Laminate

Abstract

Provided is a laminate having excellent moisture permeability and interlayer adhesion. A laminate having a base material and a moisture-permeable film in contact with at least one surface of the base material, the moisture-permeable film comprising a cured product of a moisture-curable hot-melt polyurethane resin composition, the moisture-curable polyurethane hot-melt resin composition contains a urethane prepolymer obtained by reacting a polyol (A) containing polyethylene glycol and / or a polyoxyethylidene polyoxypropylene glycol (a1) with a polyisocyanate (B), and the moisture-curable polyurethane hot-melt resin composition is characterized in that: the moisture-curable polyurethane hot-melt resin composition contains a urethane prepolymer obtained by reacting a polyol (A) containing polyethylene glycol and / or polyoxyethylidene polyoxypropylene glycol (a1) with a polyol (B);

Description

Technical Field

[0001] This invention relates to laminates having a moisture-permeable membrane. Background Technology

[0002] A permeable membrane that is both permeable to water vapor (moisture permeability) and impermeable to water (waterproofness) is used in the bonding of breathable and waterproof fabrics and synthetic leathers (hereinafter sometimes referred to as breathable and waterproof fabrics, etc.) that require moisture permeability.

[0003] Regarding breathable laminates such as breathable and waterproof fabrics, the following structure is known for example: the substrate and the breathable membrane are bonded together by a dotted or discontinuous adhesive provided on a base fabric or other substrate (for example, Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2002-370335 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] However, conventional laminates cannot maintain sufficient adhesive strength between the substrate and the moisture-permeable membrane, making them prone to interlayer delamination. In addition, because the adhesive is applied intermittently, it blocks the pores of the substrate and the moisture-permeable membrane. The partial application of the adhesive causes air permeability resistance between the substrate and the moisture-permeable membrane, resulting in a decrease in the moisture permeability of the laminate.

[0009] The present invention was made in view of the above-mentioned actual situation and provides a laminate with excellent moisture permeability and interlayer adhesion.

[0010] Methods for solving problems

[0011] The present invention includes the following embodiments.

[0012] [1] A laminate having a substrate and a moisture-permeable membrane in contact with at least one side of the substrate, the moisture-permeable membrane comprising a cured product of a moisture-curing polyurethane hot melt resin composition, the moisture-curing polyurethane hot melt resin composition comprising a urethane prepolymer obtained by reacting a polyol (A) comprising polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1) with a polyisocyanate (B).

[0013] [2] According to the laminate described in [1] above, the thickness of the moisture-permeable membrane is less than 30 μm.

[0014] [3] According to the laminate described in [1] or [2] above, wherein the polyol (A) further contains a crystalline polyester polyol (a3).

[0015] [4] The laminate according to any one of [1] to [3] above, wherein the polyol (A) further contains a polyol (a5) having three hydroxyl groups.

[0016] [5] The laminate according to any one of [1] to [4] above, wherein the proportion of the polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1) in the polyol (A) is 50% by mass or more in the total amount (100% by mass) of the polyol (A).

[0017] [6] The laminate according to any one of [1] to [5] above, wherein the proportion of the oxyethylidene structure in the polyol (A) is 10 mol / kg or more.

[0018] [7] The laminate according to any one of [1] to [6] above, wherein the interlayer bonding strength between the substrate and the moisture-permeable membrane is 20 N / 25 mm or more.

[0019] [8] The laminate according to any one of [1] to [7] above, wherein the substrate is a base fabric.

[0020] Invention Effects

[0021] According to the present invention, a laminate with excellent moisture permeability and interlayer adhesion can be provided. Detailed Implementation

[0022] The laminate of the present invention has a substrate and a moisture-permeable membrane in contact with at least one side of the substrate, the moisture-permeable membrane comprising a cured product of a moisture-curing polyurethane hot melt resin composition, the moisture-curing polyurethane hot melt resin composition comprising a urethane prepolymer obtained by reacting a polyol (A) comprising polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1) with a polyisocyanate (B).

[0023] In the laminate of the present invention, the moisture-permeable membrane, which is disposed in direct contact with one side of the substrate, also functions as an adhesive layer, eliminating the need for a separate adhesive to bond the substrate and the moisture-permeable membrane. Therefore, compared to conventional laminates formed by bonding the substrate and the moisture-permeable membrane with an intermittently applied adhesive, the interlayer adhesion between the substrate and the moisture-permeable membrane is improved under normal conditions and after durability testing. Furthermore, by bringing the moisture-permeable membrane with adhesive function into contact with the substrate, the laminate of the present invention suppresses the reduction in moisture permeability caused by the intermittently applied adhesive clogging the pores of the substrate or the moisture-permeable membrane, and the reduction in moisture permeability caused by air resistance generated at the interface between the moisture-permeable membrane and the substrate. Moreover, the laminate of the present invention bonds the substrate and the moisture-permeable membrane without the use of an adhesive, thus simplifying the manufacturing process of the laminate.

[0024] 1. Moisture permeable membrane

[0025] The moisture-permeable membrane of the present invention comprises a cured product of a moisture-curing polyurethane hot melt resin composition containing specified components.

[0026] (1) Moisture-curing polyurethane hot melt resin composition

[0027] The above-mentioned moisture-curing polyurethane hot melt resin composition contains at least a urethane prepolymer as a reaction product of polyol (A) and polyisocyanate (B). The above-mentioned moisture-curing polyurethane hot melt resin composition can function as an adhesive.

[0028] The aforementioned urethane prepolymers possess "thermal fusibility." "Thermal fusibility" refers to a property arising from the molecular structure of the selected prepolymer, and specifically the property that it is viscous at room temperature but melts upon heating, reducing its viscosity, and then transforms into a solid upon cooling, exhibiting adhesiveness. In this invention, the term "thermal fusibility" is used as a general term for properties like those described above and substances possessing such properties.

[0029] - Polyol (A) -

[0030] The aforementioned polyol (A) comprises at least the aforementioned polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1). The aforementioned component (a1) exhibits high moisture permeability due to its excellent hydrophilicity of the oxyethylene group.

[0031] From the viewpoint of the membrane's thinness, high moisture permeability, excellent mechanical strength, and flexibility, the number average molecular weight of the above-mentioned (a1) component is preferably in the range of 900 to 25,000, more preferably in the range of 1,000 to 20,000, and even more preferably in the range of 2,000 to 15,000.

[0032] In this specification, unless otherwise stated, number-average molecular weight is expressed as a value determined by gel permeation chromatography (GPC) under the conditions described below.

[0033] Measurement apparatus: High-speed GPC device (Tosoh Corporation "HLC-8220GPC")

[0034] Column: Used to connect the following columns manufactured by Tosoh Corporation in series.

