conforms to the measurement method described in JIS L 1092:2020 B method (high water pressure method). A water test is a method of evaluating the waterproofness of a membrane by maintaining a water pressure of 2,000 mmH2O for 10 minutes using a simple water pressure resistance meter. Waterproofness is determined by whether or not the membrane becomes wet after 10 minutes.

[0063] In a moisture-permeable waterproof material having a form in which the above-mentioned non-porous hydrophilic resin layer and / or a second fabric bag are further laminated, it is preferable that the water pressure resistance after 10 washes is 10,000 mmH2O or more.

[0064] The breathable waterproof material of the present invention has excellent water pressure resistance performance with washing durability and adhesion at each interface, so it can be applied as a fabric for various products requiring breathability, waterproofness, and durability, such as medical equipment like rain gear, shoes, bags, and outdoor equipment like tents.

[0065] Examples

[0066] Embodiments of the present invention are described below. Furthermore, the present invention is not limited to the embodiments shown below.

[0067] [Measurement and Evaluation Methods]

[0068] The measurement and evaluation methods are described below. In addition, if the breathable waterproof material has a non-porous hydrophilic resin layer attached, a dissimilar material (second fabric bag) attached, or both a non-porous hydrophilic resin layer and a dissimilar material (second fabric bag) attached, the non-porous hydrophilic resin layer and / or the dissimilar material (second fabric bag) shall be included in the measurement and evaluation.

[0069] (1) Distribution of silicone-based water repellent in a porous polyurethane layer

[0070] The cross-section of the breathable waterproof material was observed at 2000x magnification using a scanning electron microscope (SEM), and the presence of Si elements within the porous polyurethane layer was confirmed using energy dispersive X-ray spectroscopy (EDX) to determine the distribution situation.

[0071] (2) Internal pressure

[0072] Measurements were taken in accordance with the JIS L1092:2020 B method (high water pressure method). During measurement, a nylon-attached white cloth used for measuring colorfastness was used as a taffeta cover to suppress elongation of the breathable waterproof material being measured. When measuring water pressure resistance after 10 washes, 10 washes were repeated using the C4M method of JIS L1930 (Test Method for Practical Machinery), and then the water pressure resistance was measured.

[0073] (3) Presence or absence of water wetting by water test

[0074] The breathable waterproof material was subjected to 10 washes using the C4M method of JIS L1930 (Test Method for Utility Models). Using a simple water pressure tester, a water pressure of 2000 mmH2O was applied from the outer fabric side of the breathable waterproof material and maintained for 10 minutes. After 10 minutes, the presence or absence of wetting was checked on the outer fabric and the opposite side. It was evaluated as "A" if no wetting of the membrane was confirmed, and as "B" if wetting of the membrane was confirmed.

[0075] (4) Water vapor permeability

[0076] Measurements were taken in accordance with the JIS L1099:2021 A-1 method (calcium chloride method).

[0077] (5) Peel strength

[0078] Measurements were taken in accordance with the JIS L1086:2020 test method for adhesive wicks and adhesive fabrics.

[0079] (6) Presence or absence of delamination

[0080] For a breathable waterproof material with a non-porous hydrophilic resin layer attached, a dissimilar material (second fabric) attached, or a non-porous hydrophilic resin layer and a dissimilar material (second fabric) attached, after repeating washing 10 times according to the C4M method of JIS L1930 (Practical Test Method), an evaluation was performed by visually checking for the presence or absence of peeling or lifting of the non-porous hydrophilic resin layer or the dissimilar material (second fabric) in contact with the porous polyurethane layer from the porous polyurethane layer. If there was no lifting or peeling, it was indicated as "no delamination."

[0081] (7) Quality of breathable waterproof material

[0082] An evaluation was conducted by visually inspecting whether the coating resin used to form the porous polyurethane layer penetrated the fabric and seeped out to the back side, or whether it damaged the fabric quality (penetration to the back side, grain direction). Based on the criterion of unsuitability for medical use, cases where resin seeping out to the back side was confirmed were rated "B," and cases where it was not confirmed were rated "A."

