JP5546799B2 - Adhesive composition for two-component laminates that is less susceptible to moisture - Google Patents
Adhesive composition for two-component laminates that is less susceptible to moisture Download PDFInfo
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- JP5546799B2 JP5546799B2 JP2009135202A JP2009135202A JP5546799B2 JP 5546799 B2 JP5546799 B2 JP 5546799B2 JP 2009135202 A JP2009135202 A JP 2009135202A JP 2009135202 A JP2009135202 A JP 2009135202A JP 5546799 B2 JP5546799 B2 JP 5546799B2
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- 239000000853 adhesive Substances 0.000 title claims description 32
- 230000001070 adhesive effect Effects 0.000 title claims description 32
- 239000000203 mixture Substances 0.000 title claims description 24
- 150000003077 polyols Chemical class 0.000 claims description 149
- 229920005862 polyol Polymers 0.000 claims description 92
- 239000004814 polyurethane Substances 0.000 claims description 87
- 229920002635 polyurethane Polymers 0.000 claims description 87
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 76
- 239000012948 isocyanate Substances 0.000 claims description 33
- 150000002009 diols Chemical class 0.000 claims description 30
- 239000005056 polyisocyanate Substances 0.000 claims description 25
- 229920001228 polyisocyanate Polymers 0.000 claims description 25
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 23
- -1 diisocyanate compound Chemical class 0.000 claims description 19
- 229920000515 polycarbonate Polymers 0.000 claims description 17
- 239000004417 polycarbonate Substances 0.000 claims description 17
- 230000004888 barrier function Effects 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 239000012939 laminating adhesive Substances 0.000 claims description 9
- 229920005906 polyester polyol Polymers 0.000 claims description 8
- KZOWNALBTMILAP-JBMRGDGGSA-N ancitabine hydrochloride Chemical compound Cl.N=C1C=CN2[C@@H]3O[C@H](CO)[C@@H](O)[C@@H]3OC2=N1 KZOWNALBTMILAP-JBMRGDGGSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 96
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 36
- 239000007789 gas Substances 0.000 description 25
- 150000002513 isocyanates Chemical class 0.000 description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 21
- 239000012299 nitrogen atmosphere Substances 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- 238000010521 absorption reaction Methods 0.000 description 20
- 238000000862 absorption spectrum Methods 0.000 description 20
- 238000010992 reflux Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 238000011156 evaluation Methods 0.000 description 14
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 13
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 12
- 230000007547 defect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 229920005668 polycarbonate resin Polymers 0.000 description 7
- 239000004431 polycarbonate resin Substances 0.000 description 7
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 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 5
- AQHHHDLHHXJYJD-UHFFFAOYSA-N propranolol Chemical compound C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 AQHHHDLHHXJYJD-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 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 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 2
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- VDHWOHDSOHPGPC-UHFFFAOYSA-N 3,3-dihydroxyoxepan-2-one Chemical compound OC1(O)CCCCOC1=O VDHWOHDSOHPGPC-UHFFFAOYSA-N 0.000 description 1
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Description
本発明は、フイルム複合に使用される２液ウレタン系ラミネート用接着剤であり、硬化時に介在する水分の影響を受け難く、安定した接着性能を発現し、特に、ガスバリアー性フイルムの複合時に水分とイソシアネートとの反応による炭酸ガス発生による外観不良や接着強度不足を抑制させることができる２液配合型ウレタン系接着剤組成物に関するものである。 The present invention is a two-component urethane laminating adhesive used for film composites, is not easily affected by moisture intervening at the time of curing, and exhibits stable adhesive performance. In particular, the moisture content during gas barrier film composites The present invention relates to a two-component blended urethane-based adhesive composition that can suppress poor appearance and insufficient adhesive strength due to carbon dioxide generation due to the reaction between and isocyanate.
食品包装用や建材用シートをはじめとするラミネートシートは、一般に、ポリオール成分とポリイソシアネート成分とを配合して用いる２液硬化型ウレタン系接着剤によってフイルムを複合させているが、ポリイソシアネートのイソシアネート基は、ポリオール成分の水酸基だけでなく水と反応する性質を有す。このことから、一般にポリオールの水酸基数よりも過剰のイソシアネート基を配合させることで、水分が存在しても安定した接着強度が発現するように設計されている場合がある。しかしながら、フイルム基材に付着した水分や、ラミネート環境中、エージング環境中等に存在する水分量は一定ではないので、水分の多少により、接着強度が変動してしまう問題がある。また、イソシアネート基と水の反応は炭酸ガスの発生を伴うので、水分が多い系においては、ガスバリアー性フイルム同士を複合させた場合には、そのガスバリアー効果によって、炭酸ガスの抜け道が狭くなっているので、閉じ込められた炭酸ガスが気泡となり、外観不良や接着強度不足と云った不具合を発生する欠点がある。 Laminate sheets such as food packaging and building material sheets generally have a film combined with a two-component curable urethane adhesive that is a mixture of a polyol component and a polyisocyanate component. The group has a property of reacting with water as well as the hydroxyl group of the polyol component. For this reason, in general, by adding an isocyanate group in excess of the number of hydroxyl groups of the polyol, it may be designed so that a stable adhesive strength is expressed even in the presence of moisture. However, the moisture adhering to the film substrate and the amount of moisture present in the laminate environment, the aging environment, and the like are not constant, and there is a problem that the adhesive strength varies depending on the amount of moisture. In addition, since the reaction between isocyanate groups and water is accompanied by the generation of carbon dioxide, in gas-rich systems, when gas barrier films are combined, the gas barrier effect narrows the escape route for carbon dioxide. Therefore, the trapped carbon dioxide gas becomes bubbles, and there is a defect that a defect such as poor appearance or insufficient adhesive strength occurs.
また、２液硬化型ウレタン系接着剤において、その使用環境下に一切の水分が存在しなければ、前記した炭酸ガス発生による種々不具合は回避できるが、フイルムや加工機器類、更には、作業環境中の水分を除去することは困難であって、多少の水分があろうとも、安定した強度を発現し、且つ、炭酸ガス発生による外観不良が起きない接着剤が要求されている。 In addition, in the two-component curable urethane adhesive, if there is no moisture in the usage environment, various problems due to the generation of carbon dioxide gas can be avoided, but the film, processing equipment, and work environment can be avoided. It is difficult to remove moisture in the interior, and there is a demand for an adhesive that exhibits stable strength and does not cause poor appearance due to the generation of carbon dioxide gas, even if there is some moisture.
本発明が解決しようとする課題は、水分の影響を受け難く、安定した接着性能を与え、特に、ガスバリアー性フイルム同士の貼り合わせにおいてもガス発生に伴う外観不良や強度不足を抑制することのできる２液ウレタン系ラミネート用接着剤を提供せんとするものである。 The problem to be solved by the present invention is that it is hardly affected by moisture and gives stable adhesion performance, and in particular, it suppresses appearance defects and insufficient strength due to gas generation even in the bonding of gas barrier films. It is intended to provide a two-component urethane laminate adhesive.
本発明者らは、上記課題に鑑み鋭意研究を重ねた結果、特定の分子末端基を有すポリウレタンポリオールに、一定の範囲内でポリイソシアネートを配合して用いることにより、反応系中に存在する水分の影響を受け難く安定した接着性能を与え、特に、ガスバリアー性フイルム同士の貼り合わせにおける外観不良や強度不足を抑制することが可能となることを見出し、本発明を完成させるに至った。尚、本願で述べるガスバリアー性フイルムとは、ポリエチレンテレフタレート、ポリプロピレン、ナイロン等の合成樹脂フイルムにシリカやアルミナ等のガスバリアー性を改善する物質を蒸着して得られたフイルムで、蒸着加工後において、酸素や水蒸気透過性等のガスバリアー性が高くなった蒸着フイルムや、また、アルミニウムや銅などの金属箔の単体、若しくはこれら金属箔と合成樹脂フイルムとの複合体のことである。 As a result of intensive studies in view of the above problems, the present inventors existed in a reaction system by blending and using a polyisocyanate within a certain range in a polyurethane polyol having a specific molecular end group. It has been found that it is possible to provide stable adhesion performance that is hardly affected by moisture, and in particular, it is possible to suppress poor appearance and insufficient strength in bonding of gas barrier films to each other, thereby completing the present invention. The gas barrier film described in the present application is a film obtained by vapor-depositing a material that improves gas barrier properties such as silica and alumina on a synthetic resin film such as polyethylene terephthalate, polypropylene, and nylon. It is a vapor deposition film having improved gas barrier properties such as oxygen and water vapor permeability, a single metal foil such as aluminum or copper, or a composite of these metal foil and synthetic resin film.
