Breathable waterproof material and method for producing breathable waterproof material

Abstract

The present invention addresses the problem of providing a non-fluorine waterproof breathable textile product which has high waterproof properties and laundering durability without using a fluorine compound and in which a film or backing material laminated to the waterproof surface can have sufficient adhesive strength, and which has excellent wearing durability.　This breathable waterproof material comprises a fabric and a porous polyurethane layer formed thereon, wherein a silicone-based water repellent is adherent to the inner surfaces of pores of the porous polyurethane layer.

Description

Breathable waterproof material and method for manufacturing the same

[0001] The present invention relates to a moisture-permeable, waterproof fabric suitable for use in rainwear for sports and the like, and a method for producing the same.

[0002] Conventional wet-coating moisture-permeable waterproof materials are mainly produced by dissolving a polyurethane resin in a water-soluble solvent, mixing it with a fluorine-based water repellent, applying the mixture to a fabric, and wet gelling the resulting mixture. When the solvent is replaced with water, a porous polyurethane coating containing the fluorine-based water repellent is formed on the fabric, which is impermeable to rain and other water but allows moisture (water vapor) to pass through. Such moisture-permeable waterproof fabrics are described, for example, in Patent Documents 1 and 2.

[0003] JP-A No. 60-47954 JP-A No. 11-131373

[0004] Recent trends in regulations call for the non-use of fluorine compounds, but simply replacing fluorine-based water repellents with non-fluorine-based ones has not been enough to achieve the same level of performance.

[0005] The present invention has been made in view of the above, and aims to provide a non-fluorine waterproof, breathable textile product that has high waterproofness and washing durability, and further has sufficient adhesive strength when a film or backing material is attached to the waterproof surface, and is excellent in wear durability.

[0006] The present inventors conducted extensive research to solve the above-mentioned problems, and have now arrived at the present invention. The present invention has the following features. (1) A breathable waterproof material comprising a laminate of a fabric and a porous polyurethane layer, wherein a silicone-based water repellent is adhered to the pore surface of the porous polyurethane layer. (2) The breathable waterproof material according to (1), wherein the silicone-based water repellent is a modified silicone. (3) The breathable waterproof material according to (1) or (2), which has a water pressure resistance of 5,000 mmH2O or more after 10 washes and does not get wet in a Suter test in which a water pressure of 2,000 mmH2O is maintained for 10 minutes. (4) The breathable waterproof material according to any one of (1) to (3), wherein the peel strength between the porous polyurethane layer and the fabric is 200 cN / cm or more. (5) The moisture-permeable waterproof material according to any one of (1) to (4), further comprising a non-porous hydrophilic resin layer and / or a second fabric laminated on the surface of the porous polyurethane layer opposite to the surface laminated with the fabric. (6) The moisture-permeable waterproof material according to (5), in which there is no peeling between the porous polyurethane layer and the non-porous hydrophilic resin layer. (7) The moisture-permeable waterproof material according to claim 5, in which the water pressure resistance after 10 washes is 10,000 mmH2O or more. (8) A method for producing a moisture-permeable waterproof material comprising a porous polyurethane layer and a fabric laminated together, the method comprising the step of applying a silicone-based water repellent to the surface of the porous polyurethane layer opposite to the surface laminated with the fabric of a laminate sheet comprising the porous polyurethane layer and the fabric. (9) A method for producing a moisture-permeable waterproof material according to (8), in which a coating method is used in the step of applying the silicone-based water repellent.

[0007] The textile product of the present invention does not use any fluorine compound, yet has high water pressure resistance with high washing durability, and also has sufficient peel strength to withstand wear even when a non-porous resin layer or backing material is attached to the porous membrane surface.

[0008] Fig. 1 is a cross-sectional view showing the configuration of a breathable waterproof textile material according to one embodiment of the present invention. Fig. 2 is a cross-sectional view showing the configuration of a breathable waterproof textile material according to one embodiment of the present invention. Fig. 3 is a cross-sectional view showing the configuration of a breathable waterproof textile material according to one embodiment of the present invention. Fig. 4 is a cross-sectional view showing the configuration of a breathable waterproof textile material according to one embodiment of the present invention.

[0009] The present invention will now be described in further detail.

[0010] The moisture-permeable waterproof material of the present invention is formed by laminating a porous polyurethane layer and a fabric.

