Laminate

Abstract

To provide a laminate with excellent moisture permeability and interlayer adhesion. [Solution] A laminate comprising a base material and a moisture-permeable film in contact with at least one surface of the base material, wherein the moisture-permeable film is made of a cured product of a moisture-curable polyurethane hot-melt resin composition containing a urethane prepolymer obtained by reacting a polyol (A) containing polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1) with a polyisocyanate (B).

Description

Technical Field

[0001] The present disclosure relates to a laminate having a moisture-permeable film.

Background Art

[0002] A moisture-permeable film having water vapor permeability (moisture permeability) and water impermeability (waterproofness) is used by being laminated in a moisture-permeable waterproof fabric or synthetic leather (hereinafter sometimes referred to as a moisture-permeable waterproof fabric or the like) that requires moisture permeability.

[0003] A laminate having moisture permeability such as a moisture-permeable waterproof fabric or the like has a known structure in which the base material and the moisture-permeable film are adhered via an intermittent adhesive such as dot-shaped provided on a base material such as a base fabric (for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, a conventional laminate cannot maintain sufficient adhesive strength between the base material and the moisture-permeable film, and delamination is likely to occur. In addition, the adhesive applied intermittently blocks the pores of the base material and the moisture-permeable film, and air permeability resistance occurs between the base material and the moisture-permeable film due to the applied portion of the adhesive, etc., and the moisture permeability of the laminate may decrease.

[0006] The present disclosure has been made in view of the above circumstances, and provides a laminate excellent in moisture permeability and interlayer adhesive strength.

Means for Solving the Problems

[0007] The present disclosure includes the following embodiments. [1] A laminate comprising a base material and a moisture-permeable film in contact with at least one surface of the base material, wherein the moisture-permeable film contains a urethane prepolymer obtained by reacting a polyol (A) containing polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1) with a polyisocyanate (B), and is made of a cured product of a moisture-curable polyurethane hot-melt resin composition. [2] The laminate according to [1] above, wherein the thickness of the moisture-permeable film is less than 30 μm. [3] The laminate according to [1] or [2] above, wherein the polyol (A) further comprises a crystalline polyester polyol (a3). [4] The laminate according to any one of [1] to [3] above, wherein the polyol (A) further comprises a polyol (a5) having three hydroxyl groups. [5] The laminate according to any one of [1] to [4] above, wherein the proportion of polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1) in the polyol (A) is 50% by mass or more of the total amount (100% by mass) of the polyol (A). [6] The laminate according to any one of [1] to [5] above, wherein the proportion of oxyethylene structures in the polyol (A) is 10 mol / kg or more. [7] A laminate according to any one of [1] to [6] above, wherein the interlayer adhesive strength between the substrate and the moisture permeable film is 20 N / 25 mm or more. [8] A laminate according to any of [1] to [7] above, wherein the base material is a base fabric. [Effects of the Invention]

[0008] According to this disclosure, it is possible to provide a laminate with excellent moisture permeability and interlayer adhesion. [Modes for carrying out the invention]

[0009] The laminate of the present disclosure comprises a substrate and a moisture-permeable film in contact with at least one surface of the substrate, wherein the moisture-permeable film is made of a cured product of a moisture-curable polyurethane hot-melt resin composition containing a urethane prepolymer obtained by reacting a polyol (A) containing polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1) with a polyisocyanate (B).

[0010] The laminate of this disclosure has a moisture-permeable film provided in direct contact with one side of the substrate, which also functions as an adhesive layer, eliminating the need for a separate adhesive to bond the substrate and the moisture-permeable film. Therefore, compared to conventional laminates in which the substrate and the moisture-permeable film are bonded via intermittently applied adhesive, the interlayer adhesion between the substrate and the moisture-permeable film can be improved under normal conditions and after durability testing. Furthermore, in the laminate of this disclosure, the contact between the moisture-permeable film with adhesive function and the substrate can suppress the reduction in moisture permeability caused by the blocking of pores in the substrate and moisture-permeable film by intermittently applied adhesive, as well as the reduction in moisture permeability caused by airflow resistance at the interface between the moisture-permeable film and the substrate. Moreover, since the substrate and the moisture-permeable film are bonded without the use of adhesive in the laminate of this disclosure, the manufacturing process of the laminate can be simplified.

[0011] 1. Breathable film The moisture-permeable film in this disclosure consists of a cured product of a moisture-curing polyurethane hot-melt resin composition containing predetermined components.

[0012] (1) Moisture-curing polyurethane hot melt resin composition The above moisture-curing polyurethane hot-melt resin composition contains a urethane prepolymer which is a reaction product of at least a polyol (A) and a polyisocyanate (B). The above moisture-curing polyurethane hot-melt resin composition can function as an adhesive.

[0013] The above urethane prepolymer has "hot melt properties". "Hot melt properties" are properties resulting from the molecular structure of the selected prepolymer. At normal temperature, it is in a viscous state, but when heated, it melts and its viscosity decreases, and when it cools, it solidifies to exhibit adhesiveness. In the present disclosure, the term "hot melt" is used as a general term for the above properties and substances having such properties.

[0014] - Polyol (A)- The above polyol (A) contains at least the above polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1). Since the (a1) component has an oxyethylene group with excellent hydrophilicity, high moisture permeability can be obtained.

[0015] From the viewpoints of the thin film property, high moisture permeability, excellent mechanical strength, and flexibility of the moisture permeable film, the number average molecular weight of the above (a1) component is preferably in the range of 900 to 25000, more preferably in the range of 1000 to 20000, and still more preferably in the range of 2000 to 15000.

[0016] In this specification, the number average molecular weight indicates the value measured under the following conditions by the gel permeation chromatography (GPC) method unless otherwise specified.

[0017] Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation) Columns: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G4000" (7.8 mm I.D. × 30 cm) × 1 "TSKgel G3000" (For 7.8 mm I.D. × 30 cm) × 1 "TSKgel G2000" (7.8 mm I.D. × 30 cm) × 1 Detector: RI (Differential refractometer) Column temperature: 40 °C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard samples: Calibration curves were prepared using the following standard polystyrene samples.

