CN116004173A - UV delay curing reaction type polyurethane hot melt adhesive with high initial bonding strength, and preparation method and application thereof - Google Patents
UV delay curing reaction type polyurethane hot melt adhesive with high initial bonding strength, and preparation method and application thereof Download PDFInfo
- Publication number
- CN116004173A CN116004173A CN202211717296.XA CN202211717296A CN116004173A CN 116004173 A CN116004173 A CN 116004173A CN 202211717296 A CN202211717296 A CN 202211717296A CN 116004173 A CN116004173 A CN 116004173A
- Authority
- CN
- China
- Prior art keywords
- hot melt
- melt adhesive
- diisocyanate
- polyurethane hot
- alkali
- 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.)
- Pending
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 69
- 239000004814 polyurethane Substances 0.000 title claims abstract description 64
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 63
- 238000006757 chemical reactions by type Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 54
- 230000035755 proliferation Effects 0.000 claims abstract description 28
- 239000012948 isocyanate Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 12
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims description 68
- -1 polyol compound Chemical class 0.000 claims description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 229920005862 polyol Polymers 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 27
- 150000003077 polyols Chemical class 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 16
- 150000002009 diols Chemical class 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 14
- 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 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- 229920000515 polycarbonate Polymers 0.000 claims description 10
- 239000004417 polycarbonate Substances 0.000 claims description 10
- 238000005286 illumination Methods 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 8
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- 239000005056 polyisocyanate Substances 0.000 claims description 8
- 229920001228 polyisocyanate Polymers 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005935 nucleophilic addition reaction Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- XXSCONYSQQLHTH-UHFFFAOYSA-N 9h-fluoren-9-ylmethanol Chemical compound C1=CC=C2C(CO)C3=CC=CC=C3C2=C1 XXSCONYSQQLHTH-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 229920005906 polyester polyol Polymers 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 claims description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 229930002877 anthocyanin Natural products 0.000 claims description 4
- 235000010208 anthocyanin Nutrition 0.000 claims description 4
- 239000004410 anthocyanin Substances 0.000 claims description 4
- 150000004636 anthocyanins Chemical class 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- 229920001281 polyalkylene Polymers 0.000 claims description 4
- 150000004032 porphyrins Chemical class 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- BSKLKCJVOHJWHU-UHFFFAOYSA-N 6-hydroxyhexyl hydrogen carbonate Chemical compound OCCCCCCOC(O)=O BSKLKCJVOHJWHU-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 3
- 150000001409 amidines Chemical class 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 229920005604 random copolymer Polymers 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- VZXPHDGHQXLXJC-UHFFFAOYSA-N 1,6-diisocyanato-5,6-dimethylheptane Chemical compound O=C=NC(C)(C)C(C)CCCCN=C=O VZXPHDGHQXLXJC-UHFFFAOYSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 claims description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical class C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 2
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 claims description 2
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical compound OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 claims description 2
- IIGAAOXXRKTFAM-UHFFFAOYSA-N N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C Chemical compound N=C=O.N=C=O.CC1=C(C)C(C)=C(C)C(C)=C1C IIGAAOXXRKTFAM-UHFFFAOYSA-N 0.000 claims description 2
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- 150000008062 acetophenones Chemical class 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical class C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019256 formaldehyde Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- NFMHSPWHNQRFNR-UHFFFAOYSA-N hyponitrous acid Chemical class ON=NO NFMHSPWHNQRFNR-UHFFFAOYSA-N 0.000 claims description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 150000003505 terpenes Chemical class 0.000 claims description 2
- 235000007586 terpenes Nutrition 0.000 claims description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- AMJYHMCHKZQLAY-UHFFFAOYSA-N tris(2-isocyanatophenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound O=C=NC1=CC=CC=C1OP(=S)(OC=1C(=CC=CC=1)N=C=O)OC1=CC=CC=C1N=C=O AMJYHMCHKZQLAY-UHFFFAOYSA-N 0.000 claims description 2
- 229940075420 xanthine Drugs 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims 2
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 2
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- ANLVEXKNRYNLDH-UHFFFAOYSA-N 1,3-dioxonan-2-one Chemical compound O=C1OCCCCCCO1 ANLVEXKNRYNLDH-UHFFFAOYSA-N 0.000 claims 1
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- YWUOZTWCMHLQJI-UHFFFAOYSA-M sodium;ethoxy-ethylsulfanyl-oxido-sulfanylidene-$l^{5}-phosphane Chemical class [Na+].CCOP([O-])(=S)SCC YWUOZTWCMHLQJI-UHFFFAOYSA-M 0.000 claims 1
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
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- ICLZNGAELWYHKL-CAPFRKAQSA-N (E)-3-[5-[5-[4-(N-phenylanilino)phenyl]thiophen-2-yl]thiophen-2-yl]prop-2-enoic acid Chemical compound OC(=O)\C=C\c1ccc(s1)-c1ccc(s1)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 ICLZNGAELWYHKL-CAPFRKAQSA-N 0.000 description 3
- IKVYHNPVKUNCJM-UHFFFAOYSA-N 4-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(C(C)C)=CC=C2 IKVYHNPVKUNCJM-UHFFFAOYSA-N 0.000 description 3
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- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
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- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
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- 238000004026 adhesive bonding Methods 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- ZKDDJTYSFCWVGS-UHFFFAOYSA-M sodium;diethoxy-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Na+].CCOP([S-])(=S)OCC ZKDDJTYSFCWVGS-UHFFFAOYSA-M 0.000 description 1
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Images
Abstract
The invention belongs to the field of adhesives, and particularly relates to a UV (ultraviolet) delay curing reactive polyurethane hot melt adhesive with high initial bonding strength, and a preparation method and application thereof. The UV delay curing reaction type polyurethane hot melt adhesive with high initial bonding strength comprises isocyanate terminated polyurethane prepolymer, photo-alkaline agent, alkaline proliferation agent, photosensitizer and tackifying resin. The UV delay curing reaction type polyurethane hot melt adhesive provided by the invention has the characteristics of high initial bonding strength and suitability for opaque substrates.