以下に本発明を説明すれば、ポリウレタンポリオール（１）の全水酸基価中の５０％以上が構造式１〜６何れかの水酸基であり、上記ポリウレタンポリオール（１）に対し、ポリウレタンポリオール（１）の水酸基数／ポリイソシアネート（２）のイソシアネート基数が、１／０．５〜１／１．５の範囲で、望ましくは、ポリウレタンポリオール（１）の水酸基数／ポリイソシアネート（２）のイソシアネート基数が、１／０．５〜１／０．９の範囲で配合して用いることで水分の影響を受け難く、安定した接着性能を与え、且つ、ガスバリアー性フイルム同士の貼り合わせにおいても炭酸ガス発生による外観不良や強度不足を抑制することのできる２液ウレタン系ラミネート用接着剤組成物である。
構造式１ −Ｏ−ＣＨ2−ＣＨ2−ＣＨ2−ＣＨ2−ＯＨ
構造式２ −Ｏ−ＣＨ2−ＣＨ2−ＣＨ2−ＣＨ2−ＣＨ2−ＯＨ
構造式３ −Ｏ−ＣＨ2−ＣＨ2−ＣＨ（ＣＨ3）−ＣＨ2−ＣＨ2−ＯＨ
構造式４ −Ｏ−ＣＨ2−ＣＨ2−ＣＨ2−ＣＨ2−ＣＨ2−ＣＨ2−ＯＨ
構造式５ −Ｏ−ＣＯ−ＣＨ2−ＣＨ2−ＣＨ2−ＣＨ2−ＣＨ2−ＯＨ
構造式６ −Ｏ−ＣＨ2−（ｃｙｃｌｏ−Ｃ6Ｈ10）−ＣＨ2−ＯＨ
Describing the present invention, 50% or more of the total hydroxyl value of the polyurethane polyol (1) is a hydroxyl group of any one of the structural formulas 1 to 6, and the polyurethane polyol (1) with respect to the polyurethane polyol (1). The number of hydroxyl groups / the number of isocyanate groups of polyisocyanate (2) is preferably in the range of 1 / 0.5 to 1 / 1.5, preferably the number of hydroxyl groups of polyurethane polyol (1) / the number of isocyanate groups of polyisocyanate (2). When mixed and used in the range of 1 / 0.5 to 1 / 0.9, it is hardly affected by moisture, gives stable adhesive performance, and generates carbon dioxide gas even when bonding gas barrier films. It is an adhesive composition for a two-component urethane-based laminate that can suppress poor appearance and insufficient strength.
Structural Formula 1 —O—CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 2 —O—CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 3 —O—CH 2 —CH 2 —CH (CH 3 ) —CH 2 —CH 2 —OH
Structural Formula 4 —O—CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 5 —O—CO—CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 6 —O—CH 2 — (cyclo-C 6 H 10 ) —CH 2 —OH
また、ポリウレタンポリオール（１）の全水酸基価中の５０％以上がポリカーボネート結合を介してなる構造式１〜６の水酸基であり、上記ポリウレタンポリオール（１）に対し、ポリウレタンポリオール（１）の水酸基数／ポリイソシアネート（２）のイソシアネート基数が、１／０．５〜１／１．５の範囲で、望ましくは、ポリウレタンポリオール（１）の水酸基数／ポリイソシアネート（２）のイソシアネート基数が、１／０．５〜１／０．９の範囲で配合して用いる２液ウレタン系ラミネート用接着剤組成物である。 Further, 50% or more of the total hydroxyl value of the polyurethane polyol (1) is a hydroxyl group of structural formulas 1 to 6 formed through a polycarbonate bond, and the number of hydroxyl groups of the polyurethane polyol (1) relative to the polyurethane polyol (1). The number of isocyanate groups in / polyisocyanate (2) is in the range of 1 / 0.5 to 1 / 1.5, preferably the number of hydroxyl groups in polyurethane polyol (1) / the number of isocyanate groups in polyisocyanate (2) is 1 / It is an adhesive composition for a two-component urethane laminate used by blending in the range of 0.5 to 1 / 0.9.
先ず、ポリウレタンポリオール（１）を詳細に説明する。ポリウレタンポリオール（１）は、ポリエーテルジオール、ポリエステルジオール、ポリカーボネートジオール等のジオール成分とジイソシアネート化合物によって末端イソシアネート化合物に誘導した後に、構造式１〜６の構造を有すジオール成分である、１，４−ブタンジオール、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、ε−カプロラクトンの開環反応により得られるポリカプロラクトンジオール、シクロヘキサンジメタノールの何れか単体、或いは複数をイソシアネート基数よりも過剰の水酸基となるように反応させることで、本発明の構造式１〜６の何れかの構造を有す水酸基を分子末端に備えたポリウレタンポリオール（１）を得ることができる。 First, the polyurethane polyol (1) will be described in detail. The polyurethane polyol (1) is a diol component having a structure of structural formulas 1 to 6 after being derived into a terminal isocyanate compound by a diol component such as polyether diol, polyester diol, polycarbonate diol and the like and a diisocyanate compound. -Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1.6-hexanediol, polycaprolactone diol obtained by ring-opening reaction of ε-caprolactone, or cyclohexanedimethanol alone Alternatively, a polyurethane polyol (1) having a hydroxyl group having a structure of any one of structural formulas 1 to 6 at the molecular end of the present invention is obtained by reacting a plurality of hydroxyl groups in excess of the number of isocyanate groups. be able to.
また、ポリウレタンポリオール（１）は、ポリエーテルジオール、ポリエステルジオール、ポリカーボネートジオール等のジオール成分をジイソシアネート化合物によって末端イソシアネート化合物に誘導した後に、構造式１〜６の構造を有すジオール成分である、１，４−ブタンジオール、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、ε−カプロラクトンの開環反応により得られるポリカプロラクトンジオール、シクロヘキサンジメタノールの何れか単体、或いは複数と、ジメチルカーボネートやジエチルカーボネートとの反応から得られるポリカーボネートジオール樹脂を、イソシアネート基数よりも過剰の水酸基となるように反応させることで、本発明のカーボネート結合を介して構造式１〜６の何れかの水酸基を分子末端に備えたポリウレタンポリオール（１）を得ることができる。 The polyurethane polyol (1) is a diol component having a structure represented by structural formulas 1 to 6 after a diol component such as polyether diol, polyester diol, or polycarbonate diol is derived from a terminal isocyanate compound with a diisocyanate compound. , 4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1.6-hexanediol, polycaprolactone diol obtained by ring-opening reaction of ε-caprolactone, and cyclohexanedimethanol Or by reacting the polycarbonate diol resin obtained from the reaction of dimethyl carbonate or diethyl carbonate with a single substance or a plurality of them so that the hydroxyl group is in excess of the number of isocyanate groups, via the carbonate bond of the present invention. Any of the hydroxyl groups of the structural formula 1-6 can be obtained a polyurethane polyol (1) with a molecular end.
