JP6747900B2 - High solid adhesive composition - Google Patents
High solid adhesive composition Download PDFInfo
- Publication number
- JP6747900B2 JP6747900B2 JP2016146345A JP2016146345A JP6747900B2 JP 6747900 B2 JP6747900 B2 JP 6747900B2 JP 2016146345 A JP2016146345 A JP 2016146345A JP 2016146345 A JP2016146345 A JP 2016146345A JP 6747900 B2 JP6747900 B2 JP 6747900B2
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- Japan
- Prior art keywords
- acid
- mass
- parts
- content
- polyester polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000007787 solid Substances 0.000 title claims description 41
- 230000001070 adhesive effect Effects 0.000 title claims description 39
- 239000000853 adhesive Substances 0.000 title claims description 38
- 239000000203 mixture Substances 0.000 title claims description 17
- 229920005906 polyester polyol Polymers 0.000 claims description 27
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 22
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 22
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- 239000005056 polyisocyanate Substances 0.000 claims description 20
- 229920001228 polyisocyanate Polymers 0.000 claims description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 150000005846 sugar alcohols Polymers 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 239000005022 packaging material Substances 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000002453 shampoo Substances 0.000 claims description 4
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 125000005442 diisocyanate group Chemical group 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims 2
- 229920006267 polyester film Polymers 0.000 claims 2
- -1 polyethylene Polymers 0.000 claims 2
- 229920000573 polyethylene Polymers 0.000 claims 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 18
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 12
- 229920005862 polyol Polymers 0.000 description 12
- 150000003077 polyols Chemical class 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 239000001361 adipic acid Substances 0.000 description 8
- 235000011037 adipic acid Nutrition 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 229920001296 polysiloxane Polymers 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 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
- 239000000565 sealant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- KIJDMKUPUUYDLN-UHFFFAOYSA-N 2,2-dimethyl-4-trimethoxysilylbutan-1-amine Chemical compound CO[Si](OC)(OC)CCC(C)(C)CN KIJDMKUPUUYDLN-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- QCYAJCGCGWQKJT-UHFFFAOYSA-N 2-[3-(2-hydroxyethyl)phenyl]ethanol Chemical compound OCCC1=CC=CC(CCO)=C1 QCYAJCGCGWQKJT-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 1
- ZPQAUEDTKNBRNG-UHFFFAOYSA-N 2-methylprop-2-enoylsilicon Chemical compound CC(=C)C([Si])=O ZPQAUEDTKNBRNG-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- IFAPXTBWPQMLAF-UHFFFAOYSA-N 3-(diethoxymethylsilyl)-N-ethyl-2-methylpropan-1-amine Chemical compound CCNCC(C)C[SiH2]C(OCC)OCC IFAPXTBWPQMLAF-UHFFFAOYSA-N 0.000 description 1
- OZFSDOFRXYCNKS-UHFFFAOYSA-N 3-[diethoxy(1-phenylpropan-2-yloxy)silyl]-n-ethenylpropan-1-amine Chemical compound C=CNCCC[Si](OCC)(OCC)OC(C)CC1=CC=CC=C1 OZFSDOFRXYCNKS-UHFFFAOYSA-N 0.000 description 1
- XDFJBMAPHNLKKR-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]-n-ethyl-2-methylpropan-1-amine Chemical compound CCNCC(C)C[Si](C)(OC)OC XDFJBMAPHNLKKR-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- TUZMHNASXCXMBO-UHFFFAOYSA-N 3-methylpentane-2,2-diol Chemical compound CCC(C)C(C)(O)O TUZMHNASXCXMBO-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- OXKAXHPVFLEQHV-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropan-1-amine Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCN OXKAXHPVFLEQHV-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 1
- QLIQIXIBZLTPGQ-UHFFFAOYSA-N 4-(2-hydroxyethoxy)benzoic acid Chemical compound OCCOC1=CC=C(C(O)=O)C=C1 QLIQIXIBZLTPGQ-UHFFFAOYSA-N 0.000 description 1
- RSCUJJZVNRPPQH-UHFFFAOYSA-N 4-(dimethoxymethylsilyl)-2,2-dimethylbutan-1-amine Chemical compound COC(OC)[SiH2]CCC(C)(C)CN RSCUJJZVNRPPQH-UHFFFAOYSA-N 0.000 description 1
- KNYSNQHOKNRINQ-UHFFFAOYSA-N 4-(dimethoxymethylsilyl)-N-ethyl-2,2-dimethylbutan-1-amine Chemical compound CCNCC(C)(C)CC[SiH2]C(OC)OC KNYSNQHOKNRINQ-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical class OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- LNGJOYPCXLOTKL-UHFFFAOYSA-N cyclopentane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C1 LNGJOYPCXLOTKL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SAMYCKUDTNLASP-UHFFFAOYSA-N hexane-2,2-diol Chemical compound CCCCC(C)(O)O SAMYCKUDTNLASP-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- AMVXVPUHCLLJRE-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)hexane-1,6-diamine Chemical compound CO[Si](OC)(OC)CCCNCCCCCCN AMVXVPUHCLLJRE-UHFFFAOYSA-N 0.000 description 1
- NHBRUUFBSBSTHM-UHFFFAOYSA-N n'-[2-(3-trimethoxysilylpropylamino)ethyl]ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCNCCN NHBRUUFBSBSTHM-UHFFFAOYSA-N 0.000 description 1
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 description 1
- JHIJIKGKJSBSKN-UHFFFAOYSA-N n'-[3-tri(propan-2-yloxy)silylpropyl]ethane-1,2-diamine Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCNCCN JHIJIKGKJSBSKN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- CLYWMXVFAMGARU-UHFFFAOYSA-N n-benzyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCNCC1=CC=CC=C1 CLYWMXVFAMGARU-UHFFFAOYSA-N 0.000 description 1
- SWPRLROHVKTMPN-UHFFFAOYSA-N n-butyl-2-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CCCCNCC(C)C[Si](OC)(OC)OC SWPRLROHVKTMPN-UHFFFAOYSA-N 0.000 description 1
- YJOGKUUQSLYPQJ-UHFFFAOYSA-N n-ethyl-2,2-dimethyl-4-trimethoxysilylbutan-1-amine Chemical compound CCNCC(C)(C)CC[Si](OC)(OC)OC YJOGKUUQSLYPQJ-UHFFFAOYSA-N 0.000 description 1
- PNAUMDBGSPRGCS-UHFFFAOYSA-N n-ethyl-2-methyl-3-triethoxysilylpropan-1-amine Chemical compound CCNCC(C)C[Si](OCC)(OCC)OCC PNAUMDBGSPRGCS-UHFFFAOYSA-N 0.000 description 1
- FRDNYWXDODPUJV-UHFFFAOYSA-N n-ethyl-2-methyl-3-trimethoxysilylpropan-1-amine Chemical compound CCNCC(C)C[Si](OC)(OC)OC FRDNYWXDODPUJV-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- VAWFFNJAPKXVPH-UHFFFAOYSA-N naphthalene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(C(=O)O)=CC=C21 VAWFFNJAPKXVPH-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 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
- 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
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、ラミネート用接着剤として用いられるハイソリッド型接着剤に関する。 The present invention relates to a high solid type adhesive used as an adhesive for lamination.
