Breathable waterproof fabric

Abstract

Provided is a moisture-permeable waterproof fabric capable of reducing the environmental load thereof by being carbon neutral and having a prolonged product lifespan, and which has excellent water repellence and moisture permeability. The moisture-permeable waterproof fabric of the present invention has a porous moisture-permeable waterproof film on at least one surface of the fabric. The polyurethane, from which the moisture-permeable waterproof film is formed, is synthesized by using a polyol containing a polycarbonate diol having a plant-derived component.

Description

[Technical field]

[0001] The present invention relates to a moisture-permeable, waterproof fabric having a moisture-permeable, waterproof membrane made of polyurethane. [Background technology]

[0002] 2. Description of the Related Art Conventionally, moisture-permeable and waterproof fabrics having a moisture-permeable and waterproof membrane made of polyurethane, which has excellent moisture permeability and waterproof properties, have been proposed for use in sportswear, outdoor products, and the like.

[0003] For example, Patent Document 1 discloses a porous structure of a polyurethane resin composed of a polycarbonate diol containing a diol component having 4 to 6 carbon atoms as a constituent element and an isocyanate, and describes that the porous structure has an excellent balance between moisture permeability and water resistance.

[0004] Furthermore, Patent Document 2 discloses a waterproof fabric having a waterproof layer made of a polyurethane resin obtained from a plant-derived castor oil-based polyol polyester diol, and describes that the waterproof fabric has excellent hydrolysis resistance despite containing plant-derived components.

[0005] Furthermore, Patent Document 3 discloses a moisture-permeable, waterproof fabric having a porous resin membrane made of plant-derived sebacic acid and an ester-based urethane obtained from a diol, and describes that the moisture-permeable, waterproof fabric has performance equal to or greater than that of a fabric made using petroleum-derived polyurethane. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 5-186631 [Patent Document 2] Patent No. 5855722 [Patent Document 3] Patent No. 5680052 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the technology of Patent Document 1 has insufficient water resistance and moisture permeability, and also has a large impact on the environment since it uses petroleum-derived materials.

[0008] In addition, in the technology of Patent Document 2, since the water pressure resistance is low as shown in Examples 1 to 3 of Patent Document 2, a top coat is required to obtain the water pressure resistance required for practical use. However, there is a problem that the water vapor permeability is significantly reduced when a top coat is applied as shown in Example 4. In addition, castor oil is mixed in as an impurity during the process of refining polyether polyester diol from castor oil, and the product emits an unpleasant odor of castor oil, which is not preferable for clothing. Furthermore, there is a problem that the polymerization of polyurethane is unstable due to the mixture of castor oil as an impurity.

[0009] Furthermore, the technique of Patent Document 3 uses ester-based polyurethane, which causes the moisture-permeable waterproof film to deteriorate early due to hydrolysis.

[0010] The present invention has been made in consideration of the above problems, and aims to provide a moisture-permeable waterproof fabric that has excellent waterproofing and moisture permeability, and that can reduce the environmental burden by being carbon neutral and extending the product's lifespan through the formation of a moisture-permeable waterproof membrane from a polycarbonate-based urethane resin containing plant-derived components. [Means for solving the problem]

[0011] The present invention provides a moisture-permeable, waterproof fabric having a porous moisture-permeable, waterproof membrane on at least one side of the fabric, in which the polyurethane forming the moisture-permeable, waterproof membrane is synthesized using a polyol containing a polycarbonate diol having a plant-derived component. Effect of the Invention

[0012] According to the present invention, it is possible to provide a moisture-permeable waterproof fabric that is carbon neutral and has a long product life, thereby reducing the environmental impact, and that is excellent in waterproofness and moisture permeability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Next, the moisture-permeable, waterproof fabric of the present invention will be described in detail. The moisture-permeable waterproof fabric of the present invention is a moisture-permeable waterproof fabric having a porous moisture-permeable waterproof membrane on at least one side of the fabric, and the polyurethane that forms the moisture-permeable waterproof membrane is synthesized using a polyol containing a polycarbonate diol having a plant-derived component.

[0014] (fabric) As the fabric used in the moisture-permeable waterproof fabric of the present invention, a fabric suitable for the intended purpose can be appropriately used, and the type is not particularly limited. Examples include synthetic fibers such as nylon fibers, polyester fibers, and polyamide fibers; semi-synthetic fibers such as acetate fibers; and natural fibers such as cotton, hemp, and wool. These various fibers may be used alone or in combination of two or more types. The structure is also not particularly limited, and woven fabrics, knitted fabrics, nonwoven fabrics, and the like can be appropriately used. In addition, it is preferable to use recycled polyester yarns, recycled nylon yarns, and yarns containing plant-derived components for the fabric from the viewpoint of reducing environmental load.

[0015] (Breathable waterproof membrane) The moisture-permeable waterproof film of the moisture-permeable waterproof fabric of the present invention is made of polyurethane using a polyol containing a polycarbonate diol having a plant-derived component.

