JP2009149876A - Moisture-permeable polyurethane resin comprising plant-derived component - Google Patents
Moisture-permeable polyurethane resin comprising plant-derived component Download PDFInfo
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- JP2009149876A JP2009149876A JP2008304320A JP2008304320A JP2009149876A JP 2009149876 A JP2009149876 A JP 2009149876A JP 2008304320 A JP2008304320 A JP 2008304320A JP 2008304320 A JP2008304320 A JP 2008304320A JP 2009149876 A JP2009149876 A JP 2009149876A
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- polyurethane resin
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 89
- 150000002009 diols Chemical class 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 125000006353 oxyethylene group Chemical group 0.000 claims abstract description 39
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 230000035699 permeability Effects 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 64
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 53
- 239000004359 castor oil Substances 0.000 claims description 46
- 235000019438 castor oil Nutrition 0.000 claims description 46
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 46
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 19
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 18
- 229920000570 polyether Polymers 0.000 claims description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 13
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 10
- 239000004970 Chain extender Substances 0.000 claims description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 7
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 5
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 101
- 238000004519 manufacturing process Methods 0.000 description 33
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 31
- 229920005862 polyol Polymers 0.000 description 22
- 150000003077 polyols Chemical class 0.000 description 22
- 238000010521 absorption reaction Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
- 229960003656 ricinoleic acid Drugs 0.000 description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 2
- 238000005464 sample preparation method Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
本発明は透湿性ポリウレタン樹脂に関するものであり、特に昨今の地球温暖化対策における環境負荷の低減のために、カーボンニュートラルに寄与する植物由来成分を含有する透湿性ポリウレタン樹脂に関するものである。 The present invention relates to a moisture-permeable polyurethane resin, and more particularly to a moisture-permeable polyurethane resin containing a plant-derived component that contributes to carbon neutral in order to reduce environmental burdens in recent global warming countermeasures.
従来、透湿性防水布帛に用いる透湿性材料としては、ポリテトラフルオロエチレン樹脂を延伸して多孔質化させたフイルム、ポリウレタン樹脂の湿式成膜フイルムのような微多孔質膜を利用するものや、親水性を有するポリウレタン樹脂の無孔質膜などが知られている。 Conventionally, as a moisture-permeable material used for a moisture-permeable waterproof fabric, a film obtained by stretching a polytetrafluoroethylene resin to make it porous, a microporous film such as a wet film-forming film of polyurethane resin, A non-porous membrane of a polyurethane resin having hydrophilicity is known.
植物由来成分よりなる防水加工布帛に関しては、例えば特許文献１（特開２００２−２０５３０号公報）に、植物由来成分としてポリ乳酸樹脂を用いた多孔質防水加工布帛が開示されている。しかしながら、無孔質膜については、未だ石油系の樹脂が主体であり、植物由来の透湿性樹脂は上市されていないのが現状である。 Regarding a waterproof fabric made of a plant-derived component, for example, Patent Document 1 (Japanese Patent Laid-Open No. 2002-20530) discloses a porous waterproof fabric using a polylactic acid resin as a plant-derived component. However, as for non-porous membranes, petroleum-based resins are still mainly used, and plant-derived moisture-permeable resins are not yet on the market.
従来、無孔質膜の透湿性ポリウレタン樹脂としては、ポリウレタン樹脂中に親水性セグメントを含有させたものが使用されている。また、親水性を付与する方法として、例えば特許文献２，３（特開平３−２０３９２０号、特開２００３−２４６８３２号公報）に示されたように、ポリオール成分にポリオキシエチレングリコールやポリオキシエチレンとポリオキシプロピレンの共重合体等を用いることが知られている。 Conventionally, as a moisture-permeable polyurethane resin of a nonporous film, a polyurethane resin containing a hydrophilic segment has been used. Further, as a method for imparting hydrophilicity, for example, as disclosed in Patent Documents 2 and 3 (Japanese Patent Laid-Open Nos. 3-203920 and 2003-246732), a polyoxyethylene glycol or polyoxyethylene is added to a polyol component. It is known to use a copolymer of polyoxypropylene and the like.
本発明者らは、従来の親水性ポリオールとヒマシ油ポリオールとを使用して無孔質膜の透湿性ポリウレタン樹脂を得ることを試みたが、単に両者を共重合させただけでは、疎水性の大きいヒマシ油の影響が現れ、所望の透湿性能が得られなかった。
本発明は、上記に鑑みてなされたものであり、地球温暖化対策における環境負荷の低減のために、カーボンニュートラルに寄与する植物由来成分を含有し、かつ透湿性も良好な透湿性ポリウレタン樹脂を提供することを目的とする。 The present invention has been made in view of the above, and includes a moisture-permeable polyurethane resin containing a plant-derived component contributing to carbon neutral and having good moisture permeability in order to reduce environmental burden in measures against global warming. The purpose is to provide.
本発明者らは上記の課題を解決するために、植物由来成分を２５〜６５％（重量％、以下同様）含有するポリウレタン樹脂を使用し、かつ透湿性能を向上させる為の分子構造・設計・重合方法について鋭意検討を行った結果、高分子ジオール中でのオキシエチレン基を分散させることにより、またプレポリマー合成時に高分子ジオールを集中させることにより透湿性能の向上が達成できることを見出し、本発明の完成に至った。 In order to solve the above problems, the present inventors use a polyurethane resin containing 25 to 65% (% by weight, the same applies hereinafter) of plant-derived components, and a molecular structure / design for improving moisture permeability.・ As a result of diligent investigation on the polymerization method, it was found that the moisture permeability can be improved by dispersing the oxyethylene groups in the polymer diol, and by concentrating the polymer diol during prepolymer synthesis, The present invention has been completed.
すなわち、本発明の透湿性ポリウレタン樹脂は、植物由来の高分子ジオール成分と、オキシエチレン基を含有する高分子ジオール成分と、有機ジイソシアネート成分と、二価アルコールである鎖伸長剤成分とを含有してなる透湿性ポリウレタン樹脂であって、前記植物由来の高分子ジオール成分の含有量が樹脂成分中２５〜６５重量％であり、前記オキシエチレン基を含有する高分子ジオール成分がオキシエチレン基がランダムに分散された共重合物であり、かつ前記有機ジイソシアネート成分と前記高分子ジオールとのプレポリマーＮＣＯ／ＯＨ反応当量比を３／４以上（０．７５以上）とし、ソフトセグメントを集中させた構造を有するものとする。 That is, the moisture-permeable polyurethane resin of the present invention contains a plant-derived polymer diol component, a polymer diol component containing an oxyethylene group, an organic diisocyanate component, and a chain extender component that is a dihydric alcohol. The content of the plant-derived polymer diol component is 25 to 65% by weight in the resin component, and the polymer diol component containing the oxyethylene group is a random oxyethylene group. And a prepolymer NCO / OH reaction equivalent ratio of the organic diisocyanate component and the polymer diol of 3/4 or more (0.75 or more), and a soft segment is concentrated. It shall have.
上記植物由来の高分子ジオール成分としてはヒマシ油ジオールが好適に用いられる。 As the plant-derived polymer diol component, castor oil diol is preferably used.
ヒマシ油ジオールは、ヒマシ油系ポリエーテルポリエステルジオールであって、平均水酸基数が１．８〜２．１個であり、水酸基価が４１〜８５ｍｇＫＯＨ／ｇであるものが特に好ましい。 Castor oil diol is a castor oil-based polyether polyester diol having an average hydroxyl number of 1.8 to 2.1 and a hydroxyl value of 41 to 85 mgKOH / g.
上記鎖伸長剤成分は、エチレングリコール及び１，４−ブチレングリコールから選択された直鎖グリコールであるか、または前記直鎖グリコールと、１，３−ブチレングリコール及び１，２−プロピレングリコールから選択された分岐グリコールとの組み合わせよりなることが好ましい。 The chain extender component is a linear glycol selected from ethylene glycol and 1,4-butylene glycol, or selected from the linear glycol and 1,3-butylene glycol and 1,2-propylene glycol. It is preferable to consist of a combination with a branched glycol.
本発明のポリウレタン樹脂は、厚み１０μのフィルムのＢ−１透湿度が２，５００ｇ／ｍ２・２４ｈｒｓ以上であることが好ましい。 The polyurethane resin of the present invention preferably has a B-1 moisture permeability of a film having a thickness of 10 μm of 2,500 g / m 2 · 24 hrs or more.
本発明によれば、地球温暖化対策における環境負荷の低減のためのカーボンニュートラルを実現でき、かつ透湿性の良好な透湿性ポリウレタン樹脂無孔質膜を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the carbon neutral for reduction of the environmental load in a global warming countermeasure can be implement | achieved, and the moisture-permeable polyurethane resin nonporous film | membrane with favorable moisture permeability can be provided.
本発明の透湿性ポリウレタン樹脂は、植物、特にヒマシ油由来高分子ジオールとオキシエチレン基含有高分子ジオールと、有機ジイソシアネートと、グリコールからなる鎖伸長剤とを反応させて得られるポリウレタン樹脂である。 The moisture-permeable polyurethane resin of the present invention is a polyurethane resin obtained by reacting a plant, particularly a castor oil-derived polymer diol, an oxyethylene group-containing polymer diol, an organic diisocyanate, and a chain extender composed of glycol.
