CN114790270A - Moisture-curable polyurethane hot-melt resin composition, cured product, and laminate - Google Patents
Moisture-curable polyurethane hot-melt resin composition, cured product, and laminate Download PDFInfo
- Publication number
- CN114790270A CN114790270A CN202111494652.1A CN202111494652A CN114790270A CN 114790270 A CN114790270 A CN 114790270A CN 202111494652 A CN202111494652 A CN 202111494652A CN 114790270 A CN114790270 A CN 114790270A
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- China
- Prior art keywords
- polyol
- polyester polyol
- moisture
- mass
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 32
- 239000004814 polyurethane Substances 0.000 title claims abstract description 32
- 239000012943 hotmelt Substances 0.000 title claims abstract description 28
- 239000011342 resin composition Substances 0.000 title claims abstract description 27
- 150000003077 polyols Chemical class 0.000 claims abstract description 63
- 229920005862 polyol Polymers 0.000 claims abstract description 57
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 43
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 34
- 229920003232 aliphatic polyester Polymers 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 16
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 15
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 15
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 19
- 239000004831 Hot glue Substances 0.000 abstract description 15
- 238000005187 foaming Methods 0.000 abstract description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 13
- 238000013008 moisture curing Methods 0.000 abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 13
- 150000007519 polyprotic acids Polymers 0.000 description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- 239000005020 polyethylene terephthalate Substances 0.000 description 12
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 11
- -1 polyethylene terephthalate Polymers 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- 125000002947 alkylene group Chemical group 0.000 description 9
- 150000002009 diols Chemical class 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 4
- 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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000004566 building material Substances 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 3
- 229940035437 1,3-propanediol Drugs 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000007824 aliphatic compounds Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
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- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229940083957 1,2-butanediol Drugs 0.000 description 2
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 2
- QOFLTGDAZLWRMJ-UHFFFAOYSA-N 2-methylpropane-1,1-diol Chemical compound CC(C)C(O)O QOFLTGDAZLWRMJ-UHFFFAOYSA-N 0.000 description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- JJOJFIHJIRWASH-UHFFFAOYSA-N icosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-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
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- RKLJSBNBBHBEOT-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropanoyl) 3-hydroxy-2,2-dimethylpropanoate Chemical compound OCC(C)(C)C(=O)OC(=O)C(C)(C)CO RKLJSBNBBHBEOT-UHFFFAOYSA-N 0.000 description 1
- SZCWBURCISJFEZ-UHFFFAOYSA-N (3-hydroxy-2,2-dimethylpropyl) 3-hydroxy-2,2-dimethylpropanoate Chemical compound OCC(C)(C)COC(=O)C(C)(C)CO SZCWBURCISJFEZ-UHFFFAOYSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
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- ZABMGUITRPYVRH-UHFFFAOYSA-N 2,3,4-trimethylpentane-1,5-diol Chemical compound OCC(C)C(C)C(C)CO ZABMGUITRPYVRH-UHFFFAOYSA-N 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
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- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 description 1
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- RLWFMZKPPHHHCB-UHFFFAOYSA-N cyclopropane-1,2-dicarboxylate;hydron Chemical compound OC(=O)C1CC1C(O)=O RLWFMZKPPHHHCB-UHFFFAOYSA-N 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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- MUTGBJKUEZFXGO-UHFFFAOYSA-N hexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21 MUTGBJKUEZFXGO-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
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- 150000003022 phthalic acids Chemical class 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/302—Water
- C08G18/307—Atmospheric humidity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention addresses the problem of providing a moisture-curable polyurethane hot-melt adhesive that can exhibit adhesion to a PET substrate while ensuring transparency even after moisture curing and suppressing foaming. The moisture-curable polyurethane hot-melt resin composition of the present invention comprises a polyurethane resin having an isocyanate group, the polyurethane resin being a reaction product of a polyol (a) and a polyisocyanate (B), the polyol (a) comprising an alicyclic polyester polyol (a1), a long-chain aliphatic polyester polyol (a2), and a liquid polyester polyol (a3), the content of the alicyclic polyester polyol (a1) in the polyol (a) being 20 mass% or more, the content of the long-chain aliphatic polyester polyol (a2) in the polyol (a) being 15 mass% or more, and the content of the liquid polyester polyol (a3) in the polyol (a) being 15 mass% or more. The invention also relates to a cured product and a laminate.
