JP2012126003A - Laminate - Google Patents
Laminate Download PDFInfo
- Publication number
- JP2012126003A JP2012126003A JP2010279143A JP2010279143A JP2012126003A JP 2012126003 A JP2012126003 A JP 2012126003A JP 2010279143 A JP2010279143 A JP 2010279143A JP 2010279143 A JP2010279143 A JP 2010279143A JP 2012126003 A JP2012126003 A JP 2012126003A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- adhesive layer
- laminate
- isocyanate compound
- metal alkoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010410 layer Substances 0.000 claims abstract description 107
- -1 isocyanate compound Chemical class 0.000 claims abstract description 68
- 239000012790 adhesive layer Substances 0.000 claims abstract description 61
- 229920003023 plastic Polymers 0.000 claims abstract description 50
- 239000004033 plastic Substances 0.000 claims abstract description 50
- 239000000565 sealant Substances 0.000 claims abstract description 48
- 239000012948 isocyanate Substances 0.000 claims abstract description 43
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 39
- 239000010409 thin film Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 29
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 12
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 150000002513 isocyanates Chemical class 0.000 claims description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 4
- 229920013716 polyethylene resin Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000000758 substrate Substances 0.000 abstract description 46
- 230000004888 barrier function Effects 0.000 abstract description 13
- 230000003204 osmotic effect Effects 0.000 abstract description 2
- 238000012856 packing Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 54
- 239000000853 adhesive Substances 0.000 description 28
- 230000001070 adhesive effect Effects 0.000 description 28
- 239000007787 solid Substances 0.000 description 23
- 239000000126 substance Substances 0.000 description 18
- 238000007740 vapor deposition Methods 0.000 description 16
- 238000001125 extrusion Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003851 corona treatment Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000000470 constituent Substances 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 239000005022 packaging material Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 229910052814 silicon oxide Inorganic materials 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 229910010272 inorganic material Inorganic materials 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
- 239000004310 lactic acid Substances 0.000 description 5
- 235000014655 lactic acid Nutrition 0.000 description 5
- 229920006284 nylon film Polymers 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 229920003232 aliphatic polyester Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 150000002484 inorganic compounds Chemical class 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000003475 lamination Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 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 4
- 238000011282 treatment Methods 0.000 description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013040 bath agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- RRRXPPIDPYTNJG-UHFFFAOYSA-N perfluorooctanesulfonamide Chemical compound NS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RRRXPPIDPYTNJG-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- SSTHBHCRNGPPAI-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluoro-n,n-bis(2-hydroxyethyl)octane-1-sulfonamide Chemical compound OCCN(CCO)S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SSTHBHCRNGPPAI-UHFFFAOYSA-N 0.000 description 1
- OHPZNXYJAZBDSJ-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonic acid;2-(2-hydroxyethylamino)ethanol Chemical compound OCCNCCO.OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F OHPZNXYJAZBDSJ-UHFFFAOYSA-N 0.000 description 1
- IYGMOFAWEXCNAU-UHFFFAOYSA-N 1-fluorooctane-1-sulfonic acid Chemical compound CCCCCCCC(F)S(O)(=O)=O IYGMOFAWEXCNAU-UHFFFAOYSA-N 0.000 description 1
- WHBMMWSBFZVSSR-UHFFFAOYSA-M 3-hydroxybutyrate Chemical compound CC(O)CC([O-])=O WHBMMWSBFZVSSR-UHFFFAOYSA-M 0.000 description 1
- YXWFTAHVYOBABK-UHFFFAOYSA-N 3-isocyanatopropyl(trimethyl)silane Chemical compound C[Si](C)(C)CCCN=C=O YXWFTAHVYOBABK-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 241000047703 Nonion Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000331 Polyhydroxybutyrate Polymers 0.000 description 1
- WHBMMWSBFZVSSR-UHFFFAOYSA-N R3HBA Natural products CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 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 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
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930195712 glutamate Natural products 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- SIDINRCMMRKXGQ-UHFFFAOYSA-N perfluoroundecanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SIDINRCMMRKXGQ-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000005015 poly(hydroxybutyrate) Substances 0.000 description 1
- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 1
- 229920009537 polybutylene succinate adipate Polymers 0.000 description 1
- 239000004630 polybutylene succinate adipate Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920006381 polylactic acid film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000036299 sexual function Effects 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical group FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- UAEJRRZPRZCUBE-UHFFFAOYSA-N trimethoxyalumane Chemical compound [Al+3].[O-]C.[O-]C.[O-]C UAEJRRZPRZCUBE-UHFFFAOYSA-N 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明は、プラスチック基材の少なくとも片面上に無機酸化物からなる蒸着薄膜層を有する積層基材上に、少なくとも接着層とシーラント層が順次積層されてなる積層体であって、特に、優れたラミネート強度を有し、かつ揮発性物質が含まれている各種強浸透性内容物が作用してもプラスチック基材上の蒸着薄膜層とシーラント層間のラミネート強度が低下せず、さらには高度なガスバリア性を有することを特徴とする積層体に関する。 The present invention is a laminate in which at least an adhesive layer and a sealant layer are sequentially laminated on a laminated substrate having a vapor-deposited thin film layer made of an inorganic oxide on at least one surface of a plastic substrate. Even if various strong penetrating contents having laminate strength and containing volatile substances act, the laminate strength between the deposited thin film layer and the sealant layer on the plastic substrate does not decrease, and an advanced gas barrier is provided. The present invention relates to a laminate having characteristics.
従来、食品や医薬品などを包装するための包装材料として、例えば、層構成が、紙層／ポリエチレン層／アルミ箔層／ポリエステル層／シーラント層となっている積層体が広く使用されている。このような積層体のポリエステル層とシーラント層との貼り合わせは、通常はポリエステルフィルム上に二液硬化型ポリウレタン系のアンカーコート剤を塗布してから、シーラント層を押出ラミネートすることにより行っていた。そして、このような積層体は適度のラミネート強度やガスバリア性を有しており、食品や医薬品などを包装するための包装材料として広く使用されている。 Conventionally, as a packaging material for packaging foods, pharmaceuticals, and the like, for example, laminates having a layer configuration of paper layer / polyethylene layer / aluminum foil layer / polyester layer / sealant layer have been widely used. The lamination of the polyester layer and the sealant layer of such a laminate is usually performed by applying a two-component curable polyurethane anchor coat agent on the polyester film and then extruding the sealant layer. . Such a laminate has an appropriate laminate strength and gas barrier property, and is widely used as a packaging material for packaging foods and pharmaceuticals.
しかしながら、上述のような構成の積層体を包装材料として用い、例えば酸性物質、アルカリ性物質、香料、界面活性剤、有機溶剤などの揮発性物質を包装した場合、揮発性物質の強い浸透力によってアンカーコート剤が悪影響を受け、プラスチック基材とシーラント層間のラミネート強度が経時で低下し、その結果デラミネーション（剥離）を引き起こすことがあった。 However, when a laminate having the above-described configuration is used as a packaging material and a volatile substance such as an acidic substance, an alkaline substance, a fragrance, a surfactant, or an organic solvent is packaged, the anchor is anchored by the strong osmotic force of the volatile substance. The coating agent was adversely affected, and the laminate strength between the plastic substrate and the sealant layer decreased with time, resulting in delamination.
このようなデラミネーションは、前述したような構成の積層体の製造工程におけるラミネート加工に際して使用されるアンカーコート剤、例えばポリエステルポリオールなどの主剤とイソシアネート化合物からなる硬化剤を配合した二液硬化型ポリウレタン系のアンカーコート剤からなる接着層に、上記のような強浸透性内容物が浸透して、接着層の主剤樹脂成分の膨潤や分子量の低下が生じ、その結果、接着層の凝集力が低下して起きるものと考えられる。 Such delamination is a two-component curable polyurethane in which an anchor coat agent used in the lamination process in the production process of a laminate having the above-described structure, for example, a main component such as polyester polyol and a curing agent composed of an isocyanate compound is blended. The strong penetrating contents as described above penetrate into the adhesive layer made of an anchor coat agent, causing swelling of the main resin component of the adhesive layer and a decrease in molecular weight, resulting in a decrease in cohesive strength of the adhesive layer. It is thought that this happens.
このような状況の下、プラスチック基材上に少なくとも接着層を介してシーラント層が設けられてなる積層体において、揮発性物質が含まれている各種強浸透性内容物が作用しても、プラスチック基材とシーラント層間のラミネート強度が低下しない、包装材用途に好適に使用できる積層体の開発が強く望まれている。 Under such circumstances, even when various strongly permeable contents containing a volatile substance act on a laminate in which a sealant layer is provided on a plastic substrate through at least an adhesive layer, There is a strong demand for the development of a laminate that can be suitably used for packaging materials, in which the laminate strength between the base material and the sealant layer does not decrease.
