TWI851565B - Moisture-curing polyurethane hot-melt resin composition and article using the same - Google Patents
Moisture-curing polyurethane hot-melt resin composition and article using the same Download PDFInfo
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- TWI851565B TWI851565B TW108111639A TW108111639A TWI851565B TW I851565 B TWI851565 B TW I851565B TW 108111639 A TW108111639 A TW 108111639A TW 108111639 A TW108111639 A TW 108111639A TW I851565 B TWI851565 B TW I851565B
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- Taiwan
- Prior art keywords
- parts
- moisture
- resin composition
- polyurethane hot
- melt resin
- Prior art date
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 45
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 45
- 239000012943 hotmelt Substances 0.000 title claims abstract description 44
- 239000011342 resin composition Substances 0.000 title claims abstract description 44
- 238000013008 moisture curing Methods 0.000 title claims abstract description 43
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000001723 curing Methods 0.000 claims abstract description 19
- 150000007524 organic acids Chemical class 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 4
- -1 acrylic polyol Chemical class 0.000 claims description 48
- 229920005862 polyol Polymers 0.000 claims description 33
- 229920005906 polyester polyol Polymers 0.000 claims description 27
- 150000003077 polyols Chemical class 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 239000005056 polyisocyanate Substances 0.000 claims description 13
- 229920001228 polyisocyanate Polymers 0.000 claims description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 39
- 239000004793 Polystyrene Substances 0.000 description 16
- 229920002223 polystyrene Polymers 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 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 4
- 239000004831 Hot glue Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N beta-hydroxyethanesulfonic acid Natural products OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 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
- 239000004566 building material Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-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
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- WSFYPFLCEFLXOZ-UHFFFAOYSA-N 2-decylbutanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)CC(O)=O WSFYPFLCEFLXOZ-UHFFFAOYSA-N 0.000 description 1
- HCUZVMHXDRSBKX-UHFFFAOYSA-N 2-decylpropanedioic acid Chemical compound CCCCCCCCCCC(C(O)=O)C(O)=O HCUZVMHXDRSBKX-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UUTBBIZSIBQNEF-UHFFFAOYSA-N CC1=CC(C=CC2=CC=CC=C2)=C(C)C(C)=C1C.N=C=O.N=C=O Chemical compound CC1=CC(C=CC2=CC=CC=C2)=C(C)C(C)=C1C.N=C=O.N=C=O UUTBBIZSIBQNEF-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DTGKSKDOIYIVQL-MRTMQBJTSA-N Isoborneol Natural products C1C[C@@]2(C)[C@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-MRTMQBJTSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CVOWOOVNWMIICO-UHFFFAOYSA-N N=C=O.N=C=O.C(C1=CC=CC=C1)=CC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C(C1=CC=CC=C1)=CC1=CC=CC=C1 CVOWOOVNWMIICO-UHFFFAOYSA-N 0.000 description 1
- OMRDSWJXRLDPBB-UHFFFAOYSA-N N=C=O.N=C=O.C1CCCCC1 Chemical compound N=C=O.N=C=O.C1CCCCC1 OMRDSWJXRLDPBB-UHFFFAOYSA-N 0.000 description 1
- ZNXHWPFMNPRKQA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C(C1=CC=CC=C1)C1=CC=CC=C1 Chemical class N=C=O.N=C=O.N=C=O.C(C1=CC=CC=C1)C1=CC=CC=C1 ZNXHWPFMNPRKQA-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000000376 autoradiography Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
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- 239000007822 coupling agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- MAWOHFOSAIXURX-UHFFFAOYSA-N cyclopentylcyclopentane Chemical group C1CCCC1C1CCCC1 MAWOHFOSAIXURX-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- RQIFXTOWUNAUJC-UHFFFAOYSA-N ethanesulfinic acid Chemical compound CCS(O)=O RQIFXTOWUNAUJC-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
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Abstract
本發明提供一種濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物，其係含有具異氰酸酯基之胺基甲酸酯預聚物(i)的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物，其特徵在於，前述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物，相對於前述胺基甲酸酯預聚物(i)100質量份，更以0.2~1質量份之範圍含有由下述通式(1)所示之硬化觸媒(ii)，且相對於前述胺基甲酸酯預聚物(i)100質量份，以0.0001~0.5質量份之範圍含有包含硫原子之有機酸(iii)。又，本發明提供一種物品，其特徵在於，利用前述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物將至少二個構件進行貼合。 The present invention provides a moisture-curing polyurethane hot-melt resin composition, which is a moisture-curing polyurethane hot-melt resin composition containing a urethane prepolymer (i) having an isocyanate group. The moisture-curing polyurethane hot-melt resin composition further contains a curing catalyst (ii) represented by the following general formula (1) in an amount of 0.2 to 1 part by mass relative to 100 parts by mass of the urethane prepolymer (i), and contains an organic acid (iii) containing a sulfur atom in an amount of 0.0001 to 0.5 parts by mass relative to 100 parts by mass of the urethane prepolymer (i). Furthermore, the present invention provides an article, characterized in that at least two components are bonded together using the aforementioned moisture-curing polyurethane hot-melt resin composition.
Description
本發明係關於濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物及物品者。 The present invention relates to moisture-curing polyurethane hot-melt resin compositions and articles.
濕氣硬化型聚胺基甲酸酯熱熔黏合劑因係無溶劑，故作為環境應變型黏合劑，以纖維鍵結(fiber bonding)‧建材積層(lamination)為中心至今為止進行了各種的研究，在產業界亦被廣泛利用。 Moisture-curing polyurethane hot-melt adhesives are solvent-free, so they have been used as environmentally-strained adhesives in various researches, mainly in fiber bonding and building material lamination, and are widely used in the industry.
又，近年來，在光學零件的貼合中，受到光學零件的輕量化、薄膜化的需求高漲，而正進行將熱熔黏合劑取代至今為主流的丙烯酸系黏著劑的探討。 In addition, in recent years, in the bonding of optical parts, due to the increasing demand for lighter and thinner optical parts, hot melt adhesives are being considered to replace the acrylic adhesives that have been the mainstream so far.
作為前述黏合劑，例如，揭露有一種使用耐濕熱性熱熔黏合劑組成物的黏合劑，其特徵在於，相對於(a)流動起始溫度為55℃以上且110℃以下的聚胺基甲酸酯樹脂100重量份，摻合(b)Tg為0℃以上且110℃以下、分子量10000~25000的飽和聚酯樹脂5~150重量份、(c)軟化點為60℃以上且140℃以下、分子量700~3000的環氧樹脂10~150重量份及(d)經偶合劑進行表面處理的無機填充劑10~200重量份(例如，參照專利文獻 1)。 As the aforementioned adhesive, for example, there is disclosed an adhesive using a moisture-heat resistant hot melt adhesive composition, characterized in that (a) 100 parts by weight of a polyurethane resin having a flow starting temperature of 55°C or higher and 110°C or lower is mixed with (b) 5 to 150 parts by weight of a saturated polyester resin having a Tg of 0°C or higher and 110°C or lower and a molecular weight of 10,000 to 25,000, (c) 10 to 150 parts by weight of an epoxy resin having a softening point of 60°C or higher and 140°C or lower and a molecular weight of 700 to 3,000, and (d) 10 to 200 parts by weight of an inorganic filler surface-treated with a coupling agent (for example, refer to patent document 1).
前述黏合劑係具有實用上能使用的等級的耐濕熱性者。然而，在使用該黏合劑而貼合的積層體浸漬於水之際，水會以較短的時間侵入積層體內部，而有防水性能不充分的問題點。 The above-mentioned adhesive has a practically usable level of moisture and heat resistance. However, when the laminate bonded using the adhesive is immersed in water, the water will penetrate into the interior of the laminate in a short time, resulting in insufficient waterproof performance.