Description
Technical Field
The present invention relates to a moisture-curable polyurethane hot-melt resin composition, a cured product, and a laminate.
Background
Since hot melt adhesives have high initial adhesion and final strength, they are used in various fields such as decorative panels, automobile interior materials, and clothing materials, as typified by various building material applications. As the reactive hot melt adhesive, in addition to a moisture-curable polyurethane hot melt adhesive which exhibits final strength by moisture curing of an isocyanate group of a urethane prepolymer as a main agent thereof, an olefin hot melt adhesive, a polyester hot melt adhesive, and the like are known. In recent years, there has been an increasing demand for a building material having a high-grade feel, which is obtained by adhering a material having high transparency, such as a polyethylene terephthalate (PET) film, to a base material.
As such a hot melt adhesive having high transparency, for example, a hot melt adhesive containing an ethylene-propylene copolymer, a hydrogenated rosin-based tackifier resin, other hydrogenated tackifier resins, and an acid-modified olefin is known (see patent document 1); a crystalline polyester resin comprising a polycarboxylic acid component and a polyol component, wherein the polycarboxylic acid component contains terephthalic acid, and the polyol component contains ethylene glycol, 1, 4-butanediol, polyalkylene glycol, and diethylene glycol (see patent document 2); a hot melt adhesive comprising an ethylene-propylene copolymer, a hydrogenated tackifier resin, and a wax having a melting point of 120 to 160 ℃ (see patent document 3); a polyester resin comprising a polycarboxylic acid component and a polyhydric alcohol component as copolymerized components, an aromatic dicarboxylic acid having 8 to 14 carbon atoms and an aliphatic dicarboxylic acid having 6 or more carbon atoms as the polycarboxylic acid component, and further comprising a metal salt of an aliphatic carboxylic acid having 6 or more carbon atoms (see patent document 4).
Documents of the prior art
Patent document
[ patent document 1] Japanese patent laid-open No. 2020-2283
[ patent document 2] Japanese patent laid-open publication No. 2019-127581
[ patent document 3] Japanese patent laid-open No. 2018-154694
[ patent document 4] Japanese patent laid-open No. 2015-108113
Disclosure of Invention
Problems to be solved by the invention
However, when a reactive hot melt adhesive (RHM) is used for such applications, high transparency of the resin itself is required, and further, suppression of foaming in the RHM at the time of moisture curing is required. According to the studies of the present inventors, it is effective to use a crystalline component as a raw material in order to suppress foaming, but the crystalline component crystallizes in the obtained cured product, which causes problems such as cloudiness and deterioration in transparency.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a moisture-curable polyurethane hot-melt adhesive which can suppress foaming while ensuring transparency even after moisture curing, and further exhibits adhesiveness to a PET substrate.
Means for solving the problems
The present inventors have intensively studied and thought that an alicyclic polyester polyol, a crystalline component and a liquid polyester are combined. The present inventors have found that when alicyclic polyester polyols are combined at a specific ratio, the adhesion to a PET substrate can be ensured while suppressing foaming while maintaining transparency, and the present invention has been completed.
That is, the present invention includes the following inventions.
[1] A moisture-curable polyurethane hot-melt resin composition comprising a polyurethane resin having an isocyanate group, the polyurethane resin being a reaction product of a polyol (A) and a polyisocyanate (B), the polyol (A) comprising an alicyclic polyester polyol (a1), a long-chain aliphatic polyester polyol (a2) and a liquid polyester polyol (a3), the content of the alicyclic polyester polyol (a1) in the polyol (A) being 20% by mass or more, the content of the long-chain aliphatic polyester polyol (a2) in the polyol (A) being 15% by mass or more, and the content of the liquid polyester polyol (a3) in the polyol (A) being 15% by mass or more.
[2] The moisture-curable polyurethane hot-melt resin composition according to [1], which has a haze value of less than 20 as measured by the following method.
[ method for measuring haze value ]
The moisture-curable polyurethane hot-melt resin composition was melted at 120 ℃ for 1 hour, and coated on the release layer so that the thickness became 0.1 mm. The resultant coating layer was kept at 23 ℃ and 50% humidity for 96 hours to obtain a cured product. The haze value of the cured product was measured in accordance with JIS K7136.
