JPH06106687A - Internal container for bag-in-box - Google Patents
Internal container for bag-in-boxInfo
- Publication number
- JPH06106687A JPH06106687A JP4280514A JP28051492A JPH06106687A JP H06106687 A JPH06106687 A JP H06106687A JP 4280514 A JP4280514 A JP 4280514A JP 28051492 A JP28051492 A JP 28051492A JP H06106687 A JPH06106687 A JP H06106687A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- adhesive layer
- ethylene
- bag
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010410 layer Substances 0.000 claims abstract description 59
- 239000012790 adhesive layer Substances 0.000 claims abstract description 39
- 239000002344 surface layer Substances 0.000 claims abstract description 36
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 18
- 229920001400 block copolymer Polymers 0.000 claims abstract description 18
- 229920000570 polyether Polymers 0.000 claims abstract description 18
- 229920001971 elastomer Polymers 0.000 claims abstract description 16
- 239000000806 elastomer Substances 0.000 claims abstract description 16
- 238000007127 saponification reaction Methods 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011342 resin composition Substances 0.000 claims abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 239000005977 Ethylene Substances 0.000 claims description 20
- 229920000728 polyester Polymers 0.000 claims description 20
- 239000004711 α-olefin Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 33
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 33
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 29
- 239000007789 gas Substances 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 12
- -1 polypropylene Polymers 0.000 description 9
- 239000004677 Nylon Substances 0.000 description 8
- 229920000092 linear low density polyethylene Polymers 0.000 description 8
- 239000004707 linear low-density polyethylene Substances 0.000 description 8
- 229920001778 nylon Polymers 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 230000005856 abnormality Effects 0.000 description 5
- 125000005907 alkyl ester group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 5
- 238000004080 punching Methods 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-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
- PNVJTZOFSHSLTO-UHFFFAOYSA-N Fenthion Chemical compound COP(=S)(OC)OC1=CC=C(SC)C(C)=C1 PNVJTZOFSHSLTO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-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
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920006236 copolyester elastomer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 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
- 230000007547 defect Effects 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004649 discoloration prevention Methods 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000012545 processing Methods 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
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Packages (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、バッグインボックス用
内容器に関するもので、詳しくは、液体注入口の打ち抜
き加工性に優れ、ガスバリヤー性が長期間にわたって維
持されるバッグインボックス用内容器を提供するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inner container for a bag-in-box, and more particularly to an inner container for a bag-in-box which is excellent in punching workability of a liquid injection port and has a gas barrier property maintained for a long period of time. Is provided.
【０００２】[0002]
【従来の技術】一般に、エチレン−酢酸ビニル共重合体
ケン化物（以下、ＥＶＯＨと略記する）は、透明性、帯
電防止性、耐油性、耐溶剤性、ガスバリヤー性、保香性
などにすぐれているが、耐衝撃性、耐屈曲疲労性、延伸
性、熱成形性、吸湿又は吸水時のガスバリヤー性は低い
という欠点も有する材料である。このため、包装材料の
目的とする用途においては、ＥＶＯＨのフィルムの表裏
両面に低密度ポリエチレン、ポリプロピレン、ナイロ
ン、ポリエステルなどのフィルムを積層することによっ
てガスバリヤー性、香気保持性、食品の変色防止性など
のＥＶＯＨの特性を維持しながら、落下強度、熱成形
性、防湿性などのＥＶＯＨの欠点を補って各種包装用途
に利用されている。2. Description of the Related Art Generally, a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVOH) is excellent in transparency, antistatic property, oil resistance, solvent resistance, gas barrier property and aroma retention property. However, it is also a material having the drawback of low impact resistance, bending fatigue resistance, stretchability, thermoformability, gas barrier property during moisture absorption or water absorption. Therefore, in the intended use as a packaging material, by laminating films of low density polyethylene, polypropylene, nylon, polyester, etc. on both front and back sides of the EVOH film, gas barrier property, aroma retention property, and discoloration prevention property of foods. While maintaining the characteristics of EVOH such as the above, it is used for various packaging applications by compensating for the defects of EVOH such as drop strength, thermoformability, and moisture resistance.
【０００３】近年、ワインやジュース等の飲料用液体や
写真の現像液などの液体を輸送・保存するための包装用
容器としてバッグインボックスなるものが利用されるよ
うになってきた。このバッグインボックスなるものは、
ダンボール箱の内部に液体注入口を設けたフレキシブル
なプラスチックの包装容器を収納させたもので各種液体
の輸送手段として多用されており、そのバッグインボッ
クスの内容器として上記のＥＶＯＨ積層体も用いられる
に至っている。In recent years, a bag-in-box has come to be used as a packaging container for transporting and storing liquids for drinks such as wine and juice and liquids such as photographic developing solutions. This bag-in-box is
A cardboard box contains a flexible plastic packaging container provided with a liquid inlet, which is widely used as a means for transporting various liquids, and the EVOH laminate described above is also used as the inner container of the bag-in-box. Has reached.
【０００４】このときの該内容器の要求性能としては、
輸送時等における極めて激しい屈曲疲労に対しても優れ
たガスバリヤー性を保持することが重要であるので種々
の工夫が試みられており、直鎖状低密度ポリエチレン層
／接着剤層／ＥＶＯＨ層／接着剤／直鎖状低密度ポリエ
チレン（以下、ＬＬＤＰＥと略記する）層の積層体（特
開昭６０−１６１１４６号公報）、ＬＬＤＰＥ層／接着
剤層／ＥＶＯＨ層／接着剤層／エチレン−酢酸ビニル共
重合体樹脂層又は，二軸延伸ナイロン層又は，二軸延伸
ポリプロピレンの積層体（特開昭６０−１６８６４９号
公報）、表面層／カルボン酸変性ＬＬＤＰＥ／ＥＶＯＨ
層／カルボン酸変性ＬＬＤＰＥ／表面層の積層体（特開
昭６０−２４２０５４号公報）等が提案されている。The required performance of the inner container at this time is as follows.
Since it is important to maintain excellent gas barrier properties even during extremely severe bending fatigue during transportation, various devices have been tried, and linear low density polyethylene layer / adhesive layer / EVOH layer / Adhesive / linear low-density polyethylene (hereinafter abbreviated as LLDPE) layer laminate (JP-A-60-161146), LLDPE layer / adhesive layer / EVOH layer / adhesive layer / ethylene-vinyl acetate Copolymer resin layer, biaxially oriented nylon layer, or biaxially oriented polypropylene laminate (JP-A-60-168649), surface layer / carboxylic acid modified LLDPE / EVOH
A layer / carboxylic acid-modified LLDPE / surface layer laminate (JP-A-60-242054) has been proposed.
