JPH0523185B2 - - Google Patents
Info
- Publication number
- JPH0523185B2 JPH0523185B2 JP29794085A JP29794085A JPH0523185B2 JP H0523185 B2 JPH0523185 B2 JP H0523185B2 JP 29794085 A JP29794085 A JP 29794085A JP 29794085 A JP29794085 A JP 29794085A JP H0523185 B2 JPH0523185 B2 JP H0523185B2
- Authority
- JP
- Japan
- Prior art keywords
- packaging material
- laminated packaging
- material according
- component
- carboxylic acid
- 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 - Fee Related
Links
- 239000010410 layer Substances 0.000 claims description 84
- 238000005452 bending Methods 0.000 claims description 51
- 239000005022 packaging material Substances 0.000 claims description 42
- 230000004888 barrier function Effects 0.000 claims description 38
- -1 polyethylene Polymers 0.000 claims description 34
- 239000004698 Polyethylene Substances 0.000 claims description 29
- 229920000573 polyethylene Polymers 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 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 25
- 229920000642 polymer Polymers 0.000 claims description 24
- 239000002344 surface layer Substances 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000005977 Ethylene Substances 0.000 claims description 16
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 15
- 150000002736 metal compounds Chemical class 0.000 claims description 15
- 230000004927 fusion Effects 0.000 claims description 13
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 11
- 229920005992 thermoplastic resin Polymers 0.000 claims description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 10
- 239000004840 adhesive resin Substances 0.000 claims description 9
- 229920006223 adhesive resin Polymers 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 8
- 150000003839 salts Chemical class 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 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002076 thermal analysis method Methods 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 239000000126 substance Substances 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
- 239000000470 constituent Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 30
- 239000011347 resin Substances 0.000 description 30
- 239000010408 film Substances 0.000 description 28
- 239000007789 gas Substances 0.000 description 25
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 23
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 22
- 230000000694 effects Effects 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
- 238000009661 fatigue test Methods 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 10
- 238000007127 saponification reaction Methods 0.000 description 7
- 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
- 238000004519 manufacturing process Methods 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
- 230000000052 comparative effect Effects 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 description 4
- 150000004692 metal hydroxides Chemical class 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 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
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 239000003054 catalyst Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000021056 liquid food Nutrition 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920006284 nylon film Polymers 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 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 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 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
- 229910001882 dioxygen Inorganic materials 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
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002648 laminated material Substances 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
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003348 petrochemical agent 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
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ZWVMLYRJXORSEP-LURJTMIESA-N (2s)-hexane-1,2,6-triol Chemical compound OCCCC[C@H](O)CO ZWVMLYRJXORSEP-LURJTMIESA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- 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
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-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
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-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
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XHALKWMTKWHQLO-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxyphenyl)sulfanylphenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(SC=2C=C(C(O)=CC=2)C(C)(C)C)=C1 XHALKWMTKWHQLO-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
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 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
- 238000000071 blow moulding Methods 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
- 229910052799 carbon 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
- 230000002925 chemical effect 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
- 150000001993 dienes Chemical class 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
- 229920006244 ethylene-ethyl 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
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 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
- 238000007689 inspection Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination 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
- 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012778 molding material 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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pentâ4âenâ2âone Natural products CC(=O)CC=C PNJWIWWMYCMZRO-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
- 229920013716 polyethylene resin Polymers 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
- 239000002994 raw material Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000004576 sand Substances 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
- 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 tertâbutyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
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æã«é¢ãããDETAILED 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.
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èå±€ãç©å±€ããæ¹æ³ãæ¡çšããããB. 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 an inner container 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 oxygen and other gases are unsatisfactory, a barrier layer with even higher gas barrier properties may be provided on the base film.
A method is adopted 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.
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ã¯ãéèŠèª²é¡ã®äžã€ã§ãã€ãã 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, Even at the stage where no cracks or pinholes are created in the component,
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.
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ãŠããªãã Furthermore, JP-A-50-86579 describes a package 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.
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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.
