Moisture-permeable and waterproof fabric

Abstract

The present invention provides a moisture-permeable waterproof fabric with excellent waterproof and moisture-permeable properties that can achieve a reduction in environmental load through carbon neutrality and an extended product lifespan. The moisture-permeable waterproof fabric of the present invention is a moisture-permeable waterproof fabric having a porous moisture-permeable waterproof film on at least one side of the fabric, and the polyurethane forming the moisture-permeable waterproof film is synthesized using a polyol containing polycarbonate diol, and the polycarbonate diol has a plant-derived component.

Description

Technical Field

[0001] The present invention relates to a moisture-permeable and waterproof fabric having a moisture-permeable and waterproof film containing polyurethane. Background Art

[0002] Conventionally, for uses such as sports clothing and outdoor products, a moisture-permeable and waterproof fabric having a moisture-permeable and waterproof film containing polyurethane, which is excellent in moisture permeability and waterproofness, has been proposed.

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

[0004] In addition, Patent Document 2 discloses a waterproof processed fabric having a waterproof layer containing a polyurethane resin obtained from a plant-derived castor oil-based polyol polyester diol, and mainly describes that although the waterproof processed fabric has a plant-derived component, it has excellent hydrolysis resistance.

[0005] Furthermore, Patent Document 3 discloses a moisture-permeable and waterproof fabric having a porous resin film containing a plant-derived sebacic acid and an ester-based urethane obtained from a diol, and mainly describes that the moisture-permeable and waterproof fabric has performance equal to or better than that when using a petroleum-derived polyurethane.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Laid-Open No. 5-186631

[0009] Patent Document 2: Japanese Patent No. 5855722

[0010] Patent Document 3: Japanese Patent No. 5680052 Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] However, in the technology of Patent Document 1, water resistance and moisture permeability are insufficient, and at the same time, petroleum-derived materials are used, so the impact on the environment is large.

[0013] In addition, in the technology of Patent Document 2, as shown in Examples 1 to 3 of Patent Document 2, the water pressure resistance is low. Therefore, in order to obtain the water pressure resistance required in actual use, top surface coating is required. However, when performing top surface coating, as shown in Example 4, there is a problem that the moisture permeability is significantly reduced. In addition, during the process of purifying polyether polyol from castor oil, castor oil is mixed in as an impurity. Therefore, the product emits an unpleasant odor generated by castor oil, which is not preferable as clothing. Furthermore, due to the mixing of castor oil as an impurity, there is a problem that the polymerization of polyurethane is unstable.

[0014] Furthermore, in the technology of Patent Document 3, since an ester-based polyurethane is used, there is a problem of early deterioration of the moisture-permeable waterproof film due to hydrolysis.

[0015] The present invention has been completed in view of the above problems, and an object thereof is to provide a moisture-permeable waterproof fabric having excellent waterproof and moisture-permeability properties, which can reduce the environmental load by carbon neutrality and extending the product life by forming a moisture-permeable waterproof film from a polycarbonate-based urethane resin having a plant-derived component.

[0016] Means for Solving the Problems

[0017] The present invention is a moisture-permeable waterproof fabric having a porous moisture-permeable waterproof film on at least one side of the fabric. The polyurethane forming the moisture-permeable waterproof film is synthesized using a polyol containing polycarbonate diol, and the polycarbonate diol has a plant-derived component.

[0018] Effects of the Invention

[0019] According to the present invention, it is possible to provide a moisture-permeable waterproof fabric that can reduce the environmental load by carbon neutrality and extending the product life, and at the same time has excellent waterproof and moisture-permeability properties. Detailed Description of the Invention

[0020] Hereinafter, the moisture-permeable waterproof fabric of the present invention will be described in detail.

[0021] The moisture-permeable waterproof fabric of the present invention is a moisture-permeable waterproof fabric having a porous moisture-permeable waterproof film on at least one side of the fabric. The polyurethane forming the moisture-permeable waterproof film is synthesized using a polyol containing polycarbonate diol, and the polycarbonate diol has a plant-derived component.

[0022] (Fabric)

[0023] As the fabric used in the moisture-permeable and waterproof fabric of the present invention, a fabric suitable for the intended use can be appropriately used, and its type is not particularly limited. As examples, synthetic fibers such as nylon fiber, polyester fiber, and polyamide fiber can be mentioned; semi-synthetic fibers such as acetate fiber; and natural fibers such as cotton, hemp, and wool. These various fibers can be used alone or in combination of two or more. In addition, its texture is not particularly limited, and woven fabrics, knitted fabrics, non-woven fabrics, etc. can be appropriately used. In addition, from the viewpoint of reducing the environmental load, it is preferable to use recycled polyester filaments, recycled nylon filaments, and filaments containing components derived from plants in the fabric.

[0024] (Moisture-permeable and waterproof film)

[0025] The moisture-permeable and waterproof film of the moisture-permeable and waterproof fabric of the present invention contains polyurethane, and the polyurethane uses a polyol containing a polycarbonate diol having a component derived from a plant.

