JP4904703B2 - Heat resistant polyurethane film - Google Patents
Heat resistant polyurethane film Download PDFInfo
- Publication number
- JP4904703B2 JP4904703B2 JP2005077022A JP2005077022A JP4904703B2 JP 4904703 B2 JP4904703 B2 JP 4904703B2 JP 2005077022 A JP2005077022 A JP 2005077022A JP 2005077022 A JP2005077022 A JP 2005077022A JP 4904703 B2 JP4904703 B2 JP 4904703B2
- Authority
- JP
- Japan
- Prior art keywords
- diisocyanate
- polyurethane resin
- heat
- film
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920006264 polyurethane film Polymers 0.000 title claims description 56
- 229920005749 polyurethane resin Polymers 0.000 claims description 76
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- 229920005862 polyol Polymers 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 150000003077 polyols Chemical class 0.000 claims description 29
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 239000011342 resin composition Substances 0.000 claims description 22
- 125000005442 diisocyanate group Chemical group 0.000 claims description 16
- 239000005056 polyisocyanate Substances 0.000 claims description 15
- 229920001228 polyisocyanate Polymers 0.000 claims description 15
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 10
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- 239000012943 hotmelt Substances 0.000 description 24
- 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 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- -1 methyl glycoside Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 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 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 229930185605 Bisphenol Natural products 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-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
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-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
- 230000000903 blocking effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003999 initiator 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
- 238000010030 laminating Methods 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
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- 239000000987 azo dye Substances 0.000 description 1
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- IVCQBDFQYUAIIJ-UHFFFAOYSA-N bis(2,2,3,3-tetramethylpiperidin-1-yl) decanedioate Chemical compound CC1(C)C(C)(C)CCCN1OC(=O)CCCCCCCCC(=O)ON1C(C)(C)C(C)(C)CCC1 IVCQBDFQYUAIIJ-UHFFFAOYSA-N 0.000 description 1
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
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- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
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- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt 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
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- PVCOXMQIAVGPJN-UHFFFAOYSA-N piperazine-1,4-diamine Chemical compound NN1CCN(N)CC1 PVCOXMQIAVGPJN-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- 239000011164 primary particle Substances 0.000 description 1
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- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
本発明は、耐熱性ポリウレタンフィルムに関する。更に詳しくは、特定のポリウレタン樹脂組成物を用いてなるフィルムであって、例えば、該フィルムをホットメルト層と多層化する際に、ホットメルト層が溶融し得る温度条件下でも、該フィルムは溶融又は熱劣化せずに優れた耐熱性を堅持し、且つ優れた耐候性、耐水性、及び耐薬品性をも発揮する新規な耐熱性ポリウレタンフィルムに関する。 The present invention relates to a heat resistant polyurethane film. More specifically, a film made of a specific polyurethane resin composition, for example, when the film is multi-layered with a hot melt layer, the film melts even under temperature conditions at which the hot melt layer can melt. Alternatively, the present invention relates to a novel heat-resistant polyurethane film that maintains excellent heat resistance without thermal deterioration and also exhibits excellent weather resistance, water resistance, and chemical resistance.
従来、ポリウレタン樹脂は、機械強度、弾性などの優れた特性が得られることから接着材料、成形材料、合成皮革、人工皮革、表面処理剤、塗料、フィルム、あるいはシートなど広範囲の用途に利用されてきた。中でも特にフィルム用途に着目した場合、ポリウレタン樹脂に特有の弾性により、感触が良くソフトな風合いが得られることから、繊維やシート等の接着加工に主に用いられてきた。 Conventionally, polyurethane resins have been used in a wide range of applications such as adhesive materials, molding materials, synthetic leather, artificial leather, surface treatment agents, paints, films, and sheets because they have excellent properties such as mechanical strength and elasticity. It was. In particular, when attention is focused on film applications, it has been mainly used for bonding processing of fibers, sheets, and the like because it has a good feel and a soft texture due to the elasticity unique to polyurethane resins.
しかしながら、従来の製造方法で得られるポリウレタンフィルムは、たとえ耐熱性が良好であっても、耐候性には劣るため経時で短期間に黄変してしまい、実用性に乏しいものであった。
また逆に、従来のポリウレタンフィルムにおいて、たとえ耐候性が良好であっても、耐熱性には劣り、例えばホットメルト層と多層化する際に、ホットメルト層を溶融させる温度（通常１３０〜１８０℃程度。）には耐えられず、溶融したり破断したりする問題があった。
更に、前述のようなポリウレタンフィルムは、耐水性や耐薬品性にも劣るという問題もあった。
However, even if the polyurethane film obtained by the conventional production method has good heat resistance, it is inferior in weather resistance, and therefore yellowed in a short time with time, and has poor practicality.
On the other hand, in the conventional polyurethane film, even if the weather resistance is good, the heat resistance is inferior. For example, the temperature at which the hot melt layer is melted when multilayered with the hot melt layer (usually 130 to 180 ° C. However, it has a problem of melting or breaking.
Furthermore, the polyurethane film as described above has a problem that it is inferior in water resistance and chemical resistance.
このような問題を改良するために、例えば、熱可塑性ポリウレタン樹脂、ポリ塩化ビニル樹脂、可塑剤、微粉末合成シリカ、およびその他の添加剤を混合し、溶剤に溶かして均一溶液もしくは分散液とし、または加熱下に混練して均一の組成物とした上でフィルムに成形し、煮沸水または水蒸気中で加熱した後、急冷処理してなる熱可塑性ポリウレタン樹脂製フィルム及びその製法（特許文献１。）が提案されている。
しかしながら、かかる熱可塑性ポリウレタン樹脂製フィルムは、耐熱性、耐薬品性、耐水性などにまだ不充分であり、実用的に満足できるものではなかった。
以上のように、耐熱性、耐候性、耐水性、及び耐薬品性などの優れた性能を併せ持つポリウレタンフィルムは、未だ開発されていないのが実情であった。
In order to improve such a problem, for example, a thermoplastic polyurethane resin, a polyvinyl chloride resin, a plasticizer, fine powder synthetic silica, and other additives are mixed, dissolved in a solvent to obtain a uniform solution or dispersion, Alternatively, it is kneaded under heating to form a uniform composition, formed into a film, heated in boiling water or steam, and then rapidly cooled, and a method for producing the film (Patent Document 1). Has been proposed.
However, such a film made of a thermoplastic polyurethane resin is still unsatisfactory in terms of heat resistance, chemical resistance, water resistance and the like, and is not satisfactory in practice.
As described above, the actual situation is that a polyurethane film having excellent performance such as heat resistance, weather resistance, water resistance, and chemical resistance has not been developed yet.
本発明の目的は、それを用いてフィルム化し、ホットメルト層と多層化する際に、ホットメルト層が溶融し得る温度条件下でも、該フィルムは溶融又は熱劣化せず優れた耐熱性を堅持しており、且つ優れた耐候性、耐水性、及び耐薬品性をも発揮する新規な耐熱性ポリウレタンフィルムを提供することにある。 It is an object of the present invention to maintain excellent heat resistance without melting or thermal deterioration even under temperature conditions where the hot melt layer can be melted when it is formed into a film and multilayered with the hot melt layer. Another object of the present invention is to provide a novel heat-resistant polyurethane film that exhibits excellent weather resistance, water resistance, and chemical resistance.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、特定のポリウレタン樹脂（Ａ）と、湿式法シリカ（Ｂ）と、紫外線吸収剤（Ｃ）と、分子内にイソシアネート基を３個以上有するポリイソシアネート（Ｄ）を必須の構成成分とするポリウレタン樹脂組成物により、優れた耐熱性、耐候性、耐水性、及び耐薬品性などの優れた特性を有する耐熱性ポリウレタンフィルムを得ることができることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a specific polyurethane resin (A), a wet process silica (B), an ultraviolet absorber (C), and an isocyanate group in the molecule. A polyurethane resin composition comprising three or more polyisocyanate (D) as an essential constituent component provides a heat resistant polyurethane film having excellent characteristics such as excellent heat resistance, weather resistance, water resistance, and chemical resistance. As a result, the present invention has been completed.