又，近年來為了提升生產效率，在強力要求能縮短熟化時間(curing time)的材料之中，前述耐濕熱性熱熔黏合劑組成物雖具有所謂即使在低溫時亦可接著的優點，但在期望快速硬化之情形中，無法實際使用。又，雖亦考慮藉由添加觸媒等而提升快速硬化性的手法，但因亦擔心經時的黏度上升等，故難以實現兩者兼顧。 In recent years, in order to improve production efficiency, there is a strong demand for materials that can shorten the curing time. Although the aforementioned moisture-resistant hot melt adhesive composition has the advantage of being able to bond even at low temperatures, it cannot be used in situations where rapid curing is desired. In addition, although methods of improving rapid curing properties by adding catalysts are also considered, it is difficult to achieve both because of concerns about the increase in viscosity over time.
[專利文獻1]日本特開2003-27030號公報 [Patent Document 1] Japanese Patent Publication No. 2003-27030
本發明所欲解決的課題係提供儲存穩定性、初期接著強度、防水性、及耐落下衝撃性優異的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。 The problem that this invention aims to solve is to provide a moisture-curing polyurethane hot-melt resin composition with excellent storage stability, initial bonding strength, waterproofness, and drop impact resistance.
本發明係提供濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物、及使用其而得的物品者，其中濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物係含有具異氰酸酯基的胺 基甲酸酯預聚物(i)之濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物，其特徵在於，前述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物，相對於前述胺基甲酸酯預聚物(i)100質量份，更以0.2~1質量份的範圍含有由下述通式(1)所示之硬化觸媒(ii)，且相對於前述胺基甲酸酯預聚物(i)100質量份，以0.0001~0.5質量份的範圍含有包含硫原子的有機酸(iii)。 The present invention provides a moisture-curing polyurethane hot-melt resin composition and articles obtained using the same, wherein the moisture-curing polyurethane hot-melt resin composition is a moisture-curing polyurethane hot-melt resin composition containing an isocyanate-containing urethane prepolymer (i), and is characterized in that the moisture-curing polyurethane hot-melt resin composition further contains a curing catalyst (ii) represented by the following general formula (1) in an amount of 0.2 to 1 part by mass relative to 100 parts by mass of the urethane prepolymer (i), and contains an organic acid (iii) containing a sulfur atom in an amount of 0.0001 to 0.5 parts by mass relative to 100 parts by mass of the urethane prepolymer (i).
本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物係具有能緩和經時的黏度上升之優異儲存穩定性者。又，本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物可表現優異的初期接著強度及最終接著強度，藉由前述聚胺基甲酸酯熱熔樹脂組成物而貼合的物品係防水性、及耐落下衝撃性優異者。因此，本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物，尤其可較佳地使用在光學用構件的貼合。 The moisture-curing polyurethane hot-melt resin composition of the present invention has excellent storage stability that can mitigate the increase in viscosity over time. In addition, the moisture-curing polyurethane hot-melt resin composition of the present invention can show excellent initial bonding strength and final bonding strength, and the articles bonded by the aforementioned polyurethane hot-melt resin composition are excellent in waterproofness and resistance to drop impact. Therefore, the moisture-curing polyurethane hot-melt resin composition of the present invention can be preferably used in the bonding of optical components.
本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物係含有具異氰酸酯基的胺基甲酸酯預聚物(i)、特定量的硬化觸媒(ii)、以及特定量的有機酸(iii)者。 The moisture-curing polyurethane hot-melt resin composition of the present invention contains a urethane prepolymer (i) having an isocyanate group, a specific amount of a curing catalyst (ii), and a specific amount of an organic acid (iii).
前述具異氰酸酯基的胺基甲酸酯預聚物(i)，可使用例如，多元醇(A)與聚異氰酸酯(B)的反應物。 The aforementioned urethane prepolymer (i) having an isocyanate group may be, for example, a reaction product of a polyol (A) and a polyisocyanate (B).
作為前述多元醇(A)，可使用例如，聚醚多元醇(A-1)、結晶性聚酯多元醇(A-2)、非晶性聚酯多元醇(A-3)、丙烯酸多元醇(A-4)、聚碳酸酯多元醇、聚丁二烯多元醇、二聚物二元醇等。此等多元醇可單獨使用亦可併用二種以上。 As the aforementioned polyol (A), for example, polyether polyol (A-1), crystalline polyester polyol (A-2), amorphous polyester polyol (A-3), acrylic polyol (A-4), polycarbonate polyol, polybutadiene polyol, dimer diol, etc. can be used. These polyols can be used alone or in combination of two or more.
作為前述多元醇(A)，在前述之中，由能獲得更進一步優異的防水性、接著強度、及耐落下衝撃性之觀點而言，較佳為使用聚醚多元醇(A-1)、結晶性聚酯多元醇(A-2)、非晶性聚酯多元醇(A-3)、丙烯酸多元醇(A-4)。 As the aforementioned polyol (A), among the aforementioned, polyether polyol (A-1), crystalline polyester polyol (A-2), amorphous polyester polyol (A-3), and acrylic polyol (A-4) are preferably used from the viewpoint of obtaining further excellent waterproofness, bonding strength, and drop impact resistance.
作為前述聚醚多元醇(A-1)，可使用例如，聚乙二醇、聚丙二醇、聚丁二醇、聚四亞甲基二醇(polytetramethylene glycol)、聚氧乙烯(polyoxyethylene)聚氧基丙二醇等。 As the aforementioned polyether polyol (A-1), for example, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, etc. can be used.
作為前述聚醚多元醇(A-1)的數量平均分子量，由能獲得更進一步優異的接著初期強度、能獲得適當的晾置時間(open time)(使用可能時間)之觀點而言，較佳為500~10,000的範圍，更佳為700~5,000的範圍。此外，前述聚醚多元醇(A-1)的數量平均分子量表示藉由凝膠滲透層析(GPC)法而測定的值。 The number average molecular weight of the polyether polyol (A-1) is preferably in the range of 500 to 10,000, and more preferably in the range of 700 to 5,000, from the viewpoint of obtaining further excellent initial strength and appropriate open time (usable time). In addition, the number average molecular weight of the polyether polyol (A-1) is a value measured by gel permeation chromatography (GPC).
作為前述結晶性聚酯多元醇(A-2)，可使用例如，具有羥基的化合物與多元酸之反應物。此外，本發明中，所謂「結晶性」，表示在遵循JISK7121：2012的DSC(示差掃描熱析儀)測定中，可確認結晶熱或熔解熱的峰者，所謂「非晶性」，表示無法確認前述峰者。 As the aforementioned crystalline polyester polyol (A-2), for example, a reaction product of a compound having a hydroxyl group and a polyacid can be used. In addition, in the present invention, the so-called "crystalline" means that the peak of crystallization heat or melting heat can be confirmed in the DSC (differential scanning thermometer) measurement in accordance with JIS K7121: 2012, and the so-called "amorphous" means that the aforementioned peak cannot be confirmed.
作為前述具有羥基的化合物，可使用例如，乙二醇、丙二醇、丁二醇、戊二醇、己二醇、庚二醇、辛二醇、壬二醇、癸二醇、三羥甲丙烷、三(羥甲)乙烷、甘油等。此等化合物可單獨使用亦可併用二種以上。此等之中，由提高結晶性、能獲得更進一步優異的防水性及接著強度之觀點而言，較佳為使用選自包含丁二醇、己二醇、辛二醇、及癸二醇之群組的一種以上。 As the aforementioned compound having a hydroxyl group, for example, ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, trihydroxymethylpropane, tri(hydroxymethyl)ethane, glycerol, etc. can be used. These compounds can be used alone or in combination of two or more. Among these, from the perspective of improving crystallinity, obtaining further excellent waterproofness and bonding strength, it is preferred to use one or more selected from the group including butylene glycol, hexanediol, octanediol, and decanediol.
