JPS62197436A - Bondable resin composition and laminate obtained by using same - Google Patents
Bondable resin composition and laminate obtained by using sameInfo
- Publication number
- JPS62197436A JPS62197436A JP4103886A JP4103886A JPS62197436A JP S62197436 A JPS62197436 A JP S62197436A JP 4103886 A JP4103886 A JP 4103886A JP 4103886 A JP4103886 A JP 4103886A JP S62197436 A JPS62197436 A JP S62197436A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- carboxylic acid
- hydroxide
- metal
- copolymer
- 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
- 239000011342 resin composition Substances 0.000 title claims 2
- 229920001577 copolymer Polymers 0.000 claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 23
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 15
- 230000000737 periodic effect Effects 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 41
- 239000004840 adhesive resin Substances 0.000 claims description 36
- 229920006223 adhesive resin Polymers 0.000 claims description 36
- 230000004888 barrier function Effects 0.000 claims description 22
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 18
- -1 acrylic ester Chemical class 0.000 claims description 16
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 16
- 229920006395 saturated elastomer Polymers 0.000 claims description 15
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 14
- 229920006226 ethylene-acrylic acid Polymers 0.000 claims description 13
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 239000004417 polycarbonate Substances 0.000 claims description 9
- 229920000515 polycarbonate Polymers 0.000 claims description 9
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 8
- 150000004692 metal hydroxides Chemical class 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 7
- 229920003146 methacrylic ester copolymer Polymers 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920006222 acrylic ester polymer Polymers 0.000 claims description 5
- 238000007127 saponification reaction Methods 0.000 claims description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 2
- 235000013305 food Nutrition 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000010410 layer Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- 239000000178 monomer Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 9
- 229920001225 polyester resin Polymers 0.000 description 9
- 239000004645 polyester resin Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000005022 packaging material Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229910044991 metal oxide Chemical group 0.000 description 4
- 150000004706 metal oxides Chemical group 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 2
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920000577 Nylon 6/66 Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229940106691 bisphenol a Drugs 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 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
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011229 interlayer Substances 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
- 239000000314 lubricant Substances 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 239000012768 molten material Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 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
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-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
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-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
- 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
- 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
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- RSSGMIIGVQRGDS-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=CC=C1 RSSGMIIGVQRGDS-UHFFFAOYSA-N 0.000 description 1
- OVVCSFQRAXVPGT-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)cyclopentyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCC1 OVVCSFQRAXVPGT-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-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
- 229930185605 Bisphenol Natural products 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 240000008338 Nigella arvensis Species 0.000 description 1
- 235000007413 Nigella arvensis Nutrition 0.000 description 1
- 235000016698 Nigella sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 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
- 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000001816 cooling 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
- 230000007423 decrease 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
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process 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
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 230000003993 interaction Effects 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
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 230000007774 longterm Effects 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
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 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
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 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
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 150000001451 organic peroxides 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 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
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl 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
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
Ａ、 上の
本発明は接着性樹脂組成物および該接着性樹脂組成物を
介して、ガスバリヤ−性樹脂、特にエチレン−酢酸ビニ
ル共重合体けん化物樹脂と疎水性熱可塑性樹脂を積層し
た積層体に関する。DETAILED DESCRIPTION OF THE INVENTION A. The present invention provides an adhesive resin composition and, through the adhesive resin composition, a gas barrier resin, particularly a saponified ethylene-vinyl acetate copolymer resin, and a hydrophobic heat-resistant resin. The present invention relates to a laminate in which plastic resins are laminated.
Ｂ、 および の 占 近年の食品包装業界の技術革新はめざましい。B, and the fortune of Technological innovation in the food packaging industry in recent years has been remarkable.
例えば、衛生性、美しい外観、運搬コストの低減の為の
軽量化を目的として飽和ポリエステル等の疎水性熱可塑
性樹脂が食品包装に用いられつつある事は周知の事であ
る。しかしながらこれらの飽和ポリエステル系樹脂は酸
素とか、炭酸ガス等のバリヤー性が低く、食品、炭酸飲
料などの長期保存には適ざず、ガラス瓶、金属缶などが
多く用いられており、空缶の路上への投げすてによる公
害とか、ビンの回収に要するコストなど多くの問題があ
り、代替包装置￥器材料の開発がまたれている。For example, it is well known that hydrophobic thermoplastic resins such as saturated polyester are being used for food packaging for the purpose of reducing weight for hygiene, aesthetic appearance, and reduced transportation costs. However, these saturated polyester resins have poor barrier properties against oxygen and carbon dioxide, making them unsuitable for long-term storage of foods, carbonated drinks, etc. Glass bottles and metal cans are often used, and empty cans are stored on the street. There are many problems, such as the pollution caused by throwing bottles into the water and the cost required to collect the bottles, and efforts are being made to develop alternative packaging materials.
エチレン成分が２０〜５５モル％のエチレン−酢酸ビニ
ル共重合体けん化物樹脂は溶融成型性があり、透明性が
高く、かつガスバリヤ−性が優れた材料として食品容器
、包装材料としてすぐれた特性をそなえている。しかし
ながら他の諸物性、例えば剛性とか、耐湿性などに欠点
があり、充分満足すべきものではない。Saponified ethylene-vinyl acetate copolymer resin with an ethylene content of 20 to 55 mol% has excellent properties as a material for food containers and packaging materials as it is melt moldable, highly transparent, and has excellent gas barrier properties. Prepared. However, it has drawbacks in other physical properties, such as rigidity and moisture resistance, and is not fully satisfactory.
これに対し、疎水性熱可塑性樹脂、とくにポリエチレン
テレフタレートを主成分とする飽和ポリエステル系樹脂
は成形性、Ｉ４ｗＲ撃性と剛性のバランス、衛生性など
は優れているが、酸素や炭酸ガスなどのガスバリヤ−が
充分でなく、食品容器、包装材料としての使用に制限が
ある。On the other hand, hydrophobic thermoplastic resins, especially saturated polyester resins whose main component is polyethylene terephthalate, are excellent in moldability, balance between I4wR impact resistance and rigidity, and hygienic properties; - is not sufficient, and there are restrictions on its use as food containers and packaging materials.