[0018] (Standard polystyrene) TSKgel Standard Polystyrene A-500, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-1000, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-2500, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene A-5000, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-1, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-2, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-4, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-10, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-20, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-40, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-80, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-128, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-288, manufactured by Tosoh Corporation. TSKgel Standard Polystyrene F-550, manufactured by Tosoh Corporation.

[0019] The proportion (amount used) of component (a1) in the polyol (A) is preferably in the range of 20% to 99% by mass, 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, based on the total amount (100% by mass) of the polyol (A). When the proportion (amount used) of component (a1) in the polyol (A) is 50% by mass or more, the moisture-permeable film can be made thinner and exhibit higher moisture permeability.

[0020] The above polyol (A) may contain one or more aromatic polyester polyols (a2) in addition to the above-described component (a1). Note that aromatic polyester polyol (a2) may sometimes be referred to as component (a2). Furthermore, component (a2) does not include polyester polyol (a4), which is a reaction product (condensation product) of a polyol obtained by adding an alkylene oxide to bisphenol A and a polycarboxylic acid, as described later.

[0021] The above aromatic polyester polyol (a2) is not particularly limited, but aromatic polyester polyols having a phthalic acid skeleton are preferred. Examples of aromatic polyester polyols having a phthalic acid skeleton include reaction products of a polybasic acid containing phthalic acid and a compound having two or more hydroxyl groups.

[0022] The phthalic acids that can be used include orthophthalic acid, isophthalic acid, terephthalic acid, and phthalic anhydride. These may be used individually or in combination of two or more. In particular, the use of orthophthalic acid and / or phthalic anhydride is preferred because it can further enhance the mechanical strength and texture of the moisture-permeable film.

[0023] The phthalic acid mentioned above may be used in combination with other polybasic acids as needed. Examples of other polybasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and 1,12-dodecanedicarboxylic acid. These may be used individually or in combination of two or more.

[0024] The phthalic acid content in the polybasic acid, which is the raw material for aromatic polyester polyol (a2), is preferably 60% by mass or more, and more preferably 80% by mass or more, of the total amount (100% by mass) of the polybasic acid, from the viewpoint of easily obtaining the effects of the phthalic acid skeleton described above. It may also be 100% by mass.

[0025] Examples of compounds having two or more hydroxyl groups that can be used as raw materials for aromatic polyester polyol (a2) include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, trimethylolpropane, trimethylolethane, glycerin, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propylene glycol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, and 2-ethyl-2-butyl-1,3-propanediol. These compounds may be used individually or in combination of two or more. Among these, neopentyl glycol and diethylene glycol are preferred because they can further enhance the amorphous properties.

[0026] The number-average molecular weight of the above aromatic polyester polyol (a2) is preferably in the range of 900 to 5,000, and more preferably in the range of 1,000 to 3,000, from the viewpoint of producing a moisture-permeable film with excellent mechanical strength and texture. The number-average molecular weight of the above aromatic polyester polyol (a2) is a value measured by the same measurement method as the number-average molecular weight of component (a1) above.

[0027] The proportion (amount used) of aromatic polyester polyol (a2) in the above polyol (A) can be in the range of 0% to 60% by mass of the total amount (100% by mass) of the above polyol (A). From the viewpoint of obtaining a moisture-proof film with high moisture permeability and excellent mechanical strength in a thin film, the range of 5% to 55% by mass of the above polyol (A) is preferred, the range of 8% to 50% by mass is more preferred, and the range of 10% to 40% by mass is even more preferred.

[0028] The polyol (A) described above may contain one or more crystalline polyester polyols (a3) ​​as optional components, in addition to component (a1). Note that crystalline polyester polyol (a3) ​​may sometimes be referred to as component (a3).

[0029] The moisture-curing polyurethane hot-melt resin composition further contains crystalline polyester polyol (a3), which can further improve the adhesive strength, mechanical strength, and moisture permeability of the moisture-permeable film under normal conditions and after durability testing. In this specification, "crystalline" refers to a material in which a peak of crystallization heat or fusion heat can be confirmed by DSC (differential scanning calorimeter) measurement in accordance with JIS K7121-1987.

[0030] The above-mentioned crystalline polyester polyol (a3) ​​is obtained by a condensation reaction between a low molecular weight polyol and a polycarboxylic acid.

[0031] Low molecular weight polyols used as raw materials for crystalline polyester polyol (a3) ​​include, for example, ethylene glycol, diethylene glycol 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, and 10-decanediol, with neopentyl glycol being preferred because it results in a breathable film with a flexible texture.

[0032] Examples of polycarboxylic acids that can be used as raw materials for crystalline polyester polyol (a3) ​​include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecamethylenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydroisophthalic acid, and phthalic anhydride.

[0033] The above-mentioned crystalline polyester polyol (a3) ​​may be one or more of aliphatic, alicyclic, and aromatic, but it is preferable that it contains crystalline aliphatic polyester polyol (a3-1). The above-mentioned crystalline aliphatic polyester polyol (a3-1) can be a reaction product of a polybasic acid and a compound having two or more hydroxyl groups. Examples of the above-mentioned polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and 1,12-dodecanedicarboxylic acid. Examples of the above-mentioned compound having two or more hydroxyl groups include the compounds having two or more hydroxyl groups that were exemplified as raw materials for the above-mentioned "aromatic polyester polyol (a2)".

[0034] In particular, from the viewpoint of further increasing the mechanical strength of the moisture-permeable film, the crystalline polyester polyol (a3) ​​is preferably a crystalline aliphatic polyester polyol which is a reaction product of one or more polybasic acids selected from the group consisting of adipic acid, sebacic acid, and 1,12-dodecanedicarboxylic acid, and one or more compounds having two or more hydroxyl groups selected from the group consisting of ethylene glycol, butanediol, hexanediol, and dodecanediol.

[0035] 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, from the viewpoint of the mechanical strength and moisture permeability of the moisture-permeable film. The number-average molecular weight of the above crystalline polyester polyol (a3) ​​is a value measured by the same measurement method as the number-average molecular weight of component (a1) above.