[3] A cured product of the moisture-curable polyurethane hot-melt resin composition according to [1] or [2 ].
[4] A laminate having the cured product according to [3 ].
Effects of the invention
The moisture-curable polyurethane hot-melt resin composition of the present invention can suppress foaming while ensuring transparency even after moisture curing, and further can exhibit adhesiveness to a PET substrate.
Detailed Description
The moisture-curable polyurethane hot-melt resin composition of the present invention comprises a polyurethane resin having an isocyanate group.
The above polyurethane resin is a reaction product of a polyol (a) and a polyisocyanate (B).
The polyol (a) includes an alicyclic polyester polyol (a1), a long-chain aliphatic polyester polyol (a2), and a liquid polyester polyol (a 3).
The alicyclic polyester polyol (a1) is a polyester polyol having an alicyclic structure in the molecule, and the inclusion of the alicyclic polyester polyol (a1) can improve transparency and suppress foaming.
The alicyclic polyester polyol (a1) is preferably a reaction product of, for example, a polybasic acid containing an alicyclic structure (hereinafter, referred to as "alicyclic structure-containing polybasic acid") and a diol.
The alicyclic structure-containing polybasic acid may have an alicyclic structure, and examples thereof include 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, 1, 2-cyclopropanedicarboxylic acid, 1, 2-cyclobutanedicarboxylic acid, 1, 3-cyclobutanedicarboxylic acid, 1, 2-cyclopentanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, 1, 2-cycloheptanedicarboxylic acid, 1, 3-cycloheptanedicarboxylic acid, 1, 4-cycloheptanedicarboxylic acid, 1, 2-cyclooctanedicarboxylic acid, 1, 3-cyclooctanedicarboxylic acid, 1, 4-cyclooctanedicarboxylic acid, 1, 5-cyclooctanedicarboxylic acid, 1, 2-cyclononanedicarboxylic acid, 1, 3-cyclononanedicarboxylic acid, 1, 4-cyclononanedicarboxylic acid, 1, 5-cyclononane dicarboxylic acid, 1, 2-cyclodecane dicarboxylic acid, 1, 3-cyclodecane dicarboxylic acid, 1, 4-cyclodecane dicarboxylic acid, 1, 5-cyclodecane dicarboxylic acid, 1, 6-cyclodecane dicarboxylic acid, 1, 2, 3-cyclopropanetricarboxylic acid, 1, 2, 3-cyclobutanetricarboxylic acid, 1, 2, 3-cyclopentane tricarboxylic acid, 1, 2, 3-cycloheptane tricarboxylic acid, 1, 2, 3-cyclohexane tricarboxylic acid, dicyclohexyl-4, 4' -dicarboxylic acid and dimer acid, 1, 2-cyclohexanediacetic acid, 1, 3-cyclohexanediacetic acid, 1, 4-cyclohexanediacetic acid, and anhydrides thereof; anhydrides of hydrogenated phthalic acid and the like, and they may be used alone or in combination of two or more. Among them, dicarboxylic acids having a cyclohexane ring or derivatives thereof are preferably used, and 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, and hydrogenated phthalic anhydride are more preferably used.
The diol is not particularly limited, and examples thereof include aliphatic diols such as ethylene glycol, 1, 2-propanediol, 1, 3-butanediol, 1, 4-butanediol, 2-dimethyl-1, 3-propanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 1, 8-octanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and tripropylene glycol; alicyclic diols such as cyclopentane-1, 2-diol, cyclohexane-1, 3-diol, cyclohexane-1, 4-diol, cyclooctane-1, 4-diol, and 2, 5-norbornanediol; neopentyl glycol hydroxypivalate, 2-methylpropanediol, 2-methyl-1, 4-butanediol, neopentyl glycol, 2-dimethyl-1, 4-butanediol, 2, 3-dimethyl-1, 4-butanediol, 2-methyl-1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2, 3-dimethyl-1, 5-pentanediol, 3-ethyl-1, 5-pentanediol, 2-methyl-1, 6-hexanediol, 3-methyl-1, 6-hexanediol, 2, 3, 4-trimethyl-1, 5-pentanediol, 3-dimethyl-1, 6-hexanediol, 3-diethyl-1, side chain-containing diols such as 5-pentanediol and 3, 3-diethyl-1, 6-hexanediol; aromatic diols such as p-xylylene glycol, 4 '-methylenediphenol, 4' -dihydroxybiphenyl and 2, 5-naphthalenediol, and these diols may be used alone or in combination of two or more.
