Moisture-permeable waterproof raw material and method for manufacturing moisture-permeable waterproof raw material

Abstract

The objective of this invention is to provide a non-fluorinated, waterproof, and breathable fiber product that does not use fluorine compounds, possesses high water resistance and wash durability, and maintains sufficient adhesion even when further laminated with a waterproof membrane or lining material, resulting in excellent wear durability. This invention is a breathable and waterproof raw material, which is a breathable and waterproof raw material obtained by laminating fabric with a porous polyurethane layer, wherein an organosilicon-based water-repellent agent is attached to the inner surface of the pores of the porous polyurethane layer.

Description

Technical Field

[0001] This invention relates to a breathable and waterproof processed fabric suitable for use in raincoats such as sportswear, and a method for manufacturing the same. Background Technology

[0002] Conventional wet-coating methods for creating breathable and waterproof fabrics primarily involve dissolving polyurethane resin in a water-soluble solvent, further mixing in a fluorinated water-repellent agent, and then coating the fabric to induce wet gelation. When the solvent is replaced by water, the resulting porous polyurethane film containing the fluorinated water-repellent agent forms on the fabric, preventing the permeability of rain or other water, but allowing the permeability of moisture (water vapor). Such breathable and waterproof fabrics are described, for example, in Patent Documents 1 and 2.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 60-47954

[0006] Patent Document 2: Japanese Patent Application Publication No. 11-131373 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] Although recent regulatory trends require the absence of fluorinated compounds, simply replacing fluorinated water repellents with non-fluorinated ones does not achieve the same level of performance.

[0009] The present invention is made in view of the above circumstances, and its object is to provide a non-fluorinated waterproof and breathable fiber product that has high waterproofness, washability and durability, and can achieve sufficient adhesion even when further bonding membranes and lining materials to the waterproof surface, and has excellent wear durability.

[0010] Methods for solving problems

[0011] The inventors conducted in-depth research to solve the aforementioned problems, and as a result, completed this invention. This invention has the following structure.

[0012] (1) A breathable and waterproof raw material, which is obtained by laminating a fabric and a porous polyurethane layer, wherein an organosilicon-based water repellent is attached to the inner surface of the pores of the porous polyurethane layer.

[0013] (2) According to the breathable and waterproof raw material described in (1), the above-mentioned organosilicon water repellent is a modified organosilicon.

[0014] (3) The breathable and waterproof raw material according to (1) or (2) has a water pressure resistance of more than 5,000 mmH2O after 10 washes and does not leak water in the Suter test where the water pressure is maintained at 2,000 mmH2O for 10 minutes.

[0015] (4) According to any one of (1) to (3), the moisture-permeable and waterproof raw material, the peel strength between the porous polyurethane layer and the fabric is 200 cN / cm or more.

[0016] (5) According to any one of (1) to (4), a non-porous hydrophilic resin layer and / or a second fabric are further laminated on the side of the porous polyurethane layer opposite to the side of the fabric on which the above-mentioned fabric is laminated.

[0017] (6) According to the breathable and waterproof raw material described in (5), the porous polyurethane layer and the non-porous hydrophilic resin layer do not peel off.

[0018] (7) The breathable and waterproof raw material according to claim 5 has a water pressure resistance of more than 10,000 mmH2O after 10 washes.

[0019] (8) A method for manufacturing a breathable and waterproof material, which is a method for manufacturing a breathable and waterproof material obtained by laminating a porous polyurethane layer and a fabric, comprising the following steps: attaching an organosilicon-based water-repellent agent to the side of the laminate formed by laminating the porous polyurethane layer and the fabric, opposite to the side of the fabric laminate.

[0020] (9) According to the manufacturing method of the breathable and waterproof raw material described in (8), a coating method is used in the process of attaching the above-mentioned organosilicon water repellent.

[0021] The effects of the invention

[0022] Although the fiber products of the present invention do not use fluorine compounds, they have water pressure resistance with high wash durability, and can also obtain sufficient peel strength to withstand wear when a non-porous resin layer or lining material is laminated onto a porous membrane surface. Attached Figure Description

[0023] Figure 1 This is a cross-sectional view showing the composition of a breathable and waterproof fiber raw material according to an embodiment of the present invention.