[0036] The proportion (amount used) of crystalline polyester polyol (a3) ​​in the above polyol (A) can be in the range of 0% to 60% by mass of the total amount (100% by mass) of polyol (A). From the viewpoint of improving the texture of the moisture-proof film, a range of 1% to 55% by mass of polyol (A) is preferred, and a range of 2% to 50% by mass is more preferred.

[0037] In addition to the above-mentioned component (a1), the polyol (A) may optionally contain one or more polyester polyols (a4) (hereinafter sometimes referred to as component (a4)), which are reaction products (condensation products) of a polyol obtained by adding an alkylene oxide to bisphenol A and a polycarboxylic acid. Component (a4) is not included in components (a1) to (a3).

[0038] The number-average molecular weight of component (a4) is preferably in the range of 500 to 10000, and more preferably in the range of 1000 to 4000. Having the number-average molecular weight of component (a4) within this range reduces the viscosity of the moisture-curing polyurethane hot-melt resin composition in the heated and melted state, improving continuous coating properties during the production of moisture-permeable films. The number-average molecular weight of component (a4) is measured using the same method as the number-average molecular weight of component (a1).

[0039] The above component (a4) preferably has a glass transition temperature in the range of -50°C to 40°C. The glass transition temperature of the above component (a4) can be adjusted, for example, by adjusting the amount of alkylene oxide added to the above bisphenol A. The glass transition temperature is the endothermic peak temperature measured using a DSC (differential scanning calorimetry analyzer) in a nitrogen atmosphere from -80°C at a heating rate of 5°C / min.

[0040] The polyol obtained by adding an alkylene oxide to bisphenol A can be produced, for example, by adding an alkylene oxide to bisphenol A using a well-known and conventional method. Among these, polyether polyols obtained by adding an alkylene oxide to bisphenol A are preferred.

[0041] As the alkylene oxide that is the raw material for component (a4) above, for example, ethylene oxide, propylene oxide, etc. can be used, and among these, propylene oxide is preferred.

[0042] The alkylene oxide, which is the raw material for component (a4) above, is preferably added to the bisphenol A in an amount of 1 mole to 10 moles, more preferably in an amount of 2 moles to 8 moles, and even more preferably in an amount of 4 moles to 8 moles. Component (a4) above is compatible with other polyols and can improve the adhesive strength, moisture permeability, and flexibility of the moisture-permeable film under normal conditions and after durability testing.

[0043] The polycarboxylic acid used as a raw material for component (a4) above is preferably one or more compounds selected from the group consisting of aliphatic polycarboxylic acids, alicyclic dicarboxylic acids, and aromatic polycarboxylic acids. Examples of aliphatic polycarboxylic acids used as a raw material for component (a4) above include succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. These may be used individually or in combination of two or more. Among these, aliphatic polycarboxylic acids with 6 to 10 carbon atoms are preferred from the viewpoint of excellent initial cohesive strength and durability of the moisture-permeable film, and more specifically, compounds selected from the group consisting of sebacic acid, adipic acid, and dodecanedicarboxylic acid are preferred. Examples of aromatic polycarboxylic acids used as a raw material for component (a4) above include phthalic acid, isophthalic acid, and terephthalic acid, and isophthalic acid is preferred.

[0044] In particular, the polycarboxylic acid that is the material for component (a4) above is preferably a combination of one or more aliphatic polycarboxylic acids and one or more aromatic polycarboxylic acids, and it is preferable to use sebacic acid and isophthalic acid in combination.

[0045] When the polycarboxylic acid that is the material for component (a4) above is a mixture of aliphatic polycarboxylic acid and aromatic polycarboxylic acid, the ratio of aliphatic polycarboxylic acid to aromatic polycarboxylic acid used ([aliphatic polycarboxylic acid / aromatic polycarboxylic acid]) is preferably 10 / 90 to 50 / 50 (equivalent ratio).

[0046] The proportion (amount used) of component (a4) in the polyol (A) can be in the range of 0% to 30% by mass of the total amount (100% by mass) of polyol (A). In particular, from the viewpoint of improving compatibility with other polyols and improving the adhesive strength, moisture permeability, and flexibility of the moisture-permeable film, a range of 5% to 30% by mass is preferred, and a range of 5% to 20% by mass is more preferred, based on 100% by mass of the total amount of polyol (A).

[0047] The polyol (A) described above may contain, in addition to component (a1) described above, one or more polyols (a5) having three hydroxyl groups (hereinafter sometimes referred to as component (a5)) as an optional component. Polyol (a5) having three hydroxyl groups is a component other than components (a1) to (a4) described above. By further including polyol (a5) having three hydroxyl groups in polyol (A), the urethane prepolymer forms a cross-linked structure, further improving the balance between the mechanical strength and moisture permeability of the moisture-permeable film. Component (a5) described above is not included in components (a1) to (a4) described above.

[0048] As component (a5) above, for example, compounds having an oxyalkylene group such as glycerin, trimethylolpropane, polyoxypropylene triol, polymers of glycerin and propylene oxide, and polymers of polyoxypropylene triol and ethylene oxide can be used. These may be used alone or in combination of two or more. In particular, polyols having an oxyalkylene group are preferred as component (a5) above, and polyoxypropylene triol is more preferred, as they have good compatibility with other polyol components such as component (a1) and increase the moisture permeability and mechanical strength of the moisture-permeable film.

[0049] The number-average molecular weight of component (a5) above (particularly the polyol having three hydroxyl groups containing an oxyalkylene group) is preferably in the range of 300 to 800, as this allows for good compatibility with other polyol components such as component (a1), and further enhances the moisture permeability and mechanical strength of the moisture-permeable film. The number-average molecular weight of component (a5) above is measured using the same measurement method as the number-average molecular weight of component (a1) above.

[0050] The proportion (amount used) of component (a5) in the polyol (A) can be in the range of 0 to 10 parts by mass of the total amount (100% by mass) of polyol (A). In particular, it is preferable that the proportion is in the range of 0.01% to 10% by mass of the total amount (100% by mass) of polyol (A), more preferably 0.1% to 7% by mass, and even more preferably 0.3% to 5% by mass, as this provides good compatibility with polyol (A) and increases the moisture permeability and mechanical strength of the moisture-permeable film.