[0026] From the viewpoints of chemical resistance, low-temperature characteristics, and hydrolysis resistance, the polycarbonate diol having a component derived from a plant related to the present invention preferably uses a polycarbonate diol containing at least two diols, and at least one of the two diols is preferably a component derived from a plant. The polycarbonate diol containing two diols can be produced by polycondensing the two diols and a carbonate compound through a transesterification reaction.

[0027] For example, for the polycarbonate diol containing two diols, a polycarbonate diol having 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 as constituent elements can be preferably used.

[0028] As the diol having an alkylene group with 3 to 5 carbon atoms, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, 1,5-pentanediol, etc. can be mentioned. Among them, since the produced polyurethane can maintain a good balance between chemical resistance and low-temperature characteristics, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol are preferred, and 1,3-propanediol and 1,4-butanediol are more preferred.

[0029] As the diol having an alkylene group with 8 to 20 carbon atoms, 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, 1,20-eicosanediol, etc. can be cited. Among them, since the polyurethane produced has a good balance between chemical resistance and low-temperature characteristics, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol are preferred, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol are more preferred, and 1,10-decanediol is further preferred.

[0030] The polycarbonate diol containing 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 as constituent components can use a diol compound other than the diol having an alkylene group with 3 to 5 carbon atoms and the diol having an alkylene group with 8 to 20 carbon atoms (sometimes referred to as other diol compounds). Among them, when using other diol compounds, in order to effectively obtain the effects of the present invention, it is preferred that the proportion of the structural units derived from other diol compounds is 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and most preferably 10 mol% or less with respect to all the structural units of the polycarbonate diol.

[0031] From the viewpoint of reducing the environmental load, the diol having an alkylene group with 3 to 5 carbon atoms is preferably derived from plants. As the diol having an alkylene group with 3 to 5 carbon atoms that can be applied and is derived from plants, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, etc. can be cited.

[0032] From the viewpoint of reducing the environmental load, the diol having an alkylene group with 8 to 20 carbon atoms is preferably derived from plants. As the diol having an alkylene group with 8 to 20 carbon atoms that can be applied and is derived from plants, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,12-octadecanediol, 1,20-eicosanediol, etc. can be cited.

[0033] 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.

[0034] Regarding the polycarbonate diol having a plant-derived component used in the moisture-permeable waterproof film of the present invention, it preferably 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 1 / 9 to 8 / 2. By making the molar ratio of 1,10-decanediol to 1,4-butanediol 1 / 9 to 5 / 5, a moisture-permeable waterproof fabric excellent in water pressure resistance and moisture permeability can be obtained, and thus it is further preferred.

[0035] As the polycarbonate compound that can be used in the production of polycarbonate diol, dialkyl carbonate, diaryl carbonate, or alkylene carbonate can be cited. Specific examples of the carbonate compound include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, ethylene carbonate, etc., and diphenyl carbonate is preferred.

[0036] The polyurethane used in the moisture-permeable waterproof film of 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.

[0037] As the polyisocyanate for producing the polyurethane of the present invention, aliphatic, alicyclic, or aromatic polyisocyanate compounds can be cited. 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 obtained by converting the carboxyl group of dimer acid into 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(isocyanatomethyl)cyclohexane; aromatic diisocyanates such as xylene diisocyanate, 4,4'-diphenyl diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene 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-naphthalene diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, polymethylene polyphenyl isocyanate, phenylene diisocyanate, and m-tetramethylxylene diisocyanate; and so on. These can be used alone or in combination of two or more. In addition, from the viewpoint of reducing the environmental load, it is preferable to use an isocyanate having a plant-derived component such as 1,5-pentamethylene diisocyanate derived from plants.

[0038] As chain extenders, examples include straight-chain 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, 1,12-dodecanediol; branched-chain diols such as 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-heptanediol, 1,4-bis(hydroxymethyl)hexane, 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; ether-group-containing diols such as diethylene glycol, propylene glycol; hydroxyamines such as N-methylethanolamine, N-ethylethanolamine; polyamines such as ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, bis(2-hydroxyethyl)ethylenediamine, bis(2-hydroxyethyl)propylenediamine, 2-hydroxypropyl ethylenediamine, bis(2-hydroxypropyl)ethylenediamine, 4,4'-diphenylmethanediamine, methylenebis(orthochloroaniline), xylylenediamine, diphenyldiamine, toluenediamine, hydrazine, piperazine, N,N'-diaminopiperazine. The chain extenders can be used alone or in combination of two or more kinds.

[0039] As chain extenders, from the viewpoint of reducing the environmental load, it is preferred to use at least one of 1,3-propanediol and 1,4-butanediol derived from plants.

[0040] The polyurethane used in the moisture-permeable waterproof film of the present invention can also use a mixture of at least two of polycarbonate diol and ether-based polyol having plant-derived components as the polyol component. As the ether-based polyol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (PTMG), etc., or copolymerized polyether polyol (EO / PO) can be exemplified. From the viewpoint of improving the water pressure resistance, PTMG is preferred.

