JP7168130B1 - Urethane resin, resin composition, adhesive composition, and method for producing urethane resin - Google Patents
Urethane resin, resin composition, adhesive composition, and method for producing urethane resin Download PDFInfo
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- JP7168130B1 JP7168130B1 JP2022534327A JP2022534327A JP7168130B1 JP 7168130 B1 JP7168130 B1 JP 7168130B1 JP 2022534327 A JP2022534327 A JP 2022534327A JP 2022534327 A JP2022534327 A JP 2022534327A JP 7168130 B1 JP7168130 B1 JP 7168130B1
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- Prior art keywords
- urethane resin
- polyol
- molecular weight
- mol
- resin
- 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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- 229920002803 thermoplastic polyurethane Polymers 0.000 title claims abstract description 82
- 239000000853 adhesive Substances 0.000 title claims abstract description 16
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- 239000011342 resin composition Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 230000009477 glass transition Effects 0.000 claims abstract description 24
- 238000009826 distribution Methods 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims description 59
- 150000003077 polyols Chemical class 0.000 claims description 58
- 239000003822 epoxy resin Substances 0.000 claims description 22
- 229920000647 polyepoxide Polymers 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 229920000570 polyether Polymers 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- 239000004417 polycarbonate Substances 0.000 claims description 12
- 229920000515 polycarbonate Polymers 0.000 claims description 12
- 239000005056 polyisocyanate Substances 0.000 claims description 12
- 229920001228 polyisocyanate Polymers 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920000098 polyolefin Polymers 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 90
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 38
- 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 30
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 30
- -1 polytetramethylene Polymers 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 25
- 239000002904 solvent Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 22
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 19
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 15
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 14
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 239000007870 radical polymerization initiator Substances 0.000 description 7
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000000539 dimer Substances 0.000 description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-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 class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 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
- 238000005452 bending Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- AQHHHDLHHXJYJD-UHFFFAOYSA-N propranolol Chemical compound C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 AQHHHDLHHXJYJD-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 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 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 2
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-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
- 229930185605 Bisphenol Natural products 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-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
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-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
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-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
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010526 radical polymerization 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
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- FYRCDEARNUVZRG-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CC(C)CC(C)(C)C1 FYRCDEARNUVZRG-UHFFFAOYSA-N 0.000 description 1
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- 239000011975 tartaric acid Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- VNJISVYSDHJQFR-UHFFFAOYSA-N tert-butyl 4,4-dimethylpentaneperoxoate Chemical compound CC(C)(C)CCC(=O)OOC(C)(C)C VNJISVYSDHJQFR-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000004448 titration Methods 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
- 230000007704 transition Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/86—Chemically modified polymers by peroxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
【課題】 従来のウレタン樹脂では達成できなかった耐屈曲性、伸度に優れ、かつ張り付きのないウレタン樹脂、樹脂組成物および接着剤組成物、ならびにそのウレタン樹脂の製造方法を提供すること。【解決手段】 以下の(1)~(3)を満足するウレタン樹脂。(1)ガラス転移温度(Tg)が40℃以上である(2)重量平均分子量(Mw)が180000~2000000である(3)分子量分布(Mw/Mn)が9~200である(ここでMnは数平均分子量を表す)【選択図】 なし[PROBLEMS] To provide a urethane resin, a resin composition, an adhesive composition, and a method for producing the urethane resin, which are excellent in flex resistance and elongation and have no stickiness, which conventional urethane resins cannot achieve. SOLUTION: A urethane resin satisfying the following (1) to (3). (1) Glass transition temperature (Tg) is 40° C. or higher (2) Weight average molecular weight (Mw) is 180,000 to 2,000,000 (3) Molecular weight distribution (Mw/Mn) is 9 to 200 (where Mn represents the number average molecular weight) [Selection] None
Description
本発明は、ウレタン樹脂、樹脂組成物および接着剤組成物、ならびにウレタン樹脂の製造方法に関するものである。さらに詳しくは、耐タック性、耐屈曲性、伸度に優れる接着剤組成物に関する。 TECHNICAL FIELD The present invention relates to a urethane resin, a resin composition, an adhesive composition, and a method for producing a urethane resin. More particularly, it relates to an adhesive composition that is excellent in tack resistance, bending resistance and elongation.
ウレタン樹脂は可撓性、耐摩耗性、耐油性、耐薬品性、接着性等が良好であり、塗料、インキ、接着剤、その他のコーティング剤用途に広く用いられている。近年では、フレキシブルプリント配線板(以下FPCともいう)は、柔軟性や省スペース性が必要な電子機器の配線板材料、実装用基板材料へ適用されるなど、高耐熱性を要求される用途での使用が進んでおり、耐熱性と可撓性の両立が求められる。 Urethane resins are excellent in flexibility, abrasion resistance, oil resistance, chemical resistance, adhesiveness, etc., and are widely used for paints, inks, adhesives, and other coating agents. In recent years, flexible printed wiring boards (hereinafter also referred to as FPCs) have been used in applications that require high heat resistance, such as wiring board materials for electronic devices that require flexibility and space saving, and substrate materials for mounting. is being used, and both heat resistance and flexibility are required.
一般に、接着剤やコーティング剤の耐熱性を上げるためには、樹脂のガラス転移温度を上げる方策が知られているが、他方でガラス転移温度を上げると樹脂の柔軟性が低下し、可撓性に劣る問題が生じる。例えば特許文献1では、食品包装用のウレタン系接着剤組成物において、ガラス転移温度が高いポリオールとガラス転移温度が低いポリオールとを含有させることで、耐熱水性に優れたウレタン系接着剤組成物が提案されている(特許文献1)。 In general, it is known to raise the glass transition temperature of resins in order to increase the heat resistance of adhesives and coating agents. A problem inferior to For example, in Patent Document 1, in a urethane adhesive composition for food packaging, a urethane adhesive composition excellent in hot water resistance is produced by incorporating a polyol having a high glass transition temperature and a polyol having a low glass transition temperature. It has been proposed (Patent Document 1).
ところでFPC製造用フィルムにおいては、接着剤を離型フィルムに塗工し、製造工程までロールにて保管される場合があり、保管時に接着剤とロール状に巻かれた他方のフィルムとが張り付いてしまうという問題があった。張り付きの問題は樹脂のガラス転移温度を上げる方策が知られてはいるが、ガラス転移温度を上げると今度は可撓性の問題が生ずるため、樹脂のガラス転移温度の調整のみによって両者の課題を同時に解決することは困難であった。 By the way, in the film for manufacturing FPC, there is a case where the release film is coated with an adhesive and stored in a roll until the manufacturing process. I had a problem with it. Although it is known to solve the sticking problem by raising the glass transition temperature of the resin, raising the glass transition temperature causes the problem of flexibility. It was difficult to solve them at the same time.
本発明の目的は、従来のウレタン樹脂では達成できなかった耐屈曲性、伸度に優れ、かつ張り付きのないウレタン樹脂、樹脂組成物および接着剤組成物、ならびにそのウレタン樹脂の製造方法を提供することである。 An object of the present invention is to provide a urethane resin, a resin composition, an adhesive composition, and a method for producing the urethane resin, which have excellent flex resistance and elongation and are free from sticking, which could not be achieved with conventional urethane resins. That is.
本発明者らは、上記課題を解決するために鋭意検討した結果、特定のガラス転移温度を有しながら、平均分子量が大きく、かつ広い分子量分布を有するウレタン樹脂が、前記の可撓性および張り付きの問題の両方を解決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 by the present inventors in order to solve the above problems, it has been found that a urethane resin having a specific glass transition temperature, a large average molecular weight, and a wide molecular weight distribution has the flexibility and sticking property. The inventors have found that both of the problems can be solved, and have completed the present invention.
すなわち、本発明は以下の(1)~(3)を満足するウレタン樹脂である。
(1)ガラス転移温度(Tg)が40℃以上である
(2)重量平均分子量(Mw)が180000~2000000である
(3)分子量分布(Mw/Mn)が9~200である(ここでMnは数平均分子量を表す)That is, the present invention is a urethane resin that satisfies the following (1) to (3).
(1) Glass transition temperature (Tg) is 40° C. or higher
(2) Weight average molecular weight (Mw) is 180,000 to 2,000,000 (3) Molecular weight distribution (Mw/Mn) is 9 to 200 (where Mn represents number average molecular weight)
前記ウレタン樹脂は、水酸基またはイソシアネート基との反応性を有する官能基とラジカル重合性二重結合とを同一分子内に有する化合物(C)に由来するラジカル重合性二重結合および前記化合物(C)の重合体の少なくとも一方を構成要素として有することが好ましい。 The urethane resin contains a radically polymerizable double bond derived from a compound (C) having a functional group reactive with a hydroxyl group or an isocyanate group and a radically polymerizable double bond in the same molecule, and the compound (C). It is preferable to have at least one of the polymers of as a constituent element.
前記ウレタン樹脂はカルボキシル基を有し、酸価は50~500eq/tであることが好ましい。 The urethane resin preferably has a carboxyl group and an acid value of 50 to 500 eq/t.
前記ウレタン樹脂は、ポリオール(A)を構成単位として有することができ、前記ポリオール(A)はポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオールおよびポリオレフィンポリオールからなる群より選ばれる少なくとも1種のポリオールを含有するものであり、前記ポリオール(A)のガラス転移温度が-30~30℃であることが好ましい。 The urethane resin can have a polyol (A) as a structural unit, and the polyol (A) contains at least one polyol selected from the group consisting of polyester polyols, polyether polyols, polycarbonate polyols and polyolefin polyols. It is preferable that the glass transition temperature of the polyol (A) is -30 to 30°C.
前記ウレタン樹脂は、架橋剤を含む樹脂組成物とすることができる。前記架橋剤は、エポキシ樹脂またはイソシアネート樹脂を好ましく使用でき、前記樹脂組成物は接着剤組成物として使用できる。 The urethane resin can be a resin composition containing a cross-linking agent. An epoxy resin or an isocyanate resin can be preferably used as the cross-linking agent, and the resin composition can be used as an adhesive composition.
前記ウレタン樹脂の製造方法としては、ポリオール(A)、ポリイソシアネート化合物(B)、および前記ポリオール(A)または前記ポリイソシアネート化合物(B)との反応性を有する官能基とラジカル重合性二重結合とを同一分子内に有する化合物(C)を構成要素として有するウレタン重合体を作成後、さらにラジカル重合することにより製造することができる。 As a method for producing the urethane resin, a polyol (A), a polyisocyanate compound (B), and a functional group having reactivity with the polyol (A) or the polyisocyanate compound (B) and a radically polymerizable double bond can be produced by radical polymerization after preparing a urethane polymer having a compound (C) having in the same molecule as a constituent element.
本発明によれば、可撓性に優れ、かつ張り付きのないウレタン樹脂、樹脂組成物および接着剤組成物を提供することができる。 According to the present invention, it is possible to provide a urethane resin, a resin composition and an adhesive composition which are excellent in flexibility and do not stick.
本発明のウレタン樹脂は、以下の(1)~(3)を満足するウレタン樹脂である。
(1)ガラス転移温度(Tg)が40℃以上である
(2)重量平均分子量(Mw)が180000~2000000である
(3)分子量分布(Mw/Mn)が9~200であるThe urethane resin of the present invention is a urethane resin that satisfies the following (1) to (3).
(1) Glass transition temperature (Tg) is 40° C. or higher (2) Weight average molecular weight (Mw) is 180,000 to 2,000,000 (3) Molecular weight distribution (Mw/Mn) is 9 to 200
<要件(1)>
本発明のウレタン樹脂のガラス転移温度(Tg)は、40℃以上であることが必要である。Tgが40℃以上であることで、必要な可撓性および耐熱性を有することができる。より好ましくは45℃以上、さらに好ましくは50℃以上である。上限は特に限定されないが、実用上は60℃以下である。ガラス転移温度は、実施例に記載の方法で測定される。<Requirement (1)>
The glass transition temperature (Tg) of the urethane resin of the present invention must be 40°C or higher. A Tg of 40° C. or higher can provide necessary flexibility and heat resistance. It is more preferably 45° C. or higher, still more preferably 50° C. or higher. Although the upper limit is not particularly limited, it is practically 60°C or less. The glass transition temperature is measured by the method described in Examples.
