JP4329046B1 - 透湿フィルム、その製造方法及びそれを用いた積層体 - Google Patents
透湿フィルム、その製造方法及びそれを用いた積層体 Download PDFInfo
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- JP4329046B1 JP4329046B1 JP2009512765A JP2009512765A JP4329046B1 JP 4329046 B1 JP4329046 B1 JP 4329046B1 JP 2009512765 A JP2009512765 A JP 2009512765A JP 2009512765 A JP2009512765 A JP 2009512765A JP 4329046 B1 JP4329046 B1 JP 4329046B1
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- Prior art keywords
- moisture
- polyol
- meth
- permeable film
- acrylate
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 102
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 84
- 229920005862 polyol Polymers 0.000 claims abstract description 75
- 150000003077 polyols Chemical class 0.000 claims abstract description 74
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 65
- 239000004814 polyurethane Substances 0.000 claims abstract description 55
- 229920002635 polyurethane Polymers 0.000 claims abstract description 55
- 239000012943 hotmelt Substances 0.000 claims abstract description 51
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000011342 resin composition Substances 0.000 claims abstract description 46
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 45
- -1 polyoxyethylene Polymers 0.000 claims abstract description 44
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 31
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 28
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 26
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 22
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 238000001723 curing Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 12
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 11
- 239000004831 Hot glue Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 229920000570 polyether Polymers 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 8
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 238000000016 photochemical curing Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- VIBDJEWPNNCFQO-UHFFFAOYSA-N ethane-1,1,2-triol Chemical compound OCC(O)O VIBDJEWPNNCFQO-UHFFFAOYSA-N 0.000 claims 6
- 230000035699 permeability Effects 0.000 abstract description 37
- 239000004753 textile Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000000853 adhesive Substances 0.000 description 13
- 230000001070 adhesive effect Effects 0.000 description 13