使用できるポリカーボネート樹脂とすれば、具体的には、１，６−ヘキサンジオールから得られるポリカーボネート樹脂（宇部興産株式会社製 ＥＴＥＲＮＡＣＯＬＬ ＵＨ−５０、ＵＨ−１００，ＵＨ−２００、ＵＨ−３００）や、カプロラクトンと１，６−ヘキサンジオールから得られるポリカーボネート樹脂（宇部興産株式会社製 ＥＴＥＲＮＡＣＯＬＬ ＵＨＣ５０−２００、ＵＨＣ５０−１００）や、１，４−シクロヘキサンジメタノールから得られるポリカーボネート樹脂（宇部興産株式会社製 ＵＣ−１００）や、１，４−シクロヘキサンジメタノールと１，６−ヘキサンジオールから得られるポリカーボネート樹脂（宇部興産株式会社製 ＵＭ−９０（３／１）、ＵＭ−９０（１／１）、ＵＭ−９０（１／３）や、１，５−ペンタンジオールと１，６−ヘキサンジオールから得られるポリカーボネート樹脂（旭化成ケミカルズ株式会社製 デュラノール Ｔ５６５２、Ｔ５６５１、Ｔ５６５０Ｅ）や、１，４−ブタンジオールと１，６−ヘキサンジオールから得られるポリカーボネート樹脂（旭化成ケミカルズ株式会社製 デュラノール Ｔ４６７２、Ｔ４６７１、Ｔ４６９１）等が挙げられる。 Specific examples of the polycarbonate resin that can be used include polycarbonate resins obtained from 1,6-hexanediol (ETERNACOLL UH-50, UH-100, UH-200, UH-300 manufactured by Ube Industries, Ltd.) and caprolactone. And 1,6-hexanediol polycarbonate resin (EbeRNA UHC50-200, UHC50-100, manufactured by Ube Industries, Ltd.) and 1,4-cyclohexanedimethanol polycarbonate resin (UC-100, manufactured by Ube Industries, Ltd.) ), Polycarbonate resin obtained from 1,4-cyclohexanedimethanol and 1,6-hexanediol (UM-90 (3/1), UM-90 (1/1), UM-90 (Ube Industries, Ltd.) 1/3) and 1,5-pen Polycarbonate resin obtained from diol and 1,6-hexanediol (Duranor T5652, T5651, T5650E manufactured by Asahi Kasei Chemicals Corporation) and polycarbonate resin obtained from 1,4-butanediol and 1,6-hexanediol (Asahi Kasei Chemicals Corporation) Duranol T4672, T4671, T4691) manufactured by the company and the like.
また、末端の水酸基が構造式１〜６の何れかを備えたポリエーテルジオール、ポリエステルジオール、ポリカーボネートジオールであれば、末端イソシアネート化合物を経由せずに一段階で目的のポリウレタンポリオール（１）を得ることができる。つまり、本発明では、ポリウレタンポリオールの末端水酸基が、構造式１〜６で構成されていれば、末端イソシアネート化合物に経由せずに一段階で合成することもできる。 Further, when the terminal hydroxyl group is a polyether diol, polyester diol, or polycarbonate diol having any one of structural formulas 1 to 6, the desired polyurethane polyol (1) is obtained in one step without passing through the terminal isocyanate compound. be able to. That is, in this invention, if the terminal hydroxyl group of a polyurethane polyol is comprised by Structural formula 1-6, it can also synthesize | combine in one step, without passing through a terminal isocyanate compound.
さらに、ポリウレタンポリオール（１）について詳しく説明する。ポリウレタンポリオール（１）を合成する際に使用できるイソシアネート化合物は、ウレタン鎖伸長剤として知られる公知のイソシアネート化合物でよい。具体的には、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、ノルボルネンジイソシアネート、キシリレンジイソシアネート、トリレンジイソシアネート、水添トリレ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、水添ジフェニルメタンジイソシアネートやそれらのトリメチロールプロパンアダクト、ヌレート体、アロファネート体等が挙げられるが、主として２官能性であるジイソシアネートにて鎖伸長することが、塗工適性、接着力の面から望ましい。また、食品用途や耐候性が必要となる用途では、脂肪族系のイソシアネートの使用が望ましい。 Furthermore, the polyurethane polyol (1) will be described in detail. The isocyanate compound that can be used when synthesizing the polyurethane polyol (1) may be a known isocyanate compound known as a urethane chain extender. Specifically, hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, xylylene diisocyanate, tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate and their trimethylolpropane adduct, nurate, allophanate, etc. However, chain extension with a difunctional diisocyanate is desirable from the viewpoint of coating suitability and adhesive strength. In addition, it is desirable to use aliphatic isocyanates in food applications and applications that require weather resistance.
ポリウレタンポリオール（１）の合成は、イソシアネートと反応する水、アルコール、やアミノ基を含まないエステル系溶剤、ケトン系溶剤中で、必要に応じて有機スズ等の公知のウレタン化触媒を適量存在させ、５０℃〜９０℃程度の温度で反応させればよい。 The synthesis of the polyurethane polyol (1) is carried out by adding an appropriate amount of a known urethanization catalyst such as organic tin in water, alcohol which reacts with isocyanate, an ester solvent not containing an amino group, or a ketone solvent. The reaction may be performed at a temperature of about 50 ° C to 90 ° C.
ポリウレタンポリオール（１）の水酸基は、１０〜３０ｍｇＫＯＨ／ｇの範囲が望ましく、１０ｍｇＫＯＨ／ｇ以下の場合、得られたポリウレタンポリオール（１）の粘度が高くなり、塗工時の希釈溶剤の使用量が増える問題や塗工適性が悪くなる問題が発生する。一方、水酸基価が３０ｍｇＫＯＨ／ｇを超える場合、分子量が低い為に、ラミネート初期の接着力が劣る傾向にあり、巻き取り時に、所謂、巻きズレを引き起こすことがあるので、水酸基価は、塗工適性やラミネート初期時の物性確保の観点から、より望ましくは、１２〜２５ｍｇＫＯＨ／ｇ程度がよい。 The hydroxyl group of the polyurethane polyol (1) is preferably in the range of 10 to 30 mgKOH / g, and when it is 10 mgKOH / g or less, the viscosity of the obtained polyurethane polyol (1) becomes high, and the amount of the dilution solvent used during coating is high. Increased problems and problems of poor coating suitability occur. On the other hand, when the hydroxyl value exceeds 30 mgKOH / g, the molecular weight is low, so the adhesive strength at the initial stage of the laminate tends to be inferior. From the standpoint of suitability and securing physical properties at the initial stage of lamination, it is more preferably about 12 to 25 mg KOH / g.
得られたポリウレタンポリオール（１）は、構造式１〜６の水酸基を有さないポリオールと混合していても構わないが、混合できる範囲とすれば、混合後のポリウレタンポリオール（１）の全水酸基価中の５０％以上が、構造式１〜６の水酸基である必要があり、５０％未満の場合、従来の２液型ポリウレタン系接着剤と同様に、湿気の影響を受けてしまうので、望ましくは、構造式１〜６の水酸基を有さないポリオールとの混合は、混合後のポリウレタンポリオール（１）の全水酸基価中の７５％以上が構造式１〜６の水酸基であることが望ましく、さらには１００％が構造式１〜６の水酸基であることがより望ましい。 The obtained polyurethane polyol (1) may be mixed with a polyol having no hydroxyl group of the structural formulas 1 to 6, but if it is within the range that can be mixed, all the hydroxyl groups of the polyurethane polyol (1) after mixing. 50% or more of the valence needs to be a hydroxyl group of structural formulas 1 to 6, and when it is less than 50%, it is affected by moisture as in the case of the conventional two-component polyurethane adhesive. In the mixing with the polyol having no hydroxyl group of the structural formulas 1 to 6, it is desirable that 75% or more of the total hydroxyl value of the polyurethane polyol (1) after mixing is the hydroxyl group of the structural formulas 1 to 6, More preferably, 100% is a hydroxyl group of structural formulas 1-6.
次に硬化剤であるポリイソシアネート（２）について説明する。ポリウレタンポリオール（１）は、硬化剤であるポリイソシアネート（２）と配合して使用するが、本願目的の水分の影響を受け難く、炭酸ガスの発生に伴う外観不良や強度低下を抑制するためには、その配合比率も重要であって、ポリウレタンポリオール（１）の水酸基数／ポリイソシアネート（２）のイソシアネート基数が、１／０．５〜１／１．５の範囲でポリイソシアネートを配合すればよく、さらに望ましくは、ポリウレタンポリオール（１）の水酸基数／ポリイソシアネート（２）のイソシアネート基数が、１／０．５〜１／０．９の範囲で配合すればよい。 Next, polyisocyanate (2) which is a curing agent will be described. The polyurethane polyol (1) is used in combination with the polyisocyanate (2) which is a curing agent, but is hardly affected by moisture for the purpose of the present application, in order to suppress poor appearance and strength reduction due to the generation of carbon dioxide gas. The blending ratio is also important, and if the polyisocyanate is blended so that the number of hydroxyl groups of the polyurethane polyol (1) / the number of isocyanate groups of the polyisocyanate (2) is 1 / 0.5 to 1 / 1.5. More preferably, the number of hydroxyl groups in the polyurethane polyol (1) / the number of isocyanate groups in the polyisocyanate (2) may be blended in the range of 1 / 0.5 to 1 / 0.9.
