JP5725243B2 - Breathable tarpaulin - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention is used as a foundation for building materials (trunk edges, piers, etc.) containing insect repellents and / or preservatives (hereinafter sometimes simply referred to as “insect repellents / preservatives”). The present invention relates to a moisture permeable waterproof sheet (such as a moisture permeable waterproof sheet for a dry construction method) that can effectively prevent the intrusion of and the like.

  The outer wall of a building or structure such as a house is often finished with a dry construction method because the construction period can be shortened compared with the wet construction method. Dry type outer walls such as siding are constructed by a ventilation method for the purpose of preventing indoor condensation. In this ventilation method, in order to release moisture efficiently, a moisture-permeable waterproof sheet (a sheet that allows water vapor to pass but not water) is applied to the outdoor surface of the heat insulating material. On this surface, siding (finishing material) is applied via a plurality of long thin wooden boards (trunk edges) arranged at intervals. Therefore, a ventilation layer is formed between the moisture permeable waterproof sheet and the siding, and water vapor in the wall can be discharged to the outside, and condensation can be prevented.

As the moisture permeable waterproof sheet, for example, in Japanese Laid-8-209867 (Patent Document 1), a flash spinning method three-dimensional network fibers nonwoven having a basis weight 60~200g / ^{m 2,} proportional to the basis weight of 100 g / ^{m 2} A nonwoven fabric is disclosed which has a converted pure curvature value of at least 1.0 gf · cm ² / cm and is formed so that the light transmittance at a wavelength of 400 nm does not exceed 5%. This document describes an example of producing a nonwoven fabric by flash spinning high density polyethylene. Further, this document describes that a non-woven fabric may be adhered or impregnated with a water-repellent agent such as a fluorine-based material, a silicon-based material, or a wax-based material in order to improve water repellency.

  Japanese Patent Application Laid-Open No. 2007-332482 (Patent Document 2) discloses that at least one surface of a fabric formed of nylon fiber or the like and subjected to an aqueous water repellent treatment is formed of an aqueous resin such as polyurethane. A moisture permeable waterproof fabric in which a film having moisture and waterproof properties is laminated, wherein the water repellent is a water / oil repellent containing a polyfluoroalkyl group as a component, and perfluorooctane contained in 1 g of the fabric A moisture-permeable waterproof fabric with an acid of 10 ng / g or less is disclosed. This document describes that a film formed of an aqueous resin may be a microporous film.

  In June 2009, the Ministry of Land, Infrastructure, Transport and Tourism enacted the “Law on Promotion of the Spread of Long-Term Excellent Houses”, and if it was certified as a long-term excellent house, it would be preferential for taxation and financing. In order to receive this preferential treatment, it is necessary to ant and antiseptically treat the trunk edge. However, if the trunk edge subjected to the ant / antiseptic treatment is exposed to a large amount of rainwater, the waterproof property of the moisture permeable waterproof sheet is lowered.

JP-A-8-209867 (Claims, paragraph [0018], Examples) JP 2007-332482 A (claim, paragraph [0048], example)

  Accordingly, an object of the present invention is to provide a moisture-permeable waterproof sheet that is excellent in water repellency even when used as a foundation for building materials (instrument edges, piers, etc.) containing an insecticide / preservative (or surfactant). is there.

  Another object of the present invention is to provide a moisture permeable waterproof sheet that can improve water repellency without impairing moisture permeability.

  Still another object of the present invention is to provide a moisture-permeable waterproof sheet that is excellent in nail hole water-stopping properties (nail hole sealing properties).

  The moisture-permeable waterproof sheet has a large number of pores (or voids), and water vapor (such as moisture inside the building or structure) can pass through the pores, but water droplets (rain water, snow water, dew, etc.) ) Makes it possible to achieve both moisture permeability and waterproofness by utilizing the fact that it cannot pass through the pores due to surface tension. However, as described in the Background Art section, when a building material (such as a trunk edge) that has been subjected to ant / antiseptic treatment is exposed to rainwater, the waterproof property of the conventional moisture-permeable waterproof sheet is lowered. One reason for this is that surfactants are included in order for the ant and preservatives to penetrate into the building materials efficiently. If the building materials are exposed to rainwater, etc., the ant / preservatives containing the surfactants It is conceivable that the surface tension of water decreases, water droplets become finer and pass through the pores because of elution.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have conducted surface treatment with a treatment agent containing a specific fluorine compound on a porous hydrophobic resin sheet or hydrophobic nonwoven fabric, thereby preventing insects and antiseptics. This is because the surface energy of the sheet or nonwoven fabric can be made smaller than the surface energy of water containing an agent (or surfactant), and the passage of pores of water containing an insecticide / preservative (or surfactant) can be suppressed. The present invention has been completed by finding that the water repellency can be greatly improved even when used as a foundation for building materials containing an insecticide / preservative (or surfactant).

That is, the moisture-permeable waterproof sheet of the present invention is used as a base of a building material (for example, trunk edge, pier) containing an insect repellent and / or a preservative, and is a porous hydrophobic resin sheet (for example, a polyethylene resin sheet). ) Or a hydrophobic non-woven fabric (for example, polyethylene non-woven fabric), has a moisture permeability resistance of 0.19 m ² · s · Pa / μm or less, and is surface-treated with a treating agent containing a fluorine compound. Contains layers. The fluorine compound is a fluoroalkane in which a radical polymerizable group and / or a hydrolytic condensable group are connected via a direct bond or a linker, for example, fluoro C _1-12 alkyl (meth) acrylate, fluoro C _1-12 alkyl C _{1. It} may be at least one selected from _-4 alkoxysilane and fluoro C _1-12 alkylhalosilane. The fluorine compound may have about 4 to 8 carbon atoms substituted with fluorine atoms.

  The moisture permeable waterproof layer may be composed of a hydrophobic resin sheet having an average pore diameter of 0.5 to 100 μm. You may form at least 1 type of functional layer selected from the reinforcement layer, the slip-proof layer, and the heat-insulating layer in the at least one surface of the moisture-permeable waterproof layer.

