JP5530963B2 - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
- Publication number
- JP5530963B2 JP5530963B2 JP2011046340A JP2011046340A JP5530963B2 JP 5530963 B2 JP5530963 B2 JP 5530963B2 JP 2011046340 A JP2011046340 A JP 2011046340A JP 2011046340 A JP2011046340 A JP 2011046340A JP 5530963 B2 JP5530963 B2 JP 5530963B2
- Authority
- JP
- Japan
- Prior art keywords
- adhesive
- acid
- parts
- polyol
- maleic anhydride
- 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.)
- Active
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- 239000000853 adhesive Substances 0.000 title claims description 53
- 230000001070 adhesive effect Effects 0.000 title claims description 51
- 239000000203 mixture Substances 0.000 title claims description 27
- 150000003077 polyols Chemical class 0.000 claims description 69
- 229920005862 polyol Polymers 0.000 claims description 59
- -1 isocyanate compound Chemical class 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 26
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 21
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 238000004806 packaging method and process Methods 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 239000005022 packaging material Substances 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 3
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical class [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012939 laminating adhesive Substances 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 26
- 239000002253 acid Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000011888 foil Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 239000005056 polyisocyanate Substances 0.000 description 10
- 229920001228 polyisocyanate Polymers 0.000 description 10
- 239000004721 Polyphenylene oxide Substances 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 235000011007 phosphoric acid Nutrition 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 239000004677 Nylon Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229920001778 nylon Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- 229920005906 polyester polyol Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 5
- 229920002635 polyurethane Polymers 0.000 description 5
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 3
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 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 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000000052 vinegar Substances 0.000 description 3
- 235000021419 vinegar Nutrition 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 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 2
- 229940127554 medical product Drugs 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 2
- 229920006284 nylon film Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-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
- WVWYODXLKONLEM-UHFFFAOYSA-N 1,2-diisocyanatobutane Chemical compound O=C=NC(CC)CN=C=O WVWYODXLKONLEM-UHFFFAOYSA-N 0.000 description 1
- ZGDSDWSIFQBAJS-UHFFFAOYSA-N 1,2-diisocyanatopropane Chemical compound O=C=NC(C)CN=C=O ZGDSDWSIFQBAJS-UHFFFAOYSA-N 0.000 description 1
- XSCLFFBWRKTMTE-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCCC(CN=C=O)C1 XSCLFFBWRKTMTE-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 description 1
- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 description 1
- ROHUXHMNZLHBSF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)cyclohexane Chemical compound O=C=NCC1CCC(CN=C=O)CC1 ROHUXHMNZLHBSF-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- LHNAURKRXGPVDW-UHFFFAOYSA-N 2,3-diisocyanatobutane Chemical compound O=C=NC(C)C(C)N=C=O LHNAURKRXGPVDW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- QZWKEPYTBWZJJA-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine-4,4'-diisocyanate Chemical compound C1=C(N=C=O)C(OC)=CC(C=2C=C(OC)C(N=C=O)=CC=2)=C1 QZWKEPYTBWZJJA-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PXIPZIPSDBXFQR-UHFFFAOYSA-N 4,5-dimethyloxolan-2-one Chemical compound CC1CC(=O)OC1C PXIPZIPSDBXFQR-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
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- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
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- 239000003112 inhibitor Substances 0.000 description 1
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- 150000002596 lactones Chemical class 0.000 description 1
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- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
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- WBSRHBNFOLDTGU-UHFFFAOYSA-N nonane-1,8-diol Chemical compound CC(O)CCCCCCCO WBSRHBNFOLDTGU-UHFFFAOYSA-N 0.000 description 1
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- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
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- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
Landscapes
- Wrappers (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、各種プラスチックフィルム、および金属蒸着フィルムあるいは金属箔を複数積層して、食品、医療品、化粧品等の包装用積層体を製造する際に好適に用いられる、優れた接着機能を有する接着剤に関する。さらに、本発明は、食品、医療品、化粧品等の包装に用いられる包装用積層体に関する。 The present invention is an adhesive having an excellent adhesive function, which is suitably used for producing a laminate for packaging of foods, medical products, cosmetics, etc. by laminating a plurality of various plastic films and metal vapor deposited films or metal foils. It relates to the agent. Furthermore, this invention relates to the laminated body for packaging used for packaging of foodstuffs, medical goods, cosmetics, etc.
近年、食品、医療品、化粧品等の包装材料として、アルミニウム箔などの金属箔あるいは金属蒸着フィルムとポリエチレン、ポリプロピレン、塩化ビニル、ポリエステル、ナイロンなどのプラスチックフィルムを多層ラミネートして複合化したものが用いられている。これらのプラスチックフィルムと金属箔あるいは金属蒸着フィルムとを張り合わせる接着剤としては、芳香族多価カルボン酸無水物を反応せしめたポリマーポリオール及び有機イソシアネート化合物からなるものが知られている。 In recent years, as a packaging material for foods, medical products, cosmetics, etc., a metal foil such as aluminum foil or a metal vapor deposited film and a plastic film such as polyethylene, polypropylene, vinyl chloride, polyester, nylon, etc. are laminated and combined. It has been. As an adhesive for laminating these plastic film and metal foil or metal vapor-deposited film, an adhesive composed of a polymer polyol obtained by reacting an aromatic polyvalent carboxylic acid anhydride and an organic isocyanate compound is known.
しかし、このような接着剤は、ボイル、レトルト、ハイレトルトの高温殺菌処理を必要とする場合、処理後の積み重ねなどの作業時において、不本意の折り曲げで部分的に接着不良が発生し、外観不良の状態になること、あるいは内容物や基材によっては経時的な性能面の劣化が問題となることがあった（特開昭６０−２４３１８２）。 However, when such adhesives require high-temperature sterilization treatment of boil, retort, and high retort, adhesion failure occurs partially due to unintentional bending during work such as stacking after treatment. Depending on the contents and the substrate, deterioration of performance over time may become a problem (Japanese Patent Laid-Open No. 60-243182).
特開２００１−１５２１２７、特開２００５−１３２９０２では、スチレン−無水マレイン酸樹脂、トリメリット酸エステル無水物を導入することにより、高温殺菌処理、長期保存時の接着力維持を提案しているが、内容物が多様化している近年では処理条件も多様化し、更なる接着性能が要求されている。 In JP-A-2001-152127 and JP-A-2005-132902, by introducing a styrene-maleic anhydride resin and trimellitic acid ester anhydride, high-temperature sterilization treatment and maintaining adhesive strength during long-term storage are proposed. In recent years, when the contents are diversifying, the processing conditions are also diversifying, and further adhesion performance is required.
本発明は、硬化した際の、耐熱水性および耐酸性が優れ、接着性が経時劣化しにくい接着剤及びこれを用いた包装用積層体を提供することを目的とする。 An object of the present invention is to provide an adhesive having excellent hot water resistance and acid resistance when cured and having adhesiveness that hardly deteriorates with time, and a laminate for packaging using the same.
即ち、本発明の第１の発明は、（メタ）アクリル酸エステルと無水マレイン酸とを共重合させてなる樹脂（Ａ）、ポリマーポリオール（Ｂ）、および有機イソシアネート化合物（Ｃ）を含有することを特徴とするウレタン系接着剤組成物に関するものである。 That is, the first invention of the present invention contains a resin (A) obtained by copolymerizing (meth) acrylic acid ester and maleic anhydride, a polymer polyol (B), and an organic isocyanate compound (C). It is related with the urethane type adhesive composition characterized by these.
さらに、本発明の第２の発明は、（メタ）アクリル酸エステルと無水マレイン酸とを共重合させてなる樹脂（Ａ）を、ポリマーポリオール（Ｂ）１００重量部に対して、０．１〜１０重量部含有することを特徴とする第１の発明に記載のウレタン系接着剤組成物に関するものである。 Further, according to a second aspect of the present invention, a resin (A) obtained by copolymerizing a (meth) acrylic acid ester and maleic anhydride is added in an amount of 0.1 to 100 parts by weight of the polymer polyol (B). It contains 10 weight part, It is related with the urethane type adhesive composition as described in 1st invention characterized by the above-mentioned.