Among them, from the viewpoint of a moderate open time at low temperatures and easiness of obtaining a raw material, it is preferable to use a diol having a side chain, and it is more preferable to use neopentyl glycol, hydroxypivalyl hydroxypivalate, and 2-methylpropanediol.
The alicyclic polyester polyol (a1) is obtained by polycondensation of the alicyclic structure-containing polybasic acid and a diol by a conventionally known method. Examples of the polycondensation reaction include the following methods: the alicyclic structure-containing polybasic acid and diol are charged into a reaction vessel, and a high boiling point solvent such as xylene, an esterification catalyst, and a polymerization inhibitor are added as necessary, and subjected to dehydration condensation to thereby carry out esterification reaction. The reaction temperature of the polycondensation reaction is 140-240 ℃, more preferably 170-230 ℃, and the reaction time is 5-20 hours, more preferably 7-17 hours.
Examples of the esterification catalyst include metal oxides such as tin oxide, antimony oxide, titanium oxide and vanadium oxide, bronsted acids such as p-toluenesulfonic acid, sulfuric acid and phosphoric acid, lewis acids such as boron trifluoride complex, titanium tetrachloride and tin tetrachloride, and organic metal compounds such as calcium acetate, zinc acetate, manganese acetate, zinc stearate, alkyltin oxide and titanium alkoxide, and these may be used alone or in combination of two or more.
The amount of the esterification catalyst used is preferably 0.001 to 0.1% by mass, more preferably 0.005 to 0.03% by mass, based on the total mass of the alicyclic structure-containing polybasic acid and the diol.
Examples of the polymerization inhibitor include hydroquinone, monomethyl ether hydroquinone, methyl hydroquinone, 2, 6-di-tert-butyl-4-methylphenol, trimethy-lether hydroquinone, phenothiazine and tert-butylcatechol, and these may be used alone or in combination of two or more.
The amount of the polymerization inhibitor used is preferably 0.001 to 0.3% by mass, more preferably 0.005 to 0.07% by mass, based on the total mass of the alicyclic structure-containing polybasic acid and the diol.
The acid value of the alicyclic polyester polyol (a1) is preferably 2.0mgKOH/g or less, more preferably 0 to 1.0mgKOH/g, and particularly preferably 0 to 0.80 mgKOH/g. The acid value of the alicyclic polyester polyol (a1) is a value measured in accordance with JIS K1557-5.
The hydroxyl value of the alicyclic polyester polyol (a1) is preferably 40 to 220mgKOH/g, and more preferably 50 to 150 mgKOH/g. The hydroxyl value of the alicyclic polyester polyol (a1) can be measured in accordance with JISK 0070.
The alicyclic polyester polyol (a1) synthesized by the above method preferably has a number average molecular weight of 500 to 2500, more preferably 500 to 1500, from the viewpoint of synthesis and from the viewpoint of improving the balance between a suitable open time at low temperature and moisture-proof performance. The number average molecular weight is a value obtained by gel permeation chromatography (GPC method) using polystyrene as a molecular weight standard.
In the polyol (a), the content of the alicyclic polyester polyol (a1) is 20% by mass or more, preferably 23% by mass or more, preferably 70% by mass or less, more preferably 50% by mass or less, and still more preferably 48% by mass or less.
The long-chain aliphatic polyester polyol (a2) is an essential component for exhibiting cohesive force as an adhesive, and represents a polyester polyol in which the total number of carbon atoms of alkylene groups contained in a repeating unit is 10 or more.
From the viewpoint of suppressing foaming, the long-chain aliphatic polyester polyol (a2) is preferably represented by the following formula (1).
[ chemical formula 1]
[ in the formula (1), R 1 And R 2 Each is a linear alkylene group having an even number of carbon atoms, and R 1 And R 2 The total number of carbon atoms is 10 or more. n represents an integer of 1 to 40.]
R is as defined above 1 Which is a linear alkylene group having an even number of carbon atoms, which may be at R 1 And R 2 The total number of carbon atoms is appropriately selected within a range of 10 or more. As R 1 The alkylene group is preferably a linear alkylene group having an even number of carbon atoms of 4 or more, and more preferably a linear alkylene group having an even number of carbon atoms in the range of 4 to 10.