[0051] In addition to the above-mentioned component (a1), the polyol (A) may contain one or more other polyols (a6) other than components (a1) to (a5) as an optional component. Examples of the above-mentioned other polyols (a6) include polyester polyols, polyoxypropylene glycols, polyoxytetramethylene glycols, polyacrylic polyols, polycarbonate polyols, polybutadiene polyols, etc. These polyols may be used individually or in combination of two or more.

[0052] The proportion (content) of the oxyethylene structure (EO skeleton: -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 having the proportion of the oxyethylene structure in the polyol (A) within the above range, the moisture permeability, mechanical strength, and texture of the moisture permeable film can be improved. In particular, if the proportion (content) of the oxyethylene structure (EO skeleton: -OCCO-) in the polyol (A) is 10 mol / kg or more, the thinness, moisture permeability, and mechanical strength of the moisture permeable film can be improved. Since the oxyethylene structure is supplied from component (a1), the content of the oxyethylene structure can be appropriately determined by adjusting component (a1).

[0053] The polyol (A) above contains at least component (a1), but in a preferred embodiment, it is preferable to contain component (a1) and at least one component from the group consisting of component (a2), component (a3), and component (a5), and in particular it is preferable to contain at least component (a1) and component (a3), and more preferably it contains all four components (a1), (a2), (a3), and (a5) from the viewpoint of achieving both thinness, high moisture permeability, and adhesion of the moisture-permeable film.

[0054] -Polyisocyanate (B)- Examples of polyisocyanates (B) include aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate (e.g., 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, etc.), carbodiimide-modified diphenylmethane diisocyanate isocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, etc.; and aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, etc. These polyisocyanates may be used alone or in combination of two or more. Among these, aromatic polyisocyanates are preferred because they offer good reactivity and mechanical strength for the film, and diphenylmethane diisocyanate is even more preferred because it has a low vapor pressure when heated and melted.

[0055] The proportion (amount used) of the above polyisocyanate (B) in the total mass of the raw materials (solids) constituting the urethane prepolymer is preferably in the range of 5% to 40% by mass, and more preferably in the range of 10% to 30% by mass.

[0056] -Urethane prepolymer- The above urethane prepolymer is obtained by reacting raw materials that at least include the above polyol (A) and the above polyisocyanate (B). In particular, the above urethane prepolymer is a reaction product of polyol (A) containing the above components (a1), (a2), (a3), and (a5) and the above polyisocyanate (B), and it is preferable from the viewpoint of thinness and high moisture permeability of the moisture permeable film that the proportion of the above component (a1) in the above polyol (A) is 50% by mass or more.

[0057] The above-mentioned urethane prepolymer may have ethylenically unsaturated double bond groups as terminal functional groups at both or one of its ends, in addition to isocyanate groups. Examples of ethylenically unsaturated double bond groups include vinyl groups, allyl groups, and (meth)acrylic groups. A urethane prepolymer having ethylenically unsaturated double bond groups as terminal functional groups can be prepared, for example, by reacting an acrylate compound (e.g., a hydroxyl group-containing (meth)acrylate) with a urethane prepolymer having two or more isocyanate groups per molecule at the molecular ends.

[0058] The softening point of the above-mentioned urethane prepolymer is preferably in the range of 40 to 120°C from the viewpoint of increasing the adhesive strength of the moisture-permeable film. In this specification, the softening point refers to the temperature at which the urethane prepolymer begins to undergo thermal flow and loses its cohesive force when its temperature is gradually increased, and specifically refers to the value obtained by the ring-and-sphere method (JIS K-6301).

[0059] As a method for producing the above-mentioned urethane prepolymer, for example, the components of the polyol (A) are added to a reaction vessel containing the polyisocyanate (B), mixed, and then heated, and the reaction is carried out under conditions in which the isocyanate groups of the polyisocyanate (B) are in excess of the hydroxyl groups of the polyol (A).

[0060] When producing the above-mentioned urethane prepolymer, the equivalent ratio (NCO / OH) of the isocyanate group (NCO) of the polyisocyanate (B) to the hydroxyl group (OH) of the polyol (A) is preferably in the range of 1.1 to 5.0, and more preferably in the range of 1.5 to 3.0, from the viewpoint of being able to lower the melt viscosity of the moisture-curable urethane hot-melt resin composition that is heated and melted during the production of the moisture-permeable film, and to achieve both thinness of the moisture-permeable film and high mechanical strength.

[0061] The isocyanate group content (hereinafter abbreviated as "NCO%") of the above urethane prepolymer is preferably in the range of 1.7 to 5, and more preferably in the range of 2.0 to 4.5. Having the NCO% of the above urethane prepolymer within this range allows for a lower melt viscosity of the moisture-curing urethane hot-melt resin composition heated and melted during the production of the moisture-permeable film, resulting in a thin, moisture-permeable film free from defects such as streaks, repellency, and pinholes (hereinafter collectively referred to as "coating defects" or "defects"). The mechanical strength of the moisture-permeable film can be increased. The NCO% of the above urethane prepolymer is shown as the value measured by potentiometric titration in accordance with JIS K1603-1:2007.

[0062] The NCO gram equivalent of the above urethane prepolymer is preferably in the range of 700 to 3000, more preferably in the range of 800 to 2500, and even more preferably in the range of 900 to 2200, from the viewpoint of producing a thin film with high moisture permeability and no defects. By having the NCO gram equivalent of the above urethane prepolymer within the above range, the number average molecular weight of the urethane prepolymer can be reduced, which can lower the melt viscosity of the moisture-curing urethane hot-melt resin composition that is heated and melted during the production of the moisture-permeable film, resulting in a thin film with no defects. The NCO gram equivalent of the above urethane prepolymer is the value obtained by dividing the total value of all polyol components and isocyanate components that are materials of the urethane prepolymer by the value obtained by subtracting the polyol equivalent from the isocyanate equivalent.