<要件(2)>
本発明のウレタン樹脂の重量平均分子量(Mw)は、通常150000~2000000である。好ましくは180000以上、より好ましくは200000以上、さらに好ましくは220000以上である。また、好ましくは1800000以下、より好ましくは1700000以下、さらに好ましくは1600000以下である。重量平均分子量を前記範囲内とすることで、張り付きがない、すなわち耐タック性に優れ、かつ可撓性に優れたウレタン樹脂とすることができる。重量平均分子量は、実施例に記載の方法で測定される。<Requirement (2)>
The weight average molecular weight (Mw) of the urethane resin of the present invention is generally 150,000 to 2,000,000. It is preferably 180,000 or more, more preferably 200,000 or more, and still more preferably 220,000 or more. Also, it is preferably 1,800,000 or less, more preferably 1,700,000 or less, and still more preferably 1,600,000 or less. By setting the weight average molecular weight within the above range, it is possible to obtain a urethane resin that does not stick, that is, has excellent tack resistance and flexibility. The weight average molecular weight is measured by the method described in Examples.
<要件(3)>
本発明のウレタン樹脂の分子量分布(Mw/Mn)は9~200であることが必要である。より好ましくは10以上、さらに好ましくは15以上、最も好ましくは20以上である。また、より好ましくは180以下、さらに好ましくは170以下、最も好ましくは160以下である。分子量分布が前記範囲内であることで、高分子量でありながら、溶剤溶解性に優れたウレタン樹脂とすることができる。この理由は定かではないが、分子量分布が広いことで高分子量成分と低分子量成分が共存し、低分子量成分が高分子量成分の相溶化剤的に働くため、高分子量で優れた耐タック性を有しつつも、溶剤溶解性に優れ、加工性の良いウレタン樹脂となると考察される。分子量分布(Mw/Mn)は重量平均分子量(Mw)と数平均分子量(Mn)の比であり、前記重合平均分子量と同様、実施例に記載の方法で測定される。<Requirement (3)>
The molecular weight distribution (Mw/Mn) of the urethane resin of the present invention must be 9-200. More preferably 10 or more, still more preferably 15 or more, and most preferably 20 or more. Also, it is more preferably 180 or less, still more preferably 170 or less, and most preferably 160 or less. When the molecular weight distribution is within the above range, it is possible to obtain a urethane resin having a high molecular weight and excellent solvent solubility. The reason for this is not clear, but due to the wide molecular weight distribution, high and low molecular weight components coexist, and the low molecular weight component acts as a compatibilizer for the high molecular weight component, resulting in excellent tack resistance with high molecular weight. It is considered to be a urethane resin with excellent solvent solubility and good processability while having The molecular weight distribution (Mw/Mn) is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), and is measured by the method described in Examples in the same manner as the polymerization average molecular weight.
本発明のウレタン樹脂は、構成単位としては特に限定されず、ポリオール(A)およびポリイソシアネート化合物(B)を含む構成単位により構成されるものが使用できる。 The urethane resin of the present invention is not particularly limited as a structural unit, and one composed of a structural unit containing a polyol (A) and a polyisocyanate compound (B) can be used.
<ポリオール(A)>
本発明のウレタン樹脂を構成できるポリオール(A)(以下、成分(A)とも言う)は特に限定されず、ポリエーテルグリコール、ポリエステルグリコール、ポリエーテルエステルグリコール、ポリカーボネートグリコール、ポリオレフィングリコール、シリコンポリオールや、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、ポリテトラメチレングリコール、1,5-ペンタンジオール、1,6-ヘキサンジオール、3-メチル-1,5-ペンタンジオール、ネオペンチルグリコール、2-エチル-1,3-ヘキサングリコール、2,2,4-トリメチル-1,3-ペンタンジオール、3,3-ジメチロールヘプタン、1,9-ノナンジオールおよび2-メチル-1,8-オクタンジオール等の脂肪族グリコール、1,4-シクロヘキサンジオ-ル、1,4-シクロヘキサンジメタノール、トリシクロデカンジオール、トリシクロデカンジメチロール、スピログリコール、水素化ビスフェノールA、水素化ビスフェノールAのエチレンオキサイド付加物およびプロピレンオキサイド付加物等の脂環族グリコール、パラキシレングリコール、メタキシレングリコール、オルトキシレングリコール、1,4-フェニレングリコール、1,4-フェニレングリコ-ルのエチレンオキサイド付加物、ビスフェノールA、ビスフェノールAのエチレンオキサイド付加物およびプロピレンオキサイド付加物等の、ビスフェノール類の2つのフェノール性水酸基にエチレンオキサイド又はプロピレンオキサイドをそれぞれ1~数モル付加して得られるグリコール類等の芳香族グリコール等が挙げられる。これらを単独で、または2種以上を併用できる。<Polyol (A)>
Polyol (A) (hereinafter also referred to as component (A)) that can constitute the urethane resin of the present invention is not particularly limited, and polyether glycol, polyester glycol, polyether ester glycol, polycarbonate glycol, polyolefin glycol, silicone polyol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, polytetramethylene glycol, 1,5-pentanediol, 1 ,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexane glycol, 2,2,4-trimethyl-1,3-pentanediol, 3,3 - aliphatic glycols such as dimethylolheptane, 1,9-nonanediol and 2-methyl-1,8-octanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediol, Alicyclic glycols such as tricyclodecanedimethylol, spiroglycol, hydrogenated bisphenol A, ethylene oxide adducts and propylene oxide adducts of hydrogenated bisphenol A, paraxylene glycol, metaxylene glycol, orthoxylene glycol, 1,4 - Ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols, such as phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, bisphenol A, ethylene oxide adduct and propylene oxide adduct of bisphenol A and aromatic glycols such as glycols obtained by adding 1 to several moles of each. These can be used alone or in combination of two or more.
ポリエーテルグリコールとしては環状エーテルを開環重合して得られるもの、例えばポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等が挙げられる。ポリエステルグリコールとしてはジカルボン酸(コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、フタル酸等)又はその無水物と低分子量ジオール(エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、ポリテトラメチレングリコール、1,5-ペンタンジオール、1,6-ヘキサンジオール、3-メチル-1,5-ペンタンジオール、ネオペンチルグリコール、2-エチル-1,3-ヘキサングリコール、2,2,4-トリメチル-1,3-ペンタンジオール、3,3-ジメチロールヘプタン、1,9-ノナンジオール、2-メチル-1,8-オクタンジオール、シクロヘキサンジメタノール、ビスヒドロキシエトキシベンゼン、パラキシレングリコール、メタキシレングリコール、オルトキシレングリコール、1,4-フェニレングリコール等)との重縮合によって得られるもの、例えばポリエチレンアジペート、ポリプロピレンアジペート、ポリブチレンアジペート、ポリヘキサメチレンアジペート、ポリブチレンセバケート等、低分子量ジオールへのラクトンの開環重合によって得られるもの、例えばポリカプロラクトン、ポリメチルバレロラクトン等が挙げられる。ポリエーテルエステルグリコールとしてはポリエステルグリコールに環状エーテルを開環重合したもの、ポリエーテルグリコールとジカルボン酸とを重縮合したもの、例えばポリ(ポリテトラメチレンエーテル)アジペート等が挙げられる。ポリカーボネートグリコールとしては低分子量ジオールとアルキレンカーボネート又はジアルキルカーボネートとから脱グリコール又は脱アルコールによって得られるポリブチレンカーボネート、ポリヘキサメチレンカーボネート、ポリ(3-メチル-1,5-ペンチレン)カーボネート等が挙げられる。ポリオレフィンポリオールとしてはポリブタジエンポリオール、水添ポリブタジエンポリオール、ポリイソプレンポリオール等が挙げられる。シリコンポリオールとしてはポリジメチルシロキサンポリオール等が挙げられる。 Examples of polyether glycols include those obtained by ring-opening polymerization of cyclic ethers, such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, etc.) or their anhydrides and low molecular weight diols (ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, polytetramethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl -1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexane glycol, 2,2,4-trimethyl-1,3-pentanediol, 3,3-dimethylolheptane, 1,9- nonanediol, 2-methyl-1,8-octanediol, cyclohexanedimethanol, bishydroxyethoxybenzene, para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, etc.). Examples include polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, polybutylene sebacate and the like, and those obtained by ring-opening polymerization of lactones to low molecular weight diols, such as polycaprolactone and polymethylvalerolactone. be done. Examples of polyether ester glycol include polyester glycol obtained by ring-opening polymerization of cyclic ether, polycondensation of polyether glycol and dicarboxylic acid, such as poly(polytetramethylene ether) adipate. Examples of polycarbonate glycols include polybutylene carbonate, polyhexamethylene carbonate, poly(3-methyl-1,5-pentylene) carbonate and the like obtained by deglycol or dealcoholization from low molecular weight diol and alkylene carbonate or dialkyl carbonate. Examples of polyolefin polyols include polybutadiene polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol. Silicon polyols include polydimethylsiloxane polyols and the like.
本発明で用いられる成分(A)としては、ガラス転移温度が-30℃以上であることが好ましい。より好ましくは-25℃以上、さらに好ましくは-20℃以上である。また、30℃以下であることが好ましく、より好ましくは25℃以下、さらに好ましくは20℃以下である。ガラス転移温度を前記の範囲内とすることで、ウレタン樹脂とした際の耐タック性および可撓性が良好となる。なお、成分(A)が複数の成分により構成される場合、成分(A)のガラス転移温度は、各成分のガラス転移温度と各成分の質量比から加重平均にて計算される。 Component (A) used in the present invention preferably has a glass transition temperature of −30° C. or higher. It is more preferably -25°C or higher, still more preferably -20°C or higher. Also, it is preferably 30° C. or lower, more preferably 25° C. or lower, and still more preferably 20° C. or lower. By setting the glass transition temperature within the above range, the tack resistance and flexibility of the urethane resin are improved. In addition, when the component (A) is composed of a plurality of components, the glass transition temperature of the component (A) is calculated by weighted average from the glass transition temperature of each component and the mass ratio of each component.
<ポリイソシアネート化合物(B)>
本発明のウレタン樹脂を構成できるポリイソシアネート化合物(B)(以下、成分(B)とも言う)は、ポリイソシアネート化合物であれば特に限定されず、例えば芳香族ポリイソシアネート、脂肪族ポリイソシアネートもしくは脂環族ポリイソシアネートが挙げられる。芳香族ポリイソシアネートとしては、特に限定されないが、例えば、ジフェニルメタン-2,4’-ジイソシアネート、又は3,2’-又は3,3’-又は4,2’-又は4,3’-又は5,2’-又は5,3’-又は6,2’-又は6,3’-ジメチルジフェニルメタン-2,4’-ジイソシアネート、3,2’-又は3,3’-又は4,2’-又は4,3’-又は5,2’-又は5,3’-又は6,2’-又は6,3’-ジエチルジフェニルメタン-2,4’-ジイソシアネート、3,2’-又は3,3’-又は4,2’-又は4,3’-又は5,2’-又は5,3’-又は6,2’-又は6,3’-ジメトキシジフェニルメタン-2,4’-ジイソシアネート、ジフェニルメタン-4,4’-ジイソシアネート、ジフェニルメタン-3,3’-ジイソシアネート、ジフェニルメタン-3,4’-ジイソシアネート、ジフェニルエーテル-4,4’-ジイソシアネート、ベンゾフェノン-4,4’-ジイソシアネート、ジフェニルスルホン-4,4’-ジイソシアネート、トリレン-2,4-ジイソシアネート、トリレン-2,6-ジイソシアネート、m-キシリレンジイソシアネート、p-キシリレンジイソシアネート、ナフタレン-2,6-ジイソシアネート、4,4’-[2,2-ビス(4-フェノキシフェニル)プロパン]ジイソシアネート、3,3’または2,2’-ジメチルビフェニル-4,4’-ジイソシアネート、3,3’-または2,2’-ジエチルビフェニル-4,4’-ジイソシアネート、3,3’-ジメトキシビフェニル-4,4’-ジイソシアネート、3,3’-ジエトキシビフェニル-4,4’-ジイソシアネート等が挙げられる。耐熱性、密着性、溶解性、コスト面などを考慮すれば、ジフェニルメタン-4,4’-ジイソシアネート、トリレン-2,4-ジイソシアネート、m-キシリレンジイソシアネート、3,3’-または2,2’-ジメチルビフェニル-4,4’-ジイソシアネートが好ましい。これらを単独で、または2種以上を併用することができる。<Polyisocyanate compound (B)>
The polyisocyanate compound (B) (hereinafter also referred to as component (B)) that can constitute the urethane resin of the present invention is not particularly limited as long as it is a polyisocyanate compound, such as aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic group polyisocyanates. Examples of aromatic polyisocyanates include, but are not limited to, diphenylmethane-2,4'-diisocyanate, or 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5, 2'- or 5,3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4 ,3′- or 5,2′- or 5,3′- or 6,2′- or 6,3′-diethyldiphenylmethane-2,4′-diisocyanate, 3,2′- or 3,3′- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4 '-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4′-[2,2-bis(4- phenoxyphenyl)propane] diisocyanate, 3,3′ or 2,2′-dimethylbiphenyl-4,4′-diisocyanate, 3,3′- or 2,2′-diethylbiphenyl-4,4′-diisocyanate, 3, 3'-dimethoxybiphenyl-4,4'-diisocyanate, 3,3'-diethoxybiphenyl-4,4'-diisocyanate and the like. Considering heat resistance, adhesion, solubility, cost, etc., diphenylmethane-4,4'-diisocyanate, tolylene-2,4-diisocyanate, m-xylylene diisocyanate, 3,3'- or 2,2'-dimethylbiphenyl-4,4'-diisocyanate is preferred. These can be used alone or in combination of two or more.