軟包装材には様々な用途があるが、その中でも高い接着物性を要求されるのが、洗剤、シャンプー、リンス等の詰め替えスタンディングパウチ用の包装材である。これらの内容物には、油分、界面活性剤の他、低分子量の香料が使用されており、これが接着剤層を侵してデラミネーション等の不良に繋がり、問題となっていた。 Soft packaging materials have various uses, and among them, the ones that require high adhesive properties are packaging materials for refillable standing pouches such as detergents, shampoos and conditioners. In addition to oils and surfactants, low-molecular-weight fragrances are used in these contents, which has been a problem since it attacks the adhesive layer and leads to defects such as delamination.
従来日本国内では、シャンプー、リンス等では諸外国と比較し香りが少ないものが好まれていたが、近年消費者の嗜好が変わり、より香りの強い物を求める傾向が出てきた。そのため、外資系メーカーを中心に諸外国と同様に香りが強いものを製造してきており、従来の包装材では包装材に浸透してくる内容物に対するラミネート用接着剤の耐性(耐内容物性)が不足する結果となっている。 Conventionally, in Japan, shampoos, rinses, etc. were preferred to have less fragrance than those in other countries, but in recent years, consumers' taste has changed, and there is a tendency to demand more fragrant products. For this reason, foreign-affiliated manufacturers are mainly producing products with a strong fragrance as in other countries, and conventional packaging materials have a resistance (content resistance) of the laminating adhesive to the contents that permeate the packaging materials. The result is lacking.
一方、包装材のコスト削減の要求、環境への配慮、作業環境改善のため、接着剤のハイソリッド化による溶剤使用量削減が可能な包装材が求められている。
接着剤のハイソリッド化では、溶剤配合割合を削減しても塗工可能粘度にするため、接着剤樹脂を従来より低分子量化する必要があるが、低分子量化は耐香料性とは逆行する方向であり、両立は困難となっている。
そのため、このような高物性用途にハイソリッド接着剤が使用されることはこれまで無かったが、溶剤回収設備を持たない工場等を中心にニーズが高まっている。
On the other hand, in order to reduce the cost of packaging materials, consider the environment, and improve the working environment, there is a demand for packaging materials that can reduce the amount of solvent used by making the adhesive high solid.
In high-solidity adhesives, the adhesive resin must have a lower molecular weight than before in order to achieve a coatable viscosity even if the solvent blending ratio is reduced, but lowering the molecular weight is contrary to perfume resistance. It is a direction, and it is difficult to achieve both.
Therefore, high solid adhesives have never been used for such high physical property applications, but needs are increasing mainly in factories without solvent recovery equipment.
特許文献1には、香料、界面活性剤等の内容物を充填した場合においても、経時的な接着強度の低下がなく、長期にわたって強い接着強度を維持でき、粘度が低く塗工性にも優れた接着剤組成物で接着され形成された耐薬品性に優れた非食品包装用ラミネートフィルム積層体として、ガラス転移温度が40℃以上の有機ポリオール5〜50重量%及びガラス転移温度が40℃未満の有機ポリオール(但し、その分子中にカルボキシル基を有しない。)95〜50重量%からなる混合物、シランカップリング剤並びに有機ポリイソシアネートを含有する組成物で接着され形成された非食品包装用ラミネートフィルム積層体が記載されている。 In Patent Document 1, even when the contents such as a fragrance and a surfactant are filled, the adhesive strength does not decrease with time, the strong adhesive strength can be maintained for a long time, the viscosity is low, and the coatability is excellent. As a laminated film laminate for non-food packaging excellent in chemical resistance formed by adhering with an adhesive composition having an organic polyol having a glass transition temperature of 40° C. or higher of 5 to 50% by weight and a glass transition temperature of less than 40° C. Non-food packaging laminate formed by adhering with a composition containing 95 to 50% by weight of an organic polyol (however, having no carboxyl group in its molecule), a silane coupling agent and an organic polyisocyanate. A film laminate is described.
また、特許文献2には、従来のハイソリッド型接着剤では達成できなかった初期凝集力及び硬化後の物性を向上させ、従来の低固形成分型接着剤と同等の性能を有するハイソリッド型接着剤として、数平均分子量が10,000以下であり、一分子当り1.4〜1.8個の水酸基を有するポリオール成分並びにイソシアネート硬化剤成分とからなり、該ポリオール成分と該イソシアネート硬化剤成分は、該ポリオール成分中の水酸基に対して該イソシアネート硬化剤中のイソシアネート基が0.8〜5.0当量の割合となるように配合された固形分が40質量%以上であることを特徴とするハイソリッド型接着剤組成物が記載されている。 Further, in Patent Document 2, a high solid type adhesive having improved performance in initial cohesive force and physical properties after curing, which cannot be achieved by a conventional high solid type adhesive, and having performance equivalent to that of a conventional low solid component type adhesive. The agent has a number average molecular weight of 10,000 or less and is composed of a polyol component having 1.4 to 1.8 hydroxyl groups per molecule and an isocyanate curing agent component, and the polyol component and the isocyanate curing agent component are The solid content of the isocyanate component in the isocyanate curing agent is 40% by mass or more with respect to the hydroxyl groups in the polyol component. A high solids adhesive composition is described.
本発明では、耐内容物性に優れ、溶剤使用量削減が可能なハイソリッド型接着剤を提供することにある。 An object of the present invention is to provide a high solid type adhesive that has excellent content resistance and can reduce the amount of solvent used.