上記ポリウレタン樹脂に用いられる植物由来高分子ジオールとしては、ヒマシ油系ポリオールが挙げられる。ヒマシ油系ポリオールの分子量は通常４００〜３，０００、好ましくは９００〜３，０００である。 Examples of the plant-derived polymer diol used for the polyurethane resin include castor oil-based polyol. The molecular weight of the castor oil-based polyol is usually 400 to 3,000, preferably 900 to 3,000.
ヒマシ油は、主に次式で表されるリシノレイン酸のトリグリセライドである。
リシノレイン酸は次式で表される構造を有する化合物である。
本発明でいうヒマシ油ジオールとはヒマシ油に由来するジオールであり、中でもヒマシ油系ポリエーテルポリエステルジオールであって、平均水酸基数が１．８〜２．１個であり、水酸基価が４１〜８５ｍｇＫＯＨ／ｇであるものが好ましく、特に平均水酸基数が１．９５〜２．０５個のものを好適に用いることができる。水酸基数が２．１個を越えると３価のポリオールの分枝あるいは架橋構造の生成のために、樹脂膜を形成するためのコーティングに適したポリウレタン樹脂を得ることが困難となる。すなわち、分枝構造が増加し粘性が大きくなりすぎると、コーティングに適さなくなる。また、架橋構造になると極微量でも粘性変化が起こり、少量でも大きな粘性変化が生じ、さらに架橋量が増加するとウレタン樹脂溶液を得ることができなくなる。 The castor oil diol as referred to in the present invention is a diol derived from castor oil, among which castor oil-based polyether polyester diol has an average number of hydroxyl groups of 1.8 to 2.1, and a hydroxyl value of 41 to 41. Those having 85 mg KOH / g are preferred, and those having an average number of hydroxyl groups of 1.95 to 2.05 can be suitably used. When the number of hydroxyl groups exceeds 2.1, it is difficult to obtain a polyurethane resin suitable for coating for forming a resin film because of the generation of a trivalent polyol branch or crosslinked structure. That is, if the branch structure increases and the viscosity becomes too high, it becomes unsuitable for coating. Moreover, when it becomes a crosslinked structure, a viscosity change occurs even in a very small amount, a large viscosity change occurs even in a small amount, and if the amount of crosslinking further increases, a urethane resin solution cannot be obtained.
ポリウレタン樹脂中の植物由来高分子ジオールの含量は環境負荷の軽減の点では多い方が好ましいが、本発明の目的から、透湿性ポリウレタン樹脂機能を達成するためには２５％〜６５％とする。環境負荷、ポリウレタン樹脂性能の観点からは好ましくは３５〜５０％である。 The content of the plant-derived polymer diol in the polyurethane resin is preferably higher from the viewpoint of reducing the environmental load, but for the purpose of the present invention, it is 25% to 65% in order to achieve the moisture-permeable polyurethane resin function. From the viewpoint of environmental load and polyurethane resin performance, it is preferably 35 to 50%.
次に、オキシエチレン基含有高分子ジオールの例としては、ポリエチレングリコール（以下、ＰＥＧと略記）、ポリオキシエチレン−オキシプロピレンブロック又はランダム共重合ジオール；ポリオキシエチレン−オキシテトラメチレンブロック又はランダム共重合ジオール；エチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，６−ヘキサメチレングリコール、ビス（ヒドロキシメチル）シクロヘキサン、４，４’−ビス（２−ヒドロキシエトキシ）−ジフェニルプロパンなどの低分子グリコールのエチレンオキシド付加物；分子量１０００以下のＰＥＧとジカルボン酸（例えばコハク酸、アジピン酸、セバシン酸、テレフタル酸、イソフタル酸など）とを反応させて得られる縮合ポリエーテルエステルジオール；およびこれらの２種以上の混合物が挙げられる。 Next, examples of the oxyethylene group-containing polymer diol include polyethylene glycol (hereinafter abbreviated as PEG), polyoxyethylene-oxypropylene block or random copolymer diol; polyoxyethylene-oxytetramethylene block or random copolymer. Diols; low molecular weight glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexamethylene glycol, bis (hydroxymethyl) cyclohexane, 4,4′-bis (2-hydroxyethoxy) -diphenylpropane An ethylene oxide adduct; a condensed polyetherester diol obtained by reacting a PEG having a molecular weight of 1000 or less with a dicarboxylic acid (for example, succinic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, etc.); And mixtures of two or more thereof.
これらオキシエチレン基含有高分子ジオール中のオキシエチレン基含有量は、通常４０重量％以上、好ましくは６０重量％以上である。また、オキシエチレン基含有高分子ジオールの分子量は通常３００〜１０，０００、好ましくは３００〜３，０００である。 The oxyethylene group content in these oxyethylene group-containing polymer diols is usually 40% by weight or more, preferably 60% by weight or more. The molecular weight of the oxyethylene group-containing polymer diol is usually 300 to 10,000, preferably 300 to 3,000.
オキシエチレン基は高分子ジオール中にランダムに分散されていることが好ましい。オキシエチレン基の集中した部分に湿気や水分が集まっても他の疎水性の部分に全くない場合には、吸湿吸水・放湿放水の機能が劣った構造になっていると思われる。一方、ランダムに分散された構造は、全体的に吸湿吸水・放湿放水の機能を持ち、透湿度が向上すると考えられる。 It is preferable that the oxyethylene group is randomly dispersed in the polymer diol. If moisture or moisture collects in the concentrated oxyethylene group but does not have any other hydrophobic part, it is considered that the structure has poor function of absorbing and absorbing moisture. On the other hand, it is considered that the randomly dispersed structure has the function of moisture absorption / absorption and moisture discharge as a whole, and the moisture permeability is improved.
次に、有機ジイソシアネートの例としては、４，４’−ジフェニルメタンジイソシアネート（以下、ＭＤＩと略記する）、２，４−および／または２，６−トリレンジイソシアネート等の芳香族ジイソシアネート；ヘキサメチレンジイソシアネート、リジンジイソシアネート等の脂肪族ジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタン−４，４’−ジイソシアネート等の脂環式ジイソシアネートが挙げられ、これらの２種以上の混合物も使用可能である。これらのうち好ましいものはＭＤＩである。 Next, as examples of organic diisocyanates, aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 2,4- and / or 2,6-tolylene diisocyanate; hexamethylene diisocyanate, Aliphatic diisocyanates such as lysine diisocyanate, isophorone diisocyanate, alicyclic diisocyanates such as dicyclohexylmethane-4,4′-diisocyanate, and a mixture of two or more of these can also be used. Of these, MDI is preferred.
鎖伸長剤の例としては、エチレングリコール、１，３−ブチレングリコール、１，４−ブチレングリコール、１，２−プロピレングリコール、ジエチレングリコール、１，６−ヘキサメチレングリコールが挙げられる。好ましい例としては、エチレングリコール、１，４−ブチレングリコールから選択された直鎖グリコールと、１，３−ブチレングリコール、１，２−プロピレングリコールから選択された分岐グリコールとの２種の組み合わせが挙げられる。 Examples of chain extenders include ethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-propylene glycol, diethylene glycol, and 1,6-hexamethylene glycol. Preferred examples include two combinations of a linear glycol selected from ethylene glycol and 1,4-butylene glycol and a branched glycol selected from 1,3-butylene glycol and 1,2-propylene glycol. It is done.
分岐したグリコールの使用によりポリウレタンの結晶性が崩れ、ソフトセグメントに吸湿・吸水した後の放湿・放水時に、この結晶性の崩れた部分の効果で透湿性能が向上する。しかし、分岐グリコールを単独使用したものは軟化点が低く、用途によっては耐熱性に問題が生じる傾向がある。直鎖状グリコールと分岐状グリコールとの併用により、透湿度が向上し、耐熱性の問題も解決され、植物由来比率を向上させることができる。 Due to the use of the branched glycol, the crystallinity of the polyurethane collapses, and the moisture permeation performance is improved by the effect of the broken crystallinity at the time of moisture release / water discharge after moisture absorption / water absorption by the soft segment. However, the use of a branched glycol alone has a low softening point and tends to cause a problem in heat resistance depending on the application. The combined use of the linear glycol and the branched glycol improves moisture permeability, solves the problem of heat resistance, and can improve the plant-derived ratio.