【０００５】[0005]
【発明が解決しようとする問題点】しかしながら、上記
の如きＥＶＯＨを中間層とする積層フイルムは、耐屈曲
疲労性は向上しているものの、長期間の保存や輸送に耐
えるだけの高度のガスバリヤー性は、未だ不充分であ
る。この原因は、該内容器を製造するに当たっては、該
内容器に液体注入口を作る必要があり、該積層フィルム
に打ち抜き穴をあけるのであるが、このときＥＶＯＨ層
に柔軟性が少ないのでＥＶＯＨ層にクラックが発生し
て、このクラックが輸送時等のストレスなどにより成長
することにあり、最終的にガスバリヤー性を損なう結果
となるのである。However, the laminated film having the EVOH as the intermediate layer as described above has improved flexural fatigue resistance, but has a high gas barrier that can withstand long-term storage and transportation. The sex is still insufficient. The reason for this is that in manufacturing the inner container, it is necessary to make a liquid injection port in the inner container, and a punching hole is formed in the laminated film. At this time, however, the EVOH layer is less flexible, and therefore the EVOH layer is less flexible. This is because cracks are generated in the cracks, and these cracks grow due to stress during transportation and the like, which eventually impairs the gas barrier property.
【０００６】[0006]
【問題点を解決するための手段】そこで、本発明者ら
は、上記の問題点を解決するために鋭意研究を重ねた結
果、エチレン含有量が２０〜５０モル％、酢酸ビニル成
分のケン化度が９０モル％以上のＥＶＯＨ１００重量部
に対し、結晶融点が１５０〜２３０℃でかつ反発弾性率
が５０％以上の熱可塑性のポリエステル・ポリエーテル
ブロック共重合体エラストマーを２〜１００重量部配合
してなる樹脂組成物（Ａ）を、中間層とし、該中間層の
両側に接着剤層を設け、更に該接着剤層の外側に表面層
を設けたバッグインボックス用内容器は、液体注入口の
製造時にクラックが発生することなく、長期間にわたる
輸送時等においても良好なガスバリヤー性を維持できる
ことを見いだし本発明を完成した。ただし、ここで規定
する結晶融点及び反発弾性率とは、それぞれ偏向顕微鏡
及びＪＩＳ Ｋ ６３０１により測定される値をいう。
以下に、本発明を詳細に説明する。[Means for Solving the Problems] Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that the ethylene content is 20 to 50 mol% and the vinyl acetate component is saponified. 2 to 100 parts by weight of thermoplastic polyester / polyether block copolymer elastomer having a crystal melting point of 150 to 230 ° C. and a rebound resilience of 50% or more with respect to 100 parts by weight of EVOH having a degree of 90 mol% or more. The resin composition (A) is used as an intermediate layer, an adhesive layer is provided on both sides of the intermediate layer, and a surface layer is provided outside the adhesive layer. The present invention has been completed by finding that good gas barrier properties can be maintained even during transportation for a long period of time without the occurrence of cracks during the production of the above. However, the crystal melting point and the impact resilience defined here refer to values measured by a deflection microscope and JIS K 6301, respectively.
The present invention will be described in detail below.
【０００７】本発明で用いるＥＶＯＨは、エチレン含有
量が２０〜５０モル％、好ましくは２５〜４８モル％、
酢酸ビニル成分のケン化度が９０モル％以上、好ましく
は９８モル％以上のものが通常使用される。エチレン含
有量が２０モル％未満では高湿時の酸素遮断性が低下
し、一方５０モル％を越えると酸素遮断性等の物性が劣
化する。又、ケン化度が９０モル％未満では酸素遮断性
や耐湿性が低下する。かかるＥＶＯＨの中でも極限粘度
（１５％の含水フエノール溶液として３０℃で測定）が
０．７〜１．５ｄｌ／ｇ、好ましくは０．８〜１．３ｄ
ｌ／ｇのものが成型物の機械的強度の面で好適に使用さ
れる。The EVOH used in the present invention has an ethylene content of 20 to 50 mol%, preferably 25 to 48 mol%,
A vinyl acetate component having a saponification degree of 90 mol% or more, preferably 98 mol% or more is usually used. When the ethylene content is less than 20 mol%, the oxygen barrier property at high humidity is lowered, while when it exceeds 50 mol%, the physical properties such as oxygen barrier property are deteriorated. If the saponification degree is less than 90 mol%, the oxygen barrier property and moisture resistance will be reduced. Among such EVOH, the intrinsic viscosity (measured as a 15% hydrous phenol solution at 30 ° C.) is 0.7 to 1.5 dl / g, preferably 0.8 to 1.3 d.
The thing of 1 / g is used suitably from the viewpoint of mechanical strength of the molded product.
【０００８】又、該ＥＶＯＨは、透明性、ガスバリヤー
性などの特性を損なわない範囲で少量のプロピレン、イ
ソブテン、α−オクテン、α−ドデセン、α−オクタデ
セン等のα−オレフィン、不飽和カルボン酸又はその
塩、部分アルキルエステル、完全アルキルエステル、ニ
トリル、アミド、無水物、不飽和スルホン酸又はその塩
などのコモノマーを含んでいても差支えない。The EVOH is a small amount of α-olefins such as propylene, isobutene, α-octene, α-dodecene and α-octadecene, and unsaturated carboxylic acid within a range that does not impair properties such as transparency and gas barrier property. Alternatively, it may include a comonomer such as a salt thereof, a partial alkyl ester, a complete alkyl ester, a nitrile, an amide, an anhydride, an unsaturated sulfonic acid or a salt thereof.
【０００９】本発明に用いられる新可塑性のポリエステ
ル・ポリエーテルブロック共重合体エラストマーとは芳
香族ジカルボン酸と脂肪族グリコールのポリエステルを
ハードセグメントとし、ポリ（アルキレンオキシド）グ
リコールをソフトセグメントとするポリエステル・ポリ
エーテル型のブロック共重合体で通常の共重合ポリエス
テルエラストマーの製造方法によって得られ、芳香族ジ
カルボン酸又はその低級アルキルエステルと脂肪族グリ
コールをエステル化してハードセグメントであるポリエ
ステルを作り、次に該ポリエステルとソフトセグメント
である、ポリ（アルキレンオキシド）グリコールとを重
縮合させて熱可塑性のポリエステル・ポリエーテルブロ
ック共重合体エラストマーとする方法で製造されるもの
である。The novel plastic polyester / polyether block copolymer elastomer used in the present invention is a polyester / polyester block copolymer having aromatic dicarboxylic acid and aliphatic glycol as a hard segment and poly (alkylene oxide) glycol as a soft segment. A polyether type block copolymer is obtained by a general method for producing a copolyester elastomer, and an aromatic dicarboxylic acid or a lower alkyl ester thereof and an aliphatic glycol are esterified to produce a polyester as a hard segment. It is produced by a method of polycondensing polyester and poly (alkylene oxide) glycol, which is a soft segment, into a thermoplastic polyester / polyether block copolymer elastomer.