[0041] From the viewpoint of reducing the environmental load, the higher the proportion of the plant-derived components in the polyurethane used in the moisture-permeable waterproof film of the present invention, the more preferred. However, from the viewpoint of improving the performance of the moisture-permeable waterproof film, it is preferably 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.

[0042] For example, as a method for obtaining the polyurethane used in the moisture-permeable and waterproof film of the moisture-permeable and waterproof fabric of the present invention, the following method can be used: dissolve polyol in a polar solvent represented by dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc., methyl ethyl ketone (MEK), toluene, xylene and other solvents, add divalent isocyanate thereto, and make them react sufficiently to prepare a prepolymer having an isocyanate or hydroxyl group at the end, and then add polyols such as ethylene glycol, propylene glycol, butylene glycol, or divalent isocyanate to increase the degree of polymerization through a chain extension reaction. However, the synthesis method of the polyurethane used in the present invention is not limited to the above method.

[0043] (Moisture-permeable and waterproof fabric)

[0044] From the perspective of practical waterproofing, the hydrostatic pressure resistance of the moisture-permeable and waterproof fabric according to the present invention measured by JIS-L1092 (2009) is preferably 100 kPa or more, more preferably 150 kPa or more.

[0045] For the moisture-permeable and waterproof fabric according to the present invention, as the moisture permeability, it is preferably 104 g / m 2 ·hr or more, more preferably 300 g / m 2 ·hr or more, by the A-1 method of JIS-L1099 (2012).

[0046] For imparting moisture permeability to the polyurethane film, it can be imparted by making the polyurethane film into a porous film by a wet method.

[0047] For the pore size and pore distribution of the moisture-permeable and waterproof fabric according to the present invention, it can be freely designed within the range that satisfies the coexistence of the performance of hydrostatic pressure resistance and moisture permeability as opposing properties.

[0048] In addition, from the perspective of durability in actual use, it is preferably that the retention rate of the hydrostatic pressure resistance after 10 weeks of hydrolysis evaluation test (Jungle Test (durability test)) in a high-temperature and high-humidity tank at 70 °C and 95% relative humidity is 60% or more, more preferably 70% or more. In addition, it is preferably that the retention rate of the hydrostatic pressure resistance after 20 weeks of hydrolysis evaluation test (Jungle Test) in a high-temperature and high-humidity tank at 70 °C and 95% relative humidity is 60% or more, more preferably 65% or more.

[0049] The moisture-permeable and waterproof fabric according to the present invention is manufactured by laminating a moisture-permeable and waterproof film of polyurethane on the fabric. As the lamination method of the moisture-permeable and waterproof film, it includes a method of directly coating on the fabric (coating method); a method of laminating it on the fabric with an adhesive after separately forming the moisture-permeable and waterproof film (bonding method).

[0050] For the coating method, various coating methods such as knife coating, knife-over-roll coating, and reverse roll coating can be used.

[0051] For example, as the bonding method, a method of laminating a moisture-permeable and waterproof film formed on a release paper by coating or the like on a fabric by dot bonding or surface bonding and then peeling off the release paper can be used, but it is not limited thereto.

[0052] Industrial applicability

[0053] The moisture-permeable and waterproof fabric according to the present invention can be suitably used as clothing materials such as fishing clothes, mountain climbing clothes and other outdoor clothes, skiing-related clothes, windbreakers, sportswear, golf clothes, tennis clothes, raincoats, casual coats, indoor and outdoor work clothes, gloves, shoes and the like.

[0054] Examples

[0055] Hereinafter, the present invention will be further specifically described by way of examples, but the present invention is not limited to the following examples.

[0056] It should be noted that as the measurement method of each property in the specification of the present application including the following examples, the following method is used.

[0057] (Measurement method)

[0058] (1) Hydrostatic pressure resistance: Measured according to JIS-L1090 (2009).

[0059] (2) Moisture permeability: Measured according to Method A-1 of JIS-L1099 (2012).

[0060] (3) Texture: Sensory evaluation is carried out in two stages by hand touch.

[0061] 〇: Soft, ×: Hard

[0062] (4) Hydrolysis test (durability test): In a high-temperature and high-humidity tank at 70 °C and a relative humidity of 95%, hydrolysis is promoted for 10 weeks, and the retention rate of hydrostatic pressure resistance (the ratio of the hydrostatic pressure resistance after the test to the hydrostatic pressure resistance before the test, unit: %) is investigated. In addition, the retention rate of hydrostatic pressure resistance after 20 weeks of hydrolysis in a high-temperature and high-humidity tank at 70 °C and a relative humidity of 95% (the ratio of the hydrostatic pressure resistance after the test to the hydrostatic pressure resistance before the test, unit: %) was also studied.

[0063] (5) Urethane solution stability: The obtained polyurethane resin is cooled to 10 °C, and judged by the fluidity at this time.