即ち、本発明は、１，４−ブタンジオールを含有するポリオール（ａ）と、分子内に水酸基を２個以上有し数平均分子量が１４０〜４０００の範囲のポリオール（ｂ）と、脂環式ジイソシアネート及び／又は芳香族ジイソシアネート（ｃ）から得られるポリウレタン樹脂（Ａ）の少なくとも一種と、湿式法シリカ（Ｂ）と、紫外線吸収剤（Ｃ）と、分子内にイソシアネート基を３個以上有するポリイソシアネート（Ｄ）を必須の構成成分としてなり、前記ポリウレタン樹脂（Ａ）固形分中のジイソシアネート構成単位の含有率が１０〜４０質量％の範囲であり、前記ポリイソシアネート（Ｄ）が、イソホロンジイソシアネート、シクロヘキサンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、キシリレンジイソシアネート、及びテトラメチルキシリレンジイソシアネートからなる群より選ばれる少なくとも一つのジイソシアネートより得られるトリメチロールプロパンアダクトであって、前記ポリイソシアネート（Ｄ）の含有量がポリウレタン樹脂（Ａ）の固形分１００部に対して、５〜３０部の範囲であるポリウレタン樹脂組成物を用いてなることを特徴とする耐熱性ポリウレタンフィルムを提供するものである。
That is, the present invention relates to a polyol (a) containing 1,4-butanediol, a polyol (b) having two or more hydroxyl groups in the molecule and a number average molecular weight in the range of 140 to 4000, and an alicyclic Polyurethane resin (A) obtained from diisocyanate and / or aromatic diisocyanate (c), wet-process silica (B), ultraviolet absorber (C), and poly having three or more isocyanate groups in the molecule Isocyanate (D) is an essential constituent, the content of diisocyanate structural unit in the solid content of the polyurethane resin (A) is in the range of 10 to 40% by mass, and the polyisocyanate (D) is isophorone diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, 及 A trimethylolpropane adduct obtained from at least one diisocyanate selected from the group consisting of tetramethyl xylylene diisocyanate, the content of the polyisocyanate (D) is 100 parts of the solid content of the polyurethane resin (A), the The present invention provides a heat-resistant polyurethane film characterized by using a polyurethane resin composition in the range of 5 to 30 parts.
本発明の耐熱性ポリウレタンフィルムは、耐熱性、耐候性、耐水性、及び耐薬品性などの優れた特性を有しており、例えば、フィルム化などの成形加工の際にも熱履歴による劣化が極めて少なく、安定した連続生産が可能であり生産性にも優れる。
更に、本発明の耐熱性ポリウレタンフィルムはホットメルト層と多層化する際に、ホットメルト層が溶融し得る温度条件下でも、前記耐熱性ポリウレタンフィルムは溶融又は熱劣化せず優れた耐熱性を堅持しており、且つ優れた耐候性、耐水性、及び耐薬品性を発揮する。
The heat-resistant polyurethane film of the present invention has excellent characteristics such as heat resistance, weather resistance, water resistance, and chemical resistance.For example, deterioration due to heat history is also caused during molding processing such as film formation. Very few, stable continuous production is possible, and productivity is excellent.
Further, when the heat-resistant polyurethane film of the present invention is multilayered with the hot melt layer, the heat-resistant polyurethane film maintains excellent heat resistance without being melted or thermally deteriorated even under a temperature condition at which the hot melt layer can be melted. And excellent weather resistance, water resistance, and chemical resistance.
本発明を実施するにあたり、必要な事項を以下に述べる。
本発明の耐熱性ポリウレタンフィルムは、ポリウレタン樹脂（Ａ）の少なくとも一種と、湿式法シリカ（Ｂ）と、紫外線吸収剤（Ｃ）と、分子内にイソシアネート基を３個以上有するポリイソシアネート（Ｄ）を必須の構成成分としてなるポリウレタン樹脂組成物を用いてなるものである。
The matters necessary for carrying out the present invention are described below.
The heat-resistant polyurethane film of the present invention comprises at least one polyurethane resin (A), wet-process silica (B), an ultraviolet absorber (C), and a polyisocyanate (D) having three or more isocyanate groups in the molecule. Is a polyurethane resin composition comprising as an essential component.
まず、本発明の耐熱性ポリウレタンフィルムの製造に用いるポリウレタン樹脂組成物の必須の構成成分について、以下に説明する。
本発明で用いるポリウレタン樹脂（Ａ）とは、１，４−ブタンジオールを含有するポリオール（ａ）と、分子内に水酸基を２個以上有し数平均分子量が１４０〜４０００の範囲のポリオール（ｂ）と、脂環式ジイソシアネート及び／又は芳香族ジイソシアネート（ｃ）を用いてなり、従来公知の反応方法により得ることができ、特に限定しない。
First, the essential components of the polyurethane resin composition used in the production of the heat-resistant polyurethane film of the present invention will be described below.
The polyurethane resin (A) used in the present invention is a polyol (a) containing 1,4-butanediol and a polyol (b) having two or more hydroxyl groups in the molecule and having a number average molecular weight of 140 to 4000. ) And an alicyclic diisocyanate and / or aromatic diisocyanate (c), which can be obtained by a conventionally known reaction method, and is not particularly limited.
本発明で用いるポリウレタン樹脂（Ａ）の合成原料として用いる、イソシアネート基反応性化合物としては、１，４−ブタンジオールを含有するポリオール（ａ）、及び分子内に水酸基を２個以上有し数平均分子量が１４０〜４０００のポリオール（ｂ）を必須として用い、更に目的に応じて、アルカノールアミン及びポリアミンの中から選ばれる少なくとも一つを併用してもよい。前記ポリオール（ａ）及び前記ポリオール（ｂ）との併用により、柔軟性と強靱性を兼ね備える優れた性能のポリウレタンフィルムを得ることができる。 As an isocyanate group-reactive compound used as a raw material for synthesis of the polyurethane resin (A) used in the present invention, a polyol (a) containing 1,4-butanediol, and a number average having two or more hydroxyl groups in the molecule The polyol (b) having a molecular weight of 140 to 4000 is used as an essential component, and at least one selected from alkanolamines and polyamines may be used in combination according to the purpose. By using the polyol (a) and the polyol (b) in combination, an excellent performance polyurethane film having both flexibility and toughness can be obtained.
前記ポリウレタン樹脂（Ａ）の合成原料の一つである、前記ポリオール（ａ）、及びアルカノールアミン、あるいはポリアミンとしては、例えば、エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、２，２−ジメチル−１，３−プロパンジオール、１，６−ヘキサンジオール、３−メチル−１，５−ペンタンジオール、１，８−オクタンジオール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、シクロヘキサン−１，４−ジオール、シクロヘキサン−１，４−ジメタノール、グリセリン、トリメチロールプロパン、トリメチロールエタン、ヘキサントリオール、ペンタエリスリトール、ソルビトール、メチルグリコシドなどのポリオール、あるいはモノエタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ−メチルモノエタノールアミン、Ｎ−ブチルモノエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−ブチルジエタノールアミンなどのアルカノールアミン、あるいはエチレンジアミン、１，３−プロピレンジアミン、１，２−プロピレンジアミン、ヘキサメチレンジアミン、ヒドラジン、ピペラジン、Ｎ，Ｎ’−ジアミノピペラジン、２−メチルピペラジン、４，４’−ジアミノジシクロヘキシルメタン、イソホロンジアミン、ジアミノベンゼン、ジフェニルメタンジアミン、メチレンビスジクロロアニリンなどのポリアミンの１種又は２種以上の混合物などが挙げられる。これら化合物の中で、好ましくはグリコール類であり、より好ましくは直鎖グリコールであり、特に好ましくは１，４−ブタンジオールである。 Examples of the polyol (a) and alkanolamine or polyamine, which are one of the raw materials for synthesizing the polyurethane resin (A), include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, , 3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol , Diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, glycerin, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, sol Polyols such as Tol, methyl glycoside, monoethanolamine, diethanolamine, triethanolamine, N-methylmonoethanolamine, N-butylmonoethanolamine, N-methyldiethanolamine, alkanolamines such as N-butyldiethanolamine, or ethylenediamine, 1,3-propylenediamine, 1,2-propylenediamine, hexamethylenediamine, hydrazine, piperazine, N, N′-diaminopiperazine, 2-methylpiperazine, 4,4′-diaminodicyclohexylmethane, isophoronediamine, diaminobenzene, Examples thereof include one or a mixture of two or more polyamines such as diphenylmethanediamine and methylenebisdichloroaniline. Among these compounds, glycols are preferable, linear glycols are more preferable, and 1,4-butanediol is particularly preferable.