[0035] "TSKgel G5000" (7.8mm I.D. × 30cm) × 1 stick

[0036] "TSKgel G4000" (7.8mm I.D. × 30cm) × 1 stick

[0037] "TSKgel G3000" (7.8mm I.D. × 30cm) × 1 stick

[0038] "TSKgel G2000" (7.8mm I.D. × 30cm) × 1 stick

[0039] Detector: RI (Differential Refractometer)

[0040] Column temperature: 40℃

[0041] Eluent: Tetrahydrofuran (THF)

[0042] Flow rate: 1.0 mL / min

[0043] Injection volume: 100 μL (0.4% by mass tetrahydrofuran solution containing the sample)

[0044] Standard sample: A calibration curve was prepared using the standard polystyrene described below.

[0045] (Standard polystyrene)

[0046] TSKgel Standard Polystyrene A-500 manufactured by Tosoh Corporation

[0047] TSKgel Standard Polystyrene A-1000 manufactured by Tosoh Corporation

[0048] TSKgel Standard Polystyrene A-2500 manufactured by Tosoh Corporation

[0049] TSKgel Standard Polystyrene A-5000 manufactured by Tosoh Corporation

[0050] "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation

[0051] TSKgel Standard Polystyrene F-2 manufactured by Tosoh Corporation

[0052] TSKgel Standard Polystyrene F-4 manufactured by Tosoh Corporation

[0053] TSKgel Standard Polystyrene F-10 manufactured by Tosoh Corporation

[0054] TSKgel Standard Polystyrene F-20 manufactured by Tosoh Corporation

[0055] TSKgel Standard Polystyrene F-40 manufactured by Tosoh Corporation

[0056] TSKgel Standard Polystyrene F-80 manufactured by Tosoh Corporation

[0057] TSKgel Standard Polystyrene F-128 manufactured by Tosoh Corporation

[0058] TSKgel Standard Polystyrene F-288 manufactured by Tosoh Corporation

[0059] TSKgel Standard Polystyrene F-550 manufactured by Tosoh Corporation

[0060] From the viewpoint of the thinness and high permeability of the moisture-permeable membrane, the proportion (a1) of the above-mentioned component in the polyol (A) is preferably in the range of 20% to 99% by mass in the total amount (100% by mass) of the polyol (A), more preferably in the range of 30% to 95% by mass, even more preferably in the range of 40% to 90% by mass, and particularly preferably in the range of 50% to 85% by mass. When the proportion (a1) of the above-mentioned component in the polyol (A) is 50% by mass or more, the moisture-permeable membrane is thinner and can achieve high permeability.

[0061] In addition to component (a1) mentioned above, the aforementioned polyol (A) may also contain one or more aromatic polyester polyols (a2). It should be noted that aromatic polyester polyol (a2) is sometimes referred to as component (a2). Furthermore, component (a2) does not include the polyester polyol (a4) described later, which is a reaction product (condensation reaction product) of a polyol obtained by adding an epoxide to bisphenol A and a polycarboxylic acid.

[0062] The aromatic polyester polyol (a2) mentioned above is not particularly limited, but aromatic polyester polyols having a phthalic acid backbone are preferred. Examples of aromatic polyester polyols having a phthalic acid backbone include reaction products of polyacids containing phthalic acid and compounds having two or more hydroxyl groups.

[0063] Phthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride can be used as the aforementioned phthalic acid. These can be used alone or in combination of two or more. Among them, the use of phthalic acid and / or phthalic anhydride can further improve the mechanical strength and hand feel of the moisture-permeable membrane, and is therefore preferred.

[0064] The aforementioned phthalic acid can be used in combination with other polybasic acids as needed. Examples of these other polybasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and 1,12-dodecanedicarboxylic acid. These can be used alone or in combination of two or more.

[0065] Regarding the phthalic acid content in the polyacids used as raw materials for aromatic polyester polyols (a2), from the viewpoint of easily obtaining the aforementioned effects based on the phthalic acid skeleton, the total amount (100% by mass) of the aforementioned polyacids is preferably 60% by mass or more, more preferably 80% by mass or more. It can also be 100% by mass.

[0066] Regarding compounds with two or more hydroxyl groups that serve as raw materials for aromatic polyester polyols (a2), examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptahydrate, octanediol, nonanediol, decanediol, dodecanediol, trimethylolpropane, trimethylolethane, glycerol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, and 2-ethyl-2-butyl-1,3-propanediol. These compounds can be used alone or in combination of two or more. Among these, neopentyl glycol and diethylene glycol are preferred for further improving amorphous properties.

[0067] Regarding the number-average molecular weight of the aromatic polyester polyol (a2), from the viewpoint of manufacturing a breathable film with excellent mechanical strength and feel, a range of 900 to 5000 is preferred, and a range of 1000 to 3000 is more preferred. The number-average molecular weight of the aromatic polyester polyol (a2) was determined using the same method as that used for the number-average molecular weight of component (a1).

[0068] The proportion (amount) of aromatic polyester polyol (a2) in the above-mentioned polyol (A) can be set to a range of 0% to 60% of the total amount of the above-mentioned polyol (A) (100% by mass). From the viewpoint of obtaining a moisture-proof film with high moisture permeability and excellent mechanical strength, it is preferably a range of 5% to 55% of the above-mentioned polyol (A) in 100% by mass, more preferably a range of 8% to 50% by mass, and even more preferably a range of 10% to 40% by mass.

[0069] In addition to component (a1) mentioned above, the polyol (A) may also contain one or more crystalline polyester polyols (a3) ​​as optional components. It should be noted that the crystalline polyester polyol (a3) ​​is sometimes referred to as component (a3).

[0070] By further including crystalline polyester polyol (a3) ​​in the moisture-curing polyurethane hot melt resin composition, the bond strength, mechanical strength, and moisture permeability of the breathable membrane after normal conditions and durability tests can be further improved. It should be noted that in this specification, "crystalline" refers to a property in which a peak of heat of crystallization or heat of fusion can be confirmed in DSC (differential scanning calorimetry) measurements according to JIS K7121-1987.

[0071] The above-mentioned crystalline polyester polyol (a3) ​​is obtained by the condensation reaction of low molecular weight polyol and polycarboxylic acid.

[0072] For low molecular weight polyols used as raw materials for crystalline polyester polyols (a3), examples include ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, and 10-decanediol, with neopentyl glycol being preferred. This is because it forms a breathable film with a soft feel.

[0073] For example, succinic acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, dodecyl dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydroisophthalic acid, and phthalic anhydride can be used as the raw materials for crystalline polyester polyol (a3).