[0063] The number-average molecular weight of the above urethane prepolymer is preferably in the range of 500 to 30000. In particular, from the viewpoint of producing a moisture-permeable film without defects even when the thickness is less than 30 μm, and more preferably 20 μm or less, the number-average molecular weight is more preferably in the range of 700 to 20000, and even more preferably in the range of 1000 to 15000. The number-average molecular weight of the above urethane prepolymer is a value measured by the same measurement method as the number-average molecular weight of component (a1) above.

[0064] The above moisture-curing urethane hot melt resin composition contains the above urethane prepolymer as an essential component, but may also contain other additives as needed. Examples of these other additives include tackifiers, curing catalysts, antioxidants, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent whitening agents, silane coupling agents, thixotropic agents, waxes, fluorescent whitening agents, thermoplastic resins, thermosetting resins, dyes, conductivity enhancers, antistatic agents, moisture permeability enhancers, water repellents, oil repellents, hollow foams, water-containing compounds, flame retardants, water absorbents, moisture absorbents, deodorants, foam stabilizers, defoamers, mold inhibitors, preservatives, algaecides, pigment dispersants, inert gases, blocking inhibitors, hydrolysis inhibitors, etc. These may be used individually or in combination of two or more.

[0065] The above moisture-curing urethane hot-melt resin composition preferably has a melt viscosity at 120°C in the range of 100 to 10,000 mPa·s. This is because it results in good continuous coating properties when forming a film-like coating using the heated and melted moisture-curing urethane hot-melt resin composition. In particular, from the viewpoint of suppressing the occurrence of coating defects when forming a thin coating with a thickness of less than 30 μm (more preferably 20 μm or less) by continuous coating, the melt viscosity at 120°C is more preferably in the range of 200 to 5,000 mPa·s, even more preferably in the range of 300 to 4,000 mPa·s, and particularly preferably in the range of 400 to 3,000 mPa·s. The melt viscosity of the moisture-curing urethane hot-melt resin composition can be adjusted by the average molecular weight of the urethane prepolymer, the isocyanate group content of the urethane prepolymer, etc.

[0066] <Breathable film> The thickness of the above-mentioned moisture-permeable film is not particularly limited as long as it can exhibit practical levels of moisture permeability. However, since the thickness of the laminate of this disclosure can be reduced as it becomes thinner and more moisture-permeable, the thickness of the above-mentioned moisture-permeable film is preferably less than 30 μm, and more preferably 20 μm or less. More specifically, the thickness of the above-mentioned moisture-permeable film is preferably 3 μm to 29 μm, more preferably 5 μm to 27 μm, even more preferably 7 μm to 25 μm, and particularly preferably 9 μm to 23 μm.

[0067] The moisture permeability of the above-mentioned moisture-permeable film is not particularly limited as long as it can achieve a practical level of moisture permeability, but 4000 (g / m²) is an acceptable value. 2 A value of 50,000 (g / m³) or higher is preferable. The moisture permeability of the breathable film is a value measured in accordance with the A-1 method (calcium chloride method) of JIS L1099:2012. The upper limit of moisture permeability is not particularly limited as long as it does not impair the waterproofing function, but for example, 50,000 (g / m³) is preferable. 2 It can be less than 30,000 (g / m³) per 24 hours, for example 30,000 (g / m³). 2 It can be set to 24 hours or less.

[0068] <Method for manufacturing moisture-permeable film> The above-mentioned moisture-permeable film can be manufactured by known methods. One example of a method for manufacturing the above-mentioned moisture-permeable film is to uniformly apply a heated and melted moisture-curing urethane hot-melt resin composition onto a release substrate using a coating apparatus to form a coating film, cool and solidify the coating film, allow it to mature for a certain period of time to allow the moisture-curing of the coating film to progress, and then peel off the release substrate after maturation to obtain a moisture-permeable film.

[0069] Another example of a method for manufacturing the moisture-permeable film is to directly and uniformly apply a heated and melted moisture-curing urethane hot-melt resin composition to one side of a substrate (described later) using a coating apparatus to form a coating film on the substrate, cool and solidify the coating film, and then allow it to mature for a certain period of time to allow the moisture-curing of the coating film to proceed, thereby directly manufacturing a moisture-permeable film on the substrate.

[0070] The above-mentioned release material is not particularly limited as long as it can form a coating film and can be peeled off after the coating film has hardened. For example, release paper, release-treated cloth (i.e., cloth that has been treated for release), water-repellent cloth, olefin sheets or films made of polyethylene resin or polypropylene resin, sheets or films made of fluororesin, plastic films with release paper, and polyurethane resin films with release paper can be used.

[0071] The arithmetic mean roughness (Sa) of the above-mentioned release substrate is not particularly limited, but in order to manufacture a moisture-permeable film with a thinner film (e.g., less than 30 μm, especially 20 μm or less) without causing coating defects, it is preferable that the arithmetic mean roughness (Sa) is 0.90 μm or more, preferably 0.92 μm or more, more preferably 0.95 μm or more, even more 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 above-mentioned release substrate is not particularly limited as long as it can form a coating film of a moisture-curing polyurethane hot-melt resin composition and the cured coating film can be peeled off, but it is preferably 25 μm or less, more preferably 22 μm or less, and even more preferably 19 μm or less. Arithmetic mean roughness (Sa) is a parameter that extends the arithmetic mean height Ra of a line to a surface, and is measured using a laser microscope in accordance with ISO 25178 on the surface of a release-type substrate to which a moisture-curing urethane hot-melt resin composition is applied.

[0072] Furthermore, while the gloss of the above-mentioned release substrate is not particularly limited, it is preferable that the gloss be 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, for the production of thinner (e.g., less than 30 μm, especially 20 μm or less) moisture-permeable films without defects. The gloss of the above-mentioned release substrate is a value measured using a BYK MicroGloss 45XX measuring device in accordance with JIS Z 8741:1997, with the surface of the release substrate to which the moisture-curing urethane hot-melt resin composition is applied, at an incident light angle of 60°.