R is as defined above 2 And the above-mentioned R 1 Independently a linear alkylene group having an even number of carbon atoms, may be at R 1 And R 2 The total number of carbon atoms is appropriately selected within the range of 10 or more, and is preferably a linear alkylene group having an even number of carbon atoms of 4 or more, preferably a linear alkylene group having an even number of carbon atoms of 4 to 12 (preferably 10 to 12).
R 1 And R 2 The total number of carbon atoms of (a) is preferably 10 or more, more preferably 12 or more, for example, 30 or less, more preferably 26 or less, and further preferably 24 or less.
By using the above-mentioned R 1 And R 2 The crystallinity of the resulting urethane prepolymer is improved, and the moisture-curable polyurethane hot-melt adhesive can be obtained which can prevent the peeling of the sheet or film at a complicated shape portion of the substrate.
N in the formula (1) represents an integer of 1 to 40, preferably an integer of 9 to 25, and more preferably an integer of 9 to 15. By using a long-chain aliphatic polyester polyol having n in the above range, the cohesive force as an adhesive can be appropriately exerted.
The long-chain aliphatic polyester polyol (a2) can be produced, for example, by condensation reaction of a linear aliphatic diol having an even number of carbon atoms with a linear aliphatic dicarboxylic acid having an even number of carbon atoms. Examples of the linear aliphatic diol include ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, and 1, 10-decanediol, and 1, 6-hexanediol, 1, 8-octanediol, and 1, 10-decanediol are preferably used.
Examples of the straight-chain aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, and dodecamethylene dicarboxylic acid, and sebacic acid and 1, 12-dodecanedicarboxylic acid are preferably used.
The combination of the linear aliphatic diol and the linear aliphatic dicarboxylic acid used for the production of the long-chain aliphatic polyester polyol (a2) may be represented by R in the formula (1) 1 、R 2 The total number of carbon atoms contained in (a) is 12 or more, preferably 12 to 20. Among them, a long-chain aliphatic polyester polyol obtained by reacting 1, 6-hexanediol as the linear aliphatic diol with 1, 12-dodecanedicarboxylic acid or sebacic acid as the linear aliphatic dicarboxylic acid is preferably used. Further, the use of a long-chain aliphatic polyester polyol obtained by reacting 1, 6-hexanediol as the linear aliphatic diol with 1, 12-dodecanedicarboxylic acid as the linear aliphatic dicarboxylic acid is more preferable in terms of producing an adhesive having an initial adhesive strength of a practically sufficient level even when used under a relatively high-temperature environment.
The number average molecular weight of the long-chain aliphatic polyester polyol (a2) is preferably 10,000 or less, more preferably 5,000 or less, preferably 500 or more, more preferably 1,000 or more, and even more preferably 3,000 or more.
In the present invention, the number average molecular weight can be measured by a Gel Permeation Chromatography (GPC) method using polystyrene as a standard sample.
In view of suppressing foaming, the content of the long-chain aliphatic polyester polyol (a2) in the polyol (a) is 15 mass% or more, preferably 20 mass% or more, more preferably 22 mass% or more, preferably 65 mass% or less, more preferably 40 mass% or less, and still more preferably 35 mass% or less.
The liquid polyester polyol (a3) is an essential component for securing adhesion to a PET substrate, and it is sufficient if it is a polyester polyol which is liquid at room temperature (25 ℃), and examples thereof include a reaction product of a polybasic acid containing adipic acid and an aliphatic compound having 2 or more hydroxyl groups. The long-chain aliphatic polyester polyol (a2) is different from the liquid polyester polyol (a 3).
Examples of the polybasic acid other than adipic acid include aliphatic polybasic acids such as succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosanedioic acid, citraconic acid, itaconic acid, citraconic anhydride, and itaconic anhydride; alicyclic polybasic acids such as 1, 4-cyclohexanedicarboxylic acid, and the like. These polybasic acids may be used alone or in combination of two or more. In the polybasic acid, the amount of adipic acid used is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
Examples of the aliphatic compound having 2 or more hydroxyl groups include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, neopentyl glycol, 1, 2-butanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 2-diethyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-2-butyl-1, 3-propanediol, 2-methyl-1, linear or branched aliphatic compounds such as 8-octanediol, 2, 4-diethyl-1, 5-pentanediol, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These compounds may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining still more excellent initial bond strength and flexibility, it is more preferable to use one or more compounds selected from the group consisting of ethylene glycol, 1, 4-butanediol, neopentyl glycol, 1, 2-butanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2-ethyl-2-butyl-1, 3-propanediol, and 2, 4-diethyl-1, 5-pentanediol.