[0074] The aforementioned crystalline polyester polyol (a3) ​​can be any one or more of aliphatic, alicyclic, and aromatic compounds, with crystalline aliphatic polyester polyol (a3-1) being preferred. The aforementioned crystalline aliphatic polyester polyol (a3-1) can be the reaction product of a polybasic acid and a compound having two or more hydroxyl groups. Examples of such polybasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and 1,12-dodecanedicarboxylic acid. Furthermore, examples of compounds having two or more hydroxyl groups, exemplified as raw materials for the aforementioned "aromatic polyester polyol (a2)", include compounds having two or more hydroxyl groups.

[0075] From the viewpoint of further improving the mechanical strength of the breathable membrane, the crystalline polyester polyol (a3) ​​is preferably a crystalline aliphatic polyester polyol, which is a reaction product of one or more polyacids selected from bisaccharide, sebacic acid and 1,12-dodecanedicarboxylic acid and one or more compounds selected from ethylene glycol, butanediol, hexanediol and dodecanediol having two or more hydroxyl groups.

[0076] From the viewpoint of the mechanical strength and moisture permeability of the breathable membrane, the number average molecular weight of the crystalline polyester polyol (a3) ​​is preferably in the range of 900 to 10,000, and more preferably in the range of 1,000 to 9,000. The number average molecular weight of the crystalline polyester polyol (a3) ​​is a value obtained by measuring it using the same method as that used for the number average molecular weight of component (a1).

[0077] The proportion (amount) of crystalline polyester polyol (a3) ​​in the above polyol (A) can be set to a range of 0% to 60% of the total amount of polyol (A) (100% by mass). From the viewpoint of improving the feel of the moisture-proof film, it is preferably a range of 1% to 55% of the polyol (A) in 100% by mass, and more preferably a range of 2% to 50% by mass.

[0078] In addition to component (a1) mentioned above, the polyol (A) may also contain one or more polyester polyols (a4) (hereinafter sometimes referred to as component (a4)) as optional components. This polyester polyol (a4) is a reaction product (condensation reaction product) of a polyol obtained by adding an epoxide to bisphenol A and a polycarboxylic acid. Component (a4) is not included in components (a1) to (a3) ​​mentioned above.

[0079] The number-average molecular weight of component (a4) is preferably in the range of 500 to 10,000, more preferably in the range of 1,000 to 4,000. When the number-average molecular weight of component (a4) is within this range, the viscosity of the moisture-curing hot-melt polyurethane resin composition in the molten state decreases, improving continuous coating properties during the manufacture of a breathable membrane. The number-average molecular weight of component (a4) is a value obtained by measuring it using the same method as that used for component (a1).

[0080] The glass transition temperature of component (a4) is preferably in the range of -50°C to 40°C. The glass transition temperature of component (a4) can be adjusted, for example, by adjusting the amount of epoxide addition to the bisphenol A. The glass transition temperature is the endothermic peak temperature measured using DSC (differential scanning calorimetry) under a nitrogen atmosphere from -80°C at a heating rate of 5°C / min.

[0081] The polyol obtained by adding an epoxide to bisphenol A can be manufactured, for example, by using bisphenol A as an initiator and employing a known and conventional method to add the epoxide. Among these, a polyether polyol obtained by adding an epoxide to bisphenol A is preferred.

[0082] Regarding the alkyl oxides used as raw materials for the above-mentioned component (a4), for example, ethylene oxide, propylene oxide, etc. can be used, with propylene oxide being preferred.

[0083] The epoxide used as a raw material for component (a4) is preferably added to bisphenol A in the range of 1 to 10 moles, more preferably in the range of 2 to 8 moles, and even more preferably in the range of 4 to 8 moles. Component (a4) is well compatible with other polyols and can improve the adhesive strength, moisture permeability, and flexibility of the breathable membrane under normal conditions and after durability tests.

[0084] The polycarboxylic acid used as a raw material for component (a4) above is preferably one or more compounds selected from aliphatic polycarboxylic acids, alicyclic dicarboxylic acids, and aromatic polycarboxylic acids. For aliphatic polycarboxylic acids used as raw materials for component (a4), examples include succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. One of these can be used alone, or two or more can be used in combination. From the viewpoint of excellent initial cohesion and durability of the permeable membrane, aliphatic polycarboxylic acids with 6 to 10 carbon atoms are preferred; more specifically, compounds selected from sebacic acid, adipic acid, and dodecanedicarboxylic acid are more preferred. For aromatic polycarboxylic acids used as raw materials for component (a4), examples include phthalic acid, isophthalic acid, and terephthalic acid; isophthalic acid is preferred.

[0085] Among them, the polycarboxylic acid used as the material of component (a4) above preferably contains one or more aliphatic polycarboxylic acids and one or more aromatic polycarboxylic acids, and preferably contains sebacic acid and isophthalic acid.

[0086] When the polycarboxylic acid used as the material in component (a4) above is a mixture of aliphatic polycarboxylic acid and aromatic polycarboxylic acid, the ratio of aliphatic polycarboxylic acid to aromatic polycarboxylic acid ([aliphatic polycarboxylic acid / aromatic polycarboxylic acid]) is preferably 10 / 90 to 50 / 50 (equivalent ratio).

[0087] The proportion (a4) of the above-mentioned polyol (A) in the above-mentioned polyol (A) can be set to a range of 0% to 30% of the total amount (100% by mass) of polyol (A). From the viewpoint of improving compatibility with other polyols, improving the adhesion strength, moisture permeability and flexibility of the moisture-permeable membrane, the proportion is preferably a range of 5% to 30% of the total amount (100% by mass) of polyol (A), and more preferably a range of 5% to 20% by mass.

[0088] In addition to component (a1) mentioned above, the polyol (A) may also contain one or more polyols (a5) having three hydroxyl groups (hereinafter sometimes referred to as component (a5)) as optional components. The polyol (a5) having three hydroxyl groups is a component other than components (a1) to (a4) mentioned above. By further containing polyol (a5) having three hydroxyl groups in the polyol (A), the urethane prepolymer forms a cross-linked structure, which can further improve the balance between the mechanical strength and moisture permeability of the breathable membrane. Component (a5) is not included in components (a1) to (a4) mentioned above.

[0089] Examples of components (a5) include glycerin, trimethylolpropane, polyoxypropylene triol, polymers of glycerin and propylene oxide, and polymers of polyoxypropylene triol and ethylene oxide, which are compounds containing oxyalkylene groups. These can be used alone or in combination of two or more. Among these, from the perspective of good compatibility with other polyol components such as component (a1) and improved moisture permeability and mechanical strength of the moisture-permeable membrane, the aforementioned polyol containing oxyalkylene groups is preferred, and polyoxypropylene triol is more preferred.

