JPH0523184B2 - - Google Patents
Info
- Publication number
- JPH0523184B2 JPH0523184B2 JP29793885A JP29793885A JPH0523184B2 JP H0523184 B2 JPH0523184 B2 JP H0523184B2 JP 29793885 A JP29793885 A JP 29793885A JP 29793885 A JP29793885 A JP 29793885A JP H0523184 B2 JPH0523184 B2 JP H0523184B2
- Authority
- JP
- Japan
- Prior art keywords
- packaging material
- laminated packaging
- material according
- component
- ethylene
- 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.)
- Expired - Lifetime
Links
- 239000010410 layer Substances 0.000 claims description 82
- 238000005452 bending Methods 0.000 claims description 52
- 239000005022 packaging material Substances 0.000 claims description 46
- 230000004888 barrier function Effects 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 229920001577 copolymer Polymers 0.000 claims description 36
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 26
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- -1 Acrylic ester Chemical class 0.000 claims description 19
- 239000002344 surface layer Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000005977 Ethylene Substances 0.000 claims description 14
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 14
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 14
- 230000004927 fusion Effects 0.000 claims description 13
- 150000002736 metal compounds Chemical class 0.000 claims description 13
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 11
- 229920005992 thermoplastic resin Polymers 0.000 claims description 11
- 239000004840 adhesive resin Substances 0.000 claims description 10
- 229920006223 adhesive resin Polymers 0.000 claims description 10
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 8
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 238000002076 thermal analysis method Methods 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229920006163 vinyl copolymer Polymers 0.000 claims description 2
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 claims 1
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 31
- 239000007789 gas Substances 0.000 description 26
- 230000000694 effects Effects 0.000 description 24
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 23
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 22
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 239000004698 Polyethylene Substances 0.000 description 11
- 238000009661 fatigue test Methods 0.000 description 11
- 229920000573 polyethylene Polymers 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007127 saponification reaction Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229920001684 low density polyethylene Polymers 0.000 description 6
- 239000004702 low-density polyethylene Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000032798 delamination Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000021056 liquid food Nutrition 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920006284 nylon film Polymers 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-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
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- SGHJOQOVLLGIGF-UHFFFAOYSA-N 2-(5-chlorobenzotriazol-2-yl)-4-methylphenol Chemical compound CC1=CC=C(O)C(N2N=C3C=C(Cl)C=CC3=N2)=C1 SGHJOQOVLLGIGF-UHFFFAOYSA-N 0.000 description 1
- QTHWVXNCOOKLNV-UHFFFAOYSA-N 2-butyl-4-(3-butyl-4-hydroxyphenyl)sulfanylphenol Chemical compound C1=C(O)C(CCCC)=CC(SC=2C=C(CCCC)C(O)=CC=2)=C1 QTHWVXNCOOKLNV-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical class C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- UPIWXMRIPODGLE-UHFFFAOYSA-N butyl benzenecarboperoxoate Chemical compound CCCCOOC(=O)C1=CC=CC=C1 UPIWXMRIPODGLE-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005021 flexible packaging material Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention 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
- 238000001226 reprecipitation Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】
Ａ 産業上の利用分野
本発明はきわめて激しい屈曲疲労によつても高
度の気体遮断性が低下することのないフレキシブ
ル積層包装材に関する。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a flexible laminated packaging material whose high gas barrier properties do not deteriorate even under extremely severe bending fatigue.
Ｂ 従来技術
フレキシブル積層包装材の機能は、基本的には
被包装物の保存性、すなわち変質防止であり、そ
のために、該包装材にあつては、特に輸送振動強
度、耐屈曲疲労性が要求され、就中、所謂バツグ
インボツクスまたはバツグインカートン（以下こ
れらを総称してバツグインボツクスという）（折
り畳み可能なプラスチツクの薄肉内容器と積み重
ね性、持ち運び性、印刷適性を有する外装段ボー
ル箱とを組合せた容器）の内容物として用いられ
る場合には、高度の該特性が要求される。該包装
材は、各種プラスチツク・フイルムがそれぞれの
素材の特性を活かして積層されて用いられるが、
たとえば機械的強度を保持するための基材フイル
ムと熱シール可能な素材との組合せが最も一般的
であり、被包装物の要請に応じて、素材が選択さ
れる。就中、基材フイルムの酸素等のガス遮断性
では、不満足な用途については、さらに高度なガ
ス遮断性を有するバリヤー層を基材層上に設け、
このバリヤー層を中間層としてヒートシール可能
な素材を、少くとも一外層となる如く熱可塑性樹
脂層を積層する方法が採用される。B. Prior Art The function of flexible laminated packaging materials is basically the preservation of the packaged items, that is, the prevention of deterioration, and for this purpose, the packaging materials are particularly required to have transport vibration strength and bending fatigue resistance. In particular, so-called bag-in boxes or bag-in cartons (hereinafter collectively referred to as bag-in boxes) include a thin inner container made of foldable plastic and an outer cardboard box that is stackable, portable, and printable. When used as the contents of a combination container), a high degree of this property is required. The packaging material is made by laminating various plastic films that take advantage of the characteristics of each material.
For example, the most common combination is a base film for maintaining mechanical strength and a heat-sealable material, and the material is selected depending on the requirements of the packaged item. In particular, for applications where the base film's barrier properties against gases such as oxygen are unsatisfactory, a barrier layer with even higher gas barrier properties may be provided on the base film.
A method is employed in which a heat-sealable material is laminated with this barrier layer as an intermediate layer and a thermoplastic resin layer as at least one outer layer.
たとえば従来のバツグインボツクス内容器の材
質の基本は、必ずヒートシール部分があるので、
ヒートシール可能なポリエチレン、特に軟質ポリ
エチレンを主体としているが、バツグインボツク
スの特徴である折畳み可能であること、内容物が
液体であること等から物理的強度、前述の如く、
特に輸送振動強度、耐屈曲疲労性が求められ、こ
のために耐ストレスクラツク性が良好であること
等と相俟つて、エチレン−酢酸ビニル共重合体樹
脂がより好ましく用いられている。さらに要求性
能の高度化に伴つて、酸素等のガス遮断性が要求
される場合には、ナイロンフイルム、サランコー
ト・ナイロンフイルム、アルミ蒸着ナイロンフイ
ルム、アルミ蒸着ポリエステルフイルム等を組合
せた該内容器が実用化され始めている。高度なガ
ス遮断性を付与するためには、エチレン−酢酸ビ
ニル共重合体けん化物（以下EVOHと記す。）、
ポリ塩化ビニリデン、アルミ箔などが用いられ
る。しかしこれらはガス遮断性については優れる
が、機械的強度は一般に低く、特に屈曲疲労に耐
えられるものではない。従つて、機械的強度の優
れた基材層とヒートシール可能な素材の間に積層
されて用いられるが、なおたとえばバツグインボ
ツクス内容器の構成材として用いた場合、該構成
材にピンホール、クラツクなどを生じたり、該構
成材にピンホールを生じない段階においてさあ、
中間層として用いた該バリヤー層に生ずるクラツ
クやピンホール等に起因してバリヤー性の低下を
生ずるなどのため、はげしい屈曲疲労に対して、
優れた気体遮断性を保持することができず、実用
的に満足なものは見出されていない。ポリ塩化ビ
ニリデン樹脂を主体とする層、アルミ箔、金属な
どの蒸着樹脂層などをバリヤー層とする積層包装
材についての挙動は、たとえば特開昭55−7477号
公報に示されている。すなわち実際に該包装材を
使用し、包装された包装体の輸送、取扱後のガス
遮断性が必ずしも満足出来るものでなく、最も必
要性の高い二次流通後の実用保存性がしばしば裏
切られるのは、中間層に位置する該バリヤー層の
損傷に起因する。ガス遮断性向上のために設ける
中間層の素材としては、EVOH樹脂が最も優れ
ており、各種の多層フイルム、多層構造をもつ容
器のバリヤー材として好んで用いられる。これは
この樹脂が抜群のガスバリヤー性を有するだけで
なく、透明性、耐油性、印刷性、成形性などにも
すぐれていて、基材樹脂の特性を損うことがない
というきわめて有利な性質をもつからである。し
かるに耐屈曲疲労性を特に要求される分野には、
積層包装材のバリヤー層としてEVOH樹脂が満
足に用いられている例はみられない。就中、前述
の如く輸送振動による屈曲疲労に耐えることが強
く求められている酸素等の気体遮断性を有するバ
ツグインボツクスの内容器にEVOH樹脂が用い
られて該要求を満足するものは見出されておら
ず、優れたバリヤー性と輸送振動に耐える屈曲疲
労強度をもつたフレキシブル積層包装材の開発
は、重要課題の一つであつた。 For example, the basic material of conventional bag-in-box inner containers always has a heat-sealed part.
Although it is mainly made of heat-sealable polyethylene, especially soft polyethylene, bag-in-boxes have physical strength due to their foldability and liquid content, as mentioned above.
In particular, transportation vibration strength and bending fatigue resistance are required, and for this reason, ethylene-vinyl acetate copolymer resin is more preferably used, as it has good stress crack resistance. Furthermore, as the required performance becomes more sophisticated, when gas barrier properties such as oxygen are required, the inner container is made of a combination of nylon film, Saran-coated nylon film, aluminum-deposited nylon film, aluminum-deposited polyester film, etc. It is starting to be put into practical use. In order to provide high gas barrier properties, saponified ethylene-vinyl acetate copolymer (hereinafter referred to as EVOH),
Polyvinylidene chloride, aluminum foil, etc. are used. However, although these have excellent gas barrier properties, their mechanical strength is generally low, and they are not particularly resistant to bending fatigue. Therefore, it is used by being laminated between a base material layer with excellent mechanical strength and a heat-sealable material, but when used as a component of a bag-in-box inner container, for example, pinholes, At the stage where no cracks or pinholes are formed in the constituent material,
Due to cracks, pinholes, etc. that occur in the barrier layer used as an intermediate layer, the barrier properties deteriorate, so it is difficult to resist severe bending fatigue.
No material has been found that is unable to maintain excellent gas barrier properties and is practically satisfactory. The behavior of laminated packaging materials whose barrier layers are layers mainly composed of polyvinylidene chloride resin, aluminum foil, vapor-deposited resin layers made of metal, etc. is shown in, for example, Japanese Patent Laid-Open No. 7477/1983. In other words, when the packaging material is actually used, the gas barrier properties after transportation and handling of the packaged package are not always satisfactory, and the practical shelf life after secondary distribution, which is the most necessary, is often betrayed. is due to damage to the barrier layer located in the middle layer. EVOH resin is the best material for the intermediate layer provided to improve gas barrier properties, and is preferably used as a barrier material for various multilayer films and containers with multilayer structures. This is because this resin not only has outstanding gas barrier properties, but also has excellent transparency, oil resistance, printability, moldability, etc., and has extremely advantageous properties such as not impairing the properties of the base resin. This is because it has However, in fields where bending fatigue resistance is particularly required,
There are no examples of EVOH resin being satisfactorily used as a barrier layer in laminated packaging materials. In particular, we have found a bag-in-box that satisfies this requirement by using EVOH resin in the inner container of a bag-in box that has gas barrier properties such as oxygen, which is strongly required to withstand bending fatigue due to transportation vibrations as mentioned above. One of the important issues was the development of flexible laminated packaging materials with excellent barrier properties and bending fatigue strength that can withstand transportation vibrations.