また、本発明の第３の発明は、さらに、シランカップリング剤、リンの酸素酸、およびリン酸エポキシから選択される成分を含有することを特徴とする第１の発明また第２の発明に記載のウレタン系接着剤組成物に関するものである。 The third invention of the present invention further includes a component selected from a silane coupling agent, an oxygen acid of phosphorus, and a phosphoric acid epoxy. It is related with the urethane-type adhesive composition of description.
さらに、本発明の第４の発明は、第１ないし第３の発明のいずれか１項に記載のウレタン系接着剤組成物を含有することを特徴とする包装材用のラミネート用接着剤に関するものである。 Furthermore, a fourth invention of the present invention relates to a laminating adhesive for a packaging material, characterized by comprising the urethane-based adhesive composition described in any one of the first to third inventions. It is.
また、本発明の第５の発明は、第４の発明に記載の包装材用のラミネート用接着剤により、二つ以上の基材同士を接合してなることを特徴とする包装用積層体に関するものである。 Moreover, 5th invention of this invention is related with the laminated body for packaging characterized by joining two or more base materials with the adhesive agent for laminates for packaging materials as described in 4th invention. Is.
本発明によれば、食酢、遊離脂肪酸等を内容物とする場合のラミネート積層体のプラスチックフィルム、或いは金属箔間の接着力が、長期保管後でも変化がなく良好である。つまり、本発明の接着剤によれば、硬化した際の、耐熱水性および耐酸性が優れ、接着性が経時劣化しにくい。 According to the present invention, the adhesive strength between the plastic film or metal foil of the laminate laminate in the case of using vinegar, free fatty acid or the like as the contents is good without change even after long-term storage. That is, according to the adhesive of the present invention, when cured, the hot water resistance and acid resistance are excellent, and the adhesiveness hardly deteriorates with time.
本発明のウレタン系接着剤組成物について説明する。本発明のウレタン系接着剤組成物は（メタ）アクリル酸エステルと無水マレイン酸とを共重合させてなる樹脂（Ａ）、ポリマーポリオール（Ｂ）および有機イソシアネート化合物（Ｃ）を含むことを特徴とする。 The urethane type adhesive composition of this invention is demonstrated. The urethane-based adhesive composition of the present invention includes a resin (A) obtained by copolymerizing (meth) acrylic acid ester and maleic anhydride, a polymer polyol (B), and an organic isocyanate compound (C). To do.
＜（メタ）アクリル酸エステルと無水マレイン酸とを共重合させてなる樹脂（Ａ）＞
本発明で用いられる（メタ）アクリル酸エステルと無水マレイン酸とを共重合させてなる樹脂には、合成時の全量に対して、（メタ）アクリル酸エステルの含有量が５０〜９５％が好ましく、より好ましくは５０〜７０％、無水マレイン酸の含有量が５〜５０％が好ましく、３０〜５０％がより好ましい。無水マレイン酸の含有量が５％以上であると、長期保管時の接着力は劣化せず、また、５０％以下であると、（メタ）アクリル酸エステルと無水マレイン酸の共重合物の合成が容易である。
（メタ）アクリル酸エステルと無水マレイン酸とを共重合させてなる樹脂の数平均分子量は３００〜５００００が好ましく、より好ましくは１０００〜１２０００である。数平均分子量が３００以上であると、長期保管時の接着力の劣化がなく、また、５００００以下であると、接着剤樹脂配合物の相溶性が良好で、接着剤の塗工外観が優れる。
（メタ）アクリル酸エステルと無水マレイン酸を共重合させてなる樹脂（Ａ）の添加量は、ポリマーポリオール（Ｂ）１００重量部に対して、０．１〜１０重量部が好ましく、より好ましくは１〜５重量部である。樹脂（Ａ）の添加量がポリマーポリオール（Ｂ）に対して、０．１重量部以上だと、接着力の長期保持が可能であり、また、１０重量部以下では接着剤樹脂配合物の相溶性が良好で、接着剤の塗工外観が優れる。
<Resin (A) obtained by copolymerizing (meth) acrylic acid ester and maleic anhydride>
The resin obtained by copolymerizing the (meth) acrylic acid ester and maleic anhydride used in the present invention preferably has a (meth) acrylic acid ester content of 50 to 95% with respect to the total amount during synthesis. More preferably, the content of maleic anhydride is preferably 50 to 70%, and more preferably 5 to 50%, and more preferably 30 to 50%. When the content of maleic anhydride is 5% or more, the adhesive strength during long-term storage does not deteriorate, and when it is 50% or less, synthesis of a copolymer of (meth) acrylic acid ester and maleic anhydride Is easy.
The number average molecular weight of the resin obtained by copolymerizing (meth) acrylic acid ester and maleic anhydride is preferably 300 to 50000, more preferably 1000 to 12000. When the number average molecular weight is 300 or more, there is no deterioration of the adhesive force during long-term storage, and when it is 50000 or less, the compatibility of the adhesive resin composition is good and the coating appearance of the adhesive is excellent.
The addition amount of the resin (A) obtained by copolymerizing (meth) acrylic acid ester and maleic anhydride is preferably 0.1 to 10 parts by weight, more preferably 100 parts by weight of the polymer polyol (B). 1 to 5 parts by weight. When the addition amount of the resin (A) is 0.1 parts by weight or more with respect to the polymer polyol (B), it is possible to maintain the adhesive force for a long period of time. Good solubility and excellent adhesive appearance.
本発明に用いられる（メタ）アクリル酸エステルモノマーとしては、例えば、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸−ｉ−プロピル、メタクリル酸ブチル、メタクリル酸−ｉ−ブチル、メタクリル酸−ｔ−ブチル、メタクリル酸ペンチル、メタクリル酸ヘキシル、メタクリル酸ヘプチル、メタクリル酸オクチル、メタクリル酸ノニル、メタクリル酸デシル、メタクリル酸ヒドロキシメチル、メタクリル酸ヒドロキシエチル、メタクリル酸グリシジル、メタクリル酸２−エチルヘキシル、メタクリル酸シクロヘキシル、メタクリル酸フェニル等が挙げられる。なかでも無水マレイン酸との共重合性の観点からメタクリル酸メチルが好ましい。
（メタ）アクリル酸エステルと無水マレイン酸との共重合させてなる樹脂（Ａ）の合成方法は、ラジカル共重合法が用いられる。例えば、溶液重合、乳化重合、塊状重合、懸濁重合等から、適宜選ばれる。
Examples of the (meth) acrylic acid ester monomer used in the present invention include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid-i-propyl, butyl methacrylate, methacrylic acid-i-butyl, methacrylic acid- t-butyl, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, glycidyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Examples include cyclohexyl and phenyl methacrylate. Of these, methyl methacrylate is preferable from the viewpoint of copolymerization with maleic anhydride.
As a method for synthesizing the resin (A) obtained by copolymerizing (meth) acrylic acid ester and maleic anhydride, a radical copolymerization method is used. For example, it is appropriately selected from solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like.
＜ポリマーポリオール（Ｂ）＞
本発明で用いられるポリマーポリオールは、硬化速度の観点から、１分子中の官能基数が、２〜１０であることが好ましく、より好ましくは２〜８である。また、数平均分子量が、接着剤組成物の粘度の観点から、好ましくは５００〜１００，０００、より好ましくは１，０００〜３０，０００である。更に詳しくは、ポリマーポリオール（Ｂ）として、ポリエステルポリオール、ポリエーテルポリオール、ポリエーテルエステルポリオール、ポリエステルアミドポリオール、アクリルポリオール、ポリカーボネートポリオール、ポリヒドロキシルアルカン、ポリウレタンポリオール、ひまし油又はそれらの混合物（以下、これらを有機ポリオール（１）とする。）が挙げられる。これらのなかでも、耐熱性の観点から、ポリウレタンポリオールが好ましい。
<Polymer polyol (B)>
In the polymer polyol used in the present invention, the number of functional groups in one molecule is preferably 2 to 10, more preferably 2 to 8, from the viewpoint of curing speed. The number average molecular weight is preferably 500 to 100,000, more preferably 1,000 to 30,000, from the viewpoint of the viscosity of the adhesive composition. More specifically, as the polymer polyol (B), polyester polyol, polyether polyol, polyether ester polyol, polyester amide polyol, acrylic polyol, polycarbonate polyol, polyhydroxyl alkane, polyurethane polyol, castor oil or a mixture thereof (hereinafter referred to as these) Organic polyol (1)). Among these, polyurethane polyol is preferable from the viewpoint of heat resistance.