[0073] The heating and melting temperature of the above moisture-curing urethane 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 by continuous coating. For example, it can be in the range of 50°C to 130°C, and more preferably in the range of 80°C to 120°C.

[0074] The method for applying the above moisture-curing polyurethane hot-melt resin composition is not particularly limited as long as a film-like coating can be formed on a release-resistant substrate by continuous coating. Examples include roll coating, extrusion, gravure coating, die coating, bar coating, and knife coating.

[0075] The thickness of the coating film of the above moisture-curing polyurethane hot-melt resin composition can be the same as the thickness of the heat-melt moisture-permeable film after curing, since the coating film is formed by the heat-melted moisture-curing polyurethane hot-melt resin composition and does not contain solvents.

[0076] The coating film of the above moisture-curing urethane hot melt resin composition hardens as it reacts with the air, the release substrate in contact with the coating film, and the moisture contained in the substrate, forming a film-like cured product, which then becomes a moisture-permeable film.

[0077] The curing conditions for the above-mentioned coating film can be, for example, an ambient temperature of 20°C to 40°C, a relative humidity of 50% to 80%, and a curing period 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 a substrate. Generally, the curing of the above-mentioned coating film is carried out with the release substrate or substrate on which the coating film has been formed wound up on a roll or the like, but it may also be carried out without winding. Furthermore, the curing reaction of the coating film may begin from the moment the moisture-curing type urethane hot melt resin composition is applied to the release substrate or substrate.

[0078] If the urethane prepolymer contained in the above moisture-curing polyurethane hot melt resin composition has ethylenically unsaturated double bond groups at both or one end, the coating film may be irradiated with active energy rays. This is because, in addition to curing the coating film of the moisture-curing polyurethane hot melt resin composition with moisture, the curing reaction can be further advanced by irradiation with active energy rays.

[0079] Examples of active energy rays include ultraviolet light. The irradiation dose of active energy rays is not particularly limited as long as it is sufficient to adequately advance the curing reaction of the coating film of the moisture-curing polyurethane hot melt resin composition, but for example, 50 mJ / cm². 2 ~5000 mJ / cm 2 Preferably, 100 mJ / cm² 2 ~3000 mJ / cm 2 This is more preferable. The above irradiation dose is based on the value measured in the wavelength range of 300 to 390 nm using a UV checker UVR-N1 (manufactured by Japan Storage Battery Co., Ltd.).

[0080] Examples of known lamps that emit active energy rays include xenon lamps, xenon-mercury lamps, metal halide lamps, high-pressure mercury lamps, and low-pressure mercury lamps.

[0081] The timing of irradiating the coating film of the above moisture-curing polyurethane hot melt resin composition with active energy rays is not particularly limited, but it is preferable to do so just before winding the release substrate or substrate onto a roll or the like, from the viewpoint of preventing a decrease in surface quality. Furthermore, the moisture curing reaction and the photocuring reaction by irradiation with active energy rays may proceed simultaneously, or one curing reaction may proceed first, followed by the other curing reaction.

[0082] 2. Base material The substrate in the present invention can be appropriately selected depending on the application of the laminate, and examples include resin film, moisture permeable film, fibrous substrate, wood substrate, metal substrate, foam sheet, synthetic leather, paper, rubber substrate, glass substrate, etc.

[0083] Examples of resin films include those made from known materials such as polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, polystyrene, and TPO (Thermoplastic Olefinic Elastomer).

[0084] Examples of breathable films include resin films such as solvent-based and water-based polyurethane resins, thermoplastic polyurethane resins (TPU), thermoplastic polyester resins (TPE), porous polytetrafluoroethylene (PTFE), and polyolefin resins such as polyethylene and polypropylene.

[0085] Examples of fibrous base materials include nonwoven fabrics, woven fabrics, knitted fabrics, and base fabrics. Materials for the fibrous base material include, for example, chemical fibers such as polyester fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, and polylactic acid fibers; as well as cotton, linen, silk, wool, and blends thereof.

[0086] Examples of wood-based substrates include plywood, MDF (medium-density fiberboard), and particleboard. Examples of metal substrates include aluminum and iron.

[0087] Examples of foamed sheets include polyurethane foam.

[0088] The above substrate may be a single layer or may have a multilayer structure of two or more layers. For example, a two-layer structure of a moisture-permeable film and a foamed sheet, or a moisture-permeable film and a fibrous substrate.

[0089] The thickness of the above-mentioned substrate is determined according to the intended use, but is typically in the range of 1 to 500 mm.

[0090] 3. Laminate The laminate of this disclosure may have a moisture-permeable film provided in contact with at least one surface of the substrate, or it may be provided on both surfaces of the substrate. Furthermore, the moisture-permeable film only needs to be provided continuously (non-intermittently) on the substrate, and it is preferable that it be provided over the entire surface of one side of the substrate. Intermittent means a state in which areas where cured material of the moisture-curing polyurethane hot-melt resin composition exists and areas where the cured material does not exist are intentionally provided, such as in a dot pattern or a mesh pattern. In the laminate of this disclosure, areas where cured material of the moisture-curing polyurethane hot-melt resin composition constituting the moisture-permeable film does not exist are not intentionally provided, and the moisture-permeable film covers a wide area (preferably the entire surface) of one side of the substrate surface.

[0091] Furthermore, the laminate may have any configuration other than the substrate and the moisture-permeable film, depending on the application of the laminate. For example, the surface of the moisture-permeable film opposite to the surface in contact with the substrate may have a surface layer, a surface treatment layer having functions such as blocking prevention and water pressure resistance, etc. Alternatively, the surface of the moisture-permeable film opposite to the surface in contact with the substrate may be directly surface-treated.

[0092] In the laminate of this disclosure, the moisture-permeable film also functions as an adhesive layer, and the moisture-permeable film is provided in direct contact with one surface of the substrate. Therefore, the interlayer adhesion between the substrate and the moisture-permeable film can be increased compared to a laminate in which the moisture-permeable film and the substrate are joined via intermittently provided adhesive. The normal interlayer adhesion strength between the substrate and the moisture-permeable film 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. Furthermore, the interlayer adhesion strength after durability testing of the substrate and the moisture-permeable film is preferably 15N / 25mm or higher, more preferably 17N / 25mm or higher, and even more preferably 20N / 25mm or higher. The upper limit of the interlayer adhesive strength under normal conditions and after durability testing is not particularly limited, but it can be, for example, 50 N / 25 mm or less.