[0064] No fluidity (freezing / gelation): ×, having fluidity: 〇

[0065] <Polymerization of polyurethane resin solution (1)>

[0066] 162 g of plant-derived polyester polyol (sebacic acid-based polyester polyol, hydroxyl value of 55.1 mg KOH / g, "Ulic" (registered trademark) SE-1903 manufactured by Itochu Oil Co., Ltd.) and 250 g of dimethylformamide (hereinafter referred to as "DMF") were added to a 2 L separable flask and dissolved. While adjusting the temperature to 50 °C, 101 g of diphenylmethane diisocyanate was added, and the reaction was carried out at 50 °C for about 1 hour to prepare a prepolymer. Then, the temperature was raised to 60 °C, 16 g of ethylene glycol and 60 g of DMF were added, and a chain extension reaction was carried out at 60 °C. As the viscosity increased, 420 g of DMF was added in batches while polymerization was carried out. At the moment when the viscosity reached the specified value, 9 g of 1,2-propanediol and 115 g of DMF were added. After the reaction for about 6 to 8 hours, it was completed to obtain polyurethane 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%.

[0067] <Polymerization of polyurethane resin solution (2)>

[0068] 130 g of polycarbonate polyol (hexamethylene carbonate diol, hydroxyl value of 56.5 mg KOH / g, "Nippolan" (registered trademark) 980R manufactured by Tosoh Corporation), 32 g of polyether polyol (polytetramethylene glycol, hydroxyl value of 56.1 mg KOH / g, PTMG-2000M manufactured by Sanyo Chemical Industries, Ltd.) and 250 g of DMF were added to a 2 L separable flask and dissolved. While adjusting the temperature to 50 °C, 87 g of diphenylmethane diisocyanate was added, and the reaction was carried out at 50 °C for about 1 hour to prepare a prepolymer. Then, the temperature was raised to 60 °C, 19.4 g of ethylene glycol and 40 g of DMF were added, and a chain extension reaction was carried out at 60 °C. As the viscosity increased, 400 g of DMF was added in batches while polymerization was carried out. At the moment when the viscosity reached the specified value, 9 g of 1,2-propanediol and 110 g of DMF were added. After the reaction for about 6 to 8 hours, it was completed to obtain polyurethane resin solution (2) with a urethane resin concentration of 25.0% and a viscosity of 85,000 mPa·s (30 °C).

[0069] <Polymerization of polyurethane resin solution (3)>

[0070] 162 g of polycarbonate polyol (copolycarbonate diol with a molar ratio of 1,4-butanediol / 1,10-decanediol = 1 / 9, hydroxyl value of 56.5 mg KOH / g, manufactured by Mitsubishi Chemical Corporation, "Beneviol" (registered trademark) NL2090DB, 1,10-decanediol derived from plants), and 250 g of DMF were added to a 2 L separable flask and dissolved. While adjusting the temperature to 50 °C, 87 g of diphenylmethane diisocyanate was added, and the reaction was carried out at 50 °C for about 1 hour to prepare a prepolymer. Then, the temperature was raised to 60 °C, 16 g of ethylene glycol and 40 g of DMF were added, and the chain extension reaction was carried out at 60 °C. As the viscosity increased, 400 g of DMF was added in batches while polymerization was carried out. At the moment when the viscosity reached the specified value, 9 g of 1,2-propanediol and 110 g of DMF were added. After the reaction for about 6 - 8 hours, it was completed to obtain a polyurethane 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%.

[0071] <Polymerization of polyurethane resin solution (4)>

[0072] 162 g of polycarbonate polyol (copolycarbonate diol with a molar ratio of 1,4-butanediol / 1,10-decanediol = 5 / 5, hydroxyl value of 56.5 mg KOH / g, manufactured by Mitsubishi Chemical Corporation, "Beneviol" (registered trademark) NL2050DB, 1,10-decanediol derived from plants), and 250 g of DMF were added to a 2 L separable flask and dissolved. While adjusting the temperature to 50 °C, 87 g of diphenylmethane diisocyanate was added, and the reaction was carried out at 50 °C for about 1 hour to prepare a prepolymer. Then, the temperature was raised to 60 °C, 16 g of ethylene glycol and 40 g of DMF were added, and the chain extension reaction was carried out at 60 °C. As the viscosity increased, 400 g of DMF was added in batches while polymerization was carried out. At the moment when the viscosity reached the specified value, 9 g of 1,2-propanediol and 110 g of DMF were added. After the reaction for about 6 - 8 hours, it was completed to obtain a polyurethane 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%.