[0024] Figure 2 This is a cross-sectional view showing the composition of a breathable and waterproof fiber raw material according to an embodiment of the present invention.

[0025] Figure 3 This is a cross-sectional view showing the composition of a breathable and waterproof fiber raw material according to an embodiment of the present invention.

[0026] Figure 4 This is a cross-sectional view showing the composition of a breathable and waterproof fiber raw material according to an embodiment of the present invention. Detailed Implementation

[0027] The present invention will be described in further detail below.

[0028] The breathable and waterproof raw material of the present invention is obtained by laminating a porous polyurethane layer with a fabric.

[0029] Raw materials for the useful fibers constituting the aforementioned fabrics include polyester, nylon, acrylic fibers, polyurethane, or rayon such as acetate fibers and viscose. Furthermore, chemical fibers such as polylactic acid, aromatic polyamide, polyimide, or polyphenylene sulfide, natural fibers such as cotton, linen, silk, or wool, or blends, blends, interweaves, or cross-knits of these raw materials can also be used. Among these, substances containing polyester or nylon are preferred as raw materials for the fibers. From the viewpoint of dye migration and sublimation into the coated polyurethane resin, nylon-based fibers dyed with acid dyes are preferred. From the viewpoint of water pressure resistance, moisture permeability, and other properties, synthetic fibers based on polyester or olefins, or blends and blends with natural fibers can also be used.

[0030] Furthermore, the fibers constituting the aforementioned fabric can be either long fibers or short fibers. Additionally, the yarn used can be any of raw silk (flat yarn), plied yarn, and processed yarn. There are no particular limitations on the processed yarn; false-twist processed yarn (wool-like processed yarn, DTY, modified false-twist processed yarn, etc.), pressed processed yarn, shaped processed yarn, brushed processed yarn, taslan processed yarn, yarn length aligned processed yarn, composite processed yarn, hairy processed yarn, interwoven bundled yarn, interwoven blended yarn, etc., can be used. From the viewpoint of increasing water repellency by attaching a large amount of silicone-based water-repellent agent to the fiber surface and improving tear strength, processed yarn is preferred.

[0031] The attached diagram schematically shows a cross-sectional view of the above-mentioned fabric as a woven fabric, but it may also be a knitted fabric or a non-woven fabric.

[0032] The breathable and waterproof raw material of the present invention can also be coated with a water-repellent agent that does not contain fluorine compounds, such as an organosilicon-based water repellent agent, on the aforementioned fabric.

[0033] The timing for applying water-repellent treatment to the aforementioned fabric is preferably before laminating the porous polyurethane layer. Specifically, for example, 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, penetrant, or pH adjuster can be used. The water-repellent treatment is performed by padding, spraying, or similar methods, followed by drying and curing. Furthermore, it is preferable to impart properties that achieve a rating of 4 or higher before washing and 3 or higher after 20 washes in the JIS L1092 spray test.

[0034] Figure 1 The breathable and waterproof raw material shown is a fabric layered with a porous polyurethane layer that does not contain fluorine compounds.

[0035] It should be noted that the porous structure of the polyurethane resin shown in the attached figure is merely schematic, and the shape and size are not limited to this structure.

[0036] The polyurethane that forms the porous polyurethane layer is preferably obtained by reacting a polyol compound (A) having at least two hydroxyl groups that are reactive with isocyanate groups, 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 polar solvent (D) that is soluble in water, and stopping the polymerization using a reaction stopper (E).

[0037] The polyurethane mentioned above can be a polyurethane consisting only of urethane bonds, or it can be a polyurethane-polyurea resin containing urea bonds.

[0038] Examples of the aforementioned polyol compound (A) include, for example, polyester polyols having ester bonds, polyether polyols having ether bonds, and polycarbonate polyols having carbonate groups.