Description
Technical Field
The invention belongs to the field of adhesives, and particularly relates to a UV (ultraviolet) delay curing reactive polyurethane hot melt adhesive with high initial bonding strength, and a preparation method and application thereof.
Background
The reactive polyurethane hot melt adhesive (PUR) is characterized by no solvent, environmental protection, suitability for bonding various base materials, capability of being matched with automatic dispensing of a production line and the like, and is commonly used for bonding screens of intelligent electronic products, bonding structural members, bonding and assembling parts and the like. However, the main component of the traditional reactive polyurethane hot melt adhesive is polyurethane prepolymer blocked by isocyanate groups, the curing is realized mainly by the reaction of the isocyanate groups and moisture in the air, the reaction process is very slow, the initial bonding strength is low, longer dwell time (about 1-2 h) is needed in practical application, more dwell tools are needed to be customized and used, the production cost is high, the production efficiency is low, the bonding requirement of a large number of opaque substrates cannot be met, and the application scene is limited.
The existing reactive polyurethane hot melt adhesive mainly improves the initial bonding strength by the following methods: (1) Increasing the addition amount of the crystalline raw material, and forming crystals after cooling the crystalline raw material to improve the initial bonding strength; (2) The addition amount of the raw materials with high softening point and/or large molecular weight is increased, and the characteristic that the raw materials can be quickly changed into solid after being cooled is utilized to improve the initial strength; (3) Introducing an acrylic ester UV light curing component into the reactive polyurethane hot melt adhesive, initiating the photo-curing of an acrylic ester raw material by using UV light, and providing initial bonding strength by photo-curing resin; (4) The photo-alkali generating agent is added into the reactive polyurethane hot melt adhesive, an alkaline catalyst is generated by the photo-alkali generating agent after UV illumination, and the initial bonding strength of the reactive polyurethane hot melt adhesive is improved by utilizing the alkaline catalyst to catalyze the reaction of isocyanate and water. However, the method of improving the initial adhesive strength by forming crystals after cooling the crystalline raw material is liable to cause the problem of poor adhesive bonding reliability due to the fact that volume shrinkage occurs during crystallization of the crystalline raw material, and the adhesive can improve the initial strength by partial crystallization at the initial stage of cooling, but the adhesive has a problem of poor reliability due to a large volume shrinkage range after the crystallization is completed over time, resulting in a decrease in adhesive force to the interface. The method for improving the initial strength by utilizing the characteristics of high softening point and quick change of the high-molecular-weight raw materials into solid after cooling can lead to the problems of high melt viscosity and short open time of the reactive polyurethane hot melt adhesive, mainly because the high melt viscosity of the high-softening-point and high-molecular-weight raw materials is high, the speed of changing into solid after cooling is high, and the problems of high melt viscosity and short open time can easily occur after the high-softening-point and high-molecular-weight raw materials are added into a reactive polyurethane hot melt adhesive system. The method for introducing the acrylic ester compound into the polyurethane thermosol system is only suitable for bonding transparent substrates, cannot meet the bonding requirement of a large number of opaque substrates, has limited application scenes, and mainly is characterized in that the acrylic ester photocuring raw material can be completely cured after UV illumination, the adhesive loses wettability, and the other side of the substrate cannot be bonded after UV illumination. Although the method for improving the initial bonding strength of the reactive polyurethane hot melt adhesive by utilizing the photo-alkali generating agent can be used for bonding of opaque substrates, a relatively long time is still required to form higher initial bonding strength, mainly because the photo-alkali generating agent has low alkali generating efficiency, the generated alkali catalyzed isocyanate has low reaction efficiency with moisture, a certain pressure maintaining time is still required, and the real pressure maintaining free is difficult to realize.
Disclosure of Invention
The invention aims to overcome the defects that the traditional reactive polyurethane hot melt adhesive has low initial bonding strength and/or is not suitable for an opaque substrate, and provides a UV delay curing reactive polyurethane hot melt adhesive which has higher initial bonding strength and is suitable for a transparent substrate, and a preparation method and application thereof.
Specifically, the invention provides a UV (ultraviolet) delay curing reaction type polyurethane hot melt adhesive, which comprises the following components in parts by weight:
the photo-alkali generating agent is a compound capable of generating alkali under UV illumination;
the alkali proliferation agent is a compound capable of generating a large amount of alkali by self-catalysis under the action of alkali.