[0090] Regarding the number-average molecular weight of the aforementioned component (a5) (a polyol having an alkylene group and three hydroxyl groups), a range of 300 to 800 is preferred, considering good compatibility with other polyol components such as component (a1) and improved moisture permeability and mechanical strength of the moisture-permeable membrane. It should be noted that the number-average molecular weight of component (a5) is a value determined using the same method as that used for component (a1).

[0091] The proportion (a5) of the above-mentioned polyol (A) in the above-mentioned polyol (A) can be set to a range of 0 parts by mass to 10 parts by mass in the total amount (100% by mass) of polyol (A). From the perspective of good compatibility with the above-mentioned polyol (A) and improved moisture permeability and mechanical strength of the moisture-permeable membrane, the proportion of the above-mentioned polyol (A) in the total amount (100% by mass) is preferably a range of 0.01% by mass to 10% by mass, more preferably a range of 0.1% by mass to 7% by mass, and even more preferably a range of 0.3% by mass to 5% by mass.

[0092] In addition to the component (a1) mentioned above, the aforementioned polyol (A) may also contain one or more other polyols (a6) other than those mentioned in (a1) to (a5) as optional components. Examples of the other polyols (a6) include polyester polyols, polyoxypropylene glycol, polyoxytetramethylene glycol, polyacrylic acid polyols, polycarbonate polyols, and polybutadiene polyols. These polyols may be used alone or in combination of two or more.

[0093] The proportion (content) of the oxyethylidene structure (EO backbone: -OCCO-) in the polyol (A) is preferably in the range of 5 mol / kg to 40 mol / kg, more preferably in the range of 8 mol / kg to 30 mol / kg, and even more preferably in the range of 10 mol / kg to 25 mol / kg. By ensuring the proportion of the oxyethylidene structure in the polyol (A) is within the above range, the moisture permeability, mechanical strength, and hand feel of the moisture-permeable membrane can be improved. Specifically, if the proportion (content) of the oxyethylidene structure (EO backbone: -OCCO-) in the polyol (A) is 10 mol / kg or more, the thinness, moisture permeability, and mechanical strength of the moisture-permeable membrane can be improved. Since the oxyethylidene structure is supplied by the component (a1), the content of the oxyethylidene structure can be appropriately determined by adjusting the component (a1).

[0094] The polyol (A) mentioned above contains at least the component (a1) mentioned above. Preferably, it contains the component (a1) mentioned above and at least one component selected from the components (a2), (a3) ​​and (a5) mentioned above. It is preferred to contain at least the components (a1) and (a3). In particular, from the viewpoint of balancing the thinness, high moisture permeability and adhesion of the moisture-permeable membrane, it is more preferable to contain the four components (a1), (a2), (a3) ​​and (a5).

[0095] -Polyisocyanate (B)-

[0096] As the polyisocyanate (B), for example, aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate (e.g., 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, etc.), carbodiimide-modified diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, and naphthalene diisocyanate; and aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylphenylmethylene diisocyanate. These polyisocyanates can be used alone or in combination of two or more. Among these, aromatic polyisocyanates are preferred from the perspective of obtaining good reactivity and mechanical strength of the film, and diphenylmethane diisocyanate is more preferred from the perspective of low vapor pressure during heating and melting.

[0097] The proportion (amount) of the above-mentioned polyisocyanate (B) in the total mass of the raw materials (solid components) constituting the urethane prepolymer is preferably in the range of 5% to 40% by mass, more preferably in the range of 10% to 30% by mass.

[0098] -Carbamate prepolymer-

[0099] The aforementioned urethane prepolymer is obtained by reacting at least the aforementioned polyol (A) and the aforementioned polyisocyanate (B) as essential raw materials. From the viewpoint of the membrane's thinness and high moisture permeability, it is preferable that the aforementioned urethane prepolymer is a reaction product of polyol (A) containing the aforementioned (a1), (a2), (a3), and (a5) components with the aforementioned polyisocyanate (B), and that the proportion of the aforementioned (a1) component in the aforementioned polyol (A) is 50% by mass or more.

[0100] In addition to isocyanate groups, the aforementioned urethane prepolymers may also have olefinic unsaturated double bonds as terminal functional groups at both ends or one end. Examples of olefinic unsaturated double bonds include vinyl, allyl, and (meth)acryloyl groups. Uramate prepolymers with olefinic unsaturated double bonds at the terminal functional groups can be prepared, for example, by reacting an acrylate compound (e.g., a hydroxyl-containing (meth)acrylate) with a urethane prepolymer having two or more isocyanate groups at the terminal end of each molecule.

[0101] From the viewpoint of improving the adhesive strength of the breathable membrane, the softening point of the above-mentioned urethane prepolymer is preferably in the range of 40 to 120°C. In this specification, the softening point refers to the temperature at which the urethane prepolymer begins to flow thermally and loses its cohesiveness when the temperature of the urethane prepolymer is gradually increased; specifically, it is the value determined by the ring and ball method (JIS K-6301).

[0102] Regarding the manufacturing method of the above-mentioned urethane prepolymer, it can be manufactured, for example, by adding each component of the above-mentioned polyol (A) to a reaction vessel containing the above-mentioned polyisocyanate (B), mixing them, and heating them, and reacting under the condition that the isocyanate groups of the above-mentioned polyisocyanate (B) are in excess relative to the hydroxyl groups of the above-mentioned polyol (A).

[0103] Regarding the equivalent ratio (NCO / OH) of the isocyanate group (NCO) in the polyisocyanate (B) and the hydroxyl group (OH) in the polyol (A) during the manufacture of the above-mentioned urethane prepolymer, from the viewpoint that it can reduce the melt viscosity of the moisture-curing hot melt resin composition that is heated and melted during the manufacture of the moisture-permeable membrane, and can also take into account the thin film formation and high mechanical strength of the moisture-permeable membrane, it is preferably in the range of 1.1 to 5.0, and more preferably in the range of 1.5 to 3.0.

[0104] The isocyanate group content (hereinafter referred to as "NCO%)" of the above-mentioned urethane prepolymer is preferably in the range of 1.7 to 5, more preferably in the range of 2.0 to 4.5. By ensuring that the NCO% of the urethane prepolymer is within the above range, the melt viscosity of the moisture-curing hot-melt resin composition that is heated and melted during the manufacture of the breathable membrane can be reduced, resulting in a thin film free of defects such as streaks, dents, and pinholes (hereinafter sometimes collectively referred to as "coating defects" or "defects"). This also improves the mechanical strength of the breathable membrane. The NCO% of the above-mentioned urethane prepolymer represents a value determined by potentiometric titration according to JIS K 1603-1:2007.