  This invention also includes the method of manufacturing the moisture-permeable waterproof sheet used as a foundation | substrate of the building material containing an insect repellent and / or antiseptic | preservative. The above method is a treatment agent containing a fluorine compound, which is a fluoroalkane in which a radically polymerizable group and / or a hydrolytic condensable group are linked via a direct bond or a linker, and a solvent, and is a porous hydrophobic resin sheet or hydrophobic A step of coating or impregnating the conductive non-woven fabric and drying. In the above method, the proportion of the fluorine compound may be about 0.2 to 0.6 parts by mass with respect to 100 parts by mass of the entire treatment agent. Moreover, about 80-150 degreeC may be sufficient as drying temperature.

  The present invention also relates to a moisture permeable waterproof sheet comprising a moisture permeable waterproof layer that is used as a base material for a building material containing an insect repellent and / or a preservative and is composed of a porous hydrophobic resin sheet or a hydrophobic nonwoven fabric. A method for improving or improving water repellency is also included. This method includes a step of surface-treating the moisture-permeable waterproof layer with a treating agent containing a fluoroalkane in which a radically polymerizable group and / or a hydrolytic condensable group are linked via a direct bond or a linker.

  In this specification, the term “insect / preservative” means not only an “agent” having at least one of the insect-repellent action and antiseptic action, but also an “agent” in the form of a mixture of the insect-repellent and the preservative. "Also means.

  In the present invention, a porous hydrophobic resin sheet or a hydrophobic nonwoven fabric is surface-treated with a treatment agent containing a specific fluorine compound, so that it is used as a foundation for a building material containing an insecticide / preservative (or surfactant). However, it is excellent in water repellency. In the present invention, even if the porous film is surface-treated with a specific treatment agent, the water repellency can be improved without impairing the moisture permeability. Furthermore, in this invention, it can prevent effectively that water permeates from the clearance gap which arises in the peripheral part of a nail hole, and can improve a nail hole water stop property.

  The moisture-permeable waterproof sheet of the present invention is composed of a porous (particularly microporous) hydrophobic resin sheet or a hydrophobic non-woven fabric, and is surface-treated (coated or impregnated) with a treating agent containing a specific fluorine compound. Includes a breathable waterproof layer. Porous hydrophobic resin sheet or hydrophobic non-woven fabric can prevent the permeation of both water droplets and water vapor in the portion where pores or voids are not formed, whereas the portion where pores or voids are formed Then, since the size of water vapor is smaller than that of water droplets, water vapor can be passed without passing water droplets, and both moisture permeability and waterproofness can be achieved.

  The porous hydrophobic resin sheet is formed of a hydrophobic resin composition containing a hydrophobic resin and optionally an additive. Examples of hydrophobic resins include polyolefin resins (polyethylene resins, polypropylene resins, etc.), polystyrene resins, and the like. These hydrophobic resins may be used alone or in combination of two or more. Of these hydrophobic resins, polyethylene-based resins and polypropylene-based resins (particularly polyethylene-based resins from the viewpoint of lightness and workability) are preferable.

The polyethylene resin may be an ethylene homopolymer or an ethylene copolymer. Examples of copolymerizable monomers include α-olefins other than ethylene [eg, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 3-methylpentene, 4-methylpentene, 4-methyl- Α-C _3-10 olefins (especially α-C _3-6 olefins) such as 1-butene, 1-hexene and 1-octene], organic acid vinyl esters [for example, vinyl acetate, etc.], (meth) acrylic acid Examples thereof include alkyl esters [for example, (meth) acrylic acid C _1-6 alkyl esters such as methyl (meth) acrylate and ethyl (meth) acrylate), and combinations thereof. These copolymerizable monomers may be used alone or in combination of two or more.

  In the ethylene copolymer, the ratio (molar ratio) between ethylene and a copolymerizable monomer (for example, α-olefin other than ethylene) is the former / the latter = 50/50 to 99.9 / 0.1, Preferably it is 60 / 40-99.5 / 0.5, More preferably, it is about 70 / 30-99 / 1.

  The polyethylene resin may be, for example, low density polyethylene, medium density polyethylene, high density polyethylene, linear polyethylene (for example, linear low density polyethylene), branched polyethylene, ionomer, chlorinated polyethylene, etc. Good.

The polypropylene resin may be a propylene homopolymer or a propylene copolymer. Examples of copolymerizable monomers include α-olefins other than propylene (such as α-C _2-6 olefins other than propylene such as ethylene), organic acid vinyl esters or (meth) acrylic acid alkyl esters exemplified above, and the like. Can be illustrated. These copolymerizable monomers can be used alone or in combination of two or more.

  In the propylene-based copolymer, the ratio (molar ratio) between propylene and a copolymerizable monomer (for example, α-olefin other than propylene) is the former / the latter = 50/50 to 99.9 / 0.1, Preferably it is 60 / 40-99.5 / 0.5, More preferably, it is about 70 / 30-99 / 1.

  The polypropylene resin may be any of an isotactic body, a syndiotactic body, and an atactic body. The polypropylene resin may be a Ziegler-Natta catalyst-based polymer or a metallocene catalyst-based polymer.

  Additives include, for example, stabilizers (light stabilizers, heat stabilizers, etc.), fillers, foaming agents, flame retardants, antistatic agents, surfactants, insect repellents (anticides, etc.), preservatives (anti-proofing agents). Examples thereof include mold agents. These additives can be used alone or in combination of two or more. In the present invention, water repellency can be greatly improved even if the hydrophobic resin composition contains an additive (such as an insecticide, preservative, or surfactant) that reduces the surface tension of water.

  The hydrophobic resin sheet may be a uniaxial or biaxially stretched sheet. Further, the hydrophobic resin sheet may be a single layer sheet or a laminated sheet having two or more layers.

  The porous hydrophobic resin sheet is formed by a conventional method, for example, by forming a hydrophobic resin composition containing a hydrophobic resin and a particulate filler (calcium carbonate, silica, barium sulfate, etc.) into a sheet shape and stretching the sheet. It can be produced by a method, a method in which a hydrophobic resin composition is formed into a sheet shape, and pores are formed by laser light or punching, or a method in which a hydrophobic resin composition is foam-molded into a sheet shape.

  The average diameter of the pores of the hydrophobic resin sheet can be selected from the range of about 0.01 to 100 μm (for example, 0.05 to 50 μm), for example, 0.1 to 15 μm, preferably 0.5 to 10 μm, Preferably it is about 1-5 micrometers. If the pore diameter is too small, the moisture permeability tends to be lowered, and if the pore diameter is too large, the waterproof property tends to be lowered even if the surface treatment is performed with a treatment agent described later.