[0011] Useful fiber materials for the fabric include polyester, nylon, acrylic, polyurethane, and rayon such as acetate and viscose. In addition to these, chemical fibers such as polylactic acid, aromatic polyamide, polyimide, and polyphenylene sulfide, natural fibers such as cotton, linen, silk, and wool, and blends, mixed spinning, interwoven, or interknitted products of these materials can also be used. Among these, fibers containing polyester or nylon are preferred. From the viewpoint of dye transfer and sublimation into the polyurethane resin to be coated, nylon-based materials that can be dyed with acid dyes are preferred. From the viewpoint of performance such as water pressure resistance and moisture permeability, polyester-based or olefin-based synthetic fibers, and blends or blends with natural fibers may also be used.

[0012] The fibers constituting the fabric may be either long fibers or short fibers. The yarns using these fibers may be raw yarns (flat yarns), twisted yarns, or textured yarns. There are no particular limitations on the textured yarns, and examples that can be used include false-twist textured yarns (woolly textured yarns, DTY, improved false-twist textured yarns, etc.), forced textured yarns, shaped textured yarns, rubbed textured yarns, taslan textured yarns, length-matched textured yarns, composite textured yarns, fluff textured yarns, entangled bundled yarns, and entangled blended yarns. From the perspectives of increasing water repellency by adhering a large amount of silicone-based water repellent to the fiber surface and improving tear strength, it is preferable to use textured yarns.

[0013] In the drawings, the fabric (surface) is shown in a schematic cross section of a woven fabric, but it may be a knitted fabric or a nonwoven fabric instead of a woven fabric.

[0014] In the breathable waterproof material of the present invention, a water repellent agent that does not contain a fluorine compound, such as a silicone-based water repellent agent, may also be attached to the fabric.

[0015] The timing for applying a water-repellent finish to the fabric (surface) is preferably before laminating the porous polyurethane layer. Specifically, the water-repellent finish can be achieved by treating the fabric with a water-repellent agent that does not contain a fluorine compound, such as a silicone-based water-repellent agent, and at least one of a crosslinking agent, a penetrating agent, and a pH adjuster, using a padding method, spraying method, or the like, followed by drying and curing. It is preferable that the fabric achieves a performance of grade 4 or higher before washing and grade 3 or higher after 20 washes in the JIS L1092 spray test.

[0016] The moisture-permeable waterproof material shown in FIG. 1 is an embodiment in which a porous polyurethane layer containing no fluorine compound is laminated on a surface.

[0017] It should be noted that the pores in the polyurethane resin shown in the drawings are merely shown schematically, and the shapes and sizes are not limited to these.

[0018] The polyurethane that forms the porous polyurethane layer is preferably a polyurethane that can be obtained by reacting a polyol compound (A) having at least two hydroxyl groups reactive with an isocyanate group, an isocyanate compound (B) having an isocyanate structure and having at least two isocyanate groups, and a chain extender (C) added as needed in a reaction solution containing a water-soluble polar solvent (D), and then terminating the polymerization with a reaction terminator (E).

[0019] The polyurethane may be a polyurethane consisting of only urethane bonds, or may be a polyurethane / polyurea resin containing urea bonds.

[0020] Examples of the polyol compound (A) include polyester polyols having an ester bond, polyether polyols having an ether bond, and polycarbonate polyols having a carbonate group.

[0021] Examples of the isocyanate compound (B) include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, hexamethylene diisocyanate (HMDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), and hydrogenated MDI.

[0022] Examples of the 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.

[0023] The polar solvent (D) is not particularly limited, but is preferably one that dissolves easily in the isocyanate compound (B), and examples thereof include dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).

[0024] The reaction terminator (E) is used in the polyurethane polymerization reaction to terminate the polymerization at the target viscosity by reacting with the terminal of the chemical structure. Monohydric and polyhydric alcohols, monovalent amines, etc. can be used as the reaction terminator (E). Examples of the reaction terminator include monohydric and polyhydric alcohols (methanol, ethanol, butanol, propylene glycol, higher alcohols, higher fatty acid esters having a hydroxyl group, etc.) and monovalent amines (methylamine, butylamine, etc.).

[0025] The components (A) to (E) may be used alone or in combination of two or more.

[0026] In the polymerization of the polyurethane, the reaction temperature may be the same as that usually employed in urethanization reactions, and when a polar solvent (D) is used, the reaction temperature is usually 30 to 90°C.