[0016] From the viewpoints of chemical resistance, low-temperature characteristics, and hydrolysis resistance, the polycarbonate diol having a plant-derived component according to the present invention preferably uses a polycarbonate diol containing at least two kinds of diols, and at least one of the two kinds of diols is preferably a plant-derived component. The polycarbonate diol containing two kinds of diols can be produced by polycondensing the two kinds of diols and a carbonate compound through an ester exchange reaction.

[0017] As the polycarbonate diol containing two types of diols, for example, a polycarbonate diol containing as its constituent elements a diol having an alkylene group with 3 to 5 carbon atoms and a diol having an alkylene group with 8 to 20 carbon atoms can be preferably used.

[0018] Examples of diols having an alkylene group having 3 to 5 carbon atoms include 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 1,5-pentanediol, etc. Among these, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol are preferred, and 1,3-propanediol and 1,4-butanediol are more preferred, because they have an excellent balance of chemical resistance and low-temperature properties when made into a polyurethane.

[0019] Examples of diols having an alkylene group having 8 to 20 carbon atoms include 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. Among these, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol are preferred, as they have an excellent balance of chemical resistance and low-temperature properties when made into a polyurethane, and 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol are more preferred, and 1,10-decanediol is even more preferred.

[0020] The polycarbonate diol containing as its constituents a diol having an alkylene group with a carbon number of 3 to 5 and a diol having an alkylene group with a carbon number of 8 to 20 may use a diol compound (sometimes referred to as an other diol compound) other than the diol having an alkylene group with a carbon number of 3 to 5 and the diol having an alkylene group with a carbon number of 8 to 20. However, when using the other diol compound, in order to effectively obtain the effects of the present invention, the ratio of the structural units derived from the other diol compound to the total structural units of the polycarbonate diol is preferably 50 mol % or less, more preferably 30 mol % or less, further preferably 20 mol % or less, and most preferably 10 mol % or less.

[0021] From the viewpoint of reducing the environmental load, the diol having an alkylene group having 3 to 5 carbon atoms is preferably derived from a plant. Examples of the diol having an alkylene group having 3 to 5 carbon atoms that can be used as a plant-derived diol include 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol.

[0022] From the viewpoint of reducing the environmental load, the diol having an alkylene group having 8 to 20 carbon atoms is preferably derived from a plant. Examples of diols having an alkylene group having 8 to 20 carbon atoms 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.

[0023] The polycarbonate diol having a plant-derived component used in the moisture-permeable waterproof film of the present invention preferably contains a component derived from 1,10-decanediol as the plant-derived component.

[0024] The polycarbonate diol having a plant-derived component used in the moisture-permeable waterproof film of the present invention contains a component derived from 1,10-decanediol and a component derived from 1,4-butanediol, and the molar ratio of 1,10-decanediol to 1,4-butanediol is preferably 1 / 9 to 8 / 2. By setting the molar ratio of 1,10-decanediol to 1,4-butanediol to 1 / 9 to 5 / 5, a moisture-permeable waterproof fabric excellent in water pressure resistance and moisture permeability can be obtained, which is more preferable.

[0025] Examples of carbonate compounds that can be used in the production of polycarbonate diol include dialkyl carbonate, diaryl carbonate, and alkylene carbonate. Specific examples of carbonate compounds include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, and ethylene carbonate, and diphenyl carbonate is preferred.

[0026] The polyurethane used in the moisture-permeable waterproof film according to the present invention can be produced by reacting a polyol containing a polycarbonate diol having a plant-derived component, a polyisocyanate, and a chain extender.

[0027] The polyisocyanate used in producing the polyurethane according to the present invention may be an aliphatic, alicyclic or aromatic polyisocyanate compound. For example, aliphatic diisocyanates such as 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate and dimer diisocyanate in which the carboxyl group of a dimer acid is converted to an isocyanate group, alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and 1,3-bis(isocyanatemethyl)cyclohexane, etc. Examples of the aromatic diisocyanates include silylene 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, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, and m-tetramethyl xylylene diisocyanate. These may be used alone or in combination of two or more. Moreover, it is preferable to use an isocyanate having a plant-derived component, such as plant-derived 1,5-pentamethylene diisocyanate, from the viewpoint of reducing the environmental load.

[0028] Examples of the chain extender include linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, and 2,2-diethyl-1,3- propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-heptanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, dimer diol and other branched chain diols, diethylene glycol, Examples of the chain extender include diols having an ether group such as propylene glycol, hydroxyamines such as N-methylethanolamine and N-ethylethanolamine, and polyamines such as ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4'-diphenylmethanediamine, methylenebis(o-chloroaniline), xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine, piperazine, and N,N'-diaminopiperazine. The chain extender may be used alone or in combination of two or more.

[0029] As the chain extender, it is preferable to use at least one of plant-derived 1,3-propanediol and 1,4-butanediol from the viewpoint of reducing the environmental load.