  The hydrophobic nonwoven fabric contains at least hydrophobic fibers. Examples of hydrophobic fibers include polyolefin fibers (for example, polyethylene fibers, polypropylene fibers, ethylene-propylene copolymer fibers), polystyrene fibers, fluorine fibers, combinations thereof (composite fibers, etc.), and the like. The hydrophobic fiber is a composite fiber containing non-hydrophobic fibers (hydrophilic fibers), for example, (i) a sheath core in which the sheath component is composed of hydrophobic fibers and the core component is composed of non-hydrophobic fibers. Type fibers (concentric or eccentric), (ii) sea-island fibers in which the sea component is composed of hydrophobic fibers, and the island component is composed of non-hydrophobic fibers. Non-hydrophobic fibers include polyester fibers (for example, polyethylene terephthalate fibers and polybutylene terephthalate fibers), polyamide fibers (for example, polyamide 6 fibers and polyamide 66 fibers), and acrylic fibers (such as acrylonitrile fibers). And polyurethane fibers (for example, polyether polyol type urethane fibers, polyester type urethane fibers, etc.). These hydrophobic fibers can be used alone or in combination of two or more.

  The hydrophobic nonwoven fabric is preferably a polyolefin nonwoven fabric (polyethylene nonwoven fabric, polypropylene nonwoven fabric, etc.) containing polyolefin fibers (for example, polyethylene fibers such as high density polyethylene fibers, polypropylene fibers, etc.). In addition, as a polyethylene-type fiber and a polypropylene-type fiber, the fiber etc. which were comprised by the polyethylene-type resin and the polypropylene-type resin which were respectively illustrated by the term of the hydrophobic resin sheet are mentioned.

  The hydrophobic nonwoven fabric may contain non-hydrophobic fibers (hydrophilic fibers) as long as the effects of the present invention are not impaired. The ratio of the non-hydrophobic fiber is, for example, 10 parts by mass or less, preferably 5 parts by mass or less, more preferably 1 part by mass or less (for example, 0.001 to 0.1 mass) with respect to 100 parts by mass of the hydrophobic fiber. Part degree).

  The average fineness of the fibers (such as hydrophobic fibers) constituting the hydrophobic nonwoven fabric is, for example, about 0.1 to 5 denier, preferably about 0.2 to 4 denier, and more preferably about 0.5 to 3 denier. Good. The average fiber length may be, for example, about 10 to 150 mm, preferably about 20 to 80 mm, more preferably about 30 to 60 mm. In direct spinning methods such as spunbond, melt blow, and flash spinning, the average fiber length is infinite. There may be.

  The hydrophobic nonwoven fabric (or the fiber constituting the nonwoven fabric) may contain a conventional additive, for example, the additive exemplified in the section of the hydrophobic resin composition.

  The hydrophobic nonwoven fabric can be produced through a conventional method, for example, a web forming process including the above-described fibers and a web bonding process. Specifically, spunbonding, meltblowing, flash spinning, chemical bonding, thermal bonding, It can be produced by spun lace, needle punch, stitch bond method or the like. Among these methods, the flash spinning method is preferable from the viewpoint of strength.

  Note that an embossed recess may be formed on at least a part of one side of the hydrophobic nonwoven fabric (such as a nail or staple punching portion) from the viewpoint of forming a film by partially fusing the fibers to improve waterproofness.

The moisture permeation resistance (m ² · s · Pa / μm) of the porous hydrophobic resin sheet or the hydrophobic nonwoven fabric is, for example, 0.8 mm in accordance with JIS K7129 “Test method for water vapor permeability of plastic film and sheet”. It is 2 or less, preferably 0.19 or less (for example, about 0.05 to 0.19).

  The porous hydrophobic resin sheet or hydrophobic non-woven fabric has high waterproofness because the surface tension acts and the passage of water droplets (or voids) is suppressed if it is ordinary rainwater. However, rainwater that has penetrated building materials containing insect repellents and preservatives (or surfactants) has a reduced surface tension, and water droplets become finer and easily pass through pores (or voids). Decreases. In the present invention, the surface treatment with a treating agent containing a specific fluorine compound can reduce the surface energy of the porous hydrophobic resin sheet or hydrophobic nonwoven fabric, or can greatly improve waterproofness.

The fluorine compound is a fluoroalkane in which a radically polymerizable group and / or a hydrolytic condensable group are linked via a direct bond or a linker (for example, a fluoro C _1-12 alkane, preferably a fluoro C _2-10 alkane, more preferably Fluoro C _4-8 alkane). Examples of the linker include a divalent linker such as an alkyleneoxy group optionally substituted by an oxygen atom or a fluorine atom (C _2-4 alkyleneoxy group such as ethyleneoxy group and propyleneoxy group).

Examples of the radical polymerizable group include a vinyl group which may be substituted with a fluorine atom, a (meth) acryloyl group, and the like. Examples of the hydrolytic condensable group include substituted silyl groups such as halosilyl groups (chlorosilyl groups, etc.), hydroxysilyl groups, alkoxysilyl groups (C _1-4 alkoxysilyl groups such as methoxysilyl groups, ethoxysilyl groups, etc.). And an aryloxysilyl group. In addition, the fluorine compound may have a plurality of (for example, about 2 to 4, preferably about 2 to 3) radical polymerizable groups or hydrolysis-condensable groups.

Examples of the fluorine compound having a radical polymerizable group include fluoro C _2-6 olefins such as vinyl fluorolide, vinylidene fluoride, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene; perfluoro (methyl vinyl ether), perfluoro Fluoro (C _1-6 alkyl vinyl ether) such as fluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether); 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl ( (Meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- Such as fluoro _{C 1-12} alkyl (meth) acrylates such as perfluorooctyl) ethyl (meth) acrylate can be exemplified.