上記のような積層体の開発として、例えば、その接着層を構成する接着剤が、イソシアネート化合物および金属アルコキシドを含む組成物からなり、該組成物中におけるイソシアネート化合物と金属アルコキシドとの比（イソシアネート化合物／金属アルコキシド）が、９９／１〜６０／４０であることにより、揮発性物質が含まれている各種強浸透性内容物に対しても、プラスチック基材上の蒸着薄膜層とシーラント層間のラミネート強度が低下しない積層体の提案がある。（特許文献１参照） As the development of the laminate as described above, for example, the adhesive constituting the adhesive layer is composed of a composition containing an isocyanate compound and a metal alkoxide, and the ratio of the isocyanate compound to the metal alkoxide in the composition (isocyanate compound). / Metal alkoxide) is 99/1 to 60/40, so that the laminate between the deposited thin film layer and the sealant layer on the plastic substrate can be applied to various strongly permeable contents containing volatile substances. There is a proposal of a laminate that does not decrease in strength. (See Patent Document 1)
しかし、上述のような接着剤を極薄で塗布すると、プラスチック基材上の蒸着薄膜層に対するレベリング性（濡れ性）が悪く、不均一な接着層が形成され、十分なラミネート強度が得られる部分とそうでない部分がランダムに存在するようになり、均一なラミネート強度が得られないことがあった。 However, when the above-mentioned adhesive is applied very thinly, the leveling property (wetting property) with respect to the vapor-deposited thin film layer on the plastic substrate is poor, a non-uniform adhesive layer is formed, and sufficient laminate strength can be obtained. And the part which is not so came to exist at random, and uniform laminate strength might not be obtained.
一般に、レベリング性（濡れ性）の改善策としては、接着剤に界面活性剤を添加する手
法が用いられる。しかしながら、特許文献１のイソシアネート化合物と金属アルコキシドとの混合物からなる接着剤では、希釈溶剤として酢酸エチルを用いている為、本来水系で用いられる陰イオン界面活性剤、陽イオン界面活性剤、両性界面活性剤、非イオン界面活性剤などの各種界面活性剤を使用することができず、その結果、接着剤の極薄な均一塗布に問題があった。
In general, as a measure for improving the leveling property (wetting property), a method of adding a surfactant to an adhesive is used. However, in the adhesive composed of a mixture of an isocyanate compound and a metal alkoxide of Patent Document 1, since ethyl acetate is used as a diluent solvent, an anionic surfactant, a cationic surfactant, an amphoteric interface that are originally used in an aqueous system. Various surfactants such as an activator and a nonionic surfactant could not be used, and as a result, there was a problem with an extremely thin uniform application of the adhesive.
本発明は、上記した従来の問題点を解決するためになされたものであり、その課題とするところは、プラスチック基材の少なくとも片面上に無機酸化物からなる蒸着薄膜層と、接着層と、シーラント層が順次積層された積層体であって、特に、接着層が極薄均一で、且つ、初期ラミネート強度と、各種強浸透性内容物の充填後のラミネート強度に優れた積層体を提供することにある。 The present invention has been made in order to solve the above-mentioned conventional problems, and the problem is that a vapor-deposited thin film layer made of an inorganic oxide on at least one surface of a plastic substrate, an adhesive layer, Provided is a laminate in which sealant layers are sequentially laminated, and in particular, a laminate in which an adhesive layer is extremely thin and uniform, and has excellent initial laminate strength and laminate strength after filling with various strongly permeable contents. There is.
本発明は、上記課題を解決するためのものであり、本発明の請求項１に係る発明は、プラスチック基材と、該プラスチック基材の少なくとも片面上に、無機酸化物からなる蒸着薄膜層と、接着層と、シーラント層が順次積層された積層体であって、前記接着層が２官能以上のイソシアネート基を有するイソシアネート化合物と金属アルコキシドを含む組成物からなり、該組成物中におけるイソシアネート化合物と金属アルコキシドとの比（イソシアネート化合物／金属アルコキシド）が、９９／１〜６０／４０（重量比）で、且つ、前記接着層にフッ素系界面活性剤を５０〜１０００重量ｐｐｍ含有することを特徴とする積層体である。 This invention is for solving the said subject, The invention which concerns on Claim 1 of this invention is a plastic base material, and the vapor-deposited thin film layer which consists of an inorganic oxide on at least one side of this plastic base material, An adhesive layer and a sealant layer sequentially laminated, the adhesive layer comprising a composition containing an isocyanate compound having a bifunctional or higher functional isocyanate group and a metal alkoxide, and the isocyanate compound in the composition; The ratio to the metal alkoxide (isocyanate compound / metal alkoxide) is 99/1 to 60/40 (weight ratio), and the adhesive layer contains 50 to 1000 ppm by weight of a fluorosurfactant. It is a laminated body.
本発明の請求項２に係る発明は、前記２官能以上のイソシアネート基を有するイソシアネート化合物が、２官能のイソシアネートモノマー、またはそのアダクト、ビューレット、イソシアヌレートタイプの３官能化させたモノマーの誘導体のいずれかであることを特徴とする請求項１記載の積層体である。 In the invention according to claim 2 of the present invention, the isocyanate compound having a bifunctional or higher functional isocyanate group is a bifunctional isocyanate monomer or a derivative of a trifunctional monomer of adduct, burette or isocyanurate type. It is either, The laminated body of Claim 1 characterized by the above-mentioned.
本発明の請求項３に係る発明は、前記金属アルコキシドの金属が、ケイ素、アルミニウム、チタン、またはジルコニウムであることを特徴とする請求項１記載の積層体である。 The invention according to claim 3 of the present invention is the laminate according to claim 1, wherein the metal of the metal alkoxide is silicon, aluminum, titanium, or zirconium.
本発明の請求項４に係る発明は、前記金属アルコキシドが、シランカップリング剤であることを特徴とする請求項１〜３いずれかに記載の積層体である。 The invention according to claim 4 of the present invention is the laminate according to any one of claims 1 to 3, wherein the metal alkoxide is a silane coupling agent.
本発明の請求項５に係る発明は、前記接着層の厚みが０．００５μｍ〜１μｍであることを特徴とする請求項１〜４いずれかに記載の積層体である。 The invention according to claim 5 of the present invention is the laminate according to any one of claims 1 to 4, wherein the adhesive layer has a thickness of 0.005 μm to 1 μm.
本発明の請求項６に係る発明は、前記シーラント層が、ポリエチレン系樹脂またはポリプロピレン系樹脂からなることを特徴とする請求項１〜５のいずれかに記載の積層体である。 The invention according to claim 6 of the present invention is the laminate according to any one of claims 1 to 5, wherein the sealant layer is made of a polyethylene resin or a polypropylene resin.
本発明の積層体は、非常に薄く緻密な接着層を形成することができるため、酸性物質、アルカリ性物質、香料、界面活性剤、有機溶剤などの強浸透性内容物用の包装材料として使用してもプラスチック基材上の蒸着薄膜層とシーラント層間のラミネート強度が低下す
ることがない優れた品質を保持し、且つ、生産性向上と低コスト化が可能である。
Since the laminate of the present invention can form a very thin and dense adhesive layer, it is used as a packaging material for strongly permeable contents such as acidic substances, alkaline substances, fragrances, surfactants, and organic solvents. However, it is possible to maintain an excellent quality in which the laminate strength between the vapor-deposited thin film layer and the sealant layer on the plastic substrate does not decrease, and to improve the productivity and reduce the cost.
以下、本発明の実施の形態を図１に従って詳細に説明する。 Hereinafter, an embodiment of the present invention will be described in detail with reference to FIG.
図１は本発明の実施の形態を示す積層体の断面図である。本発明の積層体は、プラスチック基材（１）の少なくとも片面上に無機酸化物からなる蒸着薄膜層（２）と、接着層（３）と、シーラント層（４）が順次積層されたものであり、接着層（３）が２官能以上のイソシアネート基を有するイソシアネート化合物と金属アルコキシドを含む組成物からなり、
該組成物中におけるイソシアネート化合物と金属アルコキシドとの比（イソシアネート化合物／金属アルコキシド）が、９９／１〜６０／４０（重量比）で、且つ、前記接着層にフッ素系界面活性剤を５０〜１０００重量ｐｐｍ含有することを特徴とするものである。
FIG. 1 is a cross-sectional view of a laminate showing an embodiment of the present invention. The laminate of the present invention is a laminate in which a vapor-deposited thin film layer (2) made of an inorganic oxide, an adhesive layer (3), and a sealant layer (4) are sequentially laminated on at least one surface of a plastic substrate (1). The adhesive layer (3) comprises a composition containing an isocyanate compound having a bifunctional or higher isocyanate group and a metal alkoxide;
The ratio of the isocyanate compound to the metal alkoxide in the composition (isocyanate compound / metal alkoxide) is 99/1 to 60/40 (weight ratio), and the adhesive layer contains 50 to 1000 fluorine-based surfactant. It is characterized by containing ppm by weight.
＜プラスチック基材＞
本発明に係るプラスチック基材（１）としては、ポリエステルフィルムのノーマルタイプ、共重合タイプ、易接着タイプのものや、ナイロンフィルムのノーマルタイプ、易接着タイプのもの、あるいはポリプロピレンフィルムの未静防タイプ、静防タイプのものなど、様々なタイプのものが使用可能である。
<Plastic substrate>
As the plastic substrate (1) according to the present invention, polyester film normal type, copolymer type, easy adhesion type, nylon film normal type, easy adhesion type, or polypropylene film non-static type Various types such as a static-proof type can be used.