[0039] Examples of the aforementioned isocyanate compound (B) include, for example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, hexamethylene diisocyanate (HMDI), phenyl diisocyanate (XDI), tetramethylphenyl diisocyanate (TMXDI), isophorone diisocyanate (IPDI), hydrogenated MDI, etc.

[0040] Examples of chain extenders (C) include ethylene glycol, 1,4-butanediol, 1,3-butanediol (1,3-butylene diol), neopentyl glycol, 1,5-pentanediol, methylpentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol, as well as alicyclic diols such as 1,4-cyclohexanediol and hydrogenated benzenediethanol, and aromatic diols such as benzenediethanol.

[0041] There are no particular limitations on the polar solvent (D) mentioned above, but solvents that readily dissolve isocyanate compounds (B) are preferred, such as dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).

[0042] The reaction stopper (E) described above is used in polyurethane polymerization to stop polymerization at a target viscosity by reacting with the ends of the chemical structure. The reaction stopper (E) can be mono- and polyols, monoamines, etc. Examples include mono- and polyols (methanol, ethanol, butanol, propylene glycol, higher alcohols, higher fatty acid esters with hydroxyl groups, etc.) and monoamines (methylamine, butylamine, etc.).

[0043] Regarding each of the above components (A) to (E), they can be used individually or in combination of two or more.

[0044] During the above polyurethane polymerization, the reaction temperature can be the same as that commonly used in urethane esterification reactions, typically 30~90℃ when using a polar solvent (D).

[0045] As a method for laminating the porous polyurethane layer onto the fabric, a polyurethane solution containing the polyurethane can be directly coated onto the surface of the fabric and wet-cured, or a sheet of porous polyurethane layer can be made by wet curing after coating onto a substrate other than the fabric, and then the sheet can be bonded to the surface of the fabric.

[0046] As a method for coating the polyurethane solution onto the fabric or substrate, any method commonly referred to as direct coating can be used, such as knife coating, knife overroll coating, or reverse roller coating.

[0047] When fabricating the porous polyurethane layer sheet, any substrate that allows the sheet to be peeled off can be used; for example, a fabric different from the fabric itself, release paper, etc., can be used. After forming the sheet, an adhesive can be applied to its surface to bond it to the fabric. After the adhesive cures, a waterproof fabric can be obtained by peeling off the substrate.

[0048] The breathable and waterproof raw material of the present invention has an organosilicon-based water-repellent agent attached to the inner surface of the pores of the above-mentioned porous polyurethane layer.

[0049] Straight silicone oil and modified silicone oil can be used as the aforementioned organosilicon-based water repellents.

[0050] Examples of linear silicone oils include dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil.

[0051] Examples of modified silicone oils include substances obtained by modifying linear silicone oils with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol, etc.

[0052] Among modified silicone oils, reactive silicone oils with intramolecular reactive groups are preferred, and carboxyl-modified silicone oils are preferred from the viewpoint of imparting adhesion and water repellency.

[0053] Examples of organosilicon compounds used as the aforementioned organosilicon-based water repellents include substances disclosed in Japanese Patent Application Publication No. 2017-218713, Japanese Patent Application Publication No. 2017-226946, Japanese Patent Application Publication No. 2017-155095, and Japanese Patent Application Publication No. 2017-218713.

[0054] Furthermore, commercially available examples of organosilicon compounds used as the aforementioned organosilicon-based water repellents include, for instance... (Registered Trademark) SH (Matsumoto Oils Co., Ltd.) (Registered Trademark) 600E (manufactured by Nichika Chemical Co., Ltd.) SG-54 (Riken Miki Kogyo Co., Ltd.) P-290E ( (Co., Ltd.), (Registered Trademark) MR (Shin-Etsu Chemical Industry Co., Ltd.) (Registered Trademark) MF-49 (Shin-Etsu Chemical Industry Co., Ltd.) (Registered Trademarks) NR8000 (Nihon Ka Chemical Co., Ltd.), KF-96 series (Shin-Etsu Chemical Industry Co., Ltd.), KF8005 (Shin-Etsu Chemical Industry Co., Ltd.), KF8010 (Shin-Etsu Chemical Industry Co., Ltd.), KF4003 (Shin-Etsu Chemical Industry Co., Ltd.), X-22-3701E (Shin-Etsu Chemical Industry Co., Ltd.), SF-8417 ( (Co., Ltd.), BY16-880( (plant)), MQ-1600 (plant) etc.