作為前述多元酸，可使用例如，草酸、丙二酸、丁二酸、己二酸、癸二酸、壬二酸、1,12-十二烷二甲酸等。此等化合物可單獨使用亦可併用二種以上。 As the aforementioned polyacid, for example, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, 1,12-dodecanedicarboxylic acid, etc. can be used. These compounds can be used alone or in combination of two or more.
作為前述結晶性聚酯多元醇(A-2)的數量平均分子量，由能獲得更進一步優異的防水性及接著性之觀點而言，較佳為500~10,000的範圍，更佳為1,000~4,000的範圍。此外，前述結晶性聚酯多元醇(A-2)的數量平均分子量，表示藉由凝膠滲透層析(GPC)法而測定的值。 The number average molecular weight of the crystalline polyester polyol (A-2) is preferably in the range of 500 to 10,000, and more preferably in the range of 1,000 to 4,000, from the viewpoint of obtaining further excellent water resistance and adhesion. In addition, the number average molecular weight of the crystalline polyester polyol (A-2) is a value measured by gel permeation chromatography (GPC).
又，作為前述結晶性聚酯多元醇(A-2)的玻璃轉移溫度(Tg)，較佳為40~130℃的範圍。此外，前述結晶性聚酯多元醇(A-2)的玻璃轉移溫度，表示遵循JIS K 7121-1987並藉由DSC而測定的值，具體而言，表示在示差掃描型熱析儀裝置內裝入前述結晶性聚酯多元醇(A-2)，以升溫速度10℃/分鐘升溫至(Tg+50℃)後，保持3分鐘，之後進行急冷，由所得之示差熱曲線所讀取的中間點玻璃轉移溫度(Tmg)。 Furthermore, the glass transition temperature (Tg) of the crystalline polyester polyol (A-2) is preferably in the range of 40 to 130°C. In addition, the glass transition temperature of the crystalline polyester polyol (A-2) refers to the value measured by DSC in accordance with JIS K 7121-1987. Specifically, it refers to the midpoint glass transition temperature (Tmg) obtained by placing the crystalline polyester polyol (A-2) in a differential scanning thermometer, heating the temperature to (Tg+50°C) at a heating rate of 10°C/min, maintaining the temperature for 3 minutes, and then rapidly cooling the temperature.
作為使用前述結晶性聚酯多元醇(A-2)之情 形的使用量，由能獲得更進一步優異的柔軟性、接著性、及晾置時間之觀點而言，相對於前述聚醚多元醇(A-1)100質量份，較佳為20~150質量份的範圍，更佳為30~100質量份的範圍。 When the crystalline polyester polyol (A-2) is used, the amount used is preferably in the range of 20 to 150 parts by mass, and more preferably in the range of 30 to 100 parts by mass, relative to 100 parts by mass of the polyether polyol (A-1), from the viewpoint of obtaining further excellent softness, adhesion, and air-opening time.
作為前述非晶性聚酯多元醇(A-3)，可使用例如，下述具有羥基的化合物與多元酸之反應物。 As the aforementioned amorphous polyester polyol (A-3), for example, the reaction product of the following hydroxyl group-containing compound and polyacid can be used.
作為前述具有羥基的化合物，可使用例如，乙二醇、丙二醇、1,4-丁二醇、戊二醇、2,4-二乙基-1,5-戊二醇、3-甲基-1,5-戊二醇、己二醇、新戊二醇、六亞甲基二醇、甘油、三羥甲丙烷；雙酚A、雙酚F、其氧化烯(alkylene oxide)加成物等。此等化合物可單獨使用亦可併用二種以上。此等之中，由能獲得更進一步優異的耐水性、接著強度、及柔軟性之觀點而言，較佳為使用雙酚A的氧化烯加成物。又，作為前述氧化烯的加成莫耳數，較佳為2~10莫耳，更佳為4~8莫耳。 As the aforementioned compound having a hydroxyl group, for example, ethylene glycol, propylene glycol, 1,4-butanediol, pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, hexanediol, neopentyl glycol, hexamethylene glycol, glycerol, trihydroxymethylpropane; bisphenol A, bisphenol F, and its alkylene oxide adducts, etc. can be used. These compounds can be used alone or in combination of two or more. Among these, from the perspective of obtaining further excellent water resistance, bonding strength, and softness, it is preferred to use alkylene oxide adducts of bisphenol A. In addition, as the molar number of the aforementioned alkylene oxide addition, it is preferably 2 to 10 moles, and more preferably 4 to 8 moles.
作為前述多元酸，可使用己二酸、戊二酸、庚二酸、辛二酸、二聚物酸、癸二酸、十一烷二羧酸、六氫對苯二甲酸、鄰苯二甲酸、鄰苯二甲酸酐、間苯二甲酸、對苯二甲酸等。此等化合物可單獨使用亦可併用二種以上。 As the aforementioned polyacid, adipic acid, glutaric acid, pimelic acid, suberic acid, dimer acid, sebacic acid, undecanedicarboxylic acid, hexahydroterephthalic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, etc. can be used. These compounds can be used alone or in combination of two or more.
作為前述非晶性聚酯多元醇(A-3)的數量平均分子量，由能獲得更進一步優異的防水性、接著性、及柔軟性之觀點而言，較佳為500~10,000的範圍，更佳為1,000~4,000的範圍，再佳為1,000~3,000的範圍。此外，前述非晶性聚酯多元醇(A-3)的數量平均分子 量，表示藉由凝膠滲透層析(GPC)法而測定的值。 The number average molecular weight of the amorphous polyester polyol (A-3) is preferably in the range of 500 to 10,000, more preferably in the range of 1,000 to 4,000, and even more preferably in the range of 1,000 to 3,000, from the viewpoint of obtaining further excellent water resistance, adhesion, and softness. In addition, the number average molecular weight of the amorphous polyester polyol (A-3) is a value measured by gel permeation chromatography (GPC).
作為前述非晶性聚酯多元醇(A-3)的玻璃轉移溫度，由能獲得更進一步優異的防水性、接著性及柔軟性之觀點而言，較佳為-70~-10℃的範圍。此外，前述非晶性聚酯多元醇(A-3)的玻璃轉移溫度，與前述結晶性聚酯多元醇(A-2)的玻璃轉移溫度(Tg)的測定方法相同。 The glass transition temperature of the amorphous polyester polyol (A-3) is preferably in the range of -70 to -10°C from the viewpoint of obtaining further excellent waterproofness, adhesion and flexibility. In addition, the glass transition temperature of the amorphous polyester polyol (A-3) is determined in the same manner as the glass transition temperature (Tg) of the crystalline polyester polyol (A-2).
作為使用前述非晶性聚酯多元醇(A-3)之情形的使用量，由能獲得更進一步優異的防水性、柔軟性、及接著強度之觀點而言，相對於前述聚醚多元醇(A-1)100質量份，較佳為20~150質量份的範圍，更佳為25~130質量份的範圍，再佳為55~100質量份的範圍。 When the amorphous polyester polyol (A-3) is used, the amount is preferably in the range of 20 to 150 parts by mass, more preferably in the range of 25 to 130 parts by mass, and even more preferably in the range of 55 to 100 parts by mass relative to 100 parts by mass of the polyether polyol (A-1), from the viewpoint of obtaining further excellent waterproofness, softness, and bonding strength.
作為前述丙烯酸多元醇(A-4)，可使用例如，含有具羥基的(甲基)丙烯酸化合物作為必要成分的(甲基)丙烯酸化合物的聚合物。此外，本發明中，所謂「(甲基)丙烯酸化合物」，表示甲基丙烯酸化合物與丙烯酸化合物之一者或兩者，所謂「(甲基)丙烯酸酯」，表示甲基丙烯酸酯與丙烯酸酯之一者或兩者。 As the aforementioned acrylic polyol (A-4), for example, a polymer of a (meth)acrylic compound containing a (meth)acrylic compound having a hydroxyl group as an essential component can be used. In addition, in the present invention, the so-called "(meth)acrylic compound" means one or both of a methacrylic compound and an acrylic compound, and the so-called "(meth)acrylate" means one or both of a methacrylate and an acrylate.