また特開昭50−86579号公報にはポリオレフイ
ン樹脂層とEVOH層とからなり、少なくとも一
方の層にエチレン−アクリレート共重合体を添加
して、両層を強固に接着した包装材について記載
されており、また特開昭50−69162号公報には
EVOHにエチレン−酢酸ビニル共重合体を配合
した層にポリエチレン層またはエチレン−酢酸ビ
ニル共重合体層を積層して、両者を強固に接着し
た積層体について記載されているが、これらの公
報には得られた包装体が耐屈曲疲労性に優れてい
ること、さらにこれをバツグインボツクス内容器
の構成材として使用すること、さらにまた
EVOH層の両側の表面層にとくに直鎖状低密度
ポリエチレンを設けることによつて耐屈曲疲労性
の優れた包装材が得られることについて記載され
ていない。 Furthermore, JP-A-50-86579 describes a packaging material consisting of a polyolefin resin layer and an EVOH layer, in which an ethylene-acrylate copolymer is added to at least one layer to firmly adhere the two layers. Also, in Japanese Patent Application Laid-open No. 50-69162,
These publications describe a laminate in which a polyethylene layer or an ethylene-vinyl acetate copolymer layer is laminated on a layer containing EVOH and an ethylene-vinyl acetate copolymer, and the two are firmly adhered. The obtained packaging body has excellent bending fatigue resistance, and furthermore, it is possible to use it as a constituent material of a bag-in-box inner container.
There is no mention of the fact that a packaging material with excellent bending fatigue resistance can be obtained by particularly providing linear low-density polyethylene in the surface layers on both sides of the EVOH layer.
さらにまた特開昭60−161146号公報には
EVOH層の両側に直鎖状低密度ポリエチレン層
を設けることによつて、耐屈曲疲労性の優れた包
装材が得られることが記載されているが、十分な
ガス遮断性を得る為に中間層を厚くすると耐屈曲
疲労性が十分でなく、耐屈曲疲労性を十分優れた
ものにする為には中間層を薄くする必要があり、
従つてガス遮断性が十分でないという難点があつ
た。 Furthermore, in Japanese Patent Application Laid-open No. 60-161146,
It is stated that a packaging material with excellent bending fatigue resistance can be obtained by providing linear low-density polyethylene layers on both sides of the EVOH layer. If it is too thick, the bending fatigue resistance will not be sufficient, and in order to achieve sufficiently good bending fatigue resistance, it is necessary to make the intermediate layer thinner.
Therefore, there was a problem that gas barrier properties were not sufficient.
Ｃ 発明が解決しようとする問題点
EVOHフイルムは前記優れた諸特性をもつて
いる反面ポリエチレン、ポリプロピレン、ナイロ
ン熱可塑性ポリエステルなどの熱可塑性樹脂のフ
イルムに比べ耐屈曲疲労性に著しく劣るという大
きな欠点を有しており、前記屈曲疲労に強い樹脂
層と積層し、中間層としてEVOH樹脂層を用い
た複層フレキシブル包装材において、該包装材の
耐屈曲疲労性は、前記屈曲疲労に強い熱可塑性樹
脂が単体で示す耐屈曲疲労性より顕著に低下し、
より少い屈曲疲労で積層包装材にピンホールを生
ずる。本発明者らは前記のEVOHフイルムおよ
び中間層にEVOH層を含む積層包装材の耐屈曲
疲労性をその優れたガスバリアー性をそこなうこ
となく改善し、耐屈曲疲労性と気体遮断性に優れ
たフレキシブル積層包装材を開発すべく鋭意検討
を進めて本発明を完成するに至つた。C. Problems to be Solved by the Invention Although EVOH film has the above-mentioned excellent properties, it has the major drawback of being significantly inferior in bending fatigue resistance compared to films made of thermoplastic resins such as polyethylene, polypropylene, and nylon thermoplastic polyester. In a multi-layer flexible packaging material, which is laminated with the bending fatigue resistant resin layer and using an EVOH resin layer as the intermediate layer, the bending fatigue resistance of the packaging material is higher than the bending fatigue resistant thermoplastic resin layer. is significantly lower than the bending fatigue resistance shown by itself,
Less bending fatigue causes pinholes in laminated packaging materials. The present inventors have improved the bending fatigue resistance of the above-mentioned EVOH film and the laminated packaging material containing the EVOH layer as an intermediate layer without impairing its excellent gas barrier properties, and have achieved excellent bending fatigue resistance and gas barrier properties. In order to develop a flexible laminated packaging material, we have carried out intensive studies and have completed the present invention.
Ｄ 問題点を解決するための手段
本発明は、ガス遮断性を有する薄膜を中間層と
し、該中間層の両側に表面層を有し、該表面層の
少なくとも片方が熱シール可能な熱可塑性樹脂か
らなり、かつ各層が接着性樹脂層を介して配され
てなる積層包装材において、該中間層が(A)エチレ
ン成分含有量20〜55モル％、酢酸ビニル成分の90
％以上がけん化されたエチレン−酢酸ビニル共重
合体と(B)エチレン性不飽和カルボン酸もしくは該
カルボン酸無水物をグラフトしたエチレン−アク
リル酸エステルもしくは酢酸ビニル共重合体にエ
チレン性不飽和カルボン酸もしくは該カルボン酸
無水物成分に対し0.02〜0.3当量の周期律第ａ
もしくはａ族金属の水酸化物もしくは塩からな
る金属化合物を配合するか、または該金属化合物
と(C)エチレン−アクリル酸エステルもしくは酢酸
ビニル共重合体を配合し、かつ(A)、(B)および(C)の
配合量が重量基準で下記（）式、（）式を満
足する混合物である事を特徴とする耐屈曲疲労性
と気体遮断性に優れた積層包装材を提供するもの
である。D Means for Solving Problems The present invention has a thin film having gas barrier properties as an intermediate layer, surface layers on both sides of the intermediate layer, and at least one of the surface layers is made of thermoplastic resin that can be heat-sealed. In a laminated packaging material in which each layer is arranged with an adhesive resin layer interposed therebetween, the intermediate layer has (A) an ethylene component content of 20 to 55 mol% and a vinyl acetate component content of 90%.
% or more of saponified ethylene-vinyl acetate copolymer and (B) ethylene-acrylic acid ester or vinyl acetate copolymer grafted with ethylenically unsaturated carboxylic acid or said carboxylic acid anhydride, and ethylenically unsaturated carboxylic acid. Or 0.02 to 0.3 equivalent of periodic law a to the carboxylic acid anhydride component
or by blending a metal compound consisting of a hydroxide or salt of a group A metal, or by blending the metal compound with (C) an ethylene-acrylic acid ester or vinyl acetate copolymer, and (A), (B) The present invention provides a laminated packaging material having excellent bending fatigue resistance and gas barrier properties, which is a mixture in which the amounts of (C) and (C) satisfy the following formulas () and () on a weight basis. .
0.40≧(B)＋(C)／(A)＋(B)＋(C)≧0.05 ()
1.0≧(B)／(B)＋(C)≧0.01 ()
Ｅ 発明の作用効果
種々の素材または種々の素材からなる積層材の
耐屈曲疲労性の優劣は、所謂ゲルボフレツクステ
スターを用いて行う評価テストにおけるガスバリ
アー性低下の屈曲回数依存性、ピンホール発生に
至るまでの屈曲回数等のデーターから判断するこ
とができる。本発明者らは前記構造の積層フイル
ムについてゲルボフレツクステスターを用い屈曲
回数とピンホール発生数との関係、ピンホール発
生に至る屈曲回数、ピンホール発生に至るまでの
過程における屈曲回数とバリアー性との関係を測
定した。その結果、おどろくべきことに中間層が
EVOH単体である場合に比べて、ガスバリアー
性はほとんど低下しないにもかかわらず、耐屈曲
疲労性が飛躍的に向上し、またピンホール発生を
見るに至るまでガスバリアー性は殆ど低下しない
ことを見出した。したがつて本発明の包装材で変
質しやすい物品を包装し、これを輸送する場合で
も、ピンホールの発生がみられないので、被包装
物の変質を防止する事ができる。 0.40≧(B)+(C)/(A)+(B)+(C)≧0.05 () 1.0≧(B)/(B)+(C)≧0.01 () E Effects of invention Various materials The bending fatigue resistance of laminated materials made of various materials can be determined by determining the dependence of gas barrier property deterioration on the number of bends in an evaluation test conducted using a so-called Gelbo Flex Tester, the number of bends required to generate pinholes, etc. This can be determined from the data. The present inventors investigated the relationship between the number of bends and the number of pinholes, the number of bends leading to the formation of pinholes, the number of bends in the process leading to the formation of pinholes, and the barrier using a Gelbo Flex Tester for the laminated film having the above structure. We measured the relationship with gender. As a result, surprisingly, the middle class
Compared to EVOH alone, although the gas barrier property hardly deteriorates, the bending fatigue resistance improves dramatically, and the gas barrier property hardly deteriorates until pinholes are observed. I found it. Therefore, even when an article that is easily deteriorated in quality is packaged using the packaging material of the present invention and then transported, no pinholes are generated, so deterioration of the quality of the packaged object can be prevented.
本発明において(B)エチレン性不飽和カルボン酸
もしくは該カルボン酸無水物をグラフトしたエチ
レン−アクリル酸エステルもしくは酢酸ビニル共
重合体にエチレン性不飽和カルボン酸もしくは該
カルボン酸無水物成分に対し0.02〜0.3当量の周
期律表第第ａもしくはａ族の金属の水酸化物
もしくは塩からなる金属化合物を配合するか、ま
たは該金属化合物と(C)エチレン−アクリル酸エス
テルもしくは酢酸ビニル共重合体を配合した混合
物が、(A)エチレン成分含有率20〜55モル％、けん
化度90％以上のエチレン−酢酸ビニル共重合体け
ん化物樹脂の耐屈曲疲労性、成型性をかくも顕著
に向上させる機構は充分に明らかではないが、(A)
エチレン成分含有率20〜55モル％、けん化度90％
以上のエチレン−酢酸ビニル共重合体けん化物樹
脂と(B)を構成するエチレン−アクリル酸エステル
もしくは酢酸ビニル共重合体にエチレン性不飽和
カルボン酸もしくは該カルボン酸無水物をグラフ
ト重合した化合物または該化合物(C)とエチレン−
アクリル酸エステルもしくは酢酸ビニル共重合体
の混合物をグラフトされたエチレン性不飽和カル
ボン酸もしくは該カルボン酸無水物成分に対し
0.02〜0.3当量の金属水酸化物もしくは塩からな
る金属化合物と混合することにより、溶融系にお
けるレオロジー的効果、不純物の化学的作用等が
複雑に組合わさり成形性が向上し、その結果得ら
れた混合物のモルフオロジー的性質が耐屈曲疲労
性を発揮する上で好ましい状態になつたのではな
いかと推定される。 In the present invention, (B) the ethylene-acrylic ester or vinyl acetate copolymer grafted with the ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride is added to the ethylenically unsaturated carboxylic acid or the carboxylic anhydride component. Blending 0.3 equivalent of a metal compound consisting of a hydroxide or salt of a metal of Group A or Group A of the Periodic Table, or blending the metal compound with (C) ethylene-acrylic acid ester or vinyl acetate copolymer. The mechanism by which this mixture so significantly improves the bending fatigue resistance and moldability of (A) an ethylene-vinyl acetate copolymer saponified resin having an ethylene component content of 20 to 55 mol% and a saponification degree of 90% or more is explained. Although it is not clear enough, (A)
Ethylene component content 20-55 mol%, saponification degree 90%
A compound obtained by graft polymerizing an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride to the above saponified ethylene-vinyl acetate copolymer resin and the ethylene-acrylic ester or vinyl acetate copolymer constituting (B), or Compound (C) and ethylene
to ethylenically unsaturated carboxylic acids or carboxylic acid anhydride components grafted with mixtures of acrylic esters or vinyl acetate copolymers.