ポリエステルポリオールとしては、例えば、テレフタル酸、イソフタル酸、アジピン酸、アゼライン酸、セバチン酸等二塩基酸若しくはそれらのジアルキルエステル又はそれらの混合物と、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、ブチレングリコール、ネオペンチルグリコール、１，６−ヘキサンジオール、３−メチル−１，５−ペンタンジオール、３，３′−ジメチロールヘプタン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、ポリテトラメチレンエーテルグリコール等のグリコール類若しくはそれらの混合物とを反応させて得られるポリエステルポリオール或いはポリカプロラクトン、ポリバレロラクトン、ポリ（β−メチル−γ−バレロラクトン）等のラクトン類を開環重合して得られるポリエステルポリオールが挙げられる。 Examples of the polyester polyol include dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, or dialkyl esters thereof, or mixtures thereof, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neodymium. Glycols such as pentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, polytetramethylene ether glycol, or the like Ring opening polymerization of lactones such as polyester polyol or polycaprolactone, polyvalerolactone, poly (β-methyl-γ-valerolactone) obtained by reacting them with the mixture The polyester polyol obtained by combining is mentioned.
ポリエーテルポリオールとしては、例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、テトラヒドロフラン等のオキシラン化合物を、例えば、水、エチレングリコール、プロピレングリコール、トリメチロールプロパン、グリセリン等の低分量ポリオールを開始剤として重合して得られるポリエーテルポリオールが挙げられる。 As the polyether polyol, for example, an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran is polymerized using, for example, water, ethylene glycol, propylene glycol, trimethylolpropane, glycerin, and the like as a low-part polyol. The polyether polyol obtained is mentioned.
ポリエーテルエステルポリオールとしては、例えば、テレフタル酸、イソフタル酸、アジピン酸、アゼライン酸、セバチン酸等の二塩基酸若しくはそれらのジアルキルエステル又はそれらの混合物と、上記ポリエーテルポリオールを反応させて得られるポリエーテルエステルポリオールが挙げられる。 Examples of the polyether ester polyol include a polybasic acid obtained by reacting the above polyether polyol with a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid or the like or a mixture thereof. Examples include ether ester polyols.
ポリエステルアミドポリオールとしては、上記エステル化反応に際し、例えば、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン等のアミノ基を有する脂肪族ジアミンを原料としてあわせて使用することによって得られる。 The polyesteramide polyol can be obtained, for example, by using an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine as a raw material in the esterification reaction.
アクリルポリオールの例としては、１分子中に１個以上の水酸基を含むアクリル酸ヒドロキシエチル、アクリル酸ヒドロキシプロプル、アクリルヒドロキシブチル等、或いはこれらの対応するメタクリル酸誘導体等と、例えばアクリル酸、メタクリル酸又はそのエステルとを共重合することによって得られる。 Examples of acrylic polyols include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyhydroxybutyl, etc., or their corresponding methacrylic acid derivatives containing one or more hydroxyl groups in one molecule, such as acrylic acid, methacrylic acid, etc. It is obtained by copolymerizing an acid or its ester.
ポリカーボネートポリオールとしては、例えば、エチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、３−メチル−１，５−ペンタンジオール、１，９−ノナンジオール、１，８−ノナンジオール、ネオペンチルグリコール、ジエチレングリコール、ジプロピレングリコール、１，４−シクロヘキサンジオール、１，４−シクロヘキサンジメタノール、ビスフェノールＡ、水添ビスフェノールＡの中から選ばれた１種又は２種以上のグリコールをジメチルカーボネート、ジフェニルカーボネート、エチレンカーボネート、ホスゲン等との反応によって得られたものが挙げられる。 Examples of the polycarbonate polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 1,9-nonane. One selected from diol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A or The thing obtained by reaction of 2 or more types of glycol with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc. is mentioned.
ポリヒドロキシアルカンとしては、ブタジエン、又はブタジエンとアクリルアミド等と共重合して得られる液状ゴムが挙げられる。 Examples of the polyhydroxyalkane include butadiene or liquid rubber obtained by copolymerization with butadiene and acrylamide.
ポリウレタンポリオールとしては、１分子中にウレタン結合を有するポリオールであり、例えば、数平均分子量２００〜２０，０００のポリエーテルポリオール、ポリエステルポリオール、ポリエーテルエステルポリオール等と有機ポリイソシアネートとをＮＣＯ／ＯＨが１未満が好ましく、より好ましくは０．９以下で反応させて得られる。 The polyurethane polyol is a polyol having a urethane bond in one molecule. For example, NCO / OH is a polyether polyol, polyester polyol, polyether ester polyol, etc. having a number average molecular weight of 200 to 20,000 and an organic polyisocyanate. It is preferably less than 1, more preferably 0.9 or less.
本発明では、上記有機ポリオールとして、その分子中（分子内部や分子末端）にカルボキシル基を有するもの（以下、有機ポリオール（２）という。）を用いることができる。本発明で用いられる有機ポリオール（２）は、望ましくは上記の有機ポリオール（１）と多塩基酸若しくはその無水物とを反応させることにより得られる。この際用いられる有機ポリオール（１）としては、分子末端に２個以上の水酸基を含有し、数平均分子量が、好ましくは１，０００〜１００，０００、より好ましくは３，０００〜１５，０００である。前記数平均分子量が１，０００以上だと凝集力が十分であり、１００，０００以下では、合成上、末端に多塩基酸若しくはその無水物を容易に反応させることができ、増粘やゲル化がない。 In this invention, what has a carboxyl group in the molecule | numerator (the inside of a molecule | numerator or a molecular terminal) (henceforth organic polyol (2)) can be used as said organic polyol. The organic polyol (2) used in the present invention is desirably obtained by reacting the organic polyol (1) with a polybasic acid or an anhydride thereof. The organic polyol (1) used at this time contains two or more hydroxyl groups at the molecular terminals, and the number average molecular weight is preferably 1,000 to 100,000, more preferably 3,000 to 15,000. is there. When the number average molecular weight is 1,000 or more, the cohesive force is sufficient. When the number average molecular weight is 100,000 or less, polybasic acid or its anhydride can be easily reacted at the terminal for synthesis, and thickening or gelation can be achieved. There is no.