Examples of the fluorine compound having a hydrolytic condensable group include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, and 2- (perfluorobutyl) ethyltrimethoxy. Silane, 2- (perfluorobutyl) ethyltriethoxysilane, 2- (perfluorohexyl) ethyltrimethoxysilane, 2- (perfluorohexyl) ethyltriethoxysilane, 2- (perfluorooctyl) ethyltrimethoxysilane, Fluoro C _1-12 alkyl C _1-4 alkoxysilanes such as 2- (perfluorooctyl) ethyltriethoxysilane; (FluoroC _1-6 alkoxy C _1— such as 3- (perfluoroisopropoxy) propyltrimethoxysilane _{6 alkyl) C 1-4} alkoxy Silane; 3,3,3-trifluoropropylmethyldichlorosilane, 3,3,3-trifluoropropyltrichlorosilane, 2- (perfluorobutyl) ethyldimethylchlorosilane, 2- (perfluorobutyl) ethylmethyldichlorosilane, 2- (perfluorobutyl) ethyltrichlorosilane, 2- (perfluorohexyl) ethylmethyldichlorosilane, 2- (perfluorohexyl) ethyltrichlorosilane, 2- (perfluorooctyl) ethylmethyldichlorosilane, 2- (perfluorohexyl) fluoroalkyl _{C 1-12} alkyl halo silane, such as perfluorooctyl) ethyl trichlorosilane; 3- (perfluoro-isopropoxy), such as propyl trichlorosilane (fluoro _{C 1-6} alkoxy _{C 1-6} alkyl) halosilane, these silanes Examples include silanol corresponding to the compound.

Examples of the fluorine compound having both a radical polymerizable group and a hydrolytic condensable group include 1H, 1H, 2H, 2H, 11H, 12H, 12H-hexadecafluorododecane-11en-1-yltrimethoxysilane. Fluoro C _2-12 alkenyl C _1-4 alkoxy silane; 1H, 1H, 2H, 2H, 11H, 12H, 12H-fluoro C _2-12 alkenyl halo such as hexadecafluorododecane-11en-1-yltrichlorosilane Silane: Silanol corresponding to these silane compounds can be exemplified.

These fluorine compounds can be used alone or in combination of two or more. Among these fluorine compounds, a fluoro C _1-12 alkane to which a radical polymerizable group and / or a hydrolytic condensable group are directly bonded, for example, fluoro C _1-12 alkyl (meth) acrylate, fluoro C _1-12 alkyl C _1-4 alkoxysilanes (eg, fluoro C _1-12 alkyltriC _1-4 alkoxysilanes), fluoro C _1-12 alkylhalosilanes (eg, fluoro C _1-12 alkyltrihalosilanes) are preferred, especially perfluoro C _4-8 alkyl C _2-4 alkyl (meth) acrylate, perfluoro C _4-8 alkyl C _2-4 alkyl tri-C _1-2 alkoxysilane, perfluoro C _4-8 alkyl C _2-4 alkyl trihalosilane preferable.

  In the fluorine compound (or fluoroalkyl chain moiety), the number of carbon atoms substituted by fluorine atoms is, for example, 1 to 12, preferably 1 to 10, more preferably 1 to 8 (for example, 1 to 6). ), And usually about 2 to 10 (for example, 4 to 8). If the number of carbon atoms substituted with fluorine atoms is too small, the water repellency may not be sufficiently improved. If the number is too large, the cost increases and decomposition in the natural world becomes difficult and the environmental load increases.

  The treating agent usually contains a solvent in addition to the fluorine compound. Solvents include aqueous solvents such as water, alcohols (ethanol, ethylene glycol, etc.), ketones (acetone, etc.), cyclic ethers (dioxane, tetrahydrofuran, etc.), cellosolves (methyl cellosolve, etc.), carbitols ( Examples thereof include methyl ethyl carbitol) and glycol ether esters (cellosolve acetate, etc.). These solvents can be used alone or as a mixed solvent.

  The ratio of the solvent is, for example, 3 to 1100 parts by mass (for example, 5 to 1000 parts by mass), preferably 10 to 800 parts by mass (for example, 100 to 600 parts by mass), more preferably 1 part by mass of the fluorine compound. 150-500 mass parts (for example, 200-300 mass parts) may be sufficient. If the proportion of the solvent is too small, it may be difficult to uniformly treat the surface and the water repellency may be lowered. Even if the proportion of the solvent is too large, the fluidity of the treatment agent becomes high and the material tends to spill. The water repellency may be reduced.

  Examples of the surface treatment method include coating, dipping, spraying, and the like, and after these treatments, drying may be performed as necessary. A drying temperature is 50-200 degreeC, for example, Preferably it is 70-170 degreeC, More preferably, it is about 80-150 degreeC. The drying time is, for example, 1 second to 30 minutes, preferably 2 seconds to 15 minutes, and more preferably about 5 seconds to 1 minute.

  The treatment agent may contain other additives such as a stabilizer, a thickener, a viscosity modifier, an antifoaming agent, a dispersant, a leveling agent, a colorant and the like as necessary.

  The ratio of the fluorine compound can be selected from a range of about 0.1 to 40 parts by mass (for example, 0.2 to 35 parts by mass) with respect to 100 parts by mass of the entire treatment agent, for example, 0.1 to 1 part by mass. The amount may be about 0.2 to 0.6 parts by mass, more preferably about 0.3 to 0.5 parts by mass (for example, 0.4 to 0.5 parts by mass).

  The adhesion amount (or usage amount) of the treatment agent is 0.05 to 50 parts by mass (for example, 0.1 to 45 parts by mass) with respect to 100 parts by mass of the moisture-permeable and waterproof layer before the surface treatment (or after the surface treatment). For example, 0.1 to 1 part by mass, preferably 0.2 to 0.8 part by mass, and more preferably about 0.3 to 0.7 part by mass.

  The thickness (average thickness) of the moisture permeable waterproof layer is not particularly limited, and is, for example, about 10 to 500 μm, preferably about 50 to 300 μm, and more preferably about 100 to 200 μm.

The moisture permeability resistance of the moisture permeable waterproof layer can be selected from the same range (for example, 0.19 m ² · s · Pa / μm or less) as the moisture permeability resistance of the porous hydrophobic resin sheet or hydrophobic nonwoven fabric. Thus, in this invention, even if it surface-treats with the processing agent containing a fluorine compound, moisture permeability is not impaired.

  The waterproof pressure of the moisture permeable waterproof layer is 5 kPa or more (for example, 5 to 200 kPa), preferably 10 to 150 kPa, and more preferably 15 to 100 kPa (for example, 50 to 100 kPa) in accordance with JIS L1092.