By mixing with a metal compound consisting of 0.02 to 0.3 equivalents of metal hydroxide or salt, the rheological effect in the molten system, the chemical action of impurities, etc. are combined in a complex manner, resulting in improved formability. It is presumed that the morphological properties of the mixture became favorable for exhibiting bending fatigue resistance.
Ｆ 発明のより詳細な説明
以下本発明を更に詳しく説明する。本発明にお
いて中間層として使用される(A)EVOHはエチレ
ン成分含有量20〜55モル％、好適には25〜50モル
％、酢酸ビニル成分のけん化度は、90％以上であ
る。エチレン成分の含有量が20モル％以下になる
と、成形温度が分解温度に近くなり、成形が困難
になる。エチレン成分の含有量が55モル％以上に
なると、ガスバリヤー性が低下し、該包装材のガ
スバリヤー性が不満なものとなり好ましくない。
また酢酸ビニル成分のけん化度が90％未満である
と、耐屈曲疲労性は向上するものの該バリヤー性
が低下し、好ましくない。このEVOHのASTM
Ｄ−1238により190℃で測定されたメルトインデ
ツクス（MI）は0.1〜25ｇ／10分、好ましくは0.3
〜20ｇ／10分である。更にホウ酸、ホウ砂等のホ
ウ素化合物で処理したEVOH、ケイ素含有オレ
フイン性不飽和単量体、α−オレフイン、Ｎ−ビ
ニルピロリドン等の第三成分をエチレンおよび酢
酸ビニルとともに共重合し、けん化して得られる
変性EVOHについても溶融成形が可能でバリヤ
ー性、耐屈曲疲労性等本発明の効果を損なわない
範囲の物であれば使用できる。F. More detailed description of the invention The present invention will be described in more detail below. (A) EVOH used as the intermediate layer in the present invention has an ethylene component content of 20 to 55 mol%, preferably 25 to 50 mol%, and a saponification degree of the vinyl acetate component of 90% or more. When the content of the ethylene component is less than 20 mol%, the molding temperature becomes close to the decomposition temperature, making molding difficult. If the content of the ethylene component exceeds 55 mol %, the gas barrier properties of the packaging material will deteriorate and the gas barrier properties of the packaging material will be unsatisfactory, which is not preferable.
Furthermore, if the degree of saponification of the vinyl acetate component is less than 90%, although the bending fatigue resistance is improved, the barrier properties are decreased, which is not preferable. ASTM of this EVOH
Melt index (MI) measured by D-1238 at 190°C is 0.1 to 25 g/10 min, preferably 0.3
~20g/10min. Furthermore, third components such as EVOH treated with boron compounds such as boric acid and borax, silicon-containing olefinic unsaturated monomers, α-olefin, and N-vinylpyrrolidone are copolymerized with ethylene and vinyl acetate, and then saponified. The modified EVOH obtained by the process can also be used as long as it can be melt-molded and does not impair the effects of the present invention, such as barrier properties and bending fatigue resistance.
本発明に用いられる(B)成分の原料もしくは(C)成
分としてのエチレン−アクリル酸エステル共重合
体としては、例えばエチレン−アクリル酸メチル
エステル共重合体、エチレン−アクリル酸エチル
エステル共重合体、エチレン−アクリル酸ブチル
エステル共重合体、エチレン−アクリル酸ｎ−ヘ
キシルエステル共重合体、エチレン−アクリル酸
２メチル−ヘキシルエステル共重合体等である
が、中でもエチレン−アクリル酸エチルエステル
共重合体が好適に用いられる。アクリル酸エステ
ル成分の含有率は５〜45重量％が用いられるが、
中でも耐屈曲疲労性、耐衝撃性、均一混合性、成
型性の面で10〜30重量％がさらに好適である。 Examples of the ethylene-acrylic ester copolymer as the raw material for component (B) or component (C) used in the present invention include ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, These include ethylene-butyl acrylate ester copolymer, ethylene-n-hexyl acrylate copolymer, ethylene-dimethyl acrylate-hexyl ester copolymer, among others, ethylene-ethyl acrylate ester copolymer is Suitably used. The content of the acrylic ester component is 5 to 45% by weight,
Among these, 10 to 30% by weight is more preferable in terms of bending fatigue resistance, impact resistance, uniform mixability, and moldability.
また(B)成分の原料もしくは(C)成分としてのエチ
レン−酢酸ビニル共重合体の酢酸ビニル成分の含
有率は５〜55％が用いられるが、中でも耐屈曲疲
労性、耐衝撃性、均一混合性、成型性の面で15〜
40重量％がさらに好適である。 In addition, the content of vinyl acetate in the raw material for component (B) or the ethylene-vinyl acetate copolymer as component (C) is 5 to 55%. 15~ in terms of properties and moldability
40% by weight is even more preferred.
(B)成分の製造に当たつてグラフト重量に用いら
れるエチレン性不飽和カルボン酸もしくは該カル
ボン酸無水物としてはマレイン酸、アクリル酸、
イタコン酸、クロトン酸、無水マレイン酸、無水
イタコン酸等があるが、中でも無水マレイン酸が
好適である。また共重合可能な他の共単量体を同
時に共グラフトする事ができる。グラフト量は
0.001〜６重量％が用いられるが、中でも耐屈曲
疲労性、均一混合性、成型性の面で0.01〜５重量
％が更に好適である。 The ethylenically unsaturated carboxylic acid or carboxylic acid anhydride used for the graft weight in the production of component (B) is maleic acid, acrylic acid,
Examples include itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, among which maleic anhydride is preferred. Further, other copolymerizable comonomers can be simultaneously cografted. The amount of graft is
Although 0.001 to 6% by weight is used, 0.01 to 5% by weight is particularly preferred in terms of bending fatigue resistance, uniform mixing properties, and moldability.
グラフト重合の方法に特に制限は無いが、エチ
レン−アクリル酸エステル共重合体にエチレン性
不飽和カルボン酸もしくは該カルボン酸無水物
と、ジベンゾイルパーオキサイド、ジブチルパー
オキサイド、ジクミルパーオキサイド、ｔ−ブチ
ルパーベンゾエイト、ｔ−ブチルヒドロパーオキ
サイド、クメンヒドロパーオキサイド等の有機過
酸化物とを共存させて、両者に化学的結合が生じ
るように加熱反応させる。反応は例えばベンゼ
ン、トルエン、キシレン、クロルベンゼン、ｔ−
ブチルベンゼン、クメン等の溶媒の存在下もしく
は無存在下に100〜240℃の温度で行なう事が出来
るがトルエンとかキシレン等の溶媒の存在下に
110〜200℃で行なうほうが、均一な製品が得られ
るのでより好適である。 There are no particular limitations on the method of graft polymerization, but ethylene-acrylic acid ester copolymer, ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride, dibenzoyl peroxide, dibutyl peroxide, dicumyl peroxide, t- Organic peroxides such as butyl perbenzoate, t-butyl hydroperoxide, and cumene hydroperoxide are allowed to coexist, and a heating reaction is performed to form a chemical bond between the two. The reaction can be carried out, for example, with benzene, toluene, xylene, chlorobenzene, t-
It can be carried out at a temperature of 100 to 240°C in the presence or absence of a solvent such as butylbenzene or cumene, but it can be carried out in the presence of a solvent such as toluene or xylene.
It is more preferable to carry out the process at 110 to 200°C since a uniform product can be obtained.
周期律表第第ａもしくはａ族の金属水酸化
物もしくは塩からなる金属化合物としては、炭酸
ナトリウム、炭酸リチウム、炭酸マグネシウム、
酢酸ナトリウム、水酸化ナトリウム、水酸化カル
シウム、水酸化マグネシウム、水酸化カリウム等
があるが、中でも炭酸ナトリウム、酢酸ナトリウ
ム、水酸化カリウム、水酸化ナトリウム等の周期
律表第第ａの金属化合物が好適に用いられる。
なかでも水酸化ナトリウムがとりわけ好適に用い
られる。金属化合物の配合量が0.02当量以下であ
ると成形体の全体に波状の模様ができるとか、凹
凸ができるなど本発明のごとき工業的に有用な成
形体は得られない。0.3当量を越えて配合すると
エチレン性不飽和カルボン酸もしくは該カルボン
酸無水物をグラフトしたエチレン−アクリル酸エ
ステルもしくは酢酸ビニル共重合体に周期律第
ａもしくはａ族金属の水酸化物もしくは塩から
なる金属化合物を配合した樹脂が着色するとか流
動性が不良となり成形材料としては不適当な物と
なり好ましくない。 Examples of metal compounds consisting of metal hydroxides or salts of Group A or Group A of the Periodic Table include sodium carbonate, lithium carbonate, magnesium carbonate,
Examples include sodium acetate, sodium hydroxide, calcium hydroxide, magnesium hydroxide, potassium hydroxide, etc., and among them, metal compounds of item a of the periodic table such as sodium carbonate, sodium acetate, potassium hydroxide, and sodium hydroxide are preferred. used for.
Among them, sodium hydroxide is particularly preferably used. If the amount of the metal compound is less than 0.02 equivalent, the entire molded product will have a wavy pattern or unevenness, making it impossible to obtain an industrially useful molded product such as the one of the present invention. If more than 0.3 equivalents are blended, the ethylene-acrylic ester or vinyl acetate copolymer grafted with ethylenically unsaturated carboxylic acid or carboxylic acid anhydride will contain a hydroxide or salt of a metal of Group A or Group A of the Periodic Table. The resin containing the metal compound becomes colored or has poor fluidity, making it unsuitable as a molding material.