The number average molecular weight of the liquid polyester polyol (a3) is preferably 300 or more, more preferably 600 or more, still more preferably 1,000 or more, preferably 10,000 or less, and more preferably 9,000 or less, from the viewpoint of obtaining still more excellent initial bond strength and flexibility.
The glass transition temperature of the liquid polyester polyol (a3) is preferably 20 ℃ or lower, more preferably 10 ℃ or lower, further preferably 5 ℃ or lower, and may be-100 ℃ or higher and-50 ℃ or higher, for example.
The glass transition temperature can be measured by DSC in accordance with JIS K7121-1987. Specifically, a measurement sample was placed in a differential scanning calorimeter, the temperature was raised to (Tg +50 ℃) at a temperature rise rate of 10 ℃/min, and then held for 3 minutes, followed by quenching, and the glass transition temperature (Tmg) at the midpoint read from the obtained differential thermal curve was set to the glass transition temperature.
In the polyol (a), the content of the liquid polyester polyol (a3) is 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, preferably 65% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass or less.
In the polyol (a), the total content of the alicyclic polyester polyol (a1), the long-chain aliphatic polyester polyol (a2), and the liquid polyester polyol (a3) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass.
As the polyol (a), other polyols may be used as needed in addition to the alicyclic polyester polyol (a1), the long-chain aliphatic polyester polyol (a2), and the liquid polyester polyol (a 3).
Examples of the other polyols include polyester polyols, polycarbonate polyols, polyacrylic polyols, butadiene polyols, hydrogenated polybutadiene polyols, and the like, other than the above (a1), (a2), and (a 3). These polyols may be used alone or in combination of two or more.
Examples of the polyisocyanate (B) include aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate. Among these, aromatic polyisocyanates are preferably used, and diphenylmethane diisocyanate is more preferably used, from the viewpoint of obtaining further excellent reactivity and final adhesive strength.
The amount of the polyisocyanate (B) used is preferably in the range of 5 to 60 mass%, more preferably in the range of 15 to 50 mass% of the raw materials of the polyurethane resin, from the viewpoint of obtaining further excellent adhesive strength.
The urethane resin is a product obtained by reacting the polyol (a) and the polyisocyanate (B), and has an isocyanate group at a polymer end or in a molecule, which is capable of reacting with moisture present in air, a case coated with a urethane prepolymer, or an adherend to form a crosslinked structure.
The polyurethane resin can be produced, for example, by dropping the polyol (a) into a reaction vessel containing the polyisocyanate (B), heating the reaction vessel, and reacting the polyisocyanate (B) with the polyol (a) under conditions in which the isocyanate group is in excess of the hydroxyl group.
The urethane bond content of the polyurethane resin is preferably in the range of 0.5 to 3mol/kg, more preferably in the range of 0.9 to 2.7mol/kg, and still more preferably in the range of 1.1 to 2.4mol/kg, from the viewpoint of obtaining further excellent initial adhesive strength, flexibility, and low viscosity.
The equivalent ratio ([ isocyanate group/hydroxyl group ]) of the isocyanate group of the polyisocyanate (B) to the hydroxyl group of the polyol (a) in producing the polyurethane resin is preferably in the range of 1.1 to 1.5, more preferably in the range of 1.15 to 1.45, from the viewpoint of obtaining further excellent initial adhesive strength, flexibility and low viscosity.
The content of the isocyanate group (hereinafter, abbreviated as "NCO%") in the polyurethane resin is preferably in the range of 1 to 4 mass%, more preferably in the range of 1.2 to 3.5 mass% from the viewpoint of obtaining further excellent initial adhesive strength, flexibility and low viscosity. The NCO% of the polyurethane resin is expressed by JISK 1603-1: reference 2007 is a value measured by potentiometric titration.
In the moisture-curable polyurethane hot-melt resin composition, the content of the polyurethane resin is preferably 40% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass or more, with the upper limit being 100% by mass.