[0105] The NCO g-equivalent of the aforementioned urethane prepolymer is preferably in the range of 700 to 3000. From the viewpoint of forming a highly permeable membrane with thin film and no defects, it is more preferably in the range of 800 to 2500, and even more preferably in the range of 900 to 2200. By having the NCO g-equivalent of the urethane prepolymer within the above range, the number-average molecular weight of the urethane prepolymer can be reduced, and the melt viscosity of the moisture-curing hot-melt resin composition that is heated and melted during the manufacture of the permeable membrane can be reduced, resulting in a thin film and a defect-free permeable membrane. The NCO g-equivalent of the aforementioned urethane prepolymer is obtained by dividing the total value of all polyol and isocyanate components of the material used as the urethane prepolymer by subtracting the polyol equivalent from the isocyanate equivalent.

[0106] The number-average molecular weight of the above-mentioned urethane prepolymer is preferably in the range of 500 to 30,000. From the viewpoint of producing a breathable membrane without defects even when the thickness is less than 30 μm, and more preferably less than 20 μm, the number-average molecular weight is more preferably in the range of 700 to 20,000, and even more preferably in the range of 1,000 to 15,000. The number-average molecular weight of the above-mentioned urethane prepolymer is a value measured using the same method as the number-average molecular weight of the component (a1) described above.

[0107] The aforementioned moisture-curing polyurethane hot melt resin composition contains the aforementioned urethane prepolymer as an essential component, but may also contain other additives as needed. Examples of such other additives include, for instance, tackifiers, curing catalysts, antioxidants, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, optical brighteners, silane coupling agents, thixotropic agents, waxes, optical brighteners, thermoplastic resins, thermosetting resins, dyes, conductivity enhancers, antistatic agents, moisture permeability improvers, water repellents, oil repellents, hollow foams, compounds containing water of crystallization, flame retardants, water absorbents, hygroscopic agents, deodorizers, foam stabilizers, defoamers, mildew inhibitors, preservatives, algaecides, pigment dispersants, inactive gases, anti-blocking agents, and hydrolytic agents. These can be used alone or in combination of two or more.

[0108] The aforementioned moisture-curing polyurethane hot melt resin composition preferably has a melt viscosity in the range of 100 to 10000 mPa·s at 120°C. This is because continuous coating performance is improved when forming a film-like coating using the heated and melted moisture-curing polyurethane hot melt resin composition. From the viewpoint that coating defects can be suppressed when forming a thin coating with a thickness of less than 30 μm (more preferably 20 μm or less) through continuous coating, a melt viscosity in the range of 200 to 5000 mPa·s at 120°C is more preferably in the range of 300 to 4000 mPa·s, and particularly preferably in the range of 400 to 3000 mPa·s. The melt viscosity of the moisture-curing polyurethane hot melt resin composition can be adjusted by the average molecular weight of the urethane prepolymer, the isocyanate group content of the aforementioned urethane prepolymer, etc.

[0109] <Moisture permeable film>

[0110] The thickness of the aforementioned moisture-permeable membrane is not particularly limited as long as it achieves practical moisture permeability. However, the thinner the membrane and the higher its moisture permeability, the smaller the thickness of the laminate of the present invention can be. Therefore, the thickness of the aforementioned moisture-permeable membrane is preferably less than 30 μm, more preferably 20 μm or less. More specifically, the thickness of the aforementioned moisture-permeable membrane is preferably 3 μm or more and 29 μm or less, more preferably 5 μm or more and 27 μm or less, further preferably 7 μm or more and 25 μm or less, and particularly preferably 9 μm or more and 23 μm or less.

[0111] The moisture permeability of the aforementioned permeable membrane is not particularly limited as long as it exhibits practical moisture permeability performance; preferably, it is 4000 g / m³. 2 The moisture permeability of the membrane is measured according to the A-1 method (calcium chloride method) of JIS L1099:2012. There is no specific upper limit for moisture permeability as long as it does not impair the waterproof function; for example, it can be set to 50,000 g / m³. 2 / 24h) or less, for example, it can be set to 30000 (g / m 2 ( / 24h) or less.

[0112] <Manufacturing Method of Moisture-Permeable Membrane>

[0113] The aforementioned moisture-permeable membrane can be manufactured by known methods. As an example of a method for manufacturing the aforementioned moisture-permeable membrane, the following method can be used: a coating device is used to uniformly coat a heated and molten moisture-curable polyurethane hot melt resin composition onto a release substrate to form a coating film; the coating film is cooled and transformed into a solid, and then allowed to mature for a certain period of time to perform moisture curing of the coating film; after maturation, the release substrate is peeled off to obtain the moisture-permeable membrane.

[0114] In addition, as another example of the above-mentioned method for manufacturing a moisture-permeable membrane, the following method can be cited: using a coating device, a moisture-curing polyurethane hot melt resin composition that has been heated and melted is directly and uniformly coated onto one side of the substrate described below, forming a coating film on the substrate, cooling the coating film to transform it into a solid, and then allowing it to mature for a certain period of time to perform moisture curing of the coating film, thereby directly manufacturing a moisture-permeable membrane on the substrate.

[0115] As the aforementioned release substrate, there are no particular limitations as long as a coating film can be formed and the coating film can be peeled off after curing. For example, release paper, release treatment cloth (i.e., cloth that has undergone release treatment), water-repellent cloth, olefin sheets or olefin films containing polyethylene resin, polypropylene resin, etc., sheets or films containing fluororesin, plastic films with release paper, polyurethane resin films with release paper, etc.

[0116] The arithmetic mean roughness (Sa) of the aforementioned release substrate is not particularly limited. However, in terms of manufacturing without producing coating defects when manufacturing a moisture-permeable film with a thinner thickness (e.g., less than 30 μm, of which 20 μm or less), the arithmetic mean roughness (Sa) is preferably 0.90 μm or more, preferably 0.92 μm or more, more preferably 0.95 μm or more, further preferably 0.98 μm or more, and particularly preferably 1.0 μm or more. Furthermore, the upper limit of the arithmetic mean roughness (Sa) of the aforementioned release substrate is not particularly limited as long as a coating of moisture-curing polyurethane hot melt resin composition can be formed and the cured coating can be peeled off. It is preferably 25 μm or less, more preferably 22 μm or less, and further preferably 19 μm or less. The arithmetic mean roughness (Sa) is a parameter obtained by extending the arithmetic mean height Ra of a line to a surface, and is a value measured using a laser microscope according to ISO 25178 for the surface of the release substrate where the moisture-curing polyurethane hot melt resin composition is coated.