[0030] The polyurethane used in the moisture-permeable waterproof film of the present invention may also use a mixture of at least two kinds of polyol components, a polycarbonate diol having a plant-derived component, and an ether-based polyol. Examples of ether-based polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol (PTMG), and copolymer polyether polyol (EO / PO). The use of PTMG is preferable from the viewpoint of improving water pressure resistance.

[0031] The proportion of plant-derived components in the polyurethane used in the moisture-permeable waterproof membrane of the moisture-permeable waterproof fabric of the present invention is preferably higher in terms of reducing the environmental impact, but from the viewpoint of improving the performance of the moisture-permeable waterproof membrane, it is preferable that the proportion be 10% by mass or more and 65% by mass or less, and more preferably 10% by mass or more and 40% by mass or less.

[0032] As a method for obtaining the polyurethane used in the moisture-permeable waterproof film of the moisture-permeable waterproof fabric of the present invention, for example, a method can be used in which a polyol is dissolved in a polar solvent such as dimethylformamide (DMF) or dimethylsulfoxide (DMSO), or a solvent such as methyl ethyl ketone (MEK), toluene, or xylene, a divalent isocyanate is added thereto, and the mixture is sufficiently reacted to prepare a prepolymer having an isocyanate or hydroxyl group at the end, and then a diol such as ethylene glycol, propylene glycol, or butylene glycol, or a divalent isocyanate is added to increase the degree of polymerization by a chain extension reaction. However, the synthesis method of the polyurethane used in the present invention is not limited to the above method.

[0033] (Breathable waterproof fabric) From the viewpoint of practical waterproofing, the moisture-permeable waterproof fabric according to the present invention preferably has a water pressure resistance measured according to JIS-L1092 (2009) of 100 kPa or more, and more preferably 150 kPa or more.

[0034] The moisture permeable waterproof fabric of the present invention has a moisture permeability of 104 g / m2 according to the A-1 method of JIS-L1099 (2012). 2hr or more, and more preferably 300 g / m 2 hr or more.

[0035] Moisture permeability can be imparted to the polyurethane film by forming the polyurethane film into a porous film by a wet method.

[0036] The pore size and pore distribution of the moisture-permeable, waterproof fabric according to the present invention can be freely designed within a range that satisfies both the water pressure resistance and the moisture permeability, which are mutually exclusive properties.

[0037] From the viewpoint of practical durability, the water pressure resistance retention rate after a hydrolysis evaluation test (jungle test) for 10 weeks in a high-temperature, high-humidity chamber at 70° C. and a relative humidity of 95% is preferably 60% or more, more preferably 70% or more.Furthermore, the water pressure resistance retention rate after a hydrolysis evaluation test (jungle test) for 20 weeks in a high-temperature, high-humidity chamber at 70° C. and a relative humidity of 95% is preferably 60% or more, more preferably 65% ​​or more.

[0038] The moisture-permeable waterproof fabric of the present invention is manufactured by laminating a moisture-permeable waterproof layer of polyurethane to a fabric. The moisture-permeable waterproof film can be laminated by a method of directly coating the fabric (coating method) or a method of forming a moisture-permeable waterproof film separately and then laminating it to the fabric with an adhesive (bonding method).

[0039] As the coating method, various coating methods such as knife coating, knife over roll coating, and reverse roll coating can be used.

[0040] As a joining method, for example, a moisture-permeable waterproof membrane formed by coating or the like on release paper is laminated to the fabric with adhesive in dots or by full-surface adhesion, and then the release paper is peeled off, but the joining method is not limited to this. [Industrial Applicability]

[0041] The moisture-permeable waterproof fabric of the present invention can be suitably used as a clothing material for outdoor wear such as fishing wear and mountain climbing wear, ski-related wear, windbreakers, athletic wear, golf wear, tennis wear, rainwear, casual coats, indoor and outdoor work clothes, gloves, shoes, etc. EXAMPLES

[0042] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. The following methods were used to measure various properties in the present specification including the following examples.

[0043] (Measurement method) (1) Water resistance: Measured in accordance with JIS-L1092 (2009). (2) Moisture permeability: Measured according to JIS-L1099 (2012) A-1 method. (3) Feel: A sensory evaluation was conducted on a two-level scale based on the feel of the material. 〇: Soft, ×: Hard (4) Hydrolysis test (jungle test): Hydrolysis was accelerated for 10 weeks in a high-temperature, high-humidity chamber at 70°C and a relative humidity of 95%, and the water pressure retention rate (the ratio of water pressure resistance after the test to the water pressure resistance before the test, in %) was investigated. In addition, the water pressure retention rate after 20 weeks of hydrolysis in a high-temperature, high-humidity chamber at 70°C and a relative humidity of 95% was also investigated. (5) Urethane solution stability: The polyurethane resin obtained was cooled to 10° C., and the fluidity at that time was evaluated. No fluidity (frozen / gelled): ×, Fluidity: 〇