本発明の実施にあたつては(C)成分は必ずしも必
要ではないが、重量基準で下記（）式を満足す
る範囲ならば使用することができる。(C)を加える
と耐衝撃性、成形性、製造価格の面で良好とな
る。（）式の値が0.01未満であると耐屈曲疲労
性の改良効果が顕著でなく、本発明の効果は享受
出来ない。また性能上は（）式を満足する範囲
ならば十分に使用できるが、製造価格等の面で一
般的には（）式の値は0.01以上、0.4以下で使
用される場合が多い。この時(B)成分の原料に用い
たエチレン−アクリル酸エステルもしくは酢酸ビ
ニル共重合体と(C)成分に用いるエチレン−アクリ
ル酸エステルもしくは酢酸ビニル共重合体とは同
一の物であつてよいが、別種の物であつても、あ
るいは混合物であつてもよい。 In carrying out the present invention, component (C) is not necessarily required, but can be used as long as it satisfies the following formula () on a weight basis. Adding (C) improves impact resistance, moldability, and manufacturing cost. If the value of formula () is less than 0.01, the effect of improving bending fatigue resistance will not be significant, and the effects of the present invention cannot be enjoyed. In terms of performance, it can be used satisfactorily as long as it satisfies the formula (), but in terms of manufacturing costs, etc., the value of the formula () is generally used within a range of 0.01 or more and 0.4 or less. At this time, the ethylene-acrylic ester or vinyl acetate copolymer used as the raw material for component (B) and the ethylene-acrylic ester or vinyl acetate copolymer used for component (C) may be the same. , may be different types, or may be a mixture.
1.0≧(B)／(B)＋(C)≧0.01 ()
本発明の中間層を構成する(B)エチレン性不飽和
カルボン酸もしくは該カルボン酸無水物をグラフ
トしたエチレン−アクリル酸エステルもしくは酢
酸ビニル共重合体にエチレン性不飽和カルボン酸
もしくは該カルボン酸無水物成分に対し0.02〜
0.3当量の金属水酸化物もしくは塩を配合した変
性共重合体もしくは(C)エチレン−アクリル酸エス
テルもしくは酢酸ビニル共重合体と該変性共重合
体(B)の混合組成物と(A)エチレン成分含有率20〜55
モル％、けん化度90％以上のEVOHの各成分の
配合量は重量基準で下記（）式を満足すること
が耐屈曲疲労性と気体遮断性、耐衝撃性さらには
力学的性質とのバランスの面で特に重要である。
（）式の値が0.05未満であると耐屈曲疲労性の
改良効果が顕著でなく、また0.40をこえると気体
遮断性、力学的性質などの他の諸物性の低下が見
られ好ましくない。 1.0≧(B)/(B)+(C)≧0.01 () Ethylene-acrylic ester or acetic acid grafted with (B) ethylenically unsaturated carboxylic acid or carboxylic acid anhydride constituting the intermediate layer of the present invention 0.02 to 0.02 to the ethylenically unsaturated carboxylic acid or carboxylic acid anhydride component in the vinyl copolymer.
A modified copolymer blended with 0.3 equivalent of metal hydroxide or salt or a mixed composition of (C) ethylene-acrylic acid ester or vinyl acetate copolymer and the modified copolymer (B) and (A) ethylene component Content rate 20~55
The blending amount of each component of EVOH with mole% and saponification degree of 90% or more must satisfy the following formula () on a weight basis to achieve a balance between flex fatigue resistance, gas barrier property, impact resistance, and mechanical properties. This is particularly important in terms of
If the value of the formula () is less than 0.05, the effect of improving bending fatigue resistance will not be significant, and if it exceeds 0.40, other physical properties such as gas barrier properties and mechanical properties will deteriorate, which is undesirable.
0.40≧(B)＋(C)／(A)＋(B)＋(C)≧0.05 ()
本発明に用いられる(A)成分と(B)および(C)成分の
混合組成物を得るためにブレンド方法に特に制限
は無く、両者をドライブレンドする方法、あるい
は(B)成分と(C)成分をあらかじめ混合ペレツト化し
て(A)の一部にあらかじめ配合しておく方法等が任
意に選ばれる。本発明に用いられる(A)、(B)、(B)＋
(C)、(A)＋(B)＋(C)の混合組成物に対して熱可塑性樹
脂に慣用される他の添加剤を配合することができ
る。このような添加剤の例としては、酸化防止
剤、紫外線吸収剤、可塑剤、帯電防止剤、滑剤、
充填剤を挙げる事ができ、これらを本発明の作用
効果が阻害されない範囲内でブレンドすることが
できる。添加剤の具体的な例としては次の様なも
のが挙げられる。酸化防止剤：２，５−ジ−ｔ−
ブチルハイドロキノン、２，６−ジ−ｔ−ブチル
−ｐ−クレゾール、４，4′−チオビス−（６−ｔ
−ブチルフエノール、２，2′−メチレン−ビス
（４−メチル−６−ｔ−ブチルフエノール、テト
ラキス−［メチレン３−（3′，5′−ｔ−ブチル−
4′−ヒドロキシフエニル）プロピオネート［メタ
ン、オクタデシル−３−（3′，５−ジ−ｔ−ブチ
ル−4′−ヒドロキシフエニル）プロピオネート、
４，4′−チオビス−（６−ブチルフエノール）等。
紫外線吸収剤：エチル−２−シアノ−３，３−ジ
フエニルアクリレート、２−（2′−ヒドロキシ−
5′−メチルフエニル）−５−クロロベンゾトリア
ゾール、２−（2′ヒドロキシ−3′−ｔ−ブチル−
5′−メチルフエニル）−５−クロロベンゾトリア
ゾール、２−ヒドロキシ−４−メトキシベンゾフ
エノン、２，2′−ジヒドロキシ−４−メトキシベ
ンゾフエノン、２−ヒドロキシ−４−オクトキシ
ベンゾフエノン等。可塑剤：フタル酸ジメチル、
フタル酸ジエチル、フタル酸ジオクチル、ワツク
ス、流動パラフイン、リン酸エステル等。帯電防
止剤：ペンタエリスリツトモノステアレート、ソ
ルビタンモノパルミテート、硫酸化オレイン酸、
ポリエチレンオキシド、カーボワツクス等。滑
剤：エチレンビスステアロアミド、ブチルステア
レート等。着色剤：カーボンブラツク、フタロシ
アニン、キナクリドン、インドリン、アゾ系顔
料、酸かチタン、ベンガラ等。充填剤：グラスフ
アイバー、アスベスト、マイカ、バラストナイト
等。 0.40≧(B)+(C)/(A)+(B)+(C)≧0.05 () To obtain a mixed composition of component (A) and components (B) and (C) used in the present invention There is no particular restriction on the blending method, and a method of dry blending both components, or a method of premixing components (B) and (C) into pellets and blending them into a part of (A) in advance, etc., is arbitrarily selected. It will be done. (A), (B), (B)+ used in the present invention
Other additives commonly used for thermoplastic resins can be added to the mixed composition of (C) and (A)+(B)+(C). Examples of such additives include antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants,
Fillers can be mentioned, and these can be blended within a range that does not impede the effects of the present invention. Specific examples of additives include the following. Antioxidant: 2,5-di-t-
Butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4'-thiobis-(6-t
-butylphenol, 2,2'-methylene-bis(4-methyl-6-t-butylphenol, tetrakis-[methylene 3-(3',5'-t-butyl-
4'-hydroxyphenyl) propionate [methane, octadecyl-3-(3',5-di-t-butyl-4'-hydroxyphenyl) propionate,
4,4'-thiobis-(6-butylphenol), etc.
UV absorber: ethyl-2-cyano-3,3-diphenyl acrylate, 2-(2'-hydroxy-
5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'hydroxy-3'-t-butyl-
5'-methylphenyl)-5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, etc. Plasticizer: dimethyl phthalate,
Diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, phosphate esters, etc. Antistatic agents: pentaerythritol monostearate, sorbitan monopalmitate, sulfated oleic acid,
Polyethylene oxide, carbo wax, etc. Lubricants: ethylene bisstearamide, butyl stearate, etc. Coloring agents: carbon black, phthalocyanine, quinacridone, indoline, azo pigments, acid or titanium, red iron, etc. Fillers: glass fiber, asbestos, mica, ballastonite, etc.
本発明に用いられる組成物を得るための各成分
の配合手段としては、特に制限はないが、例えば
リボンブレンダー、高速ミキサー、ニーダー、ミ
キシングロール、バンバリーミキサー、押し出し
機等が例示される。 The means for blending each component to obtain the composition used in the present invention is not particularly limited, but examples thereof include a ribbon blender, high-speed mixer, kneader, mixing roll, Banbury mixer, extruder, and the like.
次に前記したEVOHの混合組成物からなる、
気体遮断性を有する中間層の両側の表面層につい
て述べる。この表面層の素材としては直鎖状低密
度ポリエチレンが最良であり、これを両側に用い
た時に対屈曲疲労性が顕著に改善される。またこ
の表面層の少なくとも片方は熱シール可能な熱可
塑性樹脂である必要がある。 Next, it consists of a mixed composition of EVOH as described above,
The surface layers on both sides of the intermediate layer having gas barrier properties will be described. The best material for this surface layer is linear low-density polyethylene, and when this is used on both sides, the bending fatigue resistance is significantly improved. Furthermore, at least one of the surface layers must be made of a heat-sealable thermoplastic resin.
本発明に使用される直鎖状低密度ポリエチレン
とは実質的に長鎖分岐を持たない直鎖状の低密度
ポリエチレンである。一般には長鎖分岐数の定量
的な尺度Ｇ＝〔η〕b／〔η〕l（〔η〕bは分岐ポリエ
チレンの極限粘度、〔η〕lは分岐ポリエチレンと
同じ分子量を持つ直鎖状ポリエチレンの極限粘
度）がほぼ１（一般的には0.9〜１の範囲にあり、
１に近い場合が多い）であり、密度が0.910〜
0.945のものである。なお従来の通常の高圧法低
密度ポリエチレンのＧ値は0.1〜0.6である。直鎖
状低密度ポリエチレンの製造法は特に制限されな
い。代表的な製造方法を例示すれば７〜45Kg／cm2
の圧力（高圧法低密度ポリエチレンの場合は通常
2000〜3000Kg／cm2）、75〜100℃の温度（高圧法低
密度ポリエチレンの場合は120〜250℃）でクロム
系触媒またはチーグラー触媒を用いて、炭素数３
以上、好ましくは４以上、さらに好ましくは５〜
10のα−オレフイン、たとえばプロピレン、ブテ
ン−１、４−メチル１−ペンテン、ヘキセン−
１、オクテン−１等のα−オレフインをランダム
共重合成分として、エチレンの共重合を行う方法
がある。重合方法としては液相法または気相法等
が用いられる。 The linear low density polyethylene used in the present invention is a linear low density polyethylene having substantially no long chain branches. In general, a quantitative measure of the number of long chain branches G = [η] b / [η] l ([η] b is the intrinsic viscosity of the branched polyethylene, [η] l is the linear polyethylene with the same molecular weight as the branched polyethylene. (intrinsic viscosity) is approximately 1 (generally in the range of 0.9 to 1,
(often close to 1), and the density is 0.910~
It is of 0.945. Note that the G value of conventional high-pressure low-density polyethylene is 0.1 to 0.6. The method for producing linear low density polyethylene is not particularly limited. An example of a typical manufacturing method is 7-45Kg/cm 2
pressure (usually for high-pressure low-density polyethylene)
2000-3000Kg/cm 2 ), at a temperature of 75-100℃ (120-250℃ for high-pressure low-density polyethylene) using a chromium-based catalyst or Ziegler catalyst,
or more, preferably 4 or more, more preferably 5 or more
10 α-olefins, such as propylene, butene-1, 4-methyl-1-pentene, hexene-1
1. There is a method of copolymerizing ethylene using α-olefin such as octene-1 as a random copolymerization component. As the polymerization method, a liquid phase method or a gas phase method is used.