[0117] Furthermore, while the gloss of the aforementioned release substrate is not particularly limited, in terms of manufacturing a thinner (e.g., less than 30 μm, of which 20 μm or less) moisture-permeable film without defects, the gloss is preferably 25.0 or less, preferably in the range of 0.1 to 25.0, more preferably in the range of 1.0 to 20.0, and even more preferably in the range of 2.0 to 17.5. The gloss of the aforementioned release substrate was measured using a BYK Micro-gross 45XX as the measuring device, according to JIS Z8741:1997, for the surface of the release substrate coated with a moisture-curing polyurethane hot-melt resin composition, at a light incident angle of 60°.

[0118] The heating and melting temperature of the above-mentioned moisture-curing polyurethane hot melt resin composition is not particularly limited as long as it can be reduced to a viscosity that allows for the formation of a film-like coating through continuous application. For example, it can be set to a range of 50°C to 130°C, and more preferably to a range of 80°C to 120°C.

[0119] The method of applying the above-mentioned moisture-curing polyurethane hot melt resin composition is not particularly limited as long as it can form a film-like coating by continuous application to a release substrate. Examples include roller coating, extrusion, gravure coating, die coating, bar coating, and doctor blade coating.

[0120] The coating is formed from a moisture-curing hot melt polyurethane resin composition that has been heated and melted, and does not contain solvent. Therefore, the thickness of the coating of the moisture-curing hot melt polyurethane resin composition can be set to be the same as the thickness of the cured heat-melted moisture-permeable membrane.

[0121] The coating of the above-mentioned moisture-curing polyurethane hot melt resin composition reacts with moisture in the air, the release substrate that the coating contacts, or the moisture contained in the substrate to form a film-like cured product, which becomes a moisture-permeable membrane.

[0122] The curing conditions for the above-mentioned coating film can be set, for example, an ambient temperature of 20°C to 40°C, a relative humidity of 50% to 80%, and a curing time of 1 to 5 days (more typically 3 days). The curing of the above-mentioned coating film is carried out on a release substrate or substrate. The curing of the above-mentioned coating film is generally carried out while the release substrate or substrate on which the above-mentioned coating film is formed is wound with rollers or the like, but it can also be carried out without winding. Furthermore, the curing reaction of the coating film can begin from the point in time when the moisture-curing polyurethane hot melt resin composition is applied to the release substrate or substrate.

[0123] When the urethane prepolymer contained in the above-mentioned moisture-curing polyurethane hot melt resin composition has olefinic unsaturated double bond groups at both ends or one end, the coating film can also be irradiated with active energy rays. This is because, in addition to using moisture to cure the coating film of the moisture-curing polyurethane hot melt resin composition, the curing reaction can be further carried out by irradiation with active energy rays.

[0124] Examples of active energy rays include ultraviolet light. The amount of active energy irradiation is not particularly limited as long as it sufficiently promotes the curing reaction of the moisture-curing polyurethane hot melt resin composition coating; for example, 50 mJ / cm² is preferred. 2 ~5000mJ / cm 2 More preferably 100 mJ / cm 2 ~3000mJ / cm 2The above-mentioned irradiation levels are based on values ​​measured using a UV detector UVR-N1 (manufactured by Nippon Battery Co., Ltd.) in the wavelength range of 300–390 nm.

[0125] As a light source for irradiating active energy rays, examples include well-known lamps such as xenon lamps, xenon-mercury lamps, metal halide lamps, high-pressure mercury lamps, and low-pressure mercury lamps.

[0126] There is no particular limitation on the timing of irradiating the coating of the above-mentioned moisture-curing polyurethane hot melt resin composition with active energy rays, but from the viewpoint of preventing a decrease in surface quality, it is preferable to irradiate the coating on a release substrate or a substrate that has been coated onto a roller or the like. Alternatively, the moisture curing reaction and the photocuring reaction based on active energy irradiation can be carried out simultaneously, or either one of the curing reactions can be carried out first, followed by the other.

[0127] 2. Substrate

[0128] The substrate in this invention can be appropriately selected according to the intended use of the laminate, and examples include resin film, breathable film, fibrous substrate, wood substrate, metal substrate, foam sheet, synthetic leather, paper, rubber substrate, glass substrate, etc.

[0129] Examples of resin films include those containing known materials such as polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polystyrene, and TPO (Thermoplastic Olefinic Elastomer).

[0130] Examples of moisture-permeable membranes include solvent-based and water-based polyurethane resins, thermoplastic polyurethane resins (TPU), thermoplastic polyester resins (TPE), porous polytetrafluoroethylene (PTFE), and polyolefin resins such as polyethylene or polypropylene.

[0131] Examples of fibrous base materials include nonwoven fabrics, woven fabrics, braided fabrics, and base fabrics. Materials used as fibrous base materials include, for example, chemical fibers such as polyester fibers, nylon fibers, acrylonitrile fibers, polyurethane fibers, acetate fibers, rayon fibers, and polylactic acid fibers; cotton, linen, silk, wool, and their blended fibers.

[0132] Examples of wood-based substrates include plywood, MDF (medium-density fiberboard), and particleboard.

[0133] Examples of metal substrates include aluminum and iron.

[0134] Examples of foamed sheets include polyurethane foam.

[0135] The aforementioned substrate can be a single layer or a multilayer structure with two or more layers. Examples include a two-layer structure of a moisture-permeable membrane and a foam sheet, and a two-layer structure of a moisture-permeable membrane and a fibrous substrate.

[0136] Regarding the thickness of the aforementioned substrate, it can be determined according to the intended use, for example, in the range of 1 to 500 mm.

[0137] 3. Laminated bodies

[0138] The laminate of the present invention can be provided as long as the moisture-permeable membrane is in contact with at least one side of the substrate, or it can be provided on both sides of the substrate.

[0139] Furthermore, the aforementioned moisture-permeable membrane only needs to be continuously (non-discontinuously) disposed on the substrate, preferably on the entire surface of one side of the substrate. "Discontinuously" refers to the intentional arrangement of areas where the cured product of the moisture-curing polyurethane hot-melt resin composition, such as dots or meshes, exists and areas where the cured product does not exist. In the laminate of the present invention, areas where the cured product of the moisture-curing polyurethane hot-melt resin composition constituting the moisture-permeable membrane does not exist are not intentionally provided, and the moisture-permeable membrane covers a wide area (preferably the entire surface) of one side of the substrate surface.

[0140] In addition to the substrate and the moisture-permeable membrane, the aforementioned laminate can have any configuration depending on its intended use. For example, the surface of the moisture-permeable membrane opposite to the surface in contact with the substrate may have a skin layer, a surface treatment layer with anti-adhesion and water pressure resistance functions, etc. Alternatively, the surface treatment may be directly applied to the surface of the moisture-permeable membrane opposite to the surface in contact with the substrate.

