Polyurethane resin composition

Abstract

A polyurethane resin composition comprising a polyurethane resin (U) and an organic solvent (S), wherein the polyurethane resin (U) has a structural unit derived from a polyoxyethylenediol (A), a structural unit derived from a polycarbonate diol (B), a structural unit derived from an aliphatic isocyanate compound (C), a structural unit derived from a C2-6 diol (D), and a structural unit derived from a C2-20 diamine (E), the structural unit derived from the aliphatic isocyanate compound (C) being either a structural unit derived from a non-cyclic aliphatic diisocyanate (c1) having a structure such that two isocyanate groups are directly bound to a non-cyclic hydrocarbon having an odd number of carbon atoms or a structural unit derived from an alicyclic diisocyanate (c2) in which the number of isocyanate groups that are directly bound to an alicyclic hydrocarbon is 0 or 1.

Description

Polyurethane resin composition 【0001】 The present disclosure relates to a polyurethane resin composition, and to a moisture-permeable, waterproof fabric, sportswear, rainwear, tents, and sanitary goods made using the same. 【0002】 Polyurethane resins are used in a variety of materials due to their excellent elasticity and durability (abrasion resistance and heat resistance), and in recent years, their excellent properties have led to expectations for their development as breathable waterproof materials, which are used in outdoor products, sportswear, sports shoes, rainwear (raincoats, etc.), tents, disposable diapers, wound dressings (bandages), etc. Polyurethane resins used in these applications are strongly required to have a balance of physical properties such as durability in addition to breathable waterproof performance. 【0003】 As a polyurethane resin for a breathable waterproof material, Patent Document 1 proposes a polyurethane resin formed from a polyurethane resin composition for a breathable waterproof fabric, which comprises an alcohol solution of a hydrophilic polyurethane resin having an oxyethylene group content of 10 to 80% by weight in the resin, and a polyisocyanate. Patent Document 2 proposes an aqueous polyurethane resin containing structural units derived from an emulsifier having a polyoxyethylene group as a side chain. Patent Document 3 also proposes a polyurethane resin obtained by curing a composition containing a monofunctional epoxy compound and a polyurethane obtained by reacting one or more polyols selected from polytetramethylene polyol, polycarbonate polyol, and polyolefin polyol with a polyisocyanate, a polyol having a carboxy group, and a chain extender. 【0004】 JP 2007-211239 A JP 2006-335951 A International Publication No. 2021 / 187504 【0005】 An object of the present disclosure is to provide a polyurethane resin composition capable of producing a breathable waterproof material having excellent breathable waterproof performance and durability. Another object of the present disclosure is to provide a breathable waterproof fabric, sportswear, rainwear, tents, and sanitary goods using the polyurethane resin composition. 【0006】 As a result of intensive research aimed at solving the above-mentioned problems, the inventors of the present disclosure have found that a breathable waterproof material with excellent breathable waterproof performance and durability can be obtained from a polyurethane resin composition containing a polyurethane resin having a specific structure and composition and an organic solvent, and that the polyurethane resin composition is suitable for applications such as breathable waterproof fabrics, sportswear, rainwear, tents, and sanitary products. That is, the present disclosure has the following characteristics. 【0007】[1] A polyurethane resin composition comprising a polyurethane resin (U) and an organic solvent (S), wherein the polyurethane resin (U) has structural units derived from a polyoxyethylene diol (A), structural units derived from a polycarbonate diol (B), structural units derived from an aliphatic isocyanate compound (C), structural units derived from a diol (D) having 2 to 6 carbon atoms, and structural units derived from a diamine (E) having 2 to 20 carbon atoms, and the structural units derived from the aliphatic isocyanate compound (C) are structural units derived from an acyclic aliphatic diisocyanate (c1) in which two isocyanate groups are directly bonded to an acyclic hydrocarbon having an odd number of carbon atoms, or structural units derived from an alicyclic diisocyanate (c2) in which the number of isocyanate groups directly bonded to the alicyclic hydrocarbon is 0 or 1. [2] The polyurethane resin composition according to [1], wherein the ratio (A) / ((A)+(B)) of the weight of the structural units derived from the polyoxyethylene diol (A) to the total weight of the structural units derived from the polyoxyethylene diol (A) and the structural units derived from the polycarbonate diol (B) in the polyurethane resin (U) is 0.50 to 0.90. [3] The polyurethane resin composition according to [1] or [2], wherein the ratio of the number of moles of nitrogen atoms derived from isocyanate groups in the structural units derived from the aliphatic isocyanate compound (C) to the number of moles of nitrogen atoms derived from amino groups in the diamine (E) is 1.5 to 2.5. [4] The polyurethane resin composition according to any of [1] to [3], wherein the structural units derived from the polyoxyethylene diol (A) are structural units derived from a polyoxyethylene diol having a hydroxyl value of 26.0 to 140.0 mgKOH / g. [5] The polyurethane resin composition according to any one of [1] to [4], wherein the structural unit derived from the polycarbonate diol (B) is a structural unit derived from a polycarbonate diol having a hydroxyl value of 32.0 to 124.7 mg KOH / g.[6] The polyurethane resin composition according to any one of [1] to [5], wherein the structural units derived from the polycarbonate diol (B) include a structural unit represented by the following formula (b1) and a structural unit represented by the following formula (b2), or a structural unit represented by the following formula (b2), and the molar ratio of the structural units (b1) / (b2) is 95 / 5 to 5 / 95: -O-R. １ -O- ...(b1) -O-R ２ -O-...(b2) (In formula (b1), R １ is a divalent alkylene group having 3 to 5 carbon atoms which may have a substituent, and in formula (b2), R ２represents a divalent alkylene group having 6 to 20 carbon atoms which may have a substituent.) [7] The polyurethane resin composition according to any one of [1] to [6], wherein the content of structural units derived from the aliphatic isocyanate compound (C) in the polyurethane resin (U) is 50% by weight or less. [8] The polyurethane resin composition according to any one of [1] to [7], wherein the diamine (E) is a diamine having 6 to 12 carbon atoms. [9] The polyurethane resin composition according to any one of [1] to [8], wherein the ratio of the total molar number of oxygen atoms derived from hydroxyl groups of the polyoxyethylene diol (A) and the polycarbonate diol (B) to the molar number of oxygen atoms derived from hydroxyl groups of the diol (D) in the polyurethane resin (U) is 0.5 to 1.5.

[10] The polyurethane resin composition according to any one of [1] to [9], wherein the ratio of the number of moles of nitrogen atoms derived from isocyanate groups of the aliphatic isocyanate compound (C) to the total number of moles of oxygen atoms derived from hydroxyl groups of the polyoxyethylene diol (A), oxygen atoms derived from hydroxyl groups of the polycarbonate diol (B), and oxygen atoms derived from hydroxyl groups of the diol (D) in the polyurethane resin (U) is 1.5 to 4.0.

[11] The polyurethane resin composition according to any one of [1] to

[10] , wherein the content of polar solvent (Y) satisfying the following conditions (y1) and (y2) in the organic solvent (S) is 5% by weight or less. (y1) Not classified as carcinogenic in the GHS (revised 9th edition) classification. (y2) Classification of acute toxicity in Category 1 to Category 3 in the GHS (revised 9th edition) classification, or classification of reproductive toxicity in Category 1A or Category 1B in the GHS (revised 9th edition) classification.

[12] The polyurethane resin composition according to any one of [1] to

[11] , wherein the organic solvent (S) comprises a monohydric alcohol having 5 or less carbon atoms, and a ketone having 6 or less carbon atoms or an ester having 8 or less carbon atoms.

[13] The polyurethane resin composition according to any one of [1] to

[12] , wherein the content of the polyurethane resin (U) in the polyurethane resin composition is 5 to 50% by weight.

[14] The polyurethane resin composition according to any one of [1] to

[13] , which contains a compound derived from biomass.