[0073] <Polymerization of polyurethane resin solution (5)>

[0074] 162 g of polycarbonate polyol (copolycarbonate diol with a molar ratio of 1,4-butanediol / 1,10-decanediol = 7 / 3, hydroxyl value of 56.5 mg KOH / g, manufactured by Mitsubishi Chemical Corporation, "Beneviol" (registered trademark) NL2030DB, 1,10-decanediol derived from plants), and 250 g of DMF were added to a 2 L separable flask and dissolved. While adjusting the temperature to 50 °C, 87 g of diphenylmethane diisocyanate was added, and the reaction was carried out at 50 °C for about 1 hour to prepare a prepolymer. Then, the temperature was raised to 60 °C, 16 g of ethylene glycol and 40 g of DMF were added, and the chain extension reaction was carried out at 60 °C. As the viscosity increased, 400 g of DMF was added in batches while polymerization was carried out. At the moment when the viscosity reached the specified value, 9 g of 1,2-propanediol and 110 g of DMF were added. After reacting for about 6 - 8 hours, a polyurethane 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% was obtained.

[0075] <Polymerization of polyurethane resin solution (6)>

[0076] 162 g of polycarbonate polyol (copolycarbonate diol with a molar ratio of 1,4-butanediol / 1,10-decanediol = 9 / 1, hydroxyl value of 55.5 mg KOH / g, manufactured by Mitsubishi Chemical Corporation, "Beneviol" (registered trademark) NL2010DB, 1,10-decanediol derived from plants), and 250 g of DMF were added to a 2 L separable flask and dissolved. While adjusting the temperature to 50 °C, 87 g of diphenylmethane diisocyanate was added, and the reaction was carried out at 50 °C for about 1 hour to prepare a prepolymer. Then, the temperature was raised to 60 °C, 16 g of ethylene glycol and 40 g of DMF were added, and the chain extension reaction was carried out at 60 °C. As the viscosity increased, 400 g of DMF was added in batches while polymerization was carried out. At the moment when the viscosity reached the specified value, 9 g of 1,2-propanediol and 110 g of DMF were added. After reacting for about 6 - 8 hours, a polyurethane 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% was obtained.

[0077] <Polymerization of polyurethane resin solution (7)>

[0078] 130 g of polycarbonate polyol (copolycarbonate diol with a molar ratio of 1,4-butanediol / 1,10-decanediol = 9 / 1, hydroxyl value of 54.5 mg KOH / g, manufactured by Mitsubishi Chemical Corporation, "Beneviol" (registered trademark) NL2010DB, 1,10-decanediol derived from plants), 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 added to a 2 L separable flask and dissolved. While adjusting the temperature to 50°C, 87 g of diphenylmethane diisocyanate was added, and the reaction was carried out at 50°C for about 1 hour to prepare a prepolymer. Then, the temperature was raised to 60°C, 16 g of ethylene glycol and 40 g of DMF were added, and the chain extension reaction was carried out at 60°C. As the viscosity increased, 400 g of DMF was added in batches while polymerization was carried out. At the moment when the viscosity reached the specified value, 9 g of 1,2-propanediol and 110 g of DMF were added. After the reaction was carried out for about 6 to 8 hours, it was completed to obtain a polyurethane resin solution (7) 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%.

[0079] <Polymerization of polyurethane resin solution (8)>

[0080] 162 g of polycarbonate polyol (copolycarbonate diol with a molar ratio of 1,4-butanediol / 1,10-decanediol = 9 / 1, hydroxyl value of 55.5 mg KOH / g, manufactured by Mitsubishi Chemical Corporation, "Beneviol" (registered trademark) NL2010DB, 1,10-decanediol derived from plants), and 250 g of DMF were added to a 2 L separable flask and dissolved. While adjusting the temperature to 50°C, 87 g of diphenylmethane diisocyanate was added, and the reaction was carried out at 50°C for about 1 hour to prepare a prepolymer. Then, the temperature was raised to 60°C, 19.6 g of plant-derived 1,3-propanediol and 50 g of DMF were added, and the chain extension reaction was carried out at 60°C. As the viscosity increased, 400 g of DMF was added in batches while polymerization was carried out. At the moment when the viscosity reached the specified value, 9 g of 1,2-propanediol and 110 g of DMF were added. After the reaction was carried out for about 6 to 8 hours, it was completed to obtain a polyurethane 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%.

[0081] [Comparative Example 1]

[0082] Nylon ripstop taffeta made of 50-denier nylon filament yarn is impregnated in a 30 g / l dilution of a fluorine-based water repellent (Nippon Kayaku Co., Ltd., "NK Guard" (registered trademark) S-07), rolled with a padding mangle so that the pick-up rate becomes 40%, dried at 120°C, heat-treated at 160°C for 30 seconds, and subjected to water repellent treatment.

[0083] Next, 6 parts by mass of silica fine powder (Nippon Aerosil Co., Ltd., "AEROSIL" (registered trademark) R-972), 1 part by mass of a fluorine water repellent (Toray Coatings Co., Ltd., SF-1011), and 1 part by mass of a crosslinking agent (Tosoh Corporation, "Coronate" (registered trademark) HX) are added to the polyurethane resin solution (1) prepared in 100 parts by mass of <Polymerization of polyurethane resin solution (1)>. It is thoroughly mixed with 50 parts by mass of DMF, dispersed and stirred with a homogenizer for about 15 minutes, and then stirred to obtain a liquid composition of a polyurethane resin composition.