[0027] The porous polyurethane layer may be laminated on the fabric by directly applying a polyurethane solution containing the polyurethane to the surface of the fabric and wet-coagulating it, or by applying the solution to a substrate other than the fabric and then wet-coagulating it to produce a sheet of the porous polyurethane layer, which is then bonded to the surface of the fabric.

[0028] The method for applying the polyurethane solution to the fabric or the substrate may be any method generally known as a direct coating method, and various coating methods such as knife coating, knife over roll coating, and reverse roll coating can be used.

[0029] When preparing a sheet of the porous polyurethane layer, the substrate may be any material from which the sheet can be peeled off, such as a fabric other than the fabric, release paper, etc. After the sheet is formed, an adhesive can be applied to the surface of the sheet to bond it to the fabric. After the adhesive has solidified, the substrate can be peeled off to obtain a waterproof fabric.

[0030] The moisture-permeable waterproof material of the present invention comprises a silicone-based water repellent agent attached to the inner surfaces of the pores of the porous polyurethane layer.

[0031] As the silicone-based water repellent, straight silicone oil and modified silicone oil can be used.

[0032] Examples of straight silicone oils include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil.

[0033] Examples of modified silicone oils include those obtained by modifying straight silicone oils with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, or the like.

[0034] Among modified silicone oils, reactive silicone oils having a reactive group in the molecule are preferred, and among these, carboxyl-modified silicone oils are preferred from the viewpoint of imparting adhesiveness and water repellency.

[0035] Examples of silicone-based compounds used as the silicone-based water repellent agent include those disclosed in JP-A-2017-218713, JP-A-2017-226946, JP-A-2017-155095, and JP-A-2017-218713.

[0036] Commercially available silicone compounds that can be used as the silicone water repellent include, for example, Gelanex (registered trademark) SH (Matsumoto Yushi Co., Ltd.), Drypon (registered trademark) 600E (Nicca Chemical Co., Ltd.), Rikenpalan SG-54 (Miki Riken Kogyo Co., Ltd.), Light Silicone P-290E (Kitahiro Chemical Co., Ltd.), Poron (registered trademark) MR (Shin-Etsu Chemical Co., Ltd.), and Poron (registered trademark) MF-49 (Shin-Etsu Chemical Co., Ltd.). ), Neoseed (registered trademark) NR8000 (Nicca Chemical Co., Ltd.), KF-96 series (Shin-Etsu Chemical Co., Ltd.), KF8005 (Shin-Etsu Chemical Co., Ltd.), KF8010 (Shin-Etsu Chemical Co., Ltd.), KF4003 (Shin-Etsu Chemical Co., Ltd.), X-22-3701E (Shin-Etsu Chemical Co., Ltd.), SF-8417 (Dow Toray Co., Ltd.), BY16-880 (Dow Toray Co., Ltd.), MQ-1600 (Dow Toray Co., Ltd.), and the like.

[0037] The moisture-permeable waterproof material of the present invention can be efficiently obtained, for example, by attaching a silicone-based water repellent to the surface of a laminate sheet formed by laminating the porous polyurethane layer and the fabric, opposite the surface where the porous polyurethane layer is laminated with the fabric. That is, the method for producing a moisture-permeable waterproof material of the present invention is a method for producing a moisture-permeable waterproof material comprising a porous polyurethane layer and a fabric, and includes a step of attaching a silicone-based water repellent to the surface of a laminate sheet formed by laminating the porous polyurethane layer and the fabric, opposite the surface where the porous polyurethane layer is laminated with the fabric.

[0038] The silicone-based water repellent agent may be applied by directly applying it to the porous polyurethane layer or by applying it from the fabric side, but in order to efficiently penetrate the silicone-based water repellent agent, it is preferable to apply it directly to the porous polyurethane layer.

[0039] The silicone-based water repellent agent can be applied by any of a variety of methods that can treat one side, such as gravure, cylinder roll, spray, kiss coater, etc.

[0040] In order to improve water resistance, it is also preferable that the moisture-permeable waterproof material of the present invention has a non-porous hydrophilic resin layer and / or a second fabric further laminated on the side of the porous polyurethane layer opposite to the side laminated with the fabric.

[0041] 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 moisture-permeable waterproof material shown in FIG.