The moisture-curable polyurethane hot-melt resin composition of the present invention may contain other additives as needed, in addition to the polyurethane resin.
As the other additives, for example, an antioxidant, a tackifier, a plasticizer, a stabilizer, a filler, a dye, a pigment, a fluorescent brightener, a silane coupling agent, a wax, and the like can be used. These additives may be used alone or in combination of two or more.
Examples of a method for obtaining a cured film of the moisture-curable polyurethane hot-melt resin composition include a method in which the moisture-curable polyurethane hot-melt resin composition is melted at 50 to 130 ℃, applied to a substrate, and moisture-cured.
Examples of the substrate include wood substrates such as plywood, MDF (medium density fiberboard), and particle board; gold base materials such as aluminum and iron; sheet-like substrates obtained using resins such as polyester, polyamide, polystyrene, polycarbonate, vinyl chloride, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyethylene, and polypropylene; calcium silicate board; paper; a metal foil; a single board; fiber base materials such as nonwoven fabrics and woven fabrics; synthesizing leather; paper; a rubber substrate; glass substrates, and the like. The thickness of the substrate is determined according to the application, and is, for example, in the range of 1 to 500 mm.
Examples of the method for applying the moisture-curable urethane hot-melt resin composition to the substrate include the following methods: coating machine modes such as a roll coating machine, a spray coating machine, a T die coating machine, a scraper coating machine and a comma coating machine are used; a moisture-curable urethane hot-melt resin composition melted at 70 to 140 ℃ is applied to a substrate by a precise method such as dispenser, spray, inkjet printing, screen printing, offset printing, and the like.
The thickness of the cured product layer of the moisture-curable urethane hot-melt composition is suitably determined depending on the application, and is, for example, in the range of 0.001 to 3 cm.
After the coating, the final adhesive strength can be obtained by aging for 0.5 to 3 days at a temperature of 20 to 80 ℃ and a relative humidity of 50 to 90%.
The moisture-curable polyurethane hot-melt resin composition of the present invention can suppress foaming while ensuring transparency even after moisture curing, and further can exhibit adhesiveness to a PET substrate. Thus, the moisture-curable polyurethane hot-melt resin composition of the present invention can be suitably used for building material panels, decorative panels, automobile interior materials, and the like.
[ examples ] A method for producing a compound
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the examples described below at all, and can be carried out by appropriately changing the examples within a range that can be adapted to the gist described above and below, and these examples are included in the technical scope of the present invention.
[ example 1]
A24-part by mass aliphatic polyester polyol (obtained by reacting diethylene glycol, neopentyl glycol, 1, 6-hexanediol and adipic acid; number average molecular weight: 2,000 or less; hereinafter referred to as "DEG/NPG/HG/AA 2000") and a 38-part by mass alicyclic polyester polyol (product of reaction of neopentyl glycol and hexahydrophthalic anhydride; number average molecular weight: 2,000; hereinafter referred to as "NPG/HHPA 2000") were charged into a four-neck flask equipped with a stirrer and a thermometer, and then a 20-part by mass crystalline polyester polyol (product of reaction of 1, 6-hexanediol and dodecanedioic acid; number average molecular weight: 3,500; hereinafter referred to as "HG/DDA 3500") was added thereto, and the mixture was heated under reduced pressure at 100 ℃ to dehydrate the mixture until the water content in the flask became 0.05% by mass. After the flask was cooled to 90 ℃, 18 parts by mass of 4, 4' -diphenylmethane diisocyanate (hereinafter, abbreviated as "MDI") melted at 70 ℃ was added and reacted at 110 ℃ for about 1 hour under a nitrogen atmosphere until the NCO% became constant, thereby obtaining a moisture-curable polyurethane hot-melt resin composition.
Example 2 and comparative examples 1 to 3
A moisture-curable polyurethane hot-melt resin composition was obtained in the same manner as in example 1, except that the amounts of the polyol and the polyisocyanate used were changed as shown in table 1.
The following evaluations were made with respect to the obtained moisture-curable polyurethane hot-melt resin composition.