本発明では、ポリエステルポリオール(A)、芳香族基を有するポリイソシアネート(B)、及びシランカップリング剤(C)を含有するハイソリッド型接着剤組成物において、
ポリエステルポリオール(A)が、多価カルボン酸と多価アルコールの重縮合物であって、多価カルボン酸中のフタル酸の含有率が40質量%以上であり、該フタル酸には、イソフタル酸とテレフタル酸を必須成分として含み、フタル酸中での何れかの含有量が50質量%以上、且つオルトフタル酸の含有量が20質量%未満である、ハイソリッド型接着剤組成物により、上記課題を解決する。
In the present invention, a high solid adhesive composition containing a polyester polyol (A), a polyisocyanate having an aromatic group (B), and a silane coupling agent (C),
The polyester polyol (A) is a polycondensation product of a polyvalent carboxylic acid and a polyhydric alcohol, and the content of phthalic acid in the polyvalent carboxylic acid is 40% by mass or more. And a terephthalic acid as essential components, the content of any one of them in phthalic acid is 50% by mass or more, and the content of orthophthalic acid is less than 20% by mass. To solve.
本発明によれば、耐内容物性に優れ、溶剤使用量削減が可能なハイソリッド型接着剤を提供することができる。 According to the present invention, it is possible to provide a high solid type adhesive which has excellent content resistance and can reduce the amount of solvent used.
即ち、本発明は、以下の項目から構成される。
1.ポリエステルポリオール(A)、芳香族基を有するポリイソシアネート(B)、及びシランカップリング剤(C)を含有するハイソリッド型接着剤組成物において、
ポリエステルポリオール(A)が、多価カルボン酸と多価アルコールの重縮合物であって、
多価カルボン酸中のフタル酸の含有率が40質量%以上であり、該フタル酸には、イソフタル酸とテレフタル酸を必須成分として含み、フタル酸中での何れかの含有量が50質量%以上、且つオルトフタル酸の含有量が20質量%未満である、ハイソリッド型接着剤組成物、
2.芳香族基を有するポリイソシアネート(B)のイソシアネート基数とポリエステルポリオール(A)の水酸基数の比率(イソシアネート基数/水酸基数)が3以上である1.に記載のハイソリッド型接着剤組成物、
3.芳香族基を有するポリイソシアネート(B)が、メタキシレンジイソシアネート、トルエンジイソシアネート、ジフェニルメタンジイソシアネート、前記ジイソシアネートと2個以上の水酸基を有するアルコールとの反応生成物、又はポリメリックジフェニルメタンジイソシアネートである請求項1又2に記載のハイソリッド型接着剤組成物、
4.ハイソリッド型接着剤組成物に対するシランカップリング剤(C)の固形分質量%が、1.5〜10質量%の範囲である1.〜3.の何れかに記載のハイソリッド型接着剤組成物、
5.1.〜4.の何れかに記載のハイソリッド型接着剤組成物を用いたラミネート用接着剤。
That is, the present invention comprises the following items.
1. A high solid adhesive composition containing a polyester polyol (A), a polyisocyanate having an aromatic group (B), and a silane coupling agent (C),
The polyester polyol (A) is a polycondensation product of a polyvalent carboxylic acid and a polyhydric alcohol,
The content of phthalic acid in the polycarboxylic acid is 40% by mass or more, and the phthalic acid contains isophthalic acid and terephthalic acid as essential components, and the content of any one of them in phthalic acid is 50% by mass. Above, and the content of orthophthalic acid is less than 20 mass%, a high solid adhesive composition,
2. The ratio of the number of isocyanate groups of the polyisocyanate (B) having an aromatic group to the number of hydroxyl groups of the polyester polyol (A) (the number of isocyanate groups/the number of hydroxyl groups) is 3 or more. A high solid adhesive composition described in
3. The polyisocyanate (B) having an aromatic group is metaxylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, a reaction product of the diisocyanate and an alcohol having two or more hydroxyl groups, or polymeric diphenylmethane diisocyanate. A high solid adhesive composition described in
4. The solid content% by mass of the silane coupling agent (C) with respect to the high solid adhesive composition is in the range of 1.5 to 10% by mass. ~3. A high solid adhesive composition according to any one of
5.1. ~4. An adhesive for lamination using the high solid adhesive composition according to any one of 1.
[ポリエステルポリオール(A)]
本発明のポリエステルポリオール(A)は、多価カルボン酸と多価アルコールの重縮合物であり、多価カルボン酸中のフタル酸の含有率が40質量%以上であって、該フタル酸中に含まれる、イソフタル酸とテレフタル酸の合計がフタル酸全体に対して50質量%以上であることに特徴を有する。50質量%未満であると、耐内容物性に劣る結果となる。
本発明では発明の効果を損なわない範囲において、他の多価カルボン酸成分を共重合させてもよい。具体的には、脂肪族多価カルボン酸としては、コハク酸、アジピン酸、アゼライン酸、セバシン酸、ドデカンジカルボン酸等を、不飽和結合含有多価カルボン酸としては、無水マレイン酸、マレイン酸、フマル酸等を、脂環族多価カルボン酸としては1,3−シクロペンタンジカルボン酸、1,4−シクロヘキサンジカルボン酸等を、芳香族多価カルボン酸としては、テレフタル酸、ピロメリット酸、トリメリット酸、1,4−ナフタレンジカルボン酸、2,5−ナフタレンジカルボン酸、2,6−ナフタレンジカルボン酸、ナフタル酸、ビフェニルジカルボン酸、ジフェン酸及びその無水物、1,2−ビス(フェノキシ)エタン−p,p’−ジカルボン酸及びこれらジカルボン酸の無水物或いはエステル形成性誘導体;p−ヒドロキシ安息香酸、p−(2−ヒドロキシエトキシ)安息香酸及びこれらのジヒドロキシカルボン酸のエステル形成性誘導体等の多塩基酸を単独で或いは二種以上の混合物で使用することができる。
[Polyester polyol (A)]
The polyester polyol (A) of the present invention is a polycondensation product of a polyvalent carboxylic acid and a polyhydric alcohol, and the content of phthalic acid in the polyvalent carboxylic acid is 40% by mass or more. It is characterized in that the total amount of isophthalic acid and terephthalic acid contained is 50% by mass or more based on the whole phthalic acid. If it is less than 50% by mass, the result is inferior in content resistance.
In the present invention, other polyvalent carboxylic acid components may be copolymerized as long as the effects of the invention are not impaired. Specifically, as the aliphatic polycarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and the like, as the unsaturated bond-containing polycarboxylic acid, maleic anhydride, maleic acid, Fumaric acid and the like, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like as alicyclic polycarboxylic acids, and terephthalic acid, pyromellitic acid, tri-tricarboxylic acid, and the like as aromatic polycarboxylic acids. Mellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, diphenic acid and its anhydride, 1,2-bis(phenoxy)ethane -P,p'-dicarboxylic acid and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids The polybasic acids can be used alone or in a mixture of two or more.