[0084] This liquid composition is coated on the above water-repellent treated nylon ripstop taffeta with a coating amount of 150 g / m 2 , immersed in a bath tank using an aqueous solution containing 20% by mass of DMF as a gelation bath for 2 minutes, subjected to film formation by the wet coagulation method, then washed with water for 10 minutes, and dried with hot air at 140°C to obtain a moisture-permeable and waterproof processed fabric having a porous structure.

[0085] For the obtained moisture-permeable and waterproof fabric, its water pressure resistance, moisture permeability, and texture are evaluated. In addition, after a durability test (temperature 70°C, humidity 95%, 10 weeks, 20 weeks), the water pressure resistance is measured and its retention rate is determined. The results are shown in Table 1.

[0086] [Comparative Example 2]

[0087] Nylon ripstop taffeta made of 50-denier nylon filament yarn is impregnated in a 30 g / l dilution of a fluorine-based water repellent (Nippon Kayaku Co., Ltd., "NK Guard" (registered trademark. The same applies hereinafter.) S-07), rolled with a padding mangle so that the pick-up rate becomes 40%, dried at 120°C, heat-treated at 160°C for 30 seconds, and subjected to water repellent treatment.

[0088] Next, 6 parts by mass of silica fine powder (Nippon Aerosil Co., Ltd., "AEROSIL" (registered trademark) R-972), 1 part by mass of fluorine-based water repellent (Toray Gore-Tex Co., Ltd., SF-1011), and 1 part by mass of crosslinking agent (Tosoh Corporation "Coronate" (registered trademark) HX) were added to 100 parts by mass of the polyurethane resin solution (2) prepared in <Polymerization of Polyurethane Resin Solution (2)>. They were thoroughly mixed with 50 parts by mass of DMF, dispersed and stirred with a homogenizer for about 15 minutes, and then stirred to obtain a liquid composition of the polyurethane resin composition.

[0089] The liquid composition was coated on the above-mentioned hydrophobic processed nylon taffeta with a coating amount of 150 g / m 2 It was immersed in a bath containing an aqueous solution of 20% by mass of DMF as a gelation bath for 2 minutes to perform film formation by the wet coagulation method, then washed with water for 10 minutes, and dried by hot air at 140 °C to obtain a moisture-permeable and waterproof processed fabric having a porous structure.

[0090] For the obtained moisture-permeable and waterproof fabric, its water pressure resistance, moisture permeability, and texture were evaluated. In addition, after performing a durability test (temperature 70 °C, humidity 95%, 10 weeks, 20 weeks), the water pressure resistance was measured and its retention rate was determined. The results are shown in Table 1.

[0091] [Example 1]

[0092] Nylon taffeta composed of 50 denier nylon filament yarns was immersed in a 30 g / l dilution of a fluorine-based water repellent (Nihon Kayaku Co., Ltd., "NK Guard" (registered trademark) S-07), rolled with a padding mangle so that the padding rate became 40%, dried at 120 °C, and heat-treated at 160 °C for 30 seconds to perform hydrophobic treatment.

[0093] Next, 6 parts by mass of silica fine powder (Nippon Aerosil Co., Ltd., "AEROSIL" (registered trademark) R-972), 1 part by mass of fluorine-based water repellent (Toray Gore-Tex Co., Ltd., SF-1011), and 1 part by mass of crosslinking agent (Tosoh Corporation "Coronate" (registered trademark) HX) were added to 100 parts by mass of the polyurethane resin solution (4) prepared in <Polymerization of Polyurethane Resin Solution (4)>. They were thoroughly mixed with 50 parts by mass of DMF, dispersed and stirred with a homogenizer for about 15 minutes, and then stirred to obtain a liquid composition of the polyurethane resin composition.

[0094] The liquid composition was coated with a coating amount of 150 g / m 2The liquid composition was applied to the above-mentioned hydrophobic-treated nylon taffeta at a coating amount, and then immersed in a bath containing an aqueous solution of 20% by mass of DMF as a gelation bath for 2 minutes to form a film by the wet coagulation method. Then, it was washed with water for 10 minutes and dried by hot air at 140 °C to obtain a moisture-permeable and waterproof processed fabric having a porous structure.

[0095] For the obtained moisture-permeable and waterproof fabric, its water pressure resistance, moisture permeability, and texture were evaluated. In addition, after a durability test (humidity 70 °C, humidity 95%, 10 weeks, 20 weeks), the water pressure resistance was measured and its retention rate was determined. The results are shown in Table 1.

[0096] [Example 2]

[0097] A nylon taffeta composed of 50-denier nylon filament yarns was immersed in a 30 g / l dilution of a fluorine-based water repellent (Nippon Kayaku Co., Ltd., "NK Guard" (registered trademark) S-07), and then rolled with a rolling machine so that the pick-up rate became 40%, and then dried at 120 °C and heat-treated at 160 °C for 30 seconds to perform the water repellent treatment.