[15] A moisture-permeable, waterproof fabric made using the polyurethane resin composition according to any one of [1] to

[14] .

[16] Sportswear made using the polyurethane resin composition according to any one of [1] to

[14] .

[17] Rainwear made using the polyurethane resin composition according to any one of [1] to

[14] .

[18] A tent made using the polyurethane resin composition according to any one of [1] to

[14] .

[19] A sanitary product made using the polyurethane resin composition according to any one of [1] to

[14] . 【0008】 According to the present disclosure, a polyurethane resin composition can be provided that can provide a breathable waterproof material having excellent breathable waterproof performance and durability. Furthermore, by using the polyurethane resin composition, breathable waterproof fabrics, sportswear, rainwear, tents, and sanitary products can be provided. 【0009】 The following describes in detail the embodiments of the present disclosure. However, the following description of the constituent elements is an example (typical example) of an embodiment of the present disclosure, and the present disclosure is not limited to the following content as long as it does not deviate from the gist of the disclosure. Furthermore, when the expression "to" is used in this specification, it is used in a sense that it includes the numerical values ​​or physical values ​​written before and after it. Furthermore, numerical values ​​or physical values ​​written as upper and lower limits are used in a sense that they include the values ​​themselves. 【0010】 One embodiment of the present disclosure is a polyurethane resin composition comprising a polyurethane resin (U) and an organic solvent (S). The polyurethane resin (U) comprises structural units derived from a polyoxyethylene diol (A), structural units derived from a polycarbonate diol (B), structural units derived from an aliphatic isocyanate compound (C), structural units derived from a diol (D) having 2 to 6 carbon atoms, and structural units derived from a diamine (E) having 2 to 20 carbon atoms, and the structural units derived from the aliphatic isocyanate compound (C) are structural units derived from an acyclic aliphatic diisocyanate (c1) in which two isocyanate groups are directly bonded to an odd-carbon acyclic hydrocarbon, or structural units derived from an alicyclic diisocyanate (c2) in which zero or one isocyanate group is directly bonded to an alicyclic hydrocarbon. 【0011】 [1. Polyurethane Resin (U)] The polyurethane resin (U) has structural units derived from a polyoxyethylene diol (A), structural units derived from a polycarbonate diol (B), structural units derived from an aliphatic isocyanate compound (C), structural units derived from a diol (D) having 2 to 6 carbon atoms, and structural units derived from a diamine (E) having 2 to 20 carbon atoms. One type of polyurethane resin (U) may be used alone, or two or more types may be used in any combination and ratio. 【0012】 The content of the polyurethane resin (U) in the polyurethane resin composition is preferably 5 to 50% by weight, more preferably 10 to 50% by weight. When the content of the polyurethane resin (U) is within the above range, viscosity adjustment during application becomes easy, and handling properties are improved. 【0013】 [1-1. Structural units derived from polyoxyethylene diol (A)] The polyoxyethylene diol (A) that provides the structural units derived from the polyoxyethylene diol (A) may be a diol whose repeating units are composed only of oxyethylene units, or may contain other units as long as the effects of the present disclosure are not impaired. Examples of other units include units derived from the isocyanate compound (c) described below. The polyoxyethylene diol (A) may be used alone or in any combination and ratio of two or more types. 【0014】 Furthermore, polyoxyethylene diol obtained by using biomass ethanol as a crude raw material and then ring-opening polymerizing biomass ethylene oxide via biomass ethylene is preferred because it is derived from biomass. 【0015】 The number average molecular weight Mn of the polyoxyethylene diol (A) is preferably 800 to 4,300, more preferably 1,000 to 3,000, and even more preferably 1,600 to 2,400. 【0016】The hydroxyl value of the polyoxyethylene diol (A) is preferably 26.0 to 140.0 mgKOH / g, more preferably 26.0 to 125.0 mgKOH / g, even more preferably 28.0 to 75.0 mgKOH / g, and particularly preferably 40.0 to 70.0 mgKOH / g. The hydroxyl value of the polyoxyethylene diol (A) is measured in accordance with Method A (a method using an acetylating reagent) of JIS K 1557-1:2007. 【0017】 When the hydroxyl value of the polyoxyethylene diol (A) is equal to or greater than the above lower limit, a moisture-permeable waterproof material having good texture and moisture permeability can be provided. When the hydroxyl value of the polyoxyethylene diol (A) is equal to or less than the above upper limit, a polyurethane resin (U) having excellent durability can be obtained. 【0018】 The polyoxyethylene diol (A) preferably has a CPR (controlled polymerization rate) value, as defined in JIS K 1557-4 (2007), of 5 or less, more preferably 3 or less, and even more preferably 1 or less. When the CPR value is 5 or less, reaction control during the polyurethane reaction, particularly in the two-stage process of the present disclosure, becomes easier, and gelation can be suppressed. 【0019】 The polyoxyethylene diol (A) may be a polyoxyethylene diol (Ac) which is a copolymer of a low-molecular-weight polyoxyethylene diol (a) and an isocyanate compound (c). 【0020】 The low-molecular-weight polyoxyethylene diol (a) is a diol whose repeating unit is an oxyethylene unit. In this specification, "low molecular weight" means that the number average molecular weight (Mn) is 1,500 or less. The low-molecular-weight polyoxyethylene diol (a) may be used alone or in any combination and ratio of two or more. 【0021】The hydroxyl value of the low-molecular-weight polyoxyethylene diol (a) is preferably 75.0 to 450.0 mgKOH / g, more preferably 80.0 to 375.0 mgKOH / g, even more preferably 90.0 to 225.0 mgKOH / g, still more preferably 100.0 to 225.0 mgKOH / g, and particularly preferably 100.0 to 150.0 mgKOH / g. The hydroxyl value of the low-molecular-weight polyoxyethylene diol (a) is measured in accordance with Method A (a method using an acetylating reagent) of JIS K 1557-1:2007. 【0022】 When the hydroxyl value of the low-molecular-weight polyoxyethylene diol (a) is equal to or greater than the above-mentioned lower limit, a moisture-permeable waterproof material having good texture and moisture permeability can be provided. When the hydroxyl value of the polyoxyethylene diol (A) is equal to or less than the above-mentioned upper limit, a polyurethane resin (U) having excellent durability can be obtained. 【0023】 Examples of the isocyanate compound (c) include the aliphatic isocyanate compound (C) and the aromatic isocyanate compound (cr) described below, and the aromatic isocyanate compound (cr) is preferred. The isocyanate compound (c) may be used alone or in any combination and ratio of two or more. 【0024】 Specific examples of the aromatic isocyanate compound (cr) include xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, and m-tetramethylxylylene diisocyanate. 【0025】Among these, the aromatic isocyanate compound (cr) is preferably selected from 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4'-diphenylmethane diisocyanate, in view of the good balance between durability and moisture permeability of the resulting polyurethane resin (U). 【0026】 Incidentally, when an aromatic isocyanate compound (cr) is used in the reaction with the low-molecular-weight polyoxyethylene diol (a), the cohesive force of the resulting polyurethane resin (U) is improved, and strength can be increased, but yellowing may occur. Therefore, when producing a polyoxyethylene diol (Ac) by reacting a low-molecular-weight polyoxyethylene diol (a) with an aromatic isocyanate compound (cr), from the viewpoint of achieving both strength and suppression of yellowing, the amount of the aromatic isocyanate compound (cr) used is preferably 5 to 30 wt %, and particularly preferably 10 to 25 wt %, based on the total amount of the aliphatic isocyanate compound (C) and the aromatic isocyanate compound (cr) used in the reaction with the polyoxyethylene diol (A). 【0027】 [1-2. Structural units derived from polycarbonate diol (B)] The polycarbonate diol (B) that provides the structural units derived from polycarbonate diol (B) has hydroxyl groups at both ends of the molecule and a carbonate bond in the main chain. The hydroxyl value of the polycarbonate diol (B) is preferably 32.0 to 124.7 mgKOH / g, more preferably 35.0 to 119.3 mgKOH / g, even more preferably 36.0 to 75.0 mgKOH / g, still more preferably 40.0 to 100.0 mgKOH / g, and particularly preferably 45.0 to 90.0 mgKOH / g. 