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æ€èšãé²ããŠæ¬çºæãå®æããã«è³ã€ããC. Problems to be Solved by the Invention Although EVOH film has the above-mentioned excellent properties, it has a major drawback in that it is significantly inferior in bending fatigue resistance compared to films made of thermoplastic resins such as polyethylene, polypropylene, nylon, and thermoplastic polyester. In a multi-layer flexible packaging material that is laminated with the bending fatigue resistant resin layer and uses an EVOH resin layer as an intermediate layer, the bending fatigue resistance of the packaging material is determined by the bending fatigue resistant thermoplastic layer. The bending fatigue resistance is significantly lower than that exhibited by the resin alone, and pinholes occur in laminated packaging materials with less bending fatigue. 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 sacrificing its excellent gas barrier properties, and improved the bending fatigue resistance and gas barrier properties. In order to develop an excellent flexible laminated packaging material, we have carried out extensive studies and have completed the present invention.
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æäŸãããã®ã§ãããD 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) a polyethylene polymer with a density of 0.91 to 0.86 g/cm 3 are grafted with an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride to form an ethylenic 0.02 to 0.3 equivalent of periodic law a or a to the unsaturated carboxylic acid or the carboxylic acid anhydride component
A metal compound consisting of a group metal hydroxide or salt is blended, or the metal compound and (C) have a density of
The mixture must contain 0.91 to 0.86 g/cm 3 of polyethylene polymer, and the amounts of (A), (B), and (C) satisfy the following formulas () and () on a weight basis. The present invention provides a laminated packaging material with excellent bending fatigue resistance.
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ç©ã®å€è³ªãé²æ¢ããããšãã§ããã0.40â§(B)+(C)/(A)+(B)+(C)â§0.05 () 1.0â§(B)/(B)+(C)â§0.01 () E Effects of the invention Various materials The superiority or inferiority of the bending fatigue resistance of laminated materials made of various materials can be determined by determining the dependence of the decrease in gas barrier properties on the number of bends in an evaluation test conducted using a so-called GELBO flex tester, the number of times of bending before pinholes occur, 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 susceptible to deterioration is packaged with the packaging material of the present invention and then transported, no pinholes will occur, so deterioration of the quality of the packaged item can be prevented.
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ã«ãªã€ãã®ã§ã¯ãªãããšæšå®ãããã In the present invention, (B) an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride is grafted onto a polyethylene polymer having a density of 0.91 to 0.86 g/cm 3 , and the ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride component is Periodic table a of 0.02 to 0.3 equivalent to
Alternatively, a metal compound consisting of a hydroxide or salt of a group A metal is blended, or a mixture of the metal compound and (C) a polyethylene polymer having a density of 0.91 to 0.86 g/cm 3 is (A). Ethylene component content 20
Although the mechanism by which the flex fatigue resistance and moldability of saponified ethylene-vinyl acetate copolymer resins with ~55 mol% and saponification degree of 90% or more are so markedly improved is not fully clear, the (A) ethylene component A saponified ethylene-vinyl acetate copolymer resin with a content of 20 to 55 mol% and a degree of saponification of 90% or more and (B) with a density of 0.91 to
A resin obtained by grafting an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride onto a polyethylene polymer of 0.86 g/cm 3 or (C) with a density of 0.91 to 0.86 g/cm 3
A mixture of a polyethylene polymer and a grafted polyethylene polymer is mixed with a metal compound consisting of a metal hydroxide or salt in an amount of 0.02 to 0.3 equivalent to the grafted ethylenically unsaturated carboxylic acid or carboxylic acid anhydride component. As a result, rheological effects in the molten system, chemical effects of impurities, etc. combine in a complex manner, improving formability,
It is presumed that the morphological properties of the resulting laminate intermediate layer were in a state favorable for exhibiting bending fatigue resistance.
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æãªããªãç¯å²ã®ç©ã§ããã°äœ¿çšã§ãããF. 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 will be lowered 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. This EVOH
The melt index (MI) measured by ASTM D-1238 at 190°C is between 0.1 and 25 g/10 minutes, preferably between 0.3 and 20 g/10 minutes. Furthermore, third components such as EVOH treated with boron compounds such as boric acid and sand, 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.