[0044] <Polymerization of Polyurethane Resin Solution (1)> 162 g of plant-derived polyester polyol (sebacic acid-based polyester polyol, hydroxyl value 55.1 mgKOH / g, "YURIC" (registered trademark) SE-1903 manufactured by Ito Oil Mills, Ltd.) and 250 g of dimethylformamide (hereinafter referred to as "DMF") were dissolved in a 2-liter separable flask, and 101 g of diphenylmethane diisocyanate was added while adjusting the temperature to 50°C, and the mixture was reacted at 50°C for about 1 hour to obtain a prepolymer. After this, the temperature was raised to 60°C, 16 g of ethylene glycol and 60 g of DMF were added, and the chain extension reaction was carried out at 60°C, and polymerization was carried out while adding 420 g of DMF in portions in accordance with the increase in viscosity. When the viscosity reached a predetermined level, 9 g of 1,2-propylene glycol and 115 g of DMF were added. The reaction was completed in approximately 6 to 8 hours, yielding a urethane resin solution (1) with a urethane resin concentration of 25.0%, a viscosity of 55,000 mPa·s (30°C), and a plant-derived ratio of 45.9%.

[0045] <Polymerization of Polyurethane Resin Solution (2)> 130g of polycarbonate polyol (hexamethylene carbonate diol, hydroxyl value 56.5mgKOH / g, Tosoh Corporation, "Nippolan" (registered trademark) 980R), 32g of polyether polyol (polytetramethylene glycol, hydroxyl value 56.1mgKOH / g, Sanyo Chemical Industries, Ltd., PTMG-2000M), and 250g of DMF were dissolved in a 2-liter separable flask, and 87g of diphenylmethane diisocyanate was added while adjusting the temperature to 50°C, and the mixture was reacted at 50°C for about 1 hour to obtain a prepolymer. After this, the temperature was raised to 60°C, 19.4g of ethylene glycol and 40g of DMF were added, and the chain extension reaction was carried out at 60°C, and polymerization was carried out while adding 400g of DMF in portions in accordance with the increase in viscosity. When the viscosity reached the specified level, 9 g of 1,2-propylene glycol and 110 g of DMF were added. The reaction was completed in approximately 6 to 8 hours, yielding a urethane resin solution (2) with a urethane resin concentration of 25.0% and a viscosity of 85,000 mPa s (30°C).

[0046] <Polymerization of Polyurethane Resin Solution (3)> 162g of polycarbonate polyol (1,4-butanediol / 1,10-decanediol = 1 / 9 molar ratio copolymerized carbonate diol, hydroxyl value 56.5mgKOH / g, manufactured by Mitsubishi Chemical Corporation, "Benebiol" (registered trademark) NL2090DB, 1,10-decanediol is plant-derived) and 250g of DMF were dissolved in a 2-liter separable flask, and 87g of diphenylmethane diisocyanate was added while adjusting the temperature to 50°C, and reacted at 50°C for about 1 hour to obtain a prepolymer. After this, the temperature was raised to 60°C, 16g of ethylene glycol and 40g of DMF were added, and a chain extension reaction was carried out at 60°C, and polymerization was carried out while adding 400g of DMF in portions in accordance with the increase in viscosity. When the viscosity increased to a predetermined level, 9g of 1,2-propylene glycol and 110g of DMF were added. The reaction was completed in approximately 6 to 8 hours, yielding a urethane resin solution (3) with a urethane resin concentration of 25.0%, a viscosity of 83,000 mPa s (30 °C), and a plant-derived ratio of 53.2%.

[0047] <Polymerization of Polyurethane Resin Solution (4)> 162g of polycarbonate polyol (1,4-butanediol / 1,10-decanediol = 5 / 5 molar ratio copolymerized carbonate diol, hydroxyl value 56.5mgKOH / g, manufactured by Mitsubishi Chemical Corporation, "Benebiol" (registered trademark) NL2050DB, 1,10-decanediol is plant-derived) and 250g of DMF were dissolved in a 2-liter separable flask, and 87g of diphenylmethane diisocyanate was added while adjusting the temperature to 50°C, and reacted at 50°C for about 1 hour to obtain a prepolymer. After this, the temperature was raised to 60°C, 16g of ethylene glycol and 40g of DMF were added, and a chain extension reaction was carried out at 60°C, and polymerization was carried out while adding 400g of DMF in portions in accordance with the increase in viscosity. When the viscosity increased to a predetermined level, 9g of 1,2-propylene glycol and 110g of DMF were added. The reaction was completed in approximately 6 to 8 hours, yielding a urethane resin solution (4) with a urethane resin concentration of 25.0%, a viscosity of 81,000 mPa s (30 °C), and a plant-derived ratio of 38.4%.