  In the moisture permeable waterproof layer, the contact angle of water (such as a 1.5 μL water droplet) may be, for example, about 105 ° to 125 °, preferably about 110 ° to 120 °. In the moisture-permeable waterproof layer before surface treatment, the contact angle of water (1.5 μL water droplets, etc.) is often less than 105 °, and the contact angle of the moisture-permeable waterproof layer is increased by surface treatment with a treatment agent. The water repellency of the water containing the insect repellent / preservative (or surfactant) can be greatly improved.

  The moisture-permeable waterproof sheet only needs to include at least a moisture-permeable waterproof layer, and a functional layer may be formed on at least one surface of the moisture-permeable waterproof layer. Examples of the functional layer include a reinforcing layer (or a protective layer), a heat shielding layer, and an anti-slip layer.

  The reinforcing layer (or protective layer) can prevent generation of cracks in the moisture-permeable waterproof layer, and can improve durability. The reinforcing layer includes a fabric (hydrophobic nonwoven fabric as exemplified above; hydrophilic nonwoven fabric such as polyester nonwoven fabric and polyamide nonwoven fabric), a thin film of metal or metal compound (silica, alumina, etc.), and this thin film is formed (deposited). It is formed of a resin sheet or the like. Among these reinforcing layers, a nonwoven fabric is preferable from the viewpoint of ensuring water vapor permeability, and a polyester-based nonwoven fabric is preferable from the viewpoint of strength and workability. In addition, in order to adjust waterproofness, you may surface-treat a reinforcement layer with the said processing agent. Moreover, the nonwoven fabric of a reinforcement layer may give embossing similarly to the nonwoven fabric of a moisture-permeable waterproof layer.

  The heat shield layer can reflect radiant heat and can improve the internal environment of the building or structure. The heat shield layer contains fine metal particles and a binder. Examples of the metal or metal compound constituting the metal fine particles include magnesium, aluminum, titanium, zinc, and metal oxides thereof. The average particle diameter of the metal fine particles is, for example, about 0.1 to 50 μm, preferably about 0.5 to 40 μm, and more preferably about 1 to 30 μm. Examples of the binder include (meth) acrylic resins, vinyl chloride resins, polyester resins, polyamide resins, polyurethane resins, and combinations thereof.

  The anti-slip layer can improve workability and safety in construction such as a roof. The anti-slip layer may be a layer containing fine particles (mineral substance particles, plastic particles, etc.) and a binder (such as the binder exemplified in the section of the thermal barrier layer), or may be a layer containing an adhesive. Adhesives (or adhesives) include vinyl chloride adhesives, vinyl acetate adhesives, polyolefin adhesives, (meth) acrylic adhesives, polyester adhesives, polyamide adhesives, polyurethane adhesives. Examples thereof include asphalt and asphalt. Further, the adhesive may be an evaporation type adhesive (solution type adhesive, latex or emulsion type adhesive, etc.), or a hot melt adhesive resin.

  The moisture permeable waterproof sheet may contain the functional layer alone or in combination of two or more. The thickness of the functional layer can be appropriately selected according to the type, and is, for example, 1 to 500 μm, preferably 5 to 400 μm, and more preferably about 10 to 300 μm.

  In addition, the moisture permeability resistance and waterproofness of a moisture-permeable waterproof sheet can each be selected from the same range as the moisture permeability resistance and waterproofness of a moisture-permeable waterproof layer.

  The moisture-permeable waterproof sheet of the present invention is used as a foundation of a building material (a building or a structural component) containing an insecticide / preservative (or a surfactant). In other words, the moisture-permeable waterproof sheet of the present invention is disposed and used on the back surface of the building material (the indoor side surface of the building or structure). Buildings or structures include, for example, houses (such as wooden houses), prefabricated (such as temporary houses), offices, lodging facilities (such as inns and lodges), entertainment facilities (such as museums, museums, theaters, and stadiums), and commerce. Facilities, tourist facilities, stations, airports, etc. can be exemplified. The moisture permeable waterproof sheet of the present invention may be applied to at least a part of the above-mentioned building or structure, for example, a roof (land roof, sloped roof, etc.), fence, ceiling, wall, sash, floor and the like. In particular, the moisture-permeable waterproof sheet of the present invention can be suitably used as a base for constituent members (trunk edge, pier, etc.) of the roof and / or outer wall.

  The active ingredient (or active ingredient) of the insect repellent / preservative (anticide / preservative, etc.) is not particularly limited, and for example, triazole compounds (for example, tebuconazole, hexaconazole, propiconazole, cyproconazole, Epoxiconazole, ipconazole, cimeconazole, metconazole, etc.), pyrethroid compounds (for example, aresulin, permethrin, tralomethrin, bifenthrin, acrinatrin, alpha cypermethrin, cyfluthrin, ciphenothrin, praretrin, etofenprox, silaflutrafen mesulin, permesline, ), Neonicotinoid (chloronicotinyl) compounds (eg thiacloprid, nitenpyram, clothianidin, imidacloprid, thiamethoxam, Cetamprid, dinotefuran, etc.), carbamate compounds (eg, carbaryl, fenocarb, propoxur, etc.), pyrrole compounds (eg, chlorfenapyr), phenylpyrazole compounds (eg, fipronil, pyriprole, etc.), semicarbazone compounds (eg, metaflumizone) , Indoxacarb, etc.), organic halogen compounds (for example, organochlorine compounds such as Kelsen; diiodomethyl-p-tolylsulfone, 3-iodo-2-propynylbutylcarbamate, 4-chlorophenyl-3-iodopropargyl formal, Organic phosphorus compounds such as 4-methoxyphenyl-3-iodopropargyl formal, triiodoallyl alcohol, etc.) (eg, oxime, pyriyl) Fenthion, fenitrothion, tetrachlorvinphos bottle phosphite, Jikurofenchion, etc. propetamphos), and others. These active ingredients may be contained in insect repellents and preservatives in the form of salts, hydrates, solvates and the like.

  The insect repellent / preservative may contain the above active ingredients alone or in combination of two or more. Among the above active ingredients, an active ingredient having a hydrophilic group capable of adsorbing water molecules and a bulky hydrophobic group for improving the permeability to the hydrophobic sheet (particularly triazole compounds such as cyproconazole) There may be. Water repellency can be improved even for water containing such active ingredients.