＜有機イソシアネート化合物（Ｃ）＞
本発明で用いられる有機イソシアネートとしては、例えば、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、１，２−プロピレンジイソシアネート、１，２−ブチレンジイソシアネート、２，３−ブチレンジイソシアネート、１，３−ブチレンジイソシアネート、２，４，４−トリメチルヘキサメチレンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、２，６−ジイソシアネートメチルカプロエート等の脂肪族ジイソシアネート；１，４−シクロヘキサンジイソシアネート、１，３−シクロヘキサンジイソシアネート、３−イソシアネートメチル−３，５，５−トリメチルシクロヘキシルイソシアネート、４，４′−メチレンビス（シクロヘキシルイソシアネート）、メチル２，４−シクロヘキサンジイソシアネート、メチル２，６−シクロヘキサンジイソシアネート、１，４−ビス（イソシアネートメチル）シクロヘキサン、１，３−ビス（イソシアネートメチル）シクロヘキサン等の脂環式ジイソシアネート；ｍ−フェニレンジイソシアネート、ｐ−フェニレンジイソシアネート、４，４′−ジフェニルジイソシアネート、１，５−ナフタレンジイソシアネート、４，４′−ジフェニルメタンジイソシアネート、２，４−２，６−トリレンジイソシアネート又は２，６−トリレンジイソシアネート若しくはその混合物、４，４′−トルイジンジイソシアネート、ジアニシジンジイソシアネート、４，４′−ジフェニルエーテルジイソシアネート等の芳香族ジイソシアネート；１，３−１，４−キシリレンジイソシアネート又は１，４−キシリレンジイソシアネート若しくはその混合物、ω，ω′−ジイソシアネート−１，４−ジエチルベンゼン、１，３−ビス（１−イソシアネート−１−メチルエチル）ベンゼン又は１，４−ビス（１−イソシアネート−１−メチルエチル）ベンゼン若しくはその混合物等の芳香族ジイソシアネート；トリフェニルメタン−４，４′，４″−トリイソシアネート、１，３，５−トリイソシアネートベンゼン、２，４，６−トリイソシアネートトルエン等の有機トリイソシアネート；４，４′−ジフェニルジメチルメタン−２，２′−５，５′−テトライソシアネート等の有機テトライソシアネート等のポリイソシアネート単量体；上記ポリイソシアネート単量体から誘導されたダイマー、トリマー、ビウレット、アロファネート；炭酸ガスと上記ポリイソシアネート単量体とから得られる２，４，６−オキサジアジントリオン環を有するポリイソシアネート；エチレングリコール、プロピレングリコール、ブチレングリコール、ヘキシレングリコール、ネオペンチルグリコール、１，６−ヘキサンジオール、３−メチル−１，５−ペンタンジオール、３，３′−ジメチロールプロパン、シクロヘキサンジメタノール、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、グリセロール、トリメチロールプロパン、ペンタエリスリトール、ソルビトール等の分子量２００未満の低分子ポリオールと上記ポリイソシアネート単量体との付加体；分子量２００〜２０，０００のポリエステルポリオール、ポリエーテルエステルポリオール、ポリエステルアミドポリオール、ポリカプロラクトンポリオール、ポリバレロラクトンポリオール、アクリルポリオール、ポリカーボネートポリオール、ポリヒドロキシアルカン、ひまし油、ポリウレタンポリオール等と上記ポリイソシアネート単量体との付加体；ポリエーテルポリオールと有機ポリイソシアネートとをＮＣＯ／ＯＨが１未満で反応させて得られるポリウレタンポリオールと上記ポリイソシアネート単量体の付加体；等が挙げられる。これらポリイソシアネート化合物は、接着剤の用途により単独或いは二種以上の混合物として適宜用いることが出来る。例えば、硬化速度、及び耐熱性の観点からは、芳香族系のポリイソシアネートが好ましい。
有機イソシアネート化合物（Ｃ）は、硬化速度の観点から、ポリマーポリオール（Ｂ）１００重量部に対して、１〜５０重量部含有することが好ましく、より好ましくは５〜３０重量部である。
<Organic isocyanate compound (C)>
Examples of the organic isocyanate used in the present invention include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene. Aliphatic diisocyanates such as diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate; 1,4-cyclohexane diisocyanate, 1,3- Cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) Nate), cycloaliphatic diisocyanates such as methyl 2,4-cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane; m-phenylene Diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-2,6-tolylene diisocyanate or 2,6-tolylene diisocyanate or Mixtures thereof, aromatic diisocyanates such as 4,4'-toluidine diisocyanate, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate; 1,3-1,4 Xylylene diisocyanate or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,3-bis (1-isocyanate-1-methylethyl) benzene or 1,4-bis Aromatic diisocyanates such as (1-isocyanate-1-methylethyl) benzene or mixtures thereof; triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6 -Organic triisocyanate such as triisocyanate toluene; Polyisocyanate monomer such as organic tetraisocyanate such as 4,4'-diphenyldimethylmethane-2,2'-5,5'-tetraisocyanate; Dimers, trimers, derived from Uret, allophanate; polyisocyanate having 2,4,6-oxadiazinetrione ring obtained from carbon dioxide and the above polyisocyanate monomer; ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3′-dimethylolpropane, cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, Adducts of low-molecular-weight polyols having a molecular weight of less than 200 such as sorbitol and the above polyisocyanate monomers; polyester polyols having a molecular weight of 200 to 20,000, polyetheresters Polyols, polyesteramide polyols, polycaprolactone polyols, polyvalerolactone polyols, acrylic polyols, polycarbonate polyols, polyhydroxyalkanes, castor oil, polyurethane polyols and the like and adducts of the above polyisocyanate monomers; polyether polyols and organic polyisocyanates And an adduct of the above-mentioned polyisocyanate monomer with a polyurethane polyol obtained by reacting NCO / OH with NCO / OH of less than 1. These polyisocyanate compounds can be appropriately used alone or as a mixture of two or more depending on the use of the adhesive. For example, aromatic polyisocyanates are preferable from the viewpoints of curing speed and heat resistance.
The organic isocyanate compound (C) is preferably contained in an amount of 1 to 50 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polymer polyol (B) from the viewpoint of curing speed.
＜シランカップリング剤＞
本発明の接着剤には、耐熱水性を高めるため、さらに、シランカップリング剤を含有させることができる。シランカップリング剤としては、例えばビニルトリメトキシシラン、ビニルトリエトキシシラン等のビニル基を有するトリアルコキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−（２−アミノエチル）３−アミノプロピルトリメトキシシラン等のアミノ基を有するトリアルコキシシラン、３−グリシドキシプロピルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン等のグリシジル基を有するトリアルコキシシラン等が挙げられる。シランカップリング剤の添加量は、接着剤の固形分を基準として０．１〜５重量％であることが好ましく、０．５〜３重量％であることがより好ましい。
<Silane coupling agent>
The adhesive of the present invention can further contain a silane coupling agent in order to increase hot water resistance. Examples of silane coupling agents include trialkoxysilanes having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane. Having a glycidyl group such as trialkoxysilane having an amino group such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane Examples include trialkoxysilane. The addition amount of the silane coupling agent is preferably 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, based on the solid content of the adhesive.
＜リンの酸素酸＞
また、本発明の接着剤には、耐酸性を高めるため、さらに、リンの酸素酸またはその誘導体を含有させることができる。リンの酸素酸またはその誘導体の内、リンの酸素酸としては、遊離の酸素酸を少なくとも１個有しているものであればよく、例えば、次亜リン酸、亜リン酸、オルトリン酸、次リン酸等のリン酸類、メタリン酸、ピロリン酸、トリポリリン酸、ポリリン酸、ウルトラリン酸等の縮合リン酸類が挙げられる。また、リンの酸素酸の誘導体としては、上記のリンの酸素酸を遊離の酸素酸を少なくとも１個残した状態でアルコール類と部分的にエステル化されたもの等が挙げられる。これらのアルコールとしては、メタノール、エタノール、エチレングリコール、グリセリン等の脂肪族アルコール、フェノール、キシレノール、ハイドロキノン、カテコール、フロログリシノール等の芳香族アルコール等が挙げられる。リンの酸素酸またはその誘導体は、２種以上を組み合わせて用いてもよい。リンの酸素酸またはその誘導体の添加量は、接着剤の固形分を基準として０．０１〜１０重量％であることが好ましく、０．０５〜５重量％であることがより好ましく、０．１〜１重量％であることが特に好ましい。
＜リン酸エポキシ＞
さらに、本発明の接着剤は、金属密着性能向上のために、リン酸エポキシを含有させることができる。リン酸エポキシとしては、DSM Resinsレジン社製URAD-DD79が挙げられる。
リン酸エポキシの添加量は、接着剤の固形分を基準として、０．０１〜１０重量％であることが好ましく、０．１〜１重量％であることが特に好ましい。
<Oxygen acid of phosphorus>
The adhesive of the present invention may further contain phosphorus oxyacid or a derivative thereof in order to increase acid resistance. Among the oxygen acids of phosphorus or derivatives thereof, the oxygen acid of phosphorus may be any one having at least one free oxygen acid, such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, Examples thereof include phosphoric acids such as phosphoric acid, and condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid. Examples of phosphorus oxyacid derivatives include those obtained by partially esterifying the above-mentioned phosphorus oxyacids with alcohols while leaving at least one free oxygen acid. Examples of these alcohols include aliphatic alcohols such as methanol, ethanol, ethylene glycol, and glycerin, and aromatic alcohols such as phenol, xylenol, hydroquinone, catechol, and phlorogricinol. Oxygen acid of phosphorus or a derivative thereof may be used in combination of two or more. The amount of phosphorus oxygen acid or its derivative added is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, based on the solid content of the adhesive. Particularly preferred is ˜1% by weight.
<Phosphate epoxy>
Furthermore, the adhesive of the present invention can contain a phosphoric acid epoxy for improving metal adhesion performance. Examples of the phosphoric acid epoxy include URAD-DD79 manufactured by DSM Resins Resin.
The addition amount of the phosphoric acid epoxy is preferably 0.01 to 10% by weight, particularly preferably 0.1 to 1% by weight, based on the solid content of the adhesive.
＜その他の添加剤＞
本発明の接着剤には、さらに、例えば、酸化防止剤、紫外線吸収剤、加水分解防止剤、防黴剤、増粘剤、可塑剤、顔料、充填剤等の添加剤を必要に応じて含有させることができる。また、硬化反応を調節するため公知の触媒、添加剤等を含有させることができる。
＜接着剤＞
本発明の接着剤は、（メタ）アクリル酸エステルと無水マレイン酸とを共重合させてなる樹脂（Ａ）、ポリマーポリオール（Ｂ）、および有機イソシアネート化合物（Ｃ）を配合し、その粘度が常温〜１５０℃、好ましくは常温〜１００℃で１００〜１０，０００ｍＰａ・ｓ、好ましくは１００〜５，０００ｍＰａ・ｓの場合は無溶剤型で用いることができる。接着剤の粘度が上記範囲より高い場合は、有機溶剤で希釈してもよい。有機溶剤としては、例えば酢酸エチル等のエステル系、メチルエチルケトン等のケトン系、トルエン、キシレン等の芳香族炭化水素系等のイソシアネートに対して不活性なものであれば必要に応じいかなるものを使用してもよい。
<Other additives>
The adhesive of the present invention further contains additives such as, for example, antioxidants, ultraviolet absorbers, hydrolysis inhibitors, antifungal agents, thickeners, plasticizers, pigments, fillers, as necessary. Can be made. Moreover, in order to adjust hardening reaction, a well-known catalyst, an additive, etc. can be contained.
<Adhesive>
The adhesive of the present invention comprises a resin (A) obtained by copolymerizing (meth) acrylic acid ester and maleic anhydride, a polymer polyol (B), and an organic isocyanate compound (C), and has a viscosity of room temperature. In the case of 100 to 10,000 mPa · s, preferably 100 to 5,000 mPa · s at room temperature to 100 ° C., preferably 100 to 5,000 mPa · s, the solventless type can be used. When the viscosity of the adhesive is higher than the above range, it may be diluted with an organic solvent. As the organic solvent, for example, any solvent may be used as long as it is inert to isocyanates such as esters such as ethyl acetate, ketones such as methyl ethyl ketone, and aromatic hydrocarbons such as toluene and xylene. May be.
本発明の接着剤は、溶剤型または無溶剤型のラミネーターによってフィルム表面に塗布し、溶剤型の場合は溶剤を揮散させた後、無溶剤型ではそのまま接着面を貼り合せ、常温または加温下に硬化させることにより使用することができる。通常、無溶剤型では塗布量が乾燥固形物量１．０〜２．０ｇ／ｍ２ 、溶剤型では乾燥固形物量２．０〜５．０ｇ／ｍ２ の範囲で使用すると好都合である。 The adhesive of the present invention is applied to the film surface with a solvent-type or solvent-free laminator, and in the case of the solvent type, after the solvent is volatilized, the adhesive surface is bonded as it is in the case of the solvent-free type, and it is kept at room temperature or under heating. It can be used by curing. Usually, it is convenient to use the coating amount in the range of 1.0 to 2.0 g / m 2 for the solid-free type in the solvent-free type and 2.0 to 5.0 g / m 2 for the solid-type in the solvent type.
＜包装用積層体＞
次に、本発明の包装用積層体について説明する。本発明の包装用積層体は、第１のシート状基材と第２のシート状基材とが、本発明の接着剤から形成される接着剤層を介して積層されているものである。
シート状基材は、包装用積層体に通常用いられているプラスチックフィルム、紙、金属箔等であり、第１のシート状基材と第２のシート状基材とは、同種のものでも異種のものでも良い。プラスチックフィルムとしては、熱可塑性樹脂や熱硬化性樹脂のフィルムを用いることができるが、熱可塑性樹脂のフィルムが好ましい。熱可塑性樹脂としては、ポリオレフィン、ポリエステル、ポリアミド、ポリスチレン、塩化ビニル樹脂、酢酸ビニル樹脂、ＡＢＳ樹脂、アクリル樹脂、アセタール樹脂、ポリカーボネート樹脂、繊維素系プラスチック等が挙げられる。
<Laminate for packaging>
Next, the packaging laminate of the present invention will be described. In the packaging laminate of the present invention, a first sheet-like substrate and a second sheet-like substrate are laminated via an adhesive layer formed from the adhesive of the present invention.
The sheet-like base material is a plastic film, paper, metal foil or the like that is usually used for a laminate for packaging, and the first sheet-like base material and the second sheet-like base material may be the same or different. May be good. As the plastic film, a thermoplastic resin film or a thermosetting resin film can be used, but a thermoplastic resin film is preferable. Examples of the thermoplastic resin include polyolefin, polyester, polyamide, polystyrene, vinyl chloride resin, vinyl acetate resin, ABS resin, acrylic resin, acetal resin, polycarbonate resin, and fiber-based plastic.
包装用積層体の厚さは、通常１０μｍ以上である。本発明の接着剤を用いて、包装用積層体を作るには、通常用いられている方法、例えば、ドライラミネーターによって接着剤を一方のシート状基材の片面に塗布し、溶剤を揮散させた後、他方のシート状基材と貼り合わせ、常温もしくは加温下に硬化させれば良い。シート状基材表面に施される接着剤量は１〜１０ｇ／ｍ２程度である。 The thickness of the packaging laminate is usually 10 μm or more. In order to make a laminate for packaging using the adhesive of the present invention, the adhesive was applied to one side of one sheet-like substrate by a commonly used method, for example, a dry laminator, and the solvent was volatilized. Then, it may be bonded to the other sheet-like substrate and cured at room temperature or under heating. The amount of adhesive applied to the sheet-like substrate surface is about 1 to 10 g / m 2 .
以下、実施例及び比較例を挙げて本発明を更に具体的に説明する。実施例及び比較例中の部、％は、特に指定がない場合は重量部、重量％を意味する。
また、本発明において「数平均分子量」とは、ゲルパーミエーションクロマトグラフィーを利用し、標準ポリスチレンの検量線を使用して算出した。酸価、水酸基価は、１ｇのポリマーポリオール当りのＫＯＨのmgで表わす。酸価はKOHによる中和滴定で、水酸基価はピリジンと無水酢酸を用いるアセチル化により測定した。
Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Parts and% in Examples and Comparative Examples mean parts by weight and% by weight unless otherwise specified.
In the present invention, the “number average molecular weight” was calculated using a standard polystyrene calibration curve using gel permeation chromatography. The acid value and hydroxyl value are expressed in mg of KOH per 1 g of polymer polyol. The acid value was measured by neutralization titration with KOH, and the hydroxyl value was measured by acetylation using pyridine and acetic anhydride.
（合成例１）（メタ）アクリル酸エステル−無水マレイン酸共重合物（Ａ−１）の合成 攪拌機、温度計、還流冷却管、滴下槽及び窒素ガス導入管を備えた反応容器に、トルエン２００部を仕込み、窒素ガスを導入しつつ、攪拌しながら１１０℃まで昇温した。次に、滴下槽１にメタクリル酸メチル９０部、アクリル酸ブチル６０部、無水マレイン酸１５０部、トルエン５０部を仕込み、滴下槽２に過酸化ベンゾイル９部をトルエン５０部に溶解せしめたものを仕込み、夫々同時に２時間かけて反応容器内の温度を１１０℃にたもちながら、攪拌下に滴下した。反応終了後、室温まで冷却し、大量のメタノールによりポリマーを沈殿、ろ過し、１２０℃で６時間乾燥し、数平均分子量３０００、酸価４８８の（メタ）アクリル酸エステル−無水マレイン酸共重合物（Ａ−１）を得た。 (Synthesis Example 1) Synthesis of (meth) acrylic acid ester-maleic anhydride copolymer (A-1) Toluene 200 was added to a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank and nitrogen gas introduction tube. The temperature was raised to 110 ° C. with stirring while introducing nitrogen gas. Next, 90 parts of methyl methacrylate, 60 parts of butyl acrylate, 150 parts of maleic anhydride and 50 parts of toluene were charged into the dropping tank 1, and 9 parts of benzoyl peroxide were dissolved in 50 parts of toluene into the dropping tank 2. The mixture was charged dropwise with stirring while maintaining the temperature in the reaction vessel at 110 ° C. over 2 hours at the same time. After completion of the reaction, the mixture was cooled to room temperature, polymer was precipitated with a large amount of methanol, filtered, dried at 120 ° C. for 6 hours, and a (meth) acrylic acid ester-maleic anhydride copolymer having a number average molecular weight of 3000 and an acid value of 488. (A-1) was obtained.
（合成例２）（メタ）アクリル酸エステル−無水マレイン酸共重合物（Ａ−２）の合成
攪拌機、温度計、還流冷却管、滴下槽及び窒素ガス導入管を備えた反応容器に、トルエン２００部を仕込み、窒素ガスを導入しつつ、攪拌しながら１１０℃まで昇温した。次に、滴下槽１にメタクリル酸メチル９０部、アクリル酸ブチル１２０部、無水マレイン酸９０部、トルエン５０部を仕込み、滴下槽２に過酸化ベンゾイル９部をトルエン５０部に溶解せしめたものを仕込み、夫々同時に２時間かけて反応容器内の温度を１１０℃にたもちながら、攪拌下に滴下した。反応終了後、室温まで冷却し、大量のメタノールによりポリマーを沈殿、ろ過し、１２０℃で６時間乾燥し、数平均分子量３５００、酸価２９８の（メタ）アクリル酸エステル−無水マレイン酸共重合物（Ａ−２）を得た。
(Synthesis Example 2) Synthesis of (meth) acrylic acid ester-maleic anhydride copolymer (A-2) Toluene 200 was added to a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank, and a nitrogen gas introduction tube. The temperature was raised to 110 ° C. with stirring while introducing nitrogen gas. Next, 90 parts of methyl methacrylate, 120 parts of butyl acrylate, 90 parts of maleic anhydride and 50 parts of toluene were charged into the dropping tank 1, and 9 parts of benzoyl peroxide were dissolved in 50 parts of toluene into the dropping tank 2. The mixture was charged dropwise with stirring while maintaining the temperature in the reaction vessel at 110 ° C. over 2 hours at the same time. After completion of the reaction, the mixture is cooled to room temperature, polymer is precipitated with a large amount of methanol, filtered, dried at 120 ° C. for 6 hours, and a (meth) acrylic acid ester-maleic anhydride copolymer having a number average molecular weight of 3500 and an acid value of 298. (A-2) was obtained.
（合成例３）スチレン−無水マレイン酸共重合物（Ａ−３）の合成
攪拌機、温度計、還流冷却管、滴下槽及び窒素ガス導入管を備えた反応容器に、トルエン２００部を仕込み、窒素ガスを導入しつつ、攪拌しながら１１０℃まで昇温した。次に、滴下槽１にスチレン１５０部、無水マレイン酸１５０部、トルエン５０部を仕込み、滴下槽２に過酸化ベンゾイル９部をトルエン５０部に溶解せしめたものを仕込み、夫々同時に２時間かけて反応容器内の温度を１１０℃にたもちながら、攪拌下に滴下した。反応終了後、室温まで冷却し、大量のメタノールによりポリマーを沈殿、ろ過し、１２０℃で６時間乾燥し、数平均分子量２８００、酸価５０１のスチレン−無水マレイン酸共重合物（Ａ−３）を得た。
(Synthesis Example 3) Synthesis of styrene-maleic anhydride copolymer (A-3) 200 parts of toluene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank, and a nitrogen gas introduction tube, and nitrogen was added. While introducing gas, the temperature was raised to 110 ° C. with stirring. Next, 150 parts of styrene, 150 parts of maleic anhydride, and 50 parts of toluene are charged into the dropping tank 1, and 9 parts of benzoyl peroxide are dissolved in 50 parts of toluene into the dropping tank 2, and each of them takes 2 hours at the same time. While maintaining the temperature in the reaction vessel at 110 ° C., the reaction vessel was added dropwise with stirring. After completion of the reaction, the mixture was cooled to room temperature, polymer was precipitated with a large amount of methanol, filtered, dried at 120 ° C. for 6 hours, and styrene-maleic anhydride copolymer (A-3) having a number average molecular weight of 2800 and an acid value of 501. Got.
（合成例４）αオレフィン−無水マレイン酸共重合物（Ａ−４）の合成
攪拌機、温度計、還流冷却管、滴下槽及び窒素ガス導入管を備えた反応容器に、トルエン２００部を仕込み、窒素ガスを導入しつつ、攪拌しながら１１０℃まで昇温した。次に、滴下槽１に１−ヘキセン１５０部、無水マレイン酸１５０部、トルエン５０部を仕込み、滴下槽２に過酸化ベンゾイル９部をトルエン５０部に溶解せしめたものを仕込み、夫々同時に２時間かけて反応容器内の温度を１１０℃にたもちながら、攪拌下に滴下した。反応終了後、室温まで冷却し、大量のメタノールによりポリマーを沈殿、ろ過し、１２０℃で６時間乾燥し、数平均分子量２９００、酸価４８７のαオレフィン−無水マレイン酸共重合物（Ａ−４）を得た。
(Synthesis Example 4) Synthesis of α-olefin-maleic anhydride copolymer (A-4) 200 parts of toluene was charged into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank, and a nitrogen gas introduction tube. While introducing nitrogen gas, the temperature was raised to 110 ° C. with stirring. Next, 150 parts of 1-hexene, 150 parts of maleic anhydride, and 50 parts of toluene were charged into the dropping tank 1, and 9 parts of benzoyl peroxide was dissolved in 50 parts of toluene into the dropping tank 2, and simultaneously for 2 hours. The reaction vessel was added dropwise with stirring while maintaining the temperature in the reaction vessel at 110 ° C. After completion of the reaction, the reaction mixture was cooled to room temperature, precipitated with a large amount of methanol, filtered, dried at 120 ° C. for 6 hours, and an α-olefin-maleic anhydride copolymer (A-4 having a number average molecular weight of 2900 and an acid value of 487). )
（合成例５）ポリマーポリオール（Ｂ−１）の合成
攪拌機、温度計、還流冷却管、滴下槽及び窒素ガス導入管を備えた反応容器に、エチレングリコール７．３部、ネオペンチルグリコール１６．３部、１，６−ヘキサンジオール１３．９部、イソフタル酸３９．４部、テレフタル酸４．４部、安息香酸１．０部、セバシン酸１８．０部を仕込み、窒素気流下で攪拌しながら２６０℃まで昇温した。酸価が５以下になるまで反応を続けた後に、徐々に減圧を行って、１ｍｍＨｇで反応を継続し、余剰のアルコールを除去して、水酸基価が１０ｍｇＫＯＨ／ｇ、数平均分子量１００００のポリマーポリオール（Ｂ−１）を得た。
(Synthesis Example 5) Synthesis of Polymer Polyol (B-1) In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank, and a nitrogen gas introduction tube, 7.3 parts of ethylene glycol and 16.3 of neopentyl glycol Part, 1,6-hexanediol 13.9 parts, isophthalic acid 39.4 parts, terephthalic acid 4.4 parts, benzoic acid 1.0 part, sebacic acid 18.0 parts, while stirring under a nitrogen stream The temperature was raised to 260 ° C. After the reaction is continued until the acid value becomes 5 or less, the pressure is gradually reduced, the reaction is continued at 1 mmHg, the excess alcohol is removed, and the polymer polyol has a hydroxyl value of 10 mgKOH / g and a number average molecular weight of 10,000. (B-1) was obtained.
（合成例６）ポリマーポリオール（Ｂ−２）の合成
上記ポリマーポリオール（Ｂ−１）３００ｇを窒素気流下で攪拌しながら過熱し、１５０℃の雰囲気中で、イソホロンジイソシアネート３ｇ添加し、攪拌を継続した。ＩＲ分析にて未反応のＮＣＯ由来の吸収が消失するまで攪拌を続け、水酸基価が８ｍｇＫＯＨ／ｇ、数平均分子量１２０００のポリマーポリオール（Ｂ−２）を得た。
(Synthesis example 6) Synthesis of polymer polyol (B-2) 300 g of the above polymer polyol (B-1) was heated while stirring under a nitrogen stream, and 3 g of isophorone diisocyanate was added in an atmosphere at 150 ° C, and stirring was continued. did. Stirring was continued until absorption due to unreacted NCO disappeared by IR analysis to obtain a polymer polyol (B-2) having a hydroxyl value of 8 mgKOH / g and a number average molecular weight of 12,000.
（合成例７）ポリマーポリオール（Ｂ−３）の合成
上記ポリマーポリオール（Ｂ−２）３００ｇを窒素気流下で攪拌しながら１８０℃まで昇温し、エチレングリコールビスアンヒドロトリテート４ｇ及び、無水トリメリット酸２ｇを仕込み、１８０℃で１時間保持し、水酸基価が５ｍｇＫＯＨ／ｇ、数平均分子量１２５００のポリマーポリオール（Ｂ−３）を得た。
(Synthesis Example 7) Synthesis of Polymer Polyol (B-3) While stirring 300 g of the above polymer polyol (B-2) under a nitrogen stream, the temperature was increased to 180 ° C., and 4 g of ethylene glycol bisanhydrotritate and 2 g of merit acid was charged and held at 180 ° C. for 1 hour to obtain a polymer polyol (B-3) having a hydroxyl value of 5 mgKOH / g and a number average molecular weight of 12,500.
（実施例１）
攪拌機、温度計、還流冷却管、滴下槽及び窒素ガス導入管を備えた反応容器に、合成例１で得た（メタ）アクリル酸エステル−無水マレイン酸共重合物（Ａ−１）２．７ｇ、合成例５で得たポリマーポリオール（Ｂ−１）９０ｇ、酢酸エチル２１０ｇ、を仕込み、窒素ガスを導入しつつ、攪拌しながら７８℃まで昇温し、１時間保持した。室温まで冷却後、リン酸０．０３６ｇ、シランカップリング剤（γ−グリシドキシプロピルトリメトキシシラン）０．２７ｇ、及び、有機イソシアネート化合物（Ｃ）として、イソホロンジイソシアネートのトリメチロールプロパン付加体（ＩＰＤＩ−ＴＭＰアダクト）と、キシリレンジイソシアネートのトリメチロールプロパン付加体（ＸＤＩ−ＴＭＰアダクト）との３／７（重量比）混合物の酢酸エチル希釈液（不揮発分７０重量％）を２２．７ｇ、酢酸エチル２１０ｇを配合し、接着剤を調合した。
Example 1
2.7 g of the (meth) acrylic acid ester-maleic anhydride copolymer (A-1) obtained in Synthesis Example 1 in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, dropping tank and nitrogen gas inlet tube. Then, 90 g of the polymer polyol (B-1) obtained in Synthesis Example 5 and 210 g of ethyl acetate were charged, and the temperature was raised to 78 ° C. with stirring while introducing nitrogen gas, and held for 1 hour. After cooling to room temperature, 0.036 g of phosphoric acid, 0.27 g of silane coupling agent (γ-glycidoxypropyltrimethoxysilane), and trimethylolpropane adduct of isophorone diisocyanate (IPDI) as the organic isocyanate compound (C) -TMP adduct) and 32.7 (weight ratio) mixture of xylylene diisocyanate trimethylolpropane adduct (XDI-TMP adduct) in an ethyl acetate dilution (non-volatile content 70 wt%) 22.7 g, ethyl acetate 210g was mix | blended and the adhesive agent was prepared.
（実施例２〜６、比較例１〜４）
表１記載の材料を使用した以外は、実施例１と同様な操作により、接着剤を調合した。
(Examples 2-6, Comparative Examples 1-4)
An adhesive was prepared in the same manner as in Example 1 except that the materials shown in Table 1 were used.
（４層複合積層体の作成）
ポリエチレンテレフタレート（ＰＥＴ）フィルム（厚さ１２μｍ）／ナイロン（ＮＹ）フィルム（厚さ１５μｍ）／アルミニウム（ＡＬ）箔（厚さ９μｍ）／未延伸ポリプロピレン（ＣＰＰ）フィルム（厚さ７０μｍ、表面コロナ放電処理）の４層複合積層体を接着剤の固形分塗布量を３．５ｇ／ｍ2として、以下に記載の方法で作成した。すなわち、接着剤溶液を常温にてラミネーターにより、まずポリエチレンテレフタレートフィルムの印刷面に塗布し、溶剤を揮散させた後、塗布面をナイロンフィルムと貼り合せた。さらに、その積層体のナイロンフィルム面に同様に接着剤溶液を塗布し、溶剤を揮散させた後、塗布面をアルミニウム箔表面と貼り合せた。ついで、その積層体のアルミニウム箔面に同様に接着剤溶液を塗布し、溶剤を揮散させた後、塗布面を未延伸ポリプロピレンフィルムと貼り合せ、４０℃で３日間保温し、４層複合積層体を作成した。表２において、ラミネート外観の○は良好、×は全面に欠膠部ありを示す。ここで、欠膠部とは、接着剤を基材へ塗布した際に、基材への濡れ性が悪いと接着剤がハジかれるが、ハジかれて塗布量が少なくなった部分を意味する。欠膠部があると、接着力が発現しない。
(Creation of a four-layer composite laminate)
Polyethylene terephthalate (PET) film (thickness 12 μm) / nylon (NY) film (thickness 15 μm) / aluminum (AL) foil (thickness 9 μm) / unstretched polypropylene (CPP) film (thickness 70 μm, surface corona discharge treatment) ) Was prepared by the method described below, with the solid coating amount of the adhesive being 3.5 g / m 2 . That is, the adhesive solution was first applied to the printing surface of the polyethylene terephthalate film at room temperature with a laminator to volatilize the solvent, and then the coated surface was bonded to the nylon film. Furthermore, the adhesive solution was similarly applied to the nylon film surface of the laminate to volatilize the solvent, and then the coated surface was bonded to the aluminum foil surface. Next, the adhesive solution was similarly applied to the aluminum foil surface of the laminate, the solvent was stripped off, the applied surface was bonded to an unstretched polypropylene film, and kept at 40 ° C. for 3 days, and a four-layer composite laminate. It was created. In Table 2, ○ of the laminate appearance is good, and × indicates that there is a chipped portion on the entire surface. Here, the chipped portion means a portion where, when the adhesive is applied to the base material, the adhesive is peeled off if the wettability to the base material is poor, but the applied amount is reduced due to the peeling. If there is a chipped part, the adhesive force is not expressed.