[0098] Next, 6 parts by mass of silica fine powder (Nippon Aerosil Co., Ltd., "AEROSIL" (registered trademark) R-972), 1 part by mass of a fluorine-based water repellent (Toray Coatings Co., Ltd., SF-1011), and 1 part by mass of a crosslinking agent (Tosoh Corporation, "Coronate" (registered trademark) HX) were added to the polyurethane resin solution (5) prepared in 100 parts by mass of <Polymerization of polyurethane resin solution (5)>, and thoroughly mixed with 50 parts by mass of DMF, dispersed and stirred with a homogenizer for about 15 minutes, and then stirred to obtain a liquid composition of the polyurethane resin composition.

[0099] The liquid composition was applied to the above-mentioned hydrophobic-treated nylon taffeta at a coating amount of 150 g / m 2 The liquid composition was applied to the above-mentioned hydrophobic-treated nylon taffeta at a coating amount, and then immersed in a bath containing an aqueous solution of 20% by mass of DMF as a gelation bath for 2 minutes to form a film by the wet coagulation method. Then, it was washed with water for 10 minutes and dried by hot air at 140 °C to obtain a moisture-permeable and waterproof processed fabric having a porous structure.

[0100] For the obtained moisture-permeable and waterproof fabric, its water pressure resistance, moisture permeability, and texture were evaluated. In addition, after a durability test (humidity 70 °C, humidity 95%, 10 weeks, 20 weeks), the water pressure resistance was measured and its retention rate was determined. The results are shown in Table 1.

[0101] [Example 3]

[0102] A nylon taffeta made of 50-denier nylon filament yarn is impregnated in a 30 g / l dilution of a fluorine-based water repellent (Nippon Kayaku Co., Ltd., "NK Guard" (registered trademark) S-07), rolled with a rolling machine so that the pick-up rate becomes 40%, dried at 120°C, heat-treated at 160°C for 30 seconds, and subjected to water repellent treatment.

[0103] Next, 6 parts by mass of silica fine powder (Nippon Aerosil Co., Ltd., "AEROSIL" (registered trademark) R-972), 1 part by mass of a fluorine water repellent (Toray Coating Systems Co., Ltd., SF-1011), and 1 part by mass of a crosslinking agent (Tosoh Corporation, "Coronate" (registered trademark) HX) are added to 100 parts by mass of the polyurethane resin solution (6) prepared in <Polymerization of Polyurethane Resin Solution (6)>. They are thoroughly mixed with 50 parts by mass of DMF, dispersed and stirred with a homogenizer for about 15 minutes, and then stirred to obtain a liquid composition of the polyurethane resin composition.

[0104] This liquid composition is coated on the above water-repellent treated nylon taffeta with a coating amount of 150 g / m 2 , impregnated in a bath tank with an aqueous solution containing 20% by mass of DMF as a gelation bath for 2 minutes, subjected to film formation using the wet coagulation method, then washed with water for 10 minutes, and dried with hot air at 140°C to obtain a moisture-permeable and waterproof processed fabric having a porous structure.

[0105] For the obtained moisture-permeable and waterproof fabric, its water pressure resistance, moisture permeability, and texture are evaluated. In addition, after a durability test (temperature 70°C, humidity 95%, 10 weeks, 20 weeks), the water pressure resistance is measured and its retention rate is calculated. The results are shown in Table 1.

[0106] [Example 4]

[0107] A nylon taffeta made of 50-denier nylon filament yarn is impregnated in a 30 g / l dilution of a fluorine-based water repellent (Nippon Kayaku Co., Ltd., "NK Guard" (registered trademark) S-07), rolled with a rolling machine so that the pick-up rate becomes 40%, dried at 120°C, heat-treated at 160°C for 30 seconds, and subjected to water repellent treatment.

[0108] Next, 6 parts by mass of silica fine powder (Nippon Aerosil Co., Ltd., "AEROSIL" (registered trademark) R-972), 1 part by mass of a fluorine-based water repellent (Toray Gore-Tex Co., Ltd., SF-1011), and 1 part by mass of a crosslinking agent (Tosoh Corporation "Coronate" (registered trademark) HX) were added to 100 parts by mass of the polyurethane resin solution (7) prepared in <Polymerization of Polyurethane Resin Solution (7)>. They were thoroughly mixed with 50 parts by mass of DMF, dispersed and stirred with a homogenizer for about 15 minutes, and then stirred to obtain a liquid composition of the polyurethane resin composition.

[0109] The liquid composition was coated on the above-mentioned hydrophobic processed nylon taffeta with a coating amount of 150 g / m 2 It was immersed in a bath containing an aqueous solution of 20% by mass of DMF as a gelation bath for 2 minutes to form a film by the wet coagulation method, then washed with water for 10 minutes, and dried by hot air at 140 °C to obtain a homogeneous and micro-porous-structured moisture-permeable and waterproof processed fabric.