[0093] The above interlayer adhesion strength is, in other words, the peel strength between the substrate and the moisture-permeable film, and is measured by the following method. Specifically, the laminate is cut to a width of 1 inch, the interlayer between the substrate and the moisture-permeable film is peeled at one end in the longitudinal direction of the laminate, and the peeled portion is grasped with each chuck using a Tensilon (Tensilon universal machine "RTC-1210A" manufactured by Orientec Co., Ltd.), and the value is measured when the part is pulled and peeled at a crosshead speed of 200 mm / min. Furthermore, the interlayer adhesion strength after the durability test is measured using the procedure described above, with the laminate left standing for three weeks in a constant temperature and humidity chamber adjusted to 70±5℃ and 95±5%RH.

[0094] The method for manufacturing the laminate according to this disclosure is not particularly limited as long as it is possible to directly provide a moisture-permeable film on one side of the substrate. One example of a method for manufacturing the laminate according to this disclosure is to place a moisture-permeable film obtained by the method for manufacturing a moisture-permeable film using a release-type substrate as described in section 1, "Moisture-Permeable Film," on one side of the substrate and bond it by heat pressing or the like.

[0095] Another example of a method for manufacturing the laminate of this disclosure is a method in which a heated and melted moisture-curing urethane hot melt resin composition is applied directly and uniformly to one side of a substrate using a coating device to form a coating film on the substrate, the coating film is cooled and solidified, and then aged for a certain period of time to allow the moisture curing of the coating film to proceed, thereby directly manufacturing a moisture-permeable film on the substrate. The application method of the moisture-curing urethane hot melt resin composition, the coating device, the aging conditions, etc., can be the same as the details of the method for manufacturing a moisture-permeable film described in section "1. Moisture-Permeable Film" above.

[0096] The applications of the laminates disclosed herein are not particularly limited, but they can be suitably used as breathable waterproof fabrics for clothing, medical and sanitary purposes, synthetic leather, building materials (building panels, decorative boards, etc.), and automotive interior materials. More specifically, they can be used in sportswear, raincoats, gloves, shoes, fire suits, military uniforms, bandage films, diaper films, wall materials, roofing materials, etc.

[0097] This disclosure is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of this disclosure and produces similar effects is included within the technical scope of this disclosure. [Examples]

[0098] The embodiments of this disclosure will be described in more detail below by showing examples and comparative examples.

[0099] The abbreviations for each material are shown below.

[0100] <Polyol (A)> <<Polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1) component>> • PEt-1: Polyoxyethylene glycol (number average molecular weight Mn; 1540, hydroxyl group equivalent (gram equivalent eq. wt); 770) • PEt-2: Polyoxyethylene glycol (number average molecular weight Mn; 2000, hydroxyl group equivalent (gram equivalent eq. wt); 1000) • PEt-3: Polyoxyethylene glycol (number average molecular weight Mn; 4000, hydroxyl group equivalent (gram equivalent eq. wt); 1550) • PEt-4: Polyoxyethylene glycol (number average molecular weight Mn; 6000, hydroxyl group equivalent (gram equivalent eq. wt); 4400) • PEt-5: Polyoxyethylene glycol (number average molecular weight Mn; 11000, hydroxyl group equivalent (gram equivalent eq. wt); 5500)

[0101] <<Aromatic polyester polyol (a2) component>> • PEs-1: Polyester polyol (reaction product of orthophthalic acid and 1,6-hexanediol, number average molecular weight Mn; 2000, hydroxyl group equivalent (gram equivalent eq. wt); 1000) PEs-2: Polyester polyol (reaction product of neopentyl glycol, diethylene glycol, and orthophthalic acid; number average molecular weight: 1000; hydroxyl group equivalent (gram equivalent eq. wt): 500)

[0102] <<Crystalline polyester polyol (a3) ​​component>> • PEs-3: Polyester polyol (reaction product of ethylene glycol, neopentyl glycol, 1,6-hexanediol, and adipic acid; number average molecular weight Mn: 5500; hydroxyl group equivalent (gram equivalent eq. wt): 2750) • PEs-4; Polyester polyol (reaction product of 1,6-hexanediol and sebacic acid, number average molecular weight Mn; 3500, hydroxyl group equivalent (gram equivalent eq. wt); 1750)

[0103] <<Polyol component (a5) containing three hydroxyl groups>> • PO-1: Polyoxypropylene triol (T-700, manufactured by Mitsui Chemicals, Inc., number average molecular weight Mn: 700, hydroxyl group equivalent (gram equivalent eq. wt): 233)

[0104] <Polyisocyanate (B)> MDI: 4,4'-diphenylmethane diisocyanate

[0105] [Preparation of moisture-curing polyurethane hot melt resin composition] (Moisture-curing polyurethane hot melt resin composition (1)) In a four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 204.6 parts by mass of "PEt-3", 64.8 parts by mass of "PEs-2", 64.8 parts by mass of "PEs-4", and 6.8 parts by mass of "PO-1" were added and mixed. The mixture was then heated under reduced pressure at 100°C until the moisture content in the flask was reduced to 0.05% by mass or less. Next, the contents of the flask were cooled to 90°C, and 91.4 parts by mass of "MDI" melted at 70°C were added. The mixture was reacted at 110°C for approximately 3 hours under a nitrogen atmosphere until the isocyanate group content became constant, thereby preparing a hot-melt urethane prepolymer (iii) and a solvent-free moisture-curing polyurethane hot-melt resin composition (1).

[0106] (Moisture-curing polyurethane hot melt resin composition (2) As shown in Table 1 below, a hot-melt urethane prepolymer (v) was prepared in the same manner as in Example 1, except that the type and amount of polyol (A) and the amount of polyisocyanate (B) were changed, to obtain a solvent-free moisture-curing polyurethane hot-melt resin composition (2).