[0055] The breathable and waterproof raw material of the present invention can be efficiently obtained, for example, by attaching an organosilicon-based water-repellent agent to the side of the porous polyurethane layer opposite to the side of the fabric layer of the laminated sheet formed by laminating the porous polyurethane layer and the fabric. That is, the method for manufacturing the breathable and waterproof raw material of the present invention is a method for manufacturing a breathable and waterproof raw material comprising a porous polyurethane layer and a fabric, comprising the following steps: attaching an organosilicon-based water-repellent agent to the side of the porous polyurethane layer opposite to the side of the fabric layer of the laminated sheet formed by laminating the porous polyurethane layer and the fabric.

[0056] As a method for adhering the silicone-based water repellent, it can be directly coated onto the aforementioned porous polyurethane layer, or it can be coated from the fabric side. Considering the efficient penetration of the silicone-based water repellent, direct coating onto the aforementioned porous polyurethane layer is preferred.

[0057] As a method for imparting the above-mentioned organosilicon-based water repellent, various methods that can perform single-sided treatment, such as gravure coating, cylinder roll coating, spraying, and kiss coating, can be selected.

[0058] From the perspective of improving water resistance, the breathable and waterproof raw material of the present invention preferably has a non-porous hydrophilic resin layer and / or a second fabric further laminated on the side opposite to the side of the porous polyurethane layer to which the fabric is laminated.

[0059] Figure 2 This indicates an effort to further improve Figure 1 The method shown is to add a non-porous hydrophilic resin layer to the breathable and waterproof raw material for the purpose of water pressure resistance.

[0060] The aforementioned non-porous hydrophilic resin layer preferably uses a hydrophilic polyurethane resin in which at least one of polyethylene glycol and polypropylene glycol is present in 20-60 mol% of the polyol component. A polyurethane resin in which polyethylene glycol is present in 20-60 mol% of the polyol component is particularly preferred. There are no particular limitations on other polyol components; for example, polyester glycol, polycarbonate glycol, and other polyether glycols can be used. As the polyisocyanate component constituting the hydrophilic polyurethane resin, known aliphatic and aromatic polyisocyanates can be used, such as hexamethylene diisocyanate, toluene diisocyanate, phenylenediamine diisocyanate, isophorone diisocyanate, and 4,4'-diphenylmethane diisocyanate.

[0061] The aforementioned hydrophilic nonporous membrane preferably possesses heat-welding properties. By possessing heat-welding properties, the hydrophilic nonporous membrane can be uniformly and tightly bonded without dissolving the microporous membrane. The heat-welding property is acquired through the use of low-melting-point raw materials and crosslinking agents.

[0062] The thickness of the aforementioned hydrophilic nonporous membrane is preferably 1 to 10 μm.

[0063] The aforementioned non-porous hydrophilic resin layer can be laminated with a highly permeable membrane using moisture-curing polyurethane hot melt adhesives, or a highly permeable resin can be coated onto the entire surface. Additionally, to improve the feel of the porous resin layer surface, partial printing can be used.

[0064] Examples of methods for forming the aforementioned non-porous hydrophilic resin layer include, for example, directly coating it onto the aforementioned porous polyurethane layer, pre-coating it onto release paper, and forming a film using an extrusion method.

[0065] Figure 3 In order to protect Figure 1 The porous polyurethane layer of the breathable and waterproof raw material shown is further bonded to the second fabric (lining material). Additionally, Figure 4 Indicates in Figure 2 The non-porous hydrophilic resin layer shown is further bonded to the fabric layer.

[0066] Figure 3 , Figure 4 The second piece of fabric is shown as a knitted fabric, but the use of woven or non-woven fabrics is not limited.