本発明の効果と該α−オレフインの炭素数と該
直鎖状低密度ポリエチレンの示差走査型熱量計の
熱分析による融解熱、さらにヤング率とに深くか
かわつており、より具体的に述べれば次の通りで
ある。直鎖状低密度ポリエチレンは本発明に好適
に用いられるが、該融解熱が25cal／ｇ以下、好
ましくは25〜5cal／ｇであるか、または20℃にお
けるヤング率が22Kg／mm2以下、好ましくは22〜３
Kg／mm2、さらに好ましくは22〜５Kg／mm2である該
ポリエチレンについて本発明の効果がより顕著で
あり、特に両者が前記領域にある場合に最も顕著
である。該融解熱、ヤング率が前記領域にあるも
のは重合法、重合条件によつて多少異るが、概し
ていえば共重合成分である該α−オレフインの含
有量が約２モル％以上、好ましくは約２〜７モル
％の領域で得られる場合が多い。共重合成分がブ
テン−１である直鎖状低密度ポリエチレンについ
ては該融解熱が15cal／ｇ以下であるか、または
20℃におけるヤング率が12Kg／mm2以下である場合
に本発明の効果はより顕著であり、特に該両者が
前記領域にある場合に最も顕著に該効果を享受す
ることができる。該融解熱、ヤング率が前記領域
にある該低密度ポリエチレンは、概していえばブ
テン−１の含有量が約４モル％以上の領域で得ら
れる場合が多い。該含有量が多くなり過ぎると、
該ポリエチレンのもつ他の物理的特性が不満足な
ものとなり、好ましくなく、該含有量は高々数モ
ル％、たとえば７モル％であることが望ましい。
また本発明の効果は前述の如く該融解熱または／
およびヤング率が前記特定の領域にある直鎖状低
密度ポリエチレンについて享受し得るが、特に炭
素数５以上、たとえば５〜10のα−オレフインを
共重合成分とする該ポリエチレンについてより顕
著に該効果を享受することができる。この場合前
述と同様の理由から、該α−オレフインの含有量
は２〜７モル％、より具体的には２〜６モル％が
好ましく、また該融解熱は前記の如く該α−オレ
フイン含有量等と関連しているが、就中該融解熱
は25〜5cal／ｇであることが好ましく、またヤン
グ率は22Kg／mm2以下、好ましくは22〜３Kg／mm2、
さらに好ましくは22〜５Kg／mm2である。該オレフ
インの中でも本発明の効果がより顕著であり、工
業的にも容易に得られる４−メチル−１−ペンテ
ンを共重合成分とする直鎖状低密度ポリエチレン
は最も好適なものの一つである。従来の高圧法低
密度ポリエチレンの場合は示差走査型熱量計の熱
分析による融解熱または／およびヤング率が前記
領域にあつても本発明の効果を享受することはで
きない。 The effects of the present invention are deeply related to the number of carbon atoms in the α-olefin, the heat of fusion of the linear low-density polyethylene determined by thermal analysis using a differential scanning calorimeter, and the Young's modulus. It is as follows. Linear low-density polyethylene is preferably used in the present invention, but it has a heat of fusion of 25 cal/g or less, preferably 25 to 5 cal/g, or a Young's modulus at 20°C of 22 Kg/mm 2 or less, preferably is 22~3
The effect of the present invention is more remarkable for the polyethylene having a weight of Kg/mm 2 , more preferably 22 to 5 Kg/mm 2 , particularly when both are in the above range. The heat of fusion and Young's modulus in the above range vary somewhat depending on the polymerization method and polymerization conditions, but generally speaking, the content of the α-olefin, which is a copolymerization component, is about 2 mol% or more, preferably It is often obtained in the range of about 2 to 7 mol%. For linear low density polyethylene whose copolymerization component is butene-1, the heat of fusion is 15 cal/g or less, or
The effect of the present invention is more remarkable when the Young's modulus at 20° C. is 12 Kg/mm 2 or less, and especially when both of them are in the above range, the effect can be most significantly enjoyed. The low-density polyethylene having the heat of fusion and Young's modulus in the above range is generally obtained in many cases with a butene-1 content of about 4 mol % or more. If the content becomes too large,
Other physical properties of the polyethylene are unsatisfactory, which is undesirable, and the content is preferably at most a few mol%, for example 7 mol%.
Further, the effect of the present invention is as described above, when the heat of fusion or
Although this effect can be enjoyed by linear low-density polyethylene whose Young's modulus is in the above-mentioned specific range, this effect is particularly noticeable in polyethylene containing an α-olefin having 5 or more carbon atoms, for example, 5 to 10 carbon atoms as a copolymer component. can be enjoyed. In this case, for the same reason as mentioned above, the content of the α-olefin is preferably 2 to 7 mol%, more specifically 2 to 6 mol%, and the heat of fusion is the same as the α-olefin content. The heat of fusion is preferably 25 to 5 cal/g, and the Young's modulus is 22 Kg/mm 2 or less, preferably 22 to 3 Kg/mm 2 .
More preferably, it is 22 to 5 Kg/mm 2 . Among these olefins, the effect of the present invention is more remarkable, and linear low-density polyethylene containing 4-methyl-1-pentene as a copolymerization component, which is easily obtained industrially, is one of the most suitable. . In the case of conventional high-pressure low-density polyethylene, the effects of the present invention cannot be enjoyed even if the heat of fusion and/or Young's modulus as determined by thermal analysis using a differential scanning calorimeter are in the above range.
本発明においては前記したとおり、中間層の両
側の表面層の素材としては直鎖状低密度ポリエチ
レンが最良であるが、その他の熱シール可能な熱
可塑性樹脂（少なくとも片側は）を用いることが
でき、他の面には熱シール不能な樹脂を用いるこ
ともできる。ここで熱シール可能な熱可塑性樹脂
としては前記した直鎖状低密度ポリエチレンの他
に高圧法低密度ポリエチレン、低圧法高密度ポリ
エチレン、ポリプロピレン、各種ナイロンの如き
ポリアミド樹脂、ポリエステル樹脂、エチレン−
酢酸ビニル共重合樹脂などがあげられる。また熱
シール不能な樹脂としては二軸延伸されたポリプ
ロピレン、ナイロンなどの如く延伸された樹脂が
あげられる。 In the present invention, as described above, the best material for the surface layers on both sides of the intermediate layer is linear low-density polyethylene, but other heat-sealable thermoplastic resins (at least on one side) may be used. However, a resin that cannot be heat-sealed can also be used for other surfaces. In addition to the above-mentioned linear low-density polyethylene, heat-sealable thermoplastic resins include high-pressure low-density polyethylene, low-pressure high-density polyethylene, polypropylene, various polyamide resins such as nylon, polyester resins, and ethylene resins.
Examples include vinyl acetate copolymer resin. Examples of resins that cannot be heat-sealed include stretched resins such as biaxially stretched polypropylene and nylon.
該表面層に用いる樹脂の溶融粘性については適
宜選択し得るが、特に共押出法により該積層材を
得る場合には用いる中間層の組成、接着性樹脂と
の溶融粘性整合性の見地から比較的類似の溶融粘
性を有するものを選定し、用いるのがより好まし
い。該表面層のASTM−Ｄ−1238により190℃で
測定したMIは0.1〜20ｇ／10min、好ましくは0.2
〜10ｇ／10minである。 The melt viscosity of the resin used for the surface layer can be selected as appropriate, but in particular when obtaining the laminate by coextrusion, the melt viscosity of the resin used for the surface layer may be selected from the viewpoint of the composition of the intermediate layer used and the melt viscosity consistency with the adhesive resin. It is more preferable to select and use those having similar melt viscosity. The MI of the surface layer measured at 190°C according to ASTM-D-1238 is 0.1 to 20g/10min, preferably 0.2
~10g/10min.
本発明の積層包装材は各層が接着性樹脂層を介
して配されて成るものであることが必要であり、
該ゲルボフレツクステスターによる耐屈曲疲労性
テスト時にデラミネーシヨンを起すものであつて
はならない。該デラミネーシヨンを起す場合には
中間層の耐屈曲疲労性の該積層による向上効果を
認められず、中間層の損傷に起因するバリヤー性
の低下現象が該積層フイルムにピンホールの発生
が認められない段階で既に認められるので、本発
明の効果を享受することができない。本発明に用
いる接着性樹脂は、実用段階で該デラミネーシヨ
ンを起さないものであればよく、特に限定されな
いが、強いて言えば柔軟性に富んだ接着性樹脂が
より好適であり、就中、直鎖状低密度ポリエチレ
ンなどの表面層、EVOH系混合組成物からなる
中間層との接着性とも相俟つて、オレフイン系重
合体にエチレン性不飽和カルボン酸又はその無水
物を化学的に（たとえば付加反応、グラフト反応
により）結合されて得られるカルボキシル基を含
有する変性オレフイン系重合体が好適である。こ
こでオレフイン系重合体とはポリエチレン（低
圧、中圧、高圧）直鎖状低密度ポリエチレン、ポ
リプロピレン、ポリブテンなどのポリオレフイ
ン、オレフインとこれと共重合しうるコモノマー
（ビニルエステル、不飽和カルボン酸エステルな
ど）との共重合体、たとえばエチレン−酢酸ビニ
ル共重合体、エチレン−アクリル酸エチルエステ
ル共重合体などを意味する。 The laminated packaging material of the present invention requires that each layer be arranged with an adhesive resin layer interposed therebetween,
It must not cause delamination during the bending fatigue resistance test using the Gelbo Flex Tester. When this delamination occurs, the effect of improving the bending fatigue resistance of the intermediate layer due to the lamination is not recognized, and the phenomenon of deterioration of barrier properties due to damage to the intermediate layer causes the occurrence of pinholes in the laminated film. Since this is already recognized at the stage where it is not possible to enjoy the effects of the present invention. The adhesive resin used in the present invention is not particularly limited as long as it does not cause delamination in the practical stage, but adhesive resins with high flexibility are more suitable, especially In combination with adhesion to the surface layer such as linear low-density polyethylene and the intermediate layer made of the EVOH mixed composition, chemically adding ethylenically unsaturated carboxylic acid or its anhydride to the olefinic polymer ( Modified olefinic polymers containing carboxyl groups obtained by bonding (for example, by addition reaction or grafting reaction) are suitable. Here, olefin polymers are polyolefins such as polyethylene (low pressure, medium pressure, high pressure), linear low density polyethylene, polypropylene, polybutene, and comonomers that can be copolymerized with olefins (vinyl esters, unsaturated carboxylic acid esters, etc.). ), such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid ethyl ester copolymer, etc.