水酸基数／イソシアネート基数が１／０．５よりも大きい場合、耐熱性が不充分となる傾向があり、１／１．５よりも小さいと、炭酸ガス発生に伴う外観不良の抑制が不充分となるので、望ましくは、水酸基数／イソシアネート基数＝１／０．５〜１／０．９の範囲となるよう配合するのがよい。 When the number of hydroxyl groups / isocyanate groups is greater than 1 / 0.5, the heat resistance tends to be insufficient, and when it is less than 1 / 1.5, insufficient suppression of appearance defects due to the generation of carbon dioxide gas is insufficient. Therefore, it is desirable that the number of hydroxyl groups / the number of isocyanate groups is 1 / 0.5 to 1 / 0.9.
使用できるポリイソシアネート（２）は、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネートや、トリレ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等のトリメチロールプロパンアダクト、アロファネート体、ヌレート体やビューレット体等であって、単体や混合して使用する事もできるが、食品用途や屋外に使用される建材用途などでは、脂肪族系のポリイソシアネートが望ましい。 Usable polyisocyanates (2) are hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, trimethylolpropane adducts such as tolylene diisocyanate and diphenylmethane diisocyanate, allophanate, nurate and burette, etc. Although they can be used as a mixture, aliphatic polyisocyanates are desirable for food applications and building materials used outdoors.
また、本発明の２液ウレタン系ラミネート用接着剤組成物は、本発明の目的が損なわれない範囲で、ウレタン化触媒、粘着付与剤、酸化防止剤、レベリング剤、紫外線吸収剤、ヒンダードアミン、消泡剤等の各種添加剤を加えることもできるし、二酸化チタン、酸化第二鉄、カーボンブラック、フタロシアニンブルー等の着色顔料や、硫酸バリウム、炭酸カルシウム、タルク等の体質顔料も含有させることができる。 In addition, the two-component urethane laminate adhesive composition of the present invention is a urethanization catalyst, tackifier, antioxidant, leveling agent, ultraviolet absorber, hindered amine, anti-oxidant, and the like within the range in which the object of the present invention is not impaired. Various additives such as foaming agents can be added, and color pigments such as titanium dioxide, ferric oxide, carbon black, phthalocyanine blue, and extender pigments such as barium sulfate, calcium carbonate, and talc can also be included. .
本発明により得られた２液ウレタン系ラミネート用接着剤は、配合接着剤を適切な粘度に溶剤にて希釈し、ドライラミネーション方式等によりフイルムに塗工し、乾燥後に別のフイルムを貼り合わせ、必要に応じて加温雰囲気下で養生させる。尚、希釈に使用する溶剤は、イソシアネートと反応するような水酸基やアミノ基を含有しない溶剤であり、具体的には、酢酸エチル、メチルエチルケトン等が挙げられる。また、接着剤の塗布量は、乾燥状態で、３〜８ｇ／ｍ2の範囲が一般的であるが、これは、フイルム種や要求される物性を考慮に入れ決めればよい。養生条件は、おおよそ、３０℃から６０℃の範囲がよく、使用する硬化剤のイソシアネート基の反応性や、反応触媒の量、種類によっても変わってくるので、予め、赤外吸収スペクトルでイソシアネートの反応速度を測定しておくことが望ましい。 The two-component urethane-based laminating adhesive obtained by the present invention is prepared by diluting the compounded adhesive with a solvent to an appropriate viscosity, applying it to a film by a dry lamination method, and bonding another film after drying, Curing in a warm atmosphere as necessary. The solvent used for dilution is a solvent that does not contain a hydroxyl group or amino group that reacts with isocyanate, and specifically includes ethyl acetate, methyl ethyl ketone, and the like. Further, the amount of adhesive applied is generally in the range of 3 to 8 g / m 2 in a dry state, and this may be determined in consideration of the film type and required physical properties. The curing conditions are generally in the range of 30 ° C to 60 ° C, and vary depending on the reactivity of the isocyanate group of the curing agent used, the amount and type of the reaction catalyst. It is desirable to measure the reaction rate.
ラミネート可能なフイルムには特に限定はなく、ポリエチレンテレフタレート、ナイロン、ポリプロピレン、ポリエチレンや、これらのフイルムにシリカやアルミナ等の蒸着が施されたガスバリアー性を有す蒸着フイルムの他、アルミ箔や銅箔等のラミネートすることができる。特に、少なくとも２層のガスバリアー性フイルムを備えたラミネートシートの接着において、炭酸ガス発生に伴う外観不良を抑える効果が大きい。 There are no particular restrictions on the film that can be laminated. Polyethylene terephthalate, nylon, polypropylene, polyethylene, and other vapor-deposited films with silica or alumina deposited on these films, as well as aluminum foil and copper. Lamination such as foil can be performed. In particular, in the adhesion of a laminate sheet provided with at least two layers of gas barrier film, the effect of suppressing appearance defects associated with the generation of carbon dioxide gas is great.
本願発明により得られた２液ウレタン系ラミネート用接着剤は、水分による影響を受け難く、特に、複合化された多層積層体中にガスバリアー性のフイルムが含まれる場合は、炭酸ガスの発生に由来する気泡による外観不良や強度不足抑制に効果が認められたことが明らかである。また本願発明は、炭酸ガス発生に伴う外観不良を抑制することができる少なくとも２層のガスバリアー性フイルムを備えたラミネートシートを提供することができたものである。 The two-component urethane-based laminate adhesive obtained by the present invention is hardly affected by moisture, and particularly when a gas barrier film is contained in the composite multilayer laminate, carbon dioxide gas is not generated. It is clear that the effect was recognized in the appearance defect and the intensity | strength shortage suppression by the bubble which originates. In addition, the present invention has been able to provide a laminate sheet provided with at least two layers of a gas barrier film capable of suppressing the appearance defect accompanying the generation of carbon dioxide gas.
以下に実施例を比較例と共に挙げて、本発明を更に詳しく説明するが、本発明はこれら実施例にのみ限定されるのものではない。なお、以下の表を含む説明において、配合量の単位は、原則として質量部である。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the description including the following table, the unit of the blending amount is in principle parts by mass.
＜ポリエステルポリオール（Ｐ）の合成＞
窒素導入管、攪拌機、精留塔、コンデンサーを備えた２Ｌのフラスコに、ネオペンチルグリコール（４３６．８ｇ）、エチレングリコール（３７．２ｇ）、アジピン酸（２６２．８ｇ）、セバシン酸（３６３．６ｇ）を加え、加熱攪拌しながら内温１８０〜２００℃で脱水縮合させた。樹脂酸価が１５ｍｇＫＯＨ／ｇになったことを確認し、窒素を吹き込みながら、２００〜２４０℃でさらに脱水反応を進め、樹脂酸価が２ｍｇ／ＫＯＨ以下になったことを確認した後に、内圧を１５Ｔｏｒｒに減圧して引き続き反応を進め、酸価０．１ｍｇＫＯＨ／ｇ以下になったことを確認して反応を終了させた。得られたポリエステル樹脂の水酸基価は１１３ｍｇＫＯＨ／ｇであり、これをポリエステルポリオール（Ｐ）とした。尚、ポリエステルポリオール（Ｐ）の分子末端の水酸基は、エチレングリコール残基および／またはネオペンチルグリコール残基であることが使用原料から判断される。
<Synthesis of polyester polyol (P)>
Into a 2 L flask equipped with a nitrogen inlet tube, a stirrer, a rectifying column and a condenser, neopentyl glycol (436.8 g), ethylene glycol (37.2 g), adipic acid (262.8 g), sebacic acid (363.6 g) The mixture was dehydrated and condensed at an internal temperature of 180 to 200 ° C. with heating and stirring. After confirming that the resin acid value was 15 mgKOH / g and further blowing dehydration at 200 to 240 ° C. while blowing nitrogen, and confirming that the resin acid value was 2 mg / KOH or less, the internal pressure was reduced. The reaction was continued by reducing the pressure to 15 Torr, and the reaction was terminated after confirming that the acid value was 0.1 mgKOH / g or less. The obtained polyester resin had a hydroxyl value of 113 mgKOH / g and was designated as polyester polyol (P). In addition, it is judged from a raw material to be used that the hydroxyl group at the molecular terminal of the polyester polyol (P) is an ethylene glycol residue and / or a neopentyl glycol residue.