[0048] <Polymerization of Polyurethane Resin Solution (5)> 162g of polycarbonate polyol (1,4-butanediol / 1,10-decanediol = 7 / 3 molar ratio copolymerized carbonate diol, hydroxyl value 56.5mgKOH / g, manufactured by Mitsubishi Chemical Corporation, "Benebiol" (registered trademark) NL2030DB, 1,10-decanediol is plant-derived) and 250g of DMF were dissolved in a 2-liter separable flask, and 87g of diphenylmethane diisocyanate was added while adjusting the temperature to 50°C, and reacted at 50°C for about 1 hour to obtain a prepolymer. After this, the temperature was raised to 60°C, 16g of ethylene glycol and 40g of DMF were added, and a chain extension reaction was carried out at 60°C, and polymerization was carried out while adding 400g of DMF in portions in accordance with the increase in viscosity. When the viscosity increased to a predetermined level, 9g of 1,2-propylene glycol and 110g of DMF were added. The reaction was completed in approximately 6 to 8 hours, yielding a urethane resin solution (5) with a urethane resin concentration of 25.0%, a viscosity of 86,000 mPa s (30 °C), and a plant-derived ratio of 27.4%.

[0049] <Polymerization of Polyurethane Resin Solution (6)> 162g of polycarbonate polyol (1,4-butanediol / 1,10-decanediol = 9 / 1 molar ratio copolymerized carbonate diol, hydroxyl value 55.5mgKOH / g, manufactured by Mitsubishi Chemical Corporation, "Benebiol" (registered trademark) NL2010DB, 1,10-decanediol is plant-derived) and 250g of DMF were dissolved in a 2-liter separable flask, and 87g of diphenylmethane diisocyanate was added while adjusting the temperature to 50°C, and reacted at 50°C for about 1 hour to obtain a prepolymer. After this, the temperature was raised to 60°C, 16g of ethylene glycol and 40g of DMF were added, and a chain extension reaction was carried out at 60°C, and polymerization was carried out while adding 400g of DMF in portions in accordance with the increase in viscosity. When the viscosity increased to a predetermined level, 9g of 1,2-propylene glycol and 110g of DMF were added. The reaction was completed in approximately 6 to 8 hours, yielding a urethane resin solution (6) with a urethane resin concentration of 25.0%, a viscosity of 85,000 mPa s (30 °C), and a plant-derived ratio of 13.4%.

[0050] <Polymerization of Polyurethane Resin Solution (7)> 130 g of polycarbonate polyol (copolymerized carbonate diol with a molar ratio of 1,4-butanediol / 1,10-decanediol of 9 / 1, hydroxyl value of 54.5 mg KOH / g, manufactured by Mitsubishi Chemical Corporation, "Benebiol" (registered trademark) NL2010DB, 1,10-decanediol is plant-derived), 32 g of polyether polyol (polytetramethylene glycol, hydroxyl value of 56.1 mg KOH / g, manufactured by Sanyo Chemical Industries, Ltd., PTMG-2000M), and 250 g of DMF were dissolved in a 2-liter separable flask, and 87 g of diphenylmethane diisocyanate was added while adjusting the temperature to 50°C. The mixture was allowed to react at 50°C for approximately 1 hour to obtain a prepolymer. After this, the temperature was raised to 60°C, 16g of ethylene glycol and 40g of DMF were added, and a chain extension reaction was carried out at 60°C. Polymerization was carried out while adding 400g of DMF in portions in accordance with the increase in viscosity. When the viscosity reached the specified level, 9g of 1,2-propylene glycol and 110g of DMF were added. The reaction was completed in approximately 6 to 8 hours, and a urethane resin solution (7) was obtained with a urethane resin concentration of 25.0%, a viscosity of 86,000 mPa s (30°C), and a plant-derived ratio of 9.4%.

[0051] <Polymerization of Polyurethane Resin Solution (8)> 162g of polycarbonate polyol (1,4-butanediol / 1,10-decanediol = 9 / 1 molar ratio copolymerized carbonate diol, hydroxyl value 55.5mgKOH / g, manufactured by Mitsubishi Chemical Corporation, "Benebiol" (registered trademark) NL2010DB, 1,10-decanediol is plant-derived) and 250g of DMF were dissolved in a 2-liter separable flask, and 87g of diphenylmethane diisocyanate was added while adjusting the temperature to 50°C, and reacted at 50°C for about 1 hour to obtain a prepolymer. After this, the temperature was raised to 60°C, and 19.6g of plant-derived 1,3-propylene glycol and 50g of DMF were added, and a chain extension reaction was carried out at 60°C, and polymerization was carried out while adding 400g of DMF in portions in accordance with the increase in viscosity. When the viscosity reached the specified level, 9 g of 1,2-propylene glycol and 110 g of DMF were added. The reaction was completed in approximately 6 to 8 hours, yielding a urethane resin solution (8) with a urethane resin concentration of 25.0%, a viscosity of 92,000 mPa s (30 °C), and a plant-derived ratio of 20.6%.