また、脂肪族ポリエステルフィルムや脂肪族芳香族ポリエステルフィルムも使用可能である。さらに、プラスチック基材の構成材料としては、乳酸を主成分とするポリマー、例えば、乳酸のみからなるホモポリマーや、乳酸を主成分とし乳酸以外のモノマー、例えばリンゴ酸、グリコール酸などのオキシ酸、３−ヒドロキシブチレート、３−ヒドロキシヴァリレート、カプロラクトン、およびコハク酸、アジピン酸などのジカルボン酸類とエチレングリコール、１，４−ブタンジオールなどのジオール類などを共重合したコポリマー、あるいはこれらの混合物などが使用可能である。それに加えて、コハク酸、アジピン酸、テレフタル酸などのジカルボン酸類と、エチレングリコール、１，４−ブタンジオールなどのジオール類との共重合体、例えばテレフタル酸を有するポリエチレンテレフタレート−サクシネート、ポリブチレンアジペート−テレフタレート、ポリテトラメチレンアジペート−テレフタレートなども使用可能である。 Moreover, an aliphatic polyester film and an aliphatic aromatic polyester film can also be used. Furthermore, as a constituent material of the plastic substrate, a polymer mainly composed of lactic acid, for example, a homopolymer composed only of lactic acid, or a monomer other than lactic acid based on lactic acid, for example, oxyacids such as malic acid and glycolic acid, Copolymers obtained by copolymerizing 3-hydroxybutyrate, 3-hydroxyvalerate, caprolactone, dicarboxylic acids such as succinic acid and adipic acid and diols such as ethylene glycol and 1,4-butanediol, or mixtures thereof Can be used. In addition, copolymers of dicarboxylic acids such as succinic acid, adipic acid and terephthalic acid and diols such as ethylene glycol and 1,4-butanediol, such as polyethylene terephthalate-succinate with terephthalic acid, polybutylene adipate -Terephthalate, polytetramethylene adipate-terephthalate, etc. can also be used.
上記プラスチック基材は、無機酸化物からなる蒸着薄膜層が安定的に形成できるための前処理として、コロナ処理やプラズマ処理などの表面処理がなされていればより好ましい。 It is more preferable that the plastic substrate is subjected to surface treatment such as corona treatment or plasma treatment as a pretreatment for stably forming a deposited thin film layer made of an inorganic oxide.
また、蒸着薄膜層との密着性を良くするための表面処理が、予め施されてないプラスチック基材を用いる場合には、蒸着薄膜加工の前に、該プラスチック基材にコロナ処理、低圧プラズマ処理、大気圧プラズマ処理、フレーム処理、イオンボンバード処理などの表面処理、さらには薬品処理、溶剤処理などの表面処理をすることができる。また、必要に応じて無機化合物を有する蒸着用プライマーの薄膜をプラスチック基材上に設けておいてもよい。さらに、金属箔並の高度なガスバリア性を付与するために蒸着薄膜層上に無機化合物を有するガスバリア性被膜層を設けてもかまわない。 In addition, when using a plastic substrate that has not been subjected to surface treatment for improving adhesion to the deposited thin film layer, the plastic substrate is subjected to corona treatment and low-pressure plasma treatment before the deposition thin film processing. Surface treatments such as atmospheric pressure plasma treatment, flame treatment, ion bombardment treatment, and further surface treatments such as chemical treatment and solvent treatment can be performed. Moreover, you may provide the thin film of the primer for vapor deposition which has an inorganic compound on the plastic base material as needed. Furthermore, a gas barrier coating layer having an inorganic compound may be provided on the vapor-deposited thin film layer in order to impart a high level of gas barrier property comparable to that of a metal foil.
特に、非常に過酷な揮発性物質が含まれている強浸透性内容物の用途には、前記プラスチック基材と蒸着薄膜層との密着性をより良くするためにプラスチック基材上に無機化合物を有する蒸着用プライマーを設けた積層体を使用することが好ましい。さらに、金属箔
並の高度なガスバリア性が必要な用途には、前記蒸着薄膜層上に無機化合物を有するガスバリア性被膜層を設けた積層体を使用することが好ましい。
In particular, for the use of strongly permeable contents containing very harsh volatile substances, an inorganic compound is added onto the plastic substrate in order to improve the adhesion between the plastic substrate and the deposited thin film layer. It is preferable to use a laminate provided with a deposition primer. Furthermore, it is preferable to use the laminated body which provided the gas barrier film layer which has an inorganic compound on the said vapor deposition thin film layer for the use which requires the high gas barrier property like metal foil.
＜蒸着薄膜層＞
前記無機酸化物からなる蒸着薄膜層は、酸化アルミニウム、酸化ケイ素、酸化マグネシウム、酸化錫などの単体や、あるいはそれらの混合物からなり、酸素や水蒸気などに対するガスバリア性を有するものであればよい。中でも酸化アルミニウム、酸化ケイ素、および酸化マグネシウムは、酸素透過率および水蒸気透過率に優れる点で、特に好ましい。
<Deposited thin film layer>
The vapor-deposited thin film layer made of the inorganic oxide may be made of a simple substance such as aluminum oxide, silicon oxide, magnesium oxide, or tin oxide, or a mixture thereof, and has a gas barrier property against oxygen, water vapor, and the like. Among these, aluminum oxide, silicon oxide, and magnesium oxide are particularly preferable because they are excellent in oxygen permeability and water vapor permeability.
＜接着層＞
前記プラスチック基材上の無機酸化物からなる蒸着薄膜層（２）に積層される接着層（３）は、厚みが０．００５μｍ〜１μｍであって、２官能以上のイソシアネート基を有するイソシアネート化合物と金属アルコキシドと、フッ素系界面活性剤の混合からなる接着剤組成物である。
<Adhesive layer>
The adhesive layer (3) laminated on the vapor-deposited thin film layer (2) made of an inorganic oxide on the plastic substrate has a thickness of 0.005 μm to 1 μm and an isocyanate compound having a bifunctional or higher functional isocyanate group; An adhesive composition comprising a mixture of a metal alkoxide and a fluorosurfactant.
接着層（３）中の２官能以上のイソシアネート基を有するイソシアネート化合物は、例えばシーラント層のような有機物に対する接着に優れる。イソシアネート化合物が1官能では、接着に関与する官能基量が少なすぎるため、その結果、接着性が劣る。また、金属アルコキシドは、例えば蒸着薄膜層のような無機物に対する接着に優れている。従って、接着層がイソシアネート化合物のみの場合、プラスチック基材上の蒸着薄膜層と接着層間のラミネート強度が弱く十分な初期強度が得られない。一方、接着層が金属アルコキシドのみの場合、接着層とシーラント層間のラミネート強度が弱く十分な初期強度が得られない。 The isocyanate compound having a bifunctional or higher functional isocyanate group in the adhesive layer (3) is excellent in adhesion to an organic substance such as a sealant layer. If the isocyanate compound is monofunctional, the amount of functional groups involved in adhesion is too small, and as a result, the adhesion is poor. Moreover, metal alkoxide is excellent in adhesion | attachment with respect to inorganic substances, such as a vapor deposition thin film layer, for example. Therefore, when the adhesive layer is only an isocyanate compound, the laminate strength between the vapor-deposited thin film layer and the adhesive layer on the plastic substrate is weak and sufficient initial strength cannot be obtained. On the other hand, when the adhesive layer is only a metal alkoxide, the laminate strength between the adhesive layer and the sealant layer is weak and sufficient initial strength cannot be obtained.
上述のイソシアネート化合物と金属アルコキシドとの混合の比（イソシアネート化合物／金属アルコキシド）は、発明者等の鋭意努力の結果、９９／１〜６０／４０、より好ましくは９９／１〜７０／３０、さらに好ましくは９９／１〜８０／２０がよいことが分った。 The mixing ratio of the above-mentioned isocyanate compound and metal alkoxide (isocyanate compound / metal alkoxide) is 99/1 to 60/40, more preferably 99/1 to 70/30, as a result of the inventors' diligent efforts. It has been found that 99/1 to 80/20 is preferable.
前記イソシアネート化合物としては、例えば、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、キシリレンジイソシアネート、イソホロンジイソシアネート、ヘキサメチレンジイソシアネート、４，４‘−ジフェニルメタンジイソシアネートおよびその水素添加体などの各種ジイソシアネート系モノマーなどが挙げられる。また、これらのジイソシアネートモノマーを、トリメチロールプロパンやグリセロールなどの３官能の活性水素含有化合物と反応させたアダクトタイプや、水と反応させたビューレットタイプや、イソシアネート基の自己重合を利用したトリマー（イソシアヌレート）タイプなど３官能性の誘導体や，それ以上の多官能性の誘導体を使用することができる。 Examples of the isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and hydrogenated products thereof. And diisocyanate monomers. In addition, adduct types obtained by reacting these diisocyanate monomers with trifunctional active hydrogen-containing compounds such as trimethylolpropane and glycerol, burette types obtained by reacting with water, and trimers utilizing self-polymerization of isocyanate groups ( A trifunctional derivative such as an isocyanurate type or a polyfunctional derivative higher than that can be used.