＜ポリウレタンポリオール（１）を得るための中間体（Ｉ）−１の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、ポリエステル（Ｐ）（３３８．２ｇ）、ネオペンチルグリコール（１８．０ｇ）、酢酸エチル（５００．０ｇ）を仕込み、攪拌しながら６０℃に加温して内容物を完全に溶解させた。２０℃まで冷却後、ジブチル錫ジラウレート（０．１ｇ）、イソホロンジイソシアネート（１４３．７ｇ）を加え加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、もはや２２７０ｃｍ-1のイソシアネートの吸収が減少しないことを確認し、中間体（Ｉ）−１の５０％酢酸エチル溶液を得た。
<Synthesis of Intermediate (I) -1 for Obtaining Polyurethane Polyol (1)>
In a nitrogen atmosphere, a 2 L flask equipped with a stirrer was charged with polyester (P) (338.2 g), neopentyl glycol (18.0 g), and ethyl acetate (500.0 g), and heated to 60 ° C. while stirring. The contents were completely dissolved. After cooling to 20 ° C., dibutyltin dilaurate (0.1 g) and isophorone diisocyanate (143.7 g) were added and heated to reflux. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 was no longer decreased, and a 50% ethyl acetate solution of intermediate (I) -1 was obtained.
＜ポリウレタンポリオール（１）を得るための中間体（Ｉ）−２の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、ポリエステル（Ｐ）（３００．２ｇ）、ネオペンチルグリコール（３６．０ｇ）、酢酸エチル（５００．０ｇ）を仕込み、攪拌しながら６０℃に加温して内容物を完全に溶解させた。２０℃まで冷却後、ジブチル錫ジラウレート（０．１ｇ）、イソホロンジイソシアネート（１６３．７ｇ）を加え加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、もはや２２７０ｃｍ-1のイソシアネートの吸収が減少しないことを確認し、中間体（Ｉ）−２の５０％酢酸エチル溶液を得た。
<Synthesis of Intermediate (I) -2 for Obtaining Polyurethane Polyol (1)>
Under a nitrogen atmosphere, a 2 L flask equipped with a stirrer was charged with polyester (P) (300.2 g), neopentyl glycol (36.0 g), and ethyl acetate (500.0 g), and heated to 60 ° C. with stirring. The contents were completely dissolved. After cooling to 20 ° C., dibutyltin dilaurate (0.1 g) and isophorone diisocyanate (163.7 g) were added and heated to reflux. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 was no longer decreased, and a 50% ethyl acetate solution of intermediate (I) -2 was obtained.
＜ポリウレタンポリオール（１）−１の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−１（９６０．８ｇ）、１，４−ブンタンジオール（１９．６ｇ）、酢酸エチル（１９．６ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（１）−１の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (1) -1>
Under a nitrogen atmosphere, a 2 L flask equipped with a stirrer was charged with intermediate (I) -1 (960.8 g), 1,4-butanediol (19.6 g), and ethyl acetate (19.6 g) for 6 hours. Heated to reflux. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 disappeared, and 50% acetic acid of polyurethane polyol (1) -1 having a hydroxyl value of 20 mgKOH / g. An ethyl solution was obtained.
＜ポリウレタンポリオール（１）−２の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−１（９５４．８ｇ）、１，５−ペンタンジオール（２２．６ｇ）、酢酸エチル（２２．６ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（１）−２の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (1) -2>
Under a nitrogen atmosphere, a 2 L flask equipped with a stirrer was charged with intermediate (I) -1 (954.8 g), 1,5-pentanediol (22.6 g), and ethyl acetate (22.6 g) for 6 hours. Heated to reflux. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 disappeared, and 50% acetic acid of polyurethane polyol (1) -2 having a hydroxyl value of 20 mgKOH / g. An ethyl solution was obtained.
＜ポリウレタンポリオール（１）−３の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−１（９４９．０ｇ）、３−メチル−１，５−ペンタンジオール（２５．５ｇ）、酢酸エチル（２５．５ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（１）−３の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (1) -3>
In a 2 L flask equipped with a stirrer under a nitrogen atmosphere, intermediate (I) -1 (949.0 g), 3-methyl-1,5-pentanediol (25.5 g), and ethyl acetate (25.5 g) were added. Charged and heated to reflux for 6 hours. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 disappeared, and 50% acetic acid of polyurethane polyol (1) -3 having a hydroxyl value of 20 mgKOH / g. An ethyl solution was obtained.
＜ポリウレタンポリオール（１）−４の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−１（９４９．０ｇ）、１，６−ヘキサンジオール（２５．５ｇ）、酢酸エチル（２５．５ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（１）−４の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (1) -4>
Under a nitrogen atmosphere, a 2 L flask equipped with a stirrer was charged with intermediate (I) -1 (949.0 g), 1,6-hexanediol (25.5 g), and ethyl acetate (25.5 g) for 6 hours. Heated to reflux. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 had disappeared. 50% acetic acid of polyurethane polyol (1) -4 having a hydroxyl value of 20 mgKOH / g An ethyl solution was obtained.
＜ポリウレタンポリオール（１）−５の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−１（８１１．２ｇ）、ネオペンチルグリコール（２．５ｇ）、酢酸エチル（２．５ｇ）を仕込み加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、もはや２２７０ｃｍ-1のイソシアネートの吸収が減少しないことを確認し、ダイセル化学工業株式会社製カプロラクトンジオール（プラクセル２０５Ｕ：水酸基価 ２１２ｍｇＫＯＨ）（９１．９ｇ）、酢酸エチル（９１．９ｇ）を加え、更に４時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（１）−５の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (1) -5>
Under a nitrogen atmosphere, a 2 L flask equipped with a stirrer was charged with intermediate (I) -1 (811.2 g), neopentyl glycol (2.5 g), and ethyl acetate (2.5 g) and heated to reflux. The product in the flask was measured by an infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 was no longer decreased. Caprolactone diol (Placcel 205U: hydroxyl value 212 mgKOH) (91) manufactured by Daicel Chemical Industries, Ltd. (91 0.9 g) and ethyl acetate (91.9 g) were added, and the mixture was further heated to reflux for 4 hours. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 disappeared, and 50% acetic acid of polyurethane polyol (1) -5 having a hydroxyl value of 20 mgKOH / g. An ethyl solution was obtained.
＜ポリウレタンポリオール（１）−６の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−１（９３８．２ｇ）、１，４−シクロヘキサンジメタノール（３０．９ｇ）、酢酸エチル（３０．９ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（１）−６の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (1) -6>
Under a nitrogen atmosphere, a 2 L flask equipped with a stirrer was charged with intermediate (I) -1 (938.2 g), 1,4-cyclohexanedimethanol (30.9 g), and ethyl acetate (30.9 g). Heated to reflux for hours. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 disappeared, and 50% acetic acid of polyurethane polyol (1) -6 having a hydroxyl value of 20 mgKOH / g. An ethyl solution was obtained.
＜ポリウレタンポリオール（１）−７の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−２（６９９．２ｇ）、ポリカーボネートジオール（デュラノールＴ５６５１：旭化成ケミカルズ株式会社製 １，５−ペンタンジオールと１，６−ヘキサンジオールから得られたポリカーボネートジオール 水酸基価１１３ｍｇＫＯＨ／ｇ）（１５０．４ｇ）、酢酸エチル（１５０．４ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（１）−７の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (1) -7>
In a 2 L flask equipped with a stirrer in a nitrogen atmosphere, intermediate (I) -2 (699.2 g), polycarbonate diol (Duranol T5651: manufactured by Asahi Kasei Chemicals Corporation 1,5-pentanediol and 1,6-hexanediol The polycarbonate diol obtained from the above was charged with a hydroxyl value of 113 mg KOH / g) (150.4 g) and ethyl acetate (150.4 g), and heated to reflux for 6 hours. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 disappeared. 50% acetic acid of polyurethane polyol (1) -7 having a hydroxyl value of 20 mgKOH / g An ethyl solution was obtained.