【0028】 When the hydroxyl value of the polycarbonate diol (B) is equal to or greater than the lower limit, a moisture-permeable waterproof material having good texture and moisture permeability can be provided. When the hydroxyl value of the polycarbonate diol (B) is equal to or less than the upper limit, a polyurethane resin (U) having excellent strength can be obtained. 【0029】The structural unit derived from the polycarbonate diol (B) preferably contains either or both of a structural unit represented by the following formula (b1) and a structural unit represented by the following formula (b2), and more preferably contains a structural unit represented by the following formula (b1) and a structural unit represented by the following formula (b2), or a structural unit represented by the following formula (b2). The molar ratio of the structural units (b1) / (b2) is usually 100 / 0 to 0 / 100, but is preferably 95 / 5 to 5 / 95. -O-R １ -O- ...(b1) -O-R ２ -O-...(b2) (In formula (b1), R １ is a divalent alkylene group having 3 to 5 carbon atoms which may have a substituent, and in formula (b2), R ２ represents a divalent alkylene group having 6 to 20 carbon atoms which may have a substituent. 【0030】 Examples of diols that provide the structural unit represented by formula (b1) include 2-methyl-1,3-propanediol and 1,4-butanediol. Among these, 1,4-butanediol is preferred as the diol that provides the structural unit represented by formula (b1), in that a polyurethane resin (U) excellent in durability and strength can be obtained. The diols that provide the structural unit represented by formula (b1) may be used alone or in any combination and ratio of two or more. 【0031】 R in the above formula (b2) ２ is preferably a divalent alkylene group having 8 to 20 carbon atoms which may have a substituent, and more preferably a divalent alkylene group having 8 to 12 carbon atoms which may have a substituent. It is also preferable that these alkylene groups are unsubstituted. 【0032】Examples of diols that provide the structural unit represented by formula (b2) include 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,12-octadecanediol, and 1,20-eicosanediol. 【0033】 Among these, in terms of achieving an excellent balance between the strength and durability of the polyurethane resin (U) and the texture of the breathable waterproof material, the diol that provides the structural unit represented by formula (b2) is preferably 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, or 1,12-dodecanediol, more preferably selected from 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol, and even more preferably 1,10-decanediol. The diol that provides the structural unit represented by formula (b2) may be used alone or in any combination and ratio of two or more. 【0034】 The structural unit represented by the formula (b1) is preferably derived from a plant, from the viewpoint of reducing the environmental load. An example of a diol that provides the structural unit represented by the formula (b1) that can be derived from a plant is 1,4-butanediol. 【0035】 The structural unit represented by the formula (b2) is preferably derived from a plant, from the viewpoint of reducing the environmental load. Examples of diols that provide the structural unit represented by the formula (b2) that can be derived from a plant include 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,12-octadecanediol, and 1,20-eicosanediol. 【0036】The molar ratio (b1) / (b2) of the structural unit represented by formula (b1) to the structural unit represented by formula (b2) is usually 100 / 0 to 0 / 100, preferably 95 / 5 to 5 / 95, more preferably 89 / 11 to 5 / 95, even more preferably 85 / 15 to 5 / 95, and particularly preferably 75 / 25 to 5 / 95. When (b1) / (b2) is within the above range, the strength and durability of the resulting polyurethane resin (U) are improved. Furthermore, by setting (b1) / (b2) within the above preferred range, a polyurethane resin composition with improved storage stability and coatability can be provided. 【0037】 Furthermore, since the polycarbonate diol (B) has poor compatibility with the polyoxyethylene diol (A), it is also necessary to combine them to have good compatibility. 【0038】 [1-3. Structural Unit Derived from Aliphatic Isocyanate Compound (C)] The aliphatic isocyanate compound (C) that provides the structural unit derived from the aliphatic isocyanate compound (C) is an acyclic aliphatic diisocyanate (c1) in which two isocyanate groups are directly bonded to an acyclic hydrocarbon having an odd number of carbon atoms, or an alicyclic diisocyanate (c2) in which the number of isocyanate groups directly bonded to an alicyclic hydrocarbon is 0 or 1. One type of aliphatic isocyanate compound (C) may be used alone, or two or more types may be used in any combination and ratio. 【0039】 Examples of the acyclic aliphatic diisocyanate (c1) include 1,5-pentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,7-heptamethylene diisocyanate, etc. Examples of the alicyclic diisocyanate (c2) include isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and norbornene diisocyanate, etc. 【0040】Among these, the aliphatic isocyanate compound (C) is preferably selected from 1,5-pentamethylene diisocyanate, 1,7-heptamethylene diisocyanate, and isophorone diisocyanate, from the viewpoint of the balance between the solubility and durability of the resulting polyurethane resin (U). Furthermore, the aliphatic isocyanate compound (C) is preferably an alicyclic diisocyanate (c2), more preferably isophorone diisocyanate, from the viewpoint of the solubility of the resulting polyurethane resin. 【0041】 The content of the structural unit derived from the aliphatic isocyanate compound (C) in the polyurethane resin (U) is preferably 10 to 50% by weight, more preferably 20 to 40% by weight, and even more preferably 25 to 33% by weight. By setting the content of the structural unit derived from the aliphatic isocyanate compound (C) within the above range, the polyurethane resin (U) has a good balance between solubility and strength. 【0042】 [1-4. Structural Units Derived from Diol (D) Having 2 to 6 Carbon Atoms] Examples of the diol (D) having 2 to 6 carbon atoms that provides the structural unit derived from the diol (D) having 2 to 6 carbon atoms include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol. Among these, ethylene glycol, 1,3-propanediol, and 1,4-butanediol are preferred because they result in good strength of the resulting polyurethane resin (U). 【0043】 The diol (D) may be used alone or as a mixture of two or more kinds in any combination and ratio. 【0044】 [1-5. Diamine (E) having 2 to 20 carbon atoms] The diamine (E) having 2 to 20 carbon atoms that provides the structural unit derived from the diamine (E) having 2 to 20 carbon atoms is preferably a diamine having 6 to 12 carbon atoms. 【0045】Examples of the diamine (E) include ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, isophoronediamine, and 4,4'-diaminodicyclohexylmethane. 【0046】 Among these, the diamine (E) is preferably ethylenediamine or isophoronediamine, as this will result in a good strength of the resulting polyurethane resin (U).Furthermore, the diamine (E) is more preferably isophoronediamine, as this will result in a good balance between the strength and solubility in a solvent of the resulting polyurethane resin (U). 【0047】 The diamine (E) may be used alone or as a mixture of two or more kinds in any combination and in any ratio. 【0048】 [1-6. Composition of Polyurethane Resin (U)] In the polyurethane resin (U), the ratio (A) / ((A)+(B)) of the weight of the structural units derived from polyoxyethylene diol (A) to the total weight of the structural units derived from polyoxyethylene diol (A) and the structural units derived from polycarbonate diol (B) is preferably 0.50 or more and 0.95 or less, more preferably 0.50 or more and 0.90 or less, even more preferably more than 0.50 and 0.90 or less, still more preferably 0.53 or more and 0.90 or less, and particularly preferably 0.55 or more and 0.85 or less. When (A) / ((A)+(B)) is within the above range, excellent moisture permeability and waterproofing performance can be exhibited. Furthermore, when (A) / ((A)+(B)) is equal to or greater than the above lower limit, the moisture permeability, solubility in organic solvent (S), and strength of the polyurethane resin (U) can be ensured. 【0049】In polyurethane resin (U), the ratio of the total molar number of oxygen atoms derived from hydroxyl groups of polyoxyethylene diol (A) and oxygen atoms derived from hydroxyl groups of polycarbonate diol (B) to the molar number of oxygen atoms derived from hydroxyl groups of diol (D), ([OH](A)+[OH](B)) / [OH](D), is preferably 0.5 to 1.5, more preferably 1.0 to 1.5. When ([OH](A)+[OH](B)) / [OH](D) is within the above range, the polyurethane resin (U) has a good balance of solubility in solvents, strength, and moisture permeability. 【0050】 In the polyurethane resin (U), the ratio [NCO] / [OH] of the number of moles of nitrogen atoms derived from isocyanate groups of the aliphatic isocyanate compound (C) to the total number of moles of oxygen atoms derived from hydroxyl groups of the polyoxyethylene diol (A), oxygen atoms derived from hydroxyl groups of the polycarbonate diol (B), and oxygen atoms derived from hydroxyl groups of the diol (D) is preferably 1.5 to 4.0, more preferably 1.5 to 3.0, and even more preferably 1.8 to 2.5. When [NCO] / [OH] is within the above range, the polyurethane resin (U) has a good balance between solubility in solvents and strength. 