[0067] The second type of fabric mentioned above can be made of various synthetic fiber plain weave fabrics (taffeta), twill fabrics, satin fabrics, and other special fabrics or knitted fabrics, and can also be made of various greige fabrics and non-woven fabrics made of natural fibers and semi-synthetic fibers. Among these, nylon tricot warp-knitted fabrics are preferred in terms of feel and other factors.

[0068] In the case of the second fabric described above, the timing for attaching the silicone-based water repellent to the porous polyurethane layer can be either before or after bonding the second fabric layer, but from the viewpoint of efficiently applying the silicone-based water repellent to the porous polyurethane layer, it is preferable to apply it before bonding.

[0069] In breathable and waterproof raw materials further laminated with the aforementioned non-porous hydrophilic resin layer and / or a second fabric, it is preferable that no peeling occurs between the aforementioned porous polyurethane layer and the aforementioned non-porous hydrophilic resin layer or the second fabric adjacent to the aforementioned porous polyurethane layer. In this invention, peeling (delamination) refers to the phenomenon where the non-porous hydrophilic resin layer detaches or floats from the porous polyurethane layer during washing.

[0070] The breathable and waterproof raw material of the present invention preferably has a peel strength of 200 cN / cm or higher between the porous polyurethane layer and the fabric. The peel strength is measured according to the test method of JIS L1086 (2020).

[0071] The breathable and waterproof raw material of this invention preferably has a water pressure resistance of 5,000 mmH2O or higher after 10 washes, and does not leak water in a Suter test held at 2,000 mmH2O for 10 minutes. The water pressure resistance test in this invention is based on the test method described in JIS L1092:2020 Method B (High Water Pressure Method). The Suter test is a method for evaluating the waterproofness of the membrane by using a simple water pressure testing machine to maintain a water pressure of 2000 mmH2O for 10 minutes. The presence or absence of wettability of the membrane after 10 minutes is used to determine the waterproofness.

[0072] The breathable and waterproof raw material further laminated with the above-mentioned non-porous hydrophilic resin layer and / or a second fabric is preferably resistant to water pressure of 10,000 mmH2O or more after 10 washes.

[0073] The breathable and waterproof raw material of the present invention has excellent wash-resistant and durable water pressure resistance and excellent adhesion at each interface. For example, it can be used as raw fabric for various products that require breathability, waterproofness and durability, such as rain gear, clothing, shoes, bags, tents and other outdoor products.

[0074] Example

[0075] The following describes embodiments of the present invention. It should be noted that the present invention is not limited to the embodiments shown below.

[0076] [Measurement and Evaluation Methods]

[0077] The following describes the testing and evaluation methods. It should be noted that in the case of breathable and waterproof raw materials with a non-porous hydrophilic resin layer, a lining material (second fabric), or a non-porous hydrophilic resin layer and a lining material (second fabric), the non-porous hydrophilic resin layer and / or the lining material (second fabric) are included as the objects of testing and evaluation.

[0078] (1) Distribution of organosilicon-based water repellent in porous polyurethane layer

[0079] The cross-section of the breathable and waterproof raw material was observed at 2000x using a scanning electron microscope (SEM), and the presence and distribution of Si elements in the porous polyurethane layer were confirmed by energy dispersive X-ray spectroscopy (EDX).

[0080] (2) Water pressure resistance

[0081] The test was conducted according to JIS L1092:2020 Method B (High Water Pressure Method). During the test, to suppress the elongation of the breathable and waterproof raw material being tested, a nylon-lined white fabric used in the color fastness test was used as the taffeta cover. To determine the water pressure resistance after 10 washes, the C4M method of JIS L1930 (Practical Machine Test Method) was used for repeated washing 10 times, followed by the water pressure test.

[0082] (3) Presence or absence of seepage based on the Suter test

[0083] The breathable and waterproof raw material was repeatedly washed 10 times using the C4M method according to JIS L1930 (Practical Machine Test Method). A simple water pressure tester was used to apply a water pressure of 2000 mmH2O to the fabric side of the breathable and waterproof raw material and maintain it for 10 minutes. After 10 minutes, it was checked whether the opposite side of the fabric was wetted. Cases where no film wetting was confirmed were rated as "A", and cases where film wetting was confirmed were rated as "B".