ポリイソシアネート化合物(B)の仕込量比は、ポリオール(A)の水酸基と成分(B)のイソシアネート基から、イソシアネート基/水酸基(NCO/OH)のモル比で1.01~5となる量比であることが好ましく、より好ましくは1.01~2である。仕込量比が1.01を下回ると分子量が低くもろい樹脂となり、一方、5を超えると反応時に粘度が高くなりゲル化しやすいため、いずれも好ましくない。なお、後記の成分(D)を含有する場合は、水酸基は成分(A)と成分(D)の水酸基の合計量として計算する。 The charge ratio of the polyisocyanate compound (B) is such that the molar ratio of isocyanate group/hydroxyl group (NCO/OH) is 1.01 to 5 from the hydroxyl group of the polyol (A) and the isocyanate group of the component (B). and more preferably 1.01 to 2. If the charge ratio is less than 1.01, the resin becomes brittle due to its low molecular weight. In addition, when the component (D) described later is contained, the hydroxyl group is calculated as the total amount of the hydroxyl groups of the component (A) and the component (D).
<水酸基またはイソシアネート基との反応性を有する官能基とラジカル重合性二重結合とを同一分子内に有する化合物(C)>
本発明のウレタン樹脂は、水酸基またはイソシアネート基との反応性を有する官能基とラジカル重合性二重結合とを同一分子内に有する化合物(C)(以下、成分(C)とも言う)を構成単位として有していてもよい。このような成分(C)の例としては、2-イソシアネートエチルメタクリレート(昭和電工社製、カレンズMOI)、2-イソシアネートエチルアクリレート(昭和電工社製、カレンズAOI)、2-(2-メタクリロイルオキシエチルオキシ)エチルイソシアネート(昭和電工社製、カレンズMOI-EG)、1,1-(ビスアクリロイルオキシメチル)エチルイソシアネート(昭和電工社製、カレンズBEI)、2-ヒドロキシエチルメタクリレート(共栄社化学社製、ライトエステルHO-250(N))、2-ヒドロキシプロピルメタクリレート(共栄社化学社製、ライトエステルHOP(N))、2-ヒドロキシエチルアクリレート(共栄社化学社製、ライトエステルHOP-A(N))、2-ヒドロキシブチルメタクリレート(共栄社化学社製、ライトエステルHOB(N))等が挙げられる。成分(C)のラジカル重合性二重結合は、ラジカル反応性の観点から、成分(C)の分子の末端に位置していることが好ましい。<Compound (C) Having a Functional Group Reactive with a Hydroxyl Group or an Isocyanate Group and a Radically Polymerizable Double Bond in the Same Molecule>
The urethane resin of the present invention comprises a compound (C) (hereinafter also referred to as component (C)) having a functional group reactive with a hydroxyl group or an isocyanate group and a radically polymerizable double bond in the same molecule as a structural unit. You may have it as Examples of such component (C) include 2-isocyanatoethyl methacrylate (manufactured by Showa Denko Co., Ltd., Karenz MOI), 2-isocyanatoethyl acrylate (manufactured by Showa Denko Co., Ltd., Karenz AOI), 2-(2-methacryloyloxyethyl Oxy) ethyl isocyanate (manufactured by Showa Denko Co., Ltd., Karenz MOI-EG), 1,1-(bisacryloyloxymethyl) ethyl isocyanate (manufactured by Showa Denko Co., Ltd., Karenz BEI), 2-hydroxyethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., Light Ester HO-250 (N)), 2-hydroxypropyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., Light Ester HOP (N)), 2-hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., Light Ester HOP-A (N)), 2 -Hydroxybutyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester HOB (N)) and the like. From the viewpoint of radical reactivity, the radically polymerizable double bond of component (C) is preferably positioned at the terminal of the molecule of component (C).
成分(C)のウレタン樹脂中における含有量は成分(B)を100重量部とした場合、1~20重量部であることが好ましく、より好ましくは2~10重量部である。成分(C)の含有量が1重量部未満の場合、ラジカル重合による高分子量化が不十分となり、20重量部を超えると、ラジカル重合時にゲル化しやすいため好ましくない。 The content of component (C) in the urethane resin is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, per 100 parts by weight of component (B). If the content of component (C) is less than 1 part by weight, the molecular weight is not sufficiently increased by radical polymerization.
<1個以上のカルボキシル基を有するポリオール(D)>
本発明のウレタン樹脂は、1個以上のカルボキシル基を有するポリオール(D)(以下、成分(D)とも言う)を構成単位として有していてもよい。このような成分(D)の例としては、3,5-ジヒドロキシ安息香酸、2,2-ビス(ヒドロキシメチル)プロピオン酸、2,2-ビス(ヒドロキシメチル)ブタン酸、2,2-ビス(2-ヒドロキシエチル)プロピオン酸、2,2-ビス(3-ヒドロキシプロピル)プロピオン酸、ビス(ヒドロキシメチル)酢酸、ビス(4-ヒドロキシフェニル)酢酸、2,2-ビス(ヒドロキシメチル)酪酸、4,4-ビス(4-ヒドロキシフェニル)ペンタン酸、酒石酸等が挙げられる。<Polyol (D) Having One or More Carboxyl Groups>
The urethane resin of the present invention may have a polyol (D) having one or more carboxyl groups (hereinafter also referred to as component (D)) as a structural unit. Examples of such component (D) include 3,5-dihydroxybenzoic acid, 2,2-bis(hydroxymethyl)propionic acid, 2,2-bis(hydroxymethyl)butanoic acid, 2,2-bis( 2-hydroxyethyl)propionic acid, 2,2-bis(3-hydroxypropyl)propionic acid, bis(hydroxymethyl)acetic acid, bis(4-hydroxyphenyl)acetic acid, 2,2-bis(hydroxymethyl)butyric acid, 4 , 4-bis(4-hydroxyphenyl)pentanoic acid, tartaric acid and the like.
本発明のウレタン樹脂は、50~500eq/tの酸価を有することが好ましい。より好ましくは80eq/t以上、さらに好ましくは100eq/t以上である。また、450eq/t以下が好ましく、さらに好ましくは400eq/t以下である。酸価を前記の範囲内とすることで、後述する架橋剤との架橋反応に使用できる。酸価が50eq/t未満であれば、架橋剤で硬化させた場合の硬化塗膜としての強度が保たれず、ひいては伸度低下、屈曲性試験にてクラックが発生しやすくなる。また、酸価が500eq/tより大きければ、架橋点が非常に多い硬化塗膜となり、可撓性が失われる。 The urethane resin of the present invention preferably has an acid value of 50-500 eq/t. It is more preferably 80 eq/t or more, still more preferably 100 eq/t or more. Also, it is preferably 450 eq/t or less, more preferably 400 eq/t or less. By setting the acid value within the above range, it can be used for a cross-linking reaction with a cross-linking agent, which will be described later. If the acid value is less than 50 eq/t, the strength of the cured coating film cannot be maintained when cured with a cross-linking agent, and as a result, the elongation decreases and cracks tend to occur in the flexibility test. On the other hand, if the acid value is more than 500 eq/t, the cured coating film will have a large number of cross-linking points, and the flexibility will be lost.
本発明のウレタン樹脂は、例えば以下の方法で製造することができる。すなわち、まず前記成分(A)、成分(B)および成分(C)を構成単位として含むウレタン重合体を、公知のプレポリマー化法によって作製する。次いでラジカル重合開始剤を添加し、成分(C)に由来するラジカル重合性二重結合をラジカル重合させることで、高分子量化かつ分子量分布の広いウレタン樹脂を製造することができる。この方法によれば、従来溶液化が困難であった高分子量の樹脂であっても、溶液の状態で製造することが可能である。なお、前記ウレタン重合体は、さらに成分(D)を構成単位として有していてもよい。 The urethane resin of the present invention can be produced, for example, by the following method. That is, first, a urethane polymer containing the component (A), component (B) and component (C) as structural units is produced by a known prepolymerization method. Then, a radical polymerization initiator is added to radically polymerize the radically polymerizable double bond derived from the component (C), whereby a urethane resin having a high molecular weight and a wide molecular weight distribution can be produced. According to this method, even high-molecular-weight resins, which have conventionally been difficult to dissolve, can be produced in the form of a solution. The urethane polymer may further have component (D) as a structural unit.
前記の方法における重合溶媒としては、イソシアネートとの反応性が低いものであれば使用することができ、例えば、アミン等の塩基性化合物を含まない溶剤が好ましい。このような溶剤としては、例えば、トルエン、キシレン、エチルベンゼン、ニトロベンゼン、シクロヘキサン、イソホロン、ジエチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、ジプロピレングリコールメチルエーテルアセテート、ジエチレングリコールエチルエーテルアセテート、メトキシプロピオン酸メチル、メトキシプロピオン酸エチル、エトキシプロピオン酸メチル、エトキシプロピオン酸エチル、酢酸エチル、酢酸n-ブチル、酢酸イソアミル、乳酸エチル、アセトン、メチルエチルケトン、シクロヘキサノン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン、N-エチルピロリドン、γ-ブチロラクトン、ジメチルスルホキシド、クロロホルム及び塩化メチレン等を挙げることができる。 As the polymerization solvent in the above method, any solvent having low reactivity with isocyanate can be used, and for example, a solvent that does not contain a basic compound such as amine is preferred. Examples of such solvents include toluene, xylene, ethylbenzene, nitrobenzene, cyclohexane, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl. ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, ethyl acetate, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methyl ethyl ketone, cyclohexanone, N,N-dimethylformamide, Examples include N,N-dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, γ-butyrolactone, dimethylsulfoxide, chloroform and methylene chloride.
ウレタン樹脂を製造する際の触媒としては通常のウレタン化反応触媒が用いられる。例えば、ジブチルチンジラウレート、ジオクチルチンジラウレート、ジブチルチンジオクトエート、スタナスオクトエート等の錫系、鉄アセチルアセトナート、塩化第二鉄等の鉄系、トリエチルアミン、ルチジン、ピコリン、ウンデセン、トリエチレンジアミン(1,4-ジアザビシクロ[2,2,2]オクタン)、DBU(1,8-ジアザビシクロ[5,4,0]-7-ウンデセン)等のアミン類等が挙げられる。 A normal urethanization reaction catalyst is used as a catalyst for producing a urethane resin. For example, tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, lutidine, picoline, undecene, triethylenediamine (1 ,4-diazabicyclo[2,2,2]octane) and DBU (1,8-diazabicyclo[5,4,0]-7-undecene).