本発明のポリウレタン樹脂を得る製造方法としては、従来の方法に準じて、まずプレポリマーを合成する方法を用いることができるが、プレポリマーの合成において、有機ジイソシアネートと高分子ジオールとの反応時に高分子ジオールを集中させる方法を用いることにより透湿性能を向上させることが可能となる。すなわち、ソフトセグメントの集中化であり、具体的には有機イソシアネートと高分子ジオールとの反応当量比を３／４〜９／１０とすることが好ましい。この反応当量比が３／４より低いと透湿性能の向上が小さい。一方、この比が１に近い程、透湿性能は向上するが、９／１０より大きくなると、場合によっては反応途中で固化するおそれがある。 As a production method for obtaining the polyurethane resin of the present invention, a method of first synthesizing a prepolymer can be used in accordance with a conventional method. However, in the synthesis of the prepolymer, a high reaction time is required during the reaction between the organic diisocyanate and the polymer diol. By using a method of concentrating molecular diols, moisture permeability can be improved. That is, the soft segment is concentrated, and specifically, the reaction equivalent ratio of the organic isocyanate and the polymer diol is preferably 3/4 to 9/10. When this reaction equivalent ratio is lower than 3/4, improvement in moisture permeability is small. On the other hand, as the ratio is closer to 1, the moisture permeation performance is improved. However, when the ratio is greater than 9/10, there is a possibility that the ratio may solidify during the reaction.
従来のプレポリマー方法では、ソフトセグメント間にハードセグメント部分が生じることにより、吸湿（吸水）による膨潤が抑えられ、よって吸湿・吸水量が抑えられると考えられるが、上記のように、ソフトセグメント間を長く（すなわち非結晶部分を大きく）することにより、吸湿・吸水量が大きくなり、かつ吸収した湿分・水分を非結晶部分から発散・放湿させ得るため、透湿度が向上すると考えられる。 In the conventional prepolymer method, it is considered that the hard segment portion is generated between the soft segments, so that the swelling due to moisture absorption (water absorption) is suppressed, and thus the moisture absorption / absorption amount is suppressed. It is considered that by increasing the length (that is, increasing the non-crystalline part), the moisture absorption / water absorption amount increases, and the absorbed moisture / moisture can be diffused / moisture-removed from the non-crystalline part.
またポリウレタン樹脂中のポリオキシエチレン基含量は通常１０〜５０重量％、好ましくは２０〜４０重量％である。１０重量％未満では透湿性が乏しく、５０重量％を超えると植物由来成分が減少するため、環境負荷軽減の観点から５０％以下が好ましい。 The polyoxyethylene group content in the polyurethane resin is usually 10 to 50% by weight, preferably 20 to 40% by weight. If it is less than 10% by weight, moisture permeability is poor, and if it exceeds 50% by weight, plant-derived components are reduced. Therefore, 50% or less is preferable from the viewpoint of reducing environmental burden.
本発明で用いられるポリウレタン樹脂の有機ジイソシアネートと、植物由来含有高分子ジオール、オキシエチレン基含有高分子ジオールおよび鎖伸長剤との割合（ＮＣＯ：ＯＨ当量比）は、通常、０．９５：１〜１．０５：１、好ましくは実質的に１：１である。ＮＣＯ／ＯＨ当量比が上記範囲外の場合にはポリウレタン樹脂の分子量が高分子量にならず、実用的に有用な物性を有するポリウレタン樹脂を製造することが困難となる。本発明のポリウレタン樹脂の分子量はそれぞれ重量平均分子量で、通常５０，０００〜４００，０００程度であり、好ましくは１００，０００〜３００，０００である。 The ratio (NCO: OH equivalent ratio) of the organic diisocyanate of the polyurethane resin used in the present invention to the plant-derived polymer diol, the oxyethylene group-containing polymer diol and the chain extender is usually 0.95: 1 to 1.05: 1, preferably substantially 1: 1. When the NCO / OH equivalent ratio is outside the above range, the molecular weight of the polyurethane resin does not become high, and it becomes difficult to produce a polyurethane resin having practically useful physical properties. The molecular weight of the polyurethane resin of the present invention is a weight average molecular weight, and is usually about 50,000 to 400,000, preferably 100,000 to 300,000.
上記ポリウレタン樹脂の製造は、イソシアネート基に対して不活性な溶媒の存在下または不存在下で行うことができる。溶媒の存在下で行う場合の有機溶媒の例としては、ジメチルホルムアミド（以下、ＤＭＦと略記する）、ジメチルアセトアミド等のアミド系溶媒；ジメチルスルホキシド等のスルホキシド系溶媒；メチルエチルケトン等のケトン系溶媒；トルエン、キシレン等の芳香族系溶媒；ジオキサン、テトラヒドロフラン等のエーテル系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒、およびこれらの２種以上の混合物が挙げられる。これらのうち好ましいものは、アミド系溶媒、ケトン系溶媒、芳香族系溶媒およびこれらの２種以上の混合物である。 The polyurethane resin can be produced in the presence or absence of a solvent inert to isocyanate groups. Examples of organic solvents in the presence of a solvent include amide solvents such as dimethylformamide (hereinafter abbreviated as DMF) and dimethylacetamide; sulfoxide solvents such as dimethyl sulfoxide; ketone solvents such as methyl ethyl ketone; toluene And aromatic solvents such as xylene; ether solvents such as dioxane and tetrahydrofuran; ester solvents such as ethyl acetate and butyl acetate; and mixtures of two or more of these. Of these, amide solvents, ketone solvents, aromatic solvents and mixtures of two or more of these are preferred.
ポリウレタン樹脂の製造に際し、反応温度はポリウレタン化反応に通常採用される温度と同様でよく、溶媒を使用する場合は通常３０〜９０℃、無溶媒の場合は通常３０〜２２０℃である。 In the production of the polyurethane resin, the reaction temperature may be the same as that usually employed in the polyurethane reaction, and is usually 30 to 90 ° C. when a solvent is used, and usually 30 to 220 ° C. when no solvent is used.
また、反応を促進させるため、ポリウレタン反応に通常使用される触媒、例えばトリエチルアミン、トリエチレンジアミン等のアミン系触媒を必要に応じて使用することができる。 Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for a polyurethane reaction, for example, amine catalysts, such as a triethylamine and a triethylenediamine, can be used as needed.
また、必要に応じて、例えば１価アルコール（エタノール、ブタノールなど）、１価アミン（メチルアミン、ブチルアミンなど）等の重合停止剤を用いることもできる。 Further, if necessary, for example, a polymerization terminator such as monohydric alcohol (ethanol, butanol, etc.), monovalent amine (methylamine, butylamine, etc.) can be used.
このようにして製造されるポリウレタン樹脂は、３０重量％（固形分）ＤＭＦ溶液として測定した溶液粘度が通常１０〜１００００ポイズ／２０℃であり、実用上好ましいのは１００〜２０００ポイズ／２０℃である。 The polyurethane resin thus produced has a solution viscosity of 10 to 10000 poise / 20 ° C. measured as a 30 wt% (solid content) DMF solution, and is preferably 100 to 2000 poise / 20 ° C. in practice. is there.
本発明のポリウレタン樹脂は、上記例示列挙した有機溶媒を含有していてもよく、その量は、通常、ポリウレタン樹脂からなる樹脂固形分濃度が５〜５０重量％となる量であり、好ましくは１０〜４０重量％となる量である。 The polyurethane resin of the present invention may contain the organic solvents enumerated above, and the amount thereof is usually an amount such that the resin solid content concentration of the polyurethane resin is 5 to 50% by weight, preferably 10 It is the amount which is ˜40% by weight.
本発明のポリウレタン樹脂を含む樹脂組成物中には、必要に応じて、耐候性、耐熱劣化等の向上のための各種安定剤や多官能イソシアネート化合物等の架橋剤、着色剤、無機充填剤、有機改質剤、その他の添加剤等を含有させることができる。 In the resin composition containing the polyurethane resin of the present invention, if necessary, various stabilizers for improving weather resistance, heat resistance deterioration and the like, crosslinking agents such as polyfunctional isocyanate compounds, colorants, inorganic fillers, An organic modifier, other additives, etc. can be contained.
上記ポリウレタン樹脂組成物を塗布して得られるポリウレタン樹脂膜の膜厚は、乾燥後において通常１〜１００μであり、２〜２０μであるのが好ましい。 The film thickness of the polyurethane resin film obtained by applying the polyurethane resin composition is usually 1 to 100 μm and preferably 2 to 20 μm after drying.
本発明のポリウレタン樹脂の熱軟化点は通常１５０℃以上であり、好ましくは１７０℃以上である。熱軟化点が１５０℃未満では耐熱ブロッキング性が乏しくなる。 The heat softening point of the polyurethane resin of the present invention is usually 150 ° C. or higher, preferably 170 ° C. or higher. When the heat softening point is less than 150 ° C., the heat blocking property is poor.
また、１００％応力は、通常２０〜１００ｋｇ／ｃｍ２であり、好ましくは３０〜６０ｋｇ／ｃｍ２である。１００％応力が２０ｋｇ／ｃｍ２未満では耐熱ブロッキング性が乏しくなる。 Moreover, 100% stress is 20-100 kg / cm < 2 > normally, Preferably it is 30-60 kg / cm < 2 >. When the 100% stress is less than 20 kg / cm 2 , the heat blocking property is poor.
以下、実施例により本発明を更に説明するが、本発明はこれに限定されるものではない。なお、実施例および比較例中の「部」は重量部、「％」は重量％を表す。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. In the examples and comparative examples, “parts” represents parts by weight, and “%” represents% by weight.