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DFDAâ1138NTãªã©ãããã The most important feature of the present invention is that a polyethylene polymer having a density of 0.91 to 0.86 g/cm 3 is used as the base for the resin component (B). If the density exceeds 0.91 g/cm 3 , the bending fatigue resistance, which is an effect of the present invention, will not be sufficient. A polyethylene polymer having a density of less than 0.86 g/cm 3 is not suitable because it does not pass through the manufacturing process sufficiently and cannot be stably supplied industrially. In order to more suitably enjoy the effects of the present invention, it is preferable to use a polyethylene polymer having a density of 0.905 to 0.87 g/cm 3 as the base. The reason for this is not necessarily clear, but it may be related to the crystallinity of the resin used as the base for component (B), but the density of the part where crystallinity is not controlled is 0.92g/ A copolymer with a density of 0.93 to 0.97 g/cm 3 is obtained by using a polyethylene polymer with a density of 0.93 to 0.97 g/cm 3 or by controlling the crystallinity by copolymerizing vinyl acetate, ethyl acrylate, etc. with ethylene. In such a case, the effects of the present invention cannot be enjoyed, and it is truly surprising that it is difficult to arrive at the present invention by analogy with the prior art. Although there are no restrictions on the method for producing such a polyethylene polymer, for example, there is a method in which ethylene and α-olefin are copolymerized at a polymerization temperature of 10 to 80° C. using a Ziegler type catalyst. As the α-olefin, those having 3 to 8 carbon atoms are used, such as propylene, butene-1, hexane-1, 4-methylpentene-1, octene-1, etc.
There is a first prize. Furthermore, various dienes such as butadiene, 1,4-hexadiene, 1,5-hexadiene, vinylnorbornene, ethylidene norbornene, and dicyclopentadiene can be added as a third monomer for copolymerization. In addition, commercially available products include, for example, Tafmer A-4085, which is marketed by Mitsui Petrochemicals, and Tafmer A
-4090, Tafmar P-0180, Tafmer P-0480 and other flexible resins DFDA-1137NT7, which are marketed by Nippon Unicar Co., Ltd.
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Examples include ethylenically unsaturated carboxylic acids and carboxylic acid anhydrides such as itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride, among which maleic anhydride is preferred. When maleic anhydride is used, it can be co-grafted simultaneously with comonomers such as ethylene, styrene, vinyl acetate, vinyl ether, etc. The amount of grafting may be 0.001 to 6% by weight, but 0.01 to 5% by weight improves bending fatigue resistance,
It is more suitable in terms of impact resistance, uniform mixability, and moldability.
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ã®ã§ãã奜é©ã§ããã There are no particular limitations on the method of graft polymerization, but it is possible to add an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride to the ethylene-acrylic ester copolymer, 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 because a uniform product can be obtained.
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ã奜ãŸãããªãã 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, sodium acetate, sodium hydroxide, calcium hydroxide, magnesium hydroxide, potassium hydroxide, etc. Among them, metal compounds of group a of the periodic table, such as sodium carbonate, sodium acetate, potassium hydroxide, and sodium hydroxide, are preferably used. 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 polyethylene polymer grafted with ethylenically unsaturated carboxylic acid or carboxylic acid anhydride and has a density of 0.91 to 0.86 g/cm 3 will be affected by periodic rule a or a.
Modified copolymers blended with metal compounds consisting of group metal hydroxides or salts are undesirable because they become colored or have poor fluidity, making them unsuitable as molding materials.
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ãããããã¯æ··åç©ã§ãã€ãŠãããã 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. If the value of formula () is less than 0.01, the effect of improving bending fatigue resistance is not 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 formula (), but in terms of manufacturing cost, etc.
The value of the formula is often used between 0.01 and 0.4. At this time, the density used for the raw material for component (B) is 0.91~
The polyethylene polymer with a density of 0.86 g/cm 3 and the polyethylene polymer with a density of 0.91 to 0.86 g/cm 3 used for component (C) may be the same, but even if they are different types, Alternatively, it may be a mixture.
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ãšèšãé¢ã§ç¹ã«éèŠã§ããã 1.0â§(B)/(B)+(C)â§0.01 () The density of (B) constituting the intermediate layer of the present invention is 0.91 to 0.86
g/cm 3 of an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride to a polyethylene polymer, and grafting 0.02 to 0.3 equivalents of periodic law a to the ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride component. Or a modified copolymer blended with a metal compound consisting of a hydroxide or salt of a Group A metal, or a mixture of (C) a polyethylene polymer with a density of 0.91 to 0.86 g/cm 3 and the modified copolymer (B). The blending amount of each component of the composition and (A) EVOH with an ethylene content of 20 to 55 mol% and a saponification degree of 90% or more must satisfy the following formula () on a weight basis for bending fatigue resistance and gas barrier properties. This is particularly important in terms of impact resistance and balance with mechanical properties.