ラジカル重合開始剤としては、例えば、アゾビスイソブチロニトリル、アゾビスジメチルバレロニトリル、アゾビスシクロヘキサンニトリル、1,1’-アゾビス(1-アセトキシ-1-フェニルエタン)、ジメチル2,2’-アゾビスイソブチレート、4,4’-アゾビス-4-シアノバレリン酸などのアゾ化合物;ベンゾイルパーオキサイド、ラウロイルパーオキサイド、アセチルパーオキサイド、カプリリルパーオキサイド、2,4-ジクロルベンゾイルパーオキサイド、イソブチルパーオキサイド、アセチルシクロヘキシルスルホニルパーオキサイド、t-ブチルパーオキシピバレート、t-ブチルパーオキシネオデカノエート、t-ブチルパーオキシネオヘプタノエート、t-ブチルパーオキシ-2-エチルヘキサノエート、1,1-ジ(t-ブチルパーオキシ)シクロヘキサン、1,1-ジ(t-ブチルパーオキシ)-3,3,5-トリメチルシクロヘキサン、1,1-ジ(t-ヘキシルパーオキシ)-3,3,5-トリメチルシクロヘキサン、ジイソプロピルパーオキシジカーボネート、ジイソブチルパーオキシジカーボネート、ジ-sec-ブチルパーオキシジカーボネート、ジ-n-ブチルパーオキシジカーボネート、ビス(2-エチルヘキシル)パーオキシジカーボネート、ビス(4-t-ブチルシクロヘキシル)パーオキシジカーボネート、t-アミルパーオキシ-2-エチルヘキサノエート、1,1,3,3-テトラメチルブチルパーオキシ-エチルヘキサノエート、1,1,2-トリメチルプロピルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシイソプロピルモノカーボネート、t-アミルパーオキシイソプロピルモノカーボネート、t-ブチルパーオキシ-2-エチルヘキシルカーボネート、t-ブチルパーオキシアリルカーボネート、t-ブチルパーオキシイソプロピルカーボネート、1,1,3,3-テトラメチルブチルパーオキシイソプロピルモノカーボネート、1,1,2-トリメチルプロピルパーオキシイソプロピルモノカーボネート、1,1,3,3-テトラメチルブチルパーオキシイソノナエート、1,1,2-トリメチルプロピルパーオキシ-イソノナエート、t-ブチルパーオキシベンゾエート、過酸化ラウロイルなどの有機過酸化物が挙げられる。 Examples of radical polymerization initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, 1,1′-azobis(1-acetoxy-1-phenylethane), dimethyl 2,2′- azo compounds such as azobisisobutyrate and 4,4'-azobis-4-cyanovaleric acid; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, caprylyl peroxide, 2,4-dichlorobenzoyl peroxide, isobutyl peroxide, acetylcyclohexylsulfonyl peroxide, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-butyl peroxy-2-ethylhexanoate, 1,1-di(t-butylperoxy)cyclohexane, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)-3 , 3,5-trimethylcyclohexane, diisopropylperoxydicarbonate, diisobutylperoxydicarbonate, di-sec-butylperoxydicarbonate, di-n-butylperoxydicarbonate, bis(2-ethylhexyl)peroxydicarbonate , bis(4-t-butylcyclohexyl)peroxydicarbonate, t-amylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-ethylhexanoate, 1,1 , 2-trimethylpropylperoxy-2-ethylhexanoate, t-butylperoxyisopropylmonocarbonate, t-amylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexylcarbonate, t-butylperoxyallyl carbonate, t-butylperoxyisopropyl carbonate, 1,1,3,3-tetramethylbutylperoxyisopropyl monocarbonate, 1,1,2-trimethylpropylperoxyisopropyl monocarbonate, 1,1,3,3-tetra Organic peroxides such as methyl butyl peroxyisononaate, 1,1,2-trimethylpropyl peroxy-isononaate, t-butyl peroxybenzoate, lauroyl peroxide and the like.
ラジカル重合開始剤の種類は、溶剤溶解性や重合温度に応じて選定され得る。例えば、本発明では特に限定されないが、ラジカル重合開始剤としては、その重合温度での半減期が10分以上3時間以内であるものが好ましい。ラジカル重合開始剤の使用量は、目標の重合率や反応条件などに応じて調整すればよく、本発明ではラジカル重合開始剤の添加量は成分(C)の仕込み量に対して0.001~15重量%であることが好ましい。これらのラジカル重合開始剤は、1種を単独で使用してもよく、2種以上を混合して使用してもよい。また、重合温度は10~180℃が好ましく、より好ましくは30~150℃である。重合時の樹脂固形分は5~95重量%が好ましく、より好ましくは20~60重量%である。 The type of radical polymerization initiator can be selected according to solvent solubility and polymerization temperature. For example, although not particularly limited in the present invention, the radical polymerization initiator preferably has a half-life of 10 minutes or more and 3 hours or less at the polymerization temperature. The amount of the radical polymerization initiator to be used may be adjusted according to the target polymerization rate and reaction conditions. 15% by weight is preferred. These radical polymerization initiators may be used singly or in combination of two or more. The polymerization temperature is preferably 10-180°C, more preferably 30-150°C. The resin solid content during polymerization is preferably 5 to 95% by weight, more preferably 20 to 60% by weight.
上記成分(A)~(D)、およびラジカル重合開始剤に加えて、任意の適切な他の成分、例えば連鎖移動剤、ブタジエンおよびスチレンブタジエンゴム(SBR)などのゴム状重合体、熱安定剤、紫外線吸収剤などを用いてもよい。なお、ここで、連鎖移動剤は、生成するウレタン樹脂や使用する原料モノマーの種類に応じて選定され得る。例えば、本発明では特に限定されないが、連鎖移動剤として、n-オクチルメルカプタン、n-ドデシルメルカプタンが好ましい。熱安定剤は、生成するウレタン樹脂の熱分解を抑制するためや、ウレタン化反応時、ラジカル重合性二重結合の熱重合を防止するために用いることもできる。熱安定剤としてはメチルハイドロキノン、t-ブチルカテコール、クロラニル等のフェノール系化合物、ジフェニルピクリルヒドラジン、ジフェニルアミン等のアミン類、塩化第2鉄、塩化第2銅等の高原子価金属塩等が挙げられる。紫外線吸収剤は、生成するウレタン樹脂の紫外線による劣化を抑制するために用いられるものである。 In addition to components (A)-(D) above, and radical polymerization initiators, any other suitable components such as chain transfer agents, rubbery polymers such as butadiene and styrene-butadiene rubbers (SBR), heat stabilizers , an ultraviolet absorber, or the like may be used. Here, the chain transfer agent can be selected according to the type of urethane resin to be produced and the raw material monomer to be used. For example, n-octylmercaptan and n-dodecylmercaptan are preferred as chain transfer agents, although they are not particularly limited in the present invention. The heat stabilizer can also be used to suppress thermal decomposition of the urethane resin to be produced and to prevent thermal polymerization of radically polymerizable double bonds during the urethanization reaction. Examples of heat stabilizers include phenolic compounds such as methylhydroquinone, t-butylcatechol and chloranil, amines such as diphenylpicrylhydrazine and diphenylamine, and high-valent metal salts such as ferric chloride and cupric chloride. be done. The ultraviolet absorber is used to suppress deterioration of the produced urethane resin due to ultraviolet rays.
<架橋剤>
本発明のウレタン樹脂は可撓性等を向上させるために各種架橋剤及び必要に応じて他の樹脂を配合して架橋塗膜を得ることができる。架橋剤としてはエポキシ樹脂、イソシアネート樹脂、シラン化合物等が挙げられる。<Crosslinking agent>
In order to improve the flexibility of the urethane resin of the present invention, various cross-linking agents and, if necessary, other resins may be added to obtain a cross-linked coating film. Examples of cross-linking agents include epoxy resins, isocyanate resins, silane compounds, and the like.
前記エポキシ樹脂としては、1分子あたり2個以上のエポキシ基を有するエポキシ樹脂であれば特に限定されない。例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型、またはそれらに水素添加したもの、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂等のグリシジルエーテル系エポキシ樹脂、ヘキサヒドロフタル酸グリシジルエステル、ダイマー酸グリシジルエステル等のグリシジルエステル系エポキシ樹脂、エポキシ化ポリブタジエン、エポキシ化大豆油等の線状脂肪族エポキシ樹脂等が挙げられる。また、前記エポキシ樹脂は例えば、シリコーン、ウレタン、ポリイミド、ポリアミド等で変性されていてもよく、分子骨格内に硫黄原子、窒素原子等を含んでいてもよい。これらの市販品としては、例えば、三菱化学(株)製の商品名jER828、1001等のビスフェノールA型エポキシ樹脂、新日鉄住金化学(株)製の商品名ST-2004、2007等の水添ビスフェノールA型エポキシ樹脂、DIC(株)製のEXA-9726、新日鉄住金化学(株)製の商品名YDF-170、2004等のビスフェノールF型エポキシ樹脂、三菱化学(株)製の商品名jER152、154、ダウケミカル社製の商品名DEN-438、DIC(株)製の商品名HP7200、HP7200H等のフェノールノボラック型エポキシ樹脂、新日鉄住金化学(株)製の商品名YDCN-700シリーズ、日本化薬(株)製の商品名EOCN-125S、103S、104S等のクレゾールノボラック型エポキシ樹脂、新日鉄住金化学(株)製の商品名YD-171等の可撓性エポキシ樹脂、三菱化学(株)製の商品名Epon1031S、チバ・スペシャルティ・ケミカルズ(株)製の商品名アラルダイト0163、ナガセケムテックス(株)製の商品名デナコールEX-611、EX-614、EX-622、EX-512、EX-521、EX-421、EX-411、EX-321等の多官能エポキシ樹脂、三菱化学(株)製の商品名エピコート604、新日鉄住金化学(株)製の商品名YH-434、チバ・スペシャルティ・ケミカルズ(株)製の商品名アラルダイトPT810等の複素環含有エポキシ樹脂、ダイセル化学工業(株)製の商品名セロキサイド2021、EHPE3150、UCC社製のERL4234等の脂環式エポキシ樹脂、DIC(株)製の商品名エピクロンEXA-1514等のビスフェノールS型エポキシ樹脂、日産化学工業(株)製のTEPIC等のトリグリシジルイソシアヌレート、三菱化学(株)製の商品名YX-4000等のビキシレノール型エポキシ樹脂、三菱化学(株)製の商品名YL-6056等のビスフェノール型エポキシ樹脂等が挙げられる。また、これらは単独で使用してもよいし、複数を組み合わせて使用しても構わない。 The epoxy resin is not particularly limited as long as it has two or more epoxy groups per molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type, or hydrogenated products thereof, phenol novolak type epoxy resin, glycidyl ether type epoxy resin such as cresol novolak type epoxy resin, glycidyl hexahydrophthalate Glycidyl ester epoxy resins such as esters and dimer acid glycidyl esters, linear aliphatic epoxy resins such as epoxidized polybutadiene and epoxidized soybean oil, and the like can be used. Further, the epoxy resin may be modified with, for example, silicone, urethane, polyimide, polyamide, or the like, and may contain a sulfur atom, a nitrogen atom, or the like in the molecular skeleton. Examples of these commercially available products include bisphenol A type epoxy resins such as jER828 and 1001 (trade names) manufactured by Mitsubishi Chemical Corporation, and hydrogenated bisphenol A such as ST-2004 and ST-2007 (trade names) manufactured by Nippon Steel & Sumikin Chemicals. type epoxy resin, EXA-9726 manufactured by DIC Corporation; DEN-438 (trade name) manufactured by Dow Chemical Co., Ltd.; HP7200 (trade name), HP7200H (trade name), etc., manufactured by DIC Corporation; YDCN-700 series (trade name); ) manufactured by EOCN-125S, 103S, 104S and other cresol novolac type epoxy resins, Nippon Steel & Sumikin Chemical Co., Ltd. manufactured by trade name YD-171 and other flexible epoxy resins, Mitsubishi Chemical Corporation trade name Epon 1031S, trade name Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Denacol EX-611, EX-614, EX-622, EX-512, EX-521, EX- manufactured by Nagase ChemteX Co., Ltd. 421, EX-411, EX-321 and other polyfunctional epoxy resins, trade name Epicoat 604 manufactured by Mitsubishi Chemical Corporation, trade name YH-434 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Ciba Specialty Chemicals Co., Ltd. Heterocycle-containing epoxy resins such as Araldite PT810 (trade name) manufactured by Daicel Chemical Industries, Ltd.; Celoxide 2021, EHPE3150 (trade names) manufactured by Daicel Chemical Industries, Ltd.; Bisphenol S type epoxy resin such as Epiclon EXA-1514, triglycidyl isocyanurate such as TEPIC manufactured by Nissan Chemical Industries, Ltd., bixylenol type epoxy resin such as YX-4000 manufactured by Mitsubishi Chemical Corporation, Mitsubishi Chemical Bisphenol type epoxy resins such as YL-6056 (trade name) manufactured by Co., Ltd. may be used. In addition, these may be used alone, or may be used in combination.