  Insecticides and preservatives usually contain a surfactant in order to improve the permeability of the active ingredient to the material to be treated. The surfactant may be an anionic surfactant, a cationic surfactant, or an amphoteric ionic surfactant, but may also be a nonionic surfactant that has high permeability to the hydrophobic sheet. In this invention, high water repellency can be exhibited also with respect to the rainwater which the nonionic surfactant eluted.

Examples of nonionic surfactants include ether types, ester types, ester ether types, nitrogen-containing types (or amine types), and the like. Examples of the ether type nonionic surfactant include (poly) alkane polyol alkyl ethers (for example, poly _C2-3 alkylene glycol mono 2-ethylhexyl ether, poly _C2-3 alkylene glycol monononyl ether, poly _C2-3). alkylene glycol mono decyl ether, poly _{C 2-3} alkylene glycol mono lauryl ether, poly _{C 2-3} alkylene glycol mono cetyl ether, poly _{C 2-3} alkylene glycol such as poly _{C 2-3} alkylene glycol monostearyl ether _{C 8- 24} alkyl ethers), (poly) alkane polyol aryl ethers (eg poly C _2-3 alkylene glycol monooctyl phenyl ether, poly C _2-3 alkylene glycol monononyl pheny) And poly _{C 2-3} alkylene glycol _{C 8-24} alkyl _{C 6-10} aryl ether such as ether), (poly) alkane polyols aralkyl ethers (e.g., poly _{C 2-3} poly _{C 2} such as alkylene glycol mono cumyl phenyl ether _-3 alkylene glycol C _6-10 aryl C _1-4 alkyl ether), polyoxyethylene polyoxypropylene block copolymer and the like.

Examples of the ester-type nonionic surfactant include fatty acid esters of trihydric or higher polyhydric alcohols, for example, glycerin C _8-24 fatty acid esters such as glycerin monostearate; pentaerythritol C ₈₋ such as pentaerythritol di-tallow fatty acid ester. ₂₄ fatty acid esters; sucrose monostearate, sucrose _{C 8-24} fatty acid esters such as sucrose dioleate ester; sorbitan _{C 8-24} fatty acid esters such as sorbitan mono- or trioleate (or sorbitol _{C 8-24} Fatty acid ester) and the like.

The ester ether type nonionic surfactant, for example, polyalkylene glycol fatty acid esters (e.g., poly C _2-3 alkylene glycol C _8-24 fatty acid esters such as polyethylene glycol monolaurate ester), trihydric or higher alcohol A fatty acid ester of a C _2-3 alkylene oxide adduct (eg, polyoxy C _2-3 alkylene glycerin C _8-24 fatty acid ester such as polyoxyethylene glycerin stearate, polyoxyethylene castor oil; polyoxyethylene sorbitan monostearate) Examples include polyoxy C _2-3 alkylene sorbitan C _8-24 fatty acid ester (or polyoxy C _2-3 alkylene sorbitol C _8-24 fatty acid ester) such as acid ester.

Examples of the nitrogen-containing nonionic surfactant (or amine-type nonionic surfactant) include C _2-3 alkylene oxide addition of C _8-24 alkylamine such as polyoxyethylene lauryl amino ether and polyoxyethylene stearyl amino ether. body, fatty acid alkanolamides or C _2-3 alkylene oxide adducts (e.g., coconut oil fatty acid diethanolamide, C _8-24 fatty acid alkanolamides or C _2-3 alkylene oxide adduct such as polyoxyethylene coconut fatty acid monoethanolamide Body etc.).

These surfactants may be used alone or in combination of two or more. Among these surfactants, in particular, nonionic surfactants having bulky hydrophobic groups excellent in permeability to hydrophobic sheets (for example, poly C _2-3 alkylene glycol C _8-24 alkyl C _6-10 aryl ether) , Poly C _2-3 alkylene glycol C _6-10 aryl C _1-4 alkyl ether). Water repellency can be improved even for water containing such a surfactant.

  The hydrophilic-lipophilic balance (HLB) of the surfactant is, for example, about 20 or less, preferably about 10 to 16, and more preferably about 11 to 15 (for example, 12 to 14). Water containing a surfactant having a relatively small HLB and high lipophilicity easily permeates the hydrophobic sheet, but is also excellent in water repellency against water containing such a surfactant.

  The insect repellent / preservative may further contain other additives. Examples of other additives include stabilizers, dispersants (such as ethanolamine), chelating agents (such as copper oxide), plasticizers, thickeners, antifoaming agents, and coloring agents. Other additives can be used alone or in combination of two or more.

  As described above, in the present invention, the moisture-permeable waterproof layer composed of the porous hydrophobic resin sheet or the hydrophobic nonwoven fabric is surface-treated with the treatment agent containing the fluorine compound. The water repellency can be remarkably improved because water containing the surfactant) can be prevented from passing through the pores.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The evaluation method of the moisture-permeable waterproof sheet of an Example and a comparative example is as follows.

[Surfactant penetration test]
After 100 μL of a surfactant (manufactured by Roche, Triton X-100) was dropped on the moisture-permeable waterproof sheets of Examples and Comparative Examples, water permeability to the back of the sheet was evaluated according to the following criteria.
◎: Even if the water containing the surfactant is dropped and left until the water evaporates, it does not penetrate at all on the back surface. ○: If the water containing the surfactant is dropped and left until the water evaporates, it slightly penetrates the back surface. Δ: When water containing a surfactant is dropped and allowed to stand for about 1 minute, it slightly penetrates the back surface. ×: When water containing a back surface active agent is dropped and left for about 1 minute, it completely penetrates to the back surface.

[Penetration test A for ants and preservatives]
Immerse it in tap water to the height of the lower half of the timber treated with anti-ant / preservative (Coppers Arch Chemical Co., Ltd., Tanaris), and laminate the moisture-permeable waterproof sheets of Examples and Comparative Examples on the timber. Then, a load of 800 g was applied from the top of the sheet and allowed to stand at room temperature for a predetermined time, and then the water permeability to the back surface of the sheet was evaluated according to the following criteria.
◎: Water does not permeate the back side even if left for 1 week ○ Water permeates the back side if left for 1 week and part of the sheet changes color to ant / preservative △: Back side if left for 1 week Water penetrates into the sheet, and the entire sheet changes to the color of the ant / preservative. X: When left for 3 days, water penetrates the back surface and the sheet changes to the color of the ant / preservative.