ポリウレタン樹脂を以下の製造例に示した方法で製造し、試験例中の熱軟化点、引張試験強度、吸水率、水膨潤度、透湿度の評価を行った。 A polyurethane resin was produced by the method shown in the following production examples, and the thermal softening point, tensile test strength, water absorption, water swelling degree, and moisture permeability in the test examples were evaluated.
〔製造例１（ポリウレタン樹脂１の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコに、乾燥窒素雰囲気下にて、ヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）１２ｇとヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）８ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）８０ｇとＤＭＦ１５０ｇを仕込み、攪拌し、均一に溶解させた。５０℃の温度調節下、ＭＤＩ７．２ｇを投入し（ソフトセグメント集約ＮＣＯ／ＯＨ当量比：３／４）、１時間反応させた後、さらにＭＤＩ５５．８ｇを添加し、プレポリマー最終反応を５０℃にて０．５時間行った。続いてＥＧ１３．４ｇをＤＭＦ５０ｇと混合し、添加後、６０℃に昇温し、鎖長延長反応を行った。途中、粘度上昇を見ながらＤＭＦ２１２ｇを分割添加し、８時間反応させて、樹脂濃度３０％、粘度２０，０００ｃｐｓ（３０℃）のポリウレタン樹脂１溶液を得た。得られたポリウレタン樹脂１の固形分中植物由来成分含有比率は１１．３％、オキシエチレン基含有比率は３６．３％である。
[Production Example 1 (Production of polyurethane resin 1)]
In a 1 L four-necked flask equipped with a stirrer and a thermometer, castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH under a dry nitrogen atmosphere / G) 12 g, castor oil diol 2 (manufactured by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g), and polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd.) ), Polyhardener D-300W, molecular weight 3,700) 80 g and DMF 150 g were charged, stirred and dissolved uniformly. Under temperature control of 50 ° C., 7.2 g of MDI was added (soft segment aggregated NCO / OH equivalent ratio: 3/4) and reacted for 1 hour, and then 55.8 g of MDI was further added, and the prepolymer final reaction was performed at 50 ° C. For 0.5 hour. Subsequently, 13.4 g of EG was mixed with 50 g of DMF, and after addition, the temperature was raised to 60 ° C. to carry out a chain extension reaction. In the middle, 212 g of DMF was added in portions while observing the increase in viscosity, and reacted for 8 hours to obtain a polyurethane resin 1 solution having a resin concentration of 30% and a viscosity of 20,000 cps (30 ° C.). In the solid content of the obtained polyurethane resin 1, the plant-derived component content ratio is 11.3% and the oxyethylene group content ratio is 36.3%.
〔製造例２（ポリウレタン樹脂２の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコに、乾燥窒素雰囲気下にて、ヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）４２ｇとヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）２８ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）３０ｇとＤＭＦ１５０ｇを仕込み、攪拌し、均一に溶解させた。５０℃の温度調節下、ＭＤＩ９．５ｇを投入し（ソフトセグメント集約ＮＣＯ／ＯＨ当量比：３／４）、１時間反応させた後、さらにＭＤＩ５３．５ｇを添加し、プレポリマー最終反応を５０℃にて０．５時間行った。続いてＥＧ１３．４ｇをＤＭＦ５０ｇと混合し、添加後、６０℃に昇温し鎖長延長反応を行った。途中、粘度上昇を見ながらＤＭＦ２１２ｇを分割添加し、８時間反応させて、樹脂濃度３０％、粘度２２，０００ｃｐｓ（３０℃）のポリウレタン樹脂２溶液を得た。得られたポリウレタン樹脂２の固形分中植物由来成分含有比率は３９．９％、オキシエチレン基含有比率は１３．７％である。
[Production Example 2 (Production of polyurethane resin 2)]
In a 1 L four-necked flask equipped with a stirrer and a thermometer, castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH under a dry nitrogen atmosphere / G) 42 g, castor oil diol 2 (manufactured by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g), and polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd.) ), Polyhardener D-300W, molecular weight 3,700) 30 g and DMF 150 g were charged, stirred and dissolved uniformly. Under temperature control of 50 ° C., 9.5 g of MDI was added (soft segment aggregated NCO / OH equivalent ratio: 3/4), reacted for 1 hour, then 53.5 g of MDI was further added, and the prepolymer final reaction was performed at 50 ° C. For 0.5 hour. Subsequently, 13.4 g of EG was mixed with 50 g of DMF, and after addition, the temperature was raised to 60 ° C. to carry out chain extension reaction. In the middle, 212 g of DMF was added in portions while observing the increase in viscosity, and reacted for 8 hours to obtain a polyurethane resin 2 solution having a resin concentration of 30% and a viscosity of 22,000 cps (30 ° C.). In the solid content of the obtained polyurethane resin 2, the plant-derived component content ratio is 39.9%, and the oxyethylene group content ratio is 13.7%.
〔製造例３（ポリウレタン樹脂３の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコに、乾燥窒素雰囲気下、ポリブチレンアジペート（日本ポリウレタン（株）製、ニッポランＮ−４０１０、分子量２，０００）７０ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）３０ｇとＤＭＦ１５０ｇを仕込み、攪拌し、均一に溶解させた。５０℃に温度調節し、ＭＤＩ６３ｇを添加し、プレポリマー法にて反応を実施した。５０℃で１時間プレポリマー合成後、ＥＧ１２．８ｇをＤＭＦ５０ｇと混合し、添加した。６０℃に昇温し、鎖長延長反応を行った。途中、粘度上昇を見ながらＤＭＦ２１０ｇを分割添加しながら８時間反応させて、樹脂濃度３０％、粘度１８，０００ｃｐｓ（３０℃）のポリウレタン樹脂３溶液を得た。得られたポリウレタン樹脂３の固形分中植物由来成分含有比率は０％、オキシエチレン基含有比率は１３．６％である。
[Production Example 3 (Production of polyurethane resin 3)]
In a 1 L four-necked flask equipped with a stirrer and a thermometer, 70 g of polybutylene adipate (manufactured by Nippon Polyurethane Co., Ltd., NIPPOLAN N-4010, molecular weight 2,000) and polyether polyol (Daiichi Kogyo Co., Ltd.) under a dry nitrogen atmosphere. 30 g of Polyhardener D-300W manufactured by Pharmaceutical Co., Ltd., molecular weight 3,700) and 150 g of DMF were charged, stirred and dissolved uniformly. The temperature was adjusted to 50 ° C., 63 g of MDI was added, and the reaction was carried out by the prepolymer method. After prepolymer synthesis at 50 ° C. for 1 hour, 12.8 g of EG was mixed with 50 g of DMF and added. The temperature was raised to 60 ° C. to carry out a chain length extension reaction. In the middle of the reaction, 210 g of DMF was added in portions while observing the increase in viscosity, and reacted for 8 hours to obtain a polyurethane resin 3 solution having a resin concentration of 30% and a viscosity of 18,000 cps (30 ° C.). In the solid content of the obtained polyurethane resin 3, the plant-derived component content ratio is 0%, and the oxyethylene group content ratio is 13.6%.
〔製造例４（ポリウレタン樹脂４の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコにヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）４２ｇと、ヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）２８ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）・３０ｇと、ＤＭＦ１５０ｇを仕込み、攪拌し溶解させた。乾燥窒素雰囲気下で５０℃に温度調節し、ＭＤＩ６３ｇを添加し、プレポリマー法にて反応を行った。５０℃で１時間後、ＥＧ１２．５ｇをＤＭＦ５０ｇと混合し添加した。６０℃に昇温し鎖長延長反応を行った。途中、粘度上昇を見ながらＤＭＦ２０９ｇを分割添加しつつ８時間反応させて、樹脂濃度３０％、粘度２１，５００ｃｐｓ（３０℃）のポリウレタン樹脂４溶液を得た。得られたポリウレタン樹脂４の固形分中植物由来成分含有比率は３９．９％、オキシエチレン基含有比率は１３．７％である。
[Production Example 4 (Production of polyurethane resin 4)]
Castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH / g) 42 g and castor oil in a 1 L four-necked flask equipped with a stirrer and a thermometer Diol 2 (produced by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g) 28 g, polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd., polyhardener D- 300 W, molecular weight 3,700) · 30 g and DMF 150 g were charged and stirred to dissolve. The temperature was adjusted to 50 ° C. in a dry nitrogen atmosphere, 63 g of MDI was added, and the reaction was performed by the prepolymer method. After 1 hour at 50 ° C., 12.5 g of EG was mixed with 50 g of DMF and added. The temperature was raised to 60 ° C. to carry out a chain extension reaction. In the middle of the reaction, 209 g of DMF was added in portions while observing the increase in viscosity, and reacted for 8 hours to obtain a polyurethane resin 4 solution having a resin concentration of 30% and a viscosity of 21,500 cps (30 ° C.). In the solid content of the obtained polyurethane resin 4, the plant-derived component content ratio is 39.9%, and the oxyethylene group content ratio is 13.7%.