[0107] (Moisture-curing polyurethane hot melt resin composition (3) As shown in Table 1 below, a hot-melt urethane prepolymer (vii) was prepared in the same manner as in Example 1, except that the type and amount of polyol (A) and the amount of polyisocyanate (B) were changed, to obtain a solvent-free moisture-curing polyurethane hot-melt resin composition (3).

[0108] [Table 1]

[0109] [Example 1] A solvent-free moisture-curing polyurethane hot-melt resin composition (1), heated and melted at 100°C, was continuously applied to the surface of a release substrate A (polyolefin-based release paper, arithmetic mean height Sa; 1.024 μm, gloss (60° gloss value); 4.7) using a roll coater to form a coating film with a thickness of 15 μm. This was then laminated to a base fabric (80 denier polyester base fabric, thickness 200 μm) using a laminator and left for 3 hours under conditions of 23°C and 65% relative humidity to obtain a laminate. Next, the coating film was matured for 24 hours or more under conditions of 23°C and 50±5% humidity to form a cured coating product (moisture-permeable film). This resulted in a processed fabric (laminated) with a two-layer structure of moisture-permeable film / base fabric.

[0110] [Example 2] A processed fabric (laminated body) was obtained in the same manner as in Example 1, except that a moisture-curing polyurethane hot-melt resin composition (2) was used to form a moisture-permeable film instead of moisture-curing polyurethane hot-melt resin composition (1).

[0111] [Example 3] A processed fabric (laminated body) was obtained in the same manner as in Example 1, except that a moisture-curing polyurethane hot-melt resin composition (3) was used to form a moisture-permeable film instead of moisture-curing polyurethane hot-melt resin composition (1).

[0112] [Comparative Example 1] After melting the moisture-curing polyurethane hot melt resin composition (1) at 100°C, apply a gravure roll coater (coating amount: 17.5±5 g / m²). 2 Using a 3-layer structure of moisture-curing polyurethane hot-melt resin composition, which was heated and melted, was intermittently coated onto a moisture-permeable film (DIC Corporation's Chrisbon S-517 processed into a 15 μm film) and then laminated with a base fabric (80 denier polyester base fabric, 200 μm thick) using a laminator to obtain a laminate. Next, the laminate was left for 24 hours or more in an atmosphere of 23°C and 50±5% humidity to obtain a processed fabric (laminated) with a 3-layer structure of moisture-permeable film / intermittent adhesive layer / base fabric.

[0113] [Comparative Examples 2-3] A processed fabric (laminated body) was obtained in the same manner as in Comparative Example 1, except that moisture-curing polyurethane hot-melt resin composition (2) or (3) was used instead of moisture-curing polyurethane hot-melt resin composition (1).

[0114] [evaluation] (Interlaminar bonding strength under normal conditions) Each of the obtained processed fabrics was cut to a width of 1 inch, and the layer between the base material and the moisture-permeable film was peeled at one end in the longitudinal direction. The peeled portion was grasped with each chuck using a Tensilon (Tensilon universal machine "RTC-1210A" manufactured by Orientec Co., Ltd.), and the peel strength was measured by tensile testing at a crosshead speed of 200 mm / min, and evaluated as follows. "T": 20N / 25cm or more. "F": Less than 20N / 25cm.

[0115] (Interlaminar bonding strength after durability testing) Each processed fabric obtained was left to stand for three weeks in a constant temperature and humidity chamber adjusted to 70±5℃ and 95±5%RH. After that, it was cut into 1-inch widths, and the layer between the base material and the moisture-permeable film was peeled off at one end in the longitudinal direction. The peeled portion was grasped with each chuck using a Tensilon (Tensilon universal machine "RTC-1210A" manufactured by Orientec Co., Ltd.), and the peel strength was measured by tensile testing at a crosshead speed of 200 mm / min, and evaluated as follows. "T": 15N / 25cm or more. "F": Less than 15N / 25cm.

[0116] The evaluation results are shown in the table below.

[0117] [Table 2]

[0118] (moisture permeability) The moisture permeability of the processed fabrics of the examples and comparative examples was measured in accordance with JIS L1099 (A-1: Calcium Chloride Method). The processed fabrics of both the examples and comparative examples all had a moisture permeability of 4000 (g / m2 / 24h) or higher. The processed fabrics of Examples 1 to 3 showed the highest moisture permeability in the order of Example 2 < Example 1 < Example 3. Furthermore, the relationship between the moisture permeability of the processed fabric of Example 1 and the processed fabric of Comparative Example 1 was Comparative Example 1 < Example 1. Similarly, the relationship between the moisture permeability of the processed fabric in Example 2 and the processed fabric in Comparative Example 2 was Comparative Example 2 < Example 2. Similarly, the relationship between the moisture permeability of the processed fabric in Example 3 and the processed fabric in Comparative Example 3 was Comparative Example 3 < Example 3.

[0119] Based on these results, the processed fabrics of Examples 1 to 3 showed superior interlayer adhesion strength under normal conditions and after durability testing, as well as superior moisture permeability, compared to the processed fabrics of Comparative Examples 1 to 3.

Claims

1. Substrate and The substrate has a moisture-permeable film in contact with at least one surface of the substrate, The moisture-permeable film is a laminate made of a cured product of a moisture-curable polyurethane hot-melt resin composition containing a urethane prepolymer obtained by reacting a polyol (A) containing polyethylene glycol and / or polyoxyethylene polyoxypropylene glycol (a1) with a polyisocyanate (B).

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

3. The laminate according to claim 1, wherein the polyol (A) further comprises a crystalline polyester polyol (a3).

4. The laminate according to claim 1, wherein the polyol (A) further comprises a 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 50% by mass or more of the total amount (100% by mass) of the polyol (A).

6. The laminate according to claim 1, wherein the proportion of oxyethylene structures in the polyol (A) is 10 mol / kg or more.

7. The laminate according to claim 1, wherein the interlayer adhesive strength between the substrate and the moisture-permeable film is 20 N / 25 mm or more.

8. The laminate according to claim 1, wherein the base material is a base fabric.

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