次に本発明の積層包装材の各層の厚さについて
述べると、該表面層の各層があまりに薄すぎる
と、たとえば10μ以下に至ると、強度などの他の
物理的特性が低下するので、10μ以上であること
が好ましく、20μ以上であることがより好適であ
る。またあまりに厚さが増加しすぎると、本発明
の効果が減殺されるので、該表面層の各層は60μ
以下で用いることがより好ましい。特にバツグイ
ンボツクスの内容器の構成材には、通常25〜60μ
の厚さ領域から内容量に応じて選定し、好適に用
いることができる。中間層のガス遮断性を有する
薄膜の厚さは40μを越えると耐屈曲疲労性が低下
し、本発明の効果が減殺されるので好ましくな
い。本発明の効果を充分に享受するためには中間
層の厚さは40μ以下が好適であり、35μ以下がよ
り好ましい。接着性樹脂層のそれぞれの厚さは２
〜10μであることが好ましい。 Next, regarding the thickness of each layer of the laminated packaging material of the present invention, if each layer of the surface layer is too thin, for example, 10μ or less, other physical properties such as strength will deteriorate, so The thickness is preferably 20μ or more, and more preferably 20μ or more. Furthermore, if the thickness increases too much, the effect of the present invention will be diminished, so each layer of the surface layer should have a thickness of 60 μm.
It is more preferable to use it below. In particular, the inner container components of bag-in boxes usually have a thickness of 25 to 60 μm.
It can be selected from the thickness range according to the internal capacity and used suitably. If the thickness of the thin film having gas barrier properties in the intermediate layer exceeds 40 μm, the bending fatigue resistance will decrease and the effects of the present invention will be diminished, which is not preferable. In order to fully enjoy the effects of the present invention, the thickness of the intermediate layer is preferably 40μ or less, more preferably 35μ or less. The thickness of each adhesive resin layer is 2
It is preferably ~10μ.
本発明の積層包装材は共押出法、押出ラミネー
シヨン法、ドライラミネーシヨン法などの公知の
方法により得られるが、共押出法が好適である。
また共押出製膜する場合、製膜時のエアースリツ
トの使用が効果的である。ここでエアースリツト
とはダイよりキヤストロール上に吐出された溶融
樹脂膜に対してキヤストロールへ密着させ、冷却
効果を高める目的でエヤーをスリツト状に吹付け
る操作を云う。また該積層包装材を用いた、バツ
グインボツクス内容器は、該積層構成のフイルム
をヒートシールし、口金を装着する方法、該積層
構成のシートを真空成形などにより容器とし、こ
れに口金を接着剤などで固定する方法、また該積
層構成の多層パリソンを溶融押出し成形し、口金
を挿入した金型ではさみ、圧縮空気で成形し、こ
の時のパリソンの熱と空気圧力で本体と口金を熱
接着するブロー成形方式など公知の方法で得るこ
とができる。 The laminated packaging material of the present invention can be obtained by known methods such as coextrusion, extrusion lamination, and dry lamination, with coextrusion being preferred.
Furthermore, when forming a film by coextrusion, it is effective to use an air slit during film formation. Here, the term "air slit" refers to an operation in which air is blown into a slit shape to bring the molten resin film discharged from the die onto the cast roll into close contact with the cast roll and to enhance the cooling effect. In addition, the bag-in-box inner container using the laminated packaging material can be produced by heat-sealing the laminated film and attaching a cap, or by vacuum forming the laminated sheet into a container and gluing the cap to it. Alternatively, the multi-layer parison with the laminated structure is melt-extruded, sandwiched between molds with a cap inserted, and molded with compressed air, and the heat of the parison and air pressure are used to heat the main body and the cap. It can be obtained by a known method such as an adhesive blow molding method.
また本発明においてはEVOH系混合組成物を
中間層とし、この両側に直鎖状低密度ポリエチレ
ン層を設けた積層材に、さらに他の層（樹脂層な
ど）を設けることは、本発明の目的が阻害されな
いかぎり自由である。 In addition, in the present invention, it is an object of the present invention to further provide other layers (resin layers, etc.) to the laminated material in which the EVOH-based mixed composition is used as an intermediate layer and linear low-density polyethylene layers are provided on both sides. is free as long as it is not obstructed.
このようにして得られた本発明の積層包装材は
水性混合物または含水物、とくに液状または含水
食品、たとえばワイン、酒などのアルコール類、
しよう油を運搬する際の容器材料として好適であ
る。すなわち該積層包装材を使用して袋（充填液
の出入れのための口金をそなえている）を作り、
この中に前記したような液状食品を充填したの
ち、この袋を密封し、これをバツグインボツクス
内に積み重ねた、いわゆるバツグインボツクスと
し、これを運搬する場合、袋（内容器）の材料で
ある積層包装材が耐屈曲性に優れているので、亀
裂などが生じず、したがつて液状食品の漏れを防
ぐことができ、また酸素の侵入による液状食品の
品質劣化を防ぐことができる。 The laminated packaging material of the present invention obtained in this way can contain aqueous mixtures or water-containing substances, particularly liquid or water-containing foods, such as alcohols such as wine and liquor,
Suitable as a container material for transporting soybean oil. That is, a bag (equipped with a cap for putting in and taking out the filling liquid) is made using the laminated packaging material,
After filling the above-mentioned liquid food into this bag, the bag is sealed and stacked inside a bag-in box to form a so-called bag-in box. When transporting this bag, the material of the bag (inner container) Since certain laminated packaging materials have excellent bending resistance, cracks do not occur, and therefore leakage of liquid foods can be prevented, and deterioration of the quality of liquid foods due to the intrusion of oxygen can be prevented.
以下、実施例をもつて更に具体的に説明する
が、これらの実施例によつて本発明は何等限定さ
れるものではない。尚実施例と比較例における試
験および評価方法は次の通りである。 Hereinafter, the present invention will be explained in more detail using examples, but the present invention is not limited to these examples in any way. The testing and evaluation methods in Examples and Comparative Examples are as follows.
メルトインデツクス（MI）
ASTM Ｄ−1238に従い、メルトインデクサー
を使用して2160ｇの荷重をかけたときの10分間の
樹脂の流量を示す。測定温度は190℃である。Melt Index (MI) In accordance with ASTM D-1238, the flow rate of resin is shown for 10 minutes when a load of 2160 g is applied using a melt indexer. The measurement temperature is 190℃.
耐屈曲疲労試験
ゲルボフレツクステスター（理学工業(株)製）を
用い、12インチ×８インチの試料片を直径3.5イ
ンチの円筒状となし、両端を把持し、初期把持間
隔７インチ、最大屈曲時の把持間隔１インチ、ス
トロークの最初の3.5インチで440度の角度のひね
りを加え、その後の2.5インチは直線水平動であ
る動作の繰返し往復動を40回／分の早さで20℃、
相対湿度65％の条件下に行なうものである。Bending fatigue test Using a Gerbo Flex Tester (manufactured by Rigaku Kogyo Co., Ltd.), a 12 inch x 8 inch sample piece was shaped into a cylinder with a diameter of 3.5 inches, gripped at both ends, and an initial grip interval of 7 inches, max. The grip distance during bending is 1 inch, the first 3.5 inches of the stroke is a twist of 440 degrees, and the next 2.5 inches are straight and horizontal movements. Repeated reciprocating motion at a rate of 40 times/minute at 20 degrees Celsius. ,
It is carried out under conditions of relative humidity of 65%.
酸素ガス透過量の測定
Modern Control仕製OX−TRAN 100を使用
し、20℃、相対湿度65％の条件下に行なつた。各
段階の屈曲疲労試験後の試料については12インチ
×８インテの平面となし、その中央部で測定し
た。Measurement of oxygen gas permeation Amount of oxygen gas permeation was carried out using OX-TRAN 100 manufactured by Modern Control under conditions of 20°C and 65% relative humidity. The samples after each stage of the bending fatigue test were made into a 12 inch x 8 inch plane, and measurements were taken at the center of the plane.
ヤング率
ASTM Ｄ−882−67に準じて20℃、相対湿度
65％の条件下に行なつた。Young's modulus 20℃, relative humidity according to ASTM D-882-67
It was carried out under 65% conditions.
Ｇ 実施例
実施例 １
アクリル酸エチルエステル成分の含有率が25重
量％、MI（190℃、2160ｇ）が6.3ｇ／10分、融点
70℃であるエチレン−アクリル酸エチルエステル
共重合体215重量部、及び無水マレイン酸1.8重量
部を精製したトルエン648重量部に溶解し、180℃
に保つた。この溶液に撹拌下に無水マレイン酸の
５重量部を溶解した精製トルエン溶液180重量部
を2.0時間で連続的に添加した。それと同時にク
メンヒドロパーオキサイド0.5重量部を溶解した
精製トルエン溶液100重量部を2.0時間で連続的に
添加した。添加終了後も引続き30分の後反応をお
こなつた。冷却後大量のメチルアルコール中に反
応液を投入してポリマーを析出させた。得られた
ポリマーを精製したトルエンを溶剤とし、メチル
アルコールを非溶剤として再沈精製を行なつた。
このものは無水マレイン酸成分を1.5重量％含有
しMIは4.3ｇ／10分であつた。G Examples Example 1 Content of acrylic acid ethyl ester component is 25% by weight, MI (190°C, 2160g) is 6.3g/10min, melting point
215 parts by weight of ethylene-acrylic acid ethyl ester copolymer at 70°C and 1.8 parts by weight of maleic anhydride were dissolved in 648 parts by weight of purified toluene, and the mixture was heated at 180°C.
I kept it. To this solution, 180 parts by weight of a purified toluene solution in which 5 parts by weight of maleic anhydride was dissolved was continuously added over 2.0 hours while stirring. At the same time, 100 parts by weight of a purified toluene solution containing 0.5 parts by weight of cumene hydroperoxide was continuously added over 2.0 hours. Post-reaction was continued for 30 minutes even after the addition was completed. After cooling, the reaction solution was poured into a large amount of methyl alcohol to precipitate a polymer. The obtained polymer was purified by reprecipitation using purified toluene as a solvent and methyl alcohol as a non-solvent.
This product contained 1.5% by weight of maleic anhydride component and had an MI of 4.3 g/10 minutes.
このようにして得られたポリマーの無水マレイ
ン酸成分に対し0.1当量の水酸化ナトリウム
（NaOH）を含有する水溶液を均一に添加し一部
乾燥後に、ベントつき押し出し機で減圧下に揮発
物を追い出しながら溶融混練ペレツト化し、変性
共重合体(B)を得た。 An aqueous solution containing 0.1 equivalent of sodium hydroxide (NaOH) was added uniformly to the maleic anhydride component of the polymer obtained in this way, and after partially drying, the volatiles were expelled under reduced pressure using a vented extruder. The mixture was melt-kneaded and pelletized to obtain a modified copolymer (B).
上記に得た変性共重合体(B)の20重量部を上記の
エチレン−アクリル酸エチルエステル共重合体(C)
の80重量部とドライブレンドし、次いで押し出し
機で溶融混練ペレツト化し、ブレンド組成物(B)＋
(C)を得た。 20 parts by weight of the modified copolymer (B) obtained above was added to the ethylene-acrylic acid ethyl ester copolymer (C).