前記ポリウレタン樹脂（Ａ）の合成原料の一つである、前記ポリオール（ａ）と、目的に応じて選択されるアルカノールアミン及びポリアミンから選ばれる少なくとも一つとの、ポリウレタン樹脂（Ａ）の固形分１００部中の含有量は好ましくは１〜１５部の範囲である。前記ポリウレタン樹脂（Ａ）が、前記ポリオール（ａ）をかかる範囲で含有すれば、優れた強靱性と耐熱性を有するポリウレタンフィルムを得ることができる。 Solid content 100 of the polyurethane resin (A), which is one of the raw materials for synthesizing the polyurethane resin (A), and the polyol (a) and at least one selected from alkanolamine and polyamine selected according to the purpose. The content in parts is preferably in the range of 1 to 15 parts. If the polyurethane resin (A) contains the polyol (a) in such a range, a polyurethane film having excellent toughness and heat resistance can be obtained.
また、前記ポリウレタン樹脂（Ａ）の合成原料の一つである、分子内に水酸基を２個以上有し数平均分子量が１４０〜４０００の範囲のポリオール（ｂ）としては、例えばポリエステルポリオール、ポリエーテルポリオール、ポリエステルエーテルポリオール、及びこれらの混合物などが挙げられ、これらは単独使用でもよく２種以上を併用してもよい。 Examples of the polyol (b), which is one of the raw materials for synthesizing the polyurethane resin (A), having two or more hydroxyl groups in the molecule and having a number average molecular weight in the range of 140 to 4000, include, for example, polyester polyols and polyethers. Examples thereof include polyols, polyester ether polyols, and mixtures thereof. These may be used alone or in combination of two or more.
前記ポリエステルポリオールとしては、特に限定しないが、例えば、エチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール、２，２−ジメチル−１，３−プロパンジオール、１，６−ヘキサンジオール、３−メチル−１，５−ペンタンジオール、１，８−オクタンジオール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、シクロヘキサン−１，４−ジオール、シクロヘキサン−１，４−ジメタノール、グリセリン、トリメチロールプロパン、トリメチロールエタン、ヘキサントリオール、ペンタエリスリトオール、ソルビトール、メチルグリコシドなどの多価アルコールの１種又は２種以上と、コハク酸、アジピン酸、グルタル酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、無水フタル酸、無水テトラヒドロフタル酸、無水グルタル酸、マレイン酸、無水マレイン酸、ヘキサヒドロイソフタル酸などの多塩基酸あるいはメチルエステル化合物などの低級アルキルエステルあるいは酸無水物の１種又は２種以上との縮合物などが挙げられる。
また、前記ポリオールを開始剤とするγ−ブチロラクトン、ε−カプロラクトンなどの開環重合体やポリ（ヘキサメチレンカーボネート）ジオールなども挙げられる。
Examples of the polyester polyol include, but are not limited to, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl- 1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1, One or more polyhydric alcohols such as 4-diol, cyclohexane-1,4-dimethanol, glycerin, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, sorbitol, methylglycoside, Succinic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, glutaric anhydride, maleic acid, Examples thereof include polybasic acids such as maleic anhydride and hexahydroisophthalic acid, lower alkyl esters such as methyl ester compounds, and condensates with one or more of acid anhydrides.
Moreover, ring-opening polymers such as γ-butyrolactone and ε-caprolactone using the polyol as an initiator, and poly (hexamethylene carbonate) diol are also included.
前記ポリエーテルポリオールとしては、特に限定しないが、例えば、前記ポリオール及びポリアミンの１種又は２種以上を開始剤とするエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、スチレンオキサイド、テトラヒドロフランなどの単独あるいは２種以上の開環重合体などが挙げられる。 Although it does not specifically limit as said polyether polyol, For example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran etc. which use 1 type, or 2 or more types of the said polyol and polyamine as an initiator individually or 2 types or more And a ring-opening polymer.
前記ポリエステルエーテルポリオールとしては、特に限定しないが、例えば、前記ポリエステルポリオール及びポリエーテルポリオールの１種又は２種以上から選ばれるポリオールの共重合体などが挙げられる。 Although it does not specifically limit as said polyester ether polyol, For example, the copolymer of the polyol chosen from the 1 type (s) or 2 or more types of the said polyester polyol and polyether polyol, etc. are mentioned.
前記ポリウレタン樹脂（Ａ）の合成原料の一つである、分子内に水酸基を２個以上有し数平均分子量が１４０〜４０００の範囲のポリオール（ｂ）の、ポリウレタン樹脂（Ａ）の固形分１００部中の含有量は、好ましくは４０〜８０部の範囲である。前記ポリウレタン樹脂（Ａ）が、前記ポリオール（ｂ）をかかる範囲で含有すれば、優れた柔軟性を有するフィルム材料を得ることができる。 The solid content 100 of the polyurethane resin (A), which is one of the synthetic raw materials for the polyurethane resin (A), is the polyol (b) having two or more hydroxyl groups in the molecule and having a number average molecular weight in the range of 140 to 4000. The content in the part is preferably in the range of 40 to 80 parts. When the polyurethane resin (A) contains the polyol (b) in such a range, a film material having excellent flexibility can be obtained.
また、前記ポリウレタン樹脂（Ａ）の合成原料で一つある脂環式ジイソシアネート及び／又は芳香族ジイソシアネート（ｃ）とは、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ナフタレンジイソシアネート、フェニレンジイソシアネート、リジンジイソシアネートなどの芳香族ジイソシアネート類、あるいはシクロヘキサンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネートなどの脂環式ジイソシアネート類、あるいはキシリレンジイソシアネート、テトラメチルキシリレンジイソシアネートなどの芳香族環にメチレン基を介してイソシアネート基が結合しているジイソシアネート類でもよく、これらの１種又は２種以上の混合物も使用できる。 The alicyclic diisocyanate and / or aromatic diisocyanate (c), which is one of the raw materials for synthesizing the polyurethane resin (A), includes, for example, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, phenylene diisocyanate, lysine diisocyanate and the like. An aromatic diisocyanate, or an alicyclic diisocyanate such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, or an aromatic ring such as xylylene diisocyanate or tetramethylxylylene diisocyanate is bonded with an isocyanate group via a methylene group. Diisocyanates may be used, and one or a mixture of two or more of these may be used.
前記ポリウレタン樹脂（Ａ）固形分中のジイソシアネート構成単位の含有率は、好ましくは１０〜４０質量％の範囲である。前記ポリウレタン樹脂（Ａ）が、前記ジイソシアネート構成単位をかかる範囲で有すれば、優れた強靱性と耐熱性を有するフィルム材料を得ることができる。 The content of the diisocyanate structural unit in the solid content of the polyurethane resin (A) is preferably in the range of 10 to 40% by mass. If the said polyurethane resin (A) has the said diisocyanate structural unit in this range, the film material which has the outstanding toughness and heat resistance can be obtained.
前記ポリウレタン樹脂（Ａ）が、ポリオール（ａ）及び／又はポリオール（ｂ）と、ビスフェノールＡ−アルキレンオキサイド付加物とを用いることが好ましく、かかるビスフェノールＡ−アルキレンオキサイド付加物としては、例えば、ビスフェノールＡのエチレンオキサイド、プロピレンオキサイド、ブチレンキサイド、及びテトラメチレンオキサイド等のアルキレンオキサイドのｎモル付加物（但し、ｎは０を超える数である。）などが挙げられる。
これらビスフェノールＡ−アルキレンオキサイド付加物の中でも、耐熱性などの特性を一層向上可能な点から、ビスフェノールＡのエチレンオキサイド２モル付加物がより好ましい。
The polyurethane resin (A) preferably uses a polyol (a) and / or a polyol (b) and a bisphenol A-alkylene oxide adduct . Examples of the bisphenol A-alkylene oxide adduct include bisphenol A N-mole adducts of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and tetramethylene oxide (where n is a number exceeding 0).
Among these bisphenol A-alkylene oxide adducts, an ethylene oxide 2 mol adduct of bisphenol A is more preferable because it can further improve characteristics such as heat resistance.
前記ビスフェノールＡ−アルキレンオキサイド付加物のポリウレタン樹脂（Ａ）１００部中の含有量は、好ましくは１〜２０部の範囲である。前記ビスフェノールＡ−アルキレンオキサイド付加物をかかる条件で用いれば、得られる耐熱性ポリウレタンフィルムを、例えばホットメルト層と多層化する際に、ホットメルト層が溶融し得る温度条件下でも、該フィルムは溶融又は熱劣化せずに優れた耐熱性を堅持し、且つ優れた耐候性をも発揮することができる。 The content of the bisphenol A-alkylene oxide adduct in 100 parts of the polyurethane resin (A) is preferably in the range of 1 to 20 parts. If the bisphenol A-alkylene oxide adduct is used under such conditions, the resulting heat-resistant polyurethane film can be melted even under temperature conditions where the hot melt layer can be melted when multilayered with the hot melt layer, for example. Alternatively, excellent heat resistance can be maintained without thermal deterioration, and excellent weather resistance can also be exhibited.