そこでエチレン−酢酸ビニル共重合体けん化物樹脂の良
好なガスバリヤ−性と飽和ポリエステル系樹脂などの疎
水性熱可塑性樹脂のすぐれた力学特性を兼ね備えた食品
容器、包装材料を得るために、これらの両者の樹脂を積
層することが考えられる。しかしながら、これらの樹脂
は相互にはほとんど親和性がなく、単なる熱接着によっ
て積層物を得ることは不可能である。Therefore, in order to obtain food containers and packaging materials that have both the good gas barrier properties of saponified ethylene-vinyl acetate copolymer resins and the excellent mechanical properties of hydrophobic thermoplastic resins such as saturated polyester resins, we have developed both these materials. It is conceivable to laminate several resins. However, these resins have little affinity with each other, and it is impossible to obtain a laminate by mere thermal bonding.
エチレン成分−アクリル酸エステルもしくは酢酸ビニル
成分−エチレン性不飽和カルボン酸もしくは該カルボン
酸無水物成分からなる重合体と飽和ポリエステル系樹脂
とが接着性を有する事は特開昭５５−７１５５６に公知
である。該公報にはエチレン−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、エチレン−アク
リル酸エステル共重合体、のごときエチレンとカルボキ
シル基含有モノマーとの共重合体にエチレン性不飽和カ
ルボン酸もしくは該カルボン酸無水物を化学的に結合せ
しめた変性エチレン−カルボキシル基含有モノマー共重
合体が飽和ポリエステル系樹脂に接着できる事を示し、
その有用性を主張している。It is known in JP-A-55-71556 that a polymer consisting of an ethylene component - an acrylic ester component or a vinyl acetate component - an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride component and a saturated polyester resin have adhesive properties. be. The publication describes copolymers of ethylene and carboxyl group-containing monomers, such as ethylene-vinyl acetate copolymers, ethylene-acrylic ester copolymers, and ethylene-acrylic ester copolymers, with ethylenically unsaturated carboxylic acids. Alternatively, it is shown that a modified ethylene-carboxyl group-containing monomer copolymer to which the carboxylic acid anhydride is chemically bonded can adhere to a saturated polyester resin,
It claims its usefulness.
また特開昭５４−１０１８８３には熱可塑性樹脂とエチ
レン−酢酸ビニル共重合体けん化物樹脂とをエチレンと
カルボキシル基含有モノマーとの共重合体にエチレン性
不飽和カルボン酸もしくは該カルボン酸無水物を化学的
に結合せしめた変性エチレン−カルボキシル基含有モノ
マー共重合体を中間層として積層できる事を示している
。ざらにまた特開昭５４−１１０２８２にはエチレンと
カルボキシル基含有モノマーとの共重合体にエチレン性
不飽和カルボン酸もしくは該カルボン酸無水物を化学的
に結合させ、かつ金属酸化物もしくは炭酸塩と反応せし
めた金属結合変性共重合体を接着層としてエチレン−酢
酸ビニル共重合体けん化物樹脂を含む積層構造物を得て
いる。Furthermore, in JP-A-54-101883, a thermoplastic resin and a saponified ethylene-vinyl acetate copolymer resin are mixed into a copolymer of ethylene and a monomer containing a carboxyl group, and an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride is added to the copolymer of ethylene and a monomer containing a carboxyl group. This shows that a chemically bonded modified ethylene-carboxyl group-containing monomer copolymer can be laminated as an intermediate layer. Furthermore, in JP-A-54-110282, an ethylenically unsaturated carboxylic acid or an anhydride of the carboxylic acid is chemically bonded to a copolymer of ethylene and a monomer containing a carboxyl group, and a metal oxide or carbonate is bonded to the copolymer. A laminated structure containing a saponified ethylene-vinyl acetate copolymer resin is obtained using the reacted metal bond modified copolymer as an adhesive layer.
しかしながらエチレン−酢酸ビニル共重合体けん化物樹
脂とポリエチレンテレフタレートを主成分とする飽和ポ
リエステル系樹脂等の疎水性熱可塑性樹脂との組合せに
おいては、エチレン成分−アクリル酸エステル成分もし
くは低級脂肪酸ビニルエステル成分−エチレン性不飽和
カルボン酸もしくは該カルボン酸無水物成分からなる共
重合体、または該共重合体に金属酸化物もしくは炭酸塩
と反応させた樹脂を接着性樹脂層に用いた時は、ある程
度の接着性を有してはいるものの、得られた成形物には
主としてガスバリヤ−性樹脂層の厚み不均一、ゲル化物
の生成によると思われる所のスジ、ブッ、波状模様の発
生など外観の不良な積層体となる等商品としての価値の
ある物は得られない。However, in the combination of a saponified ethylene-vinyl acetate copolymer resin and a hydrophobic thermoplastic resin such as a saturated polyester resin containing polyethylene terephthalate as a main component, the ethylene component - the acrylic ester component or the lower fatty acid vinyl ester component - When a copolymer consisting of an ethylenically unsaturated carboxylic acid or carboxylic acid anhydride component, or a resin made by reacting the copolymer with a metal oxide or carbonate, is used for the adhesive resin layer, a certain degree of adhesion is achieved. However, the resulting molded product has poor appearance mainly due to uneven thickness of the gas barrier resin layer and the occurrence of streaks, bumps, and wavy patterns that are thought to be caused by the formation of gelled products. Products with commercial value such as laminates cannot be obtained.