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ãŸãããªãã 0.40â§(B)+(C)/(A)+(B)+(C)â§0.05 () If the value of the formula () is less than 0.05, no improvement is seen in the bending fatigue resistance, which is not preferable. Moreover, when it exceeds 0.40, various physical properties such as gas barrier properties are deteriorated, which is not preferable.
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ãã©ã¹ããã€ãçã There are no particular restrictions on the blending method used in the present invention to obtain the mixed composition of component (A) and components (B) and (C). A method may be arbitrarily selected in which the components () are premixed into pellets and blended into a portion of the component (A) in advance. (A) used in the present invention,
Other additives commonly used in other thermoplastic resins can be added to the mixed compositions of (B), (B)+(C), and (A)+(B)+(C). Examples of such additives include antioxidants, ultraviolet absorbers, plasticizers, antistatic agents, lubricants, and fillers, and these may be blended within a range that does not impede the effects of the present invention. be able to. 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-tert-butylphenol, tetrakis-[methylene-3-(3',5'-di-
t-Butyl-4'-hydroxyphenyl)propionate]methane, octadecyl-3-(3',5-
di-t-butyl-4'-hydroxyphenyl) propionate, 4,4'-thiobis-(6-t-butylphenol), and the like. Ultraviolet 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. Plasticizers: 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, titanium oxide, red iron oxide, etc. Filler: glass fiber, asbestos, mica,
Ballast night etc.
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æ©çãäŸç€ºãããã 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.
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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.
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ãçšããããã 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 to 45Kg/cm 2
pressure (usually for high-pressure low-density polyethylene)
2000 to 3000 Kg/cm 2 ), at a temperature of 75 to 100°C (120 to 250°C in the case of high-pressure low density polyethylene), using a chromium-based catalyst or Ziegler catalyst, with a carbon number of 3 or more, preferably 4 or more, More preferably 5
~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.
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ãã 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 22~3Kg/
mm 2 , more preferably 22 to 5 Kg/mm 2 , the effect of the present invention is more remarkable, especially when both are in the above range. Those whose heat of fusion and Young's modulus are in the above-mentioned range vary somewhat depending on the polymerization method and polymerization conditions, but in other words, the content of the α-olefin, which is a copolymer component, is about 2 mol% or more, Preferably about 2-7 mol%
It is often obtained in the area of For linear low density polyethylene whose copolymerization component is butene-1, the heat of fusion is 15 cal/g or less, or 20°C
The effect of the present invention is more remarkable when the Young's modulus is 12 Kg/mm 2 or less, and especially when both 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 often obtained in a range where the butene-1 content is about 4 mol % or more. If the content is too large, other physical properties of the polyethylene become unsatisfactory, which is not preferable, and the content is preferably several mol% at most, for example 7 mol%. Further, as described above, the effects of the present invention can be enjoyed with linear low-density polyethylene whose heat of fusion and/or Young's modulus are in the specific range, but especially with α-olefins having 5 or more carbon atoms, for example, 5 to 10 carbon atoms. This effect can be enjoyed more markedly with the polyethylene containing as a copolymerization component. 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. etc., but especially the heat of fusion is
It 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 , and more preferably 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.
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ãããããã 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 heat-sealable resin can also be used for the 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.
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ã10gïŒ10minã§ããã 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.
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±éåäœãªã©ãæå³ããã 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 gelation during the bending fatigue resistance test using the Gelbo Flex Tester. When delamination occurs, no improvement in the bending fatigue resistance of the intermediate layer is observed, and the decrease in barrier properties due to damage to the intermediate layer causes pinholes to appear 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 include polyethylene (low pressure, medium pressure, high pressure), linear low density polyethylene,
Polyolefins such as polypropylene and polybutene, copolymers of olefins and comonomers (vinyl esters, unsaturated carboxylic acid esters, etc.) that can be copolymerized with the olefins, such as ethylene-vinyl acetate copolymers, ethylene-ethyl acrylate copolymers It means merging.
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ã10ÎŒã§ããããšã奜ãŸããã 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, 10ÎŒ or less, other physical properties such as strength will deteriorate, so The thickness is preferably 20ÎŒ or more, and more preferably 20ÎŒ 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 ÎŒm.