[0083] [Manufacturing Process]

[0084] (1) Preparation of outer fabric bag

[0085] Nylon ripstop taffeta composed of nylon filament yarn with a fineness of 50 denier (56 dtex) was scoured and dyed using the standard method. This fabric was immersed in a diluted solution of 30 g / l of a non-fluorine water-repellent agent (Nikka Kagaku Inc. NR-7200), woven with a mangle to achieve a compression rate of 40%, and then subjected to a drying heat treatment at 150°C for 30 seconds using a heat setter to produce a fabric for the outer layer.

[0086] (2) Preparation of a polyurethane resin composition for coating

[0087] By adding polycarbonate polyol (hexamethylene carbonate diol), polyether polyol (polytetramethylene glycol), isocyanate (diphenylmethane diisocyanate), dimethylformamide, ethylene glycol, propylene glycol monooleate, and propylene glycol to a reaction vessel equipped with a stirrer and stirring, a polycarbonate-based polyurethane resin solution with a urethane resin concentration of 25.0% and a viscosity of 82,000 mPa·s (30°C) was obtained.

[0088] 5 parts by mass of fine silica powder (manufactured by Tokuyama Co., Ltd., "Leorosil" (registered trademark) MT-10, vapor-phase reaction silica of dimethyldichlorosilane) was added to 80 parts by mass of the obtained polycarbonate-based polyurethane resin solution, and sufficiently immersed in 50 parts by mass of DMF, dispersed and stirred with a homomixer for about 15 minutes, and then stirred to obtain a liquid coating polyurethane resin composition containing a polycarbonate-based polyurethane resin.

[0089] (3) Polyurethane resin coating

[0090] The above water-repellent treated fabric bag was coated with the above coating resin composition using a knife overall coater at an application amount of 150 g / m², and the liquid composition of the polycarbonate-based polyurethane resin was wet-solidified by immersing it in a gelation bath containing an aqueous solution with 15 mass% of DMF as the coagulation liquid at 30°C for 2 minutes. Afterwards, the fabric bag was washed with water at 80°C for 10 minutes and dried with hot air at 140°C to obtain a breathable waterproof material with a porous polyurethane layer laminated thereon.

[0091] (4) Silicone water-repellent treatment

[0092] A silicone-based water-repellent agent was applied to the porous polyurethane layer side of the moisture-permeable waterproof material obtained in (3) above using a gravure roll at an application amount of 30 g / m², and the silicone-based water-repellent agent was penetrated into the porous polyurethane layer. After that, it was dried at 120°C, and then a drying heat treatment was performed at 150°C × 30 seconds.

[0093] (5) Laminate of a non-porous hydrophilic resin film

[0094] A polyurethane solution was prepared with the composition shown in Formula 1 below.

[0095] (Prescription 1)

[0096] Polyether-based polyurethane Leocoat U-6285M (Toray Kotex Corp. Leocoat (Registered Trademark) U-6285M) 100 parts by mass

[0097] MEK 50 mass parts

[0098] 50 parts by mass of toluene

[0099] The above polyurethane solution was applied to a release liner (EV130TPD manufactured by Lintec Co., Ltd.) with a clearance of 50㎛ using a knife overall coater. Subsequently, a non-porous hydrophilic resin film with a thickness of 5㎛ was obtained by hot air drying at 80℃.

[0100] After (4) above, the above non-porous hydrophilic resin film was superimposed on the porous polyurethane layer of the above moisture-permeable waterproof material, and lamination was performed using a hot laminator under conditions of a temperature of 120°C, a pressure of 0.9807 MPa (10 kg / ㎠), and a speed of 20 m / min to obtain a moisture-permeable waterproof material with a non-porous hydrophilic resin layer (indicated as “HB” in the table).