前記金属アルコキシドの金属としては、ケイ素、アルミニウム、チタン、またはジルコニウムを使用することが可能である。具体的には、テトラエトキシシラン、テトライソプロポキシシラン、テトラ−ｎ−ブトキシシラン、アルミニウムトリイソプロポキシド、アルミニウムトリエトキシド、アルミニウムトリ−ｎ−ブトキシド、アルミニウムトリメトキシド、チタニウムテトライソプロポキシド、チタニウムテトラエトキシド、チタニウムテトラ−ｎ−ブトキシド、ジルコニウムテトライソプロポキシド、ジルコニウムテトラ−ｎ−ブトキシドなどが挙げられる。以上のように金属アルコキシドには種々あるが、取り扱い性、コストなどを考えればケイ素のアルコキシドがより好ましく使用可能で、テトラアルコキシドに限定されることはなく、イソシアネート基、エポキシ基、またはアミノ基などを含有するシランカップリング剤を適宜選定して使用するのがより好ましい。シランカップリング剤の作用効果としては、例えばシーラント層のような有機物、および蒸着薄膜層のような無機物の双方に対しての接着が期待できる。 As the metal of the metal alkoxide, silicon, aluminum, titanium, or zirconium can be used. Specifically, tetraethoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, aluminum triisopropoxide, aluminum triethoxide, aluminum tri-n-butoxide, aluminum trimethoxide, titanium tetraisopropoxide, Examples thereof include titanium tetraethoxide, titanium tetra-n-butoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide. As described above, there are various types of metal alkoxides, but silicon alkoxides can be more preferably used in consideration of handling properties, cost, etc., and are not limited to tetraalkoxides, such as isocyanate groups, epoxy groups, or amino groups. It is more preferable to appropriately select and use a silane coupling agent containing As the function and effect of the silane coupling agent, for example, adhesion to both an organic material such as a sealant layer and an inorganic material such as a deposited thin film layer can be expected.
＜フッ素系界面活性剤＞
本発明に係るフッ素系界面活性剤は、分子構造中に疎水基と親水基の両方を有し、該疎水基が完全にフッ素化されたフルオロカーボン鎖（パーフルオロカーボン鎖）を有する化合物である。また、アニオンタイプ、ノニオンタイプ、カチオンタイプ、両性タイプのいずれのタイプも使用可能である。具体的には、フルオロアルキル（Ｃ２〜１０）カルボン酸、３−［フルオロアルキル（Ｃ６〜１１）オキシ］−１−アルキル（Ｃ３〜４）スルホン酸ナトリウム、３−［ω−フルオロアルカノイル（Ｃ６〜８）−Ｎ−エチルアミノ］−１−プロパンスルホン酸ナトリウム、フルオロアルキル（Ｃ１１〜２０）カルボン酸、Ｎ−パーフルオロオクタンスルホニルグルタミン酸ジナトリウム、Ｎ−［３−（パーフルオロオクタンスルホンアミド）プロピル］−Ｎ，Ｎ−ジメチル−Ｎ−カルボキシメチレンアンモニウムベタイン、パーフルオロアルキルカルボン酸（Ｃ７〜１３）、パーフルオロオクタンスルホン酸ジエタノールアミド、パーフルオロアルキル（Ｃ４〜１２）スルホン酸塩（Ｌｉ，Ｋ，Ｎａ）、パーフルオロアルキル（Ｃ６〜１０）スルホンアミドプロピルトリメチルアンモニウム塩、パーフルオロアルキル（Ｃ６〜１０）−Ｎ−エチルスルホニルグリシン塩（Ｋ）、Ｎ−プロピル−Ｎ−（２−ヒドロキシエチル）パーフルオロオクタンスルホンアミド、リン酸ビス（Ｎ−パーフルオロオクチルスルホニル−Ｎ−エチルアミノエチル）、モノパーフルオロアルキル（Ｃ６〜１６）エチルリン酸エステル、など様々なものが挙げられる。中でも本発明に係る接着剤の希釈溶剤として酢酸エチルが使用されることから、酢酸エチルに溶解するフッ素系界面活性剤がより好ましい。
<Fluorosurfactant>
The fluorosurfactant according to the present invention is a compound having both a hydrophobic group and a hydrophilic group in the molecular structure, and a fluorocarbon chain (perfluorocarbon chain) in which the hydrophobic group is completely fluorinated. In addition, any of anion type, nonion type, cation type, and amphoteric type can be used. Specifically, fluoroalkyl (C2-10) carboxylic acid, 3- [fluoroalkyl (C6-11) oxy] -1-alkyl (C3-4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6- 8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-20) carboxylic acid, N-perfluorooctanesulfonyl glutamate disodium, N- [3- (perfluorooctanesulfonamido) propyl] -N, N-dimethyl-N-carboxymethylene ammonium betaine, perfluoroalkyl carboxylic acid (C7-13), perfluorooctane sulfonic acid diethanolamide, perfluoroalkyl (C4-12) sulfonate (Li, K, Na ), Perfluoroalkyl (C6-10) Rufonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-10) -N-ethylsulfonylglycine salt (K), N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, bis (N-phosphate) Perfluorooctylsulfonyl-N-ethylaminoethyl), monoperfluoroalkyl (C6-16) ethyl phosphate, and the like. Among these, since ethyl acetate is used as a diluting solvent for the adhesive according to the present invention, a fluorosurfactant that dissolves in ethyl acetate is more preferable.
上記フッ素系界面活性剤は、他の液体に比べて表面張力が非常に小さいため、物体の表面で薄く広がる傾向がある。また、上記フッ素系界面活性剤は接着剤の希釈溶剤として用いる酢酸エチルにも、一部のものを除いてほとんど溶解することから、本発明の接着剤に極少量の添加することで、蒸着薄膜層（２）に対する接着剤のレベリング性（濡れ性）を格段に向上させることができ、さらに、接着剤を極薄に塗布しても、均一な接着層（３）の形成が可能となる。 The fluorosurfactant has a very small surface tension compared to other liquids, and therefore tends to spread thinly on the surface of the object. Further, since the above-mentioned fluorosurfactant is almost dissolved in ethyl acetate used as a diluting solvent for the adhesive, except for some, the deposited thin film can be obtained by adding a very small amount to the adhesive of the present invention. The leveling property (wetting property) of the adhesive with respect to the layer (2) can be remarkably improved, and even if the adhesive is applied very thinly, a uniform adhesive layer (3) can be formed.
また、フッ素系界面活性剤の添加量は、接着層を構成するイソシアネート化合物と金属アルコキシドとの混合物に対して、固形分比５０〜１０００重量ｐｐｍであればよいが、５０〜５００重量ｐｐｍ程度であればより好ましい。５０重量ｐｐｍ未満の添加では、プラスチック基材上の蒸着薄膜層に対する接着層のレベリング性（濡れ性）を向上させるのには不十分である。一方、１０００重量ｐｐｍを超える添加は、プラスチック基材上の蒸着薄膜層に対する接着層のレベリング性（濡れ性）を向上させるのには過剰な添加量であり、また反応後に接着層の凝集力低下に繋がる。 Moreover, the addition amount of a fluorine-type surfactant should just be 50-1000 weight ppm of solid content ratio with respect to the mixture of the isocyanate compound and metal alkoxide which comprise an contact bonding layer, but about 50-500 weight ppm. More preferably. Addition of less than 50 ppm by weight is insufficient to improve the leveling property (wetting property) of the adhesive layer with respect to the deposited thin film layer on the plastic substrate. On the other hand, the addition exceeding 1000 ppm by weight is an excessive addition amount to improve the leveling property (wetting property) of the adhesive layer with respect to the deposited thin film layer on the plastic substrate, and the cohesive strength of the adhesive layer is lowered after the reaction. It leads to.
このような構成の接着層は、プラスチック基材上の蒸着薄膜層上に、２官能以上のイソシアネート基を有するイソシアネート化合物と金属アルコキシドとの混合物と、この混合物に対して固形分比５０〜１０００重量ｐｐｍのフッ素系界面活性剤とからなる塗工液を、酢酸エチルを希釈溶剤として用い、その固形分割合を０．０１〜３重量％、好ましくは０．０５〜２重量％の割合の塗工液を塗工して薄膜を設ければよい。具体的には接着層の乾燥時の厚みが０．００５μｍ〜１μｍであれば良い。接着層の厚みが０．００５μｍ未満だと、接着剤の塗布膜厚の均一制御に限界があり、好ましくは０．０１〜０．５μｍがよい。 The adhesive layer having such a structure comprises a vapor-deposited thin film layer on a plastic substrate, a mixture of an isocyanate compound having a bifunctional or higher functional isocyanate group and a metal alkoxide, and a solid content ratio of 50 to 1000 wt. A coating liquid composed of ppm fluorosurfactant, using ethyl acetate as a diluent solvent, a solid content ratio of 0.01 to 3% by weight, preferably 0.05 to 2% by weight A thin film may be provided by applying a liquid. Specifically, the thickness when the adhesive layer is dried may be 0.005 μm to 1 μm. When the thickness of the adhesive layer is less than 0.005 μm, there is a limit to the uniform control of the coating thickness of the adhesive, and preferably 0.01 to 0.5 μm.