作為前述具羥基的(甲基)丙烯酸化合物，可使用例如，2-羥乙基(甲基)丙烯酸酯、羥丙基(甲基)丙烯酸酯、羥丁基(甲基)丙烯酸酯等。此等化合物可單獨使用亦可併用二種以上。 As the aforementioned hydroxyl-containing (meth) acrylic acid compound, for example, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, etc. can be used. These compounds can be used alone or in combination of two or more.
作為其他(甲基)丙烯酸化合物，可使用例如，(甲基)丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙 酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸十八酯、(甲基)丙烯酸異十八酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸月桂酯等(甲基)丙烯酸烷酯；(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、(甲基)丙烯酸1H,1H,5H-八氟戊酯、(甲基)丙烯酸2-(全氟辛基)乙酯等具氟原子的(甲基)丙烯酸化合物；(甲基)丙烯酸異莰酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊基乙氧基酯等具脂環結構的(甲基)丙烯酸化合物；(甲基)丙烯酸聚乙二醇單酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸甲氧基丁酯、(甲基)丙烯酸甲氧基三乙二醇酯、(甲基)丙烯酸甲氧基聚乙二醇酯等具醚基的(甲基)丙烯酸化合物；(甲基)丙烯酸苄酯、(甲基)丙烯酸2-乙基-2-甲基-[1,3]-二草酸酯-4-基-甲酯、(甲基)丙烯酸二甲基胺基乙酯等。此等化合物可單獨使用亦可併用二種以上。此等之中，由能獲得更進一步優異的防水性、接著性、及晾置時間之觀點而言，較佳為使用具羥基的(甲基)丙烯酸化合物及(甲基)丙烯酸烷酯，更佳為使用(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸甲酯及(甲基)丙烯酸正丁酯。 As other (meth)acrylic acid compounds, for example, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, octadecyl (meth)acrylate, isooctadecyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate and other (meth)acrylic acid alkyl esters; 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, octadecyl (meth)acrylate, cetyl (meth)acrylate, lauryl (meth)acrylate and other (meth)acrylic acid alkyl esters; - (meth)acrylic acid compounds having fluorine atoms such as (perfluorooctyl)ethyl ester; (meth)acrylic acid compounds having alicyclic structures such as isoborneol (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, and dicyclopentylethoxy (meth)acrylate; (meth)acrylic acid compounds having ether groups such as polyethylene glycol monoester (meth)acrylate, methoxyethyl (meth)acrylate, methoxybutyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate; benzyl (meth)acrylate, 2-ethyl-2-methyl-[1,3]-dioxalate-4-yl-methyl (meth)acrylate, and dimethylaminoethyl (meth)acrylate. These compounds may be used alone or in combination of two or more. Among these, from the perspective of obtaining further excellent water resistance, adhesion, and open time, it is preferred to use hydroxyl (meth) acrylic acid compounds and (meth) acrylic acid alkyl esters, and it is more preferred to use 2-hydroxyethyl (meth) acrylate, methyl (meth) acrylate, and n-butyl (meth) acrylate.
作為前述丙烯酸多元醇(A-4)的數量平均分子量，由能獲得更進一步優異的防水性、接著性、及晾置時間之觀點而言，較佳為5,000~100,000，更佳為10,000~30,000。此外，前述丙烯酸多元醇(A-4)的數量 平均分子量，表示藉由凝膠滲透層析(GPC)法而測定的值。 The number average molecular weight of the acrylic polyol (A-4) is preferably 5,000 to 100,000, and more preferably 10,000 to 30,000, from the viewpoint of obtaining further excellent water resistance, adhesion, and air-opening time. In addition, the number average molecular weight of the acrylic polyol (A-4) is a value measured by gel permeation chromatography (GPC).
作為前述丙烯酸多元醇(A-4)的玻璃轉移溫度，由能獲得更進一步優異的防水性、接著強度、及晾置時間之觀點而言，較佳為30~120℃的範圍，更佳為50~80℃的範圍。此外，前述丙烯酸多元醇(A-4)的玻璃轉移溫度，與前述結晶性聚酯多元醇(A-2)的玻璃轉移溫度(Tg)的測定方法相同。 The glass transition temperature of the acrylic polyol (A-4) is preferably in the range of 30 to 120°C, and more preferably in the range of 50 to 80°C, from the viewpoint of obtaining further excellent water resistance, adhesion strength, and air-opening time. In addition, the glass transition temperature of the acrylic polyol (A-4) is determined in the same manner as the glass transition temperature (Tg) of the crystalline polyester polyol (A-2).
作為使用前述丙烯酸多元醇(A-4)之情形的使用量，由能獲得更進一步優異的防水性、晾置時間、及接著強度之觀點而言，相對於前述聚醚多元醇(A-1)100質量份，較佳為20~400質量份的範圍，更佳為25~200質量份的範圍，再佳為35~150質量份的範圍。 When the acrylic polyol (A-4) is used, the amount is preferably in the range of 20 to 400 parts by mass, more preferably in the range of 25 to 200 parts by mass, and even more preferably in the range of 35 to 150 parts by mass relative to 100 parts by mass of the polyether polyol (A-1), from the viewpoint of obtaining further excellent water resistance, open time, and bonding strength.
作為前述聚異氰酸酯(B)，可使用例如，聚亞甲基聚苯基聚異氰酸酯、二苯基甲烷二異氰酸酯、碳化二亞胺改質二苯基甲烷二異氰酸酯異氰酸酯、伸苯基二異氰酸酯、甲伸苯基二異氰酸酯、萘二異氰酸酯等芳族聚異氰酸酯；六亞甲基二異氰酸酯、離胺酸二異氰酸酯、環己烷二異氰酸酯、異佛酮二異氰酸酯、二環己基甲烷二異氰酸酯、伸茬基二異氰酸酯、四甲基伸茬基二異氰酸酯等脂族或脂環族聚異氰酸酯等。此等之中，由能獲得更進一步優異的反應性及接著性之觀點而言，較佳為使用芳族聚異氰酸酯，更佳為二苯基甲烷二異氰酸酯。 As the aforementioned polyisocyanate (B), for example, aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysamine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, stilbene diisocyanate, and tetramethylstilbene diisocyanate can be used. Among these, aromatic polyisocyanate is preferred, and diphenylmethane diisocyanate is more preferred, from the perspective of obtaining further excellent reactivity and adhesion.
又，作為前述聚異氰酸酯(B)的使用量，由能 獲得更進一步優異的接著強度之觀點而言，較佳為胺基甲酸酯預聚物(i)的原料中5~60質量%的範圍，更佳為10~30質量%的範圍。 In addition, the amount of the polyisocyanate (B) used is preferably in the range of 5 to 60% by mass, and more preferably in the range of 10 to 30% by mass, in the raw material of the urethane prepolymer (i) from the viewpoint of obtaining a further excellent bonding strength.
前述胺基甲酸酯預聚物(i)係使前述多元醇(A)與前述聚異氰酸酯(B)進行反應而得者，且係在聚合物末端或分子內，具有會與空氣中或塗布有胺基甲酸酯預聚物的外殼或被著體中所存在的水分進行反應並形成交聯結構的異氰酸酯基者。 The aforementioned urethane prepolymer (i) is obtained by reacting the aforementioned polyol (A) with the aforementioned polyisocyanate (B), and has an isocyanate group at the polymer terminal or in the molecule that reacts with moisture in the air or in the outer shell or the body to which the urethane prepolymer is applied to form a cross-linked structure.