[Penetration test B for ant / preservative]
A polyvinyl chloride tube (inner diameter 40 mm) was sealed and fixed on the moisture-permeable waterproof sheets of Examples and Comparative Examples with a sealing material to prepare a test body. An aqueous solution obtained by diluting ant repellant / preservative (Tanaris) 100 times with water was poured into the polyvinyl chloride tube of the test specimen (water head 10 mm), left to stand for 24 hours, and then checked for penetration on the back surface. . Of the three specimens, the number of specimens in which water was soaked into the back of the sheet was counted and evaluated according to the following criteria.
(Double-circle): The number of the test bodies in which water permeated the sheet back surface is 0 x: The number of the test bodies in which water permeated the sheet back surface is 1 or more.

[Shower test]
A shower test was conducted using a Bundesmann rainfall tester specified in JIS L1092. The test body is a laminate of moisture-permeable waterproof sheets of Examples and Comparative Examples on a 70 mm square plywood, and a staple (thickness 0.7 mm, width 12 mm, length 8 mm) is formed in the center, and moisture-permeable It was produced by bonding the peripheral edge with a waterproof tape with an acrylic adhesive so that water did not enter between the waterproof sheet and the plywood. Test conditions were exposed to 25 mL / 2.5 minutes of rainfall for 20 minutes. Among the 10 test specimens, the number of test specimens in which water soaked into the back surface (water immersion of 5 mm or more around the staples was observed) was counted and evaluated according to the following criteria.
◎: The number of test specimens in which water is soaked on the back of the sheet is 2 or less ○: The number of test bodies in which water is soaked on the back of the sheet is 3 or more and 5 or less x: Water is soaked on the back of the sheet The number of test specimens is 6 or more.

[Nailing test]
The moisture-permeable waterproof sheets of Examples and Comparative Examples are fixed to wood with nails so that the head portion of the nail is completely in contact with the wood. Thereafter, 1 mL of an aqueous solution obtained by diluting the ant / preservative (Tanaris) 100 times was dropped on the head of the nail, and a test was performed to see if it exudes to the back surface of the sheet.
A: There is no soaking on the back side of the sheet. X: A soaking on the back side of the sheet can be confirmed.

[Moisture permeability test]
About the moisture-permeable waterproof sheet of an Example and a comparative example, moisture permeability was computed by the method based on JISZ0208, and moisture-permeable resistance was computed by the calculation formula (following formula) of JISA6111.

Pe = 574 × (1 / Rv)
(In the formula, Pe represents moisture permeability and Rv represents moisture resistance)
A: Moisture permeability resistance is 0.19 or less. X: Moisture permeability resistance is greater than 0.19.

Comparative Example 1
One surface embossed nonwoven polyester fabric (basis weight: 50g / ^{m 2)} on the other side to the microporous polyethylene sheet (average pore size 1.78Myuemu, basis weight: 30g / ^{m 2)} by laminating, moisture permeation A waterproof sheet (moisture permeability resistance: 0.11 m ³ · s · Pa / μm, thickness: 160 μm) was produced.

Comparative Example 2
Polyester one side is embossed nonwoven fabric (basis weight: 50g / ^{m 2)} on the other side to the microporous polyethylene sheet (average pore size 1.78Myuemu, basis weight: 22g / ^{m 2)} by laminating, moisture permeation A waterproof sheet (moisture permeability resistance: 0.10 m ³ · s · Pa / μm, thickness: 156 μm) was produced.

Comparative Example 3
A high-density polyethylene nonwoven fabric (moisture permeability resistance: 0.13 m ³ · s · Pa / μm, thickness: 150 μm) manufactured by flash spinning was used.

Example 1
1 g of an aqueous solution (AGE060, manufactured by Asahi Glass Co., Ltd.) containing 20% by mass of a fluorine compound having an alkyl group having 6 carbon atoms in which a hydrogen atom is substituted with a fluorine atom and having an acryloyl group as a reactive group at the terminal After immersing the moisture-permeable waterproof sheet of Comparative Example 1 in the treatment liquid added to 50 g, the moisture-permeable waterproof sheet was prepared by drying at 100 ° C. for 30 seconds.

Example 2
A moisture-permeable waterproof sheet was produced in the same manner as in Example 1 except that the moisture-permeable waterproof sheet of Comparative Example 2 was immersed in the treatment liquid.

Example 3
A moisture-permeable waterproof sheet was produced in the same manner as in Example 1 except that the moisture-permeable waterproof sheet of Comparative Example 3 was immersed in the treatment liquid.

Example 4
After immersing the moisture-permeable waterproof sheet of Comparative Example 1 in a treatment solution obtained by adding 1 g of an aqueous solution (AGE060) to 100 g of ethanol, a moisture-permeable waterproof sheet was produced by drying at 100 ° C. for 30 seconds.

Example 5
A moisture-permeable waterproof sheet was produced in the same manner as in Example 4 except that the moisture-permeable waterproof sheet of Comparative Example 2 was immersed in the treatment liquid.

Example 6
A moisture-permeable waterproof sheet was produced in the same manner as in Example 4 except that the moisture-permeable waterproof sheet of Comparative Example 3 was immersed in the treatment liquid.

Example 7
Fluorine compound having an alkyl group having 4 carbon atoms in which a hydrogen atom is substituted with a fluorine atom and having a silyl trichloride group as a reactive group at the end (manufactured by Shin-Etsu Silicone Co., Ltd., LS-912, 1H, 1H, 2H , 2H-Nonafluorohexyltrichlorosilane) 0.71 g of water and 0.1 g of 0.5N hydrochloric acid aqueous solution were added to 5 g, and the mixture was appropriately stirred at room temperature for hydrolysis, and then 8.42 g of ethanol was added to the treatment solution. Was made. After immersing the moisture-permeable waterproof sheet of Comparative Example 1 in this treatment solution, the moisture-permeable waterproof sheet was produced by drying at 100 ° C. for 30 seconds.

Example 8
A moisture-permeable waterproof sheet was produced in the same manner as in Example 7 except that the moisture-permeable waterproof sheet of Comparative Example 3 was immersed in the treatment liquid.