＜シーラント層＞
一方、接着層上に積層されるシーラント層（４）としては、ポリエチレン系樹脂やポリプロピレン系樹脂などのポリオレフィン系樹脂からなる層を具体的な例として挙げることができる。上記ポリエチレン系樹脂やポリプロピレン系樹脂は、優れた加工性や安価なコストなどの点で好ましい。このようなシーラント層の形成材料としては、さらに、高密度ポ
リエチレン、低密度ポリエチレン、中密度ポリエチレン、エチレン−αオレフィン共重合体などのエチレン系樹脂や、ホモ・ブロック・ランダムの各ポリプロピレン樹脂や、プロピレン−αオレフィン共重合体などのプロピレン系樹脂、エチレン-アクリル酸共重合体やエチレン−メタクリル酸共重合体などのエチレン−α，β不飽和カルボン酸共重合体、エチレン−アクリル酸メチルやエチレン−アクリル酸エチルやエチレン−メタクリル酸メチルやエチレン−メタクリル酸エチルなどのエチレン−α，β不飽和カルボン酸共重合体のエステル化物、カルボン酸部位をナトリウムイオン、亜鉛イオンで架橋した、エチレン−α，β不飽和カルボン酸共重合体のイオン架橋物、エチレン−無水マレイン酸グラフト共重合体やエチレン−アクリル酸エチル−無水マレイン酸のような三元共重合体に代表される酸無水物変性ポリオレフィン、エチレン−グリシジルメタクリレート共重合体などのエポキシ化合物変性ポリオレフィン、エチレン−酢酸ビニル共重合体から選ばれる樹脂の単体あるいは２種以上のブレンド物などが具体的に挙げられる。
<Sealant layer>
On the other hand, as a sealant layer (4) laminated | stacked on an contact bonding layer, the layer which consists of polyolefin resin, such as polyethylene resin and a polypropylene resin, can be mentioned as a specific example. The polyethylene resin and polypropylene resin are preferable in terms of excellent processability and low cost. As a material for forming such a sealant layer, furthermore, high density polyethylene, low density polyethylene, medium density polyethylene, ethylene-based resins such as ethylene-α olefin copolymer, homo-block / random polypropylene resins, Propylene-based resins such as propylene-α olefin copolymers, ethylene-α, β unsaturated carboxylic acid copolymers such as ethylene-acrylic acid copolymers and ethylene-methacrylic acid copolymers, ethylene-methyl acrylate and ethylene -Ethylene-α, β esterified product of ethylene-α, β-unsaturated carboxylic acid copolymer such as ethyl acrylate, ethylene-methyl methacrylate, ethylene-ethyl methacrylate, ethylene-α, wherein carboxylic acid moiety is crosslinked with sodium ion, zinc ion , Β-unsaturated carboxylic acid copolymer ionic cross-linked product, ethyl -Epoxy compound-modified polyolefins such as acid anhydride-modified polyolefins represented by terpolymers such as maleic anhydride graft copolymers and ethylene-ethyl acrylate-maleic anhydride, ethylene-glycidyl methacrylate copolymers, Specific examples thereof include a single resin or a blend of two or more resins selected from ethylene-vinyl acetate copolymers.
また、脂肪族ポリエステルや脂肪族芳香族ポリエステルも使用可能である。より具体的な例としては、コハク酸、アジピン酸などのジカルボン酸類と、エチレングリコール、１，４−ブタンジオールなどのジオール類との共重合体（例えば、ポリエチレンサクシネート、ポリブチレンサクシネート、ポリブチレンサクシネート−アジペート）、微生物産生のポリヒドロキシブチレート、ポリヒドロキシブチレート−ヴァリレート、ポリヒドロキシブチレート−ヘクサノエート、乳酸、リンゴ酸、グリコール酸などのオキシ酸の重合体またはこれらの共重合体、ポリカプロラクトン、ポリカプロラクトン−ブチレンサクシネート、アミド結合を有するポリエステル、カーボネート結合を有するポリエステルなどの脂肪族ポリエステル、あるいはテレフタル酸を有するポリエチレンテレフタレート−サクシネート、ポリブチレンアジペート−テレフタレート、ポリテトラメチレンアジペート−テレフタレートなどの脂肪族芳香族ポリエステルから選ばれる樹脂の単体あるいは２種以上のブレンド物などが挙げられる。これらの構成材料には、必要に応じて各種添加剤（酸化防止剤、粘着付与剤、充填剤、各種フィラーなど）を添加してもかまわない。 Also, aliphatic polyesters and aliphatic aromatic polyesters can be used. More specific examples include copolymers of dicarboxylic acids such as succinic acid and adipic acid and diols such as ethylene glycol and 1,4-butanediol (for example, polyethylene succinate, polybutylene succinate, poly Butylene succinate-adipate), microbial-produced polyhydroxybutyrate, polyhydroxybutyrate-valerate, polyhydroxybutyrate-hexanoate, polymers of oxyacids such as lactic acid, malic acid, glycolic acid or copolymers thereof , Polycaprolactone, polycaprolactone-butylene succinate, aliphatic polyester such as polyester having amide bond, polyester having carbonate bond, or polyethylene terephthalate-succinate having terephthalic acid, polybene Ren'ajipeto - terephthalate, polytetramethylene adipate - terephthalate and alone or two or more of the blend of resin selected from the aliphatic-aromatic polyesters, and the like. To these constituent materials, various additives (such as an antioxidant, a tackifier, a filler, and various fillers) may be added as necessary.
本発明の積層体において、蒸着薄膜層を有するプラスチック基材およびシーラント層としてともに脂肪族ポリエステルまたは脂肪族芳香族ポリエステルを使用すると、高度なガスバリア性と強浸透性内容物耐性だけでなく、生分解性機能も併せ持つこととなる。このとき蒸着薄膜層を有するプラスチック基材とシーラント層間に存在する接着層は生分解性を有していないが、接着層の厚みが０．００５μｍ〜１μｍの非常に薄い層であるために積層体の生分解性を阻害することはない。 In the laminate of the present invention, when an aliphatic polyester or an aliphatic aromatic polyester is used as a plastic substrate having a vapor-deposited thin film layer and a sealant layer, not only high gas barrier properties and strong permeable content resistance but also biodegradation It will also have sexual function. At this time, the adhesive layer existing between the plastic substrate having the vapor-deposited thin film layer and the sealant layer is not biodegradable, but because the thickness of the adhesive layer is 0.005 μm to 1 μm, it is a laminate. Does not inhibit the biodegradability of.
以上、本発明に係る積層体について説明したが、本発明の積層体は上記のような層構成のものに限定されるものではなく、包装材料としての用途を考慮し、包装材料として要求される剛性や耐久性などを向上させる目的で、他の層を介在させた構成であってもかまわない。 The laminated body according to the present invention has been described above, but the laminated body of the present invention is not limited to the layer structure as described above, and is required as a packaging material in consideration of the use as a packaging material. For the purpose of improving rigidity and durability, a configuration in which another layer is interposed may be used.
そして、このような構成の積層体は、例えば、プラスチック基材上の蒸着薄膜層上に、２官能以上のイソシアネート基を有するイソシアネート化合物と金属アルコキシドとの混合物と、この混合物に対して固形分比５０〜１０００重量ｐｐｍのフッ素系界面活性剤を加えて、更に、全固形分比が０．０１〜３重量％になるように酢酸エチルを加えて調製した接着剤を用いて、乾燥後の接着層の厚みが０．００５μｍ〜１μｍとなるように、押出ラミネート機で塗布、乾燥し、続いて、Ｔダイからポリエチレン等を押し出してシーラント層を積層することにより得ることができる。 And the laminated body of such a structure is a solid content ratio with respect to this mixture and the mixture of the isocyanate compound and metal alkoxide which have an isocyanate group more than bifunctional on the vapor deposition thin film layer on a plastic substrate, for example. Adhesion after drying using an adhesive prepared by adding 50 to 1000 ppm by weight of a fluorosurfactant and further adding ethyl acetate so that the total solid content ratio is 0.01 to 3% by weight. It can be obtained by applying and drying with an extrusion laminator so that the thickness of the layer becomes 0.005 μm to 1 μm, and then extruding polyethylene or the like from a T die and laminating a sealant layer.
上述した一例の方法等で本発明の積層体を作製することにより、プラスチック基材上の蒸着薄膜層と接着層間、および接着層とシーラント層間の初期のラミネート強度が良好で、かつ揮発性物質が含まれている各種強浸透性内容物を充填しても、プラスチック基材上の蒸着薄膜層と接着層間、および接着層とシーラント層間のラミネート強度が低下しないパウチが形成を得ることができる。 By producing the laminate of the present invention by the method of the example described above, the initial laminated strength between the deposited thin film layer and the adhesive layer on the plastic substrate and between the adhesive layer and the sealant layer is good, and the volatile substance is present. Even when the various strong permeable contents contained therein are filled, a pouch can be obtained in which the laminate strength between the deposited thin film layer and the adhesive layer on the plastic substrate and between the adhesive layer and the sealant layer does not decrease.