＜ポリウレタンポリオール（１）−８の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−２（６９９．２ｇ）、ポリカーボネートジオール（デュラノールＴ４６７１：旭化成ケミカルズ株式会社製 １，４−ブタンジオールと１，６−ヘキサンジオールから得られたポリカーボネートジオール 水酸基価１１３ｍｇＫＯＨ／ｇ）（１５０．４ｇ）、酢酸エチル（１５０．４ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（１）−８の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (1) -8>
In a 2 L flask equipped with a stirrer in a nitrogen atmosphere, intermediate (I) -2 (699.2 g), polycarbonate diol (Duranol T4671: manufactured by Asahi Kasei Chemicals Corporation 1,4-butanediol and 1,6-hexanediol The polycarbonate diol obtained from the above was charged with a hydroxyl value of 113 mg KOH / g) (150.4 g) and ethyl acetate (150.4 g), and heated to reflux for 6 hours. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 had disappeared. 50% acetic acid of polyurethane polyol (1) -8 having a hydroxyl value of 20 mgKOH / g An ethyl solution was obtained.
＜ポリウレタンポリオール（１）−９の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−２（７２４．２ｇ）、ポリカーボネートジオール（ＵＭ−９０（１／３）：宇部興産株式会社製 １，４−シクロヘキサンジメタノールと１，６−ヘキサンジオールから得られたポリカーボネートジオール 水酸基価１２５ｍｇＫＯＨ／ｇ）（１３７．９ｇ）、酢酸エチル（１３７．９ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（１）−９の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (1) -9>
Under a nitrogen atmosphere, in a 2 L flask equipped with a stirrer, intermediate (I) -2 (724.2 g), polycarbonate diol (UM-90 (1/3): Ube Industries, Ltd. 1,4-cyclohexanedimethanol Polycarbonate diol obtained from 1,6-hexanediol Hydroxyl value 125 mgKOH / g) (137.9 g) and ethyl acetate (137.9 g) were charged and heated to reflux for 6 hours. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 disappeared, and 50% acetic acid of polyurethane polyol (1) -9 having a hydroxyl value of 20 mgKOH / g. An ethyl solution was obtained.
＜ポリウレタンポリオール（１）−１０の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−２（６９９．２ｇ）、ポリカーボネートジオール（ＥＴＥＲＮＡＣＯＬＬ ＵＨＣ５０−１００：宇部興産株式会社製 カプロラクトンと１，６−ヘキサンジオールから得られたポリエステルカーボネートジオール 水酸基価１１３ｍｇＫＯＨ／ｇ）（１５０．４ｇ）、酢酸エチル（１５０．４ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（１）−１０の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (1) -10>
In a 2 L flask equipped with a stirrer under a nitrogen atmosphere, intermediate (I) -2 (699.2 g), polycarbonate diol (ETERRNACOLL UHC50-100: manufactured by Ube Industries, Ltd.) obtained from caprolactone and 1,6-hexanediol Polyester carbonate diol Hydroxyl value 113 mgKOH / g) (150.4 g) and ethyl acetate (150.4 g) were charged and heated to reflux for 6 hours. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 disappeared, and 50% acetic acid of polyurethane polyol (1) -10 having a hydroxyl value of 20 mgKOH / g. An ethyl solution was obtained.
＜ポリウレタンポリオール（１）−１１の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−２（６２４．０ｇ）、ポリカーボネートジオール（デュラノールＴ５６５１：旭化成ケミカルズ株式会社製 １，５−ペンタンジオールと１，６−ヘキサンジオールから得られたポリカーボネートジオール 水酸基価１１３ｍｇＫＯＨ／ｇ）（１８８．０ｇ）、酢酸エチル（１８８．０ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価３０ｍｇＫＯＨ／ｇのポリウレタンポリオール（１）−１１の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (1) -11>
In a 2 L flask equipped with a stirrer in a nitrogen atmosphere, intermediate (I) -2 (624.0 g), polycarbonate diol (Duranol T5651: manufactured by Asahi Kasei Chemicals Corporation 1,5-pentanediol and 1,6-hexanediol The polycarbonate diol obtained from the above was charged with a hydroxyl value of 113 mgKOH / g) (188.0 g) and ethyl acetate (188.0 g), and heated to reflux for 6 hours. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 disappeared, and 50% acetic acid of polyurethane polyol (1) -11 having a hydroxyl value of 30 mgKOH / g. An ethyl solution was obtained.
＜ポリウレタンポリオール（１）−１２の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−２（７７４．４ｇ）、ポリカーボネートジオール（デュラノールＴ５６５１：旭化成ケミカルズ株式会社製 １，５−ペンタンジオールと１，６−ヘキサンジオールから得られたポリカーボネートジオール 水酸基価１１３ｍｇＫＯＨ／ｇ）（１１２．８ｇ）、酢酸エチル（１１２．８ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価１０ｍｇＫＯＨ／ｇのポリウレタンポリオール（１）−１２の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (1) -12>
In a 2 L flask equipped with a stirrer in a nitrogen atmosphere, intermediate (I) -2 (774.4 g), polycarbonate diol (Duranol T5651: manufactured by Asahi Kasei Chemicals Corporation 1,5-pentanediol and 1,6-hexanediol The polycarbonate diol obtained from the above was charged with a hydroxyl value of 113 mg KOH / g) (112.8 g) and ethyl acetate (112.8 g), and heated to reflux for 6 hours. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of the isocyanate of 2270 cm −1 disappeared, and 50% acetic acid of polyurethane polyol (1) -12 having a hydroxyl value of 10 mgKOH / g. An ethyl solution was obtained.
次に、比較例として用いる末端に特定の構造を有さないポリウレタンポリオール（比１）〜（比５）を以下の方法にて合成した。 Next, polyurethane polyols (ratio 1) to (ratio 5) having no specific structure at the ends used as comparative examples were synthesized by the following method.
＜ポリウレタンポリオール（比１）の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−１（９５４．８ｇ）、ネオペンチルグリコール（２２．６ｇ）、酢酸エチル（２２．６ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（比１）の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (ratio 1)>
Under a nitrogen atmosphere, a 2 L flask equipped with a stirrer was charged with intermediate (I) -1 (954.8 g), neopentyl glycol (22.6 g), and ethyl acetate (22.6 g), and heated to reflux for 6 hours. It was. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 disappeared, and 50% ethyl acetate of polyurethane polyol (ratio 1) having a hydroxyl value of 20 mgKOH / g. A solution was obtained.
＜ポリウレタンポリオール（比２）の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−１（９７２．８ｇ）、エチレングリコール（１３．６ｇ）、酢酸エチル（１３．６ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（比２）の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (ratio 2)>
Under a nitrogen atmosphere, a 2 L flask equipped with a stirrer was charged with intermediate (I) -1 (972.8 g), ethylene glycol (13.6 g), and ethyl acetate (13.6 g) and heated to reflux for 6 hours. . The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 disappeared, and 50% ethyl acetate of polyurethane polyol (ratio 2) having a hydroxyl value of 20 mgKOH / g. A solution was obtained.
＜ポリウレタンポリオール（比３）の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−１（９６０．８ｇ）、プロピレングリコール（１９．６ｇ）、酢酸エチル（１９．６ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（比３）の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (ratio 3)>
Under a nitrogen atmosphere, a 2 L flask equipped with a stirrer was charged with intermediate (I) -1 (960.8 g), propylene glycol (19.6 g), and ethyl acetate (19.6 g), and heated to reflux for 6 hours. . The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 disappeared, and 50% ethyl acetate of polyurethane polyol (ratio 3) having a hydroxyl value of 20 mgKOH / g. A solution was obtained.
＜ポリウレタンポリオール（比４）の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−２（６９９．２ｇ）とポリエステルポリオール（Ｐ）（１５０．４ｇ）、酢酸エチル（１５０．４ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（比４）の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (ratio 4)>
Under a nitrogen atmosphere, a 2 L flask equipped with a stirrer was charged with intermediate (I) -2 (699.2 g), polyester polyol (P) (150.4 g), and ethyl acetate (150.4 g), and heated for 6 hours. Refluxed. The product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of isocyanate at 2270 cm −1 disappeared, and 50% ethyl acetate of polyurethane polyol (ratio 4) having a hydroxyl value of 20 mgKOH / g. A solution was obtained.