Example 9
Fluorine compound having an alkyl group having 1 carbon atom in which a hydrogen atom is substituted with a fluorine atom and having a methoxysilyl group as a reactive group at the terminal (KBE-7103, 3,3,3- 1.24 g of water and 0.2 g of 0.5N hydrochloric acid aqueous solution were added to 5 g of (trifluoropropyltrimethoxysilane), and the mixture was appropriately stirred at room temperature for hydrolysis, and then 6.86 g of ethanol was added to prepare a treatment solution. . After immersing the moisture-permeable waterproof sheet of Comparative Example 1 in this treatment solution, the moisture-permeable waterproof sheet was produced by drying at 100 ° C. for 30 seconds.

Example 10
A moisture-permeable waterproof sheet was produced in the same manner as in Example 9 except that the moisture-permeable waterproof sheet of Comparative Example 3 was immersed in the treatment liquid.

Example 11
Comparative Example 2 was added to a treatment liquid in which 0.62 g of water and 0.2 g of a 0.5N hydrochloric acid aqueous solution were added to 5 g of a fluorine compound (KBM-7103), followed by appropriate stirring at room temperature for hydrolysis, and then 680 g of ethanol was added. After immersing the moisture-permeable waterproof sheet, the moisture-permeable waterproof sheet was produced by drying at 100 ° C. for 30 seconds.

Example 12
Comparative Example 3 was added to 5 g of a fluorine compound (KBM-7103), 1.24 g of water and 0.2 g of 0.5N hydrochloric acid aqueous solution were added, and the mixture was appropriately stirred at room temperature to be hydrolyzed and then 340 g of ethanol was added. After immersing the moisture-permeable waterproof sheet, the moisture-permeable waterproof sheet was produced by drying at 100 ° C. for 30 seconds.

Example 13
After immersing the moisture-permeable waterproof sheet of Comparative Example 1 in a treatment solution obtained by adding 1 g of an aqueous solution (AGE060) to 300 g of ethanol, a moisture-permeable waterproof sheet was produced by drying at 100 ° C. for 30 seconds.

Example 14
A moisture-permeable waterproof sheet was produced in the same manner as in Example 13 except that the moisture-permeable waterproof sheet of Comparative Example 3 was immersed in the treatment liquid.

Example 15
After immersing the moisture-permeable waterproof sheet of Comparative Example 3 in a treatment solution obtained by adding 1 g of an aqueous solution (AGE060) to 40 g of ethanol, a moisture-permeable waterproof sheet was produced by drying at 100 ° C. for 30 seconds.

Example 16
1 g of an aqueous solution (AGE060) was added to 50 g of ethanol to prepare a first solution. In addition, 1.24 g of water and 0.2 g of 0.5N hydrochloric acid aqueous solution were added to 5 g of a fluorine compound (KBM-7103), and the mixture was hydrolyzed by appropriate stirring at room temperature, and then 34 g of ethanol was added to obtain the second solution. Was prepared. After immersing the moisture-permeable waterproof sheet of Comparative Example 1 in a treatment solution obtained by adding 0.2 g of the second solution to the first solution, the moisture-permeable waterproof sheet was produced by drying at 100 ° C. for 30 seconds.

Example 17
1 g of an aqueous solution (AGE060) was added to 40 g of ethanol to prepare a first solution. After immersing the moisture-permeable waterproof sheet of Comparative Example 3 in a treatment solution obtained by adding 0.2 g of the second solution obtained in Example 16 to the first solution, the solution was permeable by drying at 100 ° C. for 30 seconds. A wet waterproof sheet was prepared.

Example 18
A first solution was prepared by adding 0.9 g of an aqueous solution (AGE060) to 100 g of ethanol. After immersing the moisture-permeable waterproof sheet of Comparative Example 1 in a treatment solution obtained by adding 0.2 g of the second solution obtained in Example 16 to the first solution, the membrane was dried at 100 ° C. for 30 seconds, thereby permeable. A wet waterproof sheet was prepared.

Example 19
A moisture-permeable waterproof sheet was produced in the same manner as in Example 18 except that the moisture-permeable waterproof sheet of Comparative Example 3 was immersed in the treatment liquid.

  Table 1 shows the evaluation results of the moisture permeable waterproof sheets of the comparative example and the example.

  In Table 1, the concentration of the treatment liquid means a value calculated based on the formula: 100 × (mass of fluorine compound / total mass of the treatment liquid).

  As is clear from Table 1, the moisture-permeable waterproof sheets of the examples can effectively prevent the intrusion of water containing a surfactant or an ant / antiseptic agent without impairing the moisture permeability as compared with the comparative example. Also, it has excellent water resistance against nail holes.

  The moisture-permeable waterproof sheet of the present invention is excellent in water repellency even if it is porous, and thus can be suitably used as a base material for building materials (trunk edges, piers, etc.) containing insecticides / preservatives or surfactants. .

Claims (6)

A moisture-permeable waterproof sheet used as a base of a building material containing an insect repellent and / or a preservative,
A moisture permeable waterproof layer comprising a porous hydrophobic resin sheet or a hydrophobic nonwoven fabric and surface-treated with a treatment agent containing a fluorine compound, wherein the moisture permeable waterproof layer is 0.19 m ² · s · Pa / A moisture permeable waterproof sheet having a moisture permeability resistance of not more than μm, and wherein the fluorine compound is a fluoroalkane in which a radical polymerizable group and / or a hydrolytic condensable group are linked via a direct bond or a linker. The transparent compound according to claim 1, wherein the fluorine compound is at least one selected from fluoro C _1-12 alkyl (meth) acrylate, fluoro C _1-12 alkyl C _1-4 alkoxysilane and fluoro C _1-12 alkylhalosilane. Wet tarpaulin.   The moisture-permeable waterproof sheet according to claim 1 or 2, wherein the fluorine compound has 4 to 8 carbon atoms substituted with fluorine atoms.   The moisture-permeable waterproof sheet according to any one of claims 1 to 3, wherein the moisture-permeable waterproof layer is composed of a hydrophobic resin sheet having an average pore diameter of 0.5 to 10 µm.   The moisture-permeable waterproof sheet according to any one of claims 1 to 3, wherein the moisture-permeable waterproof layer is composed of a porous polyethylene resin sheet or a polyethylene nonwoven fabric.   The moisture-permeable waterproof sheet according to any one of claims 1 to 5, wherein at least one functional layer selected from a reinforcing layer, a slip-proof layer and a heat-insulating layer is formed on at least one surface of the moisture-permeable waterproof layer.