[0141] Regarding the laminate of the present invention, since the aforementioned moisture-permeable membrane also functions as an adhesive layer, and is configured to directly contact one surface of the substrate, the interlayer adhesion between the substrate and the moisture-permeable membrane can be improved compared to a laminate formed by bonding the moisture-permeable membrane and the substrate via an adhesive provided in an intermittent manner. The interlayer adhesion strength between the substrate and the moisture-permeable membrane under normal conditions is preferably 20 N / 25 mm or more, more preferably 22 N / 25 mm or more, and even more preferably 25 N / 25 mm or more.

[0142] In addition, the interlayer bonding strength between the substrate and the moisture-permeable membrane after the durability test is preferably 15N / 25mm or more, more preferably 17N / 25mm or more, and even more preferably 20N / 25mm or more.

[0143] It should be noted that there is no particular upper limit to the above interlayer bond strength after normal conditions and durability tests; for example, it can be set to below 50N / 25mm.

[0144] The aforementioned interlayer adhesive strength, in other words, is the peel strength between the substrate and the moisture-permeable membrane, and is determined by the following method. Specifically, the value is as follows: the laminate is cut into 1-inch wide pieces, and the substrate and moisture-permeable membrane are peeled off at one end along the longitudinal dimension of the laminate. The peeled portion is held in place by chucks using a TENSILON (Orientech Corporation TENSILON universal peeler "RTC-1210A"), and the peel is performed under tension at a crosshead speed of 200 mm / min.

[0145] In addition, the interlayer bond strength after the durability test was measured using laminates that had been left to stand for 3 weeks in a constant temperature and humidity chamber adjusted to 70±5℃ and 95±5%RH, in the order described above.

[0146] As for the manufacturing method of the laminate of the present invention, there are no particular limitations as long as the moisture-permeable membrane can be directly disposed on one side of the substrate. As an example of the manufacturing method of the laminate of the present invention, the following method can be cited: a moisture-permeable membrane obtained by using the manufacturing method of the moisture-permeable membrane of the release substrate described in item "1. Moisture-permeable membrane" above is disposed on one side of the substrate and bonded by heat pressing or the like.

[0147] Another example of the manufacturing method of the laminate of the present invention is the following method: A moisture-curing hot-melt polyurethane resin composition, heated and molten, is directly and uniformly coated onto one side of a substrate using a coating apparatus to form a coating film on the substrate. After the coating film is cooled and solidified, it is allowed to mature for a certain period of time to achieve moisture curing, thereby directly manufacturing a permeable membrane on the substrate. The coating method, coating apparatus, and maturation conditions of the moisture-curing hot-melt polyurethane resin composition can be set to be the same as the detailed description of the manufacturing method of the permeable membrane in section "1. Permeable Membrane" above.

[0148] The uses of the laminate of the present invention are not particularly limited, and it is suitable for use as breathable and waterproof fabrics for clothing, medical and hygiene purposes, synthetic leather, building materials (building material panels, decorative panels, etc.), and automotive interior materials. More specifically, it can be used, for example, for sportswear, raincoats, gloves, shoes, fire-fighting suits, military uniforms, adhesive bandages, diaper films, wall materials, roofing materials, etc.

[0149] This invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any method having a substantially the same structure as the technical concept described in the scope of this invention and achieving the same effect is included within the technical scope of this invention.

[0150] [Example]

[0151] Hereinafter, embodiments of the present invention will be described in further detail by illustrating them in examples and comparative examples.

[0152] The abbreviations for each material are shown below.

[0153] <Polyol (A)>

[0154] <<Polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1) composition>>

[0155] PEt-1: Polyoxyethylene glycol (number average molecular weight Mn: 1540, hydroxyl equivalent (gram equivalent eq.wt): 770)

[0156] ·PEt-2: Polyoxyethylene glycol (number average molecular weight Mn: 2000, hydroxyl equivalent (gram equivalent eq.wt): 1000)

[0157] PEt-3: Polyoxyethylene glycol (number average molecular weight Mn: 4000, hydroxyl equivalent (gram equivalent eq.wt): 1550)

[0158] PEt-4: Polyoxyethylene glycol (number average molecular weight Mn: 6000, hydroxyl equivalent (gram equivalent eq.wt): 4400)

[0159] PEt-5: Polyoxyethylene glycol (number average molecular weight Mn: 11000, hydroxyl equivalent (gram equivalent eq.wt): 5500)

[0160] <<Aromatic Polyester Polyol (a2) Composition>>

[0161] PEs-1: Polyester polyol (the reaction product of phthalic acid and 1,6-hexanediol, number average molecular weight Mn: 2000, hydroxyl equivalent (gram equivalent eq.wt): 1000)

[0162] ·PEs-2: Polyester polyol (reaction product of neopentyl glycol, diethylene glycol and phthalic acid, number average molecular weight: 1000, hydroxyl equivalent (gram equivalent eq.wt): 500)

[0163] <<Crystall Polyester Polyol (a3) ​​Components>>

[0164] ·PEs-3: Polyester polyol (reaction product of ethylene glycol, neopentyl glycol, 1,6-hexanediol and adipic acid, number average molecular weight Mn: 5500, hydroxyl equivalent (gram equivalent eq.wt): 2750)

[0165] ·PEs-4; Polyester polyol (reaction product of 1,6-hexanediol and sebacic acid, number average molecular weight Mn: 3500, hydroxyl equivalent (gram equivalent eq.wt): 1750)

[0166] <<Polyol (a5) component with 3 hydroxyl groups>>

[0167] ·PO-1: Polyoxypropylene triol (Mitsui Chemicals Co., Ltd. "T-700", number average molecular weight Mn: 700, hydroxyl equivalent (gram equivalent eq.wt): 233)

[0168] <Polyisocyanate (B)>

[0169] MDI: 4,4'-Diphenylmethane diisocyanate

[0170] [Preparation of moisture-curing polyurethane hot melt resin composition]

[0171] (Moisture-curing polyurethane hot melt resin composition (1))

[0172] In a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 204.6 parts by weight of "PEt-3", 64.8 parts by weight of "PEs-2", 64.8 parts by weight of "PEs-4", and 6.8 parts by weight of "PO-1" were added and mixed. The mixture was heated under reduced pressure at 100°C to dehydrate the contents of the flask until the water content was below 0.05% by weight. The contents of the flask were then cooled to 90°C, and 91.4 parts by weight of "MDI" that had been melted at 70°C were added. The mixture was reacted at 110°C for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, thus preparing a hot-melt urethane prepolymer (iii) and a solvent-free moisture-curing polyurethane hot-melt resin composition (1).