【００１０】芳香族ジカルボン酸としては、主としてテ
レフタル酸及びその低級アルキルエステルが用いられ、
その他としてはイソフタル酸、フタル酸、２，５−ノル
ボナンジカルボン酸、１，４−ナフタル酸、１，５−ナ
フタル酸、４，４−オキシ安息香酸及びそれらの低級ア
ルキルエステル等が挙げられるが中でもジメチルフタレ
ートが原料の入手し易さ、ポリエステル化速度の速いこ
と、ポリエーテルに対する影響（酸分解しない）の面か
ら特に好ましい。また、アルキレングリコールとして
は、エチレングリコール、プロピレングリコール、１，
３−ブチレングリコール、１，４−ブタンジオール、
１，６−ヘキサンジオール等が挙げられる中でも１，４
−ブタンジオールが良好な弾性特性を示し特に好まし
い。As the aromatic dicarboxylic acid, terephthalic acid and its lower alkyl ester are mainly used,
Other examples include isophthalic acid, phthalic acid, 2,5-norbonanedicarboxylic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 4,4-oxybenzoic acid and lower alkyl esters thereof. Of these, dimethyl phthalate is particularly preferable from the viewpoints of easy availability of raw materials, high polyesterification rate, and influence on polyether (no acid decomposition). Further, as the alkylene glycol, ethylene glycol, propylene glycol, 1,
3-butylene glycol, 1,4-butanediol,
Among the 1,6-hexanediol and the like, 1,4
-Butanediol is particularly preferred as it exhibits good elastic properties.
【００１１】更に、ポリ（アルキレンオキシド）グリコ
ールとしては、ポリテトラメチレングリコール、ポリエ
チレングリコール、ポリプロピレングリコール等で分子
量１０００〜４０００の物が挙げられるが中でも分子量
１０００〜２０００のポリテトラメチレングリコールが
良好な弾性特性を示し特に好ましい。該共重合体エラス
トマーの製造反応工程としては、前述の主原料を用い、
まず第一のエステル化工程で原材料仕込、昇温、撹拌開
始、触媒添加、エステル化の順に行い、次にエステル化
物に酸化防止剤や触媒を添加し、それを重縮合缶へ移送
し、昇温・減圧下で重縮合を行うのである。Further, examples of the poly (alkylene oxide) glycol include polytetramethylene glycol, polyethylene glycol, polypropylene glycol and the like having a molecular weight of 1000 to 4000. Among them, polytetramethylene glycol having a molecular weight of 1000 to 2000 has good elasticity. It shows characteristics and is particularly preferable. In the production reaction step of the copolymer elastomer, the above main raw materials are used,
First, in the first esterification step, the raw material is charged, the temperature is raised, the stirring is started, the catalyst is added, and the esterification is carried out in this order.Next, an antioxidant and a catalyst are added to the esterified product, which is transferred to a polycondensation can and raised. Polycondensation is carried out under temperature and reduced pressure.
【００１２】本発明で用いる熱可塑性のポリエステル・
ポリエーテルブロック共重合体エラストマーは結晶融点
が１５０〜２３０℃かつ反発弾性が５０％以上の値を有
するものでなければならい。結晶融点が１５０℃未満の
ものはＥＶＯＨとの融点の差が大きすぎるため配合物の
溶融成形に際して適切な加工温度が存在せず、必然的に
両樹脂の相溶性が極端に悪くなって引張時に層状に剥離
するなど成形物としての性能を劣化させる。一方結晶融
点が２３０℃を越える場合にはＥＶＯＨの耐衝撃性を向
上する効果が認められない。又反発弾性率が５０％未満
の場合は耐衝撃性向上効果が認められないのみならず、
ＥＶＯＨ単独の場合よりかえって耐衝撃性を低下させる
ことも多い。該共重合体エラストマーの結晶融点をコン
トロールするにはポリエステル部分をポリ（アルキレン
オキシド）グリコール部分の共重合比を調整すればよ
く、又反発弾性はポリ（アルキレンオキシド）グリコー
ルの種類及び分子量を調整することによりコントロール
ができる。The thermoplastic polyester used in the present invention
The polyether block copolymer elastomer must have a crystal melting point of 150 to 230 ° C. and a impact resilience of 50% or more. If the melting point of the crystal is less than 150 ° C, the difference in melting point from EVOH is too large, so that there is no suitable processing temperature for melt molding of the compound, and the compatibility of both resins is inevitably extremely deteriorated during tensioning. It deteriorates the performance as a molded product such as peeling in layers. On the other hand, when the crystal melting point exceeds 230 ° C., the effect of improving the impact resistance of EVOH is not recognized. If the impact resilience is less than 50%, not only the impact resistance improving effect is not observed, but
In many cases, the impact resistance is rather lowered as compared with the case of EVOH alone. The crystal melting point of the copolymer elastomer can be controlled by adjusting the copolymerization ratio of the polyester part to the poly (alkylene oxide) glycol part, and the impact resilience is adjusted by the kind and molecular weight of the poly (alkylene oxide) glycol. You can control it.
【００１３】このようにして得られた熱可塑性のポリエ
ステル・ポリエーテルブロック共重合体エラストマーは
ＥＶＯＨに配合されるわけであるがＥＶＯＨに対する熱
可塑性のポリエステル・ポリエーテルブロック共重合体
エラストマーの配合割合は、それが極端に小なるときは
改質効果が充分に発揮できず、一方余りに大なるときに
は機械的諸性質が劣るので、ＥＶＯＨ１００重量部に対
し熱可塑性のポリエステル・ポリエーテルブロック共重
合体エラストマーが２〜１００重量部の範囲から選択さ
れる。配合方法としては、両樹脂を粉末／粉末、粉末／
ペレット又はクラム、ペレット／粉末、ペレット／ペレ
ット又はクラムの形で混合する方法が採用される。混合
物はそのまま成形に供され、或いは一旦混合ペレットを
作製した後成形に供される。The thermoplastic polyester / polyether block copolymer elastomer thus obtained is blended with EVOH. The blending ratio of the thermoplastic polyester / polyether block copolymer elastomer to EVOH is However, when it is extremely small, the modifying effect cannot be sufficiently exhibited, while when it is too large, mechanical properties are inferior. Therefore, a thermoplastic polyester / polyether block copolymer elastomer based on 100 parts by weight of EVOH is used. It is selected from the range of 2 to 100 parts by weight. As a compounding method, both resins are powder / powder, powder /
The method of mixing in the form of pellets or crumbs, pellets / powder, pellets / pellets or crumbs is adopted. The mixture is subjected to molding as it is, or it is subjected to molding after once preparing mixed pellets.
【００１４】また、本発明の中間層の樹脂成分として、
上記のＥＶＯＨ及びポリエステル−ポリエーテルブロッ
ク共重合体エラストマー以外に、可塑剤（多価アルコー
ルなど）、安定剤、界面活性剤、架橋性物質（エポキシ
化合物、多価金属塩、無機又は有機の多塩基酸又はその
塩など）、充填剤、着色剤、補強剤としての繊維（ガラ
ス繊維、炭素繊維など）等を適当量配合することができ
る。更に、他の熱可塑性樹脂を適当量配合することもで
き、かかる熱可塑性樹脂としてはポリオレフィン（低・
中・高密度ポリエチレン、アイソタクチックポリプロピ
レン、エチレン−プロピレン共重合体、エチレン−プロ
ピレン−ジエン共重合体、エチレンと炭素数４以上のα
−オレフィンとの共重合体、エチレン−酢酸ビニル共重
合体、エチレン−アクリル酸エステル共重合体、アイオ
ノマー、ポリブテン、ポリペンテンなど）又はこれらを
不飽和カルボン酸又はその誘導体でグラフト変性した変
性ポリオレフィン、ポリアミド、例えばナイロン６／６
６共重合体、ポリ塩化ビニル、ポリ塩化ビニリデン、ポ
リエステル、ポリスチレン、ポリアクリロニトリル、ポ
リアセタール、溶融成型可能なポリビニルアルコール系
樹脂などが挙げられる。Further, as the resin component of the intermediate layer of the present invention,
In addition to the above EVOH and polyester-polyether block copolymer elastomers, plasticizers (polyhydric alcohols, etc.), stabilizers, surfactants, crosslinkable substances (epoxy compounds, polyvalent metal salts, inorganic or organic polybases) An acid or a salt thereof), a filler, a colorant, a fiber (glass fiber, carbon fiber, etc.) as a reinforcing agent, and the like can be added in appropriate amounts. Furthermore, other thermoplastic resins can be blended in appropriate amounts, and such thermoplastic resins include polyolefin (low
Medium / high density polyethylene, isotactic polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene and α having 4 or more carbon atoms
-Copolymers with olefins, ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, ionomers, polybutene, polypentene, etc.) or modified polyolefins and polyamides obtained by graft-modifying these with unsaturated carboxylic acids or their derivatives. , For example, nylon 6/6
6-copolymer, polyvinyl chloride, polyvinylidene chloride, polyester, polystyrene, polyacrylonitrile, polyacetal, melt-moldable polyvinyl alcohol resin, and the like.