前記イソシアネート樹脂としては、p-フェニレンジイソシアネート、ナフタレンジイソシアネート、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、ヘキサメチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、イソホロンジイソシアネート、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、リジンジイソシアネート等、及びこれらの3量体、水付加物、又はこれらの低分子量ポリオール付加物等が挙げられる。 Examples of the isocyanate resin include p-phenylene diisocyanate, naphthalene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, lysine diisocyanate, and these. Examples include trimers, water adducts, and low-molecular-weight polyol adducts thereof.
前記シラン化合物としてはアセトキシシラン、アルコキシシラン、ケトキシムシラン、アミノシラン、アミノキシシラン等が挙げられる。 Examples of the silane compound include acetoxysilane, alkoxysilane, ketoximesilane, aminosilane and aminoxysilane.
架橋剤の添加量は、ウレタン樹脂の酸価に対して架橋剤中の反応性官能基量が1~2倍程度になることが好ましい。また、架橋塗膜の形成は架橋剤を配合した混合物を塗布し40~200℃で数秒間~数時間加熱することによって行われる。 The amount of the cross-linking agent to be added is preferably such that the amount of reactive functional groups in the cross-linking agent is about 1 to 2 times the acid value of the urethane resin. The crosslinked coating film is formed by applying a mixture containing a crosslinker and heating at 40 to 200° C. for several seconds to several hours.
以下、実施例を挙げて本発明を具体的に説明する。 EXAMPLES The present invention will be specifically described below with reference to Examples.
<ガラス転移温度>
セイコー電子工業株式会社製の示差走査熱量分析計「DSC220型」にて、測定試料5mgをアルミパンに入れ、蓋を押さえて密封し、一度250℃で5分ホールドした後、液体窒素で急冷して、その後-150℃から250℃まで、20℃/分の昇温速度で測定した。得られた曲線から、ガラス転移温度以下のベースラインの延長線と遷移部における最大傾斜を示す接線との交点の温度をガラス転移温度とした。<Glass transition temperature>
Using a differential scanning calorimeter "DSC220" manufactured by Seiko Electronics Industry Co., Ltd., 5 mg of the measurement sample was placed in an aluminum pan, the lid was pressed and sealed, held at 250 ° C. for 5 minutes, and then rapidly cooled with liquid nitrogen. Then, the temperature was measured from -150°C to 250°C at a heating rate of 20°C/min. From the obtained curve, the temperature at the intersection of the extended line of the baseline below the glass transition temperature and the tangent line showing the maximum slope at the transition portion was defined as the glass transition temperature.
<重量平均分子量、数平均分子量および分子量分布>
ゲル浸透クロマトグラフィー(GPC)を用い、以下の条件にて測定し、解析ソフト(Lab Solutions(TM) 島津製作所社製)を用いて、標準ポリスチレンに換算した重量平均分子量、数平均分子量および分子量分布(重量平均分子量/数平均分子量)の値を算出した。
測定装置 東ソー製 HLC-8220
カラム TSKgel super HM-H 2本 およびSuperH 2500 1本を直列に接続
検出器 示差屈折率(RI)検出器
溶液調整 テトラヒドロフランを溶媒とし、サンプルの0.05重量%溶液を用いる
カラム温度 40℃
注入量 20μL
流速 0.6ml/分<Weight average molecular weight, number average molecular weight and molecular weight distribution>
Measured under the following conditions using gel permeation chromatography (GPC), and using analysis software (Lab Solutions (TM) manufactured by Shimadzu Corporation), the weight average molecular weight, number average molecular weight and molecular weight distribution converted to standard polystyrene. A value of (weight average molecular weight/number average molecular weight) was calculated.
Measuring device Tosoh HLC-8220
Column 2 TSKgel super HM-H and 1 SuperH 2500 connected in series Detector Differential refractive index (RI) detector Solution preparation Using tetrahydrofuran as solvent, 0.05% by weight solution of sample Column temperature 40°C
Injection volume 20 μL
Flow rate 0.6ml/min
<酸価>
試料0.2gを20mlのクロロホルムに溶解し、指示薬としてフェノールフタレインを用い、0.1Nの水酸化カリウムエタノール溶液で滴定した。この滴定量から、中和に消費された水酸化カリウムのmg数を樹脂1gあたりの量に換算して酸価(100eq/t=5.6mgKOH/g)を算出した。<Acid value>
0.2 g of a sample was dissolved in 20 ml of chloroform and titrated with 0.1 N potassium hydroxide ethanol solution using phenolphthalein as an indicator. From this titration amount, an acid value (100 eq/t=5.6 mgKOH/g) was calculated by converting the number of mg of potassium hydroxide consumed for neutralization into the amount per 1 g of resin.
(ウレタン樹脂組成物溶液の調製)
実施例または比較例で得られたウレタン樹脂および架橋剤を、ウレタン樹脂および架橋剤を合わせた固形分濃度が20重量%になるように、メチルエチルケトンに溶解し、ウレタン樹脂組成物溶液を調製した。架橋剤の配合量はウレタン樹脂の酸価に基づき、ウレタン樹脂の酸価(eq/t)が架橋剤の官能基当量(eq/t)の1.1倍となるような量とした。
架橋剤は以下のものを用いた。
CL-1:HP-7200(DIC社製エポキシ樹脂)エポキシ当量3,861eq/t
CL-2:jER152(三菱ケミカル社製エポキシ樹脂)エポキシ当量5,747eq/t(Preparation of urethane resin composition solution)
A urethane resin composition solution was prepared by dissolving the urethane resin and the cross-linking agent obtained in Examples or Comparative Examples in methyl ethyl ketone so that the total solid concentration of the urethane resin and the cross-linking agent was 20% by weight. The blending amount of the cross-linking agent was based on the acid value of the urethane resin so that the acid value (eq/t) of the urethane resin was 1.1 times the functional group equivalent (eq/t) of the cross-linking agent.
The following cross-linking agents were used.
CL-1: HP-7200 (Epoxy resin manufactured by DIC) Epoxy equivalent 3,861eq/t
CL-2: jER152 (epoxy resin manufactured by Mitsubishi Chemical Corporation) epoxy equivalent 5,747 eq/t
<耐タック性試験>
上記の方法で調製したウレタン樹脂組成物溶液を銅箔にアプリケータ125μmにて塗工、120℃で3分間乾燥し、塗膜を作製した。乾燥樹脂の上にポリイミドフィルム(カネカ社製 アピカル12.5NPI))を載せ、その上に荷重1kgの標準分銅を載せて40℃雰囲気下で3日静置した後、幅10mm長さ50mmに切断後、引っ張り試験機(島津製オートグラフAG-X plus)を用いて40℃の雰囲気下でポリイミドフィルムを90°の方向に50mm/分の速度で引き剥がし、接着強度を測定した。接着強度が0.1N/mm以下でタックなしと判断した。
評価 ○:タックなし(耐タック性あり)
×:タックあり(耐タック性なし)<Tack resistance test>
The urethane resin composition solution prepared by the above method was applied to a copper foil with an applicator of 125 μm and dried at 120° C. for 3 minutes to prepare a coating film. A polyimide film (Apical 12.5NPI manufactured by Kaneka) is placed on the dry resin, a standard weight with a load of 1 kg is placed on it, and it is left to stand in an atmosphere of 40 ° C for 3 days, then cut into width 10 mm length 50 mm After that, using a tensile tester (Autograph AG-X plus manufactured by Shimadzu Corporation), the polyimide film was peeled off in a 90° direction at a rate of 50 mm/min in an atmosphere of 40°C to measure the adhesive strength. Adhesion strength of 0.1 N/mm or less was judged to be no tack.
Evaluation ○: No tack (with tack resistance)
×: Tacky (no tack resistance)
<引張試験>
上記の方法で調製したウレタン樹脂組成物溶液をテフロン(登録商標)シートにアプリケータ125μmにて塗工、120℃で3分間乾燥後、さらに150℃で1時間キュアし、硬化塗膜を作製した。硬化塗膜を幅10mm長さ50mmに切断して、引張試験片とした。引っ張り試験機(島津製オートグラフAG-X plus)を用いて25℃で50mm/分の速度で引張試験し、破断に達した時の試験片の長さを測定し、以下のように評価した。
評価方法 :伸び(%)=100×(破断時の試験片の長さ-試験前の試験片の長さ)÷試験前の試験片の長さ<Tensile test>
The urethane resin composition solution prepared by the above method was applied to a Teflon (registered trademark) sheet with an applicator of 125 μm, dried at 120° C. for 3 minutes, and further cured at 150° C. for 1 hour to prepare a cured coating film. . The cured coating film was cut to a width of 10 mm and a length of 50 mm to obtain a tensile test piece. Using a tensile tester (Shimadzu Autograph AG-X plus), a tensile test was performed at 25 ° C. at a speed of 50 mm / min, and the length of the test piece when it reached breakage was measured and evaluated as follows. .
Evaluation method: Elongation (%) = 100 × (length of test piece at break - length of test piece before test) / length of test piece before test
<屈曲性試験>
上記の方法で調製したウレタン樹脂組成物溶液に、さらに着色剤としてカーボンブラック(御国色素社製 MHIブラック#C570)を、ウレタン樹脂と架橋剤の合計量100重量部に対し20重量部になるように添加し、固形分濃度が20重量%になるようにメチルエチルケトンを追加し、着色剤混合溶液を得た。
得られた着色剤混合溶液を銅箔にアプリケータ125μmにて塗工、120℃で3分間乾燥後、さらに150℃で1時間キュアし、硬化塗膜を作製した。この塗膜を曲げ半径R=0.2mmにて折り曲げ、元に戻すという作業を10回繰り返し、マイクロスコープ(KEYENCE社製 VHX-1000)にて曲面を観察し、銅箔が見えた箇所をクラックと判断した。
評価 ○:クラックなし
×:クラックあり<Flexibility test>
To the urethane resin composition solution prepared by the above method, carbon black (MHI Black #C570 manufactured by Mikuni Shiso Co., Ltd.) is added as a coloring agent so that the total amount of the urethane resin and the cross-linking agent is 100 parts by weight, and the total amount is 20 parts by weight. and methyl ethyl ketone was added so that the solid content concentration was 20% by weight to obtain a colorant mixed solution.
The resulting colorant mixed solution was applied to a copper foil with an applicator of 125 μm, dried at 120° C. for 3 minutes, and further cured at 150° C. for 1 hour to prepare a cured coating film. This coating film is bent at a bending radius of R = 0.2 mm and then returned to its original position, which is repeated 10 times. I decided.