Blend composition (B) +
I got (C).
エチレン含有率31モル％、けん化度が99.5％、
MIが1.4ｇ／10minのEVOHを(A)成分とし、該(A)
成分の80重量部と上記に得た(B)＋(C)の20重量部の
混合組成物からなる厚さ20μの中間層と該中間層
の両側に厚さ各々35μの４−メチル−１−ペンテ
ンを共重合成分とし、該共重合成分3.2モル％含
み、MIが2.1ｇ／10分の直鎖状低密度ポリエチレ
ン（LLDPE）からなる表面層を有し、各層間に
厚さ5μの酢酸ビニル含有量33重量％、無水マレ
イン酸変性度0.2重量％の変性エチレン−酢酸ビ
ニル共重合体からなる接着性樹脂層を介して配さ
れた積層フイルムを３基の押し出し機、３種５層
多層用ダイヘツドを用いて共押し出し法により得
た。中間層に用いた組成物はあらかじめ押し出し
機により混合したペレツトを用いた。得られた積
層フイルムについて、屈曲疲労試験を該積層フイ
ルムにピンホールの発生に至るまでの各段階での
酸素ガス透過量を測定した。ピンホール発生に至
るまでの屈曲疲労試験過程においては、酸素透過
量の変化はほとんど無かつた。またピンホールの
発生は該屈曲疲労試験7000往復を経過するまでみ
とめられず、7100往復経過後、ピンホールの有無
の検査に付した所ピンホール１ケが既に発生して
いるのを認めた。また各層間のデラミネーシヨン
は全く認められなかつた。なお該LLDPEのフイ
ルムを別に得てヤング率を測定した結果13Kg／mm2
であつた。 Ethylene content 31 mol%, saponification degree 99.5%,
EVOH with an MI of 1.4g/10min is used as the (A) component, and the (A)
An intermediate layer with a thickness of 20μ consisting of a mixed composition of 80 parts by weight of the components and 20 parts by weight of (B) + (C) obtained above, and 4-methyl-1 with a thickness of 35μ each on both sides of the intermediate layer. - Contains pentene as a copolymer component, contains 3.2 mol% of the copolymer component, has a surface layer made of linear low density polyethylene (LLDPE) with an MI of 2.1 g/10 minutes, and has acetic acid with a thickness of 5 μm between each layer. Three types of 5-layer multi-layer extruders are used to produce a laminated film arranged through an adhesive resin layer made of a modified ethylene-vinyl acetate copolymer with a vinyl content of 33% by weight and a degree of maleic anhydride modification of 0.2% by weight. It was obtained by a coextrusion method using a commercial die head. The composition used for the intermediate layer was pellets that had been mixed in advance using an extruder. The obtained laminated film was subjected to a bending fatigue test to measure the amount of oxygen gas permeation at each stage up to the generation of pinholes in the laminated film. During the bending fatigue test process up to the occurrence of pinholes, there was almost no change in the amount of oxygen permeation. In addition, the occurrence of pinholes was not observed until 7,000 cycles had passed in the bending fatigue test, and after 7,100 cycles, an inspection for the presence of pinholes was performed and one pinhole had already occurred. Furthermore, no delamination between the layers was observed. The Young's modulus of the LLDPE film obtained separately was 13Kg/ mm2 .
It was hot.
水酸化ナトリウムを特定量だけ添加した(B)成分
を用いることにより、耐屈曲疲労性に優れた、外
観の良好な積層フイルムが全巾にわたつて得られ
る。このことより水酸化ナトリウム添加の効果
は、比較例１との対比において明白である。 By using component (B) to which a specific amount of sodium hydroxide is added, a laminated film with excellent bending fatigue resistance and good appearance can be obtained over the entire width. From this, the effect of adding sodium hydroxide is clear in comparison with Comparative Example 1.
実施例 ２
中間層の(B)成分として用いる変性共重合体の
NaOH添加量を0.05当量とする以外は実施例１と
同様にして行なつた。屈曲疲労試験6500往復を経
過するまでみとめられず、6900往復経過後、ピン
ホールの有無の検査に付した所ピンホール１ケが
既に発生しているのを認めた。Example 2 Modified copolymer used as component (B) of intermediate layer
The same procedure as in Example 1 was conducted except that the amount of NaOH added was 0.05 equivalent. It was not noticed until after 6,500 cycles of the bending fatigue test, and after 6,900 cycles, when the pinhole was inspected, it was found that one pinhole had already occurred.
比較例 １
NaOHを無添加とする以外は実施例１と同様
にして積層フイルムを得た。得られた積層フイル
ムにはブツ状の凸凹が数多く見られた。該積層フ
イルムについて屈曲疲労テストをおこなつた。ブ
ツ状の凸凹の見られない所を選んだ試料は6000往
復まではピンホールの発生はみられず、6700往復
経過後にピンホールが一個発生していた。しかし
ながらブツ状の凸凹の有る試料では、200往復経
過後に既にピンホールが一個発生していた。ブツ
状の凸凹の見られない試料は全体の15％のみであ
り、工業的な価値は低いものであつた。Comparative Example 1 A laminated film was obtained in the same manner as in Example 1 except that NaOH was not added. Many bump-like irregularities were observed in the obtained laminated film. A bending fatigue test was conducted on the laminated film. For the sample selected from a place where no lumpy irregularities were observed, no pinholes were observed until 6,000 reciprocations, and one pinhole appeared after 6,700 reciprocations. However, in the sample with bump-like unevenness, one pinhole had already occurred after 200 reciprocations. Only 15% of the samples had no lumpy irregularities and were of low industrial value.
比較例 ２
NaOHを0.6等量添加する以外は実施例１と同
様にした。この変性共重合体は褐色に着色したも
のであつたが積層フイルムを得た。得られた積層
フイルムには褐色に着色したブツ状の凸凹が数多
く見られ工業的な価値は低いものであつた。Comparative Example 2 The same procedure as Example 1 was carried out except that 0.6 equivalents of NaOH was added. Although this modified copolymer was colored brown, a laminated film was obtained. The obtained laminated film had many brownish bumpy irregularities and was of low industrial value.
実施例 ３
実施例１において(B)＋(C)のブレンド組成物に代
えて、(B)変性共重合体を用いる以外は実施例１と
同様にして積層フイルムを得た。屈曲疲労試験
7500往復を経過するまでみとめられず、7600往復
経過後、ピンホールの有無の検査に付した所、ピ
ンホール１ケが既に発生しているのを認めた。Example 3 A laminated film was obtained in the same manner as in Example 1 except that the modified copolymer (B) was used instead of the blend composition of (B)+(C) in Example 1. bending fatigue test
It was not noticed until after 7,500 round trips, and after 7,600 round trips, when the pinhole was inspected, it was found that one pinhole had already occurred.
実施例 ４
Ｄ／Ad／Ｅ／Ad／Ｆ／Ad／Ｇなる構成の積
層フイルムを３種７層用多層ダイヘツドを有する
共押し出し設備を用いて得た。各層はそれぞれ次
に示す各樹脂および層厚さからなる。Example 4 A laminated film having the structure D/Ad/E/Ad/F/Ad/G was obtained using coextrusion equipment having a multilayer die head for three types and seven layers. Each layer consists of each resin and layer thickness shown below.
Ｅ，Ｆ：エチレン−アクリル酸エチルエステル共
重合体にかえて、酢酸ビニル成分が25重量％、
MIが6.0のエチレン−酢酸ビニル共重合体をも
ちい、かつクメンヒドロパーオキシドと無水マ
レイン酸の使用量を変更し、NaOHに代えて
炭酸ナトリウム（Na2CO3）をもちいる以外は
実施例１と同様にして無水マレイン酸成分を
2.9重量％含有し、Na2CO3を0.11当量含有する
変性共重合体(B)を得、酢酸ビニル成分が40重量
％、MIが2.3のエチレン−酢酸ビニル共重合体
を(C)成分とし、エチレン含有率38モル％、けん
化度99.4％、のEVOHを(A)成分としてＡ：Ｂ：
Ｃ＝90：５：５のブレンド組成物からなる厚さ
12μの層
Ｄ，Ｇ：４−メチル−１−ペンテンの4.1モル％
を共重合成分として含有するメルトインデツク
ス2.3ｇ／10分、DSCによる融解熱15cal／ｇの
厚さ40μのLLDPE層
Ad：酢酸ビニル含有量33重量％、無水マレイン
酸変性度0.2重量％の変性エチレン−酢酸ビニ
ル共重合体からなる接着性樹脂層、層厚さ6μ、
実施例１に準じて屈曲疲労試験を行なつた。該
屈曲疲労試験6500回後もピンホールの発生はみと
められず、6800往復経過後、ピンホールの有無の
検査に付した所ピンホール１ケが既に発生してい
るのを認めた。また各層間のデラミネーシヨンは
全く認められなかつた。なお該LLDPEのフイル
ムを別に得てヤング率を測定した結果7.5Kg／mm2
であつた。E, F: 25% by weight of vinyl acetate component instead of ethylene-acrylic acid ethyl ester copolymer,
Example 1 except that an ethylene-vinyl acetate copolymer with an MI of 6.0 was used, the amounts of cumene hydroperoxide and maleic anhydride were changed, and sodium carbonate (Na 2 CO 3 ) was used instead of NaOH. Add the maleic anhydride component in the same manner as
A modified copolymer (B) containing 2.9% by weight and 0.11 equivalent of Na 2 CO 3 was obtained, and an ethylene-vinyl acetate copolymer with a vinyl acetate component of 40% by weight and an MI of 2.3 was used as the (C) component. , ethylene content 38 mol%, saponification degree 99.4%, EVOH as component (A) A:B:
Thickness consisting of a blend composition of C=90:5:5
12μ layers D, G: 4.1 mol% of 4-methyl-1-pentene
A 40μ thick LLDPE layer Ad containing as a copolymerization component, a melt index of 2.3 g/10 min, and a heat of fusion of 15 cal/g by DSC: modified with a vinyl acetate content of 33% by weight and a degree of maleic anhydride modification of 0.2% by weight. A bending fatigue test was conducted in accordance with Example 1 using an adhesive resin layer made of ethylene-vinyl acetate copolymer and having a layer thickness of 6 μm. No pinholes were observed even after 6,500 cycles of the bending fatigue test, and after 6,800 reciprocations, an inspection for the presence of pinholes revealed that one pinhole had already occurred. Furthermore, no delamination between the layers was observed. The Young's modulus of the LLDPE film obtained separately was 7.5Kg/ mm2 .
It was hot.
炭酸ナトリウムを特定量だけ添加した(B)成分を
用いることにより、耐屈曲疲労性に優れた、外観
の良好な積層フイルムが全巾にわたつて得られ
る。このことより炭酸ナトリウム添加の効果は、
比較例３との対比において明白である。 By using component (B) to which a specific amount of sodium carbonate is added, a laminated film with excellent bending fatigue resistance and good appearance can be obtained over the entire width. From this, the effect of adding sodium carbonate is
This is clear in comparison with Comparative Example 3.