The principle of the present invention is further described below with reference to a schematic reaction diagram (fig. 1) between a photobase generator, an alkali breeder and an isocyanate double-ended polyurethane hot melt adhesive. According to the invention, the photo-alkaline agent and the alkali proliferation agent are introduced into the reactive polyurethane hot melt adhesive, and do not have alkalinity, so that alkali can be hidden in the photo-alkaline agent when UV illumination is not carried out, and the stability of the adhesive is ensured; when an alkaline environment is needed, the photo-alkaline agent is controllably triggered to generate alkali by UV light, the alkali proliferation agent can be decomposed to generate hexamethylenediamine under the action of alkali, and the hexamethylenediamine can continuously catalyze the alkali proliferation agent to continuously generate more hexamethylenediamine. Because the reactivity of the hexamethylenediamine containing amino and isocyanate is far higher than that of moisture and isocyanate, the curing of the polyurethane hot melt adhesive can be accelerated, and the initial bonding strength is remarkably improved.
In the present invention, the content of the isocyanate-terminated polyurethane prepolymer is 50 to 100 parts by weight, such as 50, 60, 70, 80, 90, 100 parts by weight and any value therebetween; the content of the photobase generator is 0.1-3 parts by weight, such as 0.1, 0.5, 1, 1.5, 2, 2.5, 3 parts by weight and any value between the two parts by weight; the content of the alkali proliferation agent is 5-15 parts by weight, such as 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts by weight and any value between the two parts by weight; the content of the photosensitizer is 0.1-5 parts by weight, such as 0.1, 0.5, 1, 2, 3, 4, 5 parts by weight and any value between them; the content of the tackifying resin is 10 to 25 parts by weight, such as 10, 12, 15, 18, 20, 22, 25 parts by weight and any value therebetween.
In the present invention, the isocyanate double-ended polyurethane prepolymer can be generally prepared from a polyol compound and a polyisocyanate compound through nucleophilic addition reaction. Wherein the polyisocyanate compound is required in an excess amount so that the resulting polyurethane prepolymer is isocyanate-double blocked, and in general, the polyol compound may be used in an amount of 40 to 70 parts by weight, such as 40, 45, 50, 55, 60, 65, 70 parts by weight and any value therebetween; the polyisocyanate compound may be used in an amount of 10 to 30 parts by weight, such as 10, 12, 15, 18, 20, 25, 28, 30 parts by weight and any value therebetween. In addition, the conditions for the nucleophilic addition reaction generally include a temperature of 70 to 90 ℃, such as 70 ℃, 72 ℃, 75 ℃, 78 ℃, 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, and any value therebetween; the rotating speed is 100-200r/min, such as 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200r/min and any value between the rotating speeds; the time is 1-5h, such as 1h, 2h, 3h, 4h, 5h and any value therebetween.
In a preferred embodiment, the polyol compound is selected from at least one of polyester polyols, polyether polyols, polycarbonate polyols and polyalkylene polyols.
In a preferred embodiment, the polyester polyol is at least one of a polyester polyol obtained by esterifying a polycarboxylic acid with a polyhydric alcohol and a poly-epsilon-caprolactone polyol obtained by ring-opening polymerization of epsilon-caprolactone. Specific examples of the polycarboxylic acid include, but are not limited to: at least one of terephthalic acid, isophthalic acid, 1, 5-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, dodecamethylene dicarboxylic acid. Specific examples of the polyol include, but are not limited to: at least one of ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol, and cyclohexanediol.
In a preferred embodiment, the polyether polyol is selected from at least one of ring-opening polymers, random and block copolymers of ethylene glycol, propylene glycol, tetrahydrofuran, 3-methyltetrahydrofuran, and bisphenol-type polyoxyalkylene modifications. The bisphenol type polyoxyalkylene modified body is a polyether polyol obtained by adding an alkylene oxide to an active hydrogen part of a bisphenol type molecular skeleton, and may be a random copolymer or a block copolymer. Specific examples of the alkylene oxide include, but are not limited to: at least one of ethylene oxide, propylene oxide, butylene oxide, and isobutylene oxide.
In a preferred embodiment, the polycarbonate polyol is selected from at least one of poly (1, 6-hexanediol carbonate) polyol, poly (1, 4-butanediol-1, 6-hexanediol carbonate) diol, poly (1, 5-pentanediol-1, 6-hexanediol carbonate) diol, poly (caprolactone) methylene glycol, poly (1, 4-cyclohexanedimethanol-1, 6-hexanediol carbonate) diol, poly (ethylene carbonate) diol, poly (propylene carbonate) diol, poly (butylene carbonate) diol, and poly (methylene carbonate) diol.
In a preferred embodiment, the polyalkylene polyol is selected from at least one of polybutadiene polyol, hydrogenated polyisoprene polyol.
In a preferred embodiment, the polyisocyanate compound is selected from at least one of isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4' -diisocyanate, hydrogenated MDI, polymeric MDI, 1, 5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate, hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate, and 1,6, 10-undecane triisocyanate.
In the invention, the photobase generator is a compound capable of generating alkali under UV light, and specifically can be at least one selected from carboxylate photobase generators, borate photobase generators, carbamate photobase generators and azacyclic amidine photobase generators. Specific examples of the carboxylate photobase generator include, but are not limited to: at least one of WPBG-168, WPBG-167, WPBG-082, WPBG-266, etc. Specific examples of the borate photobase generator include, but are not limited to: at least one of WPBG-300, WPBG-345, and the like. Specific examples of the carbamate photobase generator include, but are not limited to: at least one of WPBG-015, WPBG-018, WPBG-041, WPBG-140, WPBG-165, WPBG-172, WPBG-025, etc. Specific examples of the azacyclic amidine photobase generator include, but are not limited to: at least one of PB-D02, O0396, O0447, O0448, etc.