[0052] [Comparative Example 1] Nylon rip taffeta made of 50 denier nylon filament yarn was immersed in a 30 g / l diluted solution of a fluorine-based water repellent agent (Nicca Chemical Co., Ltd., "NK Guard" (registered trademark) S-07), squeezed with a mangle to a squeezing rate of 40%, dried at 120°C, and heat-treated at 160°C for 30 seconds to perform a water repellent treatment. Next, 100 parts by mass of the polyurethane resin solution (1) prepared in <Polymerization of polyurethane resin solution (1)> was added with 6 parts by mass of silica fine powder (AEROSIL (registered trademark) R-972, Japan Aerosil Co., Ltd.), 1 part by mass of a fluorine water repellent (SF-1011, Toray Coatex Co., Ltd.), and 1 part by mass of a crosslinking agent (Coronate (registered trademark) HX, Tosoh Corporation), and thoroughly mixed with 50 parts by mass of DMF. The mixture was dispersed and stirred for about 15 minutes using a homomixer, and then further stirred to obtain a liquid composition of a polyurethane resin composition. This is applied to the water-repellent nylon rip taffeta with a knife overroll coater at 150 g / m 2The fabric was coated with a coating amount of 100 g / m2 and immersed in a gelling bath containing an aqueous solution containing 20% ​​by mass of DMF for 2 minutes to form a film by a wet coagulation method. The fabric was then washed with water for 10 minutes and dried with hot air at 140°C to obtain a moisture-permeable, waterproof fabric with a porous structure. The obtained moisture-permeable and waterproof fabric was evaluated for water pressure resistance, moisture permeability, and texture. In addition, after a jungle test (temperature 70°C, humidity 95%, 10 weeks, 20 weeks), the water pressure resistance was measured and its retention rate was calculated. The results are shown in Table 1.

[0053] [Comparative Example 2] Nylon rip taffeta made of 50 denier nylon filament yarn was immersed in a 30 g / l diluted solution of a fluorine-based water repellent (Nicca Chemical Co., Ltd., "NK Guard" (registered trademark; the same applies below) S-07), squeezed with a mangle to a squeezing rate of 40%, dried at 120°C, and heat-treated at 160°C for 30 seconds to perform a water repellent treatment. Next, 100 parts by mass of the polyurethane resin solution (2) prepared in <Polymerization of polyurethane resin solution (2)> was added with 6 parts by mass of silica fine powder (AEROSIL R-972, Nippon Aerosil Co., Ltd.), 1 part by mass of a fluorine water repellent (SF-1011, Toray Coatex Co., Ltd.), and 1 part by mass of a crosslinking agent (Coronate HX, Tosoh Corporation), and thoroughly mixed with 50 parts by mass of DMF. The mixture was dispersed and stirred for about 15 minutes using a homomixer, and then further stirred to obtain a liquid composition of a polyurethane resin composition. This is applied to the water-repellent nylon rip taffeta with a knife overroll coater at 150 g / m 2 The fabric was coated with a coating amount of 100 g / m2 and immersed in a gelling bath containing an aqueous solution containing 20% ​​by mass of DMF for 2 minutes to form a film by a wet coagulation method. The fabric was then washed with water for 10 minutes and dried with hot air at 140°C to obtain a moisture-permeable, waterproof fabric with a porous structure. The obtained moisture-permeable and waterproof fabric was evaluated for water pressure resistance, moisture permeability, and texture. In addition, after a jungle test (temperature 70°C, humidity 95%, 10 weeks, 20 weeks), the water pressure resistance was measured and its retention rate was calculated. The results are shown in Table 1.

[0054] [Example 1] Nylon rip taffeta made of 50 denier nylon filament yarn was immersed in a 30 g / l diluted solution of a fluorine-based water repellent agent (Nicca Chemical Co., Ltd., "NK Guard" (registered trademark) S-07), squeezed with a mangle to a squeezing rate of 40%, dried at 120°C, and heat-treated at 160°C for 30 seconds to perform a water repellent treatment. Next, 100 parts by mass of the polyurethane resin solution (4) prepared in <Polymerization of polyurethane resin solution (4)> was added with 6 parts by mass of silica fine powder (AEROSIL (registered trademark) R-972, Japan Aerosil Co., Ltd.), 1 part by mass of a fluorine water repellent (SF-1011, Toray Coatex Co., Ltd.), and 1 part by mass of a crosslinking agent (Coronate (registered trademark) HX, Tosoh Corporation), and thoroughly mixed with 50 parts by mass of DMF. The mixture was dispersed and stirred for about 15 minutes using a homomixer, and then further stirred to obtain a liquid composition of a polyurethane resin composition. This is applied to the water-repellent nylon rip taffeta with a knife overroll coater at 150 g / m 2 The fabric was coated with a coating amount of 1000g, and then immersed in a gelling bath of an aqueous solution containing 20% ​​by mass of DMF for 2 minutes to form a film by a wet coagulation method. The fabric was then washed with water for 10 minutes and dried with hot air at 140°C to obtain a moisture-permeable, waterproof fabric with a porous structure. The obtained moisture-permeable and waterproof fabric was evaluated for water pressure resistance, moisture permeability, and texture. In addition, after a jungle test (temperature 70°C, humidity 95%, 10 weeks, 20 weeks), the water pressure resistance was measured and its retention rate was calculated. The results are shown in Table 1.