以下に、実施例をもって本発明の詳細な説明をする。 Hereinafter, the present invention will be described in detail with reference to examples.
（実施例１）
プラスチック基材として一方の面にコロナ処理を施し、その面に酸化アルミニウム蒸着層を形成させた厚み１２μｍのポリエチレンテレフタレートフィルムを用いた。次に、イソシアネート化合物としてイソホロンジイソシアネートモノマーを、金属アルコキシドとしてテトラエトキシシランを、９５／５（重量比）となるよう混合し、これらに対して固形分比が５０重量ｐｐｍのパーフルオロオクタンスルホン酸ジエタノールアミドを加え、さらに、全固形分比を０．５重量％となるように酢酸エチルを加えて接着剤を調整した。
Example 1
As a plastic substrate, a polyethylene terephthalate film having a thickness of 12 μm having a corona treatment on one surface and an aluminum oxide vapor deposition layer formed on the surface was used. Next, isophorone diisocyanate monomer as an isocyanate compound and tetraethoxysilane as a metal alkoxide are mixed so as to be 95/5 (weight ratio), and perfluorooctane sulfonate diethanolamine having a solid content ratio of 50 ppm by weight. The adhesive was further adjusted by adding ethyl acetate so that the total solid content ratio was 0.5% by weight.
次に、前記酸化アルミニウム蒸着層上に前記該接着剤を塗工して接着層を形成させ、オーブンにて乾燥後、その上にシーラント層として厚み４０μｍの低密度ポリエチレンをダイ下温度３２０℃、加工速度８０ｍ／ｍｉｎで押出ラミネート法により押し出して積層した。その後、５０℃で３日間のエージングを施し、積層体を得た。接着層の乾燥後の厚みは４５ｎｍであった。 Next, the adhesive is applied onto the aluminum oxide vapor deposition layer to form an adhesive layer, dried in an oven, and then a low-density polyethylene having a thickness of 40 μm is formed thereon as a sealant layer at a temperature below the die of 320 ° C. The layers were extruded and laminated by an extrusion laminating method at a processing speed of 80 m / min. Thereafter, aging was performed at 50 ° C. for 3 days to obtain a laminate. The thickness of the adhesive layer after drying was 45 nm.
（実施例２）
プラスチック基材として一方の面にコロナ処理を施し、その面に酸化アルミニウム蒸着層を形成させた厚み１５μｍのナイロンフィルムを用いた。次に、イソシアネート化合物としてトリレンジイソシアネートのアダクトタイプを、金属アルコキシドとしてアルミニウムトリイソプロポキシドを、９０／１０（重量比）となるよう混合し、これらに対して固形分比が５０重量ｐｐｍのパーフルオロオクタンスルホン酸ジエタノールアミドを加え、全固形分比を０．５重量％となるように酢酸エチルを加えて接着剤を調整した。
(Example 2)
As a plastic substrate, a nylon film having a thickness of 15 μm having a corona treatment on one surface and an aluminum oxide vapor deposition layer formed on the surface was used. Next, adduct type of tolylene diisocyanate as an isocyanate compound and aluminum triisopropoxide as a metal alkoxide are mixed so as to be 90/10 (weight ratio), and the solid content ratio is 50 wt ppm. Fluorooctanesulfonic acid diethanolamide was added, and ethyl acetate was added to adjust the adhesive so that the total solid content ratio was 0.5% by weight.
前記接着剤以外は実施例１と同様の方法で、積層体を得た。接着層の乾燥後の厚みは４５ｎｍであった。 A laminate was obtained in the same manner as in Example 1 except for the adhesive. The thickness of the adhesive layer after drying was 45 nm.
（実施例３）
プラスチック基材として一方の面にコロナ処理を施し、その面に酸化ケイ素蒸着層を形成させた厚み１２μｍのポリエチレンテレフタレートフィルムを用いた。次に、イソシアネート化合物としてイソホロンジイソシアネートのアダクトタイプを、金属アルコキシドとしてチタニウムテトラエトキシドを、８５／１５（重量比）となるよう混合し、これらに対して固形分比が１００重量ｐｐｍのＮ−プロピル−Ｎ−（２−ヒドロキシエチル）パーフルオロオクタンスルホンアミドを加え、全固形分比を０．５重量％となるように酢酸エチルを加えて接着剤を調整した。
(Example 3)
As a plastic substrate, a polyethylene terephthalate film having a thickness of 12 μm having a corona treatment on one surface and a silicon oxide vapor deposition layer formed on the surface was used. Next, an adduct type of isophorone diisocyanate as an isocyanate compound and titanium tetraethoxide as a metal alkoxide are mixed so as to be 85/15 (weight ratio), and N-propyl having a solid content ratio of 100 ppm by weight is mixed. -N- (2-hydroxyethyl) perfluorooctanesulfonamide was added, and ethyl acetate was added so that the total solid content ratio was 0.5% by weight to prepare an adhesive.
前記接着剤を用いて、シーラント層の構成材料としてエチレン−メタクリル酸共重合体を用いた以外は実施例１と同様の方法で、積層体を得た。接着層の乾燥後の厚みは６０ｎｍ、シーラント層を押出ラミネート法により接着層上に押し出して形成したときのダイ下温度は２８０℃であった。 Using the adhesive, a laminate was obtained in the same manner as in Example 1 except that an ethylene-methacrylic acid copolymer was used as a constituent material of the sealant layer. The thickness after drying of the adhesive layer was 60 nm, and the temperature under the die when the sealant layer was formed on the adhesive layer by extrusion lamination was 280 ° C.
（実施例４）
プラスチック基材として一方の面にコロナ処理を施し、その面に酸化ケイ素蒸着層を形成させた厚み１５μｍのナイロンフィルムを用いた。次に、イソシアネート化合物としてキシリレンジイソシアネートのアダクトタイプを、金属アルコキシドとしてジルコニウムテトライソプロポシキドを、８０／２０（重量比）となるよう混合し、これらに対して固形
分比が２００重量ｐｐｍのパーフルオロウンデカン酸を加え、全固形分比を０．５重量％となるように酢酸エチルを加えて接着剤を調整した。
Example 4
As a plastic substrate, a nylon film having a thickness of 15 μm in which one surface was subjected to corona treatment and a silicon oxide vapor deposition layer was formed on the surface was used. Next, the adduct type of xylylene diisocyanate as the isocyanate compound and zirconium tetraisopropoxide as the metal alkoxide are mixed so as to be 80/20 (weight ratio), and the solid content ratio is 200 ppm by weight. Perfluoroundecanoic acid was added, and ethyl acetate was added to adjust the adhesive so that the total solid content ratio was 0.5% by weight.
シーラント層の構成材料として亜鉛アイオノマーを用いた以外は実施例１と同様の方法で、積層体を得た。接着層の乾燥後の厚みは６０ｎｍ、シーラント層を押出ラミネート法により接着層上に押し出して形成したときのダイ下温度は３００℃であった。 A laminate was obtained in the same manner as in Example 1 except that zinc ionomer was used as the constituent material of the sealant layer. The thickness of the adhesive layer after drying was 60 nm, and the temperature under the die when the sealant layer was formed by extrusion extrusion onto the adhesive layer was 300 ° C.
（実施例５）
プラスチック基材として一方の面にコロナ処理を施した厚み１２μｍのポリエチレンテレフタレートフィルムを用いた。次に、その処理面に下記組成からなるプライマー層を塗布、乾燥した後、酸化アルミニウム蒸着層を形成した。
(Example 5)
As a plastic substrate, a polyethylene terephthalate film having a thickness of 12 μm and having a corona treatment on one surface was used. Next, a primer layer having the following composition was applied to the treated surface and dried, and then an aluminum oxide vapor deposition layer was formed.
［プライマーの組成］
Ａ液のアクリルポリオールの水酸基に対してＢ液のイソシアネート基が当量となるよう混合し、この混合溶液の固形分比が２．０重量％となるように酢酸エチルで希釈したプライマーの組成物。
Ａ液： 希釈溶媒（酢酸エチル）中、γ−イソシアネートプロピルトリメチルシラン
１．０重量％と、アクリルポリオール１０重量％との混合溶液
Ｂ液： イソシアネート化合物であるＸＤＩとＩＰＤＩの７／３（重量比）混合物
[Primer composition]
A primer composition prepared by mixing the hydroxyl groups of the acrylic polyol of the A liquid with an equivalent amount of the isocyanate group of the B liquid and diluting with ethyl acetate so that the solid content ratio of the mixed solution is 2.0% by weight.
Liquid A: Mixed solution of γ-isocyanatopropyltrimethylsilane 1.0% by weight and acrylic polyol 10% by weight in diluting solvent (ethyl acetate) Liquid B: 7/3 (weight ratio of XDI and IPDI as isocyanate compounds) )blend
次に、前記酸化アルミニウム蒸着層上に下記組成からなるガスバリア性コーティング剤を塗布、乾燥してガスバリア性被膜層を形成させた。 Next, a gas barrier coating agent having the following composition was applied onto the aluminum oxide vapor deposition layer and dried to form a gas barrier coating layer.