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 ÎŒm.
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 Όm, 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 40Ό or less, more preferably 35Ό or less. The thickness of each adhesive resin layer is 2
It is preferably ~10Ό.
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ãšãã§ããã 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 a blow molding method using adhesion.
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ããããèªç±ã§ããã 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.
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å質å£åãé²ãããšãã§ããã 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.
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éšããã³è©äŸ¡æ¹æ³ã¯æ¬¡ã®éãã§ããã 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.
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æš¹èã®æµéã瀺ãã枬å®æž©åºŠã¯190âã§ãããMelt Index (MI) In accordance with ASTM D-1238, this shows the resin flow rate for 10 minutes when a load of 2160 g is applied using a melt indexer. The measurement temperature is 190â.
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ã®æ¡ä»¶äžã«è¡ãªããã®ã§ãããBending 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%.
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ã®æ¡ä»¶äžã«è¡ãªã€ããYoung's modulus 20â, relative humidity according to ASTM D-882-67
It was carried out under 65% conditions.
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2.0gïŒ10åã§ãã€ããG Examples Example 1 Tafmer A-4085 (density 0.88 g/cm 3 , MI (190
â, 2160g) is 3.6g/10 minutes of polyethylene resin,
(manufactured by Mitsui Petrochemical Co., Ltd.) and 1.8 parts by weight of maleic anhydride were dissolved in 648 parts by weight of purified toluene and kept at 180°C. A purified toluene solution containing 25 parts by weight of maleic anhydride dissolved in this solution under stirring.
180 parts by weight were added continuously over 2.0 hours. At the same time, 100 parts by weight of a purified toluene solution containing 4.0 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 acetone to precipitate a polymer. The obtained polymer was purified by reprecipitation using purified toluene as a solvent and acetone as a non-solvent. This product contains 1.5% by weight of maleic anhydride component, and the MI is
It was 2.0g/10 minutes.
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ãã 20 g of an aqueous solution containing a predetermined amount of sodium hydroxide (NaOH) was added uniformly to 100 parts by weight of the polymer thus obtained, and after partially drying, it was melted using a vented extruder while expelling volatiles under reduced pressure. The mixture was kneaded and pelletized to obtain a modified copolymer (B).
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ã¿ãããŒïŒ¡â4085(C)ãšãã©ã€ãã¬ã³ããã次ãã§
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ãçµæç©(B)ïŒ(C)ãåŸãã 20 parts by weight of the modified copolymer (B) obtained above was dry blended with the above Tafmer A-4085 (C), and then melt-kneaded into pellets using an extruder to form a resin blend composition (B) + (C). I got it.
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ã€ã«ã ãå¥ã«åŸãŠã€ã³ã°çã枬å®ããçµæã13
KgïŒmm2ã§ãã€ãã On the other hand, the ethylene content was 31 mol%, and the degree of saponification was
99.5%, MI 1.4g/10min EVOH as component (A),
An intermediate layer with a thickness of 20Ό consisting of a mixed composition of 80 parts by weight of component (A) and 20 parts by weight of (B) + (C) obtained above, and 4 layers each having a thickness of 35Ό on both sides of the intermediate layer. -Methyl-1-pentene as a copolymer component, containing 3.2 mol% of the copolymer component, and having a surface layer made of linear low-density polyethylene (LLDPE) with an MI of 2.1 g/10 minutes, with a thickness between each layer. Three extruders, three extruders, It was obtained by a coextrusion method using a multilayer die head for five layers. 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 and the amount of oxygen gas permeated at each stage up to the generation of pinholes in the laminated film was measured. During the bending fatigue test process up to the occurrence of pinholes, there was almost no change in the amount of oxygen permeation. Further, the occurrence of pinholes was not observed until 7,500 cycles had passed in the bending fatigue test, and after 7,600 cycles, when the test piece was inspected for the presence of pinholes, it was found that one pinhole had already occurred. Furthermore, no delamination between the layers was observed. In addition, as a result of separately obtaining the LLDPE film and measuring the Young's modulus, it was found that it was 13
It was Kg/ mm2 .
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NaOHæ·»å éã0.05åœéãšãã以å€ã¯å®æœäŸïŒãš
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æ¢ã«çºçããŠããã®ãèªãããExample 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.