ざらに特公昭３９−６８１０には一種以上のα−オレフ
ィンと一個もしくは二個のカルボキシル基を有する一種
以上のα、β−エチレン型不飽和カルボン酸とから得ら
れた共重合体に一種以上の水に溶解し得るイオン性金属
化合物を反応させたイオン性共重合体の製造法が公知で
ある。そこでは、好適なベース共重合体は第三の共重合
し得るモノエチレン型不飽和単量体を存在きせ、または
存在させずに、エチレンをモノカルボン酸単量体と直接
共重合させたものが好適であると説明している。そして
上記ベース共重合体はＮａ＋などの金属イオンで酸基の
１０％以上を中和することにより、ゴム弾性、可撓性、
熱安定性、靭性、耐摩耗性等の固体状態における望まし
い物理的性質と溶融流動性を合わせ持った物となる事を
示し、その優位性を主張している。一方、ベース共重合
体はα−オレフィンと酸型量体をポリオレフィンのベー
スにグラフト重合させることにより得ることもできるこ
とが開示されているが、この方法はエチレンよりも大き
い分子量を有するオレフィン、例えばプロピレン、ブテ
ン−１等から得られるポリオレフィンを用いる場合に好
適であると説明しているものであり、ポリオレフィンと
してエチレン−アクリル酸エステルもしくは酢酸ビニル
共重合体が使用できるとの開示は無い。そして当該発明
は溶融係数（ＭＩ）ｈ＜０．１〜１００ｇ／ｌｏ分の樹
脂において上記のごとき物理的性質を改善する物であり
、溶融係数（ＭＩ）が１００ｇ／１０分以上の時に始め
て接着剤用および積層品用の樹脂となる事が示きれてい
る。Zarani Japanese Patent Publication No. 39-6810 describes a copolymer obtained from one or more α-olefins and one or more α, β-ethylenically unsaturated carboxylic acids having one or two carboxyl groups. A method for producing an ionic copolymer by reacting an ionic metal compound that can be dissolved in water is known. Therein, the preferred base copolymer is one in which ethylene is copolymerized directly with a monocarboxylic acid monomer, with or without the presence of a third copolymerizable monoethylenically unsaturated monomer. is said to be suitable. By neutralizing 10% or more of the acid groups with metal ions such as Na+, the base copolymer has rubber elasticity, flexibility,
It has been demonstrated that it has both desirable physical properties in the solid state, such as thermal stability, toughness, and wear resistance, as well as melt fluidity, and claims its superiority. On the other hand, it has been disclosed that the base copolymer can also be obtained by graft polymerizing an α-olefin and an acid type polymer onto a polyolefin base, but this method is not suitable for olefins having a molecular weight larger than ethylene, such as propylene. , butene-1, etc., and there is no disclosure that ethylene-acrylic acid ester or vinyl acetate copolymer can be used as the polyolefin. The invention improves the above-mentioned physical properties in resins with a melting index (MI) h < 0.1 to 100 g/lo, and only bonds when the melting index (MI) is 100 g/10 minutes or more. It has been shown that it can be used as a resin for adhesives and laminated products.
しかしながら、一種以上のα−オレフィンと一個もしく
は二個のカルボキシル基を有する一種以上のα、β−エ
チレン型不飽和カルボン酸とから得られた共重合体に、
一種以上の水に溶解し得るイオン性金属化合物を反応さ
せたイオン性共重合体はアクリル酸エステルもしくは酢
酸ビニル成分の有無に拘らず全く接着性を示きないもの
である。またプロピレン、ブテン−１等から得られるポ
リオレフィンをベース共重合体とし、酸型量体をグラフ
トし、かつ金属イオンで中和された樹脂は全く接着性を
示ざないものである。更に、ＭＩが１００ｇ／１０分以
上の時は、ＭＩが大き過ぎる為に成型が出来ない等の難
点がある。このため実質的に有用な接着性樹脂とは成り
得ないものである。However, in a copolymer obtained from one or more α-olefins and one or more α, β-ethylenically unsaturated carboxylic acids having one or two carboxyl groups,
An ionic copolymer prepared by reacting one or more water-soluble ionic metal compounds exhibits no adhesive properties regardless of the presence or absence of an acrylic ester or vinyl acetate component. Furthermore, a resin made of a polyolefin obtained from propylene, butene-1, etc. as a base copolymer, grafted with an acid type polymer, and neutralized with metal ions shows no adhesive properties at all. Furthermore, when the MI is 100 g/10 minutes or more, there is a problem that molding cannot be performed because the MI is too large. Therefore, it cannot be used as a substantially useful adhesive resin.
特開昭５４−８７７８３にはポリオレフィンの一部ある
いは全部を不飽和カルボン酸もしくはその誘導体から選
ばれた少なくとも一種以上のモノマーで変性したポリオ
レフィンと、エチレン−ビニルアルコール共重合体、ポ
リアミド樹脂あるいはポリエステル樹脂を積層するにあ
たり、少なくとも一層以上に、高級脂肪酸の金属塩、金
属酸化物、金属水酸化物、金属炭酸塩、金属硫酸塩およ
び金属ケイ酸塩から選ばれる少なくとも一種以上の金属
化合物を配合することにより、層間接着性を改良できる
ことが開示されている。JP-A-54-87783 discloses a polyolefin in which part or all of the polyolefin is modified with at least one monomer selected from unsaturated carboxylic acids or derivatives thereof, an ethylene-vinyl alcohol copolymer, a polyamide resin, or a polyester resin. When laminating, at least one metal compound selected from metal salts, metal oxides, metal hydroxides, metal carbonates, metal sulfates, and metal silicates of higher fatty acids is added to at least one layer. It is disclosed that the interlayer adhesion can be improved by the following.
該公報には、ポリオレフィンとしては、エチレン、プロ
ピレン、１−ブテン、１−ペンテン、３−メチル−１−
ブテン、１−ヘキセン、４−メチル−１−ペンテン等の
α−オレフィンの単独重合体、もしくは上記一種のモノ
マーと他のα−オレフインとの共重合体である。これら
のうちでは、中、高密度ポリエチレン、ポリプロピレン
に対して本発明の効果が顕著であることが示きれている
。またその他としてエチレン−酢酸ビニル共重合体が示
されている。In this publication, polyolefins include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-
These are homopolymers of α-olefins such as butene, 1-hexene, and 4-methyl-1-pentene, or copolymers of one of the above monomers and other α-olefins. Among these, it has been shown that the effect of the present invention is remarkable on medium- and high-density polyethylene and polypropylene. In addition, ethylene-vinyl acetate copolymer is shown.
しかしながら、該公報には、エチレン−アクリル酸エス
テル共重合体およびエチレン−メタクリル酸エステル共
重合体についての開示は無い。However, this publication does not disclose ethylene-acrylic ester copolymers and ethylene-methacrylic ester copolymers.
Ｃ０ＩＩが ° しよ“ る
この様な実情に鑑み、本発明者等は工業的共押し出し時
の接着性樹脂の必要特性の考察に基づき、接着性樹脂の
諸物性と共押し出し接着性、成型性との関係を鋭意検討
し、工業的に共押し出しを行なった時にも良好な共押し
出し接着性および良好な外観を有する積層体を得んとす
るものである。In view of the fact that C0II is increasing, the present inventors have developed various physical properties of adhesive resin, coextrusion adhesion, and moldability based on consideration of the necessary characteristics of adhesive resin during industrial coextrusion. The aim is to obtain a laminate that has good coextrusion adhesiveness and good appearance even when coextruded industrially.
Ｄ、 ′ るための
本発明はエチレン性不飽和カルボン酸もしくは該カルボ
ン酸無水物をグラフトしたエチレン−アクリル酸エステ
ルもしくはメタクリル酸エステル共重合体にエチレン性
不飽和カルボン酸もしくは該カルボン酸無水物成分に対
し０．０２〜０．６当量の周期律表第Ｉａもしくは１１
ａ族の金属の水酸化物を配合するか、または該金属水
酸化物とエチレン−アクリル酸エステルもしくはメタク
リル酸エステル共重合体を配合した接着性樹脂組成物お
よび該接着性樹脂組成物を介してガスバリヤ−性樹脂と
疎水性熱可塑性樹脂を積層した積層体である。D. The present invention for the purpose of 0.02 to 0.6 equivalents of periodic table Ia or 11
Through an adhesive resin composition containing a hydroxide of a group A metal, or a blend of the metal hydroxide and an ethylene-acrylic ester or methacrylic ester copolymer, and the adhesive resin composition. This is a laminate made of a gas barrier resin and a hydrophobic thermoplastic resin.
本発明の目的とするところは良好な層間接着性と良好な
成形性とを有する接着性樹脂組成物を提供し、かつ飽和
ポリエステル系樹脂、ポリカーボネート等の疎水性熱可
塑性樹脂の優れた力学特性とエチレン−酢酸ビニル共重
合体けん化物樹脂などのすぐれたガスバリヤ−性をあわ
せて持ち、食品容器、包装材料として優れた積層体を工
業的に得ることである。The purpose of the present invention is to provide an adhesive resin composition having good interlayer adhesion and good moldability, and which also has excellent mechanical properties of hydrophobic thermoplastic resins such as saturated polyester resins and polycarbonate. The object of the present invention is to industrially obtain a laminate made of a saponified ethylene-vinyl acetate copolymer resin that also has excellent gas barrier properties and is excellent as a food container or packaging material.
旦−且里亘羞呈
本発明によれば特定組成の変性エチレン−アクリル酸エ
ステルもしくはメタクリル酸エステル共重合体に周期律
表第ＩａもしくはＩＩ ａ族金属の水酸化物を特定範囲
だけ配合する事により共押出接着性樹脂に要求きれる接
着性と成形性の両方の性能を満足せしめることができる
。According to the present invention, a hydroxide of a metal of Group Ia or IIa of the Periodic Table is blended in a specific range into a modified ethylene-acrylic ester or methacrylic ester copolymer having a specific composition. This makes it possible to satisfy both the adhesion and moldability properties required of a coextruded adhesive resin.
その理由は明確ではないが、周期律表第ＩａもしくはＩ
Ｉ ａ族の金属の水酸化物を特定範囲だけ配合する事に
より、共押し出し成形工程において、特に溶融時におけ
る接着性樹脂組成物層と疎水性熱可塑性樹脂層の界面お
よび／もしくは接着性樹脂組成物層とガスバリヤ−性樹
脂層の界面での界面化学的相互作用、化学反応等が関係
しているのではないかと考えられる。The reason is not clear, but periodic table Ia or I
By blending the hydroxide of Group Ia metal in a specific range, the interface between the adhesive resin composition layer and the hydrophobic thermoplastic resin layer and/or the adhesive resin composition can be improved during the coextrusion molding process, especially during melting. It is thought that interfacial chemical interaction, chemical reaction, etc. at the interface between the material layer and the gas barrier resin layer are involved.
この事は、アクリル酸エステル、酢酸ビニル、メタクリ
ル酸エステル等のカルボキシル基含有モノマーとエチレ
ンの共重合体にエチレン性不飽和カルボン酸もしくは該
カルボン酸無水物を化学的に結合せしめた変性エチレン
−カルボキシル基含有モノマー共重合体あるいは該共重
合体に金属酸化物もしくは炭酸塩を反応せしめた金属結
合変性共重合体がエチレン−酢酸ビニル共重合体けん化
物樹脂とか飽和ポリエステル系樹脂等と接着性を示すと
８う公知技術、さらには金属イオンにより固体状態を改
善すると言う公知技術からは全く予想ｔこに出来ない事
であり、驚くべきである。This means that a modified ethylene-carboxylic acid is produced by chemically bonding an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride to a copolymer of ethylene and a carboxyl group-containing monomer such as acrylic acid ester, vinyl acetate, or methacrylic acid ester. A group-containing monomer copolymer or a metal bond-modified copolymer obtained by reacting the copolymer with a metal oxide or carbonate exhibits adhesive properties with saponified ethylene-vinyl acetate copolymer resin, saturated polyester resin, etc. This is surprising because it was completely unexpected based on the well-known technology that improves the solid state using metal ions.
Ｆ、 のよ な一
本発明に用いられるエチレン−アクリル酸エステル共重
合体としては、例えばエチレン−アクリル酸メチルエス
テル共重合体、エチレン−アクリル酸エチルエステル共
重合体、エチレン−アクリル酸ブチルエステル共重合体
、エチレン−アクリル酸ｎ−ヘキシルエステル共重合体
、エチレン−アクリル酸２メチル−ヘキシルエステル共
重合体等があるが、中でもエチレン−アクリル酸エチル
エステル共重合体が好適に用いられる。アクリル酸エス
テル成分の含有率は５〜４５重量％が好ましいが、中で
も接着性、成形性の面で１０〜３０重量％がきらに好適
である。エチレン−アクリル酸エステル共重合体は任意
の公知の方法で作られるもので、ＭＩが０．０１〜５０
ｇ ／ １０分の範囲で、密度が０．９２〜０．９７
ｇ／ａｍ３のものが通常使用される。Examples of the ethylene-acrylic ester copolymer used in the present invention include ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-butyl acrylate copolymer. Among them, ethylene-ethyl acrylate copolymer is preferably used. The content of the acrylic acid ester component is preferably 5 to 45% by weight, and 10 to 30% by weight is especially suitable for Kira in terms of adhesiveness and moldability. The ethylene-acrylic acid ester copolymer can be made by any known method and has an MI of 0.01 to 50.
g/10 min range, density 0.92-0.97
g/am3 is usually used.
エチレン−メタクリル酸エステル共重合体としては、例
えばエチレン−メタクリル酸メチルエステル共重合体、
エチレン−メタクリル酸エチルエステル共重合体、エチ
レン−メタクリル酸ブチルエステル共重合体、エチレン
−メタクリル酸ｎ−ヘキシルエステル共重合体、エチレ
ン−メタクリル酸２メチル−ヘキシルエステル共重合体
等がある。メタクリル酸エステル成分の含有率は５〜４
５重量％が好ましいが、中でも接着性、成形性の面で１
０〜３５重量％がきらに好適である。エチレン−メタク
リル酸エステル共重合体は任意の公知の方法で作られる
もので、ＭＩが０．０１〜５０ｇ／１０分の範囲で、密
度が０．９２〜０．９７ｇ／ｃｍ３のものが通常使用き
れる。Examples of the ethylene-methacrylic acid ester copolymer include ethylene-methacrylic acid methyl ester copolymer,
Examples include ethylene-ethyl methacrylate ester copolymer, ethylene-butyl methacrylate ester copolymer, ethylene-n-hexyl methacrylate ester copolymer, and ethylene-dimethyl methacrylate-hexyl ester copolymer. The content of methacrylic acid ester component is 5 to 4
5% by weight is preferable, but 1% by weight is preferred in terms of adhesiveness and moldability.
0 to 35% by weight is suitable for Kira. The ethylene-methacrylic acid ester copolymer can be made by any known method, and those with an MI of 0.01 to 50 g/10 min and a density of 0.92 to 0.97 g/cm3 are usually used. I can do it.
グラフトに用いられるエチレン性不飽和カルボン酸もし
くは該カルボン酸無水物としてはマレイン酸、アクリル
酸、イタコン酸、クロトン酸、無水マレイン酸、無水イ
タコン酸等のエチレン性不飽和カルボン酸もしくは該カ
ルボン酸無水物等があるが、中でも無水マレイン酸が好
適である。グラフト量は０．０１〜６重量％で良いが、
中でも０．１〜５重量％が接着性、成形性の面で更に好
適である。Ethylenically unsaturated carboxylic acids or carboxylic acid anhydrides used for grafting include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride, and the like. Among them, maleic anhydride is preferred. The amount of grafting may be 0.01 to 6% by weight, but
Among these, 0.1 to 5% by weight is more preferable in terms of adhesiveness and moldability.
グラフトの方法に特に制限は無いが、エチレン−アクリ
ル酸エステル共重合体にエチレン性不飽和カルボン酸も
しくは該カルボン酸無水物と、ジベンゾイルパーオキサ
イド、ジブチルパーオキサイド、ジクミルパーオキサイ
ド、ｔ−ブチルパーベンゾエイト、ｔ−ブチルヒドロパ
ーオキサイド、クメンヒドロパーオキサイド等の有機過
酸化物とを共存させて、両者に化学的結合が生じるよう
に加熱反応させる方法があげられる。反応は例えばベン
ゼン、トルエン、キシレン、クロルベンゼン、ｔ−ブチ
ルベンゼン、クメン等の溶媒の存在下もしくは無存在下
に１００〜２４０℃の温度で行なう事が出来るが、トル
エンとかキシレン等の溶媒の存在下に１１０〜１９０℃
で行なうほうが均一な製品が得られるのでより好適であ
る。There are no particular limitations on the grafting method, but ethylene-acrylic acid ester copolymer, ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride, and dibenzoyl peroxide, dibutyl peroxide, dicumyl peroxide, t-butyl An example is a method in which an organic peroxide such as perbenzoate, t-butyl hydroperoxide, or cumene hydroperoxide is allowed to coexist and a heating reaction is carried out so that a chemical bond is formed between the two. The reaction can be carried out at a temperature of 100 to 240°C in the presence or absence of a solvent such as benzene, toluene, xylene, chlorobenzene, t-butylbenzene, cumene, etc., but the presence of a solvent such as toluene or xylene is Below 110-190℃
It is more preferable to do this because a uniform product can be obtained.
周期律表第ＩａもしくはＩＩ ａ族の金属の水酸化物と
しては、水酸化リチウム、水酸化ナトリウム、水酸化カ
リウム、水酸化カルシウム、水酸化マグネシウム等があ
るが、中でも水酸化ナトリウムが好適に用いられる。周
期律表第ＩａもしくはＩＩ ａ族の金属の水酸化物の配
合量は該金属水酸化物の種類にもよるが、グラフトした
エチレン性不飽和カルボン酸もしくは該カルボン酸無水
物に対し０．０２〜０．６当量であるが、より好ましく
は０．０３〜０．３当量である。０．０２当量未満であ
ると成形体の全体に波状の模様ができるとか、凹凸がで
きるなど本発明の目的とする工業的に有用な成形体は得
られない。０．６当墓を越えて配合すると接着性樹脂組
成物が着色するとか、流動性が不良となり、成形材料と
しては不適当な物となり好ましくない。Hydroxides of metals in group Ia or group IIa of the periodic table include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, etc. Among them, sodium hydroxide is preferably used. It will be done. The amount of the hydroxide of a metal in group Ia or IIa of the periodic table depends on the type of metal hydroxide, but is 0.02% based on the grafted ethylenically unsaturated carboxylic acid or carboxylic acid anhydride. -0.6 equivalent, more preferably 0.03-0.3 equivalent. If the amount is less than 0.02 equivalent, a wavy pattern or unevenness will be formed on the entire molded product, and the industrially useful molded product that is the object of the present invention cannot be obtained. If the amount exceeds 0.6, the adhesive resin composition will be colored or have poor fluidity, making it unsuitable as a molding material.
本発明においてエチレン性不飽和カルボン酸もしくは該
カルボン酸無水物をグラフトしたエチレン−アクリル酸
エステルもしくはメタクリル酸エステル共重合体にエチ
レン性不飽和カルボン酸もしくは該カルボン酸無水物成
分に対し０．０２〜０．６当量の周期律表第Ｉａもしく
はＩＩ ａ族の金属の水酸化物を配合した接着性樹脂組
成物はそのままで好適に使用出来るが、場合によっては
該金属水酸化物配合接着性樹脂組成物とエチレン−アク
リル酸エステルもしくはメタクリル酸エステル共重合体
とをブレンドして使用することができる。その場合、該
金属水酸化物配合接着性樹脂組成物の配合割合は該金属
水酸化物配合接着性樹脂組成物の特性にもよるが、全組
成物に対し１〜６０％で良いが、２〜４０％が製造価格
、成形性等の面でさらに好適な場合が多い。In the present invention, the ethylene-acrylic ester or methacrylic ester copolymer grafted with the ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride is 0.02 to 0.02 to An adhesive resin composition containing 0.6 equivalent of a hydroxide of a metal in group Ia or IIa of the periodic table can be suitably used as is, but in some cases, an adhesive resin composition containing the metal hydroxide may be used. It is possible to use a blend of the compound and the ethylene-acrylic acid ester or methacrylic acid ester copolymer. In that case, the proportion of the metal hydroxide-containing adhesive resin composition may be 1 to 60% of the total composition, depending on the characteristics of the metal hydroxide-containing adhesive resin composition, but ~40% is often more preferable in terms of manufacturing cost, moldability, etc.
本発明の接着性樹脂組成物に対しては熱可塑性樹脂に慣
用される他の添加剤を配合することができる。このよう
な添加剤の例としては、酸化防止剤、紫外線吸収剤、可
塑剤、帯電防止剤、滑剤、充填剤を挙げる事ができ、こ
れらを本発明の作用効果が阻害されない範囲内でブレン
ドすることができる。添加剤の具体的な例としては次の
様なものが挙げられる。酸化防止剤＝２．５−ジーｔ−
ブチルハイドロキノン、２．６−ジーｔ−ブチルーｐ−
クレゾール、４，４°−チオビス−（６−ｔ−ブチルフ
ェノール、２．２′メチレン−ビス（４−メチル−６−
ｔ−ブチルフェノール、テトラキス−［メチレン−３−
（３′、５゛−ジ−ｔ−ブチル−４°−ヒドロキシフェ
ニル）プロピオネートコメタン、オクタデシル−３−（
３°、５−ジ−ｔ−ブチル−４′−ヒドロキシフェニル
）プロピオネート、４，４′−チオビス−（６−ｔ−ブ
チルフェノール）等。 紫外線吸収剤：エチル−２−シ
アノ−３，３−ジフェニルアクリレート、２− （２°
−ヒドロキシ−５゛−メチルフェニル）−５−クロロベ
ンゾトリアゾール、２−（２°ヒドロキシ−３°−ｔ−
ブチル−５°−メチルフェニル）−５−クロロベンゾト
リアゾール、２−ヒドロキシ−４−メトキシベンゾフェ
ノン、２．２°−ジヒドロキシ−４−メトキシベンゾフ
ェノン、２−ヒドロキシ−４−オクトキシベンゾフェノ
ン等。 可塑剤：フタル酸ジメチル、フタル酸ジエチル
、フタル酸ジオクチル、ワックス、流動パラフィン、リ
ン酸エステル等。 帯電防止剤：ペンタエリスリットモ
ノステアレート、ソルビタンモノパルミテート、硫酸化
オレイン酸、ポリエチレンオキシド、カーボワックス等
。 滑剤：エチレンビスステアロアミド、ブチルステア
レート等。 着色剤：カーボンブラック、フタロシアニ
ン、キナクリドン、インドリン、アゾ系顔料、酸化チタ
ン、ベンガラ等。 充填剤ニゲラスファイバー、アスベ
スト、マイカ、バラストナイト、ケイ酸アルミニウム等
。Other additives commonly used in thermoplastic resins can be added to the adhesive resin composition of the present invention. 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-Gt-
Butylhydroquinone, 2,6-di-t-butyl-p-
Cresol, 4,4°-thiobis-(6-t-butylphenol, 2,2'methylene-bis(4-methyl-6-
t-Butylphenol, tetrakis-[methylene-3-
(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate comethane, octadecyl-3-(
3°, 5-di-t-butyl-4'-hydroxyphenyl)propionate, 4,4'-thiobis-(6-t-butylphenol), and the like. UV absorber: ethyl-2-cyano-3,3-diphenylacrylate, 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, and the like. Plasticizer: dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, phosphate ester, etc. Antistatic agents: pentaerythritol monostearate, sorbitan monopalmitate, sulfated oleic acid, polyethylene oxide, carbowax, etc. Lubricants: ethylene bisstearamide, butyl stearate, etc. Coloring agents: carbon black, phthalocyanine, quinacridone, indoline, azo pigments, titanium oxide, red iron oxide, etc. Fillers Nigellas fiber, asbestos, mica, ballastonite, aluminum silicate, etc.
本発明の接着性樹脂組成物を得るための各成分の配合手
段としては、リボンブレンダー、高速ミキサー、ニーダ
−、ミキシングロール、バンバリーミキサ−１押し出し
機等が例示きれる。Examples of means for blending each component to obtain the adhesive resin composition of the present invention include a ribbon blender, high-speed mixer, kneader, mixing roll, and Banbury mixer 1 extruder.
この様にして得られた接着性樹脂組成物のＭＩＬＩＩＳ
Ｋ−６７６０，１９０℃、２１６０ｇ）は成形にお
いて用いられる疎水性熱可塑性樹脂とガスバリヤ−他樹
脂のＭＩにもよるが、０゜２〜５０ ｇ ／ １０分が
用いられるが、中でも０゜５〜３０が好適に用いられる
。MILIIS of the adhesive resin composition obtained in this way
K-6760, 190℃, 2160g) is used at 0°2 to 50 g/10 minutes, depending on the MI of the hydrophobic thermoplastic resin and gas barrier used in molding and other resins, but especially 0°5 to 50 g/10 minutes. 30 is preferably used.
次に本発明の積層体において用いられるガスバリヤ−他
樹脂としては、エチレン−酢酸ビニル共重合体けん化物
樹脂、６ナイロン、６−６ナイロン、６−１２ナイロン
等のポリアミド樹脂等があるが、中でもエチレン成分含
有率２０〜５５モル％、けん化度９０％以上のエチレン
−酢酸ビニル共重合体けん化物樹脂が成形性、ガスバリ
ヤ−性の面で好適に用いられる。ざらにホウ酸、ホウ砂
等のホウ素化合物で処理した該エチレンー酢酸ビニル共
重合体けん化物樹脂、共重合可能な第三成分をエチレン
および酢酸ビニルとともに共重合し、けん化して得られ
る変性樹脂についても溶融成形性があり、ガスバリヤ−
他樹脂としての諸物性を害しない範囲のものであれば本
発明の効果を享受することができる。Next, gas barrier and other resins used in the laminate of the present invention include saponified ethylene-vinyl acetate copolymer resins, polyamide resins such as nylon 6, 6-6 nylon, and 6-12 nylon, among others. A saponified ethylene-vinyl acetate copolymer resin having an ethylene component content of 20 to 55 mol% and a saponification degree of 90% or more is preferably used in terms of moldability and gas barrier properties. About the saponified ethylene-vinyl acetate copolymer resin treated with a boron compound such as boric acid or borax, and the modified resin obtained by copolymerizing a copolymerizable third component with ethylene and vinyl acetate and saponifying it. It also has melt moldability and is a gas barrier.
The effects of the present invention can be enjoyed as long as it does not impair the physical properties of other resins.
疎水性熱可塑性樹脂としては加熱溶融成形可能な樹脂な
らばいずれも使用できるが、好適には飽和ポリエステル
、ポリカーボネート、塩化ビニル、ポリスチレン、耐衝
撃性ポリスチレン、ポリエチレン、ポリプロピレン、エ
チレン−酢酸ビニル共重合体、エチレン−アクリル酸エ
ステル共重合体等があるが、中でも飽和ポリエステル、
ポリカーボネートがざらに好適に用いられる。またガス
バリヤ−他樹脂としてエチレン−酢酸ビニル共重合体け
ん化物樹脂を用いるときは、６ナイロン、６−６ナイロ
ン、６−１２ナイロン等のポリアミド樹脂を疎水性熱可
塑性樹脂として用いる事もできる。As the hydrophobic thermoplastic resin, any resin that can be heat-melted and molded can be used, but preferably saturated polyester, polycarbonate, vinyl chloride, polystyrene, high-impact polystyrene, polyethylene, polypropylene, and ethylene-vinyl acetate copolymer. , ethylene-acrylic acid ester copolymers, among others, saturated polyester,
Polycarbonate is preferably used. When a saponified ethylene-vinyl acetate copolymer resin is used as the gas barrier resin, polyamide resins such as nylon 6, 6-6 nylon, and 6-12 nylon can also be used as the hydrophobic thermoplastic resin.
飽和ポリエステルとはジカルボン酸とジオール成分とが
縮重合きれたものである。ジカルボン酸としては例えば
テレフタール酸、イソフタール酸、ナフタレンジカルボ
ン酸等の一種または二種以上を用いることができる。ざ
らに少量成分としてアジピン酸、セバシン酸等を混合し
て用いる事もできる。ジオール成分としてはエチレング
リコール、ブチレングリコール、ヘキシレングリコール
、シクロヘキサンジメタツールなどの一種または二種以
上を用いることができる。ざらに少量成分としてジエチ
レングリコール、ポリテトラメチレングリコール、ペン
タエリスリトール、ビスフェノール−Ａ、等を混合して
用いる事もできる。なかでもジカルボン酸成分としてテ
レフタール酸成分を７０モル％以上用いるときが成形物
の透明性、力学性能等の諸物性が良好であり、更に好適
である。これら飽和ポリエステルの重合度は特に制限は
無いが、フェノール／テトラクロルエタン＝５０１５０
混合溶液で３０℃で測定した［７７１ （ｄｉ／ｇ）
が０．３〜２．０が用いられる。A saturated polyester is a product obtained by polycondensation of a dicarboxylic acid and a diol component. As the dicarboxylic acid, for example, one or more of terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, etc. can be used. It is also possible to mix and use adipic acid, sebacic acid, etc. as a small amount component. As the diol component, one or more of ethylene glycol, butylene glycol, hexylene glycol, cyclohexane dimetatool, etc. can be used. It is also possible to mix and use diethylene glycol, polytetramethylene glycol, pentaerythritol, bisphenol-A, etc. as minor components. Among these, it is more preferable to use 70 mol % or more of the terephthalic acid component as the dicarboxylic acid component, since the molded product has good physical properties such as transparency and mechanical performance. The degree of polymerization of these saturated polyesters is not particularly limited, but phenol/tetrachloroethane = 50150
[771 (di/g) measured in a mixed solution at 30°C
0.3 to 2.0 is used.