【００１５】本発明のバッグインボックス用内容器は、
少なくとも表面層／接着剤層／中間層（Ａ）／接着剤層
／表面層の５層積層体からなるもので、該表面層は、密
度０．８６〜０．９５ｇ／ｃｍ３（２０℃）のエチレン
−α−オレフィン共重合体が好ましい。ここで言う密度
とは、２０℃においてＪＩＳ Ｋ ６７６０によって測
定される値であり、密度が上記範囲より小さいときは、
積層体の機械的諸物性が不足したり、ブロッキングが発
生したりする。逆に、大きいときは、耐屈曲疲労性が不
十分となり好ましくない。また、エチレン−α−オレフ
ィンとは、エチレンとブテン−１，ペンテン−１，４−
メチルペンテン−１，ヘキセン−１，オクテン−１等の
炭素数１８以下の共重合物である。The inner container for bag-in-box of the present invention is
At least a surface layer / adhesive layer / intermediate layer (A) / adhesive layer / surface layer consisting of a five-layer laminate having a density of 0.86 to 0.95 g / cm 3 (20 ° C.). The ethylene-α-olefin copolymer of is preferred. The density referred to here is a value measured by JIS K 6760 at 20 ° C. When the density is smaller than the above range,
The mechanical properties of the laminate will be insufficient, or blocking will occur. On the contrary, when it is large, the bending fatigue resistance is insufficient, which is not preferable. In addition, ethylene-α-olefin means ethylene and butene-1, pentene-1,4-
It is a copolymer having 18 or less carbon atoms such as methylpentene-1, hexene-1, and octene-1.
【００１６】これらの中でも炭素数が４〜８のα−オレ
フィンを用いたエチレン−α−オレフィン共重合体が好
適に用いられる。更に、接着剤層に用いられる接着性樹
脂としては、不飽和カルボン酸又はその無水物で変性さ
れた密度０．８６〜０．９５ｇ／ｃｍ３（測定条件は、
上記の表面層の場合と同じ）のエチレン−α−オレフィ
ン共重合体が好ましく、上記の表面層で述べたのと同じ
樹脂を不飽和カルボン酸又はその無水物で共重合又はグ
ラフト変性することにより得ることができる。勿論、変
性には、未変性のエチレン−α−オレフィン共重合体に
不飽和カルボン酸又はその無水物のブレンドも含まれ
る。不飽和カルボン酸又はその無水物としては、マレイ
ン酸、無水マレイン酸、フマル酸、アクリル酸、メタク
リル酸、クロトン酸、イタコン酸、シトラコン酸、ヘキ
サヒドロ無水フタル酸等が挙げられ、中でも、無水マレ
イン酸が好適に用いられる。Among these, an ethylene-α-olefin copolymer using an α-olefin having 4 to 8 carbon atoms is preferably used. Further, as the adhesive resin used for the adhesive layer, a density of 0.86 to 0.95 g / cm 3 modified with an unsaturated carboxylic acid or an anhydride thereof (measurement conditions are:
The same as the case of the above surface layer) ethylene-α-olefin copolymer is preferable, and the same resin as described in the above surface layer is copolymerized or graft modified with an unsaturated carboxylic acid or an anhydride thereof. Obtainable. Of course, the modification also includes blending an unmodified ethylene-α-olefin copolymer with an unsaturated carboxylic acid or an anhydride thereof. Examples of the unsaturated carboxylic acid or an anhydride thereof include maleic acid, maleic anhydride, fumaric acid, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride, and the like. Is preferably used.
【００１７】このときの、エチレン−α−オレフィン共
重合体に含有される不飽和カルボン酸又はその無水物量
は、０．０１〜１０重量％が好ましく、更に好ましく
は、０．１〜３重量％である。該変性物中の含有量が少
ないと中間層及び表面層との接着力が低下し、逆に多い
と架橋反応を起こし、成形性が悪くなり好ましくない。
また、本発明の表面層／接着剤層／中間層（Ａ）／接着
剤層／表面層の積層体の各層の厚みは、それぞれ１０〜
６００μ／２〜５０μ／１〜５０μ／２〜５０μ／１０
〜６００μの範囲から選択され、好ましくは、３０〜２
００μ／５〜１０μ／５〜３０μ／５〜１０μ／３０〜
２００μである。At this time, the amount of the unsaturated carboxylic acid or its anhydride contained in the ethylene-α-olefin copolymer is preferably 0.01 to 10% by weight, more preferably 0.1 to 3% by weight. Is. If the content in the modified product is small, the adhesive strength with the intermediate layer and the surface layer will be reduced, and conversely, if it is large, a crosslinking reaction will occur and moldability will be poor, such being undesirable.
The thickness of each layer of the surface layer / adhesive layer / intermediate layer (A) / adhesive layer / surface layer laminate of the present invention is 10 to 10, respectively.
600μ / 2-50μ / 1-50μ / 2-50μ / 10
Selected from the range of ~ 600μ, preferably 30-2
00μ / 5-10μ / 5-30μ / 5-10μ / 30-
It is 200μ.
【００１８】本発明の最大の特徴は、中間層に特定のＥ
ＶＯＨ／ポリオレフィン系樹脂溶融混合組成物を採用し
たことにあり、中間層にかかるＥＶＯＨを用いる本発明
の積層体は、表面層／接着剤層／中間層（Ａ）／接着剤
層／表面層の構成に限らず、該表面層の外側に更に層を
設けて表面層／接着剤層／中間層（Ａ）／接着剤層／表
面層／接着剤層／表面層、表面層／接着剤層／表面層／
接着剤層／中間層（Ａ）／接着剤層／表面層／接着剤層
／表面層等の６層以上の積層体とすることも可能であ
る。更に、ナイロン層を用いた、表面層／接着剤層／ナ
イロン層／中間層（Ａ）／接着剤層／表面層、表面層／
接着剤層／ナイロン層／中間層（Ａ）／ナイロン層／接
着剤層／表面層、表面層／接着剤層／ナイロン層／接着
剤層／中間層（Ａ）／接着剤層／表面層等の積層体とす
ることも可能であり、このときに、用いられるナイロン
層の樹脂としては、ナイロン６、ナイロン６／６−６、
ナイロン１２、アモルファスナイロン、又はこれらのブ
レンド物が挙げられる。The greatest feature of the present invention is that the E specific to the intermediate layer is used.