[多価アルコール]
本発明で用いる多価アルコール成分は、エチレングリコール、ジ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、ネオペンチルグリコール、シクロヘキサンジメタノール、トリシクロデカンジメタノール、及び1,3−ビスヒドロキシエチルベンゼンからなる群から選ばれる少なくとも1種を含む2価アルコールである多価アルコール成分、グリセロール、トリメチロールエタン、トリメチロールプロパン等の3価アルコールである多価アルコール成分を含有することが好ましい。
[Polyhydric alcohol]
The polyhydric alcohol component used in the present invention is at least selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, tricyclodecanedimethanol, and 1,3-bishydroxyethylbenzene. It is preferable to contain a polyhydric alcohol component which is a dihydric alcohol containing one kind and a polyhydric alcohol component which is a trihydric alcohol such as glycerol, trimethylolethane and trimethylolpropane.
本発明では前述の多価アルコール成分を用いることが好ましいが、このほか、本発明の効果を損なわない範囲において、他の多価アルコール成分を共重合させてもよい。具体的には、ジオールとしては1,5−ペンタンジオール、3−メチル−1,5−ペンタンジオール、1,6−ヘキサンジオール、メチルペンタンジオール、ジメチルブタンジオール、ブチルエチルプロパンジオール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコールが、三価以上のアルコールとしては、トリス(2−ヒドロキシエチル)イソシアヌレート、1,2,4−ブタントリオール、ペンタエリスリトール、ジペンタエリスルトール等があげられる。 In the present invention, it is preferable to use the above-mentioned polyhydric alcohol component, but other polyhydric alcohol components may be copolymerized within the range not impairing the effects of the present invention. Specific examples of the diol include 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol and triethylene. Glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol are trihydric or higher alcohols, and tris(2-hydroxyethyl)isocyanurate, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol. Etc.
前記、多価カルボン酸、多価アルコールを用いたポリエステルポリオール(A)は、公知慣用の重縮合反応により得ることができる。通常触媒を用いるが、用いられる触媒としては、モノブチル酸化錫、ジブチル酸化錫等錫系触媒、テトラ−イソプロピル−チタネート、テトラ−ブチル−チタネート等のチタン系触媒、テトラ−ブチル−ジルコネート等のジルコニア系触媒等の酸触媒が挙げられる。エステル反応に対する活性が高い、テトラ−イソプロピル−チタネート、テトラ−ブチル−チタネート等の上記チタン系触媒と上記ジルコニア触媒を組み合わせて用いることができる。前記触媒量は、使用する反応原料全質量に対して0〜1000ppm用いられ、より好ましくは0〜100ppmである。1000ppmを上回るとイソシアネート硬化剤を用いる場合にウレタン化反応を阻害する問題が生じる場合がある。 The above-mentioned polyester polyol (A) using a polyvalent carboxylic acid or a polyhydric alcohol can be obtained by a known and common polycondensation reaction. Usually, a catalyst is used. Examples of the catalyst used include tin-based catalysts such as monobutyl tin oxide and dibutyl tin oxide, titanium-based catalysts such as tetra-isopropyl-titanate and tetra-butyl-titanate, and zirconia-based catalysts such as tetra-butyl-zirconate. Examples thereof include acid catalysts such as catalysts. The titanium-based catalyst such as tetra-isopropyl titanate or tetra-butyl-titanate, which has a high activity for the ester reaction, and the zirconia catalyst can be used in combination. The catalyst amount is 0 to 1000 ppm, and more preferably 0 to 100 ppm, based on the total mass of the reaction raw materials used. If it exceeds 1000 ppm, there may occur a problem of inhibiting the urethanization reaction when an isocyanate curing agent is used.
[ポリイソシアネート化合物]
本発明のコーティング材は、前述の通りポリエステルポリオール(A)とポリイソシアネート化合物(B)との反応物である。
ポリイソシアネート化合物としては、芳香環を含有していることが好ましく、メタキシレンジイソシアネート、トルエンジイソシアネート又はジフェニルメタンジイソシアネート、又は、前記ジイソシアネートと2個以上の水酸基を有するアルコールとの反応生成物、又はポリメリックジフェニルメタンジイソシアネートであることが好ましく、中でもメタキシレンジイソシアネート及びメタキシレンジイソシアネートと2個以上の水酸基を有するアルコールとの反応生成物であることが最も好ましい。
[Polyisocyanate compound]
The coating material of the present invention is a reaction product of the polyester polyol (A) and the polyisocyanate compound (B) as described above.
The polyisocyanate compound preferably contains an aromatic ring, metaxylene diisocyanate, toluene diisocyanate or diphenylmethane diisocyanate, or a reaction product of the diisocyanate and an alcohol having two or more hydroxyl groups, or polymeric diphenylmethane diisocyanate. Are preferred, and most preferred are metaxylene diisocyanate and the reaction product of metaxylene diisocyanate with an alcohol having two or more hydroxyl groups.
[シランカップリング剤]
本発明では、ハイソリッド型接着剤組成物に対するシランカップリング剤(C)の固形分質量%が、1.5〜10質量%の範囲であることが好ましい。この範囲外であると、耐内容物性が劣ることがある。
[Silane coupling agent]
In the present invention, the solid content mass% of the silane coupling agent (C) with respect to the high solid adhesive composition is preferably in the range of 1.5 to 10 mass %. If it is out of this range, the content resistance may be poor.
本発明で用いられるシランカップリング剤(C)は、例えば、本発明で用いるシランカップリング剤(C)は、エポキシシラン(c1)とアミノシラン類(c2)等が挙げられる。 Examples of the silane coupling agent (C) used in the present invention include epoxysilane (c1) and aminosilanes (c2) as the silane coupling agent (C) used in the present invention.