【0051】 In the polyurethane resin (U), the ratio of the number of moles of nitrogen atoms derived from the isocyanate group of the aliphatic isocyanate compound (C) to the number of moles of nitrogen atoms derived from the amino group of the diamine (E) is [NCO] / [NH ２ ] is preferably 1.5 to 4.0, more preferably 1.5 to 2.5, and even more preferably 1.8 to 2.5. 【0052】 [NCO] / [NH ２ By adjusting the ratio [NCO] / [NH ２ When [NCO] / [NH ２ ] is equal to or less than the upper limit, the brittleness of the polyurethane resin (U) can be improved and the cohesive force and strength can be improved. 【0053】[1-7. Moisture permeability and waterproofing performance] The moisture permeability of the polyurethane resin (U) is preferably 50,000 to 200,000 g / m ２ / 24h, more preferably 60,000 to 200,000 g / m ２ The moisture permeability of the polyurethane resin (U) is measured by forming the polyurethane resin (U) into a film having a thickness of 20 μm and using this film as a test piece according to JIS L 1099:2021 (revised on August 20, 2021) by the B-1 method (potassium acetate method). 【0054】 When the moisture permeability of the polyurethane resin (U) is equal to or higher than the lower limit, a moisture-permeable waterproof material having sufficient moisture permeability can be produced from a polyurethane resin composition containing the polyurethane resin (U). Furthermore, since the polyurethane resin (U) has good strength, a moisture-permeable waterproof material having excellent water pressure resistance, i.e., a moisture-permeable waterproof material having sufficient waterproofness, can be produced from a polyurethane resin composition containing the polyurethane resin (U). 【0055】 [1-8. Weight-average molecular weight] The weight-average molecular weight (Mw) of the polyurethane resin (U) is preferably 10,000 to 300,000, more preferably 30,000 to 200,000, and even more preferably 50,000 to 150,000. If the weight-average molecular weight of the polyurethane resin (U) is equal to or greater than the lower limit, sufficient strength can be obtained. If the weight-average molecular weight of the polyurethane resin (U) is equal to or less than the upper limit, handling of the polyurethane resin composition becomes easy. 【0056】 The weight average molecular weight of the polyurethane resin (U) is a value calculated as polystyrene as measured by gel permeation chromatography (GPC), and the specific measurement method is as described in the Examples section below. 【0057】The molecular weight distribution of the polyurethane resin (U), weight average molecular weight / number average molecular weight (Mw / Mn), is preferably 1.5 to 3.5, more preferably 1.7 to 3.0, and even more preferably 2.0 to 2.5. If the molecular weight distribution is equal to or less than the upper limit, high molecular weight components in the polyurethane resin can be reduced, and the solubility of the polyurethane resin (U) in solvents becomes good, while if it is equal to or more than the lower limit, oligomers can be reduced, and strength and tensile strength become good. 【0058】 [1-9. Production Method of Polyurethane Resin (U)] The polyurethane resin (U) can be produced by any known production method for polyurethane resins. Specific examples include a one-stage method in which polyoxyethylene diol (A), polycarbonate diol (B), aliphatic isocyanate compound (C), C2-6 diol (D), and C2-20 diamine (E) are mixed together and reacted, and a two-stage method in which polyoxyethylene diol (A), polycarbonate diol (B), and aliphatic isocyanate compound (C) are reacted to prepare a prepolymer having isocyanate groups at both ends, and then the prepolymer is reacted with C2-6 diol (D) and C2-20 diamine (E). The two-stage method is preferred for producing the polyurethane resin (U), as it allows for a balanced dispersion of urethane bonds and urea bonds within the polymer. The polyurethane resin (U) obtained by the two-stage process disperses tension uniformly and exhibits good solubility in the organic solvent (S). 【0059】When producing the polyurethane resin (U) by a solution method, it is preferable to use a reaction solvent that is low in toxicity to the human body. Examples of reaction solvents that are low in toxicity to the human body include methyl ethyl ketone (MEK), ethyl acetate, and butyl acetate. Furthermore, when producing the polyurethane resin (U) by a solution method and using the reaction solvent as is as the organic solvent (S), the reaction solvent may contain, but preferably does not contain, a polar solvent (Y) described below. More specifically, the content of the polar solvent (Y) in the reaction solvent is preferably 0 to 40% by weight, more preferably 0 to 30% by weight, even more preferably 0 to 20% by weight, even more preferably 0 to 10% by weight, particularly preferably 0 to 5% by weight, and even more preferably 0% by weight (i.e., the reaction solvent does not contain the polar solvent (Y)). 【0060】 In producing the polyurethane resin (U), when the sum of the total number of hydroxyl groups in the polyoxyethylene diol (A) and the polycarbonate diol (B), the number of hydroxyl groups in the diol (D) having 2 to 6 carbon atoms, and the number of amino groups in the diamine (E) having 2 to 20 carbon atoms is taken as 1.0 equivalent, the amount of the aliphatic isocyanate compound (C) used is preferably 0.7 to 3.0 equivalents, more preferably 0.8 to 2.0 equivalents, and even more preferably 0.9 to 1.5 equivalents. 【0061】 When the amount of the aliphatic isocyanate compound (C) used is equal to or greater than the lower limit, the molecular weight of the resulting polyurethane resin (U) is sufficiently large, resulting in good strength of the polyurethane resin (U).When the amount of the aliphatic isocyanate compound (C) used is equal to or less than the upper limit, a highly soluble polyurethane resin (U) is obtained, and a breathable, waterproof material with good texture can be produced from a polyurethane resin composition containing the polyurethane resin (U). 【0062】 In the production of the polyurethane resin (U), the molar ratio of the isocyanate groups in the aliphatic isocyanate compound (C) to the molar ratio of the amino groups in the diamine (E) is preferably 1.5 to 4.0, more preferably 1.5 to 2.5, and even more preferably 1.8 to 2.5. 【0063】When the molar amount of isocyanate groups in the aliphatic isocyanate compound (C) is within the above range, a polyurethane resin (U) with excellent durability can be obtained. When the molar amount of isocyanate groups in the aliphatic isocyanate compound (C) is equal to or greater than the above lower limit, the number of urea bonds is prevented from becoming too large, and a polyurethane resin (U) with good flexibility, solubility, and texture can be obtained. Furthermore, when the molar amount of isocyanate groups in the aliphatic isocyanate compound (C) is equal to or less than the above upper limit, the number of urethane bonds is prevented from becoming too large, and a polyurethane resin (U) with low brittleness and good cohesive strength and strength can be obtained. 【0064】 When producing the polyurethane resin (U), known chain terminators, catalysts, additives, etc. may be used as needed. 【0065】 [Chain Terminating Agent] When producing a polyurethane resin, a chain terminator having one active hydrogen group, or one amino group and an active hydrogen group other than an amino group, may be used as needed for the purpose of controlling the molecular weight of the polyurethane resin (U). Examples of chain terminators include aliphatic monools such as methanol, ethanol, propanol, butanol, and hexanol; aliphatic monoamines such as diethylamine, dibutylamine, and n-butylamine; and alkanolamines such as monoethanolamine, diethanolamine, 2-propanolamine, and morpholine. These may be used alone, or two or more may be used in any combination and ratio. 【0066】[Catalyst] When producing the polyurethane resin (U), a known urethane polymerization catalyst, such as an amine catalyst or an organic metal salt, may be used in the polyurethane-forming reaction. Examples of the amine catalyst include triethylamine, N-ethylmorpholine, and triethylenediamine. Examples of the organic metal salt include tin compounds such as trimethyltin laurate, dibutyltin dilaurate, dioctyltin dilaurate, and dioctyltin dineodecanoate; and titanium compounds such as tetrabutoxytitanate. These may be used alone or in any combination and ratio of two or more. 