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 230000009477 glass transition Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 230000032683 aging Effects 0.000 description 8
- 238000013008 moisture curing Methods 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 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 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 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
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical class CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-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 class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 150000003505 terpenes Chemical class 0.000 description 3
- 235000007586 terpenes Nutrition 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
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- 235000019438 castor oil Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
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- 230000002940 repellent Effects 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
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- WTKWFNIIIXNTDO-UHFFFAOYSA-N 3-isocyanato-5-methyl-2-(trifluoromethyl)furan Chemical compound CC1=CC(N=C=O)=C(C(F)(F)F)O1 WTKWFNIIIXNTDO-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
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- 239000005995 Aluminium silicate Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本発明は、ビスフェノールAにアルキレンオキサイドが付加したポリオールとポリカルボン酸とを反応させて得られるポリエステルポリオール(a−1)、常温固体のポリエステルポリオール(a−2)及び1000〜25000の数平均分子量を有するポリオキシエチレングリコール(a−3)を含むポリオール(A)とポリイソシアネート(B)とを反応させて得られるウレタンプレポリマーの有するイソシアネート基の数の10%〜90%と、水酸基含有(メタ)アクリレート(C)とを反応させて得られる反応性ウレタンプレポリマー(D)、(メタ)アクリレート(E)、及び光重合開始剤(F)を含有してなる反応性ポリウレタンホットメルト樹脂組成物を硬化させて得られる透湿フィルムに関する。
【選択図】なし
Description
このように、従来の湿気硬化性ポリウレタンホットメルト樹脂組成物では、実用上十分なレベルの透湿性や柔軟性や機械的強度に加え、更に優れた耐水性を備えた透湿フィルムを得ることは困難であった。
また、前記方法で製造した透湿フィルムの表面には、毛羽立ちが発生し、実用上十分な表面品位を有しているとは言いがたいものであった。
しかし、繊維製品の外観には非常に高いレベルの品位が求められるなかで、前記透湿フィルムは、産業界から求められるレベルの表面品位には、あと一歩及ぶものではなかった。また、前記透湿フィルムは、柔軟性や機械的強度や耐水性の点でも、未だ十分といえるものではなかった。
しかし、前記透湿フィルムであっても、依然として実用上十分な柔軟性や機械的強度や耐水性を有するものではないため、本発明の課題を解決するためには、更なる改善を図る必要があった。
具体的には、優れた透湿性の付与を目的としてポリオキシエチレングリコールを必須とし、更に柔軟性や機械的強度の付与を目的として、例えば1,6−ヘキサンジオール及び1,12−ドデカン二酸を反応させて得られる長鎖脂肪族ポリエステルポリオールや、ネオペンチルグリコール及びアジピン酸を反応させて得られる分岐構造を有するポリエステルポリオール等の常温で固体の結晶性ポリエステルポリオール等を組み合わせたポリオールとポリイソシアネートとを反応させて得られるウレタンプレポリマーの使用を検討した。
しかし、前記ポリオールを組み合わせ使用して得られた透湿フィルムは、実用上十分な柔軟性や機械的強度等を有するものではなかった。