Evaluation ○: No cracks ×: Cracks present
(実施例1)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、ニューポールBPE-20T(三洋化成工業社製、ポリエーテルポリオール)45.30g(0.149モル)、PTMG2000(三菱ケミカル社製、ポリオレフィンポリオール)105.70g(0.053モル)、2,2-ジメチロールブタン酸10.57g(0.071モル)、4,4’-ジフェニルメタンジイソシアネート(MDI)63.42g(0.253モル)とカレンズMOI(昭和電工社製、2-イソシアネートエチルメタクリレート)5.85g(0.038モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.063g(0.417ミリモル)を加え、溶媒としてシクロヘキサノン137.5g、メチルエチルケトン137.5gに溶解した。その後、窒素気流下、撹拌しながら、80℃で6時間反応させた後、過酸化ラウロイル0.293g(0.735ミリモル)を添加し、さらに80℃5時間反応させた後、n-ブタノール5.85g(0.079モル)を添加し、メチルエチルケトン400.0gにて希釈し、溶液温度を室温まで冷却することにより、不揮発分25質量%の淡黄色で粘調なウレタン樹脂(PU-1)溶液を得た。
樹脂溶液を乾燥した試料10mgを重DMSO0.6mlに溶解後、その溶液をNMRチューブに充填し核磁気共鳴法(1H-NMR)で測定を行った。ロック溶媒には重DMSOを用い、積算回数は64回とした。測定装置はBRUKER社製NMR装置AVANCE-NEO 600(共鳴周波数600MHz)を用いて測定を行った。重DMSOのピークを2.5ppmとした時、ラジカル重合性二重結合に由来するピーク(5.5ppm、6.0ppm)が、ほとんどが消失していることを確認した。(Example 1)
A reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen inlet tube was charged with 45.30 g (0.149 mol) of Newpol BPE-20T (manufactured by Sanyo Chemical Industries, Ltd., polyether polyol), PTMG2000 (manufactured by Mitsubishi Chemical Corporation). , polyolefin polyol) 105.70 g (0.053 mol), 2,2-dimethylolbutanoic acid 10.57 g (0.071 mol), 4,4'-diphenylmethane diisocyanate (MDI) 63.42 g (0.253 mol) ) and 5.85 g (0.038 mol) of Karenz MOI (manufactured by Showa Denko Co., Ltd., 2-isocyanatoethyl methacrylate), and 0.063 g (0.063 g) of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst ( 0.417 mmol) was added and dissolved in 137.5 g of cyclohexanone and 137.5 g of methyl ethyl ketone as solvents. Then, after reacting at 80° C. for 6 hours while stirring under nitrogen stream, 0.293 g (0.735 mmol) of lauroyl peroxide was added and further reacted at 80° C. for 5 hours. .85 g (0.079 mol) is added, diluted with 400.0 g of methyl ethyl ketone, and the solution temperature is cooled to room temperature to obtain a pale yellow and viscous urethane resin (PU-1) having a nonvolatile content of 25% by mass. A solution was obtained.
After dissolving 10 mg of a sample obtained by drying the resin solution in 0.6 ml of heavy DMSO, the solution was filled in an NMR tube and measured by nuclear magnetic resonance ( 1 H-NMR). Deuterated DMSO was used as a lock solvent, and the number of accumulations was 64. Measurement was performed using an NMR apparatus AVANCE-NEO 600 (resonance frequency 600 MHz) manufactured by BRUKER. When the heavy DMSO peak was set at 2.5 ppm, it was confirmed that most of the peaks (5.5 ppm, 6.0 ppm) derived from radically polymerizable double bonds disappeared.
(実施例2)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、ETERNACOLL UM90(1/1)(宇部興産社製、ポリカーボネートポリオール)89.03g(0.099モル)、G-1000(日本曹達社製、ポリオレフィンポリオール)8.09g(0.008モル)、PTMG2000(三菱ケミカル社製、ポリエーテルポリオール)64.75g(0.032モル)、2,2-ジメチロールブタン酸11.33g(0.077モル)、4,4’-ジフェニルメタンジイソシアネート(MDI)51.80g(0.207モル)とカレンズMOI(昭和電工社製、2-イソシアネートエチルメタクリレート)4.56g(0.029モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.052g(0.341ミリモル)を加え、溶媒としてシクロヘキサノン137.5g、メチルエチルケトン137.5gに溶解した。その後、窒素気流下、撹拌しながら、80℃で6時間反応させた後、過酸化ラウロイル0.205g(0.515ミリモル)を添加し、さらに80℃5時間反応させた後、n-ブタノール4.56g(0.058モル)を添加し、メチルエチルケトン400.0gにて希釈し、溶液温度を室温まで冷却することにより、不揮発分25質量%の淡黄色で粘調なウレタン樹脂(PU-2)溶液を得た。実施例1と同様のNMR法にて、ラジカル重合性二重結合がほとんど消失していることを確認した。(Example 2)
ETERNACOLL UM90 (1/1) (manufactured by Ube Industries, polycarbonate polyol) 89.03 g (0.099 mol), G-1000 (Nippon Soda Co., Ltd., polyolefin polyol) 8.09 g (0.008 mol), PTMG2000 (Mitsubishi Chemical Co., Ltd., polyether polyol) 64.75 g (0.032 mol), 2,2-dimethylolbutanoic acid 11.33 g (0 077 mol), 51.80 g (0.207 mol) of 4,4′-diphenylmethane diisocyanate (MDI) and 4.56 g (0.029 mol) of Karenz MOI (manufactured by Showa Denko Co., Ltd., 2-isocyanatoethyl methacrylate). , 0.052 g (0.341 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst and dissolved in 137.5 g of cyclohexanone and 137.5 g of methyl ethyl ketone as solvents. Then, after reacting at 80° C. for 6 hours while stirring under a nitrogen stream, 0.205 g (0.515 mmol) of lauroyl peroxide was added and further reacted at 80° C. for 5 hours. .56 g (0.058 mol) is added, diluted with 400.0 g of methyl ethyl ketone, and the solution temperature is cooled to room temperature to obtain a pale yellow and viscous urethane resin (PU-2) having a nonvolatile content of 25% by mass. A solution was obtained. By the same NMR method as in Example 1, it was confirmed that most of the radically polymerizable double bonds had disappeared.
(実施例3)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、pripol2033(クローダジャパン社製、ダイマーポリオール)283.29g(0.497モル)、デュラノールT5652(旭化成ケミカルズ社製、ポリカーボネートポリオール)70.00g(0.035モル)、2,2-ジメチロールブタン酸24.90g(0.168モル)、4,4’-ジフェニルメタンジイソシアネート(MDI)168.17g(0.672モル)とカレンズMOI(昭和電工社製、2-イソシアネートエチルメタクリレート)14.78g(0.095モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.168g(1.105ミリモル)を加え、溶媒としてシクロヘキサノン362.1g、メチルエチルケトン362.1gに溶解した。その後、窒素気流下、撹拌しながら、80℃で6時間反応させた後、過酸化ラウロイル0.670g(1.681ミリモル)を添加し、さらに80℃5時間反応させた後、n-ブタノール14.78g(0.190モル)を添加し、メチルエチルケトン939.6gにて希釈し、溶液温度を室温まで冷却することにより、不揮発分25質量%の淡黄色で粘調なウレタン樹脂(PU-3)溶液を得た。実施例1と同様のNMR法にて、ラジカル重合性二重結合がほとんど消失していることを確認した。(Example 3)
283.29 g (0.497 mol) of pripol 2033 (manufactured by Croda Japan Co., dimer polyol) and 70% of Duranol T5652 (manufactured by Asahi Kasei Chemicals, polycarbonate polyol) were placed in a reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen inlet tube. .00 g (0.035 mol), 24.90 g (0.168 mol) of 2,2-dimethylolbutanoic acid, 168.17 g (0.672 mol) of 4,4'-diphenylmethane diisocyanate (MDI) and Karenz MOI ( 14.78 g (0.095 mol) of 2-isocyanatoethyl methacrylate manufactured by Showa Denko Co., Ltd. was charged, and 0.168 g (1.105 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene was used as a catalyst. was added and dissolved in 362.1 g of cyclohexanone and 362.1 g of methyl ethyl ketone as solvents. Then, after reacting at 80° C. for 6 hours while stirring under a nitrogen stream, 0.670 g (1.681 mmol) of lauroyl peroxide was added and further reacted at 80° C. for 5 hours. .78 g (0.190 mol) is added, diluted with 939.6 g of methyl ethyl ketone, and the solution temperature is cooled to room temperature to obtain a pale yellow and viscous urethane resin (PU-3) having a nonvolatile content of 25% by mass. A solution was obtained. By the same NMR method as in Example 1, it was confirmed that most of the radically polymerizable double bonds had disappeared.
(実施例4)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、GK390(東洋紡社製、ポリエステルポリオール、酸価1eq/t未満)393.53g(0.026モル)、2,2-ジメチロールブタン酸19.68g(0.133モル)、4,4’-ジフェニルメタンジイソシアネート(MDI)37.32g(0.149モル)とカレンズMOI(昭和電工社製、2-イソシアネートエチルメタクリレート)3.36g(0.022モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.037g(0.245ミリモル)を加え、溶媒としてシクロヘキサノン298.6g、メチルエチルケトン298.6gに溶解した。その後、窒素気流下、撹拌しながら、80℃で6時間反応させた後、過酸化ラウロイル0.151g(0.379ミリモル)を添加し、さらに80℃5時間反応させた後、n-ブタノール3.36g(0.044モル)を添加し、メチルエチルケトン760.0gにて希釈し、溶液温度を室温まで冷却することにより、不揮発分25質量%の淡黄色で粘調なウレタン樹脂(PU-4)溶液を得た。実施例1と同様のNMR法にて、ラジカル重合性二重結合がほとんど消失していることを確認した。(Example 4)
GK390 (manufactured by Toyobo Co., Ltd., polyester polyol, acid value less than 1 eq/t) 393.53 g (0.026 mol), 2,2-dimethylol were added to a reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen inlet tube. 19.68 g (0.133 mol) of butanoic acid, 37.32 g (0.149 mol) of 4,4′-diphenylmethane diisocyanate (MDI) and 3.36 g (2-isocyanatoethyl methacrylate, manufactured by Showa Denko Co., Ltd.) of Karenz MOI ( 0.022 mol) was charged, 0.037 g (0.245 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and 298.6 g of cyclohexanone and 298.6 g of methyl ethyl ketone were added as solvents. Dissolved. Then, after reacting at 80° C. for 6 hours while stirring under a nitrogen stream, 0.151 g (0.379 mmol) of lauroyl peroxide was added and further reacted at 80° C. for 5 hours. .36 g (0.044 mol) is added, diluted with 760.0 g of methyl ethyl ketone, and the solution temperature is cooled to room temperature to obtain a pale yellow and viscous urethane resin (PU-4) having a nonvolatile content of 25% by mass. A solution was obtained. By the same NMR method as in Example 1, it was confirmed that most of the radically polymerizable double bonds had disappeared.
(実施例5)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、UR3200(東洋紡社製、ポリウレタンポリオール、酸価1eq/t未満)394.74g(0.013モル)、2,2-ジメチロールブタン酸19.74g(0.133モル)、4,4’-ジフェニルメタンジイソシアネート(MDI)35.53g(0.142モル)とカレンズMOI(昭和電工社製、2-イソシアネートエチルメタクリレート)3.09g(0.020モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.036g(0.233ミリモル)を加え、溶媒としてシクロヘキサノン298.8g、メチルエチルケトン298.8gに溶解した。その後、窒素気流下、撹拌しながら、80℃で6時間反応させた後、過酸化ラウロイル0.139g(0.349ミリモル)を添加し、さらに80℃5時間反応させた後、n-ブタノール0.139g(0.002モル)を添加し、メチルエチルケトン760.1gにて希釈し、溶液温度を室温まで冷却することにより、不揮発分25質量%の淡黄色で粘調なウレタン樹脂(PU-5)溶液を得た。実施例1と同様のNMR法にて、ラジカル重合性二重結合がほとんど消失していることを確認した。(Example 5)
394.74 g (0.013 mol) of UR3200 (manufactured by Toyobo Co., Ltd., polyurethane polyol, acid value less than 1 eq/t) and 2,2-dimethylol were placed in a reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen inlet tube. 19.74 g (0.133 mol) of butanoic acid, 35.53 g (0.142 mol) of 4,4′-diphenylmethane diisocyanate (MDI) and 3.09 g (2-isocyanatoethyl methacrylate, manufactured by Showa Denko Co., Ltd.) of Karenz MOI ( 0.020 mol) was charged, 0.036 g (0.233 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and 298.8 g of cyclohexanone and 298.8 g of methyl ethyl ketone were added as solvents. Dissolved. After that, the mixture was reacted at 80° C. for 6 hours while stirring under a nitrogen stream, then 0.139 g (0.349 mmol) of lauroyl peroxide was added, and the mixture was further reacted at 80° C. for 5 hours. .139 g (0.002 mol) is added, diluted with 760.1 g of methyl ethyl ketone, and the solution temperature is cooled to room temperature to obtain a pale yellow and viscous urethane resin (PU-5) having a nonvolatile content of 25% by mass. A solution was obtained. By the same NMR method as in Example 1, it was confirmed that most of the radically polymerizable double bonds had disappeared.