前記エポキシシラン(c1)としては、例えば、3−メタクリロキシプロピルトリメトキシシラン、及び3−メタクリロキシプロピルトリエトキシシランなどのメタクリルシラン系シランカップリング剤;3−グリシドキシプロピ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、及び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等が挙げられる。 Examples of the epoxysilane (c1) include methacrylsilane-based silane coupling agents such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
前記アミノシラン(c2)類としては、例えば、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリイソプロポキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−(2−アミノエチル)アミノプロピルトリメトキシシラン、N−β−(アミノエチル)アミノプロピルトリメトキシシラン、γ−(2−アミノエチル)アミノプロピルメチルジメトキシシラン、γ−(2−アミノエチル)アミノプロピルトリエトキシシラン、γ−(2−アミノエチル)アミノプロピルメチルジエトキシシラン、γ−(2−アミノエチル)アミノプロピルトリイソプロポキシシラン、γ−(2−(2−アミノエチル)アミノエチル)アミノプロピルトリメトキシシラン、γ−(6−アミノヘキシル)アミノプロピルトリメトキシシラン、N−(2−アミノエチル)−3−アミノプロピルメチルジメトキシシラン、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、3−アミノプロピルトリエトキシシラン、4−アミノ−3,3−ジメチルブチルトリメトキシシラン、4−アミノ−3,3−ジメチルブチルジメトキシメチルシラン、3−(N−エチルアミノ)−2−メチルプロピルトリメトキシシラン、N−エチル−3−アミノ−2−メチルプロピルトリメトキシシラン、N−エチル−3−アミノ−2−メチルプロピルジエトキシメチルシラン、N−エチル−3−アミノ−2−メチルプロピルトリエトキシシラン、N−エチル−3−アミノ−2−メチルプロピルメチルジメトキシシラン、N−ブチル−3−アミノ−2−メチルプロピルトリメトキシシラン、3(N−メチル−2−アミノ−1−メチル−1−エトキシ)−プロピルトリメトキシシラン、N−エチル−4−アミノ−3,3−ジメチルブチルジメトキシメチルシラン、N−エチル−4−アミノ−3,3−ジメチルブチルトリメトキシシラン、γ−ウレイドプロピルトリメトキシシラン、γ−ウレイドプロピルトリエトキシシラン、N−フェニル−γ−アミノプロピルトリメトキシシラン、N−ベンジル−γ−アミノプロピルトリメトキシシラン、N−ビニルベンジル−γ−アミノプロピルトリエトキシシラン等が挙げられる。 Examples of the aminosilane (c2) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiene. Ethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, N-β-(aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2- Aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, γ-(2-(2-aminoethyl) Aminoethyl)aminopropyltrimethoxysilane, γ-(6-aminohexyl)aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3 -Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, 4-amino-3,3-dimethylbutyldimethoxymethylsilane, 3-(N-ethylamino) )-2-Methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyltrimethoxysilane, N-ethyl-3-amino-2-methylpropyldiethoxymethylsilane, N-ethyl-3-amino 2-Methylpropyltriethoxysilane, N-ethyl-3-amino-2-methylpropylmethyldimethoxysilane, N-butyl-3-amino-2-methylpropyltrimethoxysilane, 3(N-methyl-2-amino) -1-Methyl-1-ethoxy)-propyltrimethoxysilane, N-ethyl-4-amino-3,3-dimethylbutyldimethoxymethylsilane, N-ethyl-4-amino-3,3-dimethylbutyltrimethoxysilane , Γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyl Triethoxysilane etc. are mentioned.
以下、実施例にて、本発明をさらに詳細に説明する。
(実施例1)
〔主剤調製例〕
攪拌機、温度計、窒素ガス導入管、精留管、水分分離器等を備えたポリエステル反応容器に、エチレングリコール 8部、ジエチレングリコール 29部、アジピン酸19部、イソフタル酸24.2部、テレフタル酸19.8部、及びチタン触媒0.006部を仕込み、精留管上部温度が100℃を越えないように徐々に加熱して内温を240℃に保持した。酸価2mgKOH/g以下になるまでさらに反応を続けた。10mmHg以下に減圧し、1.5時間保持してエステル化反応を終了し、ポリエステルポリオールAを得た。
Hereinafter, the present invention will be described in more detail with reference to Examples.
(Example 1)
[Example of main agent preparation]
In a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction pipe, a rectification pipe, a water separator, etc., 8 parts of ethylene glycol, 29 parts of diethylene glycol, 19 parts of adipic acid, 24.2 parts of isophthalic acid, 19 parts of terephthalic acid. 0.8 part and a titanium catalyst of 0.006 part were charged and gradually heated so that the upper temperature of the rectification tube did not exceed 100° C. to keep the internal temperature at 240° C. The reaction was further continued until the acid value was 2 mgKOH/g or less. The pressure was reduced to 10 mmHg or less, and the pressure was maintained for 1.5 hours to complete the esterification reaction to obtain polyester polyol A.
〔配合液調製例〕
ポリエステルポリオールAと芳香族基を有するポリイソシアネート(DIC株式会社製KW−75)を、10:3の割合で配合し、ポリオール固形分比で表1のようにシランカップリング剤(信越シリコーン株式会社製KBM−403)を添加し、固形分40%になるように酢酸エチルを加えて調製した。
[Example of preparation of compounded liquid]
Polyester polyol A and polyisocyanate having an aromatic group (KW-75 manufactured by DIC Corporation) were mixed at a ratio of 10:3, and a silane coupling agent (Shin-Etsu Silicone Co., Ltd.) as shown in Table 1 in terms of polyol solid content ratio. KBM-403), and ethyl acetate was added so that the solid content was 40%.
(実施例2)、(実施例)3
表1に記載した配合以外は、実施例1と同様に調整を行った。
(Example 2), (Example) 3
Adjustments were made in the same manner as in Example 1 except for the formulation shown in Table 1.
(実施例4)
〔主剤調製例〕
攪拌機、温度計、窒素ガス導入管、精留管、水分分離器等を備えたポリエステル反応容器に、エチレングリコール 7部、ジエチレングリコール 27部、ネオペンチルグリコール4部、アジピン酸14部、セバシン酸1部、イソフタル酸32.9部、テレフタル酸14.1部、及びチタン触媒0.006部を仕込み、精留管上部温度が100℃を越えないように徐々に加熱して内温を240℃に保持した。酸価2mgKOH/g以下になるまでさらに反応を続けた。10mmHg以下に減圧し、1.5時間保持してエステル化反応を終了し、ポリエステルポリオールBを得た。
(Example 4)
[Example of main agent preparation]
A polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., was placed with 7 parts of ethylene glycol, 27 parts of diethylene glycol, 4 parts of neopentyl glycol, 14 parts of adipic acid, 1 part of sebacic acid. , Isophthalic acid 32.9 parts, terephthalic acid 14.1 parts, and titanium catalyst 0.006 parts were charged, and gradually heated so that the upper temperature of the rectification tube did not exceed 100°C, and the internal temperature was kept at 240°C. did. The reaction was further continued until the acid value was 2 mgKOH/g or less. The pressure was reduced to 10 mmHg or less and the pressure was maintained for 1.5 hours to complete the esterification reaction, and thus polyester polyol B was obtained.