本発明の透湿フィルムは、優れた透湿性と柔軟な風合いと機械的強度と耐水性に優れるという効果を両立した産業上有用な発明である。
前記ポリエステルポリオール(a−1)は、ビスフェノールAにアルキレンオキサイドが付加したポリエーテルポリオールとポリカルボン酸とを縮合反応させて得られるものである。
前記反応性ポリウレタンホットメルトプレポリマー(D)を製造する際に使用するポリエステルポリオール(a−2)は、低分子量ポリオールとポリカルボン酸とを縮合反応させて得られるポリエステルポリオールのうち、結晶性を有するものである。
前記(メタ)アクリレート(E)は、本発明で使用する反応性ポリウレタンホットメルト樹脂組成物の必須成分である。前記(メタ)アクリレート(E)としては、分子内に重合性二重結合を1つ有する単官能(メタ)アクリレートや、重合性二重結合を2以上有する多官能(メタ)アクリレートを使用することができる。特に柔軟な風合いに優れた透湿フィルムを得る場合には、前記(メタ)アクリレート(E)として単官能(メタ)アクリレートを使用することが好ましい。一方、特に耐久性と耐毛羽立ち性に優れた透湿フィルムを得る場合には、前記(メタ)アクリレート(E)として多官能(メタ)アクリレートを使用することが好ましい。
光重合開始剤(F)は、前記反応性ウレタンプレポリマー(D)の有する重合性不飽和二重結合の架橋反応の開始剤として作用する。
本発明の透湿フィルムの製造方法としては、以下の方法が挙げられる。
また、光硬化反応と湿気硬化反応とは同時に進行させてもよく、また、何れか一方を先に進行させ、次いで他方の硬化反応を進行させてもよい。
本発明の積層体は、前記した透湿フィルムの少なくとも一表面に、各種接着剤を間欠塗布し、該塗布面に透湿性基材が接着されたものである。
また、前記ポリオキシエチレングリコール(X−3)としては、主として2000〜25000の数平均分子量を有するものを使用することが好ましい。
前記接着剤を、透湿フィルムまたは透湿性基材に塗布する方法としては、例えばロールに彫刻を施したグラビア転写コート法、スクリーンコート法、T−ダイコート法、ギアポンプを有するダイコーター法、ファイバーコート法等が挙げられる。
ゲル濾過クロマトグラフィー(GPC)法により測定し、ポリスチレン換算で数平均分子量(Mn)を算出した。
反応性ウレタンプレポリマーの溶融粘度(mPa・s)は、コーンプレート粘度計(ICI社製。測定温度125℃)を用いて測定した。
反応性ウレタンプレポリマーのガラス転移温度(Tg)は、反応性ウレタンプレポリマーを30μmの厚みに塗布して、環境温度23℃、相対湿度65%の環境下で5日間熟成して得られたフィルムを、動的粘弾性測定装置(レオメトリック社製。周波数1Hz、昇温速度5℃/分)を用いて得られた損失正接(tanδ)のピーク温度(単位:℃)に基づいて決定した。
110℃に加熱した前記反応性ウレタンプレポリマー(D’−1)100質量部に、2−ヒドロキシエチルアクリレートの1.02質量部とオクチル酸スズの0.01質量部とを加え反応させることによって反応性ウレタンプレポリマー(D−1)を得た。前記反応性ウレタンプレポリマー(D−1)の有するイソシアネート基の数の全量に対して、2−ヒドロキシエチルアクリレートの水酸基が反応したイソシアネート基の数の割合([HEA/NCO]×100)は、15%であった。
反応性ウレタンプレポリマーの組成を、それぞれ表1及び2に記載のものに変更する以外は、合成例1及び2に記載の方法と同様の方法で、反応性ウレタンプレポリマー(D−2)〜(D−5)及び(D’−2)〜(D’−6)をそれぞれ製造した。なお、表2中のポリオキシプロピレングリコール(a−3−2)としては、数平均分子量2000のものを使用した。
100℃で加熱溶融した反応性ウレタンプレポリマー(D−1)に、トリメチロールプロパントリアクリレート、「IRGACURE 651」(チバスペシャリティ(株)製の光重合開始剤)を混合することによって、反応性ポリウレタンホットメルト樹脂組成物を製造した。
反応性ウレタンプレポリマーの組成を下記表3及び4の記載に変更する以外は、前記実施例1と同様の方法で、透湿フィルム(II)〜(XIV)及び積層体(II)〜(XIV)を製造した。
前記透湿フィルムを幅5mm×長さ7cm×厚み30μmの大きさに切り取って得られた試験フィルムの引張特性を、JIS K−7311に準拠してテンシロン((株)島津製作所製、ヘッドスピード=300mm/分)を用いて評価した。試験フィルムの柔軟性は、引張特性のうちの100%モジュラスの値に基づいて評価した。100%モジュラスの値が4.0MPa以下であるフィルムは、実用上十分なレベルの柔軟性(風合い)を有していると評価し、なかでも2.0MPa以下であるフィルムは特に好ましい柔軟性を有するものと評価した。また、透湿フィルムの強度は、破断点応力が概ね20MPa以上、かつ破断点伸度が300%以上のものが良好であると評価し、なかでも破断点応力が22MPa以上、かつ破断点伸度が750%以上のものが特に良好であると評価した。
十分に養生し硬化させた前記透湿フィルムの透湿度は、透湿性試験:JIS L−1099(A−1法:塩化カリウム法)に準じて測定した。透湿度が5000(g/m2/24hr)以上のものは、実用上十分な透湿性を有するものと評価した。
120℃で加熱溶融状態の反応性ポリウレタンホットメルト樹脂組成物を、120℃に加熱されたナイフコーターを用いて、膜厚が30μmになるように離型紙(EK−100、リンテック(株)製)上に塗布した。
○:透湿フィルムの表面にタック性や毛羽立ちが全くなく、透湿フィルムと離型紙の裏面とを容易に剥離することができた。