前記ポリウレタン樹脂（Ａ）は、１，４−ブタンジオールを含有するポリオール（ａ）と、分子内に水酸基を２個以上有し数平均分子量が１４０〜４０００の範囲のポリオール（ｂ）と、脂環式ジイソシアネート及び／又は芳香族ジイソシアネート（ｃ）から得られ、前記ジイソシアネート（ｃ）の含有率が１０〜４０質量％の範囲であって、これら化合物を原料に公知慣用の方法で反応させ得ることができ、反応方法としては、例えば、溶液反応、非水ディスパージョン反応、水性ディスパージョン反応など各種の方法が採用でき、特に限定しないが、これらの中でも、反応を制御し易い点で溶液反応が好ましい。
前記溶液反応の方法としては、例えば、反応を阻害しない溶剤でポリオール（ｂ）を希釈し、次いでポリオール（ａ）と、目的に応じてアルカノールアミン及びポリアミンの中から選ばれる少なくとも一つを併用し、イソシアネートを加えて、適切な反応条件（例えば、８０℃で３時間反応など。）にて反応させて、ポリウレタン樹脂（Ａ）の溶液を得る方法などが挙げられるが、特にこれに限定するものではない。
The polyurethane resin (A) comprises a polyol (a) containing 1,4-butanediol, a polyol (b) having two or more hydroxyl groups in the molecule and a number average molecular weight in the range of 140 to 4000, It is obtained from a cyclic diisocyanate and / or an aromatic diisocyanate (c), and the content of the diisocyanate (c) is in the range of 10 to 40% by mass, and these compounds can be reacted with raw materials by a known and conventional method. As the reaction method, for example, various methods such as solution reaction, non-aqueous dispersion reaction, aqueous dispersion reaction and the like can be adopted, and there is no particular limitation, but among these, the solution reaction is easy because the reaction is easy to control. preferable.
As the method of the solution reaction, for example, the polyol (b) is diluted with a solvent that does not inhibit the reaction, and then the polyol (a) is used in combination with at least one selected from alkanolamine and polyamine depending on the purpose. , A method of adding a isocyanate and reacting under appropriate reaction conditions (for example, reaction at 80 ° C. for 3 hours) to obtain a solution of the polyurethane resin (A), but is particularly limited thereto. is not.
また、本発明の耐熱性ポリウレタンフィルムに用いる、ポリウレタン樹脂組成物の主成分であるポリウレタン樹脂（Ａ）以外に使用可能なその他の樹脂としては、本発明の目的を阻害しない樹脂であれば特に限定せず、例えば、アクリル樹脂、ポリエステル樹脂、ポリアミド樹脂、エチレン−酢酸ビニル樹脂（ＥＶＡ）、ロジンエステル等が挙げられ、これらは単独使用でもよく２種以上を併用してもよい。 In addition to the polyurethane resin (A) that is the main component of the polyurethane resin composition used in the heat-resistant polyurethane film of the present invention, other resins that can be used are particularly limited as long as they do not impair the object of the present invention. For example, an acrylic resin, a polyester resin, a polyamide resin, an ethylene-vinyl acetate resin (EVA), a rosin ester, and the like may be used. These may be used alone or in combination of two or more.
前記ポリウレタン樹脂（Ａ）を製造する際に用いる溶剤としては、反応を阻害しない溶剤であればよく、特に限定しないが、例えば、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチルなどのエステル類、アセトン、メチルエチルケトン、メチルブチルケトン、シクロヘキサノンなどのケトン類、メチルセロソルブアセテート、ブチルセロソルブアセテートなどのエーテル類エステル、トルエン、キシレンなどの芳香族炭化水素系溶剤、ジメチルホルムアミド、ジメチルアセトアミドなどのアミド類などが挙げられ、これらを単独使用してもよく２種以上を併用してもよい。
また、ポリウレタン樹脂（Ａ）を製造する際の溶剤の使用量は、反応を阻害しない範囲であれば、特に限定しない。
The solvent used in producing the polyurethane resin (A) is not particularly limited as long as it does not inhibit the reaction. Examples thereof include esters such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, acetone. , Ketones such as methyl ethyl ketone, methyl butyl ketone and cyclohexanone, ether esters such as methyl cellosolve acetate and butyl cellosolve acetate, aromatic hydrocarbon solvents such as toluene and xylene, and amides such as dimethylformamide and dimethylacetamide These may be used alone or in combination of two or more.
Moreover, the usage-amount of the solvent at the time of manufacturing a polyurethane resin (A) will not be specifically limited if it is a range which does not inhibit reaction.
次いで、本発明の耐熱性ポリウレタンフィルムに用いるポリウレタン樹脂組成物の必須の構成成分である湿式法シリカ（Ｂ）について、以下に説明する。
一般に合成シリカは、湿式法シリカと乾式法シリカに分類される。
湿式法シリカは、ケイ酸ソーダと硫酸を混合し、ケイ酸ゾルを生成させたものである。湿式法シリカには２種類あり、一つは、ケイ酸ゾルの一次粒子を形成した後、三次元的な二次凝集体を形成しゲル化させ、これを粉砕したものであり「ゲル法シリカ」と呼ばれ、平均粒子径が通常２〜５μｍの範囲である。もう一つは、ケイ酸ゾルの二次凝集体の成長を止め、沈降したもので、「沈降法シリカ」と呼ばれ、平均粒子径が０．１μｍ以下のものである。一方、乾式法シリカは、気層中で燃焼加水分解して作るものであり、平均粒子径が０．１μｍ以下である。
Next, the wet process silica (B), which is an essential component of the polyurethane resin composition used in the heat-resistant polyurethane film of the present invention, will be described below.
In general, synthetic silica is classified into wet process silica and dry process silica.
Wet process silica is a mixture of sodium silicate and sulfuric acid to produce a silicate sol. There are two types of wet process silica. One is the one in which primary particles of silicate sol are formed, then a three-dimensional secondary aggregate is formed and gelled, and this is pulverized. The average particle size is usually in the range of 2-5 μm. The other is a silicate sol secondary aggregate that has stopped growing and settled, and is called “precipitated silica” and has an average particle size of 0.1 μm or less. On the other hand, dry process silica is produced by combustion hydrolysis in the air layer, and has an average particle size of 0.1 μm or less.
本発明の耐熱性ポリウレタンフィルムに用いるシリカとしては、湿式法シリカ（Ｂ）が好ましく、その中でも平均粒子径が２〜５μｍの範囲のゲル法シリカがより好ましい。前記湿式法シリカ（Ｂ）の平均粒子径がかかる範囲にあれば、本発明の耐熱性ポリウレタンフィルムを巻き取り工程において、優れたブロッキング防止効果を発揮し、生産工程でのトラブル防止に極めて有効である。 As the silica used in the heat-resistant polyurethane film of the present invention, wet method silica (B) is preferable, and gel method silica having an average particle diameter in the range of 2 to 5 μm is more preferable. If the average particle diameter of the wet process silica (B) is within the range, the heat-resistant polyurethane film of the present invention exhibits an excellent anti-blocking effect in the winding process, and is extremely effective in preventing troubles in the production process. is there.
前記湿式法シリカ（Ｂ）の含有量は、ポリウレタン樹脂（Ａ）１００部に対して、好ましくは５〜３０部の範囲であり、より好ましくは７〜２０部の範囲である。前記耐熱性ポリウレタンフィルムが湿式法シリカ（Ｂ）をかかる範囲で含有すれば、前記フィルムの巻き取り時のブロッキング防止に優れた効果を発揮しフィルムの生産性が向上し、付加価値の高い耐熱性ポリウレタンフィルムを得ることができる。 The content of the wet process silica (B) is preferably in the range of 5 to 30 parts, more preferably in the range of 7 to 20 parts with respect to 100 parts of the polyurethane resin (A). If the heat-resistant polyurethane film contains the wet process silica (B) in such a range, the film has an excellent effect in preventing blocking at the time of winding the film, and the productivity of the film is improved. A polyurethane film can be obtained.