[0110] For the obtained moisture-permeable and waterproof fabric, its water pressure resistance, moisture permeability, and texture were evaluated. In addition, after a durability 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.

[0111] [Example 5]

[0112] Nylon taffeta made of 50-denier nylon filament yarn was immersed in a 30 g / l dilution of a fluorine-based water repellent (Nihon Kayaku Co., Ltd., "NK Guard" (registered trademark) S-07), rolled with a padding mangle so that the padding rate became 40%, dried at 120 °C, and heat-treated at 160 °C for 30 seconds to perform hydrophobic treatment.

[0113] Next, 6 parts by mass of silica fine powder (Nippon Aerosil Co., Ltd., "AEROSIL" (registered trademark) R-972), 1 part by mass of a fluorine-based water repellent (Toray Gore-Tex Co., Ltd., SF-1011), and 1 part by mass of a crosslinking agent (Tosoh Corporation "Coronate" (registered trademark) HX) were added to 100 parts by mass of the polyurethane resin solution (8) prepared in <Polymerization of Polyurethane Resin Solution (8)>. They were thoroughly mixed with 50 parts by mass of DMF, dispersed and stirred with a homogenizer for about 15 minutes, and then stirred to obtain a liquid composition of the polyurethane resin composition.

[0114] The liquid composition was coated with a coating amount of 150 g / m 2The coating amount was used to coat the above-mentioned hydrophobically treated nylon taffeta, which was then immersed in a bath containing an aqueous solution of 20% by mass of DMF as a gelation bath for 2 minutes to form a film by the wet coagulation method. Subsequently, it was washed with water for 10 minutes and dried by hot air at 140 °C to obtain a moisture-permeable and waterproof processed fabric with a porous structure.

[0115] For the obtained moisture-permeable and waterproof fabric, its water pressure resistance, moisture permeability, and texture were evaluated. Additionally, after conducting a durability 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.

[0116] [Table 1]

[0117]

[0118] In the prior art, there are fabrics with components derived from plants as shown in Comparative Example 1 of Table 1 but with low hydrolysis resistance; and moisture-permeable and waterproof fabrics with high hydrolysis resistance but without components derived from plants as shown in Comparative Example 2. However, there are no mass-producible products with components derived from plants and excellent hydrolysis resistance.

[0119] As shown in Examples 1, 2, 3, 4, and 5, by having components derived from plants, it not only helps reduce the environmental load through carbon neutrality but also, due to the high hydrolysis resistance characteristic of polycarbonate-based urethanes, products that can withstand long-term practical use can be manufactured.

[0120] Furthermore, as shown in Example 4, by copolymerizing a plant-derived polycarbonate-based polyol with PTMG, a useful moisture-permeable and waterproof fabric with higher water pressure resistance can be obtained.

[0121] In addition, as shown in Example 5, by using a plant-derived chain extender during polyurethane polymerization, while maintaining high hydrolysis resistance, the ratio of plant-derived components can be further increased, which helps further reduce the environmental load.

Claims

1. A moisture-permeable and waterproof fabric, which is a moisture-permeable and waterproof fabric having a porous moisture-permeable and waterproof film formed by a wet method on at least one side of the fabric. The polyurethane forming the moisture-permeable and waterproof film is synthesized using a polyol containing polycarbonate diol, and the polycarbonate diol has a plant-derived component. Among them, The polycarbonate diol 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 1 / 9 to 8 / 2. The proportion of the plant-derived component in the polyurethane used in the moisture-permeable and waterproof film is 10% by mass or more and 65% by mass or less. The water pressure resistance of the moisture permeable waterproof film is 100 kPa or more, and the moisture permeability measured by the A-1 method of JIS-L1099 (2012) is 300 g / m 2 ·hr or more.

2. The moisture-permeable and waterproof fabric according to claim 1. Among them, The molar ratio of 1,10-decanediol to 1,4-butanediol is 1 / 9 to 5 / 5.

3. The moisture-permeable and waterproof fabric according to claim 1 or 2. Among them, The polyol is a mixture of at least two of the polycarbonate diol and an ether-based polyol.

4. The moisture-permeable and waterproof fabric according to claim 1 or 2. Among them, The polyurethane uses at least one of plant-derived 1,3-propanediol and 1,4-butanediol as a chain extender.

5. The moisture-permeable and waterproof fabric according to claim 1 or 2. Among them, The water pressure resistance of the moisture-permeable and waterproof film is 150 kPa or more.

6. The moisture-permeable and waterproof fabric according to claim 1 or 2. Among them, In the hydrolysis evaluation test under the conditions of a temperature of 70 °C and a humidity of 95%, the water pressure resistance retention rate after 10 weeks is 60% or more.

7. The moisture-permeable and waterproof fabric according to claim 1 or 2. Among them, In the hydrolysis evaluation test under the conditions of a temperature of 70 °C and a humidity of 95%, the water pressure resistance retention rate after 20 weeks is 60% or more.

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