〔配合液調製例〕
ポリエステルポリオールBと芳香族基を有するポリイソシアネート(DIC株式会社製KW−75)を、10:3の割合で配合し、ポリオール固形分比で2%のシランカップリング剤(信越シリコーン株式会社製KBM−403)を添加し、固形分40%になるように酢酸エチルを加えて調製した。
[Example of preparation of compounded liquid]
Polyester polyol B and polyisocyanate having an aromatic group (KW-75 manufactured by DIC Co., Ltd.) were mixed at a ratio of 10:3, and a silane coupling agent having a polyol solid content ratio of 2% (Shin-Etsu Silicone Co., Ltd. KBM). -403) was added, and ethyl acetate was added so that the solid content was 40%.
(比較例1 非ハイソリッド溶剤系接着剤)
〔主剤調製例〕
攪拌機、温度計、窒素ガス導入管、精留管、水分分離器等を備えたポリエステル反応容器に、エチレングリコール 10.0部、ネオペンチルグリコール 21.1部、1,6−ヘキサンジオール 10.0部、ツノダイム216 8.0部、イソフタル酸21.5部、テレフタル酸21.5部、アジピン酸23.4部及びチタン触媒0.006部を仕込み、精留管上部温度が100℃を越えないように徐々に加熱して内温を240℃に保持した。酸価2mgKOH/g以下になるまでさらに反応を続けた。10mmHg以下に減圧し、1.5時間保持してエステル化反応を終了し、水酸基価28の中間体ポリエステルポリオールを得た。
(Comparative Example 1 Non-high solid solvent-based adhesive)
[Example of main agent preparation]
In a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction pipe, a rectification pipe, a water separator, etc., ethylene glycol 10.0 parts, neopentyl glycol 21.1 parts, 1,6-hexanediol 10.0. , Tsunodime 216 8.0 parts, isophthalic acid 21.5 parts, terephthalic acid 21.5 parts, adipic acid 23.4 parts and titanium catalyst 0.006 parts, the rectification tube upper temperature does not exceed 100°C. Thus, the internal temperature was maintained at 240° C. by gradually heating. The reaction was further continued until the acid value was 2 mgKOH/g or less. The pressure was reduced to 10 mmHg or less, and the pressure was maintained for 1.5 hours to complete the esterification reaction to obtain an intermediate polyester polyol having a hydroxyl value of 28.
得られた中間体ポリエステルポリオールの100部に対し、イソホロンジイソシアネートを8.9部加え120℃に加熱してNCO%が3.1になるまでウレタン化の反応を行ってポリエステルウレタンポリイソシアネートを得た。これを酢酸エチル111.9部で希釈した後に40℃まで温度を下げて、50℃で約1時間保持し、不揮発分60%のポリウレタンポリエステルポリオール樹脂溶液Uを得た。 To 100 parts of the obtained intermediate polyester polyol, 8.9 parts of isophorone diisocyanate was added and heated to 120° C. to carry out urethanization reaction until NCO% became 3.1 to obtain polyester urethane polyisocyanate. .. After diluting this with 111.9 parts of ethyl acetate, the temperature was lowered to 40° C. and kept at 50° C. for about 1 hour to obtain a polyurethane polyester polyol resin solution U having a nonvolatile content of 60%.
〔配合液調製例〕
ポリオール樹脂溶液Uと芳香族基を有するポリイソシアネート(DIC株式会社製KW−75)を、8:1の割合で配合し、ポリオール固形分比で1%のシランカップリング剤(信越シリコーン株式会社製KBM−403)を添加し、固形30%になるように酢酸エチルを加えて調製した。
[Example of preparation of compounded liquid]
A polyol resin solution U and an aromatic group-containing polyisocyanate (KW-75 manufactured by DIC Co., Ltd.) were blended at a ratio of 8:1, and a silane coupling agent having a polyol solid content ratio of 1% (manufactured by Shin-Etsu Silicone Co., Ltd.). KBM-403) was added, and ethyl acetate was added so that the solid content would be 30%.
(比較例2)、(比較例3)
〔主剤調製例〕
攪拌機、温度計、窒素ガス導入管、精留管、水分分離器等を備えたポリエステル反応容器に、エチレングリコール 12部、ジエチレングリコール 8部、ネオペンチルグリコール 15部、アジピン酸 11部、イソフタル酸23.5部、テレフタル酸23.5部、ツノダイム216 7部、及びチタン触媒0.006部を仕込み、精留管上部温度が100℃を越えないように徐々に加熱して内温を240℃に保持した。酸価2mgKOH/g以下になるまでさらに反応を続けた。10mmHg以下に減圧し、1.5時間保持してエステル化反応を終了し、ポリエステルポリオールCを得た。
(Comparative Example 2), (Comparative Example 3)
[Example of main agent preparation]
In a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., ethylene glycol 12 parts, diethylene glycol 8 parts, neopentyl glycol 15 parts, adipic acid 11 parts, isophthalic acid 23. 5 parts, 23.5 parts of terephthalic acid, 7 parts of Tsunodime 2167, and 0.006 parts of titanium catalyst were charged and gradually heated so that the upper temperature of the rectification tube did not exceed 100°C, and the internal temperature was kept at 240°C. did. The reaction was further continued until the acid value was 2 mgKOH/g or less. The pressure was reduced to 10 mmHg or less and the pressure was maintained for 1.5 hours to complete the esterification reaction, whereby a polyester polyol C was obtained.
〔配合液調製例〕
ポリエステルポリオールCと芳香族基を有するポリイソシアネート(DIC株式会社製KW−75)を、比較例1では10:1、比較例2では6:1の割合で配合し、ポリオール固形分比で表2のようにシランカップリング剤(信越シリコーン株式会社製KBM−403)を添加し、固形分40%になるように酢酸エチルを加えて調製した。
[Example of preparation of compounded liquid]
Polyester polyol C and polyisocyanate having an aromatic group (KW-75 manufactured by DIC Corporation) were blended at a ratio of 10:1 in Comparative Example 1 and 6:1 in Comparative Example 2, and the solid content ratios of Table 2 As described above, a silane coupling agent (KBM-403 manufactured by Shin-Etsu Silicone Co., Ltd.) was added, and ethyl acetate was added so that the solid content was 40%.