作為前述胺基甲酸酯預聚物(i)的製造方法，例如，可藉由在裝有前述聚異氰酸酯(B)的反應容器中，滴下前述多元醇(A)後進行加熱，以前述聚異氰酸酯(B)所具有的異氰酸酯基相對於前述多元醇(A)所具有的羥基呈現過剩的條件使其進行反應，藉此而進行製造。 As a method for producing the urethane prepolymer (i), for example, the polyol (A) can be dropped into a reaction vessel containing the polyisocyanate (B) and then heated to react under conditions where the isocyanate groups of the polyisocyanate (B) are in excess relative to the hydroxyl groups of the polyol (A).
在製造前述胺基甲酸酯預聚物(i)之際，前述聚異氰酸酯(B)所具有的異氰酸酯基與前述多元醇(A)所具有的羥基之當量比([異氰酸酯基/羥基])，由能獲得更進一步優異的防水性、接著性、及柔軟性之觀點而言，較佳為1.1~5的範圍，更佳為1.5~3的範圍。 When producing the aforementioned urethane prepolymer (i), the equivalent ratio ([isocyanate group/hydroxyl group]) of the aforementioned polyisocyanate (B) to the aforementioned hydroxyl group of the aforementioned polyol (A) is preferably in the range of 1.1 to 5, and more preferably in the range of 1.5 to 3, from the viewpoint of obtaining further excellent waterproofness, adhesion, and flexibility.
作為前述胺基甲酸酯預聚物(i)的異氰酸酯基含有率(以下，簡記為「NCO%」)，由能獲得更進一步優異的防水性、接著性、及柔軟性之觀點而言，較佳為1.5~8%的範圍，更佳為1.7~5%的範圍，再佳為1.8~3的範圍。此外，前述胺基甲酸酯預聚物(i)的NCO%，表示遵循JISK1603-1：2007，藉由電位滴定法而測定的值。 The isocyanate group content (hereinafter referred to as "NCO%") of the urethane prepolymer (i) is preferably in the range of 1.5 to 8%, more preferably in the range of 1.7 to 5%, and even more preferably in the range of 1.8 to 3, from the viewpoint of obtaining further excellent waterproofness, adhesion, and flexibility. In addition, the NCO% of the urethane prepolymer (i) is a value measured by potentiometric titration in accordance with JIS K1603-1: 2007.
作為前述胺基甲酸酯預聚物(i)的黏度，由能 獲得更進一步優異的防水性及接著強度之觀點而言，較佳為在125℃的熔融黏度為1,000~50,000mPa‧s的範圍，更佳為2,000~10,000mPa‧s的範圍。此外，前述在125℃的熔融黏度，表示以錐板黏度計(ICI製)所測定的值。 As for the viscosity of the urethane prepolymer (i), from the viewpoint of obtaining further excellent waterproofness and bonding strength, the melt viscosity at 125°C is preferably in the range of 1,000 to 50,000 mPa‧s, and more preferably in the range of 2,000 to 10,000 mPa‧s. In addition, the melt viscosity at 125°C is a value measured by a cone plate viscometer (manufactured by ICI).
作為前述胺基甲酸酯預聚物(i)的軟化點，由能獲得更進一步優異的防水性、及接著強度之觀點而言，較佳為30~120℃的範圍內。此外，所謂前述軟化點，係指在使胺基甲酸酯預聚物的溫度階段地上升之情形中，開始熱流動而失去凝聚力的溫度。又，前述胺基甲酸酯預聚物(i)的軟化點，表示藉由遵循JIS K 5902的環球法所求得之值。 The softening point of the urethane prepolymer (i) is preferably in the range of 30 to 120°C from the viewpoint of obtaining further excellent waterproofness and bonding strength. In addition, the softening point refers to the temperature at which heat flow begins and cohesion is lost when the temperature of the urethane prepolymer is gradually increased. The softening point of the urethane prepolymer (i) is a value obtained by the global method in accordance with JIS K 5902.
為了獲得優異的防水性、耐落下衝撃性、及初期接著強度，前述硬化觸媒(ii)必須使用由下述通式(1)所示者。 In order to obtain excellent waterproofness, drop impact resistance, and initial bonding strength, the aforementioned curing catalyst (ii) must be represented by the following general formula (1).
(式(1)中，R1及R2分別獨立地表示氫原子或烷基，n及m分別獨立地表示1~6的整數)。 (In formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group, and n and m each independently represent an integer of 1 to 6).
作為前述硬化觸媒(ii)，由能獲得更進一步優異的初期接著強度之觀點而言，較佳為使用由下述通式(2)所示之二
又，作為前述硬化觸媒(ii)的使用量，基於獲得優異的初期接著強度，相對於前述胺基甲酸酯預聚物(i)100質量份，必須為0.2~1質量份的範圍。在相對於前述胺基甲酸酯預聚物(i)100質量份，前述硬化觸媒(ii)的使用量低於0.2質量份之情形中，尤其無法獲得所期望的初期接著強度，在大於1質量份之情形中，會膠化、或經時的黏度上升率會變高、或儲存穩定性變得極不良。作為前述硬化觸媒(ii)的使用量，由能獲得更進一步優異的儲存穩定性、最終接著強度及耐落下衝撃性之觀點而言，相對於前述胺基甲酸酯預聚物(i)100質量份，較佳為0.25~0.85質量份的範圍，更佳為0.3~0.7質量份的範圍。 In order to obtain excellent initial bonding strength, the amount of the curing catalyst (ii) used must be in the range of 0.2 to 1 part by mass relative to 100 parts by mass of the urethane prepolymer (i). If the amount of the curing catalyst (ii) used is less than 0.2 parts by mass relative to 100 parts by mass of the urethane prepolymer (i), the desired initial bonding strength cannot be obtained. If the amount of the curing catalyst (ii) used is greater than 1 part by mass, gelation may occur, the rate of increase in viscosity over time may increase, or the storage stability may become extremely poor. The amount of the curing catalyst (ii) used is preferably in the range of 0.25 to 0.85 parts by mass, and more preferably in the range of 0.3 to 0.7 parts by mass, relative to 100 parts by mass of the urethane prepolymer (i), from the viewpoint of obtaining further excellent storage stability, final bonding strength and drop impact resistance.
前述包含硫原子的有機酸(iii)係基於獲得優異儲存穩定性的必要成分。作為前述有機酸(iii)，可使用例如，磺酸化合物、亞磺酸化合物等。此等化合物可單獨使用亦可併用二種以上。 The aforementioned organic acid (iii) containing a sulfur atom is an essential component for obtaining excellent storage stability. As the aforementioned organic acid (iii), for example, sulfonic acid compounds, sulfinic acid compounds, etc. can be used. These compounds can be used alone or in combination of two or more.
作為前述磺酸化合有物，可使用例如，甲磺酸、乙磺酸、甲二磺酸、2-羥基-1-乙磺酸、磺酸乙酸、2-胺基-1-乙磺酸、三氟甲磺酸、苯磺酸、甲苯磺酸等。此等化合物可單獨使用亦可併用二種以上。 As the aforementioned sulfonic acid compound, for example, methanesulfonic acid, ethanesulfonic acid, methanedisulfonic acid, 2-hydroxy-1-ethanesulfonic acid, sulfonic acid acetic acid, 2-amino-1-ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, etc. can be used. These compounds can be used alone or in combination of two or more.
作為前述亞磺酸化合物，可使用例如，甲亞磺酸(methanesulfinic acid)、乙亞磺酸等。此等化合物可單獨使用亦可併用二種以上。 As the aforementioned sulfinic acid compound, for example, methanesulfinic acid, ethanesulfinic acid, etc. can be used. These compounds can be used alone or in combination of two or more.
作為前述有機酸(iii)，在前述者之中，由能獲得更進一步優異的儲存穩定性之觀點而言，較佳為使用磺酸化合物，更佳為甲磺酸、及/或、乙磺酸，再佳為甲磺酸。 As the aforementioned organic acid (iii), among the aforementioned, from the viewpoint of obtaining further excellent storage stability, it is preferred to use a sulfonic acid compound, more preferably methanesulfonic acid and/or ethanesulfonic acid, and even more preferably methanesulfonic acid.