［ガスバリア性コーティング剤の組成］
Ｃ液とＤ液を６０／４０（重量比）で混合したもの。
Ｃ液： テトラエトキシシラン１０．４ｇに０．１Ｎ塩酸８９．６ｇを加え、３０分間攪拌し加水分解させた固形分３．０重量％（ＳｉＯ２換算）の加水分解溶液
Ｄ液： ポリビニルアルコール３．０重量％水／イソプロピルアルコール溶液（水／イソプロピルアルコール＝９０／１０、重量比）
[Composition of gas barrier coating agent]
A mixture of liquid C and liquid D at 60/40 (weight ratio).
C solution: 89.6 g of 0.1N hydrochloric acid was added to 10.4 g of tetraethoxysilane, and the resulting mixture was hydrolyzed by stirring for 30 minutes to obtain a hydrolyzed solution having a solid content of 3.0% by weight (in terms of SiO 2 ). 0.0 wt% water / isopropyl alcohol solution (water / isopropyl alcohol = 90/10, weight ratio)
次に、イソシアネート化合物としてヘキサメチレンジイソシアネートのビューレットタイプを、金属アルコキシドとしてイソシアネート系シランカップリング剤を、７０／３０（重量比）となるよう混合し、これらに対して固形分比が５００重量ｐｐｍのペンタデカフルオロオクタン酸を加え、全固形分比を０．５重量％となるように酢酸エチルを加えて接着剤を調整した。 Next, a hexamethylene diisocyanate burette type as an isocyanate compound and an isocyanate-based silane coupling agent as a metal alkoxide are mixed so as to be 70/30 (weight ratio), and the solid content ratio is 500 ppm by weight. Of pentadecafluorooctanoic acid was added, and ethyl acetate was added so that the total solid content ratio was 0.5% by weight to prepare an adhesive.
次に、前記ガスバリア性被膜層上に、前記接着剤を用いて、シーラント層の構成材料としてランダムポリプロピレンを使用した以外は実施例１と同様の方法で、積層体を得た。接着層の乾燥後の厚みは８５ｎｍ、シーラント層を押出ラミネート法により接着層上に押し出して形成したときのダイ下温度は２７５℃であった。 Next, a laminate was obtained in the same manner as in Example 1 except that random polypropylene was used as a constituent material of the sealant layer on the gas barrier coating layer using the adhesive. The thickness after drying of the adhesive layer was 85 nm, and the temperature under the die when the sealant layer was formed by extrusion extrusion onto the adhesive layer was 275 ° C.
（実施例６）
プラスチック基材として厚み１５μｍのポリ乳酸フィルムを用い、次に、蒸着層を酸化ケイ素にした以外は実施例５と同様の方法で蒸着層を形成した。
(Example 6)
A vapor deposition layer was formed in the same manner as in Example 5 except that a polylactic acid film having a thickness of 15 μm was used as the plastic substrate, and then the vapor deposition layer was changed to silicon oxide.
次に、イソシアネート化合物としてヘキサメチレンジイソシアネートのイソシアヌレートタイプを、金属アルコキシドとしてアミノ系シランカップリング剤を、６０／４０（重量比）となるよう混合し、これらに対して固形分比が１０００重量ｐｐｍのヘプタフルオロブタン酸を加え、全固形分比を０．５重量％となるように酢酸エチルを加えて接着剤を調整した。 Next, an isocyanurate type of hexamethylene diisocyanate as an isocyanate compound and an amino silane coupling agent as a metal alkoxide are mixed so as to be 60/40 (weight ratio), and the solid content ratio is 1000 ppm by weight. Of heptafluorobutanoic acid was added, and the adhesive was adjusted by adding ethyl acetate so that the total solid content ratio was 0.5% by weight.
次に、上記接着剤を用いて、シーラント層の構成材料としてポリブチレンサクシネートを用いた以外は実施例１と同様の方法で積層体を得た。接着層の乾燥後の厚みは８５ｎｍ、シーラント層を押出ラミネート法により接着層上に押し出して形成したときのダイ下温度は２８０℃であった。 Next, a laminate was obtained in the same manner as in Example 1 except that polybutylene succinate was used as a constituent material of the sealant layer using the adhesive. The thickness of the adhesive layer after drying was 85 nm, and the temperature under the die when the sealant layer was formed by extrusion extrusion onto the adhesive layer was 280 ° C.
（比較例１）
イソシアネート化合物としてトリレンジイソシアネートのアダクトタイプを、金属アルコキシドとしてテトラエトキシシランを、３０／７０（重量比）となるよう混合し、次に全固形分比を０．５重量％となるように酢酸エチルを加えて接着剤を調整し、それ以外は実施例１と同様の方法で、積層体を得た。
(Comparative Example 1)
The adduct type of tolylene diisocyanate as the isocyanate compound and tetraethoxysilane as the metal alkoxide are mixed so as to be 30/70 (weight ratio), and then ethyl acetate is adjusted so that the total solid content ratio becomes 0.5% by weight. Was added to adjust the adhesive, and a laminate was obtained in the same manner as in Example 1 except that.
（比較例２）
プラスチック基材として一方の面にコロナ処理を施し、その面に酸化アルミニウム蒸着層を形成させた厚み１５μｍのナイロンフィルムを用いた。
(Comparative Example 2)
As a plastic substrate, a nylon film having a thickness of 15 μm having a corona treatment on one surface and an aluminum oxide vapor deposition layer formed on the surface was used.
次に、イソシアネート化合物としてイソホロンジイソシアネートのアダクトタイプを、金属アルコキシドとしてアルミニウムトリイソプロポキシドを、２０／８０（重量比）となるよう混合し、全固形分比が０．５重量％となるように酢酸エチルを加えて接着剤を調整した。それ以外は実施例１と同様の方法で、積層体を得た。 Next, the adduct type of isophorone diisocyanate as the isocyanate compound and aluminum triisopropoxide as the metal alkoxide are mixed so as to be 20/80 (weight ratio) so that the total solid content ratio becomes 0.5% by weight. Ethyl acetate was added to adjust the adhesive. Otherwise, a laminate was obtained in the same manner as in Example 1.
（比較例３）
プラスチック基材として一方の面にコロナ処理を施し、その面に酸化ケイ素蒸着層を形成させた厚み１２μｍのポリエチレンテレフタレートフィルムを用いた。
(Comparative Example 3)
As a plastic substrate, a polyethylene terephthalate film having a thickness of 12 μm having a corona treatment on one surface and a silicon oxide vapor deposition layer formed on the surface was used.
次に、キシリレンジイソシアネートのアダクトタイプの固形分比を０．５重量％となるように酢酸エチルを加えて接着剤を調整し、シーラント層の構成材料としてエチレン−メタクリル酸共重合体を使用した以外は実施例１と同様の方法で、積層体を得た。接着層の乾燥後の厚みは６０ｎｍ、シーラント層を押出ラミネート法により接着層上に押し出して形成したときのダイ下温度は２８０℃であった。 Next, an adhesive was prepared by adding ethyl acetate so that the adduct type solid content ratio of xylylene diisocyanate was 0.5% by weight, and an ethylene-methacrylic acid copolymer was used as a constituent material of the sealant layer. Except for the above, a laminate was obtained in the same manner as in Example 1. The thickness after drying of the adhesive layer was 60 nm, and the temperature under the die when the sealant layer was formed on the adhesive layer by extrusion lamination was 280 ° C.
（比較例４）
プラスチック基材として一方の面にコロナ処理を施し、その面に酸化ケイ素蒸着層を形成させた厚み１５μｍのナイロンフィルムを用いた。次に、イソシアネート化合物としてトリレンジイソシアネートのアダクトタイプを、金属アルコキシドとしてイソシアネート系シランカップリング剤を、７０／３０（重量比）となるよう混合し、固形分比が０．５重量％となるように酢酸エチルを加えて接着剤を調整した。
(Comparative Example 4)
As a plastic substrate, a nylon film having a thickness of 15 μm in which one surface was subjected to corona treatment and a silicon oxide vapor deposition layer was formed on the surface was used. Next, an adduct type of tolylene diisocyanate as an isocyanate compound and an isocyanate-based silane coupling agent as a metal alkoxide are mixed so as to be 70/30 (weight ratio), so that the solid content ratio becomes 0.5% by weight. The adhesive was adjusted by adding ethyl acetate.
次に、シーラント層の構成材料としてランダムポリプロピレンを用いた以外は実施例１と同様の方法で、積層体を得た。接着層の乾燥後の厚みは８５ｎｍ、シーラント層を押出ラミネート法により接着層上に押し出して形成したときのダイ下温度は２７５℃であった。 Next, a laminate was obtained in the same manner as in Example 1 except that random polypropylene was used as the constituent material of the sealant layer. The thickness after drying of the adhesive layer was 85 nm, and the temperature under the die when the sealant layer was formed by extrusion extrusion onto the adhesive layer was 275 ° C.