〔製造例５（ポリウレタン樹脂５の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコに乾燥窒素雰囲気下にて、ヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）４２ｇとヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）２８ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）３０ｇとＤＭＦ・１５０ｇを仕込み、攪拌し均一に溶解させた。５０℃の温度調節下、ＭＤＩ１１．３ｇを投入し（ソフトセグメント集約ＮＣＯ／ＯＨ当量比：９／１０）、１時間反応させた後、さらにＭＤＩ５１．７ｇを添加し、プレポリマ−最終反応を５０℃にて０．５時間行った。続いてＥＧ１２．５ｇをＤＭＦ５０ｇと混合し、添加後、６０℃に昇温し鎖長延長反応を行った。途中粘度上昇を見ながらＤＭＦ２０９ｇを分割添加しつつ８時間反応させて、樹脂濃度３０％、粘度２０，０００ｃｐｓ（３０℃）のポリウレタン樹脂５溶液を得た。得られたポリウレタン樹脂５の固形分中植物由来成分含有比率は３９．９％、オキシエチレン基含有比率は１３．７％である。
[Production Example 5 (Production of polyurethane resin 5)]
In a 1 L four-necked flask equipped with a stirrer and a thermometer, castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH / g) 42 g, castor oil diol 2 (manufactured by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g) and polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd.) Manufactured, polyhardener D-300W, molecular weight 3,700) 30 g and DMF 150 g were charged and stirred to dissolve uniformly. Under temperature control of 50 ° C., 11.3 g of MDI was added (soft segment aggregated NCO / OH equivalent ratio: 9/10) and reacted for 1 hour, then 51.7 g of MDI was further added, and the prepolymer-final reaction was conducted at 50 ° C. For 0.5 hour. Subsequently, 12.5 g of EG was mixed with 50 g of DMF, and after addition, the temperature was raised to 60 ° C. to carry out a chain extension reaction. While observing the increase in viscosity, 209 g of DMF was added in portions and reacted for 8 hours to obtain a polyurethane resin 5 solution having a resin concentration of 30% and a viscosity of 20,000 cps (30 ° C.). In the solid content of the obtained polyurethane resin 5, the plant-derived component content ratio is 39.9%, and the oxyethylene group content ratio is 13.7%.
〔製造例６（ポリウレタン樹脂６の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコにヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）４２ｇと、ヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）２８ｇと、ＰＥＧ（三洋化成工業（株）製、ＰＥＧ−４００、分子量４００）１０ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）２０ｇと、ＤＭＦ１５０ｇを仕込み、均一に溶解させた。５０℃の温度調節下、ＭＤＩ１６．２ｇを投入し（ソフトセグメント集約ＮＣＯ／ＯＨ当量比９／１０）、１時間反応させた後、ＭＤＩ４６．８ｇを添加しプレポリマ−最終反応を５０℃にて０．５時間行った。続いてＥＧ１１．２ｇをＤＭＦ５０ｇと混合し、添加後、６０℃に昇温し鎖長延長反応を行った。途中、粘度上昇を見ながらＤＭＦ２０６ｇを分割添加しつつ８時間反応させて、樹脂濃度３０％、粘度１９，５００（３０℃）のポリウレタン樹脂６溶液を得た。得られたポリウレタン樹脂６の固形分中植物由来成分含有比率は４０．２％、オキシエチレン基含有比率は１４．９％である。
[Production Example 6 (Production of polyurethane resin 6)]
Castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH / g) 42 g and castor oil in a 1 L four-necked flask equipped with a stirrer and a thermometer Diol 2 (manufactured by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mgKOH / g) 28 g and PEG (manufactured by Sanyo Chemical Industries, Ltd., PEG-400, molecular weight 400) 10 g, 20 g of a polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd., polyhardener D-300W, molecular weight 3,700) and 150 g of DMF were charged and dissolved uniformly. Under temperature control of 50 ° C., 16.2 g of MDI was added (soft segment aggregated NCO / OH equivalent ratio 9/10) and reacted for 1 hour, then 46.8 g of MDI was added and the prepolymer final reaction was brought to 0 ° C. at 50 ° C. For 5 hours. Subsequently, 11.2 g of EG was mixed with 50 g of DMF, and after addition, the temperature was raised to 60 ° C. to carry out a chain extension reaction. In the middle of the reaction, 206 g of DMF was added in portions while observing the increase in viscosity, and reacted for 8 hours to obtain a polyurethane resin 6 solution having a resin concentration of 30% and a viscosity of 19,500 (30 ° C.). The resulting polyurethane resin 6 has a plant-derived component content ratio of 40.2% in the solid content and an oxyethylene group content ratio of 14.9%.
〔製造例７（ポリウレタン樹脂７の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコにヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）３６ｇと、ヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）２４ｇと、ＰＥＧ（三洋化成工業（株）製、ＰＥＧ−４００、分子量４００）２０ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）２０ｇと、ＤＭＦ１５０ｇを仕込み、均一に溶解させた。５０℃の温度調節下、ＭＤＩ２０．５ｇを投入し（ソフトセグメント集約ＮＣＯ／ＯＨ当量比：９／１０）、１時間反応させた後、ＭＤＩ４２．５ｇを添加しプレポリマ−最終反応を５０℃にて０．５時間行った。続いてＥＧ１０ｇをＤＭＦ５０ｇと混合し、添加後、６０℃に昇温し鎖長延長反応を行った。途中粘度上昇を見ながらＤＭＦ２０４ｇを分割添加しつつ８時間反応させて、樹脂濃度３０％、粘度２２，５００ｃｐｓ（３０℃）のポリウレタン樹脂７溶液を得た。得られたポリウレタン樹脂７の固形分中植物由来成分含有比率は３４．７％、オキシエチレン基含有比率は２０．８％である。
[Production Example 7 (Production of polyurethane resin 7)]
Castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH / g) 36 g and castor oil in a 1 L four-necked flask equipped with a stirrer and a thermometer Diol 2 (produced by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g) and 24 g PEG (manufactured by Sanyo Chemical Industries, Ltd., PEG-400, molecular weight 400) 20 g of polyether polyol (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyhardener D-300W, molecular weight 3,700) and 150 g of DMF were charged and dissolved uniformly. Under a temperature control of 50 ° C., 20.5 g of MDI was added (soft segment aggregated NCO / OH equivalent ratio: 9/10) and reacted for 1 hour, then 42.5 g of MDI was added, and the prepolymer final reaction was performed at 50 ° C. For 0.5 hours. Subsequently, 10 g of EG was mixed with 50 g of DMF, and after addition, the temperature was raised to 60 ° C. to carry out a chain extension reaction. The reaction was carried out for 8 hours while adding 204 g of DMF while observing the increase in viscosity in the middle, to obtain a polyurethane resin 7 solution having a resin concentration of 30% and a viscosity of 22,500 cps (30 ° C.). The plant-derived component content ratio in the solid content of the obtained polyurethane resin 7 is 34.7%, and the oxyethylene group content ratio is 20.8%.
〔製造例８（ポリウレタン樹脂８の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコにヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）４５ｇと、ヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）３８ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）２５ｇと、ＤＭＦ１５０ｇを仕込み、均一に溶解させた。５０℃の温度調節下、ＭＤＩ１１．６ｇを投入し（ソフトセグメント集約ＮＣＯ／ＯＨ当量比：９／１０）、１時間反応させた後、ＭＤＩ５１．４ｇを添加し、プレポリマ−最終反応を５０℃にて０．５時間行った。続いてＥＧ１２．４ｇをＤＭＦ５０ｇと混合し、添加後、６０℃に昇温し、鎖長延長反応を行った。途中、粘度上昇を見ながらＤＭＦ２０９ｇを分割添加しつつ８時間反応させて、樹脂濃度３０％、粘度２３，５００ｃｐｓ（３０℃）のポリウレタン樹脂８溶液を得た。得られたポリウレタン樹脂８の固形分中植物由来成分含有比率は４２．８％、オキシエチレン基含有比率は１１．４％である。
[Production Example 8 (Production of polyurethane resin 8)]
Castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH / g) 45 g and castor oil in a 1 L four-necked flask equipped with a stirrer and a thermometer Diol 2 (manufactured by Ito Oil Co., Ltd., PH-5002, average hydroxyl group number: 2.03, hydroxyl group value: 43 mg KOH / g) 38 g and polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd., polyhardener D-) 300 W, molecular weight 3,700) 25 g and DMF 150 g were charged and dissolved uniformly. Under a temperature control of 50 ° C., 11.6 g of MDI was added (soft segment aggregated NCO / OH equivalent ratio: 9/10) and reacted for 1 hour, then 51.4 g of MDI was added, and the prepolymer final reaction was brought to 50 ° C. For 0.5 hours. Subsequently, 12.4 g of EG was mixed with 50 g of DMF, and after addition, the temperature was raised to 60 ° C. to perform a chain extension reaction. In the middle of the reaction, 209 g of DMF was added in portions while observing the increase in viscosity, and reacted for 8 hours to obtain a polyurethane resin 8 solution having a resin concentration of 30% and a viscosity of 23,500 cps (30 ° C.). In the solid content of the obtained polyurethane resin 8, the plant-derived component content ratio is 42.8%, and the oxyethylene group content ratio is 11.4%.