[0084] (4) Moisture permeability

[0085] The determination was performed according to JIS L1099:2021 A-1 method (calcium chloride method).

[0086] (5) Peel strength

[0087] The tests were conducted in accordance with JIS L1086:2020 Test Methods for Bonded Core Fabric and Bonded Fabric.

[0088] (6) Presence or absence of peeling (layering)

[0089] The evaluation was conducted using the C4M method (JIS L1930, Practical Machine Test Method) to repeatedly wash breathable and waterproof raw materials with a non-porous hydrophilic resin layer, a lining material (second fabric), or both a non-porous hydrophilic resin layer and a lining material (second fabric) 10 times. The evaluation was performed by visually inspecting whether the non-porous hydrophilic resin layer or the lining material (second fabric) adhering to the porous polyurethane layer peeled off or floated up from the porous polyurethane layer. If there was no floating or peeling, it was marked as "no delamination".

[0090] (7) Quality of breathable and waterproof raw materials

[0091] The presence of resin used to form the porous polyurethane layer that has seeped into the fabric and onto the back side, thus damaging the fabric quality (backside penetration, exposed base material), was visually inspected and evaluated. Based on suitability for the garment, cases where resin penetration to the back side was confirmed were rated "B," and cases where it was not confirmed were rated "A."

[0092] [Manufacturing Process]

[0093] (1) Preparation of fabrics

[0094] Nylon tear-resistant taffeta, composed of 50 denier (56 dtex) nylon filament yarn, was scourted and dyed using conventional methods. The fabric was then immersed in a 30 g / L diluted solution of a non-fluorine water-repellent agent (Nichika Chemical Co., Ltd. NR-7200), and rolled using a rolling mill to achieve a rolling yield of 40%. Finally, it underwent a heat-setting process at 150°C for 30 seconds to produce the fabric.

[0095] (2) Preparation of polyurethane resin composition for coating

[0096] Polycarbonate polyol (hexamethylene carbonate diol), polyether polyol (polytetramethylene diol), 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 polyurethane resin concentration of 25.0% and a viscosity of 82000 mPa·s (30℃).

[0097] Add silica micropowder to 80 parts by mass of the obtained polycarbonate-based polyurethane resin solution. system," (Registered trademark) MT-10, 5 parts by weight of fumed silica of dimethyl dichlorosilane, were thoroughly impregnated with 50 parts by weight of DMF, dispersed and stirred in a homogenizer for about 15 minutes, and then stirred to obtain a liquid polyurethane resin composition for coating containing polycarbonate-based polyurethane resin.

[0098] (3) Coating of polyurethane resin

[0099] Using a doctor blade roller coater with a coating amount of 150 g / m² 2 The above-mentioned water-repellent fabric is coated with the above-mentioned coating resin composition, and then immersed in a gelation bath containing an aqueous solution of DMF at 30°C for 2 minutes to wet-coagulate the liquid composition of polycarbonate-based polyurethane resin. Then, it is washed with hot water at 80°C for 10 minutes and dried with hot air at 140°C to obtain a breathable and waterproof raw material with a porous polyurethane layer laminated on the fabric.

[0100] (4) Organosilicon water-repellent treatment

[0101] On the surface of the porous polyurethane layer of the breathable and waterproof raw material obtained in (3) above, a gravure roller is used to coat it with a coating amount of 30 g / m. 2 A silicone-based water-repellent agent is applied to penetrate the porous polyurethane layer. After drying at 120°C, a heat treatment at 150°C for 30 seconds is performed.

[0102] (5) Lamination of non-porous hydrophilic resin film

[0103] A polyurethane solution was prepared using the composition shown in Formula 1 below.

[0104] (Prescription 1)

[0105] Polyether-based polyurethane U-6285M ( (Co., Ltd.) (Registered Trademark) U-6285M) 100 parts by weight

[0106] MEK 50 parts by weight

[0107] 50 parts by weight of toluene.