【0067】 [2. Organic Solvent (S)] The organic solvent (S) contained in the polyurethane resin composition according to this embodiment is not particularly limited as long as it is an organic solvent capable of dissolving the polyurethane resin. However, it is preferable that the organic solvent (S) is one or more solvents selected from the group consisting of ketone solvents, ester solvents, and alcohol solvents, and more preferably one or more solvents selected from the group consisting of ketone solvents, ester solvents, and alcohol solvents. Furthermore, it is also preferable that the organic solvent (S) is a solvent with low toxicity to the human body and / or a solvent with low environmental impact. In recent years, in order to realize a sustainable society, there has been an increasing demand for environmentally friendly products that do not expose workers and product users to solvents that are highly toxic to the human body. This is because there is a strong global demand not only for products to contain a low content of solvents that are highly toxic to the human body, but also for products to not use solvents that are highly toxic to the human body during their manufacturing process. 【0068】 In this specification, "dissolved" means that when a solution is prepared by mixing with a solvent at a temperature of 25°C to give a solids concentration of 30% by weight, the appearance of the solution is transparent 24 hours after preparation. 【0069】In this specification, a solvent with low toxicity to the human body refers to a solvent that is not classified as a highly toxic solvent to the human body, does not fall into acute toxicity categories 1 to 3, or is not recognized as carcinogenic. Acute toxicity categories and recognized carcinogenic solvents are defined in the Globally Harmonized System of Classification and Labeling of Chemicals (GHS) classification, which was recommended by the United Nations in July 2003 and has been periodically updated since then; in this specification, GHS refers to the 9th edition. The GHS classification is published on the website of the Ministry of Health, Labor and Welfare of Japan (https: / / anzeninfo.mhlw.go.jp / user / anzen / kag / ghs_symbol.html). 【0070】 In this specification, a solvent with a low environmental impact is one that requires little thermal energy when volatilizing the solvent and is highly effective in reducing carbon dioxide emissions, and is a solvent with a low boiling point of less than 100° C., rather than a boiling point of 100° C. or higher like water or amide-based organic solvents. Note that these solvents have low solubility for polyurethane resins, and therefore their use in conventional polyurethane resin compositions has often been avoided. 【0071】 Examples of ketone solvents include acetone, MEK, 2-pentanone, 3-pentanone, methyl isobutyl ketone, diisobutyl ketone, methyl isopropyl ketone, diacetone alcohol, cyclohexanone, and isophorone. Among these, from the viewpoint of the solubility and evaporation rate of the polyurethane resin (U), the ketone solvent is preferably a ketone having 6 or less carbon atoms, and more preferably MEK. One type of ketone solvent may be used alone, or two or more types may be used in any combination and ratio. 【0072】Examples of ester-based solvents include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, sec-butyl acetate, methoxybutyl acetate, amyl acetate, methyl lactate, ethyl lactate, and butyl lactate. Among these, from the viewpoint of the solubility and evaporation rate of the polyurethane resin (U), the ester-based solvent is preferably an ester having 8 or less carbon atoms, and is more preferably selected from ethyl acetate and n-butyl acetate. One type of ester-based solvent may be used alone, or two or more types may be used in any combination and ratio. 【0073】 Examples of alcohol-based solvents include methanol, ethanol, n-butanol, isobutanol, tert-butanol, sec-butanol, isopropyl alcohol, n-propyl alcohol, and 2-ethylhexanol. Among these, from the viewpoint of the solubility of the polyurethane resin (U), the alcohol-based solvent is preferably a monohydric alcohol having 5 or less carbon atoms, and more preferably isopropyl alcohol. One type of alcohol-based solvent may be used alone, or two or more types may be used in any combination and ratio. 【0074】 From the viewpoint of the solubility of the polyurethane resin (U), the organic solvent (S) is preferably a mixed solvent of a ketone solvent and an alcohol solvent, and the ratio of the ketone solvent to the alcohol solvent (ketone solvent / alcohol solvent) is preferably 70 / 30 to 95 / 5 by weight. Furthermore, from the viewpoint of the balance between the solubility of the polyurethane resin (U) and the drying property upon application, the organic solvent (S) preferably contains a monohydric alcohol having 5 or less carbon atoms and a ketone having 6 or less carbon atoms or an ester having 8 or less carbon atoms. 【0075】The organic solvent (S) may contain a polar solvent (Y) that satisfies the following (y1) and (y2). However, because the polar solvent (Y) is highly toxic to the human body, it is preferable that the content of the polar solvent (Y) in the organic solvent (S) be low, and it is more preferable that the organic solvent (S) be free of the polar solvent (Y). Many solvents known to have high solubility in general polyurethane resins fall into the polar solvent (Y) category. However, since the polyurethane resin (U) in this embodiment can be dissolved in the above-mentioned low-toxicity solvents, it is not necessary to select a highly toxic solvent such as the polar solvent (Y) as the organic solvent (S). Therefore, it is possible to set the content of the polar solvent (Y) in the organic solvent (S) to a low level. Examples of solvents that have high solubility in polyurethane resins include solvents with a polarity term (δP) of 11.0 or more in the Hansen solubility parameter. (y1) Not classified as a carcinogenic substance in the GHS (9th revised edition) classification. (y2) The substance is classified as Category 1 to 3 for acute toxicity in the GHS (revised 9th edition) classification, or as Category 1A or 1B for reproductive toxicity in the GHS (revised 9th edition) classification. The polar solvent (Y) may further satisfy the following (y3): (y3) The polar term (δP) in the Hansen solubility parameters is 11.0 or more. 【0076】 More specifically, from the viewpoint of the solubility of the polyurethane resin (U) and the burden on the human body and the environment, the content of the polar solvent (Y) in the organic solvent (S) is preferably 0 to 40% by weight, more preferably 0 to 30% by weight, even more preferably 0 to 20% by weight, still more preferably 0 to 10% by weight, particularly preferably 0 to 5% by weight, especially preferably 0 to 1% by weight, and most preferably 0% by weight (i.e., the polyurethane resin composition does not contain the polar solvent (Y)). 【0077】 Examples of the polar solvent (Y) include compounds having an amide group such as dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone, and N-ethylpyrrolidone; and compounds having a nitrile group such as acetonitrile. 【0078】[3. Additives] The polyurethane resin composition according to this embodiment may contain various additives, such as a biomass-derived compound, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a colorant, a flame retardant, and an inorganic filler, within a range that does not impair the properties of the polyurethane resin (U). One type of additive may be used alone, or two or more types may be used in any combination and in any ratio. 【0079】 The biomass-derived compound is used for the purpose of improving the bio-based content of the product. Examples of the biomass-derived compound include plant-derived fiber powders such as grape-derived fiber powder, pineapple-derived fiber powder, apple-derived fiber powder, cactus-derived fiber powder, and pulp-derived fiber powder. The biomass-derived compound may be used alone or in any combination and ratio of two or more. 【0080】 Examples of heat stabilizers include phosphorus compounds such as aliphatic, aromatic, or alkyl-substituted aromatic esters of phosphorous acid and phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, polyphosphonates, dialkyl pentaerythritol diphosphites, and dialkyl bisphenol A diphosphites; phenol derivatives, particularly hindered phenol compounds; sulfur-containing compounds such as thioethers, dithioacid salts, mercaptobenzimidazoles, thiocarbanilides, and thiodipropionates; tin compounds such as tin maleates and dibutyltin monoxide; etc. One type of heat stabilizer may be used alone, or two or more types may be used in any combination and ratio. 【0081】 The ultraviolet absorber is not particularly limited and any known additive can be selected. Examples include "TINUVIN 328" and "TINUVIN 234" (both manufactured by Ciba Specialty Chemicals Co., Ltd.). 【0082】The light stabilizer is not particularly limited and any known additive can be selected. Examples include ADK STAB LA-77 and ADK STAB LA-57 (both manufactured by ADEKA Corporation). The heat stabilizer, ultraviolet absorber, and light stabilizer may be used alone or in any combination and ratio of two or more. High molecular weight types that do not easily bleed out from the polyurethane resin are preferred. 