又，作為前述有機酸(iii)的使用量，基於獲得優異的儲存穩定性，相對於前述胺基甲酸酯預聚物(i)100質量份，必須為0.0001~0.5質量份的範圍。在相對於前述胺基甲酸酯預聚物(i)100質量份，前述有機酸(iii)的使用量低於0.0001質量份之情形中，未獲得所期望的儲存穩定性，在大於0.5質量份之情形，有會損及接著強度、耐落下衝撃性、及防水性的問題。作為前述有機酸(iii)的使用量，由能獲得更進一步優異的儲存穩定性之觀點而言，相對於前述胺基甲酸酯預聚物(i)100質量份，較佳為0.0005~0.1質量份的範圍，更佳為0.001~0.08質量份的範圍。 In order to obtain excellent storage stability, the amount of the organic acid (iii) used must be in the range of 0.0001 to 0.5 parts by mass relative to 100 parts by mass of the urethane prepolymer (i). If the amount of the organic acid (iii) used is less than 0.0001 parts by mass relative to 100 parts by mass of the urethane prepolymer (i), the desired storage stability cannot be obtained, and if it is greater than 0.5 parts by mass, there are problems that the bonding strength, drop impact resistance, and water resistance may be impaired. From the viewpoint of obtaining further excellent storage stability, the usage amount of the organic acid (iii) is preferably in the range of 0.0005 to 0.1 parts by mass, and more preferably in the range of 0.001 to 0.08 parts by mass, relative to 100 parts by mass of the urethane prepolymer (i).
作為前述硬化觸媒(ii)與有機酸(iii)的質量比[(ii)/(iii)]，由可更進一步提高兼顧儲存穩定性、初期接著強度、防水性、及耐落下衝撃性之觀點而言，較佳 為70/30~99.5/0.5的範圍，更佳為92/8~99/1的範圍。 The mass ratio [(ii)/(iii)] of the aforementioned hardening catalyst (ii) to the organic acid (iii) is preferably in the range of 70/30 to 99.5/0.5, and more preferably in the range of 92/8 to 99/1, from the viewpoint of further improving storage stability, initial adhesion strength, water resistance, and drop impact resistance.
本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物含有前述胺基甲酸酯預聚物(i)、前述硬化觸媒(ii)、及前述有機酸(iii)作為必要成分，但依據需要亦可含有其他添加劑。 The moisture-curing polyurethane hot-melt resin composition of the present invention contains the aforementioned urethane prepolymer (i), the aforementioned curing catalyst (ii), and the aforementioned organic acid (iii) as essential components, but may also contain other additives as needed.
作為前述其他添加劑，可使用例如，抗氧化劑、賦黏劑、塑化劑、穩定劑、填充材、染料、顏料、螢光增白劑、矽烷偶合劑、蠟等。此等添加劑可單獨使用亦可併用二種以上 As the aforementioned other additives, for example, antioxidants, adhesives, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent brighteners, silane coupling agents, waxes, etc. can be used. These additives can be used alone or in combination of two or more.
以上，本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物係具有能緩和經時的黏度上升之優異儲存穩定性者。又，本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物可表現優異的初期接著強度及最終接著強度，藉由前述聚胺基甲酸酯熱熔樹脂組成物而貼合的物品係防水性及耐落下衝撃性優異者。因此，本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物，不僅纖維鍵結‧建材積層用途，亦可特別適合使用在光學用構件的貼合。 As described above, the moisture-curing polyurethane hot-melt resin composition of the present invention has excellent storage stability that can mitigate the increase in viscosity over time. In addition, the moisture-curing polyurethane hot-melt resin composition of the present invention can show excellent initial bonding strength and final bonding strength, and the items bonded by the aforementioned polyurethane hot-melt resin composition are excellent in waterproofness and resistance to drop impact. Therefore, the moisture-curing polyurethane hot-melt resin composition of the present invention is not only used for fiber bonding and building material lamination, but is also particularly suitable for use in bonding optical components.
作為能用於前述光學構件之貼合的態樣，可列舉例如，行動電話、個人電腦、遊戲機、電視、汽車導航、攝像機喇叭等的密封劑。 Examples of the bonding of the aforementioned optical components include sealants for mobile phones, personal computers, game consoles, televisions, car navigation, camera speakers, etc.
在進行前述貼合之情形中，可列舉例如，將前述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物在50~130℃的溫度範圍進行加熱熔融，將該組成物塗布在其一構件上，接下來將另一構件貼合在該組成物上而獲得物 品的方法。 In the case of the aforementioned bonding, for example, the aforementioned moisture-curing polyurethane hot-melt resin composition is heated and melted in a temperature range of 50 to 130°C, the composition is applied to one component, and then another component is bonded to the composition to obtain a method of obtaining an article.
作為前述構件，可使用由例如玻璃、丙烯酸系樹脂、胺基甲酸酯系樹脂、矽系樹脂、環氧系樹脂、氟系樹脂、聚苯乙烯系樹脂、聚酯系樹脂、聚碸系樹脂、聚芳酯(polyarylate)系樹脂、聚氯乙烯樹脂、聚二氯亞乙烯、降莰烯等環烯烴系樹脂、聚烯烴系樹脂、聚醯亞胺系樹脂、脂環式聚醯亞胺系樹脂、纖維素系樹脂、PC(聚碳酸酯)、PBT(聚對苯二甲酸丁二酯)、改質PPE(聚苯醚(polyphenylene ether))、PEN(聚萘二甲酸乙二酯(polyethylene naphthalate))、PET(聚對苯二甲酸乙二酯)、乳酸聚合物、ABS樹脂、AS樹脂等而得者。又，前述構件，依據需要，亦可被施以電暈處理、電漿處理、底漆處理等。 As the aforementioned member, for example, glass, acrylic resin, urethane resin, silicone resin, epoxy resin, fluorine resin, polystyrene resin, polyester resin, polysulfone resin, polyarylate resin, polyvinyl chloride resin, polyvinylidene chloride, cycloolefin resin such as norbornene, polyolefin resin, polyimide resin, alicyclic polyimide resin, cellulose resin, PC (polycarbonate), PBT (polybutylene terephthalate), modified PPE (polyphenylene ether), PEN (polyethylene naphthalate), etc. can be used. naphthalate), PET (polyethylene terephthalate), lactic acid polymer, ABS resin, AS resin, etc. In addition, the aforementioned components can also be subjected to corona treatment, plasma treatment, primer treatment, etc. as needed.
作為塗布前述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物的方法，可列舉使用例如輥塗布機、噴霧塗布機、T-模塗機、刀式塗布機、缺角輪塗布機(comma coater)等的方法。 As a method for applying the aforementioned moisture-curing polyurethane hot-melt resin composition, there can be cited methods using, for example, a roller coater, a spray coater, a T-die coater, a knife coater, a comma coater, etc.
又，本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物因具有低黏度性、及塗布後的優異保型性，故亦可藉由分配器、噴墨印刷、網版印刷、膠版印刷等的方式進行塗布。根據此等塗布方式，因可在前述構件上欲塗布處塗布前述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物，故不會產生衝孔加工等的損耗，因此較佳。又，根據此等塗布方式，可將前述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物，以點狀、線狀、三角狀、四角狀、丸 狀、曲線等各種的形狀，在前述構件上連續或斷續地形成。 Furthermore, the moisture-curing polyurethane hot melt resin composition of the present invention has low viscosity and excellent shape retention after coating, so it can also be coated by a dispenser, inkjet printing, screen printing, offset printing, etc. According to these coating methods, since the moisture-curing polyurethane hot melt resin composition can be coated on the desired coating location on the aforementioned component, it will not cause damage such as punching processing, which is preferred. Furthermore, according to these coating methods, the moisture-curing polyurethane hot melt resin composition can be formed continuously or discontinuously on the aforementioned component in various shapes such as dots, lines, triangles, squares, balls, curves, etc.