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ãå·¥æ¥çãªäŸ¡å€ã¯äœããã®ã§ãã€ããComparative 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 location where no lumpy irregularities were observed, no pinholes were observed until 6,500 reciprocations, and one pinhole appeared after 6,600 reciprocations. However, in the sample with bump-like unevenness, one pinhole had already occurred after 200 reciprocations. Only 20% of the samples had no lumpy irregularities and were of low industrial value.
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NaOHã0.6çéæ·»å ãã以å€ã¯å®æœäŸïŒãšå
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ãèŠããå·¥æ¥çãªäŸ¡å€ã¯äœããã®ã§ãã€ããComparative 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.
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ã«ïŒã±ãæ¢ã«çºçããŠããã®ãèªãããExample 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 7000
It was not noticed until after 7,200 reciprocations had passed, and when the pinhole was inspected, it was found that one pinhole had already occurred.
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D/Ad/E/Ad/F/Ad/Gãªãæ§æã®ç©å±€ãã€ã«
ã ãïŒçš®ïŒå±€çšå€å±€ãã€ããããæããå
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æš¹èããã³å±€åããããªããExample 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.
ïŒïŒŠïŒã¿ãããŒïŒ¡â4085ã«ãããŠãã¬ãã¯ã¹
ã¬ãžã³DFDAâ1138NTïŒå¯åºŠ0.90g/cm3ãMIïŒ190
âã2160gïŒã0.4gïŒ10åãæ¥æ¬ãŠãã«ãŒç€Ÿè£œïŒ
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žã«ãªãŠã ïŒK2CO3ïŒã0.11åœéçšãã以å€ã¯
å®æœäŸïŒã®æ¹æ³ãšåæ§ã«ããŠå€æ§å
±éåäœ(B)ãåŸ
ãã E, F: Flex resin DFDA-1138NT (density 0.90g/cm 3 , MI (190
â, 2160g) is 0.4g/10 minutes, manufactured by Nippon Unicar)
A modified copolymer ( B) was obtained.
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ã ãå¥ã«åŸãŠã€ã³ã°çã枬å®ããçµæã7.5Kg/mm2
ã§ãã€ãã Tafmer P-0180 (density 0.88 g/cm 3 , MI4.5, manufactured by Mitsui Petrochemicals) was used as the (C) component resin. A layer with a thickness of 12ÎŒ consisting of a blend composition of A:B:C=90:5:5 using EVOH with an ethylene content of 38 mol% and a saponification degree of 99.4% as component (A) D, G: 4-methyl-1 - 40 ÎŒ thick LLDPE layer containing 4.1 mol% of pentene as copolymerization component, melt index 2.3 g/10 min, heat of fusion 15 cal/g by DSC Ad: 33 wt% vinyl acetate content, maleic anhydride modification The adhesive resin layer was made of a modified ethylene-vinyl acetate copolymer having a concentration of 0.2% by weight, and the layer thickness was 6 ÎŒm. A bending fatigue test was conducted in accordance with Example 1. No pinholes were observed even after 6,000 cycles of the bending fatigue test, and after 6,300 reciprocations, an inspection for the presence of pinholes revealed that one pinhole had already occurred. Furthermore, no delamination between the layers was observed. In addition, as a result of separately obtaining the LLDPE film and measuring the Young's modulus, it was 7.5Kg/mm 2
It was hot.
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ããå·¥æ¥çãªäŸ¡å€ã¯äœããã®ã§ãã€ããComparative Example 3 A laminated film was obtained in the same manner as in Example 4 except that 0.005 equivalent of potassium carbonate was added. Bumpy unevenness was observed in the obtained laminated film. A bending fatigue test was conducted on the laminated film.
5500 samples were selected where no lumpy irregularities were observed.
No pinholes were observed until the round trip, and one pinhole appeared after 5,700 round trips. However, in the sample with bump-like unevenness, pinholes were already generated after 300 reciprocations. Only 25% of the samples had no lumpy irregularities and were of low industrial value.
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žã«ãªãŠã ã1.0çéæ·»å ãã以å€ã¯å®æœäŸ
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åæ§ãæªãç©å±€ãã€ã«ã ã¯åŸãããªãã€ããComparative Example 4 The same procedure as Example 4 was carried out except that 1.0 equivalent of potassium carbonate was added. This modified copolymer had extremely poor fluidity and no laminated film could be obtained.