[0173] (Moisture-curing polyurethane hot melt resin composition (2))

[0174] Except for changing the type and amount of polyol (A) and the amount of polyisocyanate (B) as shown in Table 1 below, the same procedure as in Example 1 was followed to prepare a hot melt urethane prepolymer (v) and to prepare a solvent-free moisture-curing polyurethane hot melt resin composition (2).

[0175] (Moisture-curing polyurethane hot melt resin composition (3))

[0176] Except for changing the type and amount of polyol (A) and the amount of polyisocyanate (B) as shown in Table 1 below, the hot melt urethane prepolymer (vii) was prepared in the same manner as in Example 1, and a solvent-free moisture-curing polyurethane hot melt resin composition (3) was formed.

[0177] [Table 1]

[0178]

[0179] [Example 1]

[0180] Using a roller coater, a solvent-free, moisture-curing polyurethane hot-melt resin composition (1), which has been melted at 100°C, is continuously coated onto the surface of a release substrate A (polyolefin release paper, arithmetic mean height Sa: 1.024 μm, gloss (60° gloss value): 4.7), forming a coating film with a thickness of 15 μm. The resulting material is then laminated onto a base fabric (80 denier polyester base fabric, thickness 200 μm) using a laminator and left at 23°C and 65% relative humidity for 3 hours to obtain a laminate. This laminate is then bonded to the clothing fabric. Next, the coating film is cured at 23°C and 50±5% humidity for at least 24 hours to form a cured product of the coating film (moisture-permeable film). Thus, a processed fabric (laminate) with a two-layer structure of moisture-permeable film / base fabric is obtained.

[0181] [Example 2]

[0182] Except for using a moisture-curing polyurethane hot melt resin composition (2) instead of the moisture-curing polyurethane hot melt resin composition (1) to form a moisture-permeable membrane, the process was carried out in the same manner as in Example 1 to obtain the processed fabric (laminated body).

[0183] [Example 3]

[0184] Except for using a moisture-curing polyurethane hot melt resin composition (3) instead of the moisture-curing polyurethane hot melt resin composition (1) to form a moisture-permeable membrane, the process was carried out in the same manner as in Example 1 to obtain the processed fabric (laminated body).

[0185] [Comparative Example 1]

[0186] After the moisture-curing polyurethane hot melt resin composition (1) is melted at 100°C, it is coated using a gravure roller coater (coating amount: 17.5±5g / m). 2 A moisture-curing hot-melt polyurethane resin composition, heated and molten, is intermittently applied to a breathable membrane (a material obtained by processing CRISVON S-517 manufactured by DIC into a 15μm film). This membrane is then laminated with a base fabric (80 denier polyester base fabric, 200μm thick) using a laminator to obtain a laminate. Next, the laminate is placed in an atmosphere at 23°C and 50±5% humidity for at least 24 hours to obtain a processed fabric (laminate) with a three-layer structure of breathable membrane / intermittent adhesive layer / base fabric.

[0187] [Comparative Examples 2-3]

[0188] Except for replacing the moisture-curing polyurethane hot melt resin composition (1) with the moisture-curing polyurethane hot melt resin composition (2) or (3), the same procedure as in Comparative Example 1 was followed to obtain the processed fabric (laminated body).

[0189] [evaluate]

[0190] (Interlayer bond strength under normal conditions)

[0191] Each of the obtained processed fabrics was cut into 1-inch wide pieces. The layers between the substrate and the breathable membrane were peeled off at one end along the long dimension. The peeled parts were clamped in each chuck using a TENSILON (TENSILON universal machine "RTC-1210A" manufactured by Orientech Corporation) and stretched at a crosshead speed of 200 mm / min to determine the peel strength. The evaluation was carried out as follows.

[0192] “T”: 20N / 25cm or more.

[0193] “F”: less than 20N / 25cm.

[0194] (Interlayer bond strength after durability testing)

[0195] After the obtained processed fabrics were left to stand for 3 weeks in a constant temperature and humidity chamber adjusted to 70±5℃ and 95±5%RH, they were cut into 1-inch wide pieces. The layers between the substrate and the moisture-permeable membrane were peeled off at one end along the long dimension. The peeled parts were clamped with chucks using a TENSILON universal machine (TENSILON RTC-1210A manufactured by Orientech Corporation) and stretched at a crosshead speed of 200 mm / min to determine the peel strength. The evaluation was carried out as follows.

[0196] “T”: 15N / 25cm or more.

[0197] “F”: less than 15N / 25cm.

[0198] The evaluation results are shown in the table below.

[0199] [Table 2]

[0200]

[0201] (Moisture permeability)

[0202] The moisture permeability of the processed fabrics of the examples and comparative examples was determined according to JIS L1099 (A-1: calcium chloride method). The moisture permeability of the processed fabrics of both the examples and comparative examples was 4000 g / m². 2 / 24h) or more.

[0203] The moisture permeability of the processed fabrics in Examples 1 to 3 was increased in the order of Example 2 < Example 1 < Example 3.

[0204] In addition, the relationship between the moisture permeability of the processed fabric of Example 1 and the processed fabric of Comparative Example 1 is: Comparative Example 1 < Example 1.

[0205] Similarly, the relationship between the moisture permeability of the processed fabric of Example 2 and the processed fabric of Comparative Example 2 is: Comparative Example 2 < Example 2.

[0206] Similarly, the relationship between the moisture permeability of the processed fabric of Example 3 and the processed fabric of Comparative Example 3 is: Comparative Example 3 < Example 3.

[0207] Based on the above results, it can be seen that the processed fabrics of Examples 1-3 have superior interlayer bonding strength and moisture permeability compared with the processed fabrics of Comparative Examples 1-3, both under normal conditions and after durability tests.

Claims

1. A laminate comprising a substrate, and A moisture-permeable membrane in contact with at least one side of the substrate. The moisture-permeable membrane comprises a cured product of a moisture-curing polyurethane hot melt resin composition, which contains a urethane prepolymer obtained by reacting a polyol A comprising polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol a1 with a polyisocyanate B.

2. The laminated body according to claim 1, wherein, The thickness of the moisture-permeable membrane is less than 30 μm.

3. The laminate according to claim 1, wherein, The polyol A further contains crystalline polyester polyol a3.

4. The laminated body according to claim 1, wherein, The polyol A further contains polyol a5 having three hydroxyl groups.

5. The laminate according to claim 1, wherein, The proportion of polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol a1 in the polyol A is more than 50% by mass in the total amount of the polyol A, i.e., 100% by mass.

6. The laminate according to claim 1, wherein, The proportion of oxyethylidene structures in polyol A is above 10 mol / kg.

7. The laminated body according to claim 1, wherein, The interlayer adhesion strength between the substrate and the moisture-permeable membrane is above 20N / 25mm.

8. The laminated body according to claim 1, wherein, The substrate is a base fabric.

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