次いで、本発明の耐熱性ポリウレタンフィルムに用いるポリウレタン樹脂組成物の必須の構成成分である紫外線吸収剤（Ｃ）について、以下に説明する。
本発明の耐熱性ポリウレタンフィルムに用いる紫外線吸収剤（Ｃ）としては、特に限定しないが、例えば、メチルヒドロキシフェニルベンゾトリアゾール、ブチルメチルヒドロキシフェニルベンゾトリアゾール、ジブチルヒドロキシフェニルベンゾトリアゾールなどに代表されるベンゾトリアゾール系化合物、あるいはビス（テトラメチルピペリジル）セバケート、ビス（ペンタメチルピペリジル）セバケートなどに代表されるヒンダードアミン系化合物などが挙げられる。
Next, the ultraviolet absorbent (C), which is an essential component of the polyurethane resin composition used for the heat resistant polyurethane film of the present invention, will be described below.
Although it does not specifically limit as an ultraviolet absorber (C) used for the heat resistant polyurethane film of this invention, For example, benzotriazole represented by methylhydroxyphenyl benzotriazole, butylmethyl hydroxyphenyl benzotriazole, dibutyl hydroxyphenyl benzotriazole, etc. And hindered amine compounds represented by bis (tetramethylpiperidyl) sebacate, bis (pentamethylpiperidyl) sebacate, and the like.
前記紫外線吸収剤（Ｃ）の含有量は、ポリウレタン樹脂（Ａ）１００部に対して、好ましくは０．１〜７部の範囲である。前記耐熱性ポリウレタンフィルムが紫外線吸収剤（Ｃ）をかかる範囲で含有すれば、例えば、複層フィルム等として用いた場合、変色がなく、高品質で付加価値の高いフィルム材料を得ることができる。 The content of the ultraviolet absorber (C) is preferably in the range of 0.1 to 7 parts with respect to 100 parts of the polyurethane resin (A). If the heat-resistant polyurethane film contains the ultraviolet absorber (C) in such a range, for example, when used as a multilayer film, a film material having no discoloration and high quality and high added value can be obtained.
更に、本発明の耐熱性ポリウレタンフィルムに用いるポリウレタン樹脂組成物の必須の構成成分である、分子内にイソシアネート基を３個以上有するポリイソシアネート（Ｄ）としては、イソホロンジイソシアネート、シクロヘキサンジイソシアネート、ジシクロヘキシルメタンジイソシアネートなどの脂環式ジイソシアネート、及びキシリレンジイソシアネート、テトラメチルキシリレンジイソシアネートなどの芳香族環にメチレン基を介してイソシアネート基が結合しているジイソシアネート、などより得られるトリメチロールプロパンアダクトからなる群より選ばれる少なくとも一つが好ましく、これらポリイソシアネートの中でも、耐熱性、耐候性、耐水性、及び耐薬品性などの性能を一層向上可能な点から、キシリレンジイソシアネートのトリメチロールプロパンアダクト（ＸＤＩ−ＴＭＰ）がより好ましい。
Furthermore, polyisocyanate (D) having 3 or more isocyanate groups in the molecule, which is an essential component of the polyurethane resin composition used in the heat-resistant polyurethane film of the present invention, is isophorone diisocyanate, cyclohexane diisocyanate, dicyclohexylmethane diisocyanate. Selected from the group consisting of trimethylolpropane adducts obtained from alicyclic diisocyanates such as, and diisocyanates in which an isocyanate group is bonded via an methylene group to an aromatic ring such as xylylene diisocyanate and tetramethylxylylene diisocyanate At least one of these polyisocyanates is preferable. Among these polyisocyanates, xylylene diisocyanate can be further improved in performance such as heat resistance, weather resistance, water resistance, and chemical resistance. Over preparative trimethylolpropane adduct (XDI-TMP) is more preferable.
前記ポリイソシアネート（Ｄ）の含有量は、ポリウレタン樹脂（Ａ）１００部に対して、好ましくは５〜３０部の範囲である。前記耐熱性ポリウレタンフィルムが、ポリイソシアネート（Ｄ）をかかる範囲で含有すれば、例えば、厚み２０〜６０μｍの範囲のフィルムを形成した際に、耐熱性試験において１８０℃で１５０％の伸長に少なくとも３秒間耐えることができるほどの優れた耐熱性を有しており、且つ、耐候性試験においてサンシャインウェザーメーターによる２００時間促進試験（雰囲気温度６３℃で１２０分に一度１８分間散水。）の実施前後で、フィルムの黄変度が色差計のΔＮの差（即ち、ΔＮの差＝２００時間後のΔＮ値−０時間のΔＮ値）で２０以下であるほどの優れた耐候性を有している、例えばホットメルト層と多層化する際に、ホットメルト層が溶融し得る温度条件でも、該フィルムは溶融又は熱劣化せず優れた耐熱性を堅持し、且つ優れた耐候性、耐水性、及び耐薬品性をも有し、高品質で付加価値の高いフィルム材料を得ることができる。 The content of the polyisocyanate (D) is preferably in the range of 5 to 30 parts with respect to 100 parts of the polyurethane resin (A). If the heat-resistant polyurethane film contains polyisocyanate (D) in such a range, for example, when a film having a thickness in the range of 20 to 60 μm is formed, at least 3 in 150% elongation at 180 ° C. in the heat resistance test. Before and after the implementation of a 200-hour accelerated test with a sunshine weather meter (watering once at 120 minutes at an atmospheric temperature of 63 ° C. for 18 minutes) in a weather resistance test. The film has excellent weather resistance such that the yellowing degree of the film is 20 or less in the difference of ΔN of the colorimeter (that is, the difference of ΔN = ΔN value after 200 hours−ΔN value of 0 hour), For example, when a multilayer with a hot melt layer is used, the film maintains excellent heat resistance without melting or thermal deterioration even under temperature conditions at which the hot melt layer can be melted. A film material having weather resistance, water resistance, and chemical resistance, high quality and high added value can be obtained.
本発明の耐熱性ポリウレタンフィルムは、上記の如く、優れた耐熱性及び耐候性を兼ね備えているので、例えば、加工工程で前記耐熱性ポリウレタンフィルムをホットメルト層と多層化した際に、ホットメルト層を溶融させ得る温度条件下においても溶融又は熱劣化せず充分に耐え得ることができ、且つ苛酷な気候環境下においても性能が著しく低下することもなく、実用上何ら問題なく使用できる。
尚、本発明でいう耐熱性試験とは、ポリウレタン樹脂組成物を用いて作成したフィルムについて、ホットプレートを用いて後述する条件にて評価したものである。
また、本発明でいう耐候性試験とは、ポリウレタン樹脂組成物を用いて作成したフィルムについて、サンシャインウェザーメーターを用いて、後述する条件にて評価したものである。
Since the heat-resistant polyurethane film of the present invention has excellent heat resistance and weather resistance as described above, for example, when the heat-resistant polyurethane film is multilayered with the hot-melt layer in the processing step, the hot-melt layer It can be sufficiently tolerated without melting or heat deterioration even under temperature conditions where it can be melted, and can be used without any problem in practice without any significant deterioration in performance even under severe climatic environments.
In addition, the heat resistance test as used in the field of this invention evaluates the film created using the polyurethane resin composition on the conditions mentioned later using a hotplate.
The weather resistance test referred to in the present invention is an evaluation of a film prepared using a polyurethane resin composition under the conditions described later using a sunshine weather meter.
また、本発明の耐熱性ポリウレタンフィルムに用いるポリウレタン樹脂組成物には、酸化チタンやカーボンブラック等の各種顔料、あるいは、アゾ染料やアントラキノン染料等の各種染料、からなる群より選ばれる少なくとも一種を、ポリウレタン樹脂（Ａ）１００部に対して、好ましくは１〜４０部の範囲で配合することができ、これらを適宜選択し配合することにより、用途に応じた色目に調色することができる。
本発明の耐熱性ポリウレタンフィルムにおいて、顔料として酸化チタンを用い、その配合量を上記範囲に設定すれば、優れた隠蔽性も付与することができる。
The polyurethane resin composition used for the heat-resistant polyurethane film of the present invention includes at least one selected from the group consisting of various pigments such as titanium oxide and carbon black, or various dyes such as azo dyes and anthraquinone dyes, It can mix | blend preferably in the range of 1-40 parts with respect to 100 parts of polyurethane resins (A), and it can color to the color according to a use by selecting and mix | blending these suitably.