【0083】 Examples of colorants include dyes such as direct dyes, acid dyes, basic dyes, and metal complex dyes; inorganic pigments such as carbon black, titanium oxide, zinc oxide, iron oxide, and mica; and organic pigments such as coupling azo pigments, condensed azo pigments, anthraquinone pigments, thioindigo pigments, dioxazone pigments, and phthalocyanine pigments. One type of colorant may be used alone, or two or more types may be used in any combination and ratio. 【0084】 Examples of the flame retardant include additive or reactive flame retardants such as phosphorus- and halogen-containing organic compounds, bromine- or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, and antimony oxide. One type of flame retardant may be used alone, or two or more types may be used in any combination and ratio. 【0085】 Examples of inorganic fillers include short glass fibers, carbon fibers, alumina, talc, graphite, melamine, and clay. One type of inorganic filler may be used alone, or two or more types may be used in any combination and ratio. 【0086】 The additives may be added to the raw materials or the reaction system at any stage during the production of the polyurethane resin (U), or may be added to the polyurethane resin (U) and the organic solvent (S) when they are mixed to prepare the polyurethane composition. 【0087】 The content of the additive in the polyurethane resin composition is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, and even more preferably 0.1 to 1% by weight, based on the total amount of the polyurethane resin (U). 【0088】When the content of the additive is equal to or greater than the lower limit, the effect of the additive can be sufficiently obtained, and when the content of the additive is equal to or less than the upper limit, precipitation of the additive is less likely to occur. 【0089】 [4. Applications] The polyurethane resin composition according to this embodiment can be used in various products that require moisture permeability and waterproofness. For example, by applying the polyurethane resin composition to at least one surface of a substrate and then drying the solvent, a moisture-permeable, waterproof composite material can be produced that has a polyurethane resin layer containing the polyurethane resin (U) and a substrate layer adjacent to the polyurethane resin layer. Note that the method for producing the moisture-permeable, waterproof composite material is not limited to the above method. 【0090】 Furthermore, when the substrate is a fibrous substrate, the moisture-permeable waterproof composite material is a moisture-permeable waterproof fabric and can be applied to moisture-permeable and waterproof fabric products. The base material of the fibrous substrate may be any of cellulosic fibers such as cotton, linen, and rayon, and synthetic fibers such as polyester, polyamide, and polyolefin. The fibrous substrate can be in the form of any of woven fabrics, knitted fabrics, and nonwoven fabrics, but woven fabrics and knitted fabrics are preferred. 【0091】 The breathable waterproof fabric can be suitably used for clothing such as outdoor wear for mountain climbing, fishing, cycling, etc., ski-related wear, windbreakers, sportswear, rainwear, athletic wear, golf-related wear, and outdoor workwear; tents; mountain climbing-related materials such as tarps; and the like. 【0092】 Furthermore, the polyurethane resin composition according to this embodiment can also be suitably used in hygiene products such as disposable diapers and wound dressings such as adhesive bandages and adhesive plasters. 【0093】 The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to the following examples as long as the gist of the disclosure is not exceeded. In the following examples and comparative examples, various physical properties were measured by the following methods. 【0094】[Evaluation Method] (1) Molecular Weight A polyurethane resin was dissolved in dimethylacetamide to prepare a dimethylacetamide solution with a concentration of 0.14 wt %. The dimethylacetamide solution was injected into a GPC apparatus (manufactured by Tosoh Corporation, product name "HLC-8220GPC" (column: TSKgel GMHXL, two columns)) to measure the weight average molecular weight (Mw) of the polyurethane resin in terms of standard polystyrene. 【0095】 (2) Strength (Tensile Test) A polyurethane resin solution was applied to a fluororesin sheet (manufactured by Nitto Denko Corporation, product name "Nitoflon No. 900", thickness 0.1 mm) using a 10 mil applicator, and the applied solution was dried at 60°C for 20 minutes, and then at 80°C for 30 minutes to obtain a coating film. The coating film was then left to stand at a constant temperature and humidity of 23°C and 55% RH for 12 hours or more to obtain a polyurethane film. A 7 cm x 1 cm test piece was cut out from this polyurethane film to serve as the test piece. A tensile test was carried out on the above test specimen in accordance with JIS K 6251:2010 using a bench-top precision universal testing machine (manufactured by Shimadzu Corporation, product name "Autograph AGX-1kNX") at a chuck distance of 30 mm, a tensile speed of 200 mm / min, a temperature of 23°C, and a relative humidity of 55%, except that the test specimen was in a rectangular shape. The tensile stress (100% modulus) at the time when the test specimen was elongated by 100% was measured. 【0096】 The strength was evaluated based on the 100% modulus as follows: B: Less than 3.0 MPa A: 3.0 MPa or more but less than 5.0 MPa S: 5.0 MPa or more 【0097】(3) Tensile Strength (Breaking Strength) A polyurethane resin solution was applied to a fluororesin sheet (manufactured by Nitto Denko Corporation, product name "Nitoflon No. 900", thickness 0.1 mm) using a 10 mil applicator, and the applied solution was dried at 60°C for 20 minutes, and then at 80°C for 30 minutes to obtain a coating film. The coating film was then left to stand at a constant temperature and humidity of 23°C and 55% RH for 12 hours or more to obtain a polyurethane film. A 7 cm x 1 cm test piece was cut out from this polyurethane film. A tensile test was carried out on the above test specimen in accordance with JIS K 6251:2010 using a bench-top precision universal testing machine (manufactured by Shimadzu Corporation, product name "Autograph AGX-1kNX") at a chuck distance of 30 mm, a tensile speed of 200 mm / min, a temperature of 23°C, and a relative humidity of 55%, except that the test specimen was in a rectangular shape, and the tensile stress (tensile strength) at the time when the test specimen broke was measured. 【0098】 The tensile strength was evaluated as follows: B: Less than 17.0 MPa A: 17.0 MPa or more and less than 25.0 MPa S: 25.0 MPa or more 【0099】 (3) Moisture Permeability A polyurethane resin solution was applied to a fluororesin sheet (manufactured by Nitto Denko Corporation, product name "Nitoflon No. 900", thickness 0.1 mm) using a 4.5 mil applicator, and the applied solution was dried at 60 ° C. for 20 minutes, followed by drying at 80 ° C. for 30 minutes to obtain a polyurethane resin film with a thickness of 20 μm. Using this film, a moisture permeability test was carried out in accordance with JIS L 1099:2021 B-1 method (potassium acetate method), and the moisture permeability per 24 hours was calculated from the obtained moisture permeability. 【0100】 The moisture permeability was evaluated as follows: B: 70,000 g / m ２ / Less than 24 hours A: 70,000 g / m ２ / 24h or more, 120,000g / m ２ / Less than 24h S: 120,000g / m ２ / 24h or more, 200,000g / m ２ / 24h or less 【0101】(4) Storage Stability The polyurethane resin solution was filled into a glass bottle and sealed. After storing the glass bottle at room temperature (23°C) for one week, the appearance of the polyurethane resin solution was observed. 【0102】 The storage stability was evaluated as follows: B: Significant changes such as the generation of foreign matter and discoloration were observed in the polyurethane resin solution. A: Slight changes such as cloudiness, foreign matter, and discoloration were observed in the polyurethane resin solution. S: No change in the appearance of the polyurethane resin solution. 【0103】 (5) Coatability A solution of polyurethane resin was applied to a fluororesin sheet (manufactured by Nitto Denko Corporation, product name "Nitoflon No. 900", thickness 0.1 mm) using a 4.5 mil applicator, and the coating film immediately after application was observed. 【0104】 The coatability was evaluated as follows: B: Cracks were observed in 10 or more places on the coating film. A: Cracks were observed in less than 10 places on the coating film. S: Cracks were not observed on the coating film. 