(実施例6)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、ETERNACOLL UM90(1/1)(宇部興産社製、ポリカーボネートポリオール)107.14g(0.119モル)、PTMG2000(三菱ケミカル社製、ポリエーテルポリオール)71.43g(0.036モル)、2,2-ジメチロールブタン酸10.71g(0.072モル)、ヘキサメチレンジイソシアネート(HDI)35.71g(0.212モル)とカレンズMOI(昭和電工社製、2-イソシアネートエチルメタクリレート)4.79g(0.031モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.036g(0.234ミリモル)を加え、溶媒としてシクロヘキサノン149.4g、メチルエチルケトン149.4gに溶解した。その後、窒素気流下、撹拌しながら、80℃で6時間反応させた後、過酸化ラウロイル0.216g(0.541ミリモル)を添加し、さらに80℃5時間反応させた後、n-ブタノール4.79g(0.062モル)を添加し、メチルエチルケトン385.5gにて希釈し、溶液温度を室温まで冷却することにより、不揮発分25質量%の淡黄色で粘調なウレタン樹脂(PU-6)溶液を得た。実施例1と同様のNMR法にて、ラジカル重合性二重結合がほとんど消失していることを確認した。(Example 6)
ETERNACOLL UM90 (1/1) (manufactured by Ube Industries, polycarbonate polyol) 107.14 g (0.119 mol), PTMG2000 (manufactured by Mitsubishi Chemical Co., Ltd.), , polyether polyol) 71.43 g (0.036 mol), 2,2-dimethylolbutanoic acid 10.71 g (0.072 mol), hexamethylene diisocyanate (HDI) 35.71 g (0.212 mol) and Karenz 4.79 g (0.031 mol) of MOI (manufactured by Showa Denko KK, 2-isocyanatoethyl methacrylate) was charged, and 0.036 g (0.234 mol) of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst. millimoles) was added and dissolved in 149.4 g of cyclohexanone and 149.4 g of methyl ethyl ketone as solvents. Then, after reacting at 80° C. for 6 hours while stirring under a nitrogen stream, 0.216 g (0.541 mmol) of lauroyl peroxide was added and further reacted at 80° C. for 5 hours. .79 g (0.062 mol) is added, diluted with 385.5 g of methyl ethyl ketone, and the solution temperature is cooled to room temperature to obtain a pale yellow and viscous urethane resin (PU-6) having a nonvolatile content of 25% by mass. A solution was obtained. By the same NMR method as in Example 1, it was confirmed that most of the radically polymerizable double bonds had disappeared.
(実施例7)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、ETERNACOLL UM-90(1/1)(宇部興産社製、ポリカーボネートポリオール)99.00g(0.110モル)、PTMG2000(三菱ケミカル社製、ポリエーテルポリオール)81.00g(0.041モル)、2,2-ジメチロールブタン酸3.60g(0.024モル)、4,4’-ジフェニルメタンジイソシアネート(MDI)41.40g(0.165モル)とカレンズMOI(昭和電工社製、2-イソシアネートエチルメタクリレート)3.69g(0.024モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.041g(0.272ミリモル)を加え、溶媒としてシクロヘキサノン149.5g、メチルエチルケトン149.5gに溶解した。その後、窒素気流下、撹拌しながら、80℃で6時間反応させた後、過酸化ラウロイル0.166g(0.417ミリモル)を添加し、さらに80℃5時間反応させた後、n-ブタノール3.69g(0.048モル)を添加し、メチルエチルケトン385.5gにて希釈し、溶液温度を室温まで冷却することにより、不揮発分25質量%の淡黄色で粘調なウレタン樹脂(PU-7)溶液を得た。実施例1と同様のNMR法にて、ラジカル重合性二重結合がほとんど消失していることを確認した。(Example 7)
ETERNACOLL UM-90 (1/1) (manufactured by Ube Industries, polycarbonate polyol) 99.00 g (0.110 mol), PTMG2000 (Mitsubishi Chemical Co., Ltd., polyether polyol) 81.00 g (0.041 mol), 2,2-dimethylolbutanoic acid 3.60 g (0.024 mol), 4,4′-diphenylmethane diisocyanate (MDI) 41.40 g (0 .165 mol) and 3.69 g (0.024 mol) of Karenz MOI (manufactured by Showa Denko Co., Ltd., 2-isocyanatoethyl methacrylate) were charged, and 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst. 0.041 g (0.272 mmol) was added and dissolved in 149.5 g of cyclohexanone and 149.5 g of methyl ethyl ketone as solvents. After that, the mixture was reacted at 80° C. for 6 hours while stirring under a nitrogen stream, then 0.166 g (0.417 mmol) of lauroyl peroxide was added, and the mixture was further reacted at 80° C. for 5 hours. .69 g (0.048 mol) is added, diluted with 385.5 g of methyl ethyl ketone, and the solution temperature is cooled to room temperature to obtain a pale yellow and viscous urethane resin (PU-7) having a nonvolatile content of 25% by mass. A solution was obtained. By the same NMR method as in Example 1, it was confirmed that most of the radically polymerizable double bonds had disappeared.
(実施例8)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、ETERNACOLL UM90(1/1)(宇部興産社製、ポリカーボネートポリオール)78.95g(0.088モル)、PTMG2000(三菱ケミカル社製、ポリエーテルポリオール)78.95g(0.039モル)、2,2-ジメチロールブタン酸15.00g(0.101モル)、4,4’-ジフェニルメタンジイソシアネート(MDI)52.21g(0.209モル)とカレンズMOI(昭和電工社製、2-イソシアネートエチルメタクリレート)4.83g(0.031モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.052g(0.343ミリモル)を加え、溶媒としてシクロヘキサノン149.4g、メチルエチルケトン149.4gに溶解した。その後、窒素気流下、撹拌しながら、80℃で6時間反応させた後、過酸化ラウロイル0.218g(0.546ミリモル)を添加し、さらに80℃5時間反応させた後、n-ブタノール4.83g(0.062モル)を添加し、メチルエチルケトン384.9gにて希釈し、溶液温度を室温まで冷却することにより、不揮発分25質量%の淡黄色で粘調なウレタン樹脂(PU-8)溶液を得た。実施例1と同様のNMR法にて、ラジカル重合性二重結合がほとんど消失していることを確認した。(Example 8)
ETERNACOLL UM90 (1/1) (manufactured by Ube Industries, polycarbonate polyol) 78.95 g (0.088 mol), PTMG2000 (manufactured by Mitsubishi Chemical Co., Ltd.), , polyether polyol) 78.95 g (0.039 mol), 2,2-dimethylolbutanoic acid 15.00 g (0.101 mol), 4,4'-diphenylmethane diisocyanate (MDI) 52.21 g (0.209 mol) and 4.83 g (0.031 mol) of Karenz MOI (manufactured by Showa Denko Co., Ltd., 2-isocyanatoethyl methacrylate), and 0.052 g of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst. (0.343 mmol) was added and dissolved in 149.4 g of cyclohexanone and 149.4 g of methyl ethyl ketone as solvents. Then, after reacting at 80° C. for 6 hours while stirring under a nitrogen stream, 0.218 g (0.546 mmol) of lauroyl peroxide was added and further reacted at 80° C. for 5 hours. .83 g (0.062 mol) is added, diluted with 384.9 g of methyl ethyl ketone, and the solution temperature is cooled to room temperature to obtain a pale yellow and viscous urethane resin (PU-8) having a nonvolatile content of 25% by mass. A solution was obtained. By the same NMR method as in Example 1, it was confirmed that most of the radically polymerizable double bonds had disappeared.
(実施例9)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、pripol2033(クローダジャパン社製、ダイマーポリオール)283.29g(0.497モル)、デュラノールT5652(旭化成ケミカルズ社製、ポリカーボネートポリオール)70.00g(0.035モル)、2,2-ジメチロールブタン酸24.90g(0.168モル)、4,4’-ジフェニルメタンジイソシアネート(MDI)168.17g(0.672モル)とカレンズMOI(昭和電工社製、2-イソシアネートエチルメタクリレート)14.78g(0.095モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.168(1.105ミリモル)を加え、溶媒としてシクロヘキサノン362.1g、メチルエチルケトン362.1gに溶解した。その後、窒素気流下、撹拌しながら、80℃で6時間反応させた後、過酸化ラウロイル0.449g(1.13ミリモル)を添加し、さらに80℃5時間反応させた後、n-ブタノール14.78g(0.190モル)を添加し、メチルエチルケトン939.6gにて希釈し、溶液温度を室温まで冷却することにより、不揮発分25質量%の淡黄色で粘調なウレタン樹脂(PU-9)溶液を得た。実施例1と同様のNMR法にて、ラジカル重合性二重結合がほとんど消失していることを確認した。(Example 9)
283.29 g (0.497 mol) of pripol 2033 (manufactured by Croda Japan Co., dimer polyol) and 70% of Duranol T5652 (manufactured by Asahi Kasei Chemicals, polycarbonate polyol) were placed in a reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen inlet tube. .00 g (0.035 mol), 24.90 g (0.168 mol) of 2,2-dimethylolbutanoic acid, 168.17 g (0.672 mol) of 4,4'-diphenylmethane diisocyanate (MDI) and Karenz MOI ( 14.78 g (0.095 mol) of 2-isocyanatoethyl methacrylate manufactured by Showa Denko Co., Ltd. was charged, and 0.168 (1.105 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene was used as a catalyst. was added and dissolved in 362.1 g of cyclohexanone and 362.1 g of methyl ethyl ketone as solvents. Then, after reacting at 80° C. for 6 hours while stirring under a nitrogen stream, 0.449 g (1.13 mmol) of lauroyl peroxide was added and further reacted at 80° C. for 5 hours. .78 g (0.190 mol) is added, diluted with 939.6 g of methyl ethyl ketone, and the solution temperature is cooled to room temperature to obtain a pale yellow and viscous urethane resin (PU-9) having a nonvolatile content of 25% by mass. A solution was obtained. By the same NMR method as in Example 1, it was confirmed that most of the radically polymerizable double bonds had disappeared.
(実施例10)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、pripol2033(クローダジャパン社製、ダイマーポリオール)283.29g(0.497モル)、デュラノールT5652(旭化成ケミカルズ社製、ポリカーボネートポリオール)70.00g、(0.035モル)、2,2-ジメチロールブタン酸24.90g(0.168モル)、4,4’-ジフェニルメタンジイソシアネート(MDI)168.17g(0.672モル)とカレンズMOI(昭和電工社製、2-イソシアネートエチルメタクリレート)14.78g(0.095モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.168(1.105ミリモル)を加え、溶媒としてシクロヘキサノン362.1g、メチルエチルケトン362.1gに溶解した。その後、窒素気流下、撹拌しながら、80℃で6時間反応させた後、過酸化ラウロイル1.34g(3.36ミリモル)を添加し、さらに80℃5時間反応させた後、n-ブタノール14.78g(0.190モル)を添加し、メチルエチルケトン939.6gにて希釈し、溶液温度を室温まで冷却することにより、不揮発分25質量%の淡黄色で粘調なウレタン樹脂(PU-10)溶液を得た。実施例1と同様のNMR法にて、ラジカル重合性二重結合がほとんど消失していることを確認した。(Example 10)
283.29 g (0.497 mol) of pripol 2033 (manufactured by Croda Japan Co., dimer polyol) and 70% of Duranol T5652 (manufactured by Asahi Kasei Chemicals, polycarbonate polyol) were placed in a reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen inlet tube. .00 g, (0.035 mol), 24.90 g (0.168 mol) of 2,2-dimethylolbutanoic acid, 168.17 g (0.672 mol) of 4,4'-diphenylmethane diisocyanate (MDI) and Karenz MOI 14.78 g (0.095 mol) of 2-isocyanatoethyl methacrylate (manufactured by Showa Denko Co., Ltd.) was charged, and 0.168 (1.105 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene was used as a catalyst. ) was added and dissolved in 362.1 g of cyclohexanone and 362.1 g of methyl ethyl ketone as solvents. Then, after reacting at 80° C. for 6 hours while stirring under a nitrogen stream, 1.34 g (3.36 mmol) of lauroyl peroxide was added and further reacted at 80° C. for 5 hours. .78 g (0.190 mol) is added, diluted with 939.6 g of methyl ethyl ketone, and the solution temperature is cooled to room temperature to obtain a pale yellow and viscous urethane resin (PU-10) having a nonvolatile content of 25% by mass. A solution was obtained. By the same NMR method as in Example 1, it was confirmed that most of the radically polymerizable double bonds had disappeared.