In the heat-resistant polyurethane film of the present invention, if titanium oxide is used as a pigment and the blending amount is set in the above range, excellent concealability can be imparted.
更に、本発明の耐熱性ポリウレタンフィルムに用いるポリウレタン樹脂組成物には、レべリング剤を配合してもよく、例えば、アクリル系重合物、アクリルポリマーのアミン塩、珪素化合物、高級アルコール、ビニル系重合物、及びシリコ−ン、からなる群より選ばれる少なくとも一つが挙げられ、これらの中では、アクリル系重合体が好ましい。
前記ポリウレタン樹脂組成物における前記レベリング剤の配合量は、ポリウレタン樹脂（Ａ）１００部に対して、好ましくは０．０１〜５部の範囲であり、より好ましくは０．０５〜２部の範囲である。
一般にポリウレタン樹脂組成物の溶液に顔料などを添加して離型紙上に塗工する際に、塗工した樹脂溶液から気泡が抜け難くなる場合があるが、このようなおそれがある場合に、前記レベリング剤をかかる配合量の範囲で用いれば、表面性に優れるフィルムを得ることができる。
Furthermore, the polyurethane resin composition used in the heat-resistant polyurethane film of the present invention may contain a leveling agent, such as an acrylic polymer, an amine salt of an acrylic polymer, a silicon compound, a higher alcohol, a vinyl type. Examples include at least one selected from the group consisting of a polymer and a silicone, and among these, an acrylic polymer is preferable.
The blending amount of the leveling agent in the polyurethane resin composition is preferably in the range of 0.01 to 5 parts, more preferably in the range of 0.05 to 2 parts, relative to 100 parts of the polyurethane resin (A). is there.
In general, when a pigment or the like is added to a solution of a polyurethane resin composition and coated on a release paper, bubbles may be difficult to escape from the coated resin solution. If a leveling agent is used in the range of this compounding quantity, the film which is excellent in surface property can be obtained.
本発明の耐熱性ポリウレタンフィルムに用いるポリウレタン樹脂組成物には、安定剤、充填剤などの各種添加剤を本発明の目的を阻害しない範囲で、単独使用又は２種以上を併用することができる。
前記安定剤としては、公知慣用の安定剤が使用可能であり、例えば、ヒンダードフェノール系化合物などの酸化防止剤、カルボジイミド化合物などの加水分解防止剤などが挙げられ、特に限定しない。
前記充填剤しては、公知慣用の充填剤が使用可能であり、例えば、炭酸カルシウム、タルク、クレー、ベントナイトなどが挙げられ、特に限定しない。
In the polyurethane resin composition used for the heat-resistant polyurethane film of the present invention, various additives such as stabilizers and fillers can be used alone or in combination of two or more, as long as the object of the present invention is not impaired.
As the stabilizer, known and commonly used stabilizers can be used, and examples thereof include antioxidants such as hindered phenol compounds and hydrolysis inhibitors such as carbodiimide compounds, and are not particularly limited.
As the filler, a known and commonly used filler can be used, and examples thereof include calcium carbonate, talc, clay, bentonite and the like, and are not particularly limited.
本発明の耐熱性ポリウレタンフィルムの製造方法としては、公知慣用の製造方法が採用でき、特に限定しないが、例えば、押出成形法、ラミネート法等が挙げられる。これらの中でも、精密な製造方法として、ラミネート法が好ましく、例えば、溶液反応により得られたポリウレタン樹脂（Ａ）の溶液に、湿式法シリカ（Ｂ）と、紫外線吸収剤（Ｃ）と、架橋剤としてポリイソシアネート（Ｄ）と、その他添加剤などを配合した後、離型紙上に流延し、溶剤を乾燥した後、巻き取る方法が挙げられる。 As a method for producing the heat-resistant polyurethane film of the present invention, a publicly known and commonly used production method can be adopted and is not particularly limited, and examples thereof include an extrusion molding method and a laminating method. Among these, as a precise manufacturing method, a laminating method is preferable. For example, a wet process silica (B), an ultraviolet absorber (C), and a crosslinking agent are added to a polyurethane resin (A) solution obtained by a solution reaction. As a method, after blending polyisocyanate (D) and other additives, it is cast on a release paper, dried after the solvent is dried, and then wound up.
以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例のみに限定されるものではない。
また、文中「部」及び「％」は特に断わりのない限り質量基準である。
尚、諸特性は以下に記載した方法により評価した。
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.
In the text, “parts” and “%” are based on mass unless otherwise specified.
Various characteristics were evaluated by the methods described below.
［耐熱性ポリウレタンフィルムの作成方法］
ポリウレタン樹脂（Ａ）と、湿式法シリカ（Ｂ）と、紫外線吸収剤（Ｃ）と、ポリイソシアネート（Ｄ）と、必要に応じてその他の添加剤を配合したフィルム用ポリウレタン樹脂組成物を離型紙に塗布し、７０℃で２分間乾燥後、１４０℃で４分間乾燥し、更に、３５℃で相対湿度５０％の条件下で２日間熟成して、厚みが３５〜５０μｍの範囲の耐熱性ポリウレタンフィルムを作成した。
[Method for making heat-resistant polyurethane film]
A polyurethane resin composition for film containing a polyurethane resin (A), a wet process silica (B), an ultraviolet absorber (C), a polyisocyanate (D), and other additives as required is a release paper. , Dried at 70 ° C. for 2 minutes, then dried at 140 ° C. for 4 minutes, and further aged for 2 days at 35 ° C. under a relative humidity of 50%. A film was created.
［耐熱性試験の評価方法］
１５０％伸長させた耐熱性ポリウレタンフィルム（巾１ｃｍ）を１８０℃に設定したホットプレートの端部に３秒間押し当て、耐熱性ポリウレタンフィルムが切断するか、否かにより判断した。
耐熱性の判定基準。
◎；切断せずに、元の状態に復元する。
○；切断せずに、元の状態に復元するが、伸長し復元した部分に白く形が残る。
△；切断しないが、伸びた状態から元の状態に復元しない
×；切断した。
[Evaluation method of heat resistance test]
A 150% stretched heat resistant polyurethane film (width 1 cm) was pressed against the end of a hot plate set at 180 ° C. for 3 seconds to determine whether or not the heat resistant polyurethane film was cut.
Criteria for heat resistance.
A: Restores the original state without cutting.
○: The original state is restored without cutting, but a white shape remains in the restored and restored part.
Δ: Not cut, but not restored from the stretched state ×: Cut.
［耐候性試験の評価方法］
サンシャインスーパーロングライフウェザーメーター（スガ試験器株式会社製）を用いて、ＪＩＳ Ｚ−９１０５に準拠して、放射照度許容範囲２５５±４５Ｗ／ｍ２で２００時間促進試験（試験条件；雰囲気温度６３℃、１２０分に一度１８分間散水。）をした後、耐熱性ポリウレタンフィルムの黄変度を色差計（ミノルタ製 分光側色計 ＣＭ３５００−Ｄ）のΔＮの差で評価した。
尚、促進試験前に予め耐熱性ポリウレタンフィルムのΔＮ値を測定し、その値を０時間のΔＮ値とした。
ΔＮの差＝２００時間後のΔＮ値−０時間のΔＮ値
[Evaluation method of weather resistance test]
Using a sunshine super long life weather meter (manufactured by Suga Test Instruments Co., Ltd.), in accordance with JIS Z-9105, an irradiance allowable range of 255 ± 45 W / m 2 for 200 hours accelerated test (test conditions; ambient temperature 63 ° C. The water-resistant polyurethane film was evaluated for yellowing by the difference of ΔN of a color difference meter (spectral color meter CM3500-D manufactured by Minolta).
In addition, before the acceleration test, the ΔN value of the heat resistant polyurethane film was measured in advance, and the value was taken as the ΔN value for 0 hour.