【0105】[Raw materials, etc.] PEG2000: Polyoxyethylene diol having a number average molecular weight of 2,000 (hydroxyl value 56.1 mg KOH / g) [manufactured by Sanyo Chemical Industries, Ltd.] PEG1000: Polyoxyethylene diol having a molecular weight of 1,000 (hydroxyl value 112.1 mg KOH / g) [manufactured by Sanyo Chemical Industries, Ltd.] NL2030DB: 1,4-butanediol / 1,10-decanediol copolymer polycarbonate diol having a number average molecular weight of 2,000 (hydroxyl value 56.1 mg KOH / g) (1,4-butanediol / 1,10-decanediol = 70 / 30) [manufactured by Mitsubishi Chemical Corporation] NL2000B: 1,4-butanediol polymerized polycarbonate diol having a number average molecular weight of 2,000 (hydroxyl value 57.6 mg KOH / g) [manufactured by Mitsubishi Chemical Corporation]. UH200: 1,6-hexaneol polymerized polycarbonate diol having a number average molecular weight of 2,000 (hydroxyl value 57.5 mg KOH / g) [manufactured by UBE Corporation]. NL2010DB: 1,4-butanediol / 1,10-decanediol copolymerized polycarbonate diol having a number average molecular weight of 2,000 (hydroxyl value 56.3 mg KOH / g) (1,4-butanediol / 1,10-decanediol = 90 / 10) [manufactured by Mitsubishi Chemical Corporation]. NL2070DB: 1,4-butanediol / 1,10-decanediol copolymer polycarbonate diol having a number average molecular weight of 2,000 (hydroxyl value 56.7 mg KOH / g) (1,4-butanediol / 1,10-decanediol=29 / 71) [manufactured by Mitsubishi Chemical Corporation] IPDI: isophorone diisocyanate [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] HDI: 1,6-hexamethylene diisocyanate [manufactured by Tokyo Chemical Industry Co., Ltd.] H12MDI: 4,4'-dicyclohexylmethane diisocyanate [manufactured by Tokyo Chemical Industry Co., Ltd.] MDI: 4,4'-diphenylmethane diisocyanate [manufactured by Tosoh Corporation] TDI: toluene diisocyanate (2,4-,2,6-Mixture) [manufactured by Tokyo Chemical Industry Co., Ltd.] EG: ethylene glycol [manufactured by Tokyo Chemical Industry Co., Ltd.] IPDA: isophoronediamine [manufactured by Tokyo Chemical Industry Co., Ltd.] MO: morpholine [manufactured by Tokyo Chemical Industry Co., Ltd.] TBT: tetrabutoxy titanate [manufactured by Tokyo Chemical Industry Co., Ltd.] MEK: methyl ethyl ketone [manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.] IPA: isopropyl alcohol [Fujifilm Wako Pure Chemical Industries Co., Ltd.] 【0106】 Example 1: Production of Polyurethane Resin (U-1) A separable flask equipped with a thermocouple, a condenser, and a stirrer was placed on a 60°C oil bath. 60.0 g of PEG2000, 40.0 g of NL2030DB, 3.1 g of EG, and 44.5 g of IPDI, all preheated to 80°C, were placed in the separable flask. The atmosphere inside the separable flask was replaced with a nitrogen atmosphere, and 0.01 g of TBT was added while stirring the raw material mixture at 60 rpm. The temperature was raised to 110°C over approximately 1 hour. After reaching 110°C, the reaction solution was stirred for approximately 5 hours, and after confirming that the NCO% of the reaction solution had reached the theoretical value, the reaction solution was cooled. After cooling the reaction solution to 80°C, 304 g of MEK was added to the reaction solution and stirred until the reaction solution became homogeneous. After the reaction mixture became homogeneous, 0.044 g of malic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction mixture, followed by the addition of 76.0 g of IPA, and the mixture was stirred until the reaction mixture became homogeneous. 【0107】 Next, 15.33 g of IPDA was added to the reaction solution, and the temperature was raised to 50°C over approximately one hour. One hour after the temperature was raised, IPDA was added to the reaction solution in small amounts to adjust the viscosity of the reaction solution. The total amount of IPDA added was 0.20 g. Then, 0.78 g of MO was added to the reaction solution. After the addition of MO, the mixture was stirred at 50°C for an additional hour, yielding a polyurethane resin composition with a viscosity of 67,700 mPa·s and a solids concentration of 30.7 wt%. The properties of this polyurethane resin composition and the evaluation results of the physical properties of the polyurethane resin are shown in Table 4. 【0108】[Examples 2 to 5 and Examples 7 to 10] Production of polyurethane resins (U-2, U-3, U-4, U-5, U-7, U-8, U-9, U-10) Polyurethane resin compositions were obtained in the same manner as in Example 1, except that the raw materials were changed to the amounts shown in Table 1 or Table 2. The properties of the obtained polyurethane resin compositions and the evaluation results of the physical properties of the polyurethane resins are shown in Tables 4 and 5. 【0109】 Example 6: Production of polyurethane resin (U-6) A separable flask equipped with a thermocouple, a condenser, and a stirrer was placed on a 60°C oil bath. 100.0 g of PEG1000 and 8.6 g of TDI, which had been preheated to 60°C, were placed in the separable flask. The atmosphere inside the separable flask was replaced with a nitrogen atmosphere, and 0.01 g of TBT was added while stirring at 60 rpm, and the temperature was raised to 80°C over approximately 1 hour. After the temperature reached 80°C, infrared absorbance analysis was performed approximately 2 hours later, and a peak at 2270 cm －１ The disappearance of the terminal NCO groups was confirmed from the peak. The hydroxyl value of the obtained polyoxyethylene diol (Ac) was 52.2. 【0110】 After confirming the disappearance of the terminal NCO groups, the reaction solution was cooled, and 27.2 g of NL2030DB, 4.0 g of EG, and 57.2 g of IPDI were added to the reaction solution. The atmosphere inside the separable flask was replaced with a nitrogen atmosphere, and the reaction solution was heated to 110°C over approximately 1 hour while stirring at 60 rpm. After reaching 110°C, the reaction solution was stirred for approximately 2 hours, and after confirming that the NCO% of the reaction solution had reached the theoretical value, the reaction solution was cooled. After cooling the reaction solution to 80°C, 408.7 g of MEK was added to the reaction solution and stirred until the reaction solution became homogeneous. After the reaction solution became homogeneous, 0.059 g of malic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the reaction solution, followed by 102.2 g of IPA and stirring until the reaction solution became homogeneous. 【0111】Subsequently, 19.73 g of IPDA was added to the reaction solution, and the temperature was raised to 50°C over approximately one hour. One hour after the temperature was raised, IPDA was added to the reaction solution in small amounts to adjust the viscosity of the reaction solution. The total amount of IPDA added was 1.03 g. Subsequently, 1.19 g of MO was added to the reaction solution. After the addition of MO, the mixture was stirred at 50°C for an additional hour, yielding a polyurethane resin composition with a viscosity of 98,500 mPa·s and a solids concentration of 30.1 wt%. The properties of this polyurethane resin composition and the evaluation results of the physical properties of the polyurethane resin are shown in Table 4. 【0112】 Comparative Examples 1 to 7 Production of Polyurethane Resins (U-11 to U-17) Polyurethane resin compositions were obtained in the same manner as in Example 1, except that the amounts of raw materials were changed to those shown in Table 3. The properties of the obtained polyurethane resin compositions and the evaluation results of the physical properties of the polyurethane resins are shown in Table 6. 【0113】 【0114】 【0115】 【0116】 【0117】 【0118】 【0119】 As shown in Tables 4 and 5, it was found that the polyurethane resins contained in the polyurethane resin compositions obtained in Examples 1 to 10 had an excellent balance between moisture permeability and strength, and were soluble in solvents containing MEK as a main component. Furthermore, because these polyurethane resins can be dissolved in solvents such as MEK that are gentle on the human body and the environment, it was confirmed that there is no need to use solvents such as DMF that are harsh on the human body and the environment in the polyurethane resin production process and the moisture-permeable, waterproof fabric production process. 【0120】On the other hand, as shown in Table 6, the polyurethane resins contained in the polyurethane resin compositions obtained in Comparative Examples 1 and 3 were found to have excellent strength and tensile strength and to be soluble in solvents containing MEK as the main component, but to have insufficient moisture permeability. Furthermore, the polyurethane resin contained in the polyurethane resin composition obtained in Comparative Example 2 was found to have excellent moisture permeability and to be soluble in solvents containing MEK as the main component, but to have insufficient strength. The polyurethanes obtained in Comparative Examples 5 and 6 were found to have excellent moisture permeability and to be soluble in solvent systems containing MEK as the main component, but to have insufficient tensile strength. Furthermore, the polyurethanes obtained in Comparative Examples 4 and 7 were found to be insoluble in solvent systems containing MEK as the main component and to gel during the production process. In other words, these polyurethane resins cannot be produced using solvents that are gentle on the human body and the environment, such as MEK. Therefore, it was found that solvents that are highly hazardous to the human body and the environment, such as DMF, must be used in the polyurethane resin production process and the moisture-permeable waterproof fabric production process.