[0108] The above-mentioned polyurethane solution was applied to the release paper using a doctor blade roller coater with a gap of 50 μm. (EV130TPD) was applied. Then, it was hot-air dried at 80°C to obtain a non-porous hydrophilic resin film with a thickness of 5 μm.

[0109] The porous polyurethane layer of the breathable and waterproof raw material described in (4) above is superimposed with the above-mentioned non-porous hydrophilic resin film, and the mixture is then heat-laminated at a temperature of 120°C and a pressure of 0.9807 MPa (10 kg / cm²). 2 The material was laminated at a speed of 20 m / min to obtain a breathable and waterproof raw material with a non-porous hydrophilic resin layer (represented as "HB" in the table).

[0110] (6) Lining material bonding

[0111] Nylon Trico warp-knitted fabric (18d warp-pile plain weave: W×C=36×40) was used as the lining material (second fabric).

[0112] On the porous polyurethane layer of the breathable and waterproof raw material after (4) above, or the non-porous hydrophilic resin layer of the breathable and waterproof raw material after (5) above, polyurethane hot melt adhesive (product number: LA7575UV) is coated using a 30-mesh gravure roller, dried with hot air at 100°C, and then bonded with lining material. Under the pressing condition, it is cured at 40°C for 24 hours to obtain a breathable and waterproof raw material with lining material (second fabric).

[0113] [Example 1]

[0114] The breathable and waterproof fabric was manufactured through manufacturing processes (1) to (4). Dimethyl silicone oil (Shin-Etsu Chemical Industry 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 on both the surface of the coated porous polyurethane layer and the inner surface of the pores. Specifically, silicone-based water repellent was found to be attached to the inner surface of the pores.

[0115] [Example 2]

[0116] A breathable and waterproof fabric was manufactured through manufacturing processes (1) to (4). In process (4), a carboxyl-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd. X-22-3701E) was used as the silicone-based water repellent. The distribution of the silicone-based water repellent in the porous polyurethane layer was confirmed on both the surface of the coated porous polyurethane layer and the inner surface of the pores. Specifically, the silicone-based water repellent was found to be attached to the inner surface of the pores.

[0117] [Example 3]

[0118] The breathable and waterproof fabric obtained in Example 2 was further processed using manufacturing step (5) to obtain a breathable and waterproof fabric with a non-porous hydrophilic resin layer. Regarding the distribution of the silicone-based water-repellent agent in the porous polyurethane layer, its presence was confirmed on both the surface of the coated porous polyurethane layer and the inner surface of the pores. That is, it was confirmed that a silicone-based water-repellent agent was attached to the inner surface of the pores.

[0119] [Example 4]

[0120] Apply a coating of 60 g / m² to the side of the fabric. 2 The silicone water-repellent agent in manufacturing step (4) was applied. Otherwise, the process was the same as in Example 3, resulting in a breathable and waterproof fabric with a non-porous hydrophilic resin layer. The distribution of the silicone water-repellent agent in the porous polyurethane layer was confirmed on both the coated fabric surface and the inner pore surface. Specifically, silicone water-repellent agent was found to be attached to the inner pore surface.

[0121] [Example 5]

[0122] The breathable and waterproof fabric obtained in Example 1 was further processed using manufacturing step (5) to obtain a breathable and waterproof fabric with a non-porous hydrophilic resin layer. Regarding the distribution of the silicone-based water-repellent agent in the porous polyurethane layer, its presence was confirmed on both the surface of the coated porous polyurethane layer and the inner surface of the pores. That is, it was confirmed that a silicone-based water-repellent agent was attached to the inner surface of the pores.

[0123] [Example 6]

[0124] The coating amount of the silicone water-repellent agent in manufacturing process (4) is set to 250 g / m. 2 Otherwise, the procedure was the same as in Example 5 to obtain a breathable and waterproof fabric with a non-porous hydrophilic resin layer. Regarding the distribution of the silicone-based water-repellent agent in the porous polyurethane layer, its presence was confirmed on both the surface of the coated porous polyurethane layer and the inner surface of the pores. That is, it was confirmed that a silicone-based water-repellent agent was adhered to the inner surface of the pores.