(比較例1)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、pripol2033(クローダジャパン社製、ダイマーポリオール)139.75g(0.245モル)、2,2-ジメチロールブタン酸9.78g(0.066モル)、4,4’-ジフェニルメタンジイソシアネート(MDI)75.47g(0.302モル)とカレンズMOI(昭和電工社製、2-イソシアネートエチルメタクリレート)6.56g(0.042モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.075(0.495ミリモル)を加え、溶媒としてシクロヘキサノン137.5g、メチルエチルケトン137.5gに溶解した。その後、窒素気流下、撹拌しながら、80℃で6時間反応させた後、n-ブタノール6.56g(0.079モル)を添加し、メチルエチルケトン400.0gにて希釈し、溶液温度を室温まで冷却することにより、不揮発分25質量%の淡黄色で粘調なウレタン樹脂(PU-11)溶液を得た。実施例1と同様のNMR法にて、ラジカル重合性二重結合が残存していることを確認した。(Comparative example 1)
In a reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen inlet tube, 139.75 g (0.245 mol) of pripol 2033 (manufactured by Croda Japan, dimer polyol), 9.78 g of 2,2-dimethylolbutanoic acid ( 0.066 mol), 75.47 g (0.302 mol) of 4,4′-diphenylmethane diisocyanate (MDI) and 6.56 g (0.042 mol) of Karenz MOI (manufactured by Showa Denko Co., Ltd., 2-isocyanatoethyl methacrylate). 0.075 (0.495 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst and dissolved in 137.5 g of cyclohexanone and 137.5 g of methyl ethyl ketone as solvents. Then, after reacting at 80° C. for 6 hours while stirring under a nitrogen stream, 6.56 g (0.079 mol) of n-butanol is added, diluted with 400.0 g of methyl ethyl ketone, and the solution temperature is raised to room temperature. By cooling, a pale yellow viscous urethane resin (PU-11) solution having a non-volatile content of 25% by mass was obtained. By the same NMR method as in Example 1, it was confirmed that radically polymerizable double bonds remained.
(比較例2)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、pripol2033(クローダジャパン社製、ダイマーポリオール)139.75g(0.245モル)、2,2-ジメチロールブタン酸9.78g(0.066モル)、4,4’-ジフェニルメタンジイソシアネート(MDI)226.41g(0.906モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.075g(0.495ミリモル)を加え、溶媒としてシクロヘキサノン137.5g、メチルエチルケトン137.5gに溶解した。その後、窒素気流下、撹拌しながら、80℃で反応させたところ、MDIがポリオールに対し大過剰であるため分子量が増大していき、重合溶液がゲル化したため、ウレタン樹脂(PU-12)溶液を得ることができなかった。(Comparative example 2)
In a reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen inlet tube, 139.75 g (0.245 mol) of pripol 2033 (manufactured by Croda Japan, dimer polyol), 9.78 g of 2,2-dimethylolbutanoic acid ( 0.066 mol) and 226.41 g (0.906 mol) of 4,4'-diphenylmethane diisocyanate (MDI) were charged, and 0.075 g of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst ( 0.495 mmol) was added and dissolved in 137.5 g of cyclohexanone and 137.5 g of methyl ethyl ketone as solvents. After that, when the reaction was carried out at 80°C while stirring under a nitrogen stream, the molecular weight increased due to the large excess of MDI relative to the polyol, and the polymerization solution gelled, resulting in a urethane resin (PU-12) solution. could not get
(比較例3)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、UR3958(東洋紡社製、ポリウレタンポリオール、酸価1eq/t未満)444.66g(0.022モル)、2,2-ジメチロールブタン酸19.68g(0.133モル)、4,4’-ジフェニルメタンジイソシアネート(MDI)5.34g(0.021モル)とカレンズMOI(昭和電工社製、2-イソシアネートエチルメタクリレート)0.47g(0.003モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.005g(0.035ミリモル)を加え、溶媒としてシクロヘキサノン298.3g、メチルエチルケトン298.3gに溶解した。その後、窒素気流下、撹拌しながら、80℃で6時間反応させた後、過酸化ラウロイル0.021g(0.053ミリモル)を添加し、さらに80℃5時間反応させた後、n-ブタノール0.47g(0.006モル)を添加し、メチルエチルケトン754.4gにて希釈し、溶液温度を室温まで冷却することにより、不揮発分25質量%の淡黄色で粘調なウレタン樹脂(PU-13)溶液を得た。実施例1と同様のNMR法にて、ラジカル重合性二重結合がほとんど消失していることを確認した。(Comparative Example 3)
444.66 g (0.022 mol) of UR3958 (Toyobo Co., Ltd., polyurethane polyol, acid value less than 1 eq/t) and 2,2-dimethylol were added to a reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen inlet tube. 19.68 g (0.133 mol) of butanoic acid, 5.34 g (0.021 mol) of 4,4′-diphenylmethane diisocyanate (MDI) and 0.47 g (2-isocyanatoethyl methacrylate, manufactured by Showa Denko Co., Ltd.) of Karenz MOI ( 0.003 mol) was charged, 0.005 g (0.035 mmol) of 1,8-diazabicyclo[5.4.0]-7-undecene was added as a catalyst, and 298.3 g of cyclohexanone and 298.3 g of methyl ethyl ketone were added as solvents. Dissolved. Then, after reacting at 80° C. for 6 hours while stirring under a nitrogen stream, 0.021 g (0.053 mmol) of lauroyl peroxide was added and further reacted at 80° C. for 5 hours. .47 g (0.006 mol) is added, diluted with 754.4 g of methyl ethyl ketone, and the solution temperature is cooled to room temperature to obtain a pale yellow and viscous urethane resin (PU-13) having a nonvolatile content of 25% by mass. A solution was obtained. By the same NMR method as in Example 1, it was confirmed that most of the radically polymerizable double bonds had disappeared.
(比較例4)
攪拌装置、温度計、コンデンサー、窒素導入管を備えた反応容器に、ETERNACOLL UM90(1/1)(宇部興産社製、ポリカーボネートポリオール)77.92g(0.137モル)、PTMG2000(三菱ケミカル社製、ポリエーテルポリオール)116.88g(0.058モル)、2,2-ジメチロールブタン酸10.71g(0.072モル)、4,4’-ジフェニルメタンジイソシアネート(MDI)19.48g(0.078モル)とカレンズMOI(昭和電工社製、2-イソシアネートエチルメタクリレート)2.94g(0.019モル)を仕込み、触媒として1,8-ジアザビシクロ[5.4.0]-7-ウンデセン0.020g(0.128ミリモル)を加え、溶媒としてシクロヘキサノン148.3g、メチルエチルケトン148.3gに溶解した。その後、窒素気流下、撹拌しながら、80℃で6時間反応させた後、過酸化ラウロイル0.132g(0.331ミリモル)を添加し、さらに80℃5時間反応させた後、n-ブタノール2.94g(0.038モル)を添加し、メチルエチルケトン403.0gにて希釈し、溶液温度を室温まで冷却することにより、不揮発分25質量%の淡黄色で粘調なウレタン樹脂(PU-14)溶液を得た。実施例1と同様のNMR法にて、ラジカル重合性二重結合がほとんど消失していることを確認した。(Comparative Example 4)
ETERNACOLL UM90 (1/1) (manufactured by Ube Industries, polycarbonate polyol) 77.92 g (0.137 mol), PTMG2000 (manufactured by Mitsubishi Chemical Co., Ltd.) , polyether polyol) 116.88 g (0.058 mol), 2,2-dimethylolbutanoic acid 10.71 g (0.072 mol), 4,4'-diphenylmethane diisocyanate (MDI) 19.48 g (0.078 mol) and 2.94 g (0.019 mol) of Karenz MOI (manufactured by Showa Denko Co., Ltd., 2-isocyanatoethyl methacrylate), and 0.020 g of 1,8-diazabicyclo[5.4.0]-7-undecene as a catalyst. (0.128 mmol) was added and dissolved in 148.3 g of cyclohexanone and 148.3 g of methyl ethyl ketone as solvents. Then, after reacting at 80° C. for 6 hours while stirring under a nitrogen stream, 0.132 g (0.331 mmol) of lauroyl peroxide was added and further reacted at 80° C. for 5 hours. .94 g (0.038 mol) is added, diluted with 403.0 g of methyl ethyl ketone, and the solution temperature is cooled to room temperature to obtain a pale yellow and viscous urethane resin (PU-14) having a nonvolatile content of 25% by mass. A solution was obtained. By the same NMR method as in Example 1, it was confirmed that most of the radically polymerizable double bonds had disappeared.
上記実施例および比較例で得られたウレタン樹脂の性状を表1に、試験評価結果を表2にそれぞれ示した。 Table 1 shows the properties of the urethane resins obtained in the above Examples and Comparative Examples, and Table 2 shows the test evaluation results.
比較例1においては重量平均分子量が小さいため、引張伸びも小さく、屈曲性試験にてクラックが発生した。比較例2は、比較例1と同程度の分子量分布(Mw/Mn)となるようにウレタン重合により高分子量化を行ったが、重合溶液がゲル化し、ウレタン樹脂溶液を得られなかった。比較例3においてはポリオール全体のガラス転移温度および製造後のウレタン樹脂としてのガラス転移温度も低いため、40℃におけるタックが発生した。比較例4においては分子量分布(Mw/Mn)が高いものの、重量平均分子量が低いために伸度が低く、屈曲性試験にてクラックが発生した。一方、表2からわかるように、実施例1~10では、耐タック性、可撓性(屈曲性、伸び)が良好なウレタン樹脂が得られた。 In Comparative Example 1, since the weight average molecular weight was small, the tensile elongation was also small, and cracks occurred in the flexibility test. In Comparative Example 2, the molecular weight distribution (Mw/Mn) was increased to the same level as in Comparative Example 1 by urethane polymerization, but the polymerization solution gelled and a urethane resin solution could not be obtained. In Comparative Example 3, since the glass transition temperature of the polyol as a whole and the glass transition temperature of the urethane resin after production were both low, tack occurred at 40°C. In Comparative Example 4, although the molecular weight distribution (Mw/Mn) was high, the elongation was low due to the low weight average molecular weight, and cracks occurred in the flexibility test. On the other hand, as can be seen from Table 2, in Examples 1 to 10, urethane resins having good tack resistance and flexibility (flexibility, elongation) were obtained.
本発明のウレタン樹脂は耐タック性に優れるため、フィルムに塗工し、ロール状に保管しても張り付きの問題がない。また可撓性にも優れているため、耐屈曲性を求められる接着剤組成物として利用でき、特にFPC用接着剤として有用である。
Since the urethane resin of the present invention is excellent in tack resistance, there is no sticking problem even when it is applied to a film and stored in a roll form. Moreover, since it is excellent in flexibility, it can be used as an adhesive composition that requires bending resistance, and is particularly useful as an adhesive for FPC.
Claims (8)
(1)ガラス転移温度(Tg)が40℃以上である
(2)重量平均分子量(Mw)が180000~2000000である
(3)分子量分布(Mw/Mn)が9~200である(ここでMnは数平均分子量を表す) A urethane resin that satisfies the following (1) to (3) and has a carboxyl group .
(1) Glass transition temperature (Tg) is 40° C. or higher (2) Weight average molecular weight (Mw) is 180,000 to 2,000,000 (3) Molecular weight distribution (Mw/Mn) is 9 to 200 (where Mn represents the number average molecular weight)
(1)ガラス転移温度(Tg)が40℃以上である
(2)重量平均分子量(Mw)が180000~2000000である
(3)分子量分布(Mw/Mn)が9~200である At least a polyol (A), a polyisocyanate compound (B), a compound (C) having a functional group reactive with a hydroxyl group or an isocyanate group and a radically polymerizable double bond in the same molecule and one or more carboxyl groups A method for producing a urethane resin that satisfies the following (1) to (3), characterized by further radically polymerizing a urethane polymer having a polyol (D) having as a structural unit.
(1) Glass transition temperature (Tg) is 40° C. or higher
(2) Weight average molecular weight (Mw) is 180000 to 2000000
(3) molecular weight distribution (Mw/Mn) is 9 to 200
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