(比較例4)
〔主剤調製例〕
攪拌機、温度計、窒素ガス導入管、精留管、水分分離器等を備えたポリエステル反応容器に、エチレングリコール 8部、ジエチレングリコール 29部、アジピン酸38部、イソフタル酸25部、及びチタン触媒0.006部を仕込み、精留管上部温度が100℃を越えないように徐々に加熱して内温を240℃に保持した。酸価2mgKOH/g以下になるまでさらに反応を続けた。10mmHg以下に減圧し、1.5時間保持してエステル化反応を終了し、ポリエステルポリオールDを得た。
(Comparative example 4)
[Example of main agent preparation]
In a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction pipe, a rectification pipe, a water separator, etc., 8 parts of ethylene glycol, 29 parts of diethylene glycol, 38 parts of adipic acid, 25 parts of isophthalic acid, and a titanium catalyst of 0. 006 parts were charged and gradually heated so that the upper temperature of the rectification tube did not exceed 100°C, and the internal temperature was kept at 240°C. The reaction was further continued until the acid value was 2 mgKOH/g or less. The pressure was reduced to 10 mmHg or less and the pressure was maintained for 1.5 hours to complete the esterification reaction, and polyester polyol D was obtained.
〔配合液調製例〕
ポリエステルポリオールDと芳香族基を有するポリイソシアネート(DIC株式会社製KW−75)を、10:3の割合で配合し、ポリオール固形分比で2%のシランカップリング剤(信越シリコーン株式会社製KBM−403)を添加し、固形分40%になるように酢酸エチルを加えて調製した。
[Example of preparation of compounded liquid]
Polyester polyol D and polyisocyanate having an aromatic group (KW-75 manufactured by DIC Co., Ltd.) were blended at a ratio of 10:3, and a silane coupling agent having a polyol solid content ratio of 2% (Shin-Etsu Silicone Co., Ltd. KBM). -403) was added, and ethyl acetate was added so that the solid content was 40%.
(比較例5)、(比較例6)
〔主剤調製例〕
攪拌機、温度計、窒素ガス導入管、精留管、水分分離器等を備えたポリエステル反応容器に、エチレングリコール 8部、ジエチレングリコール 29部、アジピン酸19部、イソフタル酸を表2の割合、及びチタン触媒0.006部を仕込み、精留管上部温度が100℃を越えないように徐々に加熱して内温を240℃に保持した。酸価2mgKOH/g以下になるまでさらに反応を続けた。10mmHg以下に減圧し、1.5時間保持してエステル化反応を終了し、ポリエステルポリオールE、F、G、Hを得た。
(Comparative Example 5), (Comparative Example 6)
[Example of main agent preparation]
A polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a rectification tube, a water separator, etc., was added with ethylene glycol 8 parts, diethylene glycol 29 parts, adipic acid 19 parts, isophthalic acid in the proportions shown in Table 2, and titanium. 0.006 parts of the catalyst was charged and gradually heated so that the upper temperature of the rectification tube did not exceed 100° C. to maintain the internal temperature at 240° C. The reaction was further continued until the acid value was 2 mgKOH/g or less. The pressure was reduced to 10 mmHg or less and the pressure was maintained for 1.5 hours to complete the esterification reaction, and polyester polyols E, F, G and H were obtained.
〔配合液調製例〕
ポリエステルポリオールE、F、G、Hと芳香族基を有するポリイソシアネート(DIC株式会社製KW−75)を、10:3の割合で配合し、ポリオール固形分比で表2の割合のシランカップリング剤(信越シリコーン株式会社製KBM−403)を添加し、固形分40%になるように酢酸エチルを加えて調製した。
[Example of preparation of compounded liquid]
Polyester polyols E, F, G, H and polyisocyanate having an aromatic group (KW-75 manufactured by DIC Corporation) were mixed at a ratio of 10:3, and silane coupling was performed at a ratio of polyol solid content shown in Table 2. The agent (KBM-403 manufactured by Shin-Etsu Silicone Co., Ltd.) was added, and ethyl acetate was added so that the solid content was 40%.
(比較例7)
〔主剤調製例〕
攪拌機、温度計、窒素ガス導入管、精留管、水分分離器等を備えたポリエステル反応容器に、エチレングリコール 12部、ジエチレングリコール 8部、ネオペンチルグリコール 15部、アジピン酸 11部、イソフタル酸55部、オルトフタル酸20部、テレフタル酸25部、ツノダイム216 7部、及びチタン触媒0.006部を仕込み、精留管上部温度が100℃を越えないように徐々に加熱して内温を240℃に保持した。酸価2mgKOH/g以下になるまでさらに反応を続けた。10mmHg以下に減圧し、1.5時間保持してエステル化反応を終了し、ポリエステルポリオールIを得た。
〔配合液調製例〕
ポリエステルポリオールIと芳香族基を有するポリイソシアネート(DIC株式会社製KW−75)を、10:3の割合で配合し、ポリオール固形分比で表2のようにシランカップリング剤(信越シリコーン株式会社製KBM−403)を添加し、固形分40%になるように酢酸エチルを加えて調製した。
(Comparative Example 7)
[Example of main agent preparation]
A polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., was placed in an ethylene glycol 12 parts, diethylene glycol 8 parts, neopentyl glycol 15 parts, adipic acid 11 parts, isophthalic acid 55 parts. , 20 parts of orthophthalic acid, 25 parts of terephthalic acid, 7 parts of Tsunodime 216, and 0.006 parts of titanium catalyst were charged and gradually heated so that the upper temperature of the rectification tube does not exceed 100°C, and the internal temperature was increased to 240°C. Held The reaction was further continued until the acid value was 2 mgKOH/g or less. The pressure was reduced to 10 mmHg or less, and the pressure was maintained for 1.5 hours to complete the esterification reaction, and polyester polyol I was obtained.
[Example of preparation of compounded liquid]
Polyester polyol I and polyisocyanate having an aromatic group (KW-75 manufactured by DIC Corporation) were mixed at a ratio of 10:3, and a silane coupling agent (Shin-Etsu Silicone Co., Ltd.) as shown in Table 2 in terms of polyol solid content ratio. KBM-403) manufactured by the present invention was added, and ethyl acetate was added so that the solid content was 40%.