In the present invention, the base breeder is a compound capable of autocatalytically generating a large amount of base under the action of a base, and is preferably a 9-fluorenylmethoxycarbonyl base breeder. The 9-fluorenylmethoxycarbonyl base proliferation agent is preferably a nucleophilic addition reaction product of 9-fluorenylmethanol and an isocyanate compound. The nucleophilic addition reaction described herein is preferably carried out at a temperature of 50 to 70℃for a period of time of preferably 2 to 10 hours. The nucleophilic addition reactions described herein generally need to be performed in the presence of a catalyst such as dibutyltin dilaurate. The molar ratio of the 9-fluorenylmethanol to the isocyanate compound is preferably (1.9-2.1): 1. Specific examples of the isocyanate-based compounds include, but are not limited to: at least one of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, 4-diphenylmethane diisocyanate, and 4, 4-diisocyanate dicyclohexylmethane.
In the present invention, the photosensitizer is preferably a triplet excitation energy transfer photosensitizer and/or an electron transfer photosensitizer, and at least one of acetophenones, benzophenone, michler's ketone, benzil, benzoin ether, benzildimethylketal, benzoyl benzoate, α -acyloxime ester, tetramethylthiuram monosulfide, thioxanthone, aliphatic amine, allylthiourea, o-tolylthiourea, sodium diethyldithiophosphate, a soluble salt of aromatic sulfinic acid, N-disubstituted p-aminobenzonitrile compound, tri-N-butylphosphine, N-nitrosohydroxylamine derivative, oxazolidine compound, tetrahydro-1, 3-oxazine compound, condensate of formaldehyde or acetaldehyde with diamine, anthracene, xanthine, N-phenylglycine, anthocyanin pigment porphyrin, and anthocyanin pigment porphyrin is exemplified.
In a preferred embodiment, the tackifying resin is selected from at least one of thermoplastic acrylic resins, polyurethane resins, rosin resins, petroleum resins, terpene resins, and EVA resins.
The invention also provides a preparation method of the UV delay curing reaction type polyurethane hot melt adhesive, which comprises the following steps:
s1, adding a polyol compound and tackifying resin into a reaction kettle, heating to 110-130 ℃, and vacuum stirring and dehydrating at a rotating speed of 100-200r/min for 1-5h to obtain a pretreatment product;
s2, cooling the pretreatment product to 70-90 ℃, adding a polyisocyanate compound, and stirring and reacting for 1-5h at a rotating speed of 100-200r/min under a vacuum condition to obtain an isocyanate double-blocked polyurethane prepolymer;
and S3, stirring and reacting the isocyanate double-blocked polyurethane prepolymer, the photobase generator, the alkali proliferation agent and the photosensitizer for 0.5-1h at a rotating speed of 100-200r/min under a vacuum condition, discharging to obtain the UV delay curing reaction type polyurethane hot melt adhesive, and preserving in a vacuum light-proof sealing manner.
In addition, the invention also provides application of the UV delay curing reaction type polyurethane hot melt adhesive in bonding and sealing of electronic consumer products, automobiles and new energy batteries.
The key point of the invention is that the photo-alkali generating agent and the alkali proliferation agent are introduced into the reactive polyurethane hot melt adhesive system, the characteristics that the photo-alkali generating agent can generate alkali after UV illumination and the alkali proliferation agent can be automatically catalyzed and decomposed under the action of alkali to generate a large amount of alkali are utilized, the photo-alkali generating agent and the alkali proliferation agent system are contacted by UV illumination to generate a large amount of alkali compounds in a synergistic way, and the alkali generated by the synergistic effect of the photo-alkali generating agent and the alkali proliferation agent can participate in the curing reaction of the reactive polyurethane hot melt adhesive, thereby obviously improving the curing speed of the reactive polyurethane hot melt adhesive, improving the initial bonding strength, shortening the pressure maintaining time and improving the production efficiency. Meanwhile, the method for regulating and controlling the chemical reaction speed by triggering the luminous alkaline generator and the alkaline breeder system alkaline through UV light is used for improving the initial bonding strength, so that the introduction of excessive raw materials such as high-crystallinity, high-softening-point and high-molecular-weight resin can be avoided, and the lower melt viscosity, longer opening time and excellent reliability can be ensured. In addition, the photo-curing reaction initiated by the photo-alkaline agent and the alkali proliferation agent is different from the traditional photo-initiated free radical curing, only the photo-radiation is needed to be given in the initial stage, the photo-alkaline agent starts to produce alkali under the action of illumination, and then the alkali proliferation agent is triggered to perform self-catalytic decomposition to generate a large amount of alkali, even if the photo-radiation is not given in the subsequent stage, the photo-curing reaction initiated by the photo-alkaline agent and the alkali proliferation agent is enough to cure the reactive polyurethane hot melt adhesive under the action of alkali catalysis, and the reaction initiated by the photo-alkaline agent and the alkali proliferation agent and the reactive polyurethane hot melt adhesive has the characteristic of UV delay curing and can be applied to the adhesion of a large amount of opaque substrates. In conclusion, the UV delay curing reaction type polyurethane hot melt adhesive provided by the invention has the properties of low melt viscosity, long opening time, high initial bonding strength and suitability for opaque substrates.
Drawings
FIG. 1 is a schematic illustration of the synergistic effect of a photobase generator and an alkali breeder to accelerate isocyanate cure.