＜物性評価＞
上記の実施例１〜６及び比較例１〜４で得られた積層体を用いて、各種プラスチック基材とシーラント層間における初期のラミネート強度を測定した（表１参照）。その結果、比較例１〜４で得られた積層体はいずれも初期のラミネート強度が不均一で、パウチ形成に適する強度を有さず、以下のパウチ形成には至らなかった。一方、実施例１〜６で得られた積層体はいずれも初期のラミネート強度がパウチ形成に適した十分な強度を示した。
<Physical property evaluation>
Using the laminates obtained in Examples 1 to 6 and Comparative Examples 1 to 4, the initial laminate strength between various plastic substrates and the sealant layer was measured (see Table 1). As a result, all the laminates obtained in Comparative Examples 1 to 4 had non-uniform initial laminate strength, did not have strength suitable for pouch formation, and did not lead to the following pouch formation. On the other hand, all of the laminates obtained in Examples 1 to 6 showed sufficient strength that the initial laminate strength was suitable for pouch formation.
次に、パウチ形成に適するラミネート強度を有した実施例１〜６の積層体を用いてパウチを形成し、内容物として湿布薬（揮発性の強浸透性物質としてサリチル酸メチルやメントールを含有）と、浴用剤（揮発性の強浸透性物質として香料成分を含有）をそれぞれ充填、密封し、４０℃の恒温室内に放置した。 Next, a pouch is formed using the laminates of Examples 1 to 6 having a laminate strength suitable for pouch formation, and a poultice (containing methyl salicylate and menthol as a volatile strong permeable substance) is used as the contents. Each was filled with a bath agent (containing a fragrance component as a volatile strong penetrating substance), sealed, and left in a constant temperature room at 40 ° C.
３ヶ月経過後にこれらのパウチを恒温室から取り出し、それぞれのパウチの各種プラスチック基材とシーラント層間のラミネート強度［Ｎ／１５ｍｍ］を測定し、恒温室に入れる前のパウチにおける初期のラミネート強度と比較した。このときのラミネート強度の測定条件は、試料幅１５ｍｍのＴ型剥離で、剥離速度３００ｍｍ／ｍｉｎとした。恒温室投入前と後におけるラミネート強度の測定結果をまとめて、以下の表１に示す。 After 3 months, these pouches are removed from the temperature-controlled room, and the laminate strength [N / 15mm] between the various plastic substrates and the sealant layer of each pouch is measured and compared with the initial laminate strength in the pouch before entering the temperature-controlled room. did. The measurement conditions of the laminate strength at this time were T-type peeling with a sample width of 15 mm and a peeling speed of 300 mm / min. Table 1 below summarizes the measurement results of the laminate strength before and after entering the temperature-controlled room.
＜比較結果＞
実施例１〜６および比較例１〜４について比較結果を行った。その結果、実施例１〜６で得られた実施例品は、いずれも各種プラスチック基材とシーラント層間における初期のラミネート強度が、シーラント切れを示すほど強固であった。また、揮発性物質を含む湿布薬や浴用剤を入れて４０℃で３ヶ月間保存したパウチにおいてもラミネート強度に変化はなく、初期のラミネート強度を十分に保っていた。
<Comparison result>
The comparison result was performed about Examples 1-6 and Comparative Examples 1-4. As a result, in all of the Example products obtained in Examples 1 to 6, the initial laminate strength between the various plastic substrates and the sealant layer was so strong that the sealant was broken. Further, even in the pouch stored with a poultice containing a volatile substance and a bath agent and stored at 40 ° C. for 3 months, the laminate strength did not change, and the initial laminate strength was sufficiently maintained.
一方、比較例１〜４で得られた比較品は、いずれも各種プラスチック基材とシーラント層間における初期のラミネート強度が、接着層のプラスチック基材に対するレベリング性（濡れ性）が悪く、十分なラミネート強度が得られる部分とそうでない部分がランダムに存在し、ラミネート強度に不均一が生じていたことから、包装材料への使用には適さないことが判明した。 On the other hand, all of the comparative products obtained in Comparative Examples 1 to 4 have sufficient initial laminate strength between various plastic substrates and the sealant layer, and the leveling property (wetability) of the adhesive layer to the plastic substrate is poor. It was found that the portion where the strength was obtained and the portion where the strength was not obtained were present at random, and the laminate strength was non-uniform, so that it was not suitable for use as a packaging material.
上記のように、実施例１〜６で得られた実施例品は、比較例１〜４で得られた比較品に比べて、いずれも良好な結果を示した。 As described above, all of the example products obtained in Examples 1 to 6 showed better results than the comparative products obtained in Comparative Examples 1 to 4.
１・・・・プラスチック基材
２・・・・蒸着薄膜層
３・・・・接着層
４・・・・シーラント層
DESCRIPTION OF SYMBOLS 1 ... Plastic substrate 2 ... Deposition thin film layer 3 ... Adhesive layer 4 ... Sealant layer
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010279143A JP5668450B2 (en) | 2010-12-15 | 2010-12-15 | Laminated body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010279143A JP5668450B2 (en) | 2010-12-15 | 2010-12-15 | Laminated body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2012126003A true JP2012126003A (en) | 2012-07-05 |
| JP5668450B2 JP5668450B2 (en) | 2015-02-12 |
Family
ID=46643615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010279143A Active JP5668450B2 (en) | 2010-12-15 | 2010-12-15 | Laminated body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5668450B2 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986002041A1 (en) * | 1984-09-28 | 1986-04-10 | Fujimori Kogyo Co., Ltd. | Film laminate for sterile flexible containers |
| JPH09194808A (en) * | 1996-01-18 | 1997-07-29 | Nippon Soda Co Ltd | Aqueous adhesive |
| JP2007030341A (en) * | 2005-07-27 | 2007-02-08 | Mitsubishi Plastics Ind Ltd | Gas barrier laminate for hot water treatment |
| JP2008094051A (en) * | 2006-10-16 | 2008-04-24 | Toppan Printing Co Ltd | Laminates and packaging material |
| JP2009012310A (en) * | 2007-07-05 | 2009-01-22 | Toppan Printing Co Ltd | Gas barrier film |
| JP2010069625A (en) * | 2008-09-16 | 2010-04-02 | Toppan Printing Co Ltd | Laminate |
-
2010
- 2010-12-15 JP JP2010279143A patent/JP5668450B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1986002041A1 (en) * | 1984-09-28 | 1986-04-10 | Fujimori Kogyo Co., Ltd. | Film laminate for sterile flexible containers |
| JPS62502112A (en) * | 1984-09-28 | 1987-08-20 | 藤森工業株式会社 | Film laminate for sterile flexible containers |
| JPH09194808A (en) * | 1996-01-18 | 1997-07-29 | Nippon Soda Co Ltd | Aqueous adhesive |
| JP2007030341A (en) * | 2005-07-27 | 2007-02-08 | Mitsubishi Plastics Ind Ltd | Gas barrier laminate for hot water treatment |
| EP1908582A1 (en) * | 2005-07-27 | 2008-04-09 | Mitsubishi Plastics Inc. | Gas barrier laminate for use in hot water treatment |
| JP2008094051A (en) * | 2006-10-16 | 2008-04-24 | Toppan Printing Co Ltd | Laminates and packaging material |
| JP2009012310A (en) * | 2007-07-05 | 2009-01-22 | Toppan Printing Co Ltd | Gas barrier film |
| JP2010069625A (en) * | 2008-09-16 | 2010-04-02 | Toppan Printing Co Ltd | Laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5668450B2 (en) | 2015-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5446442B2 (en) | Laminated body | |
| TW384258B (en) | Barrier composite film and preparation thereof | |
| WO2016158794A1 (en) | Laminated film, and bag for packaging | |
| JP4765090B2 (en) | Laminated film for moisture-proof film and method for producing the same | |
| JP4894177B2 (en) | Laminated body | |
| JP2008094051A (en) | Laminates and packaging material | |
| JP2010149389A (en) | Laminated body | |
| JP2008265155A (en) | Laminated body, and its manufacturing method | |
| JP5668450B2 (en) | Laminated body | |
| JP5119956B2 (en) | Manufacturing method of laminate | |
| JP5625560B2 (en) | Laminated body | |
| JP5942469B2 (en) | Laminate, pouch | |
| JP5115027B2 (en) | Manufacturing method of laminate | |
| JP2017226423A (en) | Paper container for liquid | |
| JP5549064B2 (en) | Laminated body | |
| JP2000025145A (en) | Barrier laminate, packaging material using the same, and packed body using the same | |
| JP2007237712A (en) | Polyamide based film laminate | |
| JP2012121151A (en) | Laminate and packaging material | |
| JP2006187908A (en) | Laminate | |
| JP2011110741A (en) | Laminate | |
| JP5516030B2 (en) | Gas barrier laminate and encapsulated display device including the same | |
| JP2007181943A (en) | Laminate | |
| JP2015229296A (en) | Laminate and pouch | |
| JP5320838B2 (en) | Laminated body | |
| JP2003055512A (en) | Adhesive resin composition, and laminate and package each including layer made from the composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20131121 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140813 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140826 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20141017 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20141118 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20141201 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5668450 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |