JP2004285183A - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
- Publication number
- JP2004285183A JP2004285183A JP2003078393A JP2003078393A JP2004285183A JP 2004285183 A JP2004285183 A JP 2004285183A JP 2003078393 A JP2003078393 A JP 2003078393A JP 2003078393 A JP2003078393 A JP 2003078393A JP 2004285183 A JP2004285183 A JP 2004285183A
- Authority
- JP
- Japan
- Prior art keywords
- polyol
- adhesive composition
- organic
- acid
- urethane
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 239000000853 adhesive Substances 0.000 title claims abstract description 49
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 49
- 150000003077 polyols Chemical class 0.000 claims abstract description 71
- 229920005862 polyol Polymers 0.000 claims abstract description 69
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 21
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 21
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 239000005001 laminate film Substances 0.000 claims description 6
- 235000013305 food Nutrition 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 2
- -1 polyethylene Polymers 0.000 abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011888 foil Substances 0.000 abstract description 14
- 230000004888 barrier function Effects 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 239000002985 plastic film Substances 0.000 abstract description 9
- 229920006255 plastic film Polymers 0.000 abstract description 9
- 239000004698 Polyethylene Substances 0.000 abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 8
- 229920000573 polyethylene Polymers 0.000 abstract description 8
- 239000004677 Nylon Substances 0.000 abstract description 4
- 239000004743 Polypropylene Substances 0.000 abstract description 4
- 229920001778 nylon Polymers 0.000 abstract description 4
- 229920000728 polyester Polymers 0.000 abstract description 4
- 229920001155 polypropylene Polymers 0.000 abstract description 4
- 239000005022 packaging material Substances 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract 1
- 238000003475 lamination Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 30
- 229920005906 polyester polyol Polymers 0.000 description 19
- 239000002253 acid Substances 0.000 description 18
- 239000003822 epoxy resin Substances 0.000 description 15
- 229920000647 polyepoxide Polymers 0.000 description 15
- 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 13
- 150000007519 polyprotic acids Polymers 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 150000008064 anhydrides Chemical class 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000002648 laminated material Substances 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 4
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229920006284 nylon film Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- DSNHSQKRULAAEI-UHFFFAOYSA-N 1,4-Diethylbenzene Chemical compound CCC1=CC=C(CC)C=C1 DSNHSQKRULAAEI-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- YPQKTLPPOXNDMC-UHFFFAOYSA-N isocyanic acid;methylcyclohexane Chemical compound N=C=O.CC1CCCCC1 YPQKTLPPOXNDMC-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 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
- 239000003921 oil Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 229920003226 polyurethane urea Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000005591 trimellitate group Chemical group 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 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
- 239000008096 xylene Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-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
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-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
- UFXYYTWJETZVHG-UHFFFAOYSA-N 1,3-diisocyanatobutane Chemical compound O=C=NC(C)CCN=C=O UFXYYTWJETZVHG-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
- 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
- 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
- LHNAURKRXGPVDW-UHFFFAOYSA-N 2,3-diisocyanatobutane Chemical compound O=C=NC(C)C(C)N=C=O LHNAURKRXGPVDW-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-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
- 229940018563 3-aminophenol Drugs 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
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-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
- QGNGOGOOPUYKMC-UHFFFAOYSA-N 4-hydroxy-6-methylaniline Chemical compound CC1=CC(O)=CC=C1N QGNGOGOOPUYKMC-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-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
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 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
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、ウレタン系接着剤組成物に関し、より詳細には、耐熱水性、作業性に優れ、良好な外観を示す各種プラスチックフィルム、金属箔、金属蒸着フィルム等からなるラミネート複合フィルム用のウレタン系接着剤組成物に関する。
【０００２】
【従来の技術】
従来、例えば食品、医療品、化粧品等の包装用材料として、ポリエチレン、ポリプロピレン、ナイロン、ポリエステル等のプラスチックフィルム、金属蒸着フィルム、アルミ箔等の金属箔をラミネートした多層複合用フィルムが広く使用されている。これらのプラスチックフィルム、金属蒸着フィルム、金属箔等を接着するのに有機ポリオールと有機イソシアネートを組み合せたウレタン系接着剤が知られている。近年、環境対応型のフィルムとして、プラスチックフィルムにポリ塩化ビニリデン（ＰＶＤＣ）をコートしたガスバリア性フィルムがあり、その代替フィルムとして、シリカやアルミナ等の金属酸化物をポリエステルフィルムやポリアミドフィルム等のプラスチックフィルムに蒸着した透明蒸着フィルムが増加して来た。又、従来のアルミニウム等の金属箔と同様のガスバリア性を確保するために、これらの透明蒸着フィルム同士をラミネートしたガスバリア性や保香等を保持しようとする動きが活発化して来た。
【０００３】
しかし、これらをラミネートする接着剤としてウレタン系接着剤が多く用いられているが、従来のウレタン系接着剤でこれらのガスバリア性の高いフィルム同士をラミネートすると、ウレタン系接着剤に存在する遊離の有機ポリイソシアネートと水との反応で生成する炭酸ガスがフィルム界面に溜まり、気泡による外観不良を起こすことがあった。そのため、これらを改善するために有機ポリオールに対する有機ポリイソシアネートの配合割合を減少して製造したウレタン系接着剤を用いて炭酸ガスの発生率を下げる方法が採られている。しかし、この方法では有機ポリイソシアネートの量が不十分となり満足した接着性、耐熱性、耐水性等が得られない欠点を有していた。又、有機ポリオールの分子量を大きくして水酸基の含有量を少なくすることで、使用する有機ポリイソシアネートの量を減らす方法もある。しかし、この方法では有機ポリオールの分子量を大きくなることから、接着剤を使用する際の溶液粘度が高くなり、塗工性、作業性等が不利になることがあった。更に、炭酸ガスが発生しない硬化形態型のアミン−エポキシ硬化系接着剤を使用すると、良好なラミネート外観が得られるものの、耐熱性、耐水性等が不十分であった。
【０００４】
又、上記の欠点を解決するため、例えば、多官能ポリウレタン尿素ポリオール樹脂組成物を用いる提案（特開２０００−７７４８号公報）もあるが、ガスバリア性の高いフィルム同士をラミネートする場合には性能が充分とは言えず、従来公知のウレタン系接着剤では、未だ上記の各欠点を解決することができないのが現状である。
【特許文献１】
特開２０００−７７４８号公報
【０００５】
【発明が解決しようとする課題】
本発明は、ガスバリア性の高いフィルム同士をラミネートする場合、ラミネートフィルム間の接着性に優れ、得られるラミネートフィルム積層体が良好な外観を示すことができるウレタン系接着剤組成物を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために種々検討した結果、分岐構造を持つ多官能基を有する有機ポリオールと有機ポリイソシアネートを成分とする組成物が本発明の目的を達成し得ることを見出だし、本発明に到達した。
【０００７】
すなわち、本発明は、３個以上のヒドロキシル基を有するポリオールに由来する官能基を持つ基を分岐して結合した有機ポリオール並びに有機ポリイソシアネートを必須成分とするウレタン系接着剤組成物を要旨とする。
【０００８】
又、本発明の組成物は、更にシランカップリング剤及び／又はリンの酸素酸若しくはその誘導体を必須成分とすることを特徴とする。
又、本発明の組成物は、上記有機ポリオール中の上記官能基を持つ基の含有量が１０モル％以下であることを特徴とする。
【０００９】
更に、本発明は、食品包装ラミネート用であるウレタン系接着剤組成物を要旨とする。
【００１０】
更に、本発明は、上記のウレタン系接着剤組成物で接着され形成されたラミネートフィルム積層体を要旨とする。
【００１１】
【発明の実施の形態】
本発明で用いられる有機ポリオールとしては、１分子中の官能基数が約２〜６、好ましくは約２〜４で、数平均分子量が約５００〜１００，０００、好ましくは１，０００〜３０，０００の化合物が挙げられる。更に詳しくは、ポリエステルポリオール、ポリエーテルポリオール、ポリエーテルエステルポリオール、ポリウレタンポリオール、ポリエステルアミドポリオール、ポリカーボネートポリオール又はそれらの混合物が挙げられる。
【００１２】
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ジオ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。
【００１３】
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。
【００１４】
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。
【００１５】
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、好ましくは０．９以下で反応させて得られる。用い得る有機ポリ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−又は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−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−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−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脂肪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との付加体等が挙げられる。
【００１６】
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。
【００１７】
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種以上のジオール類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。
【００１８】
本発明で用いられる有機ポリオールは、３個以上のヒドロキシル基を有するポリオールに由来する官能基を持つ基を分岐して結合しているものである。官能基としては、ヒドロキシル基、エステル基、エーテル基、カルボニル基等の含酸素基が挙げられる。有機ポリオール中のポリオールに由来する官能基を持つ基の含有量は、１０モル％以下が好ましく、更に好ましくは５モル％以下、特に好ましくは３モル％以下である。
【００１９】
３個以上のヒドロキシル基を有するポリオールとしては、グルセリン、トリメチロールプロパン、ペンタエリトリトール等が挙げられる。上記官能基を持つ基を分岐して結合した有機ポリオールは、上記有機ポリオールを調製する際に、前記ジオール類若しくはそれらの混合物に、上記の３個以上のヒドロキシル基を有するポリオールを混合して反応させることにより製造することができる他、上記有機ポリオールに、上記の３個以上のヒドロキシル基を有するポリオールを用いて反応させることにより製造することができる。
【００２０】
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。本発明で用いることができる有機ポリオール（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１，０００〜１００，０００、好ましくは３，０００〜１５，０００のものが好ましく使用される。１，０００以下では凝集力が不十分であり、１００，０００以上では、合成上、末端に多塩基酸若しくはその無水物を反応させることは難しく、著しい増粘やゲル化する可能性もある。
【００２１】
多塩基酸若しくはその無水物としては、例えば、フタル酸、トリメリット酸、ピロメリット酸等の芳香族系多塩基酸及びそれらの無水物が挙げられるが、それらの無水物である無水フタル酸、無水トリメリット酸、無水ピロメリット酸等が特に好適である。更に、これらの無水物から誘導されたエチレングリコールビスアンヒドロトリメリテート、グリセリントリスアンヒドロトリメリテート、エチレングリコールビスアンヒドロピロメリテート、グリセリントリスアンヒドロピロメリテート、又ロジン成分のアビエチン酸や、Ｃ１０Ｈ１６ジエン化合物及びこれらの混合物に無水マレイン酸を付加反応させた誘導体等を使用することができる。
【００２２】
有機ポリオール（２）は、上記有機ポリオールの合成後、多塩基酸若しくはその無水物、好ましくは多塩基酸無水物を加熱下に添加して行なわれるが、有機ポリオールの合成の際、多価カルボン酸と多価アルコールから一段階で分子内部或いは分子末端にカルボキシル基を含有するものを得ることが可能である。これらの多塩基酸若しくは多塩基酸無水物との反応は、本発明による接着剤組成物の接着性能、例えば、耐熱水性、耐油性、耐酸性等を向上させるのに、促進効果を示す。有機ポリオールと多塩基酸若しくは多塩基酸無水物の反応は、多塩基酸若しくは多塩基酸無水物の開環反応によるエステル化反応が主反応になるように、反応温度を２００℃以下、好ましくは１５０〜１８０℃の範囲に制御する必要がある。
【００２３】
本発明で用いられる有機ポリイソシアネートとしては、上記有機ポリオールの中のポリウレタンポリオールを調製する際に用い得る前記有機ポリイソシアネートの中から選択することができる。
【００２４】
本発明で用いられるシランカップリング剤としては、下記一般式（Ｉ）又は（ＩＩ）で示されるものならいずれも使用することができる。
【００２５】
Ｒ−Ｓｉ≡Ｘ３ （Ｉ）
Ｒ−Ｓｉ≡Ｒ１Ｘ２ （ＩＩ）
式中、Ｒはビニル基、エポキシ基、アミノ基、イミノ基又はメルカプト基を有する有機基を、Ｒ１は低級アルキル基、Ｘはメトキシ基、エトキシ基又は塩素原子を表す。シランカップリング剤としては、例えば、ビニルトリクロルシラン等のクロロシラン、Ｎ−（ジメトキシメチルシリルプロピル）エチレンジアミン、Ｎ−（トリエトキシシリルプロピル）エチレンジアミン等のアミノシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン等のエポキシシラン、ビニルトリエトキシシラン等のビニルシラン等が挙げられる。
【００２６】
本発明で用いられるリンの酸素酸又はその誘導体としては、遊離の酸素酸を少なくとも１個以上有しているものであればいずれでもよく、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。又、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個以上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。リンの酸素酸又はその誘導体は、１種に限らず２種以上を用いることができる。
【００２７】
本発明の接着剤組成物は、上記有機ポリオールにシランカップリング剤又は上記リンの酸素酸若しくはその誘導体を混合することができるが、上記有機ポリオールとシランカップリング剤又は上記リンの酸素酸若しくはその誘導体を混合する場合、それらを単に混合してもよいが、有機溶剤の存在下、それらを混合するのが望ましい。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いかなるものを使用してもよい。
【００２８】
シランカップリング剤の使用量は、接着剤組成物に対して０．１〜５質量％の範囲が好ましい。その使用量が０．１質量％未満では、アルミニウム箔等の金属箔に対する接着性が不十分となり、５質量％を超えると接着剤の凝集力が低下し、耐熱性が低下する。リンの酸素酸若しくはその誘導体は、接着剤組成物に対して０．０１〜１０質量％、好ましくは０．０５〜５質量％、更に好ましくは０．１〜１質量％になるような範囲で用いられる。その使用量が０．０１質量％未満では、アルミニウム箔等の金属箔の内層側の耐酸性が不十分となり、１０質量％を超えると、アルミニウム箔等の金属箔の内層側並びに外層側における耐水性が不十分となる。
【００２９】
本発明の接着剤組成物は、必要に応じて更にエポキシ樹脂を配合することができる。用いられるエポキシ樹脂としては、例えば、ジフェノールメタン（ビスフェノールＦ）、ジフェノールエタン、ジフェノールプロパン（ビスフェノールＡ）、ポリビニルフェノール、ポリイソプロペニルフェノール、四臭化ビスフェノールＡ、１，１−ビス−（４−ヒドロキシフェニル）−１−フェニルエタン、１，１−ビス−（４−ヒドロキシフェニル）−１，１−ジメチルメタン等から誘導されるエポキシ化合物；フェノールノボラック、臭素化フェノールノボラック、クレゾールノボラック、臭素化クレゾールノボラック、レゾルシンノボラック、臭素化レゾルシンノボラック等から誘導されるノボラック系樹脂；レゾルシン、ヒドロキノン、メチルレゾルシン、四塩化ビスフェノールＡ等から誘導される多価フェノール系エポキシ樹脂；アニリン、ｐ−アミノフェノール、ｍ−アミノフェノール、ｐ−アミノ−ｍ−クレゾール、４，４′−ジアミノジフェニルメタン等から誘導されるアミン系エポキシ樹脂；ｐ−オキシ安息香酸、ｍ−オキシ安息香酸、テレフタル酸、イソフタル酸等の芳香族カルボン酸から誘導されるグリシジルエステル系化合物；５，５′−ジメチルヒダントイン等から誘導されるヒダントイン系エポキシ樹脂；２，２′−ビス（４−（３，４−エポキシシクロヘキシル）プロパン、２，２′−ビス（４−（２，３−エポキシシクロヘキシル）プロパン、ビニルシクロヘキセンオキサイド等の脂環式エポキシ樹脂；その他、例えばトリグリシジルイソシアヌレート、２，４，６−トリグリシドキシ−５−トリアジン等を挙げることができ、これらの変性物であるダイマー酸変性エポキシ樹脂、ウレタン変性エポキシ樹脂等やビスフェノールＡ型エポキシ樹脂の水添物である水添ビスフェノールＡ型エポキシ樹脂等も使用可能である。上記エポキシ樹脂は２種以上用いてもよい。
【００３０】
上記のエポキシ樹脂は、市販されており、必要に応じてそれらの市販品から適宜選択して用いることができる。市販品の具体例としては、例えば、油化シェルエポキシ社製、商品名：エピコート１００２（ビスフェノールＡ型エポキシ樹脂）；東都化成社製、商品名：ＳＴ−３０００（水添ビスフェノールＡ型エポキシ樹脂）；東都化成社製、商品名：ＹＤ−１７２（ダイマー酸変性エポキシ樹脂）等が挙げられる。勿論これらに限定されないことは言うまでもない。
【００３１】
又、これらのエポキシ樹脂に、それらの粘度を低下させることを目的として、エポキシ基を分子内に有する例えばブチルグリシジルエーテルのような低分子量のエポキシ化合物を少量配合することができ、得られる接着剤の粘度を調整することができる。エポキシ樹脂は、接着剤組成物に対して１〜５０質量％、好ましくは１〜３０質量％となる範囲で配合される。
【００３２】
本発明の接着剤組成物は、上記各成分を配合することにより製造することができるが、更に、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、消泡剤等の添加剤を必要に応じて配合することができる。又、硬化反応を調節するため公知の触媒、添加剤等を使用することができる。
【００３３】
本発明の接着剤組成物は、使用する際に、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。上記組成物の粘度が上記範囲より高い場合、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ていかなるものを使用してもよい。
【００３４】
本発明の接着剤組成物を使用する具体的な処方としては、有機ポリオールと有機ポリイソシアネートを、有機ポリオール中の水酸基、更にカルボキシル基を有する場合はそれらの合計に対して、有機ポリイソシアネートのイソシアネート基が当量比にして１．０〜５．０倍になるよう配合される。次いで、溶剤型、無溶剤型のラミネーターによって接着剤組成物を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、常温又は加温下に硬化させる。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。
【００３５】
本発明の接着剤組成物は、従来技術で得られなかったバリア性の高いフィルム同士の貼り合せ後のラミネート外観が優れており、更に、ポリエステル、ポリアミド、ポリエチレン、ポリプロピレン等のプラスチックフィルム、アルミニウム、酸化珪素、酸化アルミニウム等を蒸着したプラスチックフィルム、ステンレス鋼、鉄、銅、鉛等の金属に優れた接着強度、耐熱水性を示す。
【００３６】
【実施例】
次に、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％及び部は、断りがない限りは総て質量基準である。
【００３７】
（合成例１）
イソフタル酸２９５．４ｇ、テレフタル酸２９５．４ｇ、エチレングリコール９１．０ｇ、ネオペンチルグリコール７６．３ｇ、ジエチレングリコール７７．８ｇ、１，６−ヘキサンジオール２３１．０ｇ、トリメチロールプロパン３．３ｇを仕込み、２００〜２３０℃で６時間エステル化反応を行い、所定量の水の留出後、アジピン酸１２９．９ｇを加え、更に２００〜２３０℃で６時間エステル化反応を行い、所定量の水の留出後、テトライソブチルチタネート０．３ｇを添加し徐々に減圧し、１．３〜２．７ｈＰａ、２３０〜２５０℃で６時間エステル交換反応を行い、重量平均分子量１５，０００のポリエステルポリオールを得た。得られたポリエステルポリオール中の官能基を持つ基の含有量は、０．５モル％であった。更にこのポリエステルポリオールを酢酸エチルにて不揮発分６０％に調整した有機ポリオール溶液Ａを得た。
【００３８】
（合成例２）
トリメチロールプロパンの使用量を１０ｇにした以外は、合成例１と同様にして、重量平均分子量２０，０００のポリエステルポリオールを得た。得られたポリエステルポリオール中の官能基を持つ基の含有量は、１．５モル％であった。更にこのポリエステルポリオールを酢酸エチルにて不揮発分６０％に調整した有機ポリオール溶液Ｂを得た。
【００３９】
（合成例３）
トリメチロールプロパンを使用しなかった以外は、合成例１と同様にして、重量平均分子量１４，０００のポリエステルポリオールを得た。更にこのポリエステルポリオールを酢酸エチルにて不揮発分６０％に調整した有機ポリオール溶液Ｃを得た。
【００４０】
（合成例４）
合成例１と同様にして得られたポリエステルポリオール４００ｇに、無水トリメリット酸を９．９ｇ添加し、１８０℃で２時間反応させて、重量平均分子量１８，０００のポリエステルポリオールを得た。更にこのポスエステルポリオールを酢酸エチルにて不揮発分６０％に調整した有機ポリオール溶液Ｄを得た。
【００４１】
（合成例５）
イソフタル酸４６４．１ｇ、エチレングリコール８０．９ｇ、ネオペンチルグリコール２０２．４ｇ、トリメチロールプロパン９．９ｇを仕込み、１６０〜２００℃で６時間エステル化反応を行い、所定量の水の留出後、セバシン酸１９４．１ｇ、アジピン酸５０．９ｇを加え、更に１８０〜２４０℃でエステル化反応を行い、酸価が２０以下になったところで、テトライソブチルチタネート０．３ｇを添加し徐々に減圧し、１．３〜２．７ｈＰａ、２３０〜２５０℃で６時間エステル交換反応を行い、ポリエステルポリオールを得た。このポリエステルポリオール４００ｇに、イソホロンジイソシアネートを２０．０ｇ加え、１５０℃で２時間反応させて、重量平均分子量３７，０００のポリウレタンポリオールを得た。得られたポリウレタンポリオール中の官能基を持つ基の含有量は、１．５モル％であった。更にこのポリウレタンポリオールを酢酸エチルにて不揮発分５０％に調整した有機ポリオール溶液Ｅを得た。
【００４２】
（合成例６）
イソフタル酸１１６．５ｇ、テレフタル酸１１６．５ｇ、エチレングリコール１４８．８ｇを仕込み、２００〜２２０℃で８時間エステル化反応を行い、所定量の水の留出後、アゼライン酸１１２．８ｇを加え、更に２００〜２２０℃で４時間エステル化反応を行った。所定量の水の留出後、テトライソブチルチタネート０．１３ｇを添加し徐々に減圧し、１．３〜２．７ｈＰａ、２３０〜２５０℃で３時間エステル交換反応を行い、重量平均分子量６５，０００のポリエステルポリオールを得た。更にこのポリエステルポリオールを酢酸エチルにて不揮発分４５％に調整した有機ポリオール溶液Ｆを得た。
【００４３】
（実施例１〜６）
有機ポリオール溶液Ａ、Ｂ若しくはＤ、下記に示すシランカップリング剤若しくはリンの酸素酸又は下記に示すシランカップリング剤及びリンの酸素酸並びに下記に示す有機ポリイソシアネートを表１に示す割合で配合すると共に、得られる組成物の不揮発分が３０％となるように酢酸エチルを加えて、接着剤組成物を得た。
【００４４】
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（信越シリコーン社製）
リンの酸素酸：８５％オルトリン酸
有機ポリイソシアネート：ヘキサメチレンジイソシアネートビュレット（住友バイエルウレタン社製）の７５％酢酸エチル希釈品
【００４５】
（比較例１〜４）
有機ポリオール溶液Ｃ、Ｅ若しくはＦ、上記に示すシランカップリング剤及び上記に示す有機ポリイソシアネートを表１に示す割合で配合すると共に、実施例１〜６と同様にして接着剤組成物を得た。
【００４６】
（比較例５）
末端にアミノ基を有するポリウレタン尿素からなる有機ポリオール（商品名：ＡＤ−３９３、東洋モートン社製）１００部とエポキシ樹脂（商品名：ＣＡＴ−ＥＰ１、東洋モートン社製）７．０部を配合した後、得られる組成物の不揮発分が３０％となるように酢酸エチルを加えて、接着剤組成物を得た。
【００４７】
実施例及び比較例で得られた接着剤組成物を各々使用し、下記の方法で複合フィルムを作成した後、得られた各フィルムについて、下記の試験を行い、それらの結果を表２に示した。又、不揮発分を３０％に調整した接着剤組成物を用いて下記の方法で作業性を調べ、それらの結果を表２に示した。
【００４８】
（複合フィルムの作成）
得られた接着剤組成物を用いて、構成１：透明蒸着ポリエチレンテレフタレートフィルム（東洋メタライジング社製、商品名：１０１１ＨＧ、厚さ１２μｍ）／透明蒸着ポリエチレンテレフタレートフィルム（同上、厚さ１２μｍ）、構成２：ナイロンフィルム（ユニチカ社製、商品名：エンブレムＲＴ、厚さ１５μｍ）／インキ（印刷層）／未延伸ポリエチレンフィルム（東セロ社製、商品名：ＴＵＸ−ＴＣＳ、厚さ５０μｍ、表面コロナ放電処理）の各２層複合ラミネート材を以下に記載の方法で作成した。すなわち、構成１の場合、接着剤組成物を常温にてラミネーターにより、まず透明蒸着ポリエチレンテレフタレートフィルムの蒸着面に塗布し、溶剤を含むものはそれを揮散させた後、塗布面を透明蒸着ポリエチレンテレフタレートフィルムの蒸着面と貼り合せた。又、構成２の場合、ナイロンフィルムの印刷層の面に同様に接着剤を塗布し、溶剤を含むものは揮散させ、塗布面に未延伸ポリエチレンフィルムを貼り合せ、所定の温度雰囲気下に一定時間保温し、複合フィルムを作成した。
【００４９】
（バリア構成外観）
構成１の複合ラミネート材の外観を目視で評価した。
（作業性）
Ｎｏ．３ザーンカップ（離合社製）を使用し、２５℃で粘度（秒数）を測定した。秒数が２０秒を超えれば作業性が悪く、２０秒以下であれば作業性は良好と判断される。
【００５０】
（耐熱水性試験）
（１）剥離強度試験
構成２の複合ラミネート材から３００ｍｍ×１５ｍｍの大きさの試験片を作成し、引張り試験機を用い、温度２０℃、相対湿度６５％の条件下、Ｔ型剥離により剥離速度３０ｃｍ／分で、ナイロンフィルムと未延伸ポリエチレンフィルムの間の無地部と印刷層との剥離強度（Ｎ／１５ｍｍ）を測定した。又、構成２の複合ラミネート材を使用して、１４ｃｍ×１８ｃｍの大きさのパウチを作成し、内容物として食酢、サラダ油、ケチャップを重量比で１：１：１に配合した擬似食品２００ｇを真空充填した。このパウチを９８℃の熱水中で３０分間加熱殺菌した（ボイル）後、上記と同様にして、剥離強度を測定した。表２の数値は、５個の試験片の平均値である。
【００５１】
（２）剥離状態観察試験
上記（１）と同様にして擬似食品を充填し、９８℃の熱水中で３０分間加熱殺菌したパウチについて、ナイロンフィルムと未延伸ポリエチレンフィルム間の剥離状態を観察した。表２において、○は剥離なし、△は部分剥離、×は完全剥離をそれぞれ示す。
【００５２】
【表１】
【表２】
表２から、本発明の組成物は、ガスバリア性の高いフィルム同士の複合ラミネートフィルム用接着剤として仕上がり外観、接着性の点で優れていることが判る。
【００５５】
【発明の効果】
本発明の組成物は、例えばガスバリア性の高いフィルム同士のラミネートにおいても、ラミネートフィルム積層体の外観が良好で、かつアルミニウムのような金属箔と、ポリエステル、ナイロン、ポリエチレン、ポリプロピレン等のプラスチックフィルムの間で優れた接着力、耐熱水性を示し、接着性が十分な包装材が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a urethane-based adhesive composition, and more specifically, urethane-based for laminated composite film composed of various plastic films, metal foils, metal-deposited films, etc. that have excellent hot water resistance, workability, and good appearance. The present invention relates to an adhesive composition.
[0002]
[Prior art]
Conventionally, as a packaging material for foods, medical products, cosmetics, etc., a multilayer composite film in which a plastic film such as polyethylene, polypropylene, nylon, and polyester, a metal vapor deposition film, and a metal foil such as an aluminum foil are laminated is widely used. Yes. A urethane-based adhesive in which an organic polyol and an organic isocyanate are combined to bond these plastic films, metal vapor deposition films, metal foils, and the like is known. In recent years, as an environmentally friendly film, there is a gas barrier film in which a plastic film is coated with polyvinylidene chloride (PVDC). As an alternative film, a metal oxide such as silica or alumina is used as a plastic film such as a polyester film or a polyamide film. There has been an increase in the number of transparent deposited films deposited on the surface. In addition, in order to ensure the same gas barrier properties as those of conventional metal foils such as aluminum, movements to keep the gas barrier properties, incense retention, etc. obtained by laminating these transparent deposited films have been activated.
[0003]
However, urethane adhesives are often used as adhesives to laminate them, but when these films with high gas barrier properties are laminated with conventional urethane adhesives, free organic substances present in the urethane adhesives are used. Carbon dioxide gas generated by the reaction between polyisocyanate and water may accumulate at the film interface, resulting in poor appearance due to bubbles. Therefore, in order to improve these, a method of reducing the generation rate of carbon dioxide gas by using a urethane-based adhesive produced by reducing the blending ratio of the organic polyisocyanate to the organic polyol is employed. However, this method has a disadvantage that the amount of organic polyisocyanate is insufficient and satisfactory adhesion, heat resistance, water resistance and the like cannot be obtained. There is also a method of reducing the amount of organic polyisocyanate to be used by increasing the molecular weight of the organic polyol and reducing the hydroxyl group content. However, this method increases the molecular weight of the organic polyol, which increases the solution viscosity when using the adhesive, which may be disadvantageous in terms of coating properties and workability. Furthermore, when a cured form-type amine-epoxy curable adhesive that does not generate carbon dioxide gas is used, a good laminate appearance is obtained, but heat resistance, water resistance, etc. are insufficient.
[0004]
In addition, in order to solve the above drawbacks, for example, there is a proposal (Japanese Patent Laid-Open No. 2000-7748) using a polyfunctional polyurethaneurea polyol resin composition. However, when laminating films having high gas barrier properties, performance is improved. The current situation is that the above-mentioned drawbacks cannot be solved with the conventionally known urethane adhesives.
[Patent Document 1]
JP 2000-7748 A
[0005]
[Problems to be solved by the invention]
When laminating films having high gas barrier properties, the present invention provides a urethane-based adhesive composition that is excellent in adhesiveness between laminate films and that the resulting laminate film laminate can exhibit a good appearance. Objective.
[0006]
[Means for Solving the Problems]
As a result of various studies to solve the above problems, the present inventors have found that a composition comprising an organic polyol having a branched polyfunctional group and an organic polyisocyanate can achieve the object of the present invention. We found out and reached the present invention.
[0007]
That is, the gist of the present invention is an urethane-based adhesive composition containing as an essential component an organic polyol in which a group having a functional group derived from a polyol having three or more hydroxyl groups is branched and bonded, and an organic polyisocyanate. .
[0008]
In addition, the composition of the present invention is characterized by further containing a silane coupling agent and / or phosphorus oxyacid or a derivative thereof as an essential component.
The composition of the present invention is characterized in that the content of the group having the functional group in the organic polyol is 10 mol% or less.
[0009]
Furthermore, the gist of the present invention is a urethane adhesive composition for food packaging laminate.
[0010]
Furthermore, the gist of the present invention is a laminate film laminate formed by bonding with the above urethane-based adhesive composition.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
As the organic polyol used in the present invention, the number of functional groups in one molecule is about 2 to 6, preferably about 2 to 4, and the number average molecular weight is about 500 to 100,000, preferably 1,000 to 30,000. The compound of this is mentioned. More specifically, a polyester polyol, a polyether polyol, a polyether ester polyol, a polyurethane polyol, a polyester amide polyol, a polycarbonate polyol or a mixture thereof can be mentioned.
[0012]
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, neo Diols 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 a mixture The polyester polyol obtained in this way is mentioned.
[0013]
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.
[0014]
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.
[0015]
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 obtained by reacting at less than 1, preferably 0.9 or less. Examples of organic polyisocyanates that can be used include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, Aliphatic diisocyanates such as 2,4,4- or 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), methyl 2,4-cyclohexanedi Alicyclic diisocyanates such as cyanate, methyl 2,6-cyclohexane diisocyanate, 1,4-bis (isocyanate methyl) cyclohexane, 1,3-bis (isocyanate methyl) cyclohexane, m-phenylene diisocyanate, p-phenylene diisocyanate, 4, 4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4'-toluidine diisocyanate, dianisidine diisocyanate, 4 Aromatic diisocyanates such as 4,4'-diphenyl ether diisocyanate, 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω'-diisocyanate Aromatic aliphatic diisocyanates such as 1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene or mixtures thereof, triphenylmethane-4,4 ', 4 "-tri Isocyanates, organic triisocyanates such as 1,3,5-triisocyanate benzene, 2,4,6-triisocyanate toluene, 4,4'-diphenyldimethylmethane-2,2'-5,5'-tetraisocyanate, etc. 2,4,6-Oxadia obtained from polyisocyanate monomer such as organic tetraisocyanate, dimer, trimer, biuret, allophanate, carbon dioxide gas and polyisocyanate monomer derived from polyisocyanate monomer Adducts with polyisocyanates having a gintrione ring It is.
[0016]
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.
[0017]
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 Examples thereof include those obtained by reacting two or more diols with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene and the like.
[0018]
The organic polyol used in the present invention is one in which a group having a functional group derived from a polyol having three or more hydroxyl groups is branched and bonded. Examples of the functional group include oxygen-containing groups such as a hydroxyl group, an ester group, an ether group, and a carbonyl group. The content of the group having a functional group derived from the polyol in the organic polyol is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 3 mol% or less.
[0019]
Examples of the polyol having three or more hydroxyl groups include glycerin, trimethylolpropane, pentaerythritol and the like. The organic polyol in which the group having a functional group is branched and bonded is reacted by mixing the polyol having three or more hydroxyl groups with the diol or a mixture thereof when preparing the organic polyol. In addition, it can be produced by reacting the above organic polyol with the above polyol having three or more hydroxyl groups.
[0020]
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) that can be used in the present invention is desirably obtained by reacting the organic polyol with a polybasic acid or an anhydride thereof. As the organic polyol used at this time, those having two or more hydroxyl groups at the molecular terminals and having a number average molecular weight of 1,000 to 100,000, preferably 3,000 to 15,000 are preferably used. If it is 1,000 or less, the cohesive force is insufficient, and if it is 100,000 or more, it is difficult to react a polybasic acid or its anhydride at the terminal for synthesis, and there is a possibility of significant thickening or gelation.
[0021]
Examples of the polybasic acid or anhydride thereof include aromatic polybasic acids such as phthalic acid, trimellitic acid, and pyromellitic acid, and anhydrides thereof. Phthalic anhydride that is an anhydride thereof, Trimellitic anhydride, pyromellitic anhydride and the like are particularly suitable. In addition, ethylene glycol bisanhydro trimellitate, glycerin tris anhydro trimellitate, ethylene glycol bis anhydro pyromellitate, glycerin tris anhydro pyromellitate derived from these anhydrides, and rosin component abietic acid Or C 10 H 16 Diene compounds and derivatives obtained by adding maleic anhydride to a mixture of these may be used.
[0022]
The organic polyol (2) is prepared by adding a polybasic acid or an anhydride thereof, preferably a polybasic acid anhydride under heating after the synthesis of the organic polyol. It is possible to obtain an acid and a polyhydric alcohol containing a carboxyl group in the molecule or at the molecule end in one step. The reaction with these polybasic acids or polybasic acid anhydrides has an accelerating effect to improve the adhesive performance of the adhesive composition according to the present invention, such as hot water resistance, oil resistance, acid resistance and the like. The reaction between the organic polyol and the polybasic acid or polybasic acid anhydride is performed at a reaction temperature of 200 ° C. or less, preferably so that the esterification reaction by the ring-opening reaction of the polybasic acid or polybasic acid anhydride becomes the main reaction It is necessary to control in the range of 150-180 degreeC.
[0023]
As organic polyisocyanate used by this invention, it can select from the said organic polyisocyanate which can be used when preparing the polyurethane polyol in the said organic polyol.
[0024]
As the silane coupling agent used in the present invention, any one represented by the following general formula (I) or (II) can be used.
[0025]
R-Si≡X 3 (I)
R-Si≡R 1 X 2 (II)
In the formula, R represents an organic group having a vinyl group, an epoxy group, an amino group, an imino group, or a mercapto group, 1 Represents a lower alkyl group, and X represents a methoxy group, an ethoxy group or a chlorine atom. Examples of the silane coupling agent include chlorosilanes such as vinyltrichlorosilane, aminosilanes such as N- (dimethoxymethylsilylpropyl) ethylenediamine and N- (triethoxysilylpropyl) ethylenediamine, γ-glycidoxypropyltrimethoxysilane, γ -Epoxy silanes such as glycidoxypropyltriethoxysilane, vinyl silanes such as vinyl triethoxysilane, and the like.
[0026]
The phosphorus oxygen acid or derivative thereof used in the present invention 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 hypophosphoric acid, and condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid. Examples of the phosphorus oxyacid derivative include those obtained by partially esterifying the phosphorus oxyacid with alcohols in a state where at least one free oxyacid is left. 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. The oxygen acid of phosphorus or a derivative thereof is not limited to one type, and two or more types can be used.
[0027]
In the adhesive composition of the present invention, the organic polyol can be mixed with the silane coupling agent, the oxygen acid of phosphorus or a derivative thereof, but the organic polyol and the silane coupling agent or the oxygen acid of phosphorus or the When mixing the derivatives, they may simply be mixed, but it is desirable to mix them in the presence of an organic solvent. Any organic 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. .
[0028]
The amount of the silane coupling agent used is preferably in the range of 0.1 to 5% by mass with respect to the adhesive composition. If the amount used is less than 0.1% by mass, the adhesiveness to a metal foil such as an aluminum foil is insufficient, and if it exceeds 5% by mass, the cohesive force of the adhesive is lowered and the heat resistance is lowered. The oxygen acid of phosphorus or its derivative is 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.1 to 1% by weight, based on the adhesive composition. Used. If the amount used is less than 0.01% by mass, the acid resistance on the inner layer side of the metal foil such as aluminum foil becomes insufficient, and if it exceeds 10% by mass, the water resistance on the inner layer side and the outer layer side of the metal foil such as aluminum foil The property becomes insufficient.
[0029]
The adhesive composition of the present invention can further contain an epoxy resin as necessary. Examples of the epoxy resin used include diphenolmethane (bisphenol F), diphenolethane, diphenolpropane (bisphenol A), polyvinylphenol, polyisopropenylphenol, bisphenol tetrabromide A, 1,1-bis- ( Epoxy compounds derived from 4-hydroxyphenyl) -1-phenylethane, 1,1-bis- (4-hydroxyphenyl) -1,1-dimethylmethane, etc .; phenol novolak, brominated phenol novolak, cresol novolak, bromine Novolak resins derived from cresol novolak, resorcin novolak, brominated resorcin novolak, etc .; polyhydric phenol epoxy trees derived from resorcin, hydroquinone, methylresorcin, bisphenol A tetrachloride, etc. An amine-based epoxy resin derived from aniline, p-aminophenol, m-aminophenol, p-amino-m-cresol, 4,4′-diaminodiphenylmethane, etc .; p-oxybenzoic acid, m-oxybenzoic acid, Glycidyl ester compounds derived from aromatic carboxylic acids such as terephthalic acid and isophthalic acid; Hydantoin epoxy resins derived from 5,5′-dimethylhydantoin and the like; 2,2′-bis (4- (3,4) -Alicyclic epoxy resins such as epoxycyclohexyl) propane, 2,2'-bis (4- (2,3-epoxycyclohexyl) propane, vinylcyclohexene oxide; and others such as triglycidyl isocyanurate, 2,4,6- And triglycidoxy-5-triazine, etc. It is also possible to use dimer acid-modified epoxy resins, urethane-modified epoxy resins, etc., hydrogenated bisphenol A-type epoxy resins that are hydrogenated products of bisphenol A-type epoxy resins, etc. Two or more of the above epoxy resins may be used. .
[0030]
The above epoxy resins are commercially available, and can be appropriately selected from those commercially available products as necessary. Specific examples of commercially available products include, for example, manufactured by Yuka Shell Epoxy Co., Ltd., trade name: Epicoat 1002 (bisphenol A type epoxy resin); manufactured by Toto Kasei Co., Ltd., trade name: ST-3000 (hydrogenated bisphenol A type epoxy resin). Manufactured by Toto Kasei Co., Ltd., trade name: YD-172 (dimer acid-modified epoxy resin) and the like. Of course, it is needless to say that the present invention is not limited to these.
[0031]
Moreover, for the purpose of reducing the viscosity of these epoxy resins, a small amount of a low molecular weight epoxy compound such as butyl glycidyl ether having an epoxy group in the molecule can be blended, and the resulting adhesive The viscosity can be adjusted. An epoxy resin is mix | blended in the range used as 1-50 mass% with respect to adhesive composition, Preferably it is 1-30 mass%.
[0032]
The adhesive composition of the present invention can be produced by blending the above-mentioned components, and further includes, for example, an antioxidant, an ultraviolet absorber, a hydrolysis inhibitor, an antifungal agent, a thickener, a plasticizer. Additives such as agents, pigments, fillers and antifoaming agents can be blended as necessary. In addition, known catalysts, additives and the like can be used to control the curing reaction.
[0033]
When the adhesive composition of the present invention is used, the viscosity is from normal temperature to 150 ° C., preferably from normal temperature to 100 ° C., 100 to 10,000 mPa · s, preferably 100 to 5,000 mPa · s. It can be used in a solvent type. When the viscosity of the composition is higher than the above range, it may be diluted with an organic solvent. Any organic solvent may be used as necessary 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.
[0034]
As a specific prescription using the adhesive composition of the present invention, an organic polyol and an organic polyisocyanate are combined. When an organic polyol has a hydroxyl group and further a carboxyl group, the organic polyisocyanate is added to the total of them. It mix | blends so that group may become 1.0-5.0 times by equivalent ratio. Next, the adhesive composition is applied to the film surface with a solvent-type or solvent-free laminator, and in the case of the solvent type, the solvent is volatilized. Harden. Normally, in the solventless type, the coating amount is 1.0 to 2.0 g / m in dry solid amount. 2 In the solvent type, the dry solid content is 2.0 to 5.0 g / m. 2 It is convenient to use in the range of.
[0035]
The adhesive composition of the present invention has an excellent laminate appearance after bonding of films having a high barrier property that could not be obtained by the prior art, and further, plastic films such as polyester, polyamide, polyethylene, and polypropylene, aluminum, Excellent adhesion strength and hot water resistance for plastic films deposited with silicon oxide, aluminum oxide, etc., stainless steel, iron, copper, lead and other metals.
[0036]
【Example】
Next, the present invention will be described more specifically with reference to examples and comparative examples. All percentages and parts in Examples and Comparative Examples are based on mass unless otherwise specified.
[0037]
(Synthesis Example 1)
295.4 g of isophthalic acid, 295.4 g of terephthalic acid, 91.0 g of ethylene glycol, 76.3 g of neopentyl glycol, 77.8 g of diethylene glycol, 231.0 g of 1,6-hexanediol, and 3.3 g of trimethylolpropane were charged. Perform esterification reaction at ˜230 ° C. for 6 hours, distill a predetermined amount of water, add 129.9 g of adipic acid, and further carry out esterification reaction at 200-230 ° C. for 6 hours to distill a predetermined amount of water. Thereafter, 0.3 g of tetraisobutyl titanate was added and the pressure was gradually reduced, and a transesterification reaction was performed at 1.3 to 2.7 hPa and 230 to 250 ° C. for 6 hours to obtain a polyester polyol having a weight average molecular weight of 15,000. The content of the group having a functional group in the obtained polyester polyol was 0.5 mol%. Further, an organic polyol solution A in which this polyester polyol was adjusted to 60% nonvolatile content with ethyl acetate was obtained.
[0038]
(Synthesis Example 2)
A polyester polyol having a weight average molecular weight of 20,000 was obtained in the same manner as in Synthesis Example 1, except that the amount of trimethylolpropane used was 10 g. The content of the group having a functional group in the obtained polyester polyol was 1.5 mol%. Further, an organic polyol solution B in which this polyester polyol was adjusted to 60% nonvolatile content with ethyl acetate was obtained.
[0039]
(Synthesis Example 3)
A polyester polyol having a weight average molecular weight of 14,000 was obtained in the same manner as in Synthesis Example 1 except that trimethylolpropane was not used. Furthermore, an organic polyol solution C in which this polyester polyol was adjusted to 60% nonvolatile content with ethyl acetate was obtained.
[0040]
(Synthesis Example 4)
To 400 g of the polyester polyol obtained in the same manner as in Synthesis Example 1, 9.9 g of trimellitic anhydride was added and reacted at 180 ° C. for 2 hours to obtain a polyester polyol having a weight average molecular weight of 18,000. Further, an organic polyol solution D in which the posester polyol was adjusted to 60% nonvolatile content with ethyl acetate was obtained.
[0041]
(Synthesis Example 5)
464.1 g of isophthalic acid, 80.9 g of ethylene glycol, 202.4 g of neopentyl glycol, and 9.9 g of trimethylolpropane are charged, and esterification is performed at 160 to 200 ° C. for 6 hours. After distilling a predetermined amount of water, 194.1 g of sebacic acid and 50.9 g of adipic acid were added, and further an esterification reaction was performed at 180 to 240 ° C. When the acid value became 20 or less, 0.3 g of tetraisobutyl titanate was added and the pressure was gradually reduced. A transesterification reaction was performed at 1.3 to 2.7 hPa and 230 to 250 ° C. for 6 hours to obtain a polyester polyol. 20.0 g of isophorone diisocyanate was added to 400 g of this polyester polyol and reacted at 150 ° C. for 2 hours to obtain a polyurethane polyol having a weight average molecular weight of 37,000. The content of the group having a functional group in the obtained polyurethane polyol was 1.5 mol%. Further, an organic polyol solution E in which this polyurethane polyol was adjusted to 50% nonvolatile content with ethyl acetate was obtained.
[0042]
(Synthesis Example 6)
116.5 g of isophthalic acid, 116.5 g of terephthalic acid, and 148.8 g of ethylene glycol are charged, and esterification is performed at 200 to 220 ° C. for 8 hours. After distilling a predetermined amount of water, 112.8 g of azelaic acid is added, Furthermore, esterification was performed at 200 to 220 ° C. for 4 hours. After distilling a predetermined amount of water, 0.13 g of tetraisobutyl titanate was added and the pressure was gradually reduced, and a transesterification reaction was performed at 1.3 to 2.7 hPa and 230 to 250 ° C. for 3 hours to obtain a weight average molecular weight of 65,000. The polyester polyol was obtained. Further, an organic polyol solution F in which the polyester polyol was adjusted to 45% nonvolatile content with ethyl acetate was obtained.
[0043]
(Examples 1-6)
The organic polyol solution A, B or D, the silane coupling agent or phosphorus oxygen acid shown below, or the following silane coupling agent and phosphorus oxygen acid and the organic polyisocyanate shown below are blended in the proportions shown in Table 1. At the same time, ethyl acetate was added so that the non-volatile content of the obtained composition was 30% to obtain an adhesive composition.
[0044]
Silane coupling agent: γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone)
Oxygen acid of phosphorus: 85% orthophosphoric acid
Organic polyisocyanate: Diluted 75% ethyl acetate of hexamethylene diisocyanate burette (manufactured by Sumitomo Bayer Urethane Co., Ltd.)
[0045]
(Comparative Examples 1-4)
The organic polyol solution C, E or F, the silane coupling agent shown above, and the organic polyisocyanate shown above were blended in the proportions shown in Table 1, and an adhesive composition was obtained in the same manner as in Examples 1-6. .
[0046]
(Comparative Example 5)
100 parts of an organic polyol (trade name: AD-393, manufactured by Toyo Morton Co., Ltd.) made of polyurethane urea having an amino group at the terminal and 7.0 parts of an epoxy resin (trade name: CAT-EP1, manufactured by Toyo Morton Co., Ltd.) were blended. Then, ethyl acetate was added so that the non volatile matter of the obtained composition might be 30%, and the adhesive composition was obtained.
[0047]
Each of the adhesive compositions obtained in Examples and Comparative Examples was used, and after making a composite film by the following method, each film obtained was subjected to the following test, and the results are shown in Table 2. It was. Moreover, workability | operativity was investigated by the following method using the adhesive composition which adjusted the non volatile matter to 30%, and those results were shown in Table 2.
[0048]
(Create composite film)
Using the obtained adhesive composition, constitution 1: transparent vapor-deposited polyethylene terephthalate film (manufactured by Toyo Metallizing Co., Ltd., trade name: 1011HG, thickness 12 μm) / transparent vapor-deposited polyethylene terephthalate film (same as above, thickness 12 μm), constitution 2: Nylon film (manufactured by Unitika, trade name: Emblem RT, thickness 15 μm) / ink (printing layer) / unstretched polyethylene film (trade name: TUX-TCS, thickness 50 μm, surface corona discharge treatment, manufactured by Tosero) Each of the two-layer composite laminate materials was prepared by the method described below. That is, in the case of configuration 1, the adhesive composition is first applied to the vapor-deposited surface of the transparent vapor-deposited polyethylene terephthalate film at room temperature with a laminator. The film was bonded to the vapor deposition surface. In the case of configuration 2, similarly, an adhesive is applied to the surface of the nylon film printed layer, the solvent-containing material is volatilized, an unstretched polyethylene film is bonded to the coated surface, and a predetermined temperature is maintained for a certain period of time. Insulated to create a composite film.
[0049]
(Barrier configuration appearance)
The appearance of the composite laminate material of Configuration 1 was visually evaluated.
(Workability)
No. The viscosity (seconds) was measured at 25 ° C. using a 3 Zahn cup (manufactured by Koseisha). If the number of seconds exceeds 20 seconds, workability is poor, and if it is 20 seconds or less, workability is determined to be good.
[0050]
(Heat resistance test)
(1) Peel strength test
A test piece having a size of 300 mm × 15 mm was prepared from the composite laminate material of configuration 2, and nylon was peeled off at 30 cm / min by T-type peeling under a condition of a temperature of 20 ° C. and a relative humidity of 65% using a tensile tester. The peel strength (N / 15 mm) between the plain portion between the film and the unstretched polyethylene film and the printed layer was measured. Also, using the composite laminate material of Configuration 2, create a 14cm x 18cm size pouch, vacuum 200g of simulated foods containing vinegar, salad oil, and ketchup in a 1: 1: 1 ratio by weight. Filled. This pouch was sterilized by heating in 98 ° C. hot water for 30 minutes (boiled), and the peel strength was measured in the same manner as described above. The numerical values in Table 2 are average values of five test pieces.
[0051]
(2) Peeling state observation test
The peeled state between the nylon film and the unstretched polyethylene film was observed for the pouch filled with the pseudo food as in the above (1) and sterilized by heating in 98 ° C. hot water for 30 minutes. In Table 2, o indicates no peeling, Δ indicates partial peeling, and x indicates complete peeling.
[0052]
[Table 1]
[Table 2]
From Table 2, it can be seen that the composition of the present invention is excellent in terms of finished appearance and adhesiveness as an adhesive for composite laminate films between films having high gas barrier properties.
[0055]
【The invention's effect】
The composition of the present invention has a good appearance of a laminate film laminate, for example, even when laminating films having high gas barrier properties, and a metal foil such as aluminum and plastic films such as polyester, nylon, polyethylene, and polypropylene. A packaging material exhibiting excellent adhesive strength and hot water resistance and having sufficient adhesiveness can be obtained.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2003078393A JP4420375B2 (en) | 2003-03-20 | 2003-03-20 | Laminate film laminate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003078393A JP4420375B2 (en) | 2003-03-20 | 2003-03-20 | Laminate film laminate |
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| JP2004285183A true JP2004285183A (en) | 2004-10-14 |
| JP4420375B2 JP4420375B2 (en) | 2010-02-24 |
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| JP2003078393A Expired - Lifetime JP4420375B2 (en) | 2003-03-20 | 2003-03-20 | Laminate film laminate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008156502A (en) * | 2006-12-25 | 2008-07-10 | Hitachi Kasei Polymer Co Ltd | Two-part curing type adhesive |
| JP2009248454A (en) * | 2008-04-07 | 2009-10-29 | Dainippon Printing Co Ltd | Gas-barrier laminate and packaging container |
| EP2289983A1 (en) | 2009-09-01 | 2011-03-02 | Fujifilm Corporation | Composite film |
| JP2011083912A (en) * | 2009-10-13 | 2011-04-28 | Fujicopian Co Ltd | Hard coat layer transfer sheet |
| JP2011184602A (en) * | 2010-03-10 | 2011-09-22 | Toyo Ink Sc Holdings Co Ltd | Adhesive for lamination and method for producing the same |
| JP2013043936A (en) * | 2011-08-24 | 2013-03-04 | Dic Corp | Resin composition for solventless adhesive and adhesive |
| JP6416450B1 (en) * | 2017-02-06 | 2018-10-31 | ユニチカ株式会社 | Polyester resin composition, adhesive and laminate |
| WO2019116903A1 (en) * | 2017-12-12 | 2019-06-20 | Dic株式会社 | Solventless lamination adhesive, cured product therefrom, laminate, and packaging body |
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| JPH08183829A (en) * | 1994-12-28 | 1996-07-16 | Takeda Chem Ind Ltd | Polyurethane adhesive composition |
| JP2000063790A (en) * | 1998-08-20 | 2000-02-29 | Dainichiseika Color & Chem Mfg Co Ltd | Adhesive composition for pouch |
| JP2002069291A (en) * | 2000-08-24 | 2002-03-08 | Mitsui Takeda Chemicals Inc | Rigid urethane resin composition for coated flooring |
| JP2002249745A (en) * | 2001-02-27 | 2002-09-06 | Mitsui Takeda Chemicals Inc | Two-part curable solventless adhesive composition |
| JP2002275447A (en) * | 2001-03-16 | 2002-09-25 | Toyobo Co Ltd | Adhesive for inorganic vapor-deposited film |
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| JPS5490239A (en) * | 1977-12-27 | 1979-07-17 | Takeda Chem Ind Ltd | Adhesive composition for plastic/metal foil composite packaging material |
| JPH08183829A (en) * | 1994-12-28 | 1996-07-16 | Takeda Chem Ind Ltd | Polyurethane adhesive composition |
| JP2000063790A (en) * | 1998-08-20 | 2000-02-29 | Dainichiseika Color & Chem Mfg Co Ltd | Adhesive composition for pouch |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008156502A (en) * | 2006-12-25 | 2008-07-10 | Hitachi Kasei Polymer Co Ltd | Two-part curing type adhesive |
| JP2009248454A (en) * | 2008-04-07 | 2009-10-29 | Dainippon Printing Co Ltd | Gas-barrier laminate and packaging container |
| EP2289983A1 (en) | 2009-09-01 | 2011-03-02 | Fujifilm Corporation | Composite film |
| JP2011083912A (en) * | 2009-10-13 | 2011-04-28 | Fujicopian Co Ltd | Hard coat layer transfer sheet |
| JP2011184602A (en) * | 2010-03-10 | 2011-09-22 | Toyo Ink Sc Holdings Co Ltd | Adhesive for lamination and method for producing the same |
| JP2013043936A (en) * | 2011-08-24 | 2013-03-04 | Dic Corp | Resin composition for solventless adhesive and adhesive |
| JP6416450B1 (en) * | 2017-02-06 | 2018-10-31 | ユニチカ株式会社 | Polyester resin composition, adhesive and laminate |
| WO2019116903A1 (en) * | 2017-12-12 | 2019-06-20 | Dic株式会社 | Solventless lamination adhesive, cured product therefrom, laminate, and packaging body |
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| JP4420375B2 (en) | 2010-02-24 |
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