Detailed Description
The present invention will be described in detail by examples. The examples of embodiments are intended to illustrate the invention and are not to be construed as limiting the invention. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Synthesis example 1 Synthesis of an alkali proliferation agent
13.93g (0.071 mol) of 9-fluorenylmethanol, 80mL of anhydrous toluene, 0.1g of dibutyltin dilaurate were put into a three-necked flask equipped with a stirring paddle, a thermometer and a condensing reflux tube, the temperature was controlled at 40℃under the protection of nitrogen, 5.97g (0.036 mol) of an anhydrous toluene solution of Hexamethylene Diisocyanate (HDI) was slowly added dropwise, the temperature was raised to 60℃after the completion of the dropwise addition, the reaction was stirred in a nitrogen atmosphere for 4 hours, then cooled to room temperature, the product was washed with acetone to obtain a precipitate, and recrystallized in cyclohexanone to obtain a colorless crystal product, which was designated as an alkali-proliferation agent B1.
Synthesis example 2 Synthesis of an alkali proliferation agent
12.70g (0.065 mol) of 9-fluorenylmethanol, 80mL of anhydrous toluene and 0.06g of dibutyltin dilaurate are added into a three-port bottle provided with a stirring paddle, a thermometer and a condensing reflux pipe, nitrogen is introduced for protection, 7.20g (0.032 mol) of an anhydrous toluene solution of isophorone diisocyanate (IPDI) is slowly added dropwise at the temperature of 40 ℃, the temperature is raised to 60 ℃ after the dropwise addition, the mixture is stirred and reacted for 4 hours in a nitrogen environment, the mixture is cooled to room temperature, the product is washed by acetone to obtain a precipitate, and the precipitate is recrystallized in cyclohexanone to obtain a pale yellow crystal product which is marked as an alkali proliferation agent B2.
Synthesis example 3 Synthesis of an alkali proliferation agent
Into a three-necked flask equipped with a stirring paddle, a thermometer and a condensing reflux tube, 11.93g (0.061 mol) of 9-fluorenylmethanol, 80mL of anhydrous toluene and 0.1g of dibutyltin dilaurate were added, the temperature was controlled at 40℃under the protection of nitrogen, 7.97g (0.030 mol) of an anhydrous toluene solution of 4, 4-dicyclohexylmethane (HMDI) was slowly added dropwise, the temperature was raised to 60℃after the completion of the dropwise addition, the mixture was stirred and reacted in a nitrogen atmosphere for 4 hours, and then cooled to room temperature, the product was washed with acetone to obtain a precipitate, and recrystallized in cyclohexanone to obtain a colorless crystal product, which was designated as an alkali-proliferating agent B3.
Example 1
29.48 parts of polyhexamethylene adipate glycol with average molecular weight 3500, 16.84 parts of polyoxypropylene ether glycol with average molecular weight 2000, 16.84 parts of polyadipic neopentyl glycol with average molecular weight 2000 and 13.00 parts of acrylic resin BR113 are added into a reaction bottle, heated to 110 ℃, dehydrated for 2 hours under 150r/min stirring, cooled to 80 ℃, added with 12.63 parts of 4,4' -diphenylmethane diisocyanate (MDI), reacted for 2 hours under vacuum at 150r/min stirring speed, then added into a reaction kettle with 0.2 part of photo-alkaline agent WPBG025, 1 part of photosensitizer 4-isopropylthioxanthone and 10 parts of alkali breeder B1, mixed for 1 hour under vacuum at 150r/min stirring speed, discharged, and finally the UV delay curing reaction type polyurethane hot melt adhesive with high initial bonding strength is obtained, and the UV delay curing reaction type polyurethane hot melt adhesive is stored in a sealed manner under vacuum.
Example 2
29.55 parts of polybutylene adipate glycol with average molecular weight of 3000, 19.70 parts of polytetrahydrofuran ether glycol with average molecular weight of 2000, 14.78 parts of polyhexamethylene isophthalate glycol with average molecular weight of 1500 and 15.00 parts of acrylic resin MB-2952 are added into a reaction bottle, heated to 110 ℃, dehydrated for 2 hours under the stirring condition of 150r/min, cooled to 80 ℃, added with 14.78 parts of 4,4' -diphenylmethane diisocyanate (MDI), reacted for 2 hours under the stirring condition of 150r/min, then added with 1.00 parts of photobase generator WPBG025, 0.20 parts of photosensitizer 4-isopropylthioxanthone and 5.0 parts of alkali breeder B1, mixed for 1 hour under the stirring condition of 150r/min, discharged, and finally the UV-delayed curing reaction type polyurethane hot melt adhesive with high initial bonding strength is obtained, and the UV-delayed curing reaction type polyurethane hot melt adhesive is preserved in a vacuum sealing mode.
Example 3
According to parts by weight, 25.98 parts of polyhexamethylene adipate glycol with average molecular weight of 2000, 12.99 parts of polytetrahydrofuran ether glycol with average molecular weight of 2000, 12.99 parts of poly (1, 6-hexanediol carbonate) with average molecular weight of 2000 and 20.00 parts of acrylic resin BR106 are added into a reaction bottle, heated to 110 ℃, dehydrated for 2 hours under 150r/min stirring condition, cooled to 80 ℃, added with 10.04 parts of Hexamethylene Diisocyanate (HDI) under vacuum condition, reacted for 2 hours under 150r/min stirring speed, then added into a reaction kettle with 1.50 parts of photo-alkaline agent WPBG041, 1.50 parts of photosensitizer 4-isopropyl thioxanthone and 15.0 parts of alkali breeder B1, mixed for 1 hour under vacuum condition at 150r/min stirring speed, discharged, and finally the UV-delayed-curing reactive polyurethane hot melt adhesive with high initial bonding strength is obtained, and the UV-curable reactive polyurethane hot melt adhesive with high initial bonding strength is preserved under vacuum sealing.