〔製造例９（ポリウレタン樹脂９の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコにヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）３０ｇと、ヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）２０ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）５０ｇと、ＤＭＦ１５０ｇを仕込み、均一に溶解させた。５０℃の温度調節下、ＭＤＩ１０．２ｇを投入し（ソフトセグメント集約ＮＣＯ／ＯＨ当量比：９／１０）、１時間反応させた後、ＭＤＩ５２．８ｇを添加し、プレポリマ−最終反応を５０℃にて０．５時間行った。続いてＥＧ１２．８ｇをＤＭＦ５０ｇと混合し、添加後、６０℃に昇温し、鎖長延長反応を行った。途中、粘度上昇を見ながらＤＭＦ２１０ｇを分割添加しつつ８時間反応させて、樹脂濃度３０％、粘度１９，５００ｃｐｓポイズ（３０℃）のポリウレタン樹脂９溶液を得た。得られたポリウレタン樹脂９の固形分中植物由来成分含有比率は２８．４％、オキシエチレン基含有比率は２２．８％である。
[Production Example 9 (Production of polyurethane resin 9)]
Castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH / g) and castor oil in a 1 L four-necked flask equipped with a stirrer and a thermometer Diol 2 (produced by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mgKOH / g) 20 g, polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd., polyhardener D- (300 W, molecular weight 3,700) 50 g and DMF 150 g were charged and dissolved uniformly. Under temperature control of 50 ° C., 10.2 g of MDI was added (soft segment aggregated NCO / OH equivalent ratio: 9/10) and reacted for 1 hour, then 52.8 g of MDI was added, and the prepolymer-final reaction was brought to 50 ° C. For 0.5 hours. Subsequently, 12.8 g of EG was mixed with 50 g of DMF, and after addition, the temperature was raised to 60 ° C. to carry out a chain extension reaction. In the middle of the reaction, 210 g of DMF was added in portions while observing the increase in viscosity, and reacted for 8 hours to obtain a polyurethane resin 9 solution having a resin concentration of 30% and a viscosity of 19,500 cps poise (30 ° C.). The resulting polyurethane resin 9 has a plant-derived component content ratio of 28.4% in the solid content and an oxyethylene group content ratio of 22.8%.
〔製造例１０（ポリウレタン樹脂１０の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコにヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）４２ｇと、ヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）２８ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）３０ｇと、ＤＭＦ１５０ｇを仕込み、均一に溶解させた。５０℃の温度調節下、ＭＤＩ１１．３ｇを投入し（ソフトセグメント集約ＮＣＯ／ＯＨ当量比：９／１０）、１時間反応させた後、ＭＤＩ５１．７ｇを添加し、プレポリマ−最終反応を５０℃にて０．５時間行った。続いて１，４−ブチレングリコール１８．１ｇをＤＭＦ５０ｇと混合し、添加後、６０℃に昇温し、鎖長延長反応を行った。途中粘度上昇を見ながらＤＭＦ２２３ｇを分割添加しながら８時間反応させて樹脂濃度３０％、粘度２０，５００ｃｐｓ（３０℃）のポリウレタン樹脂１０溶液を得た。得られたポリウレタン樹脂１０の固形分中植物由来成分含有比率３８．６％、オキシエチレン基含有比率は１３．２％である。
[Production Example 10 (Production of polyurethane resin 10)]
Castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH / g) 42 g and castor oil in a 1 L four-necked flask equipped with a stirrer and a thermometer Diol 2 (produced by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g) 28 g, polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd., polyhardener D- 300 W, molecular weight 3,700) 30 g and DMF 150 g were charged and dissolved uniformly. Under temperature control of 50 ° C., 11.3 g of MDI was added (soft segment aggregated NCO / OH equivalent ratio: 9/10) and reacted for 1 hour, then 51.7 g of MDI was added, and the prepolymer-final reaction was brought to 50 ° C. For 0.5 hours. Subsequently, 18.1 g of 1,4-butylene glycol was mixed with 50 g of DMF, and after addition, the temperature was raised to 60 ° C. to carry out a chain extension reaction. While observing the increase in viscosity, 223 g of DMF was added in portions while reacting for 8 hours to obtain a polyurethane resin 10 solution having a resin concentration of 30% and a viscosity of 20,500 cps (30 ° C.). The resulting polyurethane resin 10 has a plant-derived component content ratio of 38.6% in solid content and an oxyethylene group content ratio of 13.2%.
〔製造例１１（ポリウレタン樹脂１１の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコにヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）４２ｇと、ヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）２８ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）３０ｇと、ＤＭＦ１５０ｇを仕込み、均一に溶解させた。５０℃の温度調節下、ＭＤＩ１１．３ｇを投入し（ソフトセグメント集約ＮＣＯ／ＯＨ当量比：９／１０）、１時間反応させた後、ＭＤＩ５１．７ｇを添加しプレポリマー最終反応を５０℃にて０．５時間行った。続いて１，３−ブチレングリコール（以下、１，３−ＢＧと略記する）１８．１ｇをＤＭＦ５０ｇと混合し、添加後、６０℃に昇温して鎖長延長反応を行った。途中、粘度上昇を見ながらＤＭＦ２２３ｇを分割添加しながら８時間反応させて、樹脂濃度３０％、粘度２０，５００ｃｐｓ（３０℃）のポリウレタン樹脂１１溶液を得た。得られたポリウレタン樹脂１１の固形分中植物由来成分含有比率３８．６％、オキシエチレン基含有比率は１３．２％である。
[Production Example 11 (Production of polyurethane resin 11)]
Castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH / g) 42 g and castor oil in a 1 L four-necked flask equipped with a stirrer and a thermometer Diol 2 (produced by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g) 28 g, polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd., polyhardener D- 300 W, molecular weight 3,700) 30 g and DMF 150 g were charged and dissolved uniformly. Under temperature control of 50 ° C., 11.3 g of MDI was added (soft segment aggregated NCO / OH equivalent ratio: 9/10) and reacted for 1 hour, then 51.7 g of MDI was added, and the prepolymer final reaction was performed at 50 ° C. For 0.5 hours. Subsequently, 18.1 g of 1,3-butylene glycol (hereinafter abbreviated as 1,3-BG) was mixed with 50 g of DMF, and after addition, the temperature was raised to 60 ° C. to carry out a chain extension reaction. In the middle of the reaction, 223 g of DMF was added in portions while observing the increase in viscosity, and reacted for 8 hours to obtain a polyurethane resin 11 solution having a resin concentration of 30% and a viscosity of 20,500 cps (30 ° C.). In the solid content of the obtained polyurethane resin 11, the plant-derived component content ratio is 38.6%, and the oxyethylene group content ratio is 13.2%.
〔製造例１２（ポリウレタン樹脂１２の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコにヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）４２ｇと、ヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）２８ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）３０ｇと、ＤＭＦ１５０ｇを仕込み、均一に溶解させた。５０℃の温度調節下、ＭＤＩ１１．３ｇを投入し（ソフトセグメント集約ＮＣＯ／ＯＨ当量比：９／１０）、１時間反応させた後、ＭＤＩ５１．７ｇを添加し、プレポリマー最終反応を５０℃にて０．５時間行った。続いて１，２−プロピレングリコール（以下、１，２−ＰＧと略記する）１５．５ｇをＤＭＦ５０ｇと混合し添加後、６０℃に昇温して鎖長延長反応を行った。途中、粘度上昇を見ながらＤＭＦ２１７ｇを分割添加しつつ８時間反応させて、樹脂濃度３０％、粘度２１，５００ｃｐｓ（３０℃）のポリウレタン樹脂１２溶液を得た。得られたポリウレタン樹脂１２の固形分中植物由来成分含有比率は３９．２％、オキシエチレン基含有比率は１３．４％である。
[Production Example 12 (Production of polyurethane resin 12)]
Castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH / g) 42 g and castor oil in a 1 L four-necked flask equipped with a stirrer and a thermometer Diol 2 (produced by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g) 28 g, polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd., polyhardener D- 300 W, molecular weight 3,700) 30 g and DMF 150 g were charged and dissolved uniformly. Under temperature control of 50 ° C., 11.3 g of MDI was added (soft segment aggregated NCO / OH equivalent ratio: 9/10) and reacted for 1 hour, then 51.7 g of MDI was added, and the prepolymer final reaction was brought to 50 ° C. For 0.5 hours. Subsequently, 15.5 g of 1,2-propylene glycol (hereinafter abbreviated as 1,2-PG) was mixed with DMF 50 g, added, and then heated to 60 ° C. to carry out a chain extension reaction. In the middle of the reaction, 217 g of DMF was added in portions while observing the increase in viscosity, and reacted for 8 hours to obtain a polyurethane resin 12 solution having a resin concentration of 30% and a viscosity of 21,500 cps (30 ° C.). The plant-derived component content ratio in the solid content of the obtained polyurethane resin 12 is 39.2%, and the oxyethylene group content ratio is 13.4%.