[0042] The nonporous hydrophilic resin layer preferably uses a hydrophilic polyurethane resin 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 restrictions on the other polyol component, but examples include polyester glycol, polycarbonate glycol, and other polyether glycols. As the polyisocyanate component constituting the hydrophilic polyurethane resin, known aliphatic polyisocyanates and aromatic polyisocyanates can be used, such as hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate, isophorone diisocyanate, and 4,4'-diphenylmethane diisocyanate.

[0043] The hydrophilic nonporous membrane preferably has heat-sealing properties. By having heat-sealing properties, the hydrophilic nonporous membrane can be uniformly adhered to the microporous membrane without dissolving it. Heat-sealing properties are imparted by using a low-melting point material or a crosslinking agent.

[0044] The thickness of the hydrophilic non-porous membrane is preferably 1 to 10 μm.

[0045] The nonporous hydrophilic resin layer may be formed by laminating a highly moisture-permeable film with a moisture-curable polyurethane hot melt or by coating the entire surface with a highly moisture-permeable resin. Furthermore, the nonporous hydrophilic resin layer may be partially printed to improve the design and texture of the porous resin layer surface.

[0046] Examples of methods for forming the non-porous hydrophilic resin layer include a method of directly coating the non-porous polyurethane layer, a method of applying the non-porous hydrophilic resin layer in advance to a release paper or the like, and a method of forming a film by extrusion.

[0047] Figure 3 shows an embodiment in which a second fabric (backing material) is further laminated to protect the porous polyurethane layer of the moisture-permeable waterproof material shown in Figure 1. Figure 4 shows an embodiment in which an additional fabric layer is laminated to the surface of the non-porous hydrophilic resin layer of the embodiment shown in Figure 2.

[0048] Although the second fabric is shown as a knitted fabric in FIGS. 3 and 4, this does not limit the use of a woven fabric or a nonwoven fabric.

[0049] The second fabric may be a plain weave (taffeta), twill, satin, or other special woven or knitted fabric made of various synthetic fibers, or a variety of fabrics or nonwoven fabrics made of natural or semi-synthetic fibers. Of these, nylon tricot knitted fabrics are more preferred in terms of texture, etc.

[0050] In the case of an embodiment having the second fabric, the silicone-based water repellent agent may be attached to the porous polyurethane layer either before or after bonding the second fabric layer, but from the viewpoint of efficiently applying the silicone-based water repellent agent to the porous polyurethane layer, it is preferable to apply it before bonding.

[0051] In the moisture-permeable waterproof material having the nonporous hydrophilic resin layer and / or the second fabric further laminated thereon, it is preferable that there is no delamination between the porous polyurethane layer and the nonporous hydrophilic resin layer or the second fabric in contact with the porous polyurethane layer. In the present invention, delamination refers to the phenomenon in which the nonporous hydrophilic resin layer peels off or floats from the porous polyurethane layer during washing.

[0052] In the moisture-permeable waterproof material of the present invention, the peel strength between the porous polyurethane layer and the fabric is preferably 200 cN / cm or more. The peel strength is measured according to the measurement method of JIS L1086 (2020).

[0053] 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 Suter test in which a water pressure of 2,000 mmH2O is maintained for 10 minutes. The water pressure resistance test in the present invention conforms to the measurement method described in JIS L 1092:2020 Method B (high water pressure method). The Suter 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 measuring device. Waterproofness is determined by whether or not the membrane remains wet after 10 minutes.

[0054] In the moisture-permeable waterproof material in an embodiment in which the non-porous hydrophilic resin layer and / or the second fabric is further laminated, it is preferable that the water pressure resistance after 10 washings is 10,000 mmH2O or more.

[0055] The breathable waterproof material of the present invention has excellent water pressure resistance with washing durability and excellent adhesion at each interface, and can be used as a fabric for various products that require breathable waterproofness and durability, such as clothing such as rain gear, shoes, bags, tents, and other outdoor goods.

[0056] Examples of the present invention will be described below, but the present invention is not limited to the examples shown below.

[0057] [Measurement and evaluation methods] The measurement and evaluation methods are described below. When the moisture-permeable waterproof material has a nonporous hydrophilic resin layer, a backing (second fabric), or a nonporous hydrophilic resin layer and a backing (second fabric), the nonporous hydrophilic resin layer and / or the backing (second fabric) are included in the measurement and evaluation.