[0101] (6) Joining of materials

[0102] Nylon tricot (18d half tricot: W×C=36×40) was used as the material (second fabric).

[0103] Polyurethane hot melt (product number LA7575UV) is applied with a 30-mesh gravure roll on the porous polyurethane layer of the breathable waterproof material after (4) above, or on the non-porous hydrophilic resin layer of the breathable waterproof material after (5) above, and after hot air drying at 100°C, the materials are bonded and compressed and aged at 40°C for 24 hours to obtain a breathable waterproof material with a material (second fabric bag) attached.

[0104] [Example 1]

[0105] A breathable waterproof processed fabric was manufactured by manufacturing processes (1) to (4). However, dimethyl silicone oil (Shin-Etsu Kagaku Kogyo Co., Ltd. KF-96) was used as the silicone-based water-repellent in manufacturing process (4). The distribution of the silicone-based water-repellent in the porous polyurethane layer was confirmed to be present on the surface of the porous polyurethane layer side where the coating was performed and on the inner surface of the holes. That is, it was confirmed that the silicone-based water-repellent was attached to the inner surface of the holes.

[0106] [Example 2]

[0107] A breathable waterproof fabric was manufactured by manufacturing processes (1) to (4). However, carboxyl-modified silicone oil (Shin-Etsu Kagaku Kogyo Co., Ltd. X-22-3701E) was used as the silicone-based water-repellent in manufacturing process (4). The distribution of the silicone-based water-repellent in the porous polyurethane layer was confirmed to be present on the surface of the porous polyurethane layer side where the coating was performed and on the inner surface of the holes. That is, it was confirmed that the silicone-based water-repellent was attached to the inner surface of the holes.

[0108] [Example 3]

[0109] The moisture-permeable waterproof processed fabric obtained in Example 2 was further processed by the manufacturing process (5) to obtain a moisture-permeable waterproof processed fabric with a non-porous hydrophilic resin layer attached. The distribution of the silicone-based water repellent in the porous polyurethane layer was confirmed to be present on the surface of the porous polyurethane layer side where the coating was performed and on the inner surface of the holes. That is, it was confirmed that the silicone-based water repellent was attached to the inner surface of the holes.

[0110] [Example 4]

[0111] In the manufacturing process (4), the silicone water-repellent was applied to the outer surface at an application amount of 60 g / m². Except for this, the process was carried out in the same manner as in Example 3 to obtain a breathable waterproof processed fabric with a non-porous hydrophilic resin layer attached. The distribution of the silicone-based water-repellent in the porous polyurethane layer was confirmed to be present on the outer surface where the application was performed and on the inner surface of the holes. That is, it was confirmed that the silicone-based water-repellent was attached to the inner surface of the holes.

[0112] [Example 5]

[0113] The moisture-permeable waterproof processed fabric obtained in Example 1 was further processed by the manufacturing process (5) to obtain a moisture-permeable waterproof processed fabric with a non-porous hydrophilic resin layer attached. The distribution of the silicone-based water repellent in the porous polyurethane layer was confirmed to be present on the surface of the porous polyurethane layer side where the coating was performed and on the inner surface of the holes. That is, it was confirmed that the silicone-based water repellent was attached to the inner surface of the holes.

[0114] [Example 6]

[0115] A moisture-permeable waterproof processed fabric with a non-porous hydrophilic resin layer attached was obtained by making the same as Example 5, except that the amount of silicone water-repellent applied in the manufacturing process (4) was 250 g / m². The distribution of the silicone-based water-repellent in the porous polyurethane layer was confirmed to be present on the surface of the porous polyurethane layer side where the coating was performed and on the inner surface of the holes. That is, it was confirmed that the silicone-based water-repellent was attached to the inner surface of the holes.