比較例 ３
炭酸ナトリウムを0.005等量添加する以外は実
施例４と同様にし積層フイルムを得た。得られた
積層フイルムにはブツ状の凸凹が見られた。該積
層フイルムについて屈曲疲労テストをおこなつ
た。ブツ状の凸凹の見られない所を選んだ試料は
5500往復まではピンホールの発生はみられず、
5700往復経過後にビンホールが一個発生してい
た。しかしながらブツ状の凸凹の有る試料では、
300往復経過後に既にピンホールが一個発生して
いた。ブツ状の凸凹の見られない試料は全体の25
％のみであり工業的な価値は低いものであつた。Comparative Example 3 A laminated film was obtained in the same manner as in Example 4 except that 0.005 equivalent of sodium carbonate was added. Bumpy unevenness was observed in the obtained laminated film. A bending fatigue test was conducted on the laminated film. The sample was selected from a place where no lumpy irregularities were observed.
No pinholes were observed until 5500 round trips.
One bottle hole occurred after 5,700 round trips. However, for samples with bumpy unevenness,
After 300 round trips, one pinhole had already occurred. The total number of samples with no lumpy irregularities was 25.
%, and its industrial value was low.
比較例 ４
炭酸ナトリウムを1.0等量添加する以外は実施
例４と同様にした。この変性共重合体はきわめて
流動性が悪く積層フイルムは得られなかつた。Comparative Example 4 The same procedure as Example 4 was carried out except that 1.0 equivalent of sodium carbonate was added. This modified copolymer had extremely poor fluidity and no laminated film could be obtained.
Claims (1)
間層の両側に表面層を有し、該表面層の少なくと
も片方が熱シール可能な熱可塑性樹脂からなり、
かつ各層が接着性樹脂層を介して配されてなる積
層包装材において、該中間層が(A)エチレン成分含
有量20〜55モル％、酢酸ビニル成分の90％以上が
けん化されたエチレン−酢酸ビニル共重合体と(B)
エチレン性不飽和カルボン酸もしくは該カルボン
酸無水物をグラフトしたエチレン−アクリル酸エ
ステルもしくは酢酸ビニル共重合体にエチレン性
不飽和カルボン酸もしくは該カルボン酸無水物成
分に対し0.02〜0.3当量の周期律第ａもしくは
ａの族金属の水酸化物もしくは塩からなる金属
化合物を配合するか、または該金属化合物と(C)エ
チレン−アクリル酸エステルもしくは酢酸ビニル
共重合体を配合し、かつ(A)、(B)および(C)の配合量
が重量基準で下記（）式、（）式を満足する
混合物である事を特徴とする耐屈曲疲労性と気体
遮断性に優れた積層包装材。 0.40≧(B)＋(C)／(A)＋(B)＋(C)≧0.05 () 1.0≧(B)／(B)＋(C)≧0.01 () ２ アクリル酸エステルがアクリル酸エチルエス
テルである特許請求の範囲第１項に記載の積層包
装材。 ３ エチレン性不飽和カルボン酸もしくは該カル
ボン酸無水物が無水マレイン酸である特許請求の
範囲第１項に記載の積層包装材。 ４ アクリル酸エステルがアクリル酸エチルエス
テルであり、エチレン性不飽和カルボン酸もしく
は該カルボン酸無水物が無水マレイン酸である特
許請求の範囲第１項に記載の積層包装材。 ５ 金属化合物が周期律第ａ族金属の水酸化物
もしくは塩である特許請求の範囲第１〜４項のい
ずれかに記載の積層包装材。 ６ 金属化合物が水酸化ナトリウムである特許請
求の範囲第１〜５項のいずれかに記載の積層包装
材。 ７ 接着性樹脂層の厚さが１〜20μである特許請
求の範囲第１〜６項のいずれかに記載の積層包装
材。 ８ 表面層の少なくとも一方が直鎖状低密度ポリ
エチレンである特許請求の範囲第１〜７項のいず
れかに記載の積層包装材。 ９ 表面層の少なくとも一方が炭素数４以上のα
−オレフインを共重合成分とし、示差走査型熱量
計の熱分析に基づく融解熱が25cal／ｇ以下であ
る直鎖状低密度ポリエチレンである特許請求の範
囲第８項に記載の積層包装材。 １０ 直鎖状低密度ポリエチレンがブテン−１を
共重合成分とし、示差走査型熱量計の熱分析に基
づく融解熱が25cal／ｇ以下である直鎖状低密度
ポリエチレンである特許請求の範囲第８項に記載
の積層包装材。 １１ 直鎖状低密度ポリエチレンが４−メチルペ
ンテンを共重合成分とし、示差走査型熱量計の熱
分析に基づく融解熱が25cal／ｇ以下である直鎖
状低密度ポリエチレンである特許請求の範囲第８
項に記載の積層包装材。 １２ 直鎖状低密度ポリエチレンが20℃における
ヤング率が12Kg／mm2以下である特許請求の範囲第
８〜１１項のいずれかに記載の積層包装材。 １３ 表面層の一方が熱シール可能な熱可塑性樹
脂である特許請求の範囲第１〜１２項のいずれか
に記載の積層包装材。 １４ 熱シール可能な熱可塑性樹脂が酢酸ビニル
成分を７重量％以上含有するエチレン−酢酸ビニ
ル共重合体である特許請求の範囲第１３項に記載
の積層包装材。 １５ 積層包装材が包装充填物が水性混合物また
は含水物である包装容器の構成材であることを特
徴とする特許請求の範囲第１４項に記載の積層包
装材。 １６ 該包装材がバツグインボツクス内容器の構
成材である特許請求の範囲第１５項に記載の積層
包装材。[Scope of Claims] 1. A thin film having gas barrier properties is used as an intermediate layer, and surface layers are provided on both sides of the intermediate layer, and at least one of the surface layers is made of a heat-sealable thermoplastic resin,
In a laminated packaging material in which each layer is arranged with an adhesive resin layer in between, the intermediate layer is (A) ethylene-acetic acid containing 20 to 55 mol% of ethylene component and at least 90% of the vinyl acetate component being saponified. Vinyl copolymer and (B)
An ethylene-acrylic ester or vinyl acetate copolymer grafted with an ethylenically unsaturated carboxylic acid or carboxylic acid anhydride is added with a periodic formula of 0.02 to 0.3 equivalent to the ethylenically unsaturated carboxylic acid or carboxylic acid anhydride component. Blending a metal compound consisting of a hydroxide or salt of group a or a group metal, or blending the metal compound with (C) ethylene-acrylic acid ester or vinyl acetate copolymer, and (A), ( A laminated packaging material with excellent bending fatigue resistance and gas barrier properties, characterized by being a mixture in which the blending amounts of B) and (C) satisfy the following formulas () and () on a weight basis. 0.40≧(B)+(C)/(A)+(B)+(C)≧0.05 () 1.0≧(B)/(B)+(C)≧0.01 () 2 Acrylic ester is ethyl acrylate The laminated packaging material according to claim 1, which is an ester. 3. The laminated packaging material according to claim 1, wherein the ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride is maleic anhydride. 4. The laminated packaging material according to claim 1, wherein the acrylic acid ester is acrylic acid ethyl ester, and the ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride is maleic anhydride. 5. The laminated packaging material according to any one of claims 1 to 4, wherein the metal compound is a hydroxide or salt of a metal of group a of the periodic table. 6. The laminated packaging material according to any one of claims 1 to 5, wherein the metal compound is sodium hydroxide. 7. The laminated packaging material according to any one of claims 1 to 6, wherein the adhesive resin layer has a thickness of 1 to 20 μm. 8. The laminated packaging material according to any one of claims 1 to 7, wherein at least one of the surface layers is made of linear low-density polyethylene. 9 α in which at least one of the surface layers has 4 or more carbon atoms
- The laminated packaging material according to claim 8, which is linear low-density polyethylene containing olefin as a copolymer component and having a heat of fusion of 25 cal/g or less based on thermal analysis using a differential scanning calorimeter. 10 Claim 8, wherein the linear low-density polyethylene is linear low-density polyethylene that contains butene-1 as a copolymerization component and has a heat of fusion of 25 cal/g or less based on thermal analysis with a differential scanning calorimeter. The laminated packaging material described in Section. 11 Claim No. 1, wherein the linear low-density polyethylene is a linear low-density polyethylene that contains 4-methylpentene as a copolymer component and has a heat of fusion of 25 cal/g or less based on thermal analysis using a differential scanning calorimeter. 8
The laminated packaging material described in Section. 12. The laminated packaging material according to any one of claims 8 to 11, wherein the linear low-density polyethylene has a Young's modulus of 12 Kg/mm 2 or less at 20°C. 13. The laminated packaging material according to any one of claims 1 to 12, wherein one of the surface layers is a heat-sealable thermoplastic resin. 14. The laminated packaging material according to claim 13, wherein the heat-sealable thermoplastic resin is an ethylene-vinyl acetate copolymer containing 7% by weight or more of a vinyl acetate component. 15. The laminated packaging material according to claim 14, wherein the laminated packaging material is a constituent material of a packaging container in which the packaging filler is an aqueous mixture or a water-containing substance. 16. The laminated packaging material according to claim 15, wherein the packaging material is a component of a bag-in-box inner container.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29793885A JPS62152847A (en) | 1985-12-27 | 1985-12-27 | Laminated packaging material having excellent resistance to fatigue from flexing and gas barriering property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29793885A JPS62152847A (en) | 1985-12-27 | 1985-12-27 | Laminated packaging material having excellent resistance to fatigue from flexing and gas barriering property |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62152847A JPS62152847A (en) | 1987-07-07 |
| JPH0523184B2 true JPH0523184B2 (en) | 1993-03-31 |
Family
ID=17853035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29793885A Granted JPS62152847A (en) | 1985-12-27 | 1985-12-27 | Laminated packaging material having excellent resistance to fatigue from flexing and gas barriering property |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62152847A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3268813B2 (en) * | 1992-03-13 | 2002-03-25 | 日本合成化学工業株式会社 | Resin composition and method for producing the same |
| JP7070414B2 (en) | 2017-06-27 | 2022-05-18 | 三菱ケミカル株式会社 | Ethylene-vinyl alcohol-based copolymer composition, ethylene-vinyl alcohol-based copolymer composition for melt molding, pellets and multilayer structures |
| CN111032775B (en) | 2017-10-27 | 2022-08-19 | 三菱化学株式会社 | Ethylene-vinyl alcohol copolymer resin composition, multilayer structure, and package |
| WO2019103079A1 (en) | 2017-11-22 | 2019-05-31 | 日本合成化学工業株式会社 | Ethylene-vinyl alcohol copolymer composition, multilayer structure and package |
| EP3904091B1 (en) | 2018-12-26 | 2024-05-22 | Mitsubishi Chemical Corporation | Ethylene-vinyl alcohol copolymer resin composition, multilayer structure and package |
-
1985
- 1985-12-27 JP JP29793885A patent/JPS62152847A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62152847A (en) | 1987-07-07 |
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