[0058] (1) Distribution of silicone-based water repellent agent in porous polyurethane layer A cross section of the breathable waterproof material was observed at 2000x magnification using a scanning electron microscope (SEM), and the presence of Si element in the porous polyurethane layer was confirmed using energy dispersive X-ray spectroscopy (EDX), and the distribution state was identified.

[0059] (2) Water Pressure Resistance The measurement was performed in accordance with JIS L1092:2020 Method B (high water pressure method). During the measurement, a nylon-attached white cloth used for measuring color fastness was used as a taffeta cover to prevent stretching of the breathable waterproof material being measured. When measuring water pressure resistance after 10 washes, the material was washed 10 times using the C4M method of JIS L1930 (practical machine test method), and then the water pressure resistance was measured.

[0060] (3) Presence or absence of water wetting by Suter test The breathable waterproof material was washed 10 times according to the C4M method of JIS L1930 (practical machine test method). Using a simple water pressure resistance measuring device, a water pressure of 2000 mmH2O was applied to the outer surface of the breathable waterproof material and maintained for 10 minutes, and the presence or absence of wetting on the surface opposite the outer surface after 10 minutes was confirmed. Those in which wetting of the membrane was not confirmed were rated "A", and those in which wetting of the membrane was confirmed were rated "B".

[0061] (4) Moisture permeability Measured in accordance with JIS L1099:2021 A-1 method (calcium chloride method).

[0062] (5) Peel strength Measured in accordance with JIS L1086:2020 Test method for adhesive interlinings and adhesive fabrics.

[0063] (6) Whether or not there is peeling (delamination) The moisture-permeable waterproof material with non-porous hydrophilic resin layer, with backing material (second fabric), or with non-porous hydrophilic resin layer and backing material (second fabric) is washed 10 times by the C4M method of JIS L1930 (practical machine test method), and then visually check whether or not there is peeling or floating phenomenon of the non-porous hydrophilic resin layer or backing material (second fabric) that contacts with porous polyurethane layer from porous polyurethane layer, and evaluate.If there is no floating or peeling, it is marked as "no delamination".

[0064] (7) Quality of the breathable waterproof material The coating resin used to form the porous polyurethane layer was visually inspected to see if it penetrated the fabric and damaged the fabric quality (through-through, staining). Based on the criteria of unsuitability for clothing, those in which resin bleed-through was confirmed were rated "B," and those in which no bleed-through was confirmed were rated "A."

[0065] [Manufacturing process] (1) Preparation of outer fabric Nylon ripstop taffeta composed of 50 denier (56 dtex) nylon filament yarn was scoured and dyed by conventional methods. This fabric was immersed in a diluted solution of 30 g / L of a non-fluorine-based water repellent (NR-7200, manufactured by Nicca Chemical Co., Ltd.), wrung with a mangle to a wringing rate of 40%, and then subjected to a dry heat treatment at 150°C for 30 seconds in a heat setter to produce an outer fabric.

[0066] (2) Preparation of Polyurethane Resin Composition for Coating Use Polycarbonate polyol (hexamethylene carbonate diol), polyether polyol (polytetramethylene glycol), isocyanate (diphenylmethane diisocyanate), dimethylformamide, ethylene glycol, propylene glycol monooleate, and propylene glycol were added to a reaction vessel equipped with a stirrer and stirred to obtain a polycarbonate-based polyurethane resin solution with a urethane resin concentration of 25.0% and a viscosity of 82,000 mPa s (30°C).

[0067] To 80 parts by mass of the obtained polycarbonate-based polyurethane resin solution, 5 parts by mass of fine silica powder (manufactured by Tokuyama Corporation, "Reolosil" (registered trademark) MT-10, silica obtained by gas phase reaction of dimethyldichlorosilane) was added, and the mixture was thoroughly immersed in 50 parts by mass of DMF, dispersed and stirred for about 15 minutes using a homomixer, and then further stirred to obtain a liquid polyurethane resin composition for coating containing a polycarbonate-based polyurethane resin.

[0068] (3) Coating with polyurethane resin The coating resin composition was applied to the water-repellent treated fabric in an amount of 150 g / m ２ The fabric was coated with a knife-over-roll coater at 1000 W / m² and then immersed in a gelling bath containing an aqueous solution containing 15% by mass of DMF for 2 minutes at 30°C to wet-coagulate the liquid polycarbonate-based polyurethane resin composition. The fabric was then washed with warm water at 80°C for 10 minutes and dried with hot air at 140°C to obtain a moisture-permeable, waterproof material in which a porous polyurethane layer was laminated on the fabric.