Since the VOH / polyolefin resin melt-mixed composition is employed, the laminate of the present invention using EVOH for the intermediate layer has a surface layer / adhesive layer / intermediate layer (A) / adhesive layer / surface layer Not limited to the structure, a surface layer / adhesive layer / intermediate layer (A) / adhesive layer / surface layer / adhesive layer / surface layer, surface layer / adhesive layer / Surface layer /
It is also possible to form a laminate of 6 or more layers such as adhesive layer / intermediate layer (A) / adhesive layer / surface layer / adhesive layer / surface layer. Further, using a nylon layer, surface layer / adhesive layer / nylon layer / intermediate layer (A) / adhesive layer / surface layer, surface layer /
Adhesive layer / nylon layer / intermediate layer (A) / nylon layer / adhesive layer / surface layer, surface layer / adhesive layer / nylon layer / adhesive layer / intermediate layer (A) / adhesive layer / surface layer, etc. It is also possible to use a laminated body of Nylon 6, Nylon 6 / 6-6, Nylon 6 / 6-6,
Nylon 12, amorphous nylon, or blends thereof may be mentioned.
【００１９】また、本発明の積層体の表面層や接着剤層
には、成形加工性の向上のために酸化防止剤、スリップ
剤、ハイドロタルサイト類、帯電防止剤、可塑剤、着色
剤等を本発明の効果を阻害しない範囲で添加することも
できる。本発明のバッグインボックス用内容器は、主
に、ヒートシール法及びブロー成形法により製造するこ
とができる。ヒートシール法では、インフレーション法
又はスラットフイルム法により製膜された中間層用及び
表面層用のフィルムを、接着剤層を介してドライラミし
た積層体又は各層を共押出法等により積層した積層体を
そのまま、あるいは必要に応じて２重又は３重に重ね合
わせて、液体注入口の密封栓取り付け用の穴を打ち抜
き、その穴に、あらかじめ射出成形で成形した液体注入
口の密封栓をヒートシール法で融着させる。そのとき
に、該積層体と打ち抜き処理のしていない別の積層体と
を合わせて四方ヒートシールしてバッグインボックス用
内容器とする。ブロー成形法では、押出機から押し出さ
れた円筒状の上記の積層体を金型で型締めして成形す
る。液体注入口の密封栓は、あらかじめ射出成形で成形
したものを金型内にセットしておき、ブロー成形時に成
形容器と融着させる。その後、液体注入口をあける。In the surface layer and the adhesive layer of the laminate of the present invention, antioxidants, slip agents, hydrotalcites, antistatic agents, plasticizers, colorants, etc. are added to improve moldability. Can be added within a range that does not impair the effects of the present invention. The inner container for bag-in-box of the present invention can be manufactured mainly by a heat sealing method and a blow molding method. In the heat-sealing method, a film for the intermediate layer and the surface layer formed by the inflation method or the slat film method, a laminated body obtained by dry laminating through an adhesive layer or a laminated body in which each layer is laminated by a coextrusion method or the like is used. As it is, or if necessary, double or triple layers are piled up, a hole for attaching a sealing plug of the liquid injection port is punched out, and a sealing plug of the liquid injection port formed by injection molding in advance is heat-sealed into the hole. Fuse with. At that time, the laminated body and another laminated body which has not been punched out are combined and heat-sealed in four directions to form an inner container for bag-in-box. In the blow molding method, the above-mentioned cylindrical laminated body extruded from the extruder is clamped with a mold to form it. The sealing plug of the liquid injection port, which has been molded by injection molding in advance, is set in the mold and is fused with the molding container during blow molding. Then open the liquid inlet.
【００２０】[0020]
【作用】本発明のバッグインボックス用内容器は、中間
層に特定のポリエステル・ポリエーテルブロック共重合
体を含有したＥＶＯＨ層を用いているので、該内容器の
製造時の打ち抜き工程において、クラックが発生するこ
となく長期間のガスバリヤー性に優れたバッグインボッ
クス用内容器が得られる。The inner container for bag-in-box according to the present invention uses an EVOH layer containing a specific polyester / polyether block copolymer as an intermediate layer, and therefore cracks in the punching process during the production of the inner container. It is possible to obtain an inner container for a bag-in-box, which is excellent in gas barrier property for a long period of time without generation of gas.
【００２１】[0021]
【実施例】以下に、実施例を挙げて本発明を具体的に説
明する。尚、実施例中「部」、「％」とあるのは、特に
断わりのない限り、重量基準を意味する。ポリエステル・ポリエーテルブロック共重合体エラスト
マーの製造 容量１００ｌの反応缶に窒素ガス雰囲気下でジメチルテ
レフタレート９７０部、１，４−ブタンジオール６３０
部、平均分子量１０００のポリテトラメチレングリコー
ル１３５０部を仕込み、その後触媒としてテトラブチル
チタネート１．０部を添加し、約２２０℃で２時間、エ
ステル化反応を行った。その後ヒンダードフェノール系
の酸化防止剤Ｉｒｇａｎｏｘ１３３０（チバガイキー社
製）を１．９部及びテトラブチルチタネートを４．５部
添加し、重縮合反応缶に移送した。そこで減圧を行い真
空度１Ｔｏｒｒ以下までもっていき、反応温度２４０〜
２５０℃で重縮合反応を行い、撹拌速度２０ｒｐｍでト
ルク上昇が認められなくなるまで約３時間反応させてポ
リエステル・ポリエーテルブロック共重合体エラストマ
ー（Ｐ−１）を得た。Ｐ−１の結晶温度は１７８℃、反
発弾性率は７８％であった。以下同様にして表１に示す
如くポリエステル・ポリエーテルブロック共重合体エラ
ストマー（Ｐ−２〜６）を製造した。特性を表２に示
す。EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, "part" and "%" mean weight basis unless otherwise specified. Polyester / polyether block copolymer elastomer
970 parts of dimethyl terephthalate and 630 parts of 1,4-butanediol were placed in a reactor having a manufacturing capacity of 100 liters under a nitrogen gas atmosphere.
Part, 1350 parts of polytetramethylene glycol having an average molecular weight of 1000, was charged, and then 1.0 part of tetrabutyl titanate was added as a catalyst, and an esterification reaction was carried out at about 220 ° C. for 2 hours. Thereafter, 1.9 parts of a hindered phenolic antioxidant Irganox 1330 (manufactured by Ciba-Gaiki) and 4.5 parts of tetrabutyl titanate were added and transferred to a polycondensation reaction can. Therefore, the pressure is reduced to bring the degree of vacuum to 1 Torr or less, and the reaction temperature is 240 to
A polycondensation reaction was carried out at 250 ° C., and a reaction was carried out at a stirring speed of 20 rpm for about 3 hours until no torque increase was observed to obtain a polyester / polyether block copolymer elastomer (P-1). The crystal temperature of P-1 was 178 ° C, and the impact resilience was 78%. In the same manner, polyester / polyether block copolymer elastomers (P-2 to 6) were produced as shown in Table 1. The characteristics are shown in Table 2.