作為前述濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物的硬化物層(接著層)的厚度，可依據使用用途而適當設定，但可列舉例如10μm~5mm的範圍。 The thickness of the cured layer (bonding layer) of the aforementioned moisture-curing polyurethane hot-melt resin composition can be appropriately set according to the intended use, but can be, for example, in the range of 10μm to 5mm.
作為前述貼合後的熟成條件，例如可在溫度20~80℃、相對濕度50~90%RH、0.5~3日之間進行適當決定。 As the aging conditions after the bonding, for example, the temperature can be set between 20~80℃, relative humidity 50~90%RH, and 0.5~3 days.
以下，藉由實施例而更詳細地說明本發明。 The present invention is described in more detail below through examples.
在具備溫度計、攪拌機及冷卻管的反應容器中，裝入甲基乙基酮300質量份，在容器內溫度成為80℃後，添加將甲基丙烯酸340質量份、甲基丙烯酸丁酯340質量份、甲基丙烯酸2-羥乙酯10質量份、偶氮雙異丁腈8.5質量份溶解於甲基乙基酮160質量份而成者，進行混合，使其反應16小時，藉此獲得丙烯酸多元醇-1(非揮發成分：52質量%，黏度：20,000mPa‧s(23℃))。 300 parts by mass of methyl ethyl ketone was placed in a reaction container equipped with a thermometer, a stirrer and a cooling tube. After the temperature in the container reached 80°C, 340 parts by mass of methacrylic acid, 340 parts by mass of butyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate and 8.5 parts by mass of azobisisobutyronitrile dissolved in 160 parts by mass of methyl ethyl ketone were added and mixed. The mixture was reacted for 16 hours to obtain acrylic polyol-1 (non-volatile component: 52% by mass, viscosity: 20,000 mPa‧s (23°C)).
在具備溫度計、攪拌機、惰性氣體導入口及回流冷卻器的四口燒瓶中，裝填聚丙二醇(數量平均分子 量：1,000)15質量份、聚丙二醇(數量平均分子量：2,000，以下簡稱為「PPG2000」)15質量份、結晶性聚酯多元醇(使1,6-己二醇與1,12-十二烷二甲酸進行反應者，數量平均分子量：3,500)20質量份、非晶性聚酯多元醇(使雙酚A的氧化丙烯6莫耳加成物與癸二酸、間苯二甲酸進行反應者，數量平均分子量：2,000)7.5質量份、非晶性聚酯多元醇(使新戊二醇、二乙二醇、1,6-己二醇及己二酸進行反應者，數量平均分子量：2,000)7.5質量份、20質量份之將丙烯酸多元醇-1的溶劑進行乾燥而固體化者，在減壓下以100℃進行脫水直到多元醇混合物中的水分含有率成為0.05質量%以下為止。 In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux cooler, 15 parts by mass of polypropylene glycol (number average molecular weight: 1,000), 15 parts by mass of polypropylene glycol (number average molecular weight: 2,000, hereinafter referred to as "PPG2000"), 20 parts by mass of crystalline polyester polyol (reacted with 1,6-hexanediol and 1,12-dodecanedicarboxylic acid, number average molecular weight: 3,500), 20 parts by mass of amorphous polyester polyol (reacted with propylene oxide of bisphenol A) and 1,2-dodecanedicarboxylic acid. 6 mol adduct reacted with sebacic acid and isophthalic acid, number average molecular weight: 2,000) 7.5 mass parts, amorphous polyester polyol (neopentyl glycol, diethylene glycol, 1,6-hexanediol and adipic acid reacted, number average molecular weight: 2,000) 7.5 mass parts, 20 mass parts of the solvent of acrylic polyol-1 dried and solidified, dehydrated at 100°C under reduced pressure until the water content in the polyol mixture becomes less than 0.05 mass %.
接下來，容器內溫度冷卻至70℃後，添加4,4’-二苯基甲烷二異氰酸酯(MDI)15.5質量份，升溫至100℃，使其反應約3小時直到NCO基含有率成為固定，獲得具異氰酸酯基的胺基甲酸酯預聚物(i-1)。 Next, after the temperature in the container was cooled to 70°C, 15.5 parts by weight of 4,4'-diphenylmethane diisocyanate (MDI) was added, the temperature was raised to 100°C, and the reaction was allowed to proceed for about 3 hours until the NCO group content became constant, thereby obtaining a urethane prepolymer (i-1) having an isocyanate group.
前述合成例中，多元醇的數量平均分子量表示藉由凝膠滲透層析(GPC)法並以下述條件進行測定的值。 In the above synthesis examples, the number average molecular weight of the polyol represents the value measured by gel permeation chromatography (GPC) under the following conditions.
測定裝置：高速GPC裝置(Tosoh股份有限公司製「HLC-8220GPC」) Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Co., Ltd.)
管柱：將Tosoh股份有限公司製的下述管柱進行串聯而使用。 Column: The following columns manufactured by Tosoh Co., Ltd. were connected in series and used.
「TSKgel G5000」(7.8mmI.D.×30cm)×1根 "TSKgel G5000" (7.8mmI.D.×30cm)×1 piece
「TSKgel G4000」(7.8mmI.D.×30cm)×1根 "TSKgel G4000" (7.8mmI.D.×30cm)×1
「TSKgel G3000」(7.8mmI.D.×30cm)×1根 "TSKgel G3000" (7.8mmI.D.×30cm)×1 piece
「TSKgel G2000」(7.8mmI.D.×30cm)×1根 "TSKgel G2000" (7.8mmI.D.×30cm)×1 piece
偵檢器：RI(差示折射計) Detector: RI (differential refractometer)
管柱溫度：40℃ Column temperature: 40℃
溶析液：四氫呋喃(THF) Solvent: Tetrahydrofuran (THF)
流速：1.0mL/分鐘 Flow rate: 1.0mL/min
注入量：100μL(試料濃度0.4質量%的四氫呋喃溶液) Injection volume: 100μL (sample concentration 0.4 mass% tetrahydrofuran solution)
標準試料：使用下述的標準聚苯乙烯，製作校正曲線。 Standard sample: Use the following standard polystyrene to prepare the calibration curve.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯A-500」 "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Co., Ltd.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯A-1000」 "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Co., Ltd.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯A-2500」 "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Co., Ltd.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯A-5000」 "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Co., Ltd.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-1」 "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Co., Ltd.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-2」 "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Co., Ltd.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯 F-4」 "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Co., Ltd.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-10」 "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Co., Ltd.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-20」 "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Co., Ltd.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-40」 "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Co., Ltd.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-80」 "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Co., Ltd.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-128」 "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Co., Ltd.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-288」 "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Co., Ltd.
Tosoh股份有限公司製「TSKgel標準聚苯乙烯F-550」 "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Co., Ltd.
將由合成例2所得之胺基甲酸酯預聚物(i-1)100質量份、雙(2,6-二甲基
除了將使用的硬化觸媒(ii)及有機酸(iii)的種類及/或量如表1~2所示般進行變更以外，與實施例1同樣地 進行，獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物。 Except for changing the type and/or amount of the curing catalyst (ii) and organic acid (iii) used as shown in Tables 1-2, the same method as Example 1 was followed to obtain a moisture-curing polyurethane hot-melt resin composition.
於實施例及比較例中，在剛獲得濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物後，立刻將濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物在110℃進行熔融，取樣1ml，以錐板黏度計(40P cone，轉子旋轉數：50rpm)測定黏度。 In the embodiments and comparative examples, immediately after obtaining the moisture-curing polyurethane hot-melt resin composition, the moisture-curing polyurethane hot-melt resin composition was melted at 110°C, and 1 ml of the sample was taken to measure the viscosity using a cone viscometer (40P cone, rotor rotation number: 50 rpm).