[0069] (4) Silicone Water-Repellent Treatment A silicone-based water-repellent agent was applied in an amount of 30 g / m to the porous polyurethane layer side of the breathable waterproof material obtained in (3) above. ２ The silicone water repellent was applied using a gravure roll at a temperature of 100°C, and the silicone water repellent was allowed to penetrate into the porous polyurethane layer. After that, the film was dried at 120°C, and then subjected to a dry heat treatment at 150°C for 30 seconds.

[0070] (5) Lamination of non-porous hydrophilic resin film A polyurethane solution was prepared according to the composition shown in the following Formulation 1. (Formulation 1) Polyether polyurethane Leocoat U-6285M (Leocoat (registered trademark) U-6285M, manufactured by Toray Coatex Co., Ltd.) 100 parts by mass MEK 50 parts by mass Toluene 50 parts by mass

[0071] The polyurethane solution was applied onto release paper (EV130TPD manufactured by Lintec Corporation) with a clearance of 50 μm using a knife over roll coater, followed by hot air drying at 80° C. to obtain a non-porous hydrophilic resin film having a thickness of 5 μm.

[0072] The non-porous hydrophilic resin film was superimposed on the porous polyurethane layer of the moisture-permeable waterproof material after (4) above, and laminated in a hot laminator at a temperature of 120°C and a pressure of 0.9807 MPa (10 kg / cm ２ ), lamination was carried out under the conditions of 20 m / min and a speed of 20 m / min to obtain a moisture-permeable, waterproof material with a non-porous hydrophilic resin layer (represented as "HB" in the table).

[0073] (6) Bonding of Backing Material Nylon tricot (18d half tricot: W×C=36×40) was used as the backing material (second fabric).

[0074] A polyurethane hot melt (product number LA7575UV) was applied using a 30-mesh gravure roll onto the porous polyurethane layer of the breathable waterproof material after (4) above, or onto the non-porous hydrophilic resin layer of the breathable waterproof material after (5) above, and after hot air drying at 100°C, a backing material was attached and aged at 40°C for 24 hours while still pressed together, to obtain a breathable waterproof material with a backing material (second fabric).

[0075] Example 1 A moisture-permeable, waterproof fabric was produced by manufacturing steps (1) to (4). However, dimethyl silicone oil (KF-96, Shin-Etsu Chemical Co., Ltd.) was used as the silicone-based water repellent in manufacturing step (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 where the coating was applied, as well as on the inner surface of the pores. In other words, it was confirmed that the silicone-based water repellent was attached to the inner surface of the pores.

[0076] Example 2 A moisture-permeable, waterproof fabric was produced by manufacturing steps (1) to (4). However, a carboxyl-modified silicone oil (X-22-3701E, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silicone-based water repellent in manufacturing step (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 where the coating was applied, as well as on the inner surface of the pores. In other words, it was confirmed that the silicone-based water repellent was attached to the inner surface of the pores.

[0077] [Example 3] The moisture-permeable waterproof fabric obtained in Example 2 was further processed in the manufacturing process (5) to obtain a moisture-permeable waterproof fabric with a non-porous hydrophilic resin layer. The distribution of the silicone-based water repellent agent 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 surface inside the pores. In other words, it was confirmed that the silicone-based water repellent agent was attached to the surface inside the pores.

[0078] [Example 4] In the manufacturing process (4), the silicone water repellent agent was applied to the outer surface at a coating amount of 60 g / m ２ The coating was applied in the same manner as in Example 3, and a moisture-permeable, waterproof fabric with a non-porous hydrophilic resin layer was obtained. The distribution of the silicone-based water repellent agent in the porous polyurethane layer was confirmed to be present on the surface on the outer side where the coating was applied, as well as on the inner surface of the pores. In other words, it was confirmed that the silicone-based water repellent agent was attached to the inner surface of the pores.

[0079] [Example 5] The moisture-permeable waterproof fabric obtained in Example 1 was further processed in the manufacturing process (5) to obtain a moisture-permeable waterproof fabric with a non-porous hydrophilic resin layer. The distribution of the silicone-based water repellent agent 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 surface inside the pores. In other words, it was confirmed that the silicone-based water repellent agent was attached to the surface inside the pores.