(比較例8)、(比較例9)
芳香族基を有するポリイソシアネートを脂肪族ポリイソシアネートに変えた以外は実施例1と同様にして、調整した。
(Comparative Example 8), (Comparative Example 9)
Preparation was carried out in the same manner as in Example 1 except that the polyisocyanate having an aromatic group was changed to an aliphatic polyisocyanate.
以下の各項目について、評価を行った。
[耐内容物性]
上記の主剤、硬化剤、触媒、溶剤を配合した後、この配合液をフィルムに塗布量が固形分3.5g/m2程度となるように塗布し、ドライヤーで乾燥後、カレンダーロールでこのフィルムの塗布面と別のシーラントフィルムと塗布面に密着させ、ラミネートフィルムを作製した。ラミネートフィルムの構成はONY/アルミ蒸着PET/LLDPEで作製した。このラミネートフィルムを40℃の恒温槽に入れ、4日間エージング後、シーラントが内側になるように折り曲げ、折り曲げ部位を1atm、180℃、1秒間でヒートシールして袋を作製、内容物を充填して開口部をヒートシールし、50℃の恒温槽に入れ、2週間、4週間促進試験を行った後、これを幅15mmになるように短冊状に切り、剥離試験機を用いて剥離速度300mm/分、T型剥離にて接着強度を測定した。
The following items were evaluated.
[Content resistance]
After blending the above-mentioned main ingredient, curing agent, catalyst and solvent, this blended solution is coated on a film so that the solid content is about 3.5 g/m 2 , dried with a drier, and the film is then rolled with a calender roll. A sealant film different from the coated surface of (1) and a coated surface were brought into close contact with each other to prepare a laminated film. The laminate film was made by ONY/aluminum vapor deposition PET/LLDPE. This laminated film is put in a constant temperature bath at 40° C., after aging for 4 days, folded so that the sealant is on the inside, and the folded portion is heat-sealed at 1 atm, 180° C. for 1 second to make a bag, and the contents are filled. After heat-sealing the opening, put it in a constant temperature bath at 50°C for 2 weeks and 4 weeks, and perform an accelerated test, cut it into strips with a width of 15 mm, and use a peel tester to peel at a speed of 300 mm. /Min, the adhesive strength was measured by T-type peeling.
評価5:LLDPEの伸び、もしくはフィルム基材の表層破壊
評価4:PET/接着剤間の剥離で接着力3.0[N/15mm]以上
評価3:PET/接着剤間の剥離で接着力2.0[N/15mm]以上
評価2:PET/接着剤間の剥離で接着力2.0[N/15mm]未満
評価1:接着剤の凝集破壊
Evaluation 5: Elongation of LLDPE or surface layer breakage of film substrate Evaluation 4: Adhesive strength of 3.0 [N/15 mm] or more by peeling between PET/adhesive Evaluation 3: Adhesive strength by peeling between PET/adhesive 2 0.0 [N/15 mm] or more Evaluation 2: Adhesion strength of less than 2.0 [N/15 mm] due to peeling between PET/adhesive Evaluation 1: Adhesive cohesive failure
[塗工粘度]
上記の主剤、硬化剤、触媒、溶剤を配合した後、この配合液を25℃の恒温水槽に20分入れた後、ザーンカップ3番で粘度を測定した。
評価○:ザーンカップ#3粘度17秒未満
評価×:ザーンカップ#3粘度17秒以上
[Coating viscosity]
After blending the above-mentioned main agent, curing agent, catalyst and solvent, this blended solution was placed in a constant temperature water bath at 25° C. for 20 minutes, and then the viscosity was measured with Zahn cup No. 3.
Evaluation ◯: Zahn cup #3 viscosity less than 17 seconds Evaluation X: Zahn cup #3 viscosity 17 seconds or more
[主剤樹脂溶液の外観]
主剤調整液を室温で1ヶ月放置した後、目視評価を行った。
評価◎:無色透明
評価○:軽度の着色もしくは微白濁
評価△:重度の着色
評価×:濁沈
[Appearance of base resin solution]
After leaving the base material preparation liquid for one month at room temperature, visual evaluation was performed.
Evaluation ◎: colorless and transparent Evaluation ○: slight coloring or slight turbidity evaluation △: severe coloring evaluation ×: turbidity
<耐内容物性の剥離界面の説明>
・PET表層:接着剤ではなくPETフィルムの表層から剥離
・PET/ad:PETフィルムと接着剤間の剥離
・ad:接着剤の凝集破壊
<Explanation of peeling interface for content resistance>
・PET surface layer: peeled from the surface layer of the PET film, not the adhesive ・PET/ad: peeling between the PET film and the adhesive ・ad: cohesive failure of the adhesive
本発明のハイソリッド型接着剤組成物は、洗剤、シャンプー、リンス等の詰め替えスタンディングパウチ用の包装材に用いることができる。 The high solid adhesive composition of the present invention can be used as a packaging material for refillable standing pouches such as detergents, shampoos and rinses.
Claims (3)
前記接着剤層が、ポリエステルポリオール(A)、芳香族基を有するポリイソシアネート(B)、シランカップリング剤(C)、及び溶剤を含有するハイソリッド型接着剤組成物の硬化塗膜であり、
前記ポリエステルポリオール(A)が、多価カルボン酸と多価アルコールの重縮合物であって、前記多価カルボン酸中のフタル酸の含有率が40質量%以上であり、前記フタル酸には、イソフタル酸とテレフタル酸を必須成分として含み、前記フタル酸中でのイソフタル酸の含有量が50質量%以上、且つオルトフタル酸の含有量が20質量%未満であり、
前記ポリエステルポリオール(A)に対するシランカップリング剤(C)の固形分質量%が1.5〜10質量%である積層体。 A polyester film, a polyethylene film, including an adhesive layer for bonding the polyester film and the polyethylene film,
The adhesive layer is a cured coating film of a high solid adhesive composition containing a polyester polyol (A), a polyisocyanate having an aromatic group (B) , a silane coupling agent (C), and a solvent ,
The polyester polyol (A) is a polycondensate of a polyhydric alcohol and a polycarboxylic acid, wherein is a phthalate content in the polyvalent carboxylic acid 40 mass% or more, the phthalic acid, Isophthalic acid and terephthalic acid are included as essential components, the content of isophthalic acid in the phthalic acid is 50% by mass or more, and the content of orthophthalic acid is less than 20% by mass.
A laminate in which the solid content mass% of the silane coupling agent (C) is 1.5 to 10 mass% with respect to the polyester polyol (A).
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