Claims (1)
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å è£ æã[Claims] 1. A thin film having gas barrier properties is used as an intermediate layer, a surface layer is provided on both sides of the intermediate layer, at least one of the surface layers is made of a heat-sealable thermoplastic resin layer, and each layer is made of a heat-sealable thermoplastic resin layer. In a laminated packaging material arranged through an adhesive resin layer, the intermediate layer has (A) an ethylene content
Ethylene-vinyl acetate copolymer in which 20 to 55 mol% and 95% or more of the vinyl acetate component has been saponified and (B) a polyethylene polymer with a density of 0.91 to 0.86 g/ cm3 , ethylenically unsaturated carboxylic acid or The carboxylic acid anhydride is grafted to the ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride component to
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 is blended, or the metal compound and (C) have a density of 0.91 to 0.86 g/
cm 3 of polyethylene polymer, and (A), (B)
The blending amount of (C) and (C) is based on the following formula (),
A laminated packaging material with excellent bending fatigue resistance, characterized by being a mixture that satisfies formula (). 0.40â§(B)+(C)/(A)+(B)+(C)â§0.05 () 1.0â§(B)/(B)+(C)â§0.01 () 2 Ethylenically unsaturated carboxylic acid or The laminated packaging material according to claim 1, wherein the carboxylic acid anhydride is maleic anhydride. 3. The laminated packaging material according to claim 1 or 2, wherein the metal compound is a metal compound consisting of a hydroxide or salt of a Group A metal of the periodic table. 4. The laminated packaging material according to any one of claims 1 to 3, wherein the metal compound is sodium hydroxide. 5. The laminated packaging material according to any one of claims 1 to 4, wherein the adhesive resin layer has a thickness of 1 to 20 ÎŒm. 6. The laminated packaging material according to any one of claims 1 to 5, wherein at least one of the surface layers is made of linear low-density polyethylene. 7 α in which at least one of the surface layers has 4 or more carbon atoms
- The laminated packaging material according to claim 6, which is linear low-density polyethylene containing olefin as a copolymerization component and having a heat of fusion of 25 cal/g or less based on thermal analysis using a differential scanning calorimeter. 8. Claim 6, wherein the linear low-density polyethylene is linear low-density polyethylene that contains butene-1 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. The laminated packaging material described in Section. 9. Claim No. 9, wherein the linear low-density polyethylene is a linear low-density polyethylene that contains 4-methylpentene as a copolymerization component and has a heat of fusion of 25 cal/g or less based on thermal analysis using a differential scanning calorimeter. Laminated packaging material according to item 6. 10. The laminated packaging material according to any one of claims 6 to 9, wherein the linear low-density polyethylene has a Young's modulus of 12 Kg/cm 2 or less at 20°C. 11. The laminated packaging material according to any one of claims 1 to 10, wherein one of the surface layers is a heat-sealable thermoplastic resin. 12. The laminated packaging material according to claim 11, wherein the heat-sealable thermoplastic resin is an ethylene-vinyl acetate copolymer containing 7% by weight or more of a vinyl acetate component. 13. The laminated packaging material according to claim 12, 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. 14. The laminated packaging material according to claim 13, wherein the packaging material is a component of a bag-in-box inner container.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29794085A JPS62152848A (en) | 1985-12-27 | 1985-12-27 | Laminated packaging material having excellent resistance to fatigue from flexing |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP29794085A JPS62152848A (en) | 1985-12-27 | 1985-12-27 | Laminated packaging material having excellent resistance to fatigue from flexing |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62152848A JPS62152848A (en) | 1987-07-07 |
JPH0523185B2 true JPH0523185B2 (en) | 1993-03-31 |
Family
ID=17853061
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP29794085A Granted JPS62152848A (en) | 1985-12-27 | 1985-12-27 | Laminated packaging material having excellent resistance to fatigue from flexing |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62152848A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002338769A (en) * | 2001-05-15 | 2002-11-27 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and laminate |
MX2016012886A (en) * | 2014-04-01 | 2016-12-12 | Dow Global Technologies Llc | Multi-layer films and articles made therefrom. |
-
1985
- 1985-12-27 JP JP29794085A patent/JPS62152848A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS62152848A (en) | 1987-07-07 |
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