[ method for evaluating transparency ]
The moisture-curable polyurethane hot-melt adhesives obtained in examples and comparative examples were melted at 120 ℃ for 1 hour, and then a film having a thickness of 0.10mm was formed on the inner side of the release paper using a roll coater. Thereafter, the mixture was cured at 23 ℃ C.. times.50% humidity for 4 days or more to completely progress the moisture curing reaction. The haze value of the RHM film after curing was measured by a haze meter and evaluated as follows.
". o": the haze value is less than 20.
"×": the haze value is 20 or more.
[ method for evaluating foam appearance ]
The moisture-curable polyurethane hot-melt adhesives obtained in examples and comparative examples were melted at 120 ℃ for 1 hour, and then a film having a thickness of 0.10mm was formed on the inner side of the release paper using a roll coater. Thereafter, the mixture was cured for 12 hours or more at 40 ℃ C. x 50% humidity to allow the moisture curing reaction to proceed as quickly as possible. The RHM film after curing was visually observed and evaluated as follows.
"] in the following ratio: the bubbles were not visually confirmed.
"×": the bubbles were visually confirmed.
[ evaluation method of adhesiveness of PET ]
The moisture-curable polyurethane hot-melt adhesives obtained in examples and comparative examples were melted at 120 ℃ for 1 hour and then applied to a PET sheet at a thickness of 0.05mm using an applicator. And (3) attaching the melamine decorative board by using a compression roller. After being left in an environment of 23 ℃ C.. times.50% humidity for 4 days, a 180 ℃ peel test was performed with a width of 2.5 cm. The peel strength was measured and evaluated as follows.
". o": the peel strength is 40N/inch or more.
"×": the peel strength is less than 40N/inch.
The evaluation results are shown in table 1.
[ TABLE 1]
Examples 1 to 2 are examples of the present invention, and the transparency was maintained and foaming was suppressed even after moisture curing, and the adhesion to the PET substrate was also good.
Comparative example 1 is an example in which the content of the long-chain aliphatic polyester polyol is small, and foaming at the time of moisture curing is not sufficiently suppressed.
Comparative example 2 is an example in which the content of the liquid polyester polyol is small, and adhesion to the PET substrate is insufficient.
Comparative example 3 is an example in which the content of the alicyclic polyester polyol is small, and transparency is insufficient.
Industrial applicability
The moisture-curable polyurethane hot-melt resin composition of the present invention can suppress foaming while ensuring transparency even after moisture curing, and further can exhibit adhesiveness to a PET substrate. Thus, the moisture-curable polyurethane hot-melt resin composition of the present invention can be suitably used for building material panels, decorative panels, automobile interior materials, and the like.
Claims (4)
1. A moisture-curable polyurethane hot-melt resin composition comprising a polyurethane resin having an isocyanate group,
the polyurethane resin is the reaction product of a polyol a and a polyisocyanate B,
the polyol A comprises alicyclic polyester polyol a1, long-chain aliphatic polyester polyol a2 and liquid polyester polyol a3,
the content of the alicyclic polyester polyol a1 in the polyol A is 20 mass% or more,
the content of the long-chain aliphatic polyester polyol a2 in the polyol A is 15 mass% or more,
the content of the liquid polyester polyol a3 in the polyol a is 15 mass% or more.
2. The moisture-curable polyurethane hot-melt resin composition according to claim 1, having a haze value of less than 20 as measured by the following method,
[ method for measuring haze value ]
Melting the moisture-curable polyurethane hot-melt resin composition at 120 ℃ for 1 hour, and coating the composition on a release layer so that the thickness becomes 0.1 mm; maintaining the obtained coating layer for 96 hours in an environment with the temperature of 23 ℃ and the humidity of 50% to obtain a cured product; the haze value of the cured product was measured in accordance with JIS K7136.
3. A cured product of the moisture-curable polyurethane hot-melt resin composition according to claim 1 or 2.
4. A laminate comprising the cured product according to claim 3.
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| CN202111494652.1A Pending CN114790270A (en) | 2021-01-26 | 2021-12-07 | Moisture-curable polyurethane hot-melt resin composition, cured product, and laminate |
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| Country | Link |
|---|---|
| JP (1) | JP2022114432A (en) |
| CN (1) | CN114790270A (en) |
-
2021
- 2021-11-16 JP JP2021186246A patent/JP2022114432A/en active Pending
- 2021-12-07 CN CN202111494652.1A patent/CN114790270A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP2022114432A (en) | 2022-08-05 |
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