Claims

[Claim 1] A polyurethane resin composition comprising a polyurethane resin (U) and an organic solvent (S), The polyurethane resin (U) has structural units derived from polyoxyethylene diol (A), polycarbonate diol (B), aliphatic isocyanate compound (C), a diol having 2 to 6 carbon atoms (D), and a diamine having 2 to 20 carbon atoms (E). A polyurethane resin composition in which the structural unit derived from the aliphatic isocyanate compound (C) is a structural unit derived from an acyclic aliphatic diisocyanate (c1) in which two isocyanate groups are directly bonded to an acyclic hydrocarbon having an odd number of carbon atoms, or a structural unit derived from an alicyclic diisocyanate (c2) in which the number of isocyanate groups directly bonded to an alicyclic hydrocarbon is 0 or 1. [Claim 2] The polyurethane resin composition according to claim 1, wherein the ratio (A) / ((A)+(B)) of the weight of structural units derived from polyoxyethylene diol (A) to the total weight of structural units derived from polyoxyethylene diol (A) and structural units derived from polycarbonate diol (B) in the polyurethane resin (U) is 0.50 to 0.

90. [Claim 3] The polyurethane resin composition according to claim 1, wherein the ratio of the number of moles of nitrogen atoms derived from the isocyanate group in the structural unit derived from the aliphatic isocyanate compound (C) to the number of moles of nitrogen atoms derived from the amino group in the diamine (E) is 1.5 to 2.

5. [Claim 4] The polyurethane resin composition according to claim 1, wherein the structural unit derived from the polyoxyethylenediol (A) is a structural unit derived from a polyoxyethylenediol having a hydroxyl value of 26.0 to 140.0 mgKOH / g. [Claim 5] The polyurethane resin composition according to claim 1, wherein the structural unit derived from the polycarbonate diol (B) is a structural unit derived from a polycarbonate diol having a hydroxyl value of 32.0 to 124.7 mgKOH / g. [Claim 6] The polyurethane resin composition according to claim 1, wherein the structural units derived from the polycarbonate diol (B) include a structural unit represented by the following formula (b1) and a structural unit represented by the following formula (b2), and the molar ratio of each structural unit (b1) / (b2) is 95 / 5 to 5 / 95. -O-R １ -O- ・・・(b1) -O-R ２ -O- ・・・(b2) (In formula (b1), R １ R is a divalent alkylene group having 3 to 5 carbon atoms, which may have substituents, in formula (b2), ２ This represents a divalent alkylene group having 6 to 20 carbon atoms, which may have substituents. [Claim 7] The polyurethane resin composition according to claim 1, wherein the content of structural units derived from the aliphatic isocyanate compound (C) in the polyurethane resin (U) is 50% by weight or less. [Claim 8] The polyurethane resin composition according to claim 1, wherein the diamine (E) is a diamine having 6 to 12 carbon atoms. [Claim 9] The polyurethane resin composition according to claim 1, wherein the ratio of the total number of moles of oxygen atoms derived from the hydroxyl groups of the polyoxyethylene diol (A) and the polycarbonate diol (B) to the number of moles of oxygen atoms derived from the hydroxyl groups of the diol (D) in the polyurethane resin (U) is 0.5 to 1.

5. [Claim 10] The polyurethane resin composition according to claim 1, wherein the ratio of the number of moles of nitrogen atoms derived from the isocyanate group of the aliphatic isocyanate compound (C) to the total number of moles of oxygen atoms derived from the hydroxyl group of the polyoxyethylene diol (A), oxygen atoms derived from the hydroxyl group of the polycarbonate diol (B), and oxygen atoms derived from the hydroxyl group of the diol (D) in the polyurethane resin (U) is 1.5 to 4.

0. [Claim 11] The polyurethane resin composition according to claim 1, wherein the polyurethane resin (U) further comprises structural units derived from a monoamine having a primary amino group or a monoamine having a secondary amino group or both. [Claim 12] The polyurethane resin composition according to claim 1, wherein the content of a polar solvent (Y) satisfying the following conditions (y1) and (y2) in the organic solvent (S) is 5% by weight or less. (y1) Not classified as carcinogenic according to the GHS (9th revised edition) classification. (y2) The acute toxicity is classified as Category 1 to Category 3 in the GHS (Revised 9th Edition) classification, or the reproductive toxicity is classified as Category 1A or Category 1B in the GHS (Revised 9th Edition) classification. [Claim 13] The polyurethane resin composition according to claim 1, wherein the organic solvent (S) comprises a monohydric alcohol having 5 or fewer carbon atoms and a ketone having 6 or fewer carbon atoms or an ester having 8 or fewer carbon atoms. [Claim 14] The polyurethane resin composition according to claim 1, wherein the content of the polyurethane resin (U) in the polyurethane resin composition is 5 to 50% by weight. [Claim 15] The polyurethane resin composition according to claim 1, comprising a biomass-derived compound. [Claim 16] A breathable waterproof fabric made using the polyurethane resin composition described in any one of claims 1 to 15. [Claim 17] A polyurethane resin composition according to any one of claims 1 to 15 is used to make a sports Tweer. [Claim 18] Rainwear made using the polyurethane resin composition described in any one of claims 1 to 15. [Claim 19] A tent made using the polyurethane resin composition described in any one of claims 1 to 15. [Claim 20] A sanitary product comprising a polyurethane resin composition according to any one of claims 1 to 15.