[0055] [Example 2] Nylon rip taffeta made of 50 denier nylon filament yarn was immersed in a 30 g / l diluted solution of a fluorine-based water repellent agent (Nicca Chemical Co., Ltd., "NK Guard" (registered trademark) S-07), squeezed with a mangle to a squeezing rate of 40%, dried at 120°C, and heat-treated at 160°C for 30 seconds to perform a water repellent treatment. Next, 100 parts by mass of the polyurethane resin solution (5) prepared in <Polymerization of polyurethane resin solution (5)> was added with 6 parts by mass of silica fine powder (AEROSIL (registered trademark) R-972, Japan Aerosil Co., Ltd.), 1 part by mass of a fluorine water repellent (SF-1011, Toray Coatex Co., Ltd.), and 1 part by mass of a crosslinking agent (Coronate (registered trademark) HX, Tosoh Corporation), and thoroughly mixed with 50 parts by mass of DMF. The mixture was dispersed and stirred for about 15 minutes using a homomixer, and then further stirred to obtain a liquid composition of a polyurethane resin composition. This is applied to the water-repellent nylon rip taffeta with a knife overroll coater at 150 g / m 2 The fabric was coated with a coating amount of 1000g, and then immersed in a gelling bath of an aqueous solution containing 20% ​​by mass of DMF for 2 minutes to form a film by a wet coagulation method. The fabric was then washed with water for 10 minutes and dried with hot air at 140°C to obtain a moisture-permeable, waterproof fabric with a porous structure. The obtained moisture-permeable and waterproof fabric was evaluated for water pressure resistance, moisture permeability, and texture. In addition, after a jungle test (temperature 70°C, humidity 95%, 10 weeks, 20 weeks), the water pressure resistance was measured and its retention rate was calculated. The results are shown in Table 1.

[0056] [Example 3] Nylon rip taffeta made of 50 denier nylon filament yarn was immersed in a 30 g / l diluted solution of a fluorine-based water repellent agent (Nicca Chemical Co., Ltd., "NK Guard" (registered trademark) S-07), squeezed with a mangle to a squeezing rate of 40%, dried at 120°C, and heat-treated at 160°C for 30 seconds to perform a water repellent treatment. Next, 100 parts by mass of the polyurethane resin solution (6) prepared in <Polymerization of polyurethane resin solution (6)> was added with 6 parts by mass of silica fine powder (AEROSIL R-972, Nippon Aerosil Co., Ltd.), 1 part by mass of a fluorine water repellent (SF-1011, Toray Coatex Co., Ltd.), and 1 part by mass of a crosslinking agent (Coronate HX, Tosoh Corporation), and thoroughly mixed with 50 parts by mass of DMF. The mixture was dispersed and stirred for about 15 minutes using a homomixer, and then further stirred to obtain a liquid composition of a polyurethane resin composition. This is applied to the water-repellent nylon rip taffeta with a knife overroll coater at 150 g / m2 The fabric was coated with a coating amount of 1000g, and then immersed in a gelling bath of an aqueous solution containing 20% ​​by mass of DMF for 2 minutes to form a film by a wet coagulation method. The fabric was then washed with water for 10 minutes and dried with hot air at 140°C to obtain a moisture-permeable, waterproof fabric with a porous structure. The obtained moisture-permeable and waterproof fabric was evaluated for water pressure resistance, moisture permeability, and texture. In addition, after a jungle test (temperature 70°C, humidity 95%, 10 weeks, 20 weeks), the water pressure resistance was measured and its retention rate was calculated. The results are shown in Table 1.

[0057] [Example 4] Nylon rip taffeta made of 50 denier nylon filament yarn was immersed in a 30 g / l diluted solution of a fluorine-based water repellent agent (Nicca Chemical Co., Ltd., "NK Guard" (registered trademark) S-07), squeezed with a mangle to a squeezing rate of 40%, dried at 120°C, and heat-treated at 160°C for 30 seconds to perform a water repellent treatment. Next, 100 parts by mass of the polyurethane resin solution (7) prepared in <Polymerization of polyurethane resin solution (7)> ​​was added with 6 parts by mass of silica fine powder (AEROSIL R-972, Nippon Aerosil Co., Ltd.), 1 part by mass of a fluorine water repellent (SF-1011, Toray Coatex Co., Ltd.), and 1 part by mass of a crosslinking agent (Coronate HX, Tosoh Corporation), and thoroughly mixed with 50 parts by mass of DMF. The mixture was dispersed and stirred for about 15 minutes using a homomixer, and then further stirred to obtain a liquid composition of a polyurethane resin composition. This is applied to the water-repellent nylon rip taffeta with a knife overroll coater at 150 g / m 2 The fabric was coated with a coating amount of 100 g of DMF and immersed in a gelling bath containing an aqueous solution containing 20% ​​by mass of DMF for 2 minutes to form a film by a wet coagulation method. The fabric was then washed with water for 10 minutes and dried with hot air at 140°C to obtain a moisture-permeable, waterproof fabric with a homogenous, fine porous structure. The obtained moisture-permeable and waterproof fabric was evaluated for water pressure resistance, moisture permeability, and texture. In addition, after a jungle test (temperature 70°C, humidity 95%, 10 weeks, 20 weeks), the water pressure resistance was measured and its retention rate was calculated. The results are shown in Table 1.