＜ポリウレタンポリオール（比５）の合成＞
窒素雰囲気下、攪拌機を備えた２Ｌのフラスコに、中間体（Ｉ）−２（６９９．２ｇ）とポリプロピレングリコール（三洋化成工業株式会社製 サンニックス ＰＰ−１０００ 水酸基価 １１３ｍｇＫＯＨ／ｇ（１５０．４ｇ）、酢酸エチル（１５０．４ｇ）を仕込み、６時間加熱還流させた。赤外吸収スペクトルにて、フラスコ内の生成物を測定し、２２７０ｃｍ-1のイソシアネートの吸収が消失していることを確認し、水酸基価２０ｍｇＫＯＨ／ｇのポリウレタンポリオール（比５）の５０％酢酸エチル溶液を得た。
<Synthesis of polyurethane polyol (ratio 5)>
Under a nitrogen atmosphere, in a 2 L flask equipped with a stirrer, intermediate (I) -2 (699.2 g) and polypropylene glycol (Sanix Kasei Kogyo Sannix PP-1000 hydroxyl value 113 mg KOH / g (150.4 g) Then, ethyl acetate (150.4 g) was charged and heated to reflux for 6 hours, and the product in the flask was measured by infrared absorption spectrum, and it was confirmed that the absorption of 2270 cm −1 isocyanate had disappeared. A 50% ethyl acetate solution of a polyurethane polyol (ratio 5) having a hydroxyl value of 20 mgKOH / g was obtained.
＜ポリイソシアネート（２）−１の調整＞
窒素雰囲気下、ＨＤＩのヌレート体（旭化成ケミカルズ株式会社製 デュラネートＴＰＡ−１００、イソシアネート含有量２３％）の１００ｇを５００ｍｌのフラスコに仕込み、酢酸エチル（１００ｇ）を加え、攪拌して均一にし、固形分５０％のポリイソシアネート（２）−１を得た。
<Preparation of polyisocyanate (2) -1>
In a nitrogen atmosphere, 100 g of HDI nurate (Duranate TPA-100 manufactured by Asahi Kasei Chemicals Co., Ltd., 23% isocyanate content) was charged into a 500 ml flask, added with ethyl acetate (100 g), and stirred to homogenize the solid content. 50% of polyisocyanate (2) -1 was obtained.
＜ポリイソシアネート（２）−２の調整＞
窒素雰囲気下、イソホロンジイソシアネートのトリメチロールプロパンアダクト体（三井化学ポリウレタン社製 タケネート Ｄ１４０Ｎ、イソシアネート含有量１０．５％）の２００ｇを５００ｍｌのフラスコに仕込み、酢酸エチル（１００．０ｇ）を加え、攪拌して均一にし、固形分５０％のポリイソシアネート（２）−２を得た。
<Preparation of polyisocyanate (2) -2>
In a nitrogen atmosphere, 200 g of a trimethylolpropane adduct of isophorone diisocyanate (Takenate D140N manufactured by Mitsui Chemicals Polyurethanes, isocyanate content 10.5%) was charged into a 500 ml flask, and ethyl acetate (100.0 g) was added and stirred. To obtain polyisocyanate (2) -2 having a solid content of 50%.
得られたポリウレタンポリオール（１）−１〜（１）−１２および比較例として使用するポリウレタンポリオール（比１）〜（比５）の水酸基価と末端構造を表１に記す。 Table 1 shows the hydroxyl values and terminal structures of the obtained polyurethane polyols (1) -1 to (1) -12 and the polyurethane polyols (ratio 1) to (ratio 5) used as comparative examples.
また、先に得られたポリウレタンポリオール（１）−４および（１）−７に、各々ポリウレタンポリオール（比１）および（比４）を表２に示す重量比にて配合し、混合系のポリウレタンポリオール（１）−１３〜（１）−１６とそれらの比較例として、ポリウレタンポリオール（比６）と（比７）を得た。
また、得られた実施例のポリウレタンポリオール（１）−１〜（１）−１６、比較例のポリウレタンポリオール（比１）〜（比７）に、硬化剤であるポリイソシアネート（２）−１および（２）−２を表３に示す水酸基数／イソシアネート基数となるよう配合して、実施例１から実施例２０および比較例１から比較例１２の接着剤を配合した。
配合接着剤は、酢酸エチルを用いて固形分２５％に調整後、バーコーターにて乾燥塗布量４．５ｇ／ｍ2となるように、シリカ蒸着フイルム（ＭＯＳ ＳＲ：尾池工業株式会社製 ＰＥＴ原反 １２μｍ）の蒸着が施されている面に塗工した。ドライヤーにて酢酸エチルを揮発させた後に、もう一方のフイルムを貼り合せ、６０℃のホットプレート上にてニップした。得られたラミネートシートは、養生条件１として、４０℃×２０％湿度の雰囲気下で、および、養生条件２として、４０℃×５０％湿度の雰囲気下で５日間養生させた。尚、貼り合わせたフイルム構成は以下に示す。
［貼り合せフイルム構成］
構成１．ＭＯＳ ＳＲ 蒸着面／接着剤／蒸着面 ＭＯＳ ＳＲ
構成２．ＭＯＳ ＳＲ 蒸着面／接着剤／コロナ面 無延伸ポリプロピレン ６０μｍ
The blended adhesive was adjusted to a solid content of 25% using ethyl acetate, and then a silica-deposited film (MOS SR: PET made by Oike Kogyo Co., Ltd.) was applied with a bar coater to a dry coating amount of 4.5 g / m 2. Coating was performed on the surface on which the original film (12 μm) was deposited. After volatilizing ethyl acetate with a dryer, the other film was bonded and nipped on a hot plate at 60 ° C. The obtained laminate sheet was cured under curing condition 1 under an atmosphere of 40 ° C. × 20% humidity and as curing condition 2 under an atmosphere of 40 ° C. × 50% humidity for 5 days. The laminated film configuration is shown below.
[Laminated film composition]
Configuration 1. MOS SR Deposition surface / Adhesive / Deposition surface MOS SR
Configuration 2. MOS SR Deposition surface / Adhesive / Corona surface Unstretched polypropylene 60μm
養生の終了したラミネートシートについて、構成１については、ガス発生による外観不良の程度を目視で評価した。尚、外観不良の評価基準は以下の通り。また、構成２については、１５ｍｍ幅の試験片を作製し、引っ張り試験機により５０ｍｍ／ｍｉｎの引っ張り速度にて、Ｔ型剥離によりラミネート強度を測定した。
［外観不良の評価基準］
発泡が観察されない（評価１）
僅かに発泡が観察される（評価２）
発泡が観察される（評価３）
激しく発泡が観察される（評価４）
非常に激しい発泡が観察される(評価５）
About the laminated sheet which the curing was complete | finished, about the structure 1, the grade of the external appearance defect by gas generation was evaluated visually. The evaluation criteria for poor appearance are as follows. For configuration 2, a 15 mm wide test piece was prepared, and the laminate strength was measured by T-type peeling at a pulling rate of 50 mm / min with a tensile tester.
[Evaluation criteria for appearance defects]
No foaming is observed (Evaluation 1)
Slight foaming is observed (Evaluation 2)
Foaming is observed (Evaluation 3)
Vigorous foaming is observed (Evaluation 4)
Very intense foaming is observed (Evaluation 5)
構成１のラミネートシート外観評価については、外観不良評価基準に基づき評価を行い、評価１および２を合格判定とし、評価３〜５を不合格判定とした。構成２のラミネートシートのラミネート強度については、測定結果を示し、条件１と条件２との強度差が、０．６Ｎ未満を合格、０．６Ｎ以上を不合格とした。これらの外観評価およびラミネート強度評価（単位：Ｎ／１５ｍｍ）の結果は表４に示した。
以上のように、上記の各実施例に係る２液配合型ウレタン系接着剤によって、水分の影響を受け難く、ガスバリアー性フイルム同士の貼りあわせ時にしばしば問題となる、炭酸ガスの発生に伴う外観不良や強度不足等を抑制することが確認されたものである。 As described above, the two-component mixed urethane adhesive according to each of the above embodiments is hardly affected by moisture and often causes a problem when the gas barrier films are bonded to each other. It has been confirmed that defects and insufficient strength are suppressed.