ΔN difference = ΔN value after 200 hours−ΔN value at 0 hour
［耐水性及び耐溶剤性（耐トルエン性）の評価方法］
後述する合成例５で調製したホットメルト用ポリウレタン樹脂（Ｅ）の溶液を、離型紙上に乾燥後の樹脂厚が５０μｍになるように流延し、７０℃で３分間乾燥、次いで１３０℃で３分間乾燥し、ポリウレタンのホットメルトフィルムを得た。１０ｃｍ×１０ｃｍの２枚の耐熱性ポリウレタンフィルムの間に、９ｃｍ×７ｃｍのホットメルトフィルムをはさみ込み、１５０℃に設定した熱プレスにより、１ｋｇ／ｃｍ２の面圧で５秒間圧着して多層フィルムを得た。得られた多層フィルムを用いて、水及びトルエン中に２５℃で１２時間浸漬し、表面の外観（浮き、ハガレ等）の状態を目視観察し、下記の基準に従い４段階評価を行った。
耐水性及び耐溶剤性（耐トルエン性）の評価基準。
◎；浮き、ハガレが全く無し。
○；浮き、ハガレが僅かにあり。
△；約半分に浮き、ハガレがあり。
×：処理後落下。
[Method for evaluating water resistance and solvent resistance (toluene resistance)]
A hot melt polyurethane resin (E) solution prepared in Synthesis Example 5 described later is cast on a release paper so that the resin thickness after drying is 50 μm, dried at 70 ° C. for 3 minutes, and then at 130 ° C. Drying for 3 minutes gave a polyurethane hot melt film. A multi-layer film in which a hot-melt film of 9 cm × 7 cm is sandwiched between two heat-resistant polyurethane films of 10 cm × 10 cm and is pressed for 5 seconds at a surface pressure of 1 kg / cm 2 by a hot press set at 150 ° C. Got. Using the obtained multilayer film, it was immersed in water and toluene at 25 ° C. for 12 hours, the surface appearance (floating, peeling, etc.) was visually observed, and four-stage evaluation was performed according to the following criteria.
Evaluation criteria for water resistance and solvent resistance (toluene resistance).
A: No floating or peeling.
○: Floating and slightly peeled.
Δ: Floating in about half and peeling.
X: Dropped after treatment.
［耐ブロッキング試験の評価方法］
耐熱性ポリウレタンフィルムを、５ｃｍ×５ｃｍの大きさに切り出して試験片とし、重ね合わせ、７０℃雰囲気下荷重２００ｇ／ｃｍ２をかけ、２４時間後に剥がす操作を行い、剥離するか否かで評価する。
耐ブロッキング性の評価基準。
○：剥離する
×：剥離しない
[Evaluation method for anti-blocking test]
A heat-resistant polyurethane film is cut into a size of 5 cm × 5 cm to form a test piece, which is superposed, subjected to a load of 200 g / cm 2 under a 70 ° C. atmosphere, peeled off after 24 hours, and evaluated by whether or not it is peeled off. .
Evaluation criteria for blocking resistance.
○: Peel ×: Do not peel
［数平均分子量の測定方法］
測定機種；東ソー株式会社製ＧＰＣ ＨＬＣ８２２０
カラム ；東ソーゲル ＨＸＬシリーズ使用
測定条件；測定溶媒ＴＨＦ溶液、測定温度４０℃
[Measurement method of number average molecular weight]
Measurement model: GPC HLC8220 manufactured by Tosoh Corporation
Column: Tosohel HXL series used Measurement conditions: Measurement solvent THF solution, Measurement temperature 40 ° C
［合成例１］《ポリウレタン樹脂（Ａ−１）の溶液の調製》
数平均分子量（Ｍｎ）が２０００のポリブチレンアジペートジオールの１００部を、ジメチルホルムアミド（ＤＭＦ）／メチルエチルケトン（ＭＥＫ）＝５０／５０質量比の混合溶剤で希釈し、１，４−ブタンジオール（ＢＧ）を８．４部及びジフェニルメタンジイソシアネート（ＭＤＩ）を３５．０部加えて、８０℃で３時間反応させた後、更に必要量のＭＤＩを追加し、樹脂濃度５０％であり、２５℃における粘度が３０，０００ｍＰａ・ｓのポリウレタン樹脂（Ａ−１）（ジイソシアネート構成単位の含有率＝２４質量％）の溶液を得た。
[Synthesis Example 1] << Preparation of solution of polyurethane resin (A-1) >>
100 parts of polybutylene adipate diol having a number average molecular weight (Mn) of 2000 are diluted with a mixed solvent of dimethylformamide (DMF) / methyl ethyl ketone (MEK) = 50/50 mass ratio to obtain 1,4-butanediol (BG). 8.4 parts and 35.0 parts of diphenylmethane diisocyanate (MDI) were allowed to react at 80 ° C. for 3 hours, and then the required amount of MDI was further added, the resin concentration was 50%, and the viscosity at 25 ° C. A solution of 30,000 mPa · s polyurethane resin (A-1) (diisocyanate structural unit content = 24 mass%) was obtained.
［合成例２］《ポリウレタン樹脂（Ａ−２）の溶液の調製》
数平均分子量（Ｍｎ）が２０００のポリブチレンアジペートジオールの１００部及びビスフェノールＡ−エチレンオキサイド２モル付加物の１２部を、ジメチルホルムアミド（ＤＭＦ）／メチルエチルケトン（ＭＥＫ）＝５０／５０重量比の混合溶剤で希釈し、１，４−ブタンジオール（ＢＧ）を６部及びジフェニルメタンジイソシアネート（ＭＤＩ）を３８．０部加えて、８０℃で３時間反応させた後、更に必要量のＭＤＩを追加し、樹脂濃度５０％であり、２５℃における粘度が３１，０００ｍＰａ・ｓのポリウレタン樹脂
（Ａ−２）（ジイソシアネート構成単位の含有率＝２４質量％）の溶液を得た。
[Synthesis Example 2] << Preparation of solution of polyurethane resin (A-2) >>
A mixed solvent of 100 parts of polybutylene adipate diol having a number average molecular weight (Mn) of 2000 and 12 parts of bisphenol A-ethylene oxide 2-mole adduct in a dimethylformamide (DMF) / methyl ethyl ketone (MEK) = 50/50 weight ratio. After adding 6 parts of 1,4-butanediol (BG) and 38.0 parts of diphenylmethane diisocyanate (MDI), the mixture was reacted at 80 ° C. for 3 hours. A solution of a polyurethane resin (A-2) having a concentration of 50% and a viscosity at 25 ° C. of 31,000 mPa · s (content of diisocyanate structural unit = 24% by mass) was obtained.
［合成例３］《ポリウレタン樹脂（Ａ−３）の溶液の調製》
ジフェニルメタンジイソシアネート（ＭＤＩ）のかわりに、イソホロンジイソシアネート（ＩＰＤＩ）を３３．０部使用する以外は、合成例２と同様にして合成し、樹脂濃度５０％であり、２５℃における粘度が３３，０００ｍＰａ・ｓのポリウレタン樹脂（Ａ−３）（イソシアネート含有率＝２２％）の溶液を得た。
[Synthesis Example 3] << Preparation of polyurethane resin (A-3) solution >>
The compound was synthesized in the same manner as in Synthesis Example 2 except that 33.0 parts of isophorone diisocyanate (IPDI) was used instead of diphenylmethane diisocyanate (MDI), the resin concentration was 50%, and the viscosity at 25 ° C. was 33,000 mPa · A solution of polyurethane resin (A-3) (isocyanate content = 22%) was obtained.
［合成例４］《ポリウレタン樹脂（Ａ−４）の溶液の調製》
ジフェニルメタンジイソシアネート（ＭＤＩ）のかわりに、ヘキサメチレンジイソシアネート（ＨＤＩ）を２５．０部使用する以外は、合成例２と同様にして合成し、樹脂濃度５０％であり、２５℃における粘度が３２，０００ｍＰａ・ｓのポリウレタン樹脂（Ａ−４）（ジイソシアネート構成単位の含有率＝１７質量％）の溶液を得た。
[Synthesis Example 4] << Preparation of solution of polyurethane resin (A-4) >>
Synthesis was conducted in the same manner as in Synthesis Example 2 except that 25.0 parts of hexamethylene diisocyanate (HDI) was used instead of diphenylmethane diisocyanate (MDI), the resin concentration was 50%, and the viscosity at 25 ° C. was 32,000 mPas. A solution of polyurethane resin (A-4) of s (content of diisocyanate structural unit = 17% by mass) was obtained.