[0125] [Example 7]

[0126] The breathable and waterproof fabric obtained in Example 2 was further processed using manufacturing step (6) to obtain a breathable and waterproof fabric with a lining material (second fabric). Regarding the distribution of the silicone-based water-repellent agent in the porous polyurethane layer, its presence was confirmed on both the surface of the coated porous polyurethane layer and the inner surface of the pores. That is, it was confirmed that a silicone-based water-repellent agent was attached to the inner surface of the pores.

[0127] [Example 8]

[0128] The breathable and waterproof fabric obtained in Example 2 was further processed by manufacturing steps (5) and (6) in sequence to obtain a breathable and waterproof fabric with a non-porous hydrophilic resin layer and a lining material (second fabric). Regarding the distribution of the silicone-based water repellent in the porous polyurethane layer, its presence was confirmed on the surface of the coated porous polyurethane layer and the inner surface of the pores. That is, it was confirmed that the silicone-based water repellent was attached to the inner surface of the pores.

[0129] [Comparative Example 1]

[0130] The breathable and waterproof fabric is manufactured through manufacturing processes (1) to (3).

[0131] [Comparative Example 2]

[0132] In manufacturing step (2), 1 part by weight of carboxyl-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd. X-22-3701E) was added to the coating resin composition, and the process was otherwise the same as in Comparative Example 1 to obtain a breathable and waterproof fabric. Regarding the distribution of the silicone-based water repellent in the porous polyurethane layer, it was not found to be concentrated on the inner surface of the pores, but rather within the polyurethane resin. That is, no silicone-based water repellent was attached to the inner surface of the pores.

[0133] Regarding the breathable and waterproof raw materials obtained in each embodiment and comparative example, the distribution of silicone-based water repellent in the porous polyurethane layer, water pressure resistance (initial and after 10 washes), Suter test (after 10 washes), moisture permeability (A-1), peel strength, presence or absence of delamination after 10 washes, and quality were measured and evaluated. The results are shown in Tables 1 and 2.

[0134] [Table 1]

[0135]

[0136] [Table 2]

[0137]

[0138] Explanation of symbols

[0139] 1: Cloth (fabric)

[0140] 2: Porous polyurethane layer

[0141] 3: Non-porous hydrophilic resin layer

[0142] 4: Second fabric (lining material).

Claims

1. A moisture-permeable waterproof raw material obtained by laminating a cloth and a porous polyurethane, wherein, An organosilicon-based water-repellent agent is attached to the inner surface of the pores of the porous polyurethane layer.

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

3. The breathable and waterproof raw material according to claim 1 or 2 has a water pressure resistance of more than 5,000 mmH2O after 10 washes and does not leak water in a Suter test where the water pressure is maintained at 2,000 mmH2O for 10 minutes.

4. The breathable and waterproof raw material according to claim 1 or 2, wherein the peel strength between the porous polyurethane layer and the fabric is above 200 cN / cm.

5. The breathable and waterproof raw material according to claim 1 or 2, wherein a non-porous hydrophilic resin layer and / or a second fabric are further laminated on the side of the porous polyurethane layer opposite to the side on which the fabric is laminated.

6. The breathable and waterproof raw material according to claim 5, wherein no peeling occurs between the porous polyurethane layer and the non-porous hydrophilic resin layer or the second fabric in contact with the porous polyurethane layer.

7. The breathable and waterproof raw material according to claim 5 has a water pressure resistance of 10,000 mmH2O or higher after 10 washes.

8. A method for manufacturing a breathable and waterproof raw material, comprising the following steps: attaching an organosilicon-based water-repellent agent to the side of the porous polyurethane layer opposite to the fabric layer of the laminate formed by the porous polyurethane layer and the fabric.

9. The method for manufacturing the breathable and waterproof raw material according to claim 8, wherein a coating method is used in the process of adhering the organosilicon-based water-repellent agent.

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