Example 4
According to parts by weight, 29.32 parts of polycaprolactone diol with average molecular weight of 3000, 9.77 parts of polyoxypropylene ether diol with average molecular weight of 1000, 19.55 parts of poly-1, 5-pentanediol-1, 6-hexanediol ester diol with average molecular weight of 2000 and 12.00 parts of acrylic resin BR116 are added into a reaction bottle, heated to 110 ℃, dehydrated for 2 hours under 150r/min stirring condition, cooled to 80 ℃, added with 15.36 parts of 4, 4-diisocyanate dicyclohexylmethane (HMDI), reacted for 2 hours under vacuum condition at 150r/min stirring speed, then added with 2.0 parts of photo-alkali generating agent WPBG041, 2.0 parts of photosensitizer 2, 4-diethylthianthrene-9-ketone and 10.0 parts of alkali proliferation agent B2, mixed for 1 hour under vacuum condition at 150r/min stirring speed, discharged, and finally obtained the UV delayed curing reaction type polyurethane hot melt adhesive with high initial bonding strength is preserved under vacuum sealing.
Example 5
According to parts by weight, 16.07 parts of polybutylene adipate glycol with average molecular weight of 1000, 16.07 parts of polycaprolactone glycol with average molecular weight of 1000, 16.07 parts of poly-1, 6-hexanediol carbonate with average molecular weight of 1000 and 10.00 parts of acrylic resin BR115 are added into a reaction bottle, heated to 110 ℃, vacuum dehydrated for 2 hours under 150r/min stirring condition, cooled to 80 ℃, 27.79 parts of 4, 4-diisocyanate dicyclohexylmethane (HMDI) is added, reacted for 2 hours under vacuum condition at a stirring speed of 150r/min, then 1.0 part of photo-alkali generating agent WPBG018, 1.0 part of photosensitizer 2, 4-diethyl thioxanthene-9-one and 12.0 parts of alkali proliferation agent B3 are added into the reaction kettle, and after being mixed for 1 hour under vacuum condition at a stirring speed of 150r/min, the UV delayed curing reaction type polyurethane hot melt adhesive with high initial bonding strength is obtained, and is stored in a vacuum sealed manner.
Example 6
According to parts by weight, 28.58 parts of polybutylene adipate glycol with average molecular weight 3500, 16.33 parts of polypropylene oxide ether glycol with average molecular weight 2000, 16.33 parts of poly-1, 4-butanediol-1, 6-hexanediol ester glycol with average molecular weight 2000 and 16.00 parts of acrylic resin BR106 are added into a reaction bottle, heated to 110 ℃, dehydrated for 2 hours under 150r/min stirring condition, cooled to 80 ℃, added with 16.33 parts of 4,4' -diphenylmethane diisocyanate (MDI), reacted for 2 hours under vacuum condition at 150r/min stirring speed, then added into a reaction kettle with 1.3 parts of photo-alkaline generator WPBG018, 1.2 parts of photosensitizer 2, 4-diethyl thianthrene-9-one and 8.0 parts of alkali breeder B3, mixed for 1 hour under vacuum condition at 150r/min stirring speed, discharged, and finally obtained the UV-delayed-curing reaction type polyurethane hot melt adhesive with high initial bonding strength is sealed and preserved under vacuum condition.
Comparative example 1
A reactive polyurethane hot melt adhesive was prepared in the same manner as in example 1, except that no photobase generator, photosensitizer and alkali breeder were added, and the rest of the conditions were the same as in example 1, to obtain a reference reactive polyurethane hot melt adhesive, which was stored in a sealed manner under vacuum in a dark place.
Comparative example 2
A reactive polyurethane hot melt adhesive was prepared in the same manner as in example 2, except that the same parts by weight of photobase generator was used as the alkali proliferation agent, and the rest of the conditions were the same as in example 1, to obtain a reference reactive polyurethane hot melt adhesive, which was stored in a sealed manner under vacuum in a dark place.
Comparative example 3
A reactive polyurethane hot melt adhesive was prepared in the same manner as in example 3, except that the same parts by weight of photobase generator was used as the alkali proliferation agent, and the rest of the conditions were the same as in example 1, to obtain a reference reactive polyurethane hot melt adhesive, which was stored in a sealed manner under vacuum in a dark place.
Test case
The samples of the examples and comparative examples were subjected to comparative tests as follows:
(1) Melt viscosity: and (3) placing the polyurethane hot melt adhesive which is sealed well in a cylinder heater at 110 ℃ for 10min, at this time, pouring the hot melt adhesive into a sleeve in a Brookfield-DV2T viscometer rapidly, setting the temperature of the heater at 110 ℃ and keeping for 10min, so that the internal temperature of the hot melt adhesive is uniform and defoamed. The constant temperature melt viscosity of the hot melt adhesive was measured at 110 ℃. The results are shown in Table 1.