[0058] [Example 5] Nylon rip taffeta made of 50 denier nylon filament yarn was immersed in a 30 g / l diluted solution of a fluorine-based water repellent agent (Nicca Chemical Co., Ltd., "NK Guard" (registered trademark) S-07), squeezed with a mangle to a squeezing rate of 40%, dried at 120°C, and heat-treated at 160°C for 30 seconds to perform a water repellent treatment. Next, 100 parts by mass of the polyurethane resin solution (8) prepared in <Polymerization of polyurethane resin solution (8)> was added with 6 parts by mass of silica fine powder (AEROSIL (registered trademark) R-972, Japan Aerosil Co., Ltd.), 1 part by mass of a fluorine water repellent (SF-1011, Toray Coatex Co., Ltd.), and 1 part by mass of a crosslinking agent (Coronate (registered trademark) HX, Tosoh Corporation), and thoroughly mixed with 50 parts by mass of DMF. The mixture was dispersed and stirred for about 15 minutes using a homomixer, and then further stirred to obtain a liquid composition of a polyurethane resin composition. This is applied to the water-repellent nylon rip taffeta with a knife overroll coater at 150 g / m 2 The fabric was coated with a coating amount of 100 g / m2 and immersed in a gelling bath containing an aqueous solution containing 20% ​​by mass of DMF for 2 minutes to form a film by a wet coagulation method. The fabric was then washed with water for 10 minutes and dried with hot air at 140°C to obtain a moisture-permeable, waterproof fabric with a porous structure. The obtained moisture-permeable and waterproof fabric was evaluated for water pressure resistance, moisture permeability, and texture. In addition, after a jungle test (temperature 70°C, humidity 95%, 10 weeks, 20 weeks), the water pressure resistance was measured and its retention rate was calculated. The results are shown in Table 1.

[0059] [Table 1]

[0060] Previous technologies have existed that have a plant-derived component but low hydrolysis resistance as shown in Comparative Example 1 in Table 1, and that have high hydrolysis resistance but no plant-derived component as shown in Comparative Example 2, but there have been no mass-producible products that have plant-derived components and excellent hydrolysis resistance. As shown in Examples 1, 2, 3, 4, and 5, the inclusion of plant-derived ingredients contributes to reducing the environmental impact by being carbon neutral, while the high hydrolysis resistance, a characteristic of polycarbonate-based urethane, makes it possible to produce products that can withstand long-term practical use. Furthermore, as shown in Example 4, by copolymerizing plant-derived polycarbonate-based polyol with PTMG, a useful moisture-permeable, waterproof fabric having higher water pressure resistance can be obtained. Furthermore, as shown in Example 5, by using a plant-derived chain extender during polyurethane polymerization, it is possible to further increase the plant-derived ratio while maintaining high hydrolysis resistance, thereby further contributing to reducing the environmental impact.

Claims

1. A moisture-permeable waterproof fabric having a porous moisture-permeable waterproof membrane on at least one side of the fabric, The polyurethane forming the moisture-permeable waterproof film is synthesized using a polyol containing a polycarbonate diol having a plant-derived component, The polycarbonate diol contains a component derived from plant-derived 1,10-decanediol and a component derived from 1,4-butanediol, and the molar ratio of the 1,10-decanediol to the 1,4-butanediol is 1 / 9 to 8 / 2.

2. A breathable waterproof fabric as described in claim 1, wherein the molar ratio of 1,10-decanediol to 1,4-butanediol is 1 / 9 to 5 / 5.

3. 3. The moisture-permeable waterproof fabric according to claim 1, wherein the polyol is a mixture of at least two kinds of polyols, the polycarbonate diol and an ether-based polyol.

4. The moisture-permeable waterproof fabric according to any one of claims 1 to 3, wherein the polyurethane uses at least one of plant-derived 1,3-propanediol and 1,4-butanediol as a chain extender.

5. The moisture-permeable waterproof fabric according to any one of claims 1 to 4, wherein the moisture-permeable waterproof membrane has a water pressure resistance of 10 kPa or more.

6. The moisture-permeable waterproof fabric according to any one of claims 1 to 4, wherein the moisture-permeable waterproof membrane has a water pressure resistance of 100 kPa or more.

7. The moisture-permeable waterproof fabric according to any one of claims 1 to 4, wherein the moisture-permeable waterproof membrane has a water pressure resistance of 150 kPa or more.

8. The moisture-permeable waterproof fabric according to any one of claims 1 to 7, which has a water pressure resistance retention rate of 60% or more after 10 weeks in a hydrolysis evaluation test at a temperature of 70°C and a humidity of 95%.

9. The moisture-permeable waterproof fabric according to any one of claims 1 to 7, which has a water pressure resistance retention rate of 60% or more after 20 weeks in a hydrolysis evaluation test at a temperature of 70°C and a humidity of 95%.

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