【００２２】[0022]
【表１】 ジカルボン酸成分(部) グリコール成分（部） ＤＭＴＰ ＳｅｂＡ １.４ＢＧ ＰＴＭＧ ＰＥＧ ＥＧ Ｐ−１ ９７０ − ６３０ １３５０ − − (分子量1000) Ｐ−２ １９４０ − １３５０ １３５０ − − (分子量1000) Ｐ−３ ７７０ − ４００ ２０００ − − (分子量1000) Ｐ−４ ７７０ − ４００ − ２００ − (分子量300) Ｐ−５ ７７０ ２１０ ６３０ １３５０ − − (分子量1000) Ｐ−６ ９７０ − − １００ − ４３０ (分子量1000) ＤＭＴＰ；ジメチルテレフタレート、１．４ＢＧ；１．
４ブタンジオール ＳｅｂＡ；セバシン酸、ＰＴＭＧ；ポリテトラメチレン
グリコール ＰＥＧ；ポリエチレングリコール、ＥＧ；エチレングリ
コール[Table 1] Dicarboxylic acid component (part) Glycol component (part) DMTP SebA 1.4BG PTMG PEG EG P-1 970-630 1350- (Molecular weight 1000) P-2 1940-1350 1350- (Molecular weight 1000) P -3 770 - 400 2000 - - (molecular weight 1000) P-4 770 - 400 - 200 - (molecular weight 300) P-5 770 210 630 1350 - - ( molecular weight 1000) P-6 970 - - 100 - 430 ( molecular weight 1000 ) DMTP; dimethyl terephthalate, 1.4BG;
4-butanediol SebA; sebacic acid, PTMG; polytetramethylene glycol PEG; polyethylene glycol, EG; ethylene glycol
【００２３】[0023]
【表２】 [Table 2]
【００２４】実施例１ ３種５層の共押出装置を用いて、中間層がエチレン含有
量が３０モル％，ケン化度が９９．５モル％のＥＶＯＨ
１００部と結晶融点が１７８℃でかつ反発弾性率が７８
％の熱可塑性のポリエステル・ポリエーテルブロック共
重合体エラストマー（Ｐ−１）３５部を配合した樹脂組
成物の層（Ａ−１）、両外層がＭＩ（メルトインデック
ス）２．５ｇ／１０分（１９０℃、荷重２１６０ｇ），
密度０．８９０ｇ／ｃｍ３，エチレン含有量９０モル％
のエチレン−１−ブテンランダム共重合体ＬＬＤＰＥ
（Ｂ−１）、中間層と両外層との間の接着剤層が（Ｂ−
１）に無水マレイン酸を０．５％グラフトしたＭＩが
３．０ｇ／１０分（１９０℃、荷重２１６０ｇ）の変性
ＬＬＤＰＥ（Ｃ−１）とからなる（Ｂ−１）／（Ｃ−
１）／（Ａ−１）／（Ｃ−１）／（Ｂ−１）が３５μ／
１０μ／１０μ／１０μ／３５μの構成を有する５層共
押出積層フィルムを下記の如き共押出成形条件で得た。Example 1 An EVOH having an ethylene content of 30 mol% and a saponification degree of 99.5 mol% was used for the intermediate layer by using a coextrusion device of 5 layers of 3 types.
100 parts, the crystal melting point is 178 ° C, and the impact resilience is 78
% Thermoplastic resin / polyether block copolymer elastomer (P-1) 35 parts resin layer (A-1), both outer layers are MI (melt index) 2.5 g / 10 min ( 190 ° C, load 2160g),
Density 0.890 g / cm 3 , ethylene content 90 mol%
Ethylene-1-butene random copolymer LLDPE
(B-1), the adhesive layer between the intermediate layer and both outer layers is (B-
(B-1) / (C-) consisting of modified LLDPE (C-1) having an MI obtained by grafting 0.5% maleic anhydride on 1) at 3.0 g / 10 min (190 ° C, load 2160 g).
1) / (A-1) / (C-1) / (B-1) is 35 μ /
A 5-layer coextrusion laminated film having a constitution of 10 μ / 10 μ / 10 μ / 35 μ was obtained under the following coextrusion molding conditions.
【００２５】共押出成形条件 ： 押出機（Ａ）：３０ｍｍф，スクリュー；フルフライト
型，Ｌ／Ｄ；２８ 温度条件（℃）：供給部；１８０，圧縮部；２００，計
量部；２２０ 吐 出 量 ：１．５ｋｇ／ｈｒ 押出機（Ｂ）：３０ｍｍф，スクリュー；フルフライト
型，Ｌ／Ｄ；２６ 温度条件（℃）：供給部；１６０，圧縮部；２００，計
量部；２２０ 吐 出 量 ：３．０ｋｇ／ｈｒ 押出機（Ｃ）：４０ｍｍф，スクリュー；フルフライト
型，Ｌ／Ｄ；２４ 温度条件（℃）：供給部；２００，圧縮部；２１０，計
量部；２１０ 吐 出 量 ：１０．０ｋｇ／ｈｒ フィードブロック温度：２２０℃ ダイ温度：２２０℃Coextrusion molding conditions : Extruder (A): 30 mmΦ, screw; full flight type, L / D; 28 Temperature conditions (° C.): supply part; 180, compression part; 200, metering part; 220 discharge amount : 1.5 kg / hr Extruder (B): 30 mmΦ, screw; full flight type, L / D; 26 Temperature condition (° C): Feeding part; 160, Compressing part; 200, Measuring part; 220 Discharge amount: 3 0.0 kg / hr Extruder (C): 40 mmΦ, screw; full flight type, L / D; 24 Temperature condition (° C): Feeding unit; 200, Compressing unit; 210, Measuring unit; 210 Discharge amount: 10.0 kg / Hr Feed block temperature: 220 ℃ Die temperature: 220 ℃
【００２６】得られた積層フィルム（５００ｍｍ×７０
０ｍｍ）を２枚重ねにして、打ち抜き機により、液体注
入用の穴（直径４３ｍｍ）をあけた。次に、穴のあけて
いない積層フィルム（５００ｍｍ×７００ｍｍの２枚重
ね）を上記の積層フィルムと重ね合わせて四方ヒートシ
ールしてバッグインボックス用内容器を製造した。その
際に、液体注入用の穴に高密度ポリエチレン製の密封栓
を取り付け回りを熱シールして密着固定した。次に、か
かる内容器をダンボール箱に入れ、その中に水を約１８
リットル入れて約２０００ｋｍの走行輸送テストを行っ
た。上記テスト後、内容器の密封栓回りの積層フィルム
の状況をＳＥＭ（電子顕微鏡，５００倍）で目視観察し
た。なお、テスト前後の該内容器の酸素透過率（ｃｃ／
ａｉｒ・ｂａｇ・ｄａｙ）を２０℃，６５％ＲＨの条件
下でＭｏｄｅｒｎ Ｃｏｎｔｏｒｏｌ社製の酸素透過率
測定器（ＯＸ−ＴＲＡＮ１０／５０）を用いて調べた。The resulting laminated film (500 mm × 70
(0 mm) were piled up, and a hole (diameter 43 mm) for liquid injection was opened by a punching machine. Next, a laminated film having no holes (500 mm × 700 mm, two sheets stacked) was laminated with the above laminated film and heat-sealed on four sides to manufacture an inner container for bag-in-box. At that time, a sealing plug made of high-density polyethylene was attached to the hole for injecting the liquid, and the periphery was heat-sealed and fixed tightly. Next, put the inner container in a cardboard box, and fill it with about 18
A running transportation test of about 2000 km was performed with the liters put. After the above test, the state of the laminated film around the sealing stopper of the inner container was visually observed by SEM (electron microscope, 500 times). The oxygen transmission rate (cc /
air * bag * day) was examined under the conditions of 20 [deg.] C. and 65% RH using an oxygen permeability measuring device (OX-TRAN10 / 50) manufactured by Modern Control.