將在實施例及比較例所得之濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物，在50℃的條件下放置4週後，同樣地進行，測定黏度。 The moisture-curing polyurethane hot-melt resin composition obtained in the embodiment and comparative example was placed at 50°C for 4 weeks and then the viscosity was measured in the same manner.
若經時黏度的值除以初期黏度的值之數小於1.3則評價為「○」，若為1.3以上則評價為「×」。 If the value of the time-dependent viscosity divided by the value of the initial viscosity is less than 1.3, the evaluation is "○", and if it is 1.3 or more, the evaluation is "×".
將由實施例及比較例所得之濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物在110℃進行熔融，使用經預先加熱至110℃之內徑0.4mm的分配針(dispenser needle)(Musashi Engineering股份有限公司製「ML-5000Xii)，以噴出壓力：0.3MPa、速度：50mm/秒鐘，在中央已開有1cm直徑的孔之PC板(5cm×9cm)上，以成為1吋的圓形且0.2mm厚度之方式，進行塗布，從其上方貼合丙烯酸板(5cm×5cm)後，放置在溫度23℃、 濕度50%的恆溫恆濕槽中，藉此製作物品。 The moisture-curing polyurethane hot melt resin composition obtained from the embodiment and the comparative example was melted at 110°C, and a dispenser needle (ML-5000Xii manufactured by Musashi Engineering Co., Ltd.) with an inner diameter of 0.4 mm preheated to 110°C was used to apply the composition in a 1-inch circular shape and 0.2 mm thickness on a PC plate (5cm×9cm) with a 1cm diameter hole in the center at a spray pressure of 0.3MPa and a speed of 50mm/sec. An acrylic plate (5cm×5cm) was attached from above, and the composition was placed in a constant temperature and humidity tank at a temperature of 23°C and a humidity of 50% to produce an article.
將利用前述[物品的製作方法]且放置在恆溫恆濕槽中經過30分鐘的物品取出，使用自動放射攝影術(島津製作所股份有限公司AUTOGRAPH「AGS-X」，以十字頭速度：10mm/分鐘的條件，測定物品的推強度(push strength)、初期接著強度(N/cm2)。此外，若初期接著強度為70N/cm2以上，則判定為具有優異的初期接著強度。 The article was taken out after being placed in the constant temperature and humidity chamber for 30 minutes using the above-mentioned [Article Production Method], and the push strength and initial bonding strength (N/cm 2 ) of the article were measured using autoradiography (Autograph "AGS-X" produced by Shimadzu Corporation, at a crosshead speed of 10 mm/min). In addition, if the initial bonding strength is 70 N/cm 2 or more, it is judged to have excellent initial bonding strength.
將利用前述[物品的製作方法]且放置在恆溫恆濕槽中經過48小時後的物品取出，同樣地使用TENSILON，測定最終接著強度(N/cm2)。 The article was taken out after being placed in the constant temperature and humidity chamber for 48 hours using the aforementioned [Article Manufacturing Method], and the final bonding strength (N/cm 2 ) was measured using TENSILON in the same manner.
將以前述[最終接著強度的測定方法]測定接著強度後的物品，利用杜邦式落下衝撃試驗機，從丙烯酸板經由撃芯，以荷重：100g、高度：10cm給予三次衝撃，若未發生PC板的剝落，則進一步以增高10cm高度的條件，分別持續耐落下衝撃性試驗。分別藉由目視觀察而確認有無剝落，評價產生剝落的高度(cm)。此外，若為30cm以上則判定為耐落下衝撃性優異。 The items after the joint strength is measured by the aforementioned [Method for Determining Final Joint Strength] are subjected to three impacts with a DuPont drop impact tester from an acrylic plate through a punch core, with a load of 100g and a height of 10cm. If no peeling of the PC plate occurs, the drop impact resistance test is continued with a further increase of 10cm in height. The presence or absence of peeling is confirmed by visual observation, and the height (cm) at which peeling occurs is evaluated. In addition, if it is 30cm or more, it is judged to be excellent in drop impact resistance.
將由實施例及比較例所得之濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物在110℃進行熔融，使用經預先加熱至110℃之內徑0.4mm的分配針(Musashi Engineering股份有限公司製「ML-5000Xii)，以噴出壓力：0.3MPa、速度：50mm/秒鐘，在中央未開孔的PC板(5cm×9cm)上，以成為1吋的圓形且0.2mm厚之方式進行塗布，從其上方將丙烯酸板(5cm×5cm)貼合後，放置在溫度23℃、濕度50%的恆溫恆濕槽中48小時，藉此製作評價用物品。 The moisture-curing polyurethane hot melt resin composition obtained from the examples and comparative examples was melted at 110°C and applied on a PC board (5cm×9cm) without a hole in the center in a 1-inch circular shape and 0.2mm thick using a dispensing needle ("ML-5000Xii" manufactured by Musashi Engineering Co., Ltd.) preheated to 110°C with an inner diameter of 0.4mm at a spray pressure of 0.3MPa and a speed of 50mm/second. An acrylic plate (5cm×5cm) was attached from above and placed in a constant temperature and humidity tank at a temperature of 23°C and a humidity of 50% for 48 hours to produce an evaluation item.
使此評價用物品進行水浸漬(23℃、0.5小時)後，遵循JIS IPX-7，進行有無對物品內部的水侵入之評價，未被確認到水的侵入者因防水性優異而評價為「○」，確認到水的侵入者則評價為「×」。 After the evaluation item is immersed in water (23°C, 0.5 hours), the item is evaluated for water intrusion in accordance with JIS IPX-7. If no water intrusion is confirmed, it is evaluated as "○" due to excellent waterproof performance, and if water intrusion is confirmed, it is evaluated as "×".
可知本發明的濕氣硬化型聚胺基甲酸酯熱熔樹脂組成物之實施例1~6係儲存穩定性、初期接著強度、防水性、及耐落下衝撃性優異。 It can be seen that Examples 1 to 6 of the moisture-curing polyurethane hot-melt resin composition of the present invention are excellent in storage stability, initial adhesion strength, waterproofness, and drop impact resistance.
另一方面，比較例1為硬化觸媒(ii)的使用量低於本發明所規定之範圍的態樣，初期接著強度及防水性為不良。 On the other hand, in Comparative Example 1, the amount of curing catalyst (ii) used is lower than the range specified in the present invention, and the initial bonding strength and waterproofness are poor.
比較例2為硬化觸媒(ii)的使用量大於本發明所規定之範圍的態樣，已膠化。 Comparative Example 2 is a state where the amount of hardening catalyst (ii) used is greater than the range specified in the present invention and has been gelled.
比較例3為有機酸(iii)的使用量低於本發明所規定之範圍的態樣，儲存穩定性、耐落下衝撃性及防水性為不良。 Comparative Example 3 is a state where the amount of organic acid (iii) used is lower than the range specified in the present invention, and the storage stability, drop impact resistance and waterproofness are poor.
比較例4為有機酸(iii)的使用量大於本發明所規定之範圍的態樣，初期黏度、初期接著強度、耐落下衝撃性及防水性為不良。 Comparative Example 4 is a state where the amount of organic acid (iii) used is greater than the range specified in the present invention, and the initial viscosity, initial bonding strength, drop impact resistance and waterproofness are poor.
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| WO2019060681A1 (en) * | 2017-09-22 | 2019-03-28 | Henkel IP & Holding GmbH | Solvent free liquid moisture curable polyurethane compositions with long open times and fast cure rates |
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| TW201345939A (en) * | 2012-04-12 | 2013-11-16 | Dainippon Ink & Chemicals | Moisture-curable polyurethane hot-melt resin composition, adhesive, and article |
| WO2019060681A1 (en) * | 2017-09-22 | 2019-03-28 | Henkel IP & Holding GmbH | Solvent free liquid moisture curable polyurethane compositions with long open times and fast cure rates |
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