(2) Open time after UV light: the hot melt adhesives obtained in examples and comparative examples were applied to a polycarbonate substrate with a width of about 2mm using a dispenser, and immediately after dispensing, the adhesive lines were irradiated with a 365nm UV-LED light source with an irradiation energy of 10000mJ/cm 2 Starting timing after irradiation, lightly touching the glue line with a finger, and recording the time as the opening time after UV irradiation when the glue line is not sticky. The results are shown in Table 1.
(3) Adhesive strength (polycarbonate transparent substrate): the hot melt adhesives obtained in examples and comparative examples were dispensed at 110℃using a dispenser, a 25mm rectangular frame was coated on a polycarbonate substrate with a width of about 1mm, and 10000mJ/cm was irradiated with a 365nm UV-LED light source 2 After the irradiation, attaching another polycarbonate substrate on the polycarbonate substrate, then respectively curing the bonding sample pieces in an environment of 50-60% RH at 25 ℃ for 10min, 30min, 1h, 1d and 3d, using a universal material testing machine to run the manufactured bonding sample pieces along the drawing direction at a speed of 10mm/min until the bonding of the sample pieces fails, recording the maximum force value displayed by the instrument, and calculating the bonding strength of the hot melt adhesive to the polycarbonate substrate by combining the bonding area. The results are shown in Table 1.
(4) Adhesive strength (stainless steel opaque substrate): the hot melt adhesives obtained in examples and comparative examples were dispensed at 110℃using a dispenser, a 25.7mm long adhesive line was coated on an opaque stainless steel substrate with a width of about 1mm, and then 10000mJ/cm of the adhesive line was irradiated with a 365nm UV-LED light source 2 After irradiation, bonding another stainless steel substrate, solidifying the bonding sample piece in an environment of 25 ℃ and 50-60%RH for 24 hours, using a universal material tester to run the manufactured bonding sample piece along the shearing direction at a speed of 100mm/min until the bonding of the sample piece fails, recording the maximum force value displayed by the instrument, and calculating the bonding strength of the hot melt adhesive to the stainless steel substrate by combining the bonding area. The results obtained are shown in Table 1.
TABLE 1
As can be seen from example 1 and comparative example 1, the UV-retarded curing reactive polyurethane hot melt adhesive of the present invention has similar melt viscosity and open time as the conventional reactive polyurethane hot melt adhesive, and has good workability. In addition, the adhesive strength of the UV delay curing adhesive is far higher than that of the traditional reactive polyurethane hot melt adhesive after being cured for 10min, which shows that the curing speed is high and the initial adhesive strength is high. As can be seen from the comparison of the example 2 and the comparative example 2, the example 3 and the comparative example 3, compared with the prior art that only the photo-alkali generating agent is introduced into the reactive polyurethane hot melt adhesive, the invention can greatly improve the initial bonding strength of the reactive polyurethane hot melt adhesive by introducing the alkali proliferation agent to cooperate with the photo-alkali generating agent, is expected to obviously shorten the pressure maintaining time, and can even realize the pressure maintaining-free effect.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations may be made in the above embodiments by those skilled in the art without departing from the spirit and principles of the invention.
Claims (10)
1. The UV delay curing reaction type polyurethane hot melt adhesive is characterized by comprising the following components in parts by weight:
the photo-alkali generating agent is a compound capable of generating alkali under UV illumination;
the alkali proliferation agent is a compound capable of generating a large amount of alkali by self-catalysis under the action of alkali.
2. The UV-delay curing reactive polyurethane hot melt adhesive of claim 1, wherein the isocyanate-terminated polyurethane prepolymer is prepared from a polyol compound and a polyisocyanate compound by nucleophilic addition reaction.
3. The UV-delay curing reactive polyurethane hot melt adhesive of claim 2, wherein the polyol compound is selected from at least one of polyester polyols, polyether polyols, polycarbonate polyols, and polyalkylene polyols;
preferably, the polyester polyol is at least one of polyester polyol obtained by esterification reaction of polybasic carboxylic acid and polyol and poly-epsilon-caprolactone polyol obtained by ring-opening polymerization of epsilon-caprolactone; the polybasic carboxylic acid is selected from at least one of terephthalic acid, isophthalic acid, 1, 5-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid and dodecamethylene dicarboxylic acid; the polyalcohol is at least one selected from ethylene glycol, propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hexanediol, diethylene glycol and cyclohexanediol;
preferably, the polyether polyol is selected from at least one of ring-opening polymers, random copolymers and block copolymers of ethylene glycol, propylene glycol, tetrahydrofuran, 3-methyltetrahydrofuran, and bisphenol-type polyoxyalkylene modifications; the bisphenol type polyoxyalkylene modifier is polyether polyol obtained by carrying out addition reaction on active hydrogen part of a bisphenol type molecular skeleton by adopting alkylene oxide, wherein the alkylene oxide is at least one selected from ethylene oxide, propylene oxide, butylene oxide and isobutene oxide;
preferably, the polycarbonate polyol is selected from at least one of poly (1, 6-hexanediol carbonate) polyol, poly (1, 4-butanediol-1, 6-hexanediol carbonate) diol, poly (1, 5-pentanediol-1, 6-hexanediol carbonate) diol, poly (caprolactone) methylene glycol, poly (1, 4-cyclohexanedimethanol-1, 6-hexanediol carbonate) diol, poly (ethylene carbonate) diol, poly (propylene carbonate) diol, poly (butylene carbonate) diol, and poly (hexamethylene carbonate) diol;
preferably, the polyalkylene polyol is selected from at least one of polybutadiene polyol, hydrogenated polyisoprene polyol.