【００２７】実施例２〜４ 表３に示す中間層、接着剤層、表面層を用いて、実施例
１と同様に内容器を作製して評価を行った。 比較例１〜５ 表３に示す中間層、接着剤層、表面層を用いて、実施例
１と同様に内容器を作製して評価を行った。実施例及び
比較例の評価結果を表３に示す。Examples 2 to 4 Using the intermediate layer, adhesive layer and surface layer shown in Table 3, an inner container was prepared and evaluated in the same manner as in Example 1. Comparative Examples 1 to 5 An inner container was prepared and evaluated in the same manner as in Example 1 using the intermediate layer, the adhesive layer, and the surface layer shown in Table 3. Table 3 shows the evaluation results of the examples and comparative examples.
【００２８】[0028]
【表３】 積 層 構 成1) 評 価 項 目 中間層 表面層 接着剤層 ＳＥＭ観察 酸素透過率2) 実施例１ Ａ−１ Ｂ−１ Ｃ−１ 異状無し ０.０８／０.０８ 実施例２ Ａ−２ Ｂ−２ Ｃ−２ 異状無し ０.１１／０.１５ 実施例３ Ａ−３ Ｂ−３ Ｃ−３ 異状無し ０.９０／０.９０実施例４ Ａ−１ Ｂ−４ Ｃ−１ 異状無し ０.０８／０.１０ 比較例１ Ａ−４ Ｂ−１ Ｃ−１ クラック発生 ０.０７／２００＜ 比較例２ Ａ−５ Ｂ−１ Ｃ−１ ＊ ＊ 比較例３ Ａ−６ Ｂ−１ Ｃ−１ クラック発生 ０.０９／２００＜ 比較例４ Ａ−７ Ｂ−１ Ｃ−１ 異状無し ２００＜／２００＜比較例５ Ａ−８ Ｂ−１ Ｃ−１ クラック発生 ０.０６／２００＜ [Table 3] Laminated layer composition 1) Evaluation item Intermediate layer Surface layer Adhesive layer SEM observation Oxygen permeability 2) Example 1 A-1 B-1 C-1 No abnormalities 0.08 / 0.08 Implementation Example 2 A-2 B-2 C-2 No abnormalities 0.11 / 0.15 Example 3 A-3 B-3 C-3 No abnormalities 0.90 / 0.90 Example 4 A-1 B-4 C-1 No abnormalities 0.08 / 0.10 Comparative example 1 A-4 B-1 C-1 Crack generation 0.07 / 200 <Comparative example 2 A-5 B-1 C-1 ** Comparative example 3A -6 B-1 C-1 crack generation 0.09 / 200 <Comparative example 4 A-7 B-1 C-1 No abnormalities 200 </ 200 < Comparative example 5 A-8 B-1 C-1 Crack generation 0 0.06 / 200 <
【００２９】１）各構成樹脂は、以下のとおり。 Ａ−１；上記の（Ａ−１） Ａ−２；エチレン含有量が４０モル％、ケン化度が９
８．０モル％のＥＶＯＨ１００部と（Ｐ−２）１０部を
配合 Ａ−３；エチレン含有量が３０モル％、ケン化度が９
９．２モル％のＥＶＯＨ１００部と（Ｐ−３）６５部を
配合 Ａ−４；エチレン含有量が３０モル％、ケン化度が９
９．５モル％のＥＶＯＨ１００部と（Ｐ−４）３５部を
配合 Ａ−５；エチレン含有量が３０モル％、ケン化度が９
９．５モル％のＥＶＯＨ１００部と（Ｐ−５）３５部を
配合 Ａ−６；エチレン含有量が３０モル％、ケン化度が９
９．５モル％のＥＶＯＨ１００部と（Ｐ−６）３５部を
配合 Ａ−７；エチレン含有量が３０モル％、ケン化度が９
９．５モル％のＥＶＯＨ１００部と（Ｐ−１）１５０部
を配合 Ａ−８；エチレン含有量が３０モル％、ケン化度が９
９．５モル％のＥＶＯＨのみ1) The constituent resins are as follows. A-1: the above (A-1) A-2; ethylene content of 40 mol%, saponification degree of 9
100 parts of 8.0 mol% EVOH and 10 parts of (P-2) are blended A-3; ethylene content 30 mol%, saponification degree 9
100 parts of 9.2 mol% EVOH and 65 parts of (P-3) are blended A-4; ethylene content 30 mol%, saponification degree 9
100 parts of 9.5 mol% EVOH and 35 parts of (P-4) are blended A-5; ethylene content 30 mol%, saponification degree 9
100 parts of 9.5 mol% EVOH and 35 parts of (P-5) are blended A-6; ethylene content is 30 mol% and saponification degree is 9
100 parts of 9.5 mol% EVOH and 35 parts of (P-6) are blended A-7; ethylene content 30 mol%, saponification degree 9
100 parts of 9.5 mol% EVOH and 150 parts of (P-1) are mixed A-8; ethylene content is 30 mol%, saponification degree is 9
9.5 mol% EVOH only
【００３０】Ｂ−１；ＭＩ２．５ｇ／１０分、密度０．
８９０ｇ／ｃｍ３、エチレン含有量９０モル％のエチレ
ン−１−ブテンランダム共重合体 Ｂ−２；ＭＩ４．０ｇ／１０分、密度０．８７２ｇ／ｃ
ｍ３、エチレン含有量８２モル％のエチレン−１−ブテ
ンランダム共重合体 Ｂ−３；ＭＩ０．８ｇ／１０分、密度０．８６４ｇ／ｃ
ｍ３、エチレン含有量８０モル％のエチレン−プロピレ
ン共重合体 Ｂ−４；ＭＩ２．０ｇ／１０分、密度０．９２０ｇ／ｃ
ｍ３、エチレン含有量９７モル％のエチレン−４−メチ
ルペンテン−１共重合体 Ｃ−１；上記Ｂ−１に無水マレイン酸を０．５％グラフ
トしたもの。 Ｃ−２；上記Ｂ−２に無水マレイン酸を２．５％グラフ
トしたもの１０部にＢ−１を９０部ブレンドしたもの。 Ｃ−３；上記Ｂ−３に無水マレイン酸を１０％グラフト
したもの。 ２）酸素透過率は、テスト前／テスト後の値でそれぞれ
表している。 ＊ 積層体製造時に、ゲルが多量発生し、積層体の成形
加工が不可能であった。B-1: MI 2.5 g / 10 minutes, density 0.