〔製造例１３（ポリウレタン樹脂１３の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコにヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）４２ｇと、ヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）２８ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）３０ｇと、ＤＭＦ１５０ｇを仕込み、均一に溶解させた。５０℃の温度調節下、ＭＤＩ１１．３ｇを投入し（ソフトセグメント集約ＮＣＯ／ＯＨ当量比：９／１０）、１時間反応させた後、ＭＤＩ５１．７ｇを添加し、プレポリマー最終反応を５０℃にて０．５時間行った。続いてＥＧ１０．１ｇと１，３−ＢＧ３．５ｇをＤＭＦ５０ｇと混合し添加後、６０℃に昇温して鎖長延長反応を行った。途中、粘度上昇を見ながらＤＭＦ２０４ｇを分割添加しつつ８時間反応させて、樹脂濃度３０％、粘度２３，５００ｃｐｓ（３０℃）のポリウレタン樹脂１３溶液を得た。得られたポリウレタン樹脂１３の固形分中植物由来成分含有比率は３９．６％、オキシエチレン基含有比率は１３．６％である。
[Production Example 13 (Production of polyurethane resin 13)]
Castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH / g) 42 g and castor oil in a 1 L four-necked flask equipped with a stirrer and a thermometer Diol 2 (produced by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g) 28 g, polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd., polyhardener D- 300 W, molecular weight 3,700) 30 g and DMF 150 g were charged and dissolved uniformly. Under temperature control of 50 ° C., 11.3 g of MDI was added (soft segment aggregated NCO / OH equivalent ratio: 9/10) and reacted for 1 hour, then 51.7 g of MDI was added, and the prepolymer final reaction was brought to 50 ° C. For 0.5 hours. Subsequently, 10.1 g of EG and 3.5 g of 1,3-BG were mixed with 50 g of DMF, added, and then heated to 60 ° C. to carry out a chain extension reaction. In the middle of the reaction, 204 g of DMF was added in portions while observing the increase in viscosity, and reacted for 8 hours to obtain a polyurethane resin 13 solution having a resin concentration of 30% and a viscosity of 23,500 cps (30 ° C.). The resulting polyurethane resin 13 has a plant-derived component content ratio of 39.6% and an oxyethylene group content ratio of 13.6% in the solid content.
〔製造例１４（ポリウレタン樹脂１４の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコにヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）４２ｇと、ヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）２８ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）３０ｇと、ＤＭＦ１５０ｇを仕込み、均一に溶解させた。５０℃の温度調節下、ＭＤＩ１１．３ｇを投入し（ソフトセグメント集約ＮＣＯ／ＯＨ当量比：９／１０）、１時間反応させた後、ＭＤＩ５１．７ｇを添加しプレポリマー最終反応を５０℃にて０．５時間行った。続いてＥＧ９．７ｇと１，２−ＰＧ３．５ｇをＤＭＦ５０ｇと混合し添加後、６０℃に昇温して鎖長延長反応を行った。途中粘度上昇を見ながらＤＭＦ２０３ｇを分割添加しつつ８時間反応させて、樹脂濃度３０％、粘度２２，５００ｃｐｓ（３０℃）のポリウレタン樹脂１４溶液を得た。得られたポリウレタン樹脂１４の固形分中植物由来成分含有比率は３９．６％、オキシエチレン基含有比率は１３．６％である。
[Production Example 14 (Production of polyurethane resin 14)]
Castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH / g) 42 g and castor oil in a 1 L four-necked flask equipped with a stirrer and a thermometer Diol 2 (produced by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mg KOH / g) 28 g, polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd., polyhardener D- 300 W, molecular weight 3,700) 30 g and DMF 150 g were charged and dissolved uniformly. Under temperature control of 50 ° C., 11.3 g of MDI was added (soft segment aggregated NCO / OH equivalent ratio: 9/10) and reacted for 1 hour, then 51.7 g of MDI was added, and the prepolymer final reaction was performed at 50 ° C. For 0.5 hours. Subsequently, 9.7 g of EG and 3.5 g of 1,2-PG were mixed with 50 g of DMF, added, and then heated to 60 ° C. to carry out a chain extension reaction. The reaction was allowed to proceed for 8 hours while adding 203 g of DMF in portions while observing the increase in viscosity in the middle of the process to obtain a polyurethane resin 14 solution having a resin concentration of 30% and a viscosity of 22,500 cps (30 ° C.). The obtained polyurethane resin 14 has a plant-derived component content ratio of 39.6% and an oxyethylene group content ratio of 13.6% in the solid content.
〔製造例１５（ポリウレタン樹脂１５の製造）〕
攪拌機および温度計を備えた１Ｌ四つ口フラスコにヒマシ油ジオール１（伊藤製油（株）製、Ｈ−５６、平均水酸基数：２．０３個、水酸基価：８３ｍｇＫＯＨ／ｇ）４８ｇと、ヒマシ油ジオール２（伊藤製油（株）製、ＰＨ−５００２、平均水酸基数：２．０３個、水酸基価：４３ｍｇＫＯＨ／ｇ）３２ｇと、ポリエーテルポリオール（第一工業製薬（株）製、ポリハードナーＤ−３００Ｗ、分子量３，７００）２０ｇと、ＤＭＦ１５０ｇを仕込み、均一に溶解させた。５０℃の温度調節下、ＭＤＩ１１．９ｇを投入し（ソフトセグメント集約ＮＣＯ／ＯＨ当量比：９／１０）、１時間反応させた後、ＭＤＩ５１．１ｇを添加し、プレポリマー最終反応を５０℃にて０．５時間行った。続いてＥＧ９．９ｇと１，３−ＢＧ３．５ｇをＤＭＦ５０ｇと混合し、添加後、６０℃に昇温して鎖長延長反応を行った。途中粘度上昇を見ながらＤＭＦ２０４ｇを分割添加しつつ８時間反応させて、樹脂濃度３０％、粘度２０，５００ｃｐｓ（３０℃）のポリウレタン樹脂１５溶液を得た。得られたポリウレタン樹脂１５の固形分中植物由来成分含有比率４６．３％、オキシエチレン基含有比率は９．３％である。
[Production Example 15 (Production of polyurethane resin 15)]
Castor oil diol 1 (manufactured by Ito Oil Co., Ltd., H-56, average number of hydroxyl groups: 2.03, hydroxyl value: 83 mgKOH / g) 48 g and castor oil in a 1 L four-necked flask equipped with a stirrer and a thermometer Diol 2 (manufactured by Ito Oil Co., Ltd., PH-5002, average number of hydroxyl groups: 2.03, hydroxyl value: 43 mgKOH / g) 32 g, polyether polyol (Daiichi Kogyo Seiyaku Co., Ltd., polyhardener D- 300 W, molecular weight 3,700) 20 g and DMF 150 g were charged and dissolved uniformly. Under temperature control of 50 ° C., 11.9 g of MDI was added (soft segment aggregated NCO / OH equivalent ratio: 9/10) and reacted for 1 hour, then 51.1 g of MDI was added, and the prepolymer final reaction was brought to 50 ° C. For 0.5 hours. Subsequently, 9.9 g of EG and 3.5 g of 1,3-BG were mixed with 50 g of DMF, and after addition, the temperature was raised to 60 ° C. to perform a chain extension reaction. The reaction was carried out for 8 hours while adding 204 g of DMF while observing the increase in viscosity in the middle, to obtain a polyurethane resin 15 solution having a resin concentration of 30% and a viscosity of 20,500 cps (30 ° C.). The polyurethane resin 15 obtained has a plant-derived component content ratio of 46.3% and an oxyethylene group content ratio of 9.3% in the solid content.
熱軟化点、引張試験、水膨潤度、吸水率、透湿度の評価は以下の方法により行った。結果を、表１、表２、表３に示す。 Evaluation of thermal softening point, tensile test, degree of water swelling, water absorption rate, and moisture permeability was carried out by the following methods. The results are shown in Table 1, Table 2, and Table 3.
（１）熱軟化点測定方法
試料片の作成：試験用塗膜の作成樹脂濃度が２０％になるようにＤＭＦで調整し、脱泡した。次に、ガラス板上に１．０ｍｍ厚みに塗布し、８０℃の循風乾燥機で２時間乾燥し、更に１４０℃の乾燥機で３０分乾燥し、膜厚約１５０μの塗膜を作成した。この塗膜を４０ｍｍ四方にカットし、ガラス板から剥がした。
(1) Thermal softening point measurement method Preparation of sample piece: Preparation of coating film for test Adjustment was made with DMF so that the resin concentration was 20%, and defoaming was performed. Next, it was applied to a glass plate to a thickness of 1.0 mm, dried for 2 hours with a circulating dryer at 80 ° C., and further dried for 30 minutes with a dryer at 140 ° C. to form a coating film having a thickness of about 150 μm. . This coating film was cut into a 40 mm square and peeled off from the glass plate.