[0080] [Example 6] The amount of silicone water repellent applied in the production process (4) was 250 g / m ２A moisture-permeable, waterproof fabric with a nonporous hydrophilic resin layer was obtained in the same manner as in Example 5, except that the silicone-based water repellent agent was distributed in the porous polyurethane layer, and its presence was confirmed on the surface of the porous polyurethane layer where it was applied, as well as on the inner surface of the pores. In other words, it was confirmed that the silicone-based water repellent agent was attached to the inner surface of the pores.

[0081] [Example 7] The moisture-permeable waterproof fabric obtained in Example 2 was further processed in the manufacturing process (6) to obtain a moisture-permeable waterproof fabric with a backing material (second fabric).The distribution of the silicone-based water repellent agent 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 surface inside the pores.In other words, it was confirmed that the silicone-based water repellent agent was attached to the surface inside the pores.

[0082] [Example 8] The moisture-permeable waterproof fabric obtained in Example 2 is further processed in the manufacturing process (5) and (6) in this order, to obtain a moisture-permeable waterproof fabric with a non-porous hydrophilic resin layer and a backing material (second fabric).The distribution of the silicone-based water repellent agent in the porous polyurethane layer can be confirmed to be present on the surface of the porous polyurethane layer side that is applied and on the surface inside the pores.In other words, it can be confirmed that the silicone-based water repellent agent is attached to the surface inside the pores.

[0083] Comparative Example 1 A moisture-permeable waterproof fabric was produced by the production steps (1) to (3).

[0084] Comparative Example 2 A moisture-permeable, waterproof fabric was obtained in the same manner as in Comparative Example 1, except that 1 part by mass of carboxyl-modified silicone oil (X-22-3701E, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the coating resin composition in production step (2). The silicone-based water repellent agent was not unevenly distributed on the pore surfaces, but was present within the polyurethane resin. In other words, the silicone-based water repellent agent was not attached to the pore surfaces.

[0085] The moisture-permeable waterproof materials obtained in each Example and Comparative Example were measured and evaluated for the distribution of the silicone-based water repellent agent in the porous polyurethane layer, water pressure resistance (initial, after 10 washes), Suter test (after 10 washes), moisture permeability (A-1), peel strength, and the presence or absence of delamination and quality after 10 washes. The results are shown in Tables 1 and 2.

[0086]

[0087]

[0088] 1: Fabric (surface) 2: Porous polyurethane layer 3: Non-porous hydrophilic resin layer 4: Second fabric (backing material)

Claims

1. A moisture-permeable waterproof material comprising a laminate of a fabric and a porous polyurethane layer, in which a silicone-based water repellent agent is adhered to the inner pore surfaces of the porous polyurethane layer.

2. The breathable waterproof material according to claim 1, wherein the silicone-based water repellent is a modified silicone.

3. A breathable waterproof material according to claim 1 or 2, which has a water pressure resistance of 5,000 mmH2O or more after 10 washes and does not get wet in a Suter test in which a water pressure of 2,000 mmH2O is maintained for 10 minutes.

4. The moisture-permeable waterproof material according to claim 1 or 2, wherein the peel strength between the porous polyurethane layer and the fabric is 200 cN / cm or more.

5. A moisture-permeable waterproof material as described in claim 1 or 2, in which a non-porous hydrophilic resin layer and / or a second fabric is further laminated on the side of the porous polyurethane layer opposite to the side laminated to the fabric.

6. The moisture-permeable waterproof material according to claim 5, wherein there is no peeling between the porous polyurethane layer and either the nonporous hydrophilic resin layer or the second fabric which is in contact with the porous polyurethane layer.

7. The moisture-permeable waterproof material according to claim 5, which has a water pressure resistance of 10,000 mmH2O or more after 10 washes.

8. A method for producing a moisture-permeable waterproof material in which a porous polyurethane layer and a fabric are laminated, the method including a step of adhering a silicone-based water repellent to the side of a laminate sheet in which the porous polyurethane layer and the fabric are laminated, opposite the side on which the porous polyurethane layer is laminated with the fabric.

9. The method for producing the moisture-permeable waterproof material according to claim 8, wherein a coating method is used in the step of adhering the silicone-based water repellent agent.