890 g / cm 3 , ethylene-1-butene random copolymer with ethylene content 90 mol% B-2; MI 4.0 g / 10 min, density 0.872 g / c
m 3 , ethylene-1-butene random copolymer with ethylene content 82 mol% B-3; MI 0.8 g / 10 min, density 0.864 g / c
m 3 , ethylene-propylene copolymer having an ethylene content of 80 mol% B-4; MI 2.0 g / 10 min, density 0.920 g / c
m 3, an ethylene content of 97 mol% ethylene-4-methylpentene-1 copolymer C-1; the B-1 to those grafted with maleic anhydride 0.5%. C-2: A blend of 90 parts of B-1 and 10 parts of the above B-2 grafted with 2.5% of maleic anhydride. C-3: 10% maleic anhydride grafted onto B-3 above. 2) The oxygen transmission rate is represented by the value before and after the test. * A large amount of gel was generated during the production of the laminated body, making it impossible to form the laminated body.
【００３１】[0031]
【発明の効果】本発明のバッグインボックス用内容器
は、中間層に特定のポリエステル・ポリエーテルブロッ
ク共重合体を含有したＥＶＯＨ層を用いているので、該
内容器の製造時の打ち抜き工程において、クラックが発
生することなくガスバリヤー性に優れたバッグインボッ
クス用内容器が得られ、長時間の輸送等の衝撃にも耐え
得ることができ極めて有用性が高いものである。INDUSTRIAL APPLICABILITY The inner container for bag-in-box of the present invention uses the EVOH layer containing the specific polyester / polyether block copolymer as the intermediate layer, and therefore, in the punching step during the production of the inner container. In addition, an inner container for a bag-in-box which is excellent in gas barrier property without generation of cracks can be obtained, and it can withstand impacts such as long-term transportation and is extremely useful.
【手続補正書】[Procedure amendment]
【提出日】平成５年９月２８日[Submission date] September 28, 1993
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１７[Correction target item name] 0017
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１７】このときの、エチレン−α−オレフィン共
重合体に含有される不飽和カルボン酸又はその無水物量
は、０．０１〜１０重量％が好ましく、更に好ましく
は、０．１〜３重量％である。該変性物中の含有量が少
ないと中間層及び表面層との接着力が低下し、逆に多い
と架橋反応を起こし、成形性が悪くなり好ましくない。
また、本発明の表面層／接着剤層／中間層（Ａ）／接着
剤層／表面層の積層体の各層の厚みは、それぞれ１０〜
６００μ／２〜５０μ／１〜１００μ／２〜５０μ／１
０〜６００μの範囲から選択され、好ましくは、３０〜
２００μ／５〜１０μ／５〜３０μ／５〜１０μ／３０
〜２００μである。At this time, the amount of the unsaturated carboxylic acid or its anhydride contained in the ethylene-α-olefin copolymer is preferably 0.01 to 10% by weight, more preferably 0.1 to 3% by weight. Is. If the content in the modified product is small, the adhesive strength with the intermediate layer and the surface layer will be reduced, and conversely, if it is large, a crosslinking reaction will occur and moldability will be poor, such being undesirable.
The thickness of each layer of the surface layer / adhesive layer / intermediate layer (A) / adhesive layer / surface layer laminate of the present invention is 10 to 10, respectively.
600μ / 2-50μ / 1-100μ / 2-50μ / 1
It is selected from the range of 0 to 600 μ, and preferably 30 to
200 μ / 5 to 10 μ / 5 to 30 μ / 5 to 10 μ / 30
~ 200μ.
Claims (3)
酸ビニル成分のケン化度が９０モル％以上のエチレン−
酢酸ビニル共重合体ケン化物１００重量部に対し、結晶
融点が１５０〜２３０℃でかつ反発弾性率が５０％以上
の熱可塑性のポリエステル・ポリエーテルブロック共重
合体エラストマーを２〜１００重量部配合してなる樹脂
組成物（Ａ）を、中間層とし、該中間層の両側に接着剤
層を設け、更に該接着剤層の外側に表面層を設けたこと
を特徴とするバッグインボックス用内容器。1. Ethylene having an ethylene content of 20 to 50 mol% and a saponification degree of a vinyl acetate component of 90 mol% or more.
2 to 100 parts by weight of a thermoplastic polyester / polyether block copolymer elastomer having a crystal melting point of 150 to 230 ° C. and a repulsion elastic modulus of 50% or more is added to 100 parts by weight of a saponified vinyl acetate copolymer. An inner container for bag-in-box, comprising a resin composition (A) as an intermediate layer, an adhesive layer provided on both sides of the intermediate layer, and a surface layer provided outside the adhesive layer. .
ｍ３（２０℃）のエチレン−α−オレフィン共重合体か
らなる請求項１記載のバッグインボックス用内容器。2. The surface layer has a density of 0.86 to 0.95 g / c.
The inner container for bag-in-box according to claim 1, comprising an ethylene-α-olefin copolymer of m 3 (20 ° C.).
水物で変性された密度０．８６〜０．９５ｇ／ｃｍ
３（２０℃）のエチレン−α−オレフィン共重合体から
なる請求項１記載のバッグインボックス用内容器。3. The density of the adhesive layer modified with an unsaturated carboxylic acid or an anhydride thereof 0.86 to 0.95 g / cm 3.
The inner container for bag-in-box according to claim 1, which is composed of an ethylene-α-olefin copolymer of 3 (20 ° C).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28051492A JP3169282B2 (en) | 1992-09-25 | 1992-09-25 | Inner container for bag-in-box |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28051492A JP3169282B2 (en) | 1992-09-25 | 1992-09-25 | Inner container for bag-in-box |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06106687A true JPH06106687A (en) | 1994-04-19 |
| JP3169282B2 JP3169282B2 (en) | 2001-05-21 |
Family
ID=17626164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28051492A Expired - Fee Related JP3169282B2 (en) | 1992-09-25 | 1992-09-25 | Inner container for bag-in-box |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3169282B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011111803A1 (en) * | 2010-03-10 | 2011-09-15 | 日本合成化学工業株式会社 | Resin composition and multilayer structure using same |
-
1992
- 1992-09-25 JP JP28051492A patent/JP3169282B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011111803A1 (en) * | 2010-03-10 | 2011-09-15 | 日本合成化学工業株式会社 | Resin composition and multilayer structure using same |
| JP2011208134A (en) * | 2010-03-10 | 2011-10-20 | Nippon Synthetic Chem Ind Co Ltd:The | Resin composition and multilayer structure using same |
| CN102782040A (en) * | 2010-03-10 | 2012-11-14 | 日本合成化学工业株式会社 | Resin composition and multilayer structure using same |
| US8883920B2 (en) | 2010-03-10 | 2014-11-11 | The Nippon Synthetic Chemical Industry Co., Ltd. | Resin composition and multilayer structural body employing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3169282B2 (en) | 2001-05-21 |
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