△:透湿フィルムの表面に若干のタック性と毛羽立ちとが見られるものの、透湿フィルムと離型紙の裏面とを容易に剥離することができた。
×:透湿フィルムと離型紙の裏面とを剥離することができなかった。
透湿フィルムの耐水性は、水膨潤度に基づいて評価した。具体的には、縦10cm、横10cmの大きさに裁断した透湿フィルムを、水中に24時間浸漬した後の透湿フィルムの寸法を測定した。浸漬前の寸法と比較して、浸漬後の透湿フィルムの縦及び横の寸法の変化が、概ね20%以内であるものは耐水性に優れると評価し、20%を超えるものは、水に対する膨潤度が大きいため、フィルム強度の低下や洗濯時の剥がれや浮きが発生しやすく耐水性に劣るものであると評価した。なお、表3中の実施例1の評価「16*16」は、前記浸漬後のフィルムの縦の寸法が、浸漬前の寸法よりも16%大きく、横の寸法も同様に16%大きくなったことを示す。
前記積層体を手で折り曲げることにより、それらの風合いを下記の5段階で評価した。5段階評価のうち、3以下であることが、実用上好ましい。
2:透湿フィルムと繊維質基材に一体感はあまりないが、優れた柔軟性を有する。
3:良好な柔軟性を有する。
4:折り曲げた際に少し硬さを感じ、多少のバリバリとした音及び感触がする。
5:折り曲げる際にある程度の力を必要とし、折り曲げた際にはバリバリという音がする。
十分に養生し硬化させた前記積層体の透湿度は、透湿性試験:JIS L−1099(A−1法:塩化カリウム法)に準じて測定した。透湿度が6000(g/m2/24hr)以上のものは、実用上十分な透湿性を有するものと評価した。
「A−1000」:数平均分子量1000のポリエチレングリコールジアクリレート
Claims (8)
- ビスフェノールAにアルキレンオキサイドが付加したポリオールとポリカルボン酸とを反応させて得られるポリエステルポリオール(a−1)、常温固体のポリエステルポリオール(a−2)、及び1000〜25000の数平均分子量を有するポリオキシエチレングリコール(a−3)を含むポリオール(A)とポリイソシアネート(B)とを反応させて得られるウレタンプレポリマーの有するイソシアネート基の数の10%〜90%と、水酸基含有(メタ)アクリレート(C)とを反応させて得られる反応性ウレタンプレポリマー(D)、(メタ)アクリレート(E)、及び光重合開始剤(F)を含有してなる反応性ポリウレタンホットメルト樹脂組成物を硬化させて得られる透湿フィルム。
- 前記ポリオール(A)が、前記ポリオール(A)の全量100質量部に対して、前記ポリエステルポリオール(a−1)を5〜30質量部、前記ポリエステルポリオール(a−2)を10〜30質量部、及び前記ポリオキシエチレングリコール(a−3)を30〜85質量部含むものである、請求項1に記載の透湿フィルム。
- 前記ポリエステルポリオール(a−1)が、ビスフェノールAに4〜8モルのプロピレンオキサイドが付加したポリエーテルポリオールと、セバシン酸及びイソフタル酸とを縮合反応させて得られるものである、請求項1に記載の透湿フィルム。
- 前記ポリエステルポリオール(a−2)が、1,6−ヘキサンジオール及びネオペンチルグリコールを含むポリオールと、アジピン酸とを反応させて得られるものである、請求項1に記載の透湿フィルム。
- 前記(メタ)アクリレート(E)が、ポリエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリレート、これらのエチレンオキサイド付加物、及びプロピレンオキサイド付加物からなる群より選ばれる1種以上の多官能(メタ)アクリレートである、請求項1に記載の透湿フィルム。
- 厚みが5〜50μmの範囲である請求項1に記載の透湿フィルム。
- ビスフェノールAにアルキレンオキサイドが付加したポリオールとポリカルボン酸とを反応させて得られるポリエステルポリオール(a−1)、常温固体のポリエステルポリオール(a−2)、及び1000〜25000の数平均分子量を有するポリオキシエチレングリコール(a−3)を含むポリオール(A)とポリイソシアネート(B)とを反応させて得られるウレタンプレポリマーの有するイソシアネート基の数の10%〜90%と、水酸基含有(メタ)アクリレート(C)とを反応させて得られる反応性ウレタンプレポリマー(D)、(メタ)アクリレート(E)、及び光重合開始剤(F)を含有してなる加熱溶融状態の反応性ポリウレタンホットメルト樹脂組成物を、厚さ5〜50μmのフィルム状に成形し、光硬化反応と湿気硬化反応とを順次または同時に進行させる、透湿フィルムの製造方法。
- ビスフェノールAにアルキレンオキサイドが付加したポリオールとポリカルボン酸とを反応させて得られるポリエステルポリオール(a−1)、常温固体のポリエステルポリオール(a−2)、及び1000〜25000の数平均分子量を有するポリオキシエチレングリコール(a−3)を含むポリオール(A)とポリイソシアネート(B)とを反応させて得られるウレタンプレポリマーの有するイソシアネート基の数の10%〜90%と、水酸基含有(メタ)アクリレート(C)とを反応させて得られる反応性ウレタンプレポリマー(D)、多官能(メタ)アクリレート(E)、及び光重合開始剤(F)を含有してなる反応性ポリウレタンホットメルト樹脂組成物を硬化させて得られた透湿フィルムの片面又は両面に、加熱溶融状態の反応性ポリウレタンホットメルト接着剤を間欠塗布し、該塗布面上に透湿性基材が接着された積層体。
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