Claims (7)
上記ポリウレタンポリオール（１）はその末端に水酸基を備え、当該末端の水酸基はその全水酸基価中の５０％以上がウレタン結合を介してなる構造式１〜６何れかの水酸基であり、
且つ、上記ポリウレタンポリオール（１）は少なくともポリエステルポリオール（Ｐ）（但し、２種以下のモノマーから成るポリエステルポリオール（Ｐ）を除く）から形成される化学構造を含み、上記ポリウレタンポリオール（１）の水酸基数と上記ポリイソシアネート（２）のイソシアネート基数とが、水酸基数／イソシアネート基数＝１／０．５〜１／１．５の範囲で配合して用いる水分の影響を受け難い２液ラミネート用接着剤組成物。
構造式１ −Ｏ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＯＨ
構造式２ −Ｏ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＯＨ
構造式３ −Ｏ−ＣＨ２−ＣＨ２−ＣＨ（ＣＨ３）−ＣＨ２−ＣＨ２−ＯＨ
構造式４ −Ｏ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＯＨ
構造式５ −Ｏ−ＣＯ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＯＨ
構造式６ −Ｏ−ＣＨ２−（ｃｙｃｌｏ−Ｃ６Ｈ１０）−ＣＨ２−ＯＨ In the two-component laminating adhesive composition used for adhesion between the films of the laminate sheet, the two-component laminating adhesive composition is used by blending the polyisocyanate (2) with the polyurethane polyol (1). ,
The polyurethane polyol (1) has a hydroxyl group at the terminal, and the hydroxyl group at the terminal is a hydroxyl group of any one of structural formulas 1 to 6 in which 50% or more of the total hydroxyl value is via a urethane bond,
The polyurethane polyol (1) includes a chemical structure formed from at least a polyester polyol (P) (excluding a polyester polyol (P) composed of 2 or less monomers), and the hydroxyl group of the polyurethane polyol (1). Number and the number of isocyanate groups of the polyisocyanate (2) are mixed and used in the range of hydroxyl number / isocyanate group = 1 / 0.5 to 1 / 1.5. Composition.
Structural Formula 1 —O—CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 2 —O—CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 3 —O—CH 2 —CH 2 —CH (CH 3 ) —CH 2 —CH 2 —OH
Structural Formula 4 —O—CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 5 —O—CO—CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 6 —O—CH 2 — (cyclo-C 6 H 10 ) —CH 2 —OH
構造式１ −Ｏ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＯＨ
構造式２ −Ｏ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＯＨ
構造式３ −Ｏ−ＣＨ２−ＣＨ２−ＣＨ（ＣＨ３）−ＣＨ２−ＣＨ２−ＯＨ
構造式４ −Ｏ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＯＨ
構造式５ −Ｏ−ＣＯ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＯＨ
構造式６ −Ｏ−ＣＨ２−（ｃｙｃｌｏ−Ｃ６Ｈ１０）−ＣＨ２−ＯＨ In the two-component laminating adhesive composition used for adhesion between the films of the laminate sheet, the two-component laminating adhesive composition is used by blending the polyisocyanate (2) with the polyurethane polyol (1). , 50% or more of the total hydroxyl value of the polyurethane polyol (1) is a hydroxyl group of any one of structural formulas 1 to 6 via a polycarbonate bond, and the number of hydroxyl groups of the polyurethane polyol (1) and the polyisocyanate (2 The number of isocyanate groups in (2) is an adhesive composition for two-component laminates that is less susceptible to the effects of moisture used by blending the number of hydroxyl groups / the number of isocyanate groups = 1 / 0.5 to 1 / 1.5.
Structural Formula 1 —O—CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 2 —O—CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 3 —O—CH 2 —CH 2 —CH (CH 3 ) —CH 2 —CH 2 —OH
Structural Formula 4 —O—CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 5 —O—CO—CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 6 —O—CH 2 — (cyclo-C 6 H 10 ) —CH 2 —OH
上記ポリウレタンポリオール（１）は、その末端の水酸基が構造式１〜６の何れかを備えたものであり、且つ、その全水酸基価中の５０％以上が構造式１〜６何れかの水酸基であり、
且つ、上記ポリウレタンポリオール（１）は少なくともポリエステルポリオール（Ｐ）（但し、２種以下のモノマーから成るポリエステルポリオール（Ｐ）を除く）から形成される化学構造を含み、上記のポリウレタンポリオール（１）は、ジオール成分とジイソシアネート化合物によって末端イソシアネート化合物に誘導した後に、上記の構造式１〜６の何れかの構造を有するジオールの水酸基をイソシアネート基と反応させることで、上記の構造式１〜６の何れかの構造を有する水酸基を分子末端に備えているものであり、上記ポリウレタンポリオール（１）の水酸基数と上記ポリイソシアネート（２）のイソシアネート基数とが、水酸基数／イソシアネート基数＝１／０．５〜１／１．５の範囲で配合して用いる水分の影響を受け難い２液ラミネート用接着剤組成物。
構造式１ −Ｏ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＯＨ
構造式２ −Ｏ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＯＨ
構造式３ −Ｏ−ＣＨ２−ＣＨ２−ＣＨ（ＣＨ３）−ＣＨ２−ＣＨ２−ＯＨ
構造式４ −Ｏ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＯＨ
構造式５ −Ｏ−ＣＯ−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＣＨ２−ＯＨ
構造式６ −Ｏ−ＣＨ２−（ｃｙｃｌｏ−Ｃ６Ｈ１０）−ＣＨ２−ＯＨ In the two-component laminating adhesive composition used for adhesion between the films of the laminate sheet, the two-component laminating adhesive composition is used by blending the polyisocyanate (2) with the polyurethane polyol (1). ,
The polyurethane polyol (1) has a terminal hydroxyl group having any one of structural formulas 1 to 6, and 50% or more of the total hydroxyl value is a hydroxyl group of any one of structural formulas 1 to 6. Yes,
The polyurethane polyol (1) includes a chemical structure formed from at least a polyester polyol (P) (excluding a polyester polyol (P) composed of 2 or less monomers), and the polyurethane polyol (1) After the diol component and the diisocyanate compound lead to a terminal isocyanate compound, the hydroxyl group of the diol having the structure of any one of the above structural formulas 1 to 6 is reacted with the isocyanate group, whereby any one of the above structural formulas 1 to 6 The number of hydroxyl groups of the polyurethane polyol (1) and the number of isocyanate groups of the polyisocyanate (2) is the number of hydroxyl groups / the number of isocyanate groups = 1 / 0.5. Less affected by moisture used by blending in the range of ~ 1 / 1.5 Liquid laminating adhesive composition.
Structural Formula 1 —O—CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 2 —O—CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 3 —O—CH 2 —CH 2 —CH (CH 3 ) —CH 2 —CH 2 —OH
Structural Formula 4 —O—CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 5 —O—CO—CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —OH
Structural Formula 6 —O—CH 2 — (cyclo-C 6 H 10 ) —CH 2 —OH
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| JP6439237B2 (en) * | 2013-06-19 | 2018-12-19 | Dic株式会社 | Novel polyester polyurethane polyol, polyol component for two-component laminate adhesive, resin composition, curable resin composition, adhesive for two-component laminate, and solar cell backsheet |
| EP3312208B1 (en) * | 2015-06-18 | 2023-02-22 | DIC Corporation | Two-part curable composition, two-part-type adhesive agent, two-part-type coating agent, and laminate |
| EP3317317A1 (en) * | 2015-07-02 | 2018-05-09 | Dow Global Technologies LLC | Laminating adhesive-polyester-polycarbonate-polyol systems |
| JP6780356B2 (en) * | 2016-08-05 | 2020-11-04 | 大日本印刷株式会社 | A display device using a backlight light source provided with a barrier film for a wavelength conversion sheet, a wavelength conversion sheet using a barrier film for a wavelength conversion sheet, and |
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