4. The UV-delay curing reactive polyurethane hot melt adhesive of claim 2, wherein the polyisocyanate compound is selected from at least one of isophorone diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4, 4' -diisocyanate, hydrogenated MDI, polymeric MDI, 1, 5-naphthalene diisocyanate, norbornane diisocyanate, tolidine diisocyanate, xylylene diisocyanate, hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate, tetramethylxylene diisocyanate, and 1,6, 10-undecane triisocyanate.
5. The UV-delay curing reactive polyurethane hot melt adhesive of any one of claims 1-4, wherein the photobase generator is selected from at least one of carboxylate photobase generators, borate photobase generators, carbamate photobase generators, and azacyclic amidine photobase generators.
6. The UV-delay curing reactive polyurethane hot melt adhesive of any one of claims 1-4, wherein the alkali breeder is a 9-fluorenylmethoxycarbonyl-based alkali breeder; preferably, the 9-fluorenylmethoxycarbonyl base proliferation agent is a nucleophilic addition reaction product of 9-fluorenylmethanol and an isocyanate compound; preferably, the isocyanate compound is at least one selected from isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, 4-diphenylmethane diisocyanate and 4, 4-diisocyanate dicyclohexylmethane.
7. The UV-delay curing reactive polyurethane hot melt adhesive according to any one of claims 1-4, wherein the photosensitizer is selected from at least one of acetophenones, benzophenones, michler's ketones, benzils, benzoins, benzoin ethers, benzil dimethyl ketals, benzoyl benzoates, α -acyl oxime esters, tetramethylthiuram monosulfide, thioxanthones, aliphatic amines, allylthioureas, o-tolylthioureas, sodium diethyldithiophosphates, soluble salts of aromatic sulfinic acids, N-disubstituted p-aminobenzonitriles, tri-N-butylphosphines, N-nitrosohydroxylamine derivatives, oxazolidine compounds, tetrahydro-1, 3-oxazine compounds, condensates of formaldehyde or acetaldehyde with diamines, anthracene, xanthine, N-phenylglycine, anthocyanin pigment porphyrins, and anthocyanin pigment porphyrins.
8. The UV-delay curing reactive polyurethane hot melt adhesive of any one of claims 1-4, wherein the tackifying resin is selected from at least one of thermoplastic acrylic resins, polyurethane resins, rosin resins, petroleum resins, terpene resins, and EVA resins.
9. A process for preparing a UV-delay curing reactive polyurethane hot melt adhesive as claimed in any one of claims 1 to 8, comprising the steps of:
s1, adding a polyol compound and tackifying resin into a reaction kettle, heating to 110-130 ℃, and vacuum stirring and dehydrating at a rotating speed of 100-200r/min for 1-5h to obtain a pretreatment product;
s2, cooling the pretreatment product to 70-90 ℃, adding a polyisocyanate compound, and stirring and reacting for 1-5h at a rotating speed of 100-200r/min under a vacuum condition to obtain an isocyanate double-blocked polyurethane prepolymer;
and S3, stirring and reacting the isocyanate double-blocked polyurethane prepolymer, the photobase generator, the alkali proliferation agent and the photosensitizer for 0.5-1h at a rotating speed of 100-200r/min under a vacuum condition, discharging to obtain the UV delay curing reaction type polyurethane hot melt adhesive, and preserving in a vacuum light-proof sealing manner.
10. Use of the UV-delay curing reactive polyurethane hotmelt as claimed in any of claims 1 to 8 for the bonding and sealing of consumer electronics, automobiles and new energy batteries.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116855221A (en) * | 2023-07-12 | 2023-10-10 | 韦尔通科技股份有限公司 | UV (ultraviolet) delay curing polyurethane adhesive and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679829A (en) * | 2007-06-14 | 2010-03-24 | 积水化学工业株式会社 | Photocurable pressure-sensitive adhesive composition |
| US20110097669A1 (en) * | 2007-08-09 | 2011-04-28 | Hiroji Fukui | Photocurable composition |
| CN112724915A (en) * | 2020-12-29 | 2021-04-30 | 厦门韦尔通科技有限公司 | Reactive polyurethane hot melt adhesive with multiple curing modes and preparation method thereof |
| CN112724907A (en) * | 2020-12-29 | 2021-04-30 | 厦门韦尔通科技有限公司 | Light-moisture-curing polyurethane hot-melt adhesive for bonding opaque substrates and preparation method thereof |
-
2022
- 2022-12-29 CN CN202211717296.XA patent/CN116004173A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101679829A (en) * | 2007-06-14 | 2010-03-24 | 积水化学工业株式会社 | Photocurable pressure-sensitive adhesive composition |
| US20110097669A1 (en) * | 2007-08-09 | 2011-04-28 | Hiroji Fukui | Photocurable composition |
| CN112724915A (en) * | 2020-12-29 | 2021-04-30 | 厦门韦尔通科技有限公司 | Reactive polyurethane hot melt adhesive with multiple curing modes and preparation method thereof |
| CN112724907A (en) * | 2020-12-29 | 2021-04-30 | 厦门韦尔通科技有限公司 | Light-moisture-curing polyurethane hot-melt adhesive for bonding opaque substrates and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116855221A (en) * | 2023-07-12 | 2023-10-10 | 韦尔通科技股份有限公司 | UV (ultraviolet) delay curing polyurethane adhesive and preparation method thereof |
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