熱軟化点の測定：得られた塗膜について、１００ｇ分銅を膜上に置き、各設定温度の乾燥機中に６０分放置したのちに取り出し、分銅を除いたときに膜上に分銅跡が残らない温度を軟化点（℃）とした。 Measurement of thermal softening point: About the obtained coating film, a 100 g weight is placed on the film, left in a dryer at each set temperature for 60 minutes, and then taken out. When the weight is removed, a trace of weight remains on the film. The softening point (° C.) was defined as the temperature at which no temperature was present.
（２）引張強度測定方法
上記（１）項の試料作成方法で得られた塗膜を使用した。２０ｍｍ×８０ｍｍの大きさにカットされた試験片をオリエンテック社製ＳＴＡ−１２２５引張試験機を使って引っ張り速度１００ｍｍ／分で、室温で、１００％応力（ｋｇ／ｃｍ２）、３００％応力（ｋｇ／ｃｍ２）、抗張力（ｋｇ／ｃｍ２）、及び破断伸度を測定した。
(2) Tensile strength measuring method The coating film obtained by the sample preparation method of the said (1) term was used. A test piece cut to a size of 20 mm × 80 mm was pulled at 100 mm / min using an Orientec STA-1225 tensile tester at room temperature, 100% stress (kg / cm 2 ), 300% stress ( kg / cm 2 ), tensile strength (kg / cm 2 ), and elongation at break.
（３）吸水率（％）及び水膨潤度（％）の測定方法
上記（１）項の試料作成方法で得られた塗膜を使用した。得られた塗膜（約１５０μ）を１０ｃｍ×１０ｃｍ片に切り取り、２０℃×６５％ＲＨ雰囲気中に３時間放置後基準重量（Ｗ０）を測定した。次に２５℃恒温水槽に５時間放置した後、取り出し、水分をふき取った塗膜の重量（Ｗ１）を測定し、次式を用いて算出した。
吸水量（％）＝（Ｗ１−Ｗ０）×１００／Ｗ０
(3) Measuring method of water absorption rate (%) and water swelling degree (%) The coating film obtained by the sample preparation method of the said (1) term was used. The obtained coating film (about 150 μm) was cut into 10 cm × 10 cm pieces, allowed to stand in a 20 ° C. × 65% RH atmosphere for 3 hours, and then the reference weight (W0) was measured. Next, after leaving it in a constant temperature water bath at 25 ° C. for 5 hours, it was taken out, and the weight (W1) of the coating film from which water had been wiped off was measured and calculated using the following formula.
Water absorption (%) = (W1-W0) × 100 / W0
また水膨潤度は重量測定時に寸法（Ｌ１）を測定し、次式を用いて算出した。
（元寸法は１０ｃｍ）◎
水膨潤度（％）＝（Ｌ１−１０）×１００／１０
Further, the degree of water swelling was calculated by using the following equation after measuring the dimension (L1) during weight measurement.
(Original size is 10cm)
Water swelling degree (%) = (L1-10) × 100/10
（４）透湿度測定方法
試験用塗膜試料の作成：樹脂濃度が１５％になるようにＤＭＦで調整した樹脂溶液を脱泡した。次に、離型紙上に０．１ｍｍ厚みに塗布し、１００℃の循風乾燥機で１時間乾燥した後に放冷し、塗膜を離型紙から剥がした。厚み１０μの塗膜が得られた。
(4) Moisture permeability measurement method Preparation of test coating film sample: The resin solution adjusted with DMF was degassed so that the resin concentration was 15%. Next, it was applied to a release paper to a thickness of 0.1 mm, dried with a circulating dryer at 100 ° C. for 1 hour, allowed to cool, and the coating film was peeled off from the release paper. A coating film having a thickness of 10 μm was obtained.
透湿度はＪＩＳ規格Ｌ−１０９９のＢ−１法に従って測定した。なお透湿度の評価としては、２５００ｇ／ｍ２・２４Ｈｒ以上は透湿性能があると判断した。 The moisture permeability was measured according to the B-1 method of JIS standard L-1099. In addition, as evaluation of moisture permeability, it was judged that 2500 g / m 2 · 24Hr or more has moisture permeability.
表１から分かるように、オキシエチレン基の導入を多くする事により、大きな透湿性能が得られるが、ヒマシ油含有率が２５％以上でないとカーボンニュートラルという目標が達成できない。また、アジペート系のポリエステルジオールに比べ、ヒマシ油ポリオール共重合物は透湿性が低く、通常のプレポリマー重合方法ではヒマシ油成分（植物由来成分）が多くなると所望の透湿性能が得られないが、本発明では、ソフトセグメント間を長く（すなわち非結晶部分を大きく）することにより、吸湿・吸水量を大きくし、非結晶部分から発散・放湿させることにより、透湿度が向上すると考えられる。 As can be seen from Table 1, a large moisture permeability can be obtained by increasing the introduction of oxyethylene groups, but the target of carbon neutral cannot be achieved unless the castor oil content is 25% or more. In addition, castor oil polyol copolymer has low moisture permeability compared to adipate-based polyester diol, and the desired moisture permeability performance cannot be obtained if the amount of castor oil component (plant-derived component) is increased by a normal prepolymer polymerization method. In the present invention, it is considered that the moisture permeability is improved by increasing the moisture absorption / water absorption amount by increasing the distance between the soft segments (that is, by increasing the non-crystalline portion), and divergence / moisture release from the amorphous portion.
表２に示された結果からは、オキシエチレン基を分散させるほど透湿度が向上できることが分かる。ポリオキシエチレン／ポリオキシプロピレンの共重合物（以下、ＰＯ／ＥＯと略記）とポリオキシエチレン重合物（ＰＥＧ）の分子鎖への導入では、ＰＥＧの導入によりオキシエチレン基の量は増えるが、ＰＯ／ＥＯに比べると、透湿度の向上が劣ることからソフトセグメント中にオキシエチレン基がより分散されていた方が良いことが分かる。オキシエチレン基の集中した部分に湿気・水分が集まっても他の疎水性の部分には全くない場合、吸湿吸水・放湿放水の機能が劣った構造になるが、分散された構造は全体的に吸湿吸水・放湿放水の機能を持ち、透湿度が良好になると考えられる。 From the results shown in Table 2, it can be seen that the moisture permeability can be improved as the oxyethylene group is dispersed. When polyoxyethylene / polyoxypropylene copolymer (hereinafter abbreviated as PO / EO) and polyoxyethylene polymer (PEG) are introduced into the molecular chain, the amount of oxyethylene groups increases due to the introduction of PEG. Compared to PO / EO, the improvement in moisture permeability is inferior, so it can be seen that oxyethylene groups should be more dispersed in the soft segment. If moisture or moisture collects in the concentrated oxyethylene group, but there is no other hydrophobic part at all, the function of absorbing and absorbing moisture is poor, but the dispersed structure is overall It has a function of moisture absorption / absorption / moisture discharge, and moisture permeability is considered to be good.
表３に示された結果からは、分岐したグリコールの使用により透湿性能が向上することが分かる。これは、ポリウレタンの結晶性が崩れ、ソフトセグメントに吸湿・吸水した後の放湿・放水時に、この結晶性の崩れた部分の効果で透湿性能が向上する（直鎖状グリコールより透湿度が高い）ためと考えられる。 From the results shown in Table 3, it can be seen that the use of branched glycol improves the moisture permeability. This is because the crystallinity of the polyurethane collapses, and the moisture permeation performance is improved by the effect of the part where the crystallinity is lost during moisture release / water discharge after moisture absorption / water absorption by the soft segment (the moisture permeability is higher than that of the linear glycol). High).
但し、鎖伸長剤として分岐グリコールを単独使用したものは軟化点が低く、用途によっては耐熱性（耐熱ブロッキング性）に問題が生じる場合があるが、直鎖状グリコールと分岐グリコールとの併用により、この耐熱性の問題も解決されることが分かる。 However, the use of a branched glycol alone as a chain extender has a low softening point and may cause a problem in heat resistance (heat blocking resistance) depending on the use, but by using a linear glycol and a branched glycol in combination, It can be seen that this problem of heat resistance is also solved.
Claims (5)
前記植物由来の高分子ジオール成分の含有量が樹脂成分中２５〜６５重量％であり、
前記オキシエチレン基を含有する高分子ジオール成分がオキシエチレン基がランダムに分散された共重合物であり、かつ
前記有機ジイソシアネート成分と前記高分子ジオールとのプレポリマーＮＣＯ／ＯＨ反応当量比を３／４以上（０．７５以上）とし、ソフトセグメントを集中させた構造を有することを特徴とする透湿性ポリウレタン樹脂。 A moisture-permeable polyurethane resin comprising a plant-derived polymer diol component, a polymer diol component containing an oxyethylene group, an organic diisocyanate component, and a chain extender component that is a dihydric alcohol,
The content of the plant-derived polymer diol component is 25 to 65% by weight in the resin component,
The polymer diol component containing the oxyethylene group is a copolymer in which oxyethylene groups are randomly dispersed, and the prepolymer NCO / OH reaction equivalent ratio of the organic diisocyanate component and the polymer diol is 3 / A moisture-permeable polyurethane resin characterized by having a structure in which soft segments are concentrated to 4 or more (0.75 or more).
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