[0116] [Example 7]

[0117] The moisture-permeable waterproof processed fabric obtained in Example 2 was further processed by the manufacturing process (6) to obtain a moisture-permeable waterproof processed fabric with a different material (second fabric bag) attached. The distribution of the silicone-based water repellent in the porous polyurethane layer was confirmed to be present on the surface of the porous polyurethane layer side where the coating was performed and on the inner surface of the holes. That is, it was confirmed that the silicone-based water repellent was attached to the inner surface of the holes.

[0118] [Example 8]

[0119] The processing of manufacturing processes (5) and (6) was further performed in this order on the breathable waterproof processed fabric obtained in Example 2 to obtain a breathable waterproof processed fabric with a non-porous hydrophilic resin layer and a material (second fabric bag) attached. The distribution of the silicone-based water repellent in the porous polyurethane layer was confirmed to be present on the surface of the porous polyurethane layer side where the coating was performed and on the inner surface of the holes. That is, it was confirmed that the silicone-based water repellent was attached to the inner surface of the holes.

[0120] [Comparative Example 1]

[0121] A breathable waterproof fabric was manufactured by manufacturing processes (1) to (3).

[0122] [Comparative Example 2]

[0123] A breathable waterproof processed fabric was obtained in the same manner as Comparative Example 1, except that 1 mass of carboxyl-modified silicone oil (Shin-Etsu Kagaku Kogyo Co., Ltd. X-22-3701E) was added to the resin composition for coating in the manufacturing process (2). It was confirmed that the distribution of the silicone-based water repellent in the porous polyurethane layer was not concentrated on the inner surface of the holes, but was present within the polyurethane resin. That is, the silicone-based water repellent was not attached to the inner surface of the holes.

[0124] For the breathable waterproof materials obtained in each example and comparative example, the distribution of silicone-based water repellent in the porous polyurethane layer, water pressure resistance (initial, after 10 washes), water test (after 10 washes), moisture permeability (A-1), peel strength, and the presence and quality of delamination after 10 washes were measured and evaluated. The results are shown in Tables 1 and 2.

[0125]

[0126] Explanation of the symbols

[0127] 1: Four-back (outer fabric) 2: Porous polyurethane layer 3: Non-functional hydrophilic resin layer 4: Second Backline (Lee Jae)

Claims

Claim 1 A breathable waterproof material comprising a laminated fabric and a porous polyurethane layer, wherein a silicone-based water-repellent agent is attached to the inner surface of the holes of the porous polyurethane layer. Claim 2 A breathable waterproof material according to claim 1, wherein the silicone-based water-repellent agent is modified silicone. Claim 3 A breathable waterproof material according to claim 1 or 2, having a water pressure resistance of 5,000 mmH2O or more after 10 washes and not getting wet in a water test maintained at a pressure of 2,000 mmH2O for 10 minutes. Claim 4 A breathable waterproof material according to claim 1 or 2, wherein the peel strength of the porous polyurethane layer and the fabric is 200 cN / cm or more. Claim 5 A breathable waterproof material according to claim 1 or 2, wherein a non-porous hydrophilic resin layer and / or a second fabric layer are further laminated on the side opposite to the side of the porous polyurethane layer laminated with the fabric layer. Claim 6 In claim 5, a breathable waterproof material in which there is no peeling between the porous polyurethane layer and the non-porous hydrophilic resin layer or the second fabric layer in contact with the porous polyurethane layer. Claim 7 In claim 5, a breathable waterproof material having a water pressure resistance of 10,000 mmH2O or more after 10 washes. Claim 8 A method for manufacturing a breathable waterproof material having a porous polyurethane layer and a fabric layer laminated thereon, comprising the step of attaching a silicone-based water-repellent agent to the side opposite to the laminated surface of the porous polyurethane layer with the fabric layer of a laminated sheet formed by laminating the porous polyurethane layer and the fabric layer. Claim 9 A method for manufacturing a breathable waterproof material according to claim 8, using a coating method in the process of attaching the silicone-based water-repellent agent.

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