（ラミネート強度試験）
上記のようにして作成した４層複合積層体から１５ｍｍ×３００ｍｍの大きさの試験片を作り、引張り試験機を用い、温度２０℃、相対湿度６５％の条件下で、Ｔ型剥離により、剥離速度３０ｃｍ／分で、ＰＥＴフィルム／ＮＹフィルム間、ＮＹフィルム／ＡＬ箔間、およびＡＬ箔／ＣＰＰフィルム間のラミネート強度（Ｎ／１５ｍｍ）を測定した。表２の数値は、５個の試験片の平均値である。測定はレトルトの前後でそれぞれ行った。レトルト条件は、（株）日坂製作所製「RCS-60SPXTG」レトルト試験機により、１０ｒ．ｐ．ｍ．、１３５℃、３０分、３ＭＰａの加圧下で熱水殺菌を行った。
(Lamination strength test)
A test piece having a size of 15 mm × 300 mm was prepared from the four-layer composite laminate prepared as described above, and peeled off by T-type peeling at a temperature of 20 ° C. and a relative humidity of 65% using a tensile tester. Laminate strength (N / 15 mm) between PET film / NY film, NY film / AL foil, and AL foil / CPP film was measured at a speed of 30 cm / min. The numerical values in Table 2 are average values of five test pieces. The measurement was performed before and after the retort. The retort conditions were measured with a “RCS-60SPXTG” retort tester manufactured by Nisaka Manufacturing Co., Ltd. p. m. , Sterilized with hot water under a pressure of 3 MPa at 135 ° C. for 30 minutes.
（耐熱水性試験）
各々の４層複合積層体を使用して、未延伸ポリプロピレンが内側となるように２１ｃｍ×３０ｃｍの大きさのパウチを作成し、内容物として水１ｋｇを真空充填した。このパウチを（株）日坂製作所製「RCS-60SPXTG」レトルト試験機により、１０ｒ．ｐ．ｍ．、１３５℃、３０分、３ＭＰａの加圧下で熱水殺菌を行った後、ＰＥＴフィルム／ＮＹフィルム間、ＮＹフィルム／ＡＬ箔間およびＡＬ箔／ＣＰＰフィルム間の剥離状態を観察した。表２において、剥離外観の○は良好（剥離なし）、△は部分的に剥離あり、×は全面に剥離ありを示す。
(Heat resistance test)
Using each of the four-layer composite laminates, pouches having a size of 21 cm × 30 cm were prepared so that unstretched polypropylene was inside, and 1 kg of water was vacuum-filled as the contents. This pouch was measured with a “RCS-60SPXTG” retort tester manufactured by Nisaka Manufacturing Co., Ltd. for 10 r. p. m. After sterilizing with hot water under a pressure of 3 MPa at 135 ° C. for 30 minutes, the peeled state between the PET film / NY film, between the NY film / AL foil, and between the AL foil / CPP film was observed. In Table 2, ○ of the peeling appearance is good (no peeling), Δ is partially peeled, and x indicates peeling on the entire surface.
（耐酸性試験１）
各々の４層複合積層体を使用して、未延伸ポリプロピレンが内側となるように９ｃｍ×１３ｃｍの大きさのパウチを作成し、内容物として４．２重量％以上の濃度を有する食酢を充填した。このパウチを（株）日坂製作所製「RCS-60SPXTG」レトルト試験機により、３ｒ．ｐ．ｍ．、１３５℃、３０分、３ＭＰａの加圧下で熱水殺菌を行った後、６０℃、２週間保存後および６０℃、４週間保存後のＡＬ箔／ＣＰＰフィルム間の剥離状態を観察した。表２において、剥離外観の○は良好（剥離なし）、△は部分的に剥離あり、×は全面に剥離ありを示す。
(Acid resistance test 1)
Using each 4-layer composite laminate, a pouch having a size of 9 cm × 13 cm was prepared so that the unstretched polypropylene was inside, and the contents were filled with vinegar having a concentration of 4.2% by weight or more. . This pouch was measured with a “RCS-60SPXTG” retort testing machine manufactured by Hisaka Manufacturing Co., Ltd. p. m. After sterilizing with hot water under a pressure of 3 MPa at 135 ° C. for 30 minutes, the peeled state between the AL foil / CPP film after storage at 60 ° C. for 2 weeks and after storage at 60 ° C. for 4 weeks was observed. In Table 2, ○ of the peeling appearance is good (no peeling), Δ is partially peeled, and x indicates peeling on the entire surface.
（耐酸性試験２）
各々の４層複合積層体を使用して、未延伸ポリプロピレンが内側となるように９ｃｍ×１３ｃｍの大きさのパウチを作成し、内容物として４．２重量％以上の濃度を有する食酢を充填した。このパウチを未処理で、６０℃、２週間保存後および６０℃、４週間保存後のＡＬ箔／ＣＰＰフィルム間の剥離状態を観察した。表２において、剥離外観の○は良好（剥離なし）、△は部分的に剥離あり、×は全面に剥離ありを示す。
結果を表２に示す。
Using each 4-layer composite laminate, a pouch having a size of 9 cm × 13 cm was prepared so that the unstretched polypropylene was inside, and the contents were filled with vinegar having a concentration of 4.2% by weight or more. . This pouch was untreated, and the peeled state between the AL foil / CPP film was observed after storage at 60 ° C. for 2 weeks and after storage at 60 ° C. for 4 weeks. In Table 2, ○ of the peeling appearance is good (no peeling), Δ is partially peeled, and x indicates peeling on the entire surface.
The results are shown in Table 2.
Claims (4)
ポリマーポリオール（Ｂ）、および
有機イソシアネート化合物（Ｃ）を含有し、
前記（メタ）アクリル酸エステルと無水マレイン酸とを共重合させてなる樹脂（Ａ）を、前記ポリマーポリオール（Ｂ）１００重量部に対して、０．１〜１０重量部含有することを特徴とするウレタン系接着剤組成物。 Resin (A) obtained by copolymerizing (meth) acrylic acid ester and maleic anhydride,
Containing a polymer polyol (B), and an organic isocyanate compound (C) ,
The resin (A) obtained by copolymerizing the (meth) acrylic acid ester and maleic anhydride is contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymer polyol (B). Urethane-based adhesive composition.
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| WO2014208432A1 (en) * | 2013-06-24 | 2014-12-31 | Dic株式会社 | Laminating adhesive agent composition |
| JP6210306B2 (en) * | 2013-12-19 | 2017-10-11 | Dic株式会社 | Solvent-free two-component curable laminate adhesive composition |
| JP2016050238A (en) * | 2014-08-29 | 2016-04-11 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition for laminated sheet |
| JP6476830B2 (en) * | 2014-12-18 | 2019-03-06 | Dic株式会社 | Mineral oil barrier packaging material and package using the same |
| JP6481403B2 (en) * | 2015-02-16 | 2019-03-13 | Dic株式会社 | Mineral oil barrier packaging material and package using the same |
| JP6481406B2 (en) * | 2015-02-18 | 2019-03-13 | Dic株式会社 | Mineral oil barrier packaging material and package using the same |
| JP6939011B2 (en) * | 2017-03-28 | 2021-09-22 | 東洋インキＳｃホールディングス株式会社 | Urethane-based adhesive composition and laminate |
| JP7030266B2 (en) * | 2017-12-25 | 2022-03-07 | 東洋インキＳｃホールディングス株式会社 | glue |
| WO2020066652A1 (en) * | 2018-09-25 | 2020-04-02 | Dic株式会社 | Separation/recovery method for laminated film |
| JP6881547B2 (en) | 2018-12-28 | 2021-06-02 | 東洋インキＳｃホールディングス株式会社 | Solvent-free adhesive composition and laminate |
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