［合成例５］《ポリウレタン樹脂（Ａ−５）の溶液の調製》
数平均分子量（Ｍｎ）が２０００のポリブチレンアジペートジオールの１００部を、ジメチルホルムアミド（ＤＭＦ）／メチルエチルケトン（ＭＥＫ）＝５０／５０質量比の混合溶剤で希釈し、ジフェニルメタンジイソシアネート（ＭＤＩ）を５．０部加えて、８０℃で３時間反応させた後、更に必要量のＭＤＩを追加し、樹脂濃度５０％であり、２５℃における粘度が２０，０００ｍＰａ・ｓのポリウレタン樹脂（Ａ−５）（ジイソシアネート構成単位の含有率＝９質量％）の溶液を得た。
[Synthesis Example 5] << Preparation of solution of polyurethane resin (A-5) >>
100 parts of polybutylene adipate diol having a number average molecular weight (Mn) of 2000 are diluted with a mixed solvent of dimethylformamide (DMF) / methyl ethyl ketone (MEK) = 50/50 mass ratio, and diphenylmethane diisocyanate (MDI) is 5.0. In addition, after reacting at 80 ° C. for 3 hours, a necessary amount of MDI was further added, and a polyurethane resin (A-5) (diisocyanate) having a resin concentration of 50% and a viscosity at 25 ° C. of 20,000 mPa · s. A solution having a constitutional unit content of 9% by mass was obtained.
［合成例６］《ホットメルトフィルム用ポリウレタン樹脂（Ｅ）の溶液の調製》
数平均分子量（Ｍｎ）が６００のポリブチレンアジペートジオールの１００部を、ジメチルホルムアミド（ＤＭＦ）／メチルエチルケトン（ＭＥＫ）＝３０／７０重量比の混合溶剤で希釈し、１，４−ブタンジオール（ＢＧ）を０．７部及びジフェニルメタンジイソシアネート（ＭＤＩ）を４２．５部加えて、８０℃で３時間反応させて、更に必要量のＭＤＩを追加し、樹脂濃度５０％であり、２５℃における粘度が２５，０００ｍＰａ・ｓのホットメルトフィルム用ポリウレタン樹脂（Ｅ）の溶液を得た。
[Synthesis Example 6] << Preparation of solution of polyurethane resin (E) for hot melt film >>
100 parts of polybutylene adipate diol having a number average molecular weight (Mn) of 600 is diluted with a mixed solvent of dimethylformamide (DMF) / methyl ethyl ketone (MEK) = 30/70 weight ratio to obtain 1,4-butanediol (BG). 0.74 parts and 42.5 parts of diphenylmethane diisocyanate (MDI) were reacted at 80 ° C. for 3 hours, and the necessary amount of MDI was further added. The resin concentration was 50%, and the viscosity at 25 ° C. was 25. A solution of polyurethane resin (E) for hot melt film of 1,000 mPa · s was obtained.
［実施例１］
（１）耐熱性ポリウレタンフィルムの作成
合成例１で調製したポリウレタン樹脂（Ａ−１）１００部（固形分）と、湿式法シリカ（東ソー・シリカ株式会社製、商標；ニップジェル、粒子径２．２〜２．８μｍ）１４部、ヒンダードアミン２部、及びキシリレンジイソシアネートのトリメチロールプロパンアダクト（ＸＤＩ−ＴＭＰ）１４部を混合した。このようにして得たポリウレタン樹脂組成物の溶液を離型紙上に乾燥後の樹脂厚が５０μｍになるように流延し、７０℃で２分間乾燥、次いで１４０℃で４分間乾燥し、更に３５℃で相対湿度５０％で２日間熟成して本発明の耐熱性ポリウレタンフィルムを得た。
（２）ホットメルトフィルムの作成
合成例５で調製したホットメルト用ポリウレタン樹脂（Ｅ）の溶液を、離型紙上に乾燥後の樹脂厚が５０μｍになるように流延し、７０℃で３分間乾燥、次いで１３０℃で３分間乾燥し、ポリウレタンのホットメルトフィルムを得た。
（３）多層フィルムの作成
前記（１）で作成した１０ｃｍ×１０ｃｍの２枚の耐熱性ポリウレタンフィルムの間に、前記（２）で作成した９ｃｍ×７ｃｍのホットメルトフィルムをはさみ込み、１５０℃に設定した熱プレスにより、１ｋｇ／ｃｍ２の面圧で５秒間圧着して、多層フィルムを得た。
上記の如くして得た各種フィルムの評価結果を表１に示した。
[Example 1]
(1) Preparation of heat-resistant polyurethane film 100 parts (solid content) of polyurethane resin (A-1) prepared in Synthesis Example 1 and wet method silica (trademark; manufactured by Tosoh Silica Co., Ltd .; nip gel, particle size 2.2) ˜2.8 μm), 14 parts of hindered amine, and 14 parts of xylylene diisocyanate trimethylolpropane adduct (XDI-TMP). The polyurethane resin composition solution thus obtained was cast on a release paper so that the resin thickness after drying was 50 μm, dried at 70 ° C. for 2 minutes, then dried at 140 ° C. for 4 minutes, and further 35 The heat-resistant polyurethane film of the present invention was obtained by aging at 50 ° C. and 50% relative humidity for 2 days.
(2) Preparation of hot melt film The solution of the polyurethane resin for hot melt (E) prepared in Synthesis Example 5 was cast on a release paper so that the resin thickness after drying was 50 μm, and then at 70 ° C. for 3 minutes. Drying was followed by drying at 130 ° C. for 3 minutes to obtain a polyurethane hot melt film.
(3) Preparation of multilayer film The 9 cm × 7 cm hot melt film prepared in (2) above is sandwiched between two 10 cm × 10 cm heat resistant polyurethane films prepared in (1) above, and the temperature is increased to 150 ° C. The multilayer film was obtained by press-bonding at a surface pressure of 1 kg / cm 2 for 5 seconds with the set hot press.
The evaluation results of various films obtained as described above are shown in Table 1.
［実施例２］〜［実施例５］
実施例１と同様の操作にて表１に示した原料組成を配合して、ポリウレタン樹脂組成物を調製し、これを用いて本発明の耐熱性ポリウレタンフィルムを作成した。上記の如くして得た各種耐熱性ポリウレタンフィルムの評価結果を表１及び表２に示した。
[Example 2] to [Example 5]
The raw material composition shown in Table 1 was blended by the same operation as in Example 1 to prepare a polyurethane resin composition, and the heat resistant polyurethane film of the present invention was prepared using the polyurethane resin composition. The evaluation results of various heat-resistant polyurethane films obtained as described above are shown in Tables 1 and 2.
［比較例１］〜［比較例６］
実施例１と同様の操作にて表１及び表２に示した原料組成を配合してポリウレタン樹脂組成物を得て、更に、ポリウレタンフィルムを作成した。その評価結果を比較例１〜５として表２及び表３に示したが、耐熱性や耐候性などの諸特性のバランスに著しく劣っていた。
[Comparative Example 1] to [Comparative Example 6]
The raw material compositions shown in Table 1 and Table 2 were blended by the same operation as in Example 1 to obtain a polyurethane resin composition, and a polyurethane film was further prepared. Although the evaluation result was shown in Table 2 and Table 3 as Comparative Examples 1-5, it was remarkably inferior in the balance of various characteristics, such as heat resistance and a weather resistance.
注１）
ＸＤＩ−ＴＭＰ；キシリレンジイソシアネートのトリメチロールプロパンアダクト
ＩＰＤＩ−ＴＭＰ；イソホロンジイソシアネートのトリメチロールプロパンアダクト
Note 1)
XDI-TMP; Trimethylolpropane adduct of xylylene diisocyanate IPDI-TMP; Trimethylolpropane adduct of isophorone diisocyanate
注２）
多層フィルムの構成；耐熱性ポリウレタンフィルム／ホットメルトフィルム／耐熱性ポリウレタンフィルム
Note 2)
Composition of multilayer film: heat resistant polyurethane film / hot melt film / heat resistant polyurethane film
注３）
ＨＤＩ−ＴＭＰ；ヘキサメチレンジイソソアネートのトリメチロールプロパンアダクト
Note 3)
HDI-TMP; trimethylolpropane adduct of hexamethylene diisosonate
注４）
ＭＤＩ−ＴＭＰ；ジフェニルメタンジイソシアネートのトリメチロールプロパンアダクト
Note 4)
MDI-TMP; trimethylolpropane adduct of diphenylmethane diisocyanate
本発明の耐熱性ポリウレタンフィルムは、耐熱性、耐候性、耐水性、及び耐溶剤性に優れており、例えば、被覆フィルム、複層フィルム、衣料などの広範囲の用途に極めて有用である。
The heat-resistant polyurethane film of the present invention is excellent in heat resistance, weather resistance, water resistance, and solvent resistance, and is extremely useful for a wide range of applications such as coating films, multilayer films, and clothing.
Claims (4)
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