ポリカーボネートとしては、芳香族ポリカーボネートが
好ましく、該ポリカーボネートとしてはジヒドロキシア
リール化合物とホスゲンあるいはジフェニルカーボネー
ト等と反応きせた重合体または共重合体である。上記ジ
ヒドロキシアリール化合物としてはビスフェノールＡ１
ビス（４−ヒドロキシフェニル）メタン、１．１−ビス
（４−ヒドロキシフェニル）エタン、２．２−ビス（４
−ヒドロキシフェニル）ブタン、ビス（４−ヒドロキシ
フェニル）フェニルメタン、２．２−ビス（４−ヒドロ
キシフェニル）シクロペンタン、１，１−ビス（４−ヒ
ドロキシフェニル）シクロヘキサン、４．４°−ヒドロ
キシジフェニルエーテル、４，４°−ジヒドロキシフェ
ニルスルフィド、４，４°−ジヒドロキシジフェニルス
ルホキシド、４．４’−ジヒドロキシジフェニルスルホ
ン等があげられる。これらは単独または数種混合した使
用されるが、これらの他にハイドロキノン、レゾルシン
、４．４°−ジヒドロキシフェニル等を適宜混合して重
合してもよい。The polycarbonate is preferably an aromatic polycarbonate, and the polycarbonate is a polymer or copolymer obtained by reacting a dihydroxyaryl compound with phosgene, diphenyl carbonate, or the like. As the dihydroxyaryl compound, bisphenol A1
Bis(4-hydroxyphenyl)methane, 1.1-bis(4-hydroxyphenyl)ethane, 2.2-bis(4
-hydroxyphenyl)butane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4.4°-hydroxydiphenyl ether , 4,4°-dihydroxyphenyl sulfide, 4,4°-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, and the like. These may be used alone or in combination, but in addition to these, hydroquinone, resorcinol, 4.4°-dihydroxyphenyl, etc. may be appropriately mixed and polymerized.
これらのポリカーボネートのうち代表的なものは、ビス
フェノールＡとホスゲンの反応により得られた重合体で
あり、塩化メチレンを溶媒として２０ ｔｌｔ’測定し
た［ｎｌ （ｄ １／ｇ） が０．１〜１が用いられ
る。Typical of these polycarbonates is a polymer obtained by the reaction of bisphenol A and phosgene, which was measured at 20 tlt' using methylene chloride as a solvent [nl (d 1/g) of 0.1 to 1]. is used.
本発明でガスバリヤ−性樹脂と疎水性熱可塑性樹脂を接
着性樹脂組成物を介して積層した積層体の構成としては
、Ａ／Ｂ／Ｃの三種三層の構成Ａ／Ｂ／Ｃ／Ｂ／Ａ、Ｃ
／Ｂ／Ａ／Ｂ／Ｃ，Ａ／Ｂ／Ｃ／Ｂ／Ａ ’ 、Ｃ／Ｂ
／Ａ／Ｂ／Ｃ’ （但しＡ、Ａ’はガスバリヤ−性樹
脂、Ｂは接着性樹脂組成物、Ｃ，Ｃ’は疎水性熱可塑性
樹脂）の対称もしくは非対称の三種五層の構成とか、更
にＡ。In the present invention, the structure of the laminate in which a gas barrier resin and a hydrophobic thermoplastic resin are laminated via an adhesive resin composition includes three types of three layers A/B/C/B/B/C. A, C
/B/A/B/C, A/B/C/B/A', C/B
/A/B/C' (where A and A' are gas barrier resins, B is adhesive resin composition, and C and C' are hydrophobic thermoplastic resins), symmetrical or asymmetric three-type five-layer structure, More A.
Ｂ、Ｃのそれぞれを多層にして多種多層の構成がある。There are various types of multilayer configurations in which each of B and C is multilayered.
積層体を得る方法としては、ダイ内ラミネート法、ダイ
外うミネート法プレスによる熱圧着等の方法があるが、
ダイ内ラミネート法において最も好適に適用できる。ま
たＴダイ法、リングダイ法による押し出し成形法におい
て最も好適に適用できるものであるが、ざらにダイレク
トブロー成形法、インジェクションブロー成形法等にも
好適に適用できる。この様にして得られた積層体はすぐ
れたガスバリヤ−性とすぐれた力学特性をあわせて持ち
、食品容器（カップ、ボトル）、包装材料として有用な
物である。さらにこの様にして得られた積層体は一軸あ
るいは二軸延伸、深絞り、ブロー成形等の工程を経る事
によって、より有用な物とする事ができる。また本発明
で得られた積層体を更に合成樹脂フィルム、金属、紙等
とラミネートすることも出来る。Methods for obtaining a laminate include in-die lamination, out-of-die lamination, thermocompression bonding using a press, etc.
It can be most suitably applied to the in-die lamination method. Moreover, although it is most suitably applicable to extrusion molding methods using the T-die method and ring die method, it is also suitably applicable to rough direct blow molding methods, injection blow molding methods, and the like. The laminate thus obtained has both excellent gas barrier properties and excellent mechanical properties, and is useful as food containers (cups, bottles) and packaging materials. Furthermore, the laminate thus obtained can be made more useful by undergoing processes such as uniaxial or biaxial stretching, deep drawing, and blow molding. Further, the laminate obtained in the present invention can be further laminated with a synthetic resin film, metal, paper, etc.
以下、実施例をもって更に詳しく本発明を説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
Ｕ匠
実施例１〜４
アクリル酸エチルエステル成分の含有率が２５重量％、
ＭＩ （１９０℃、２１６０ｇ）が６．３ｇ７１０分、
密度が０．９３６ｇ／ｃｍ３、融点が７０℃であるエチ
レン−アクリル酸エチルエステル共重合体２１５重量部
及び無水マレイン酸１．８重量部を精製トルエン６４８
重量部に溶解し、１８０℃に保った。このｉｌＦ液に漫
拌下に無水マレイン酸の５重量部を溶解した精製トルエ
ン溶液１８０重量部を２．０時間で連続的に添加した。U Takumi Examples 1 to 4 The content of the acrylic acid ethyl ester component was 25% by weight,
MI (190℃, 2160g) is 6.3g 710 minutes,
215 parts by weight of ethylene-acrylic acid ethyl ester copolymer having a density of 0.936 g/cm3 and a melting point of 70°C and 1.8 parts by weight of maleic anhydride were mixed with 648 parts by weight of purified toluene.
It was dissolved in parts by weight and kept at 180°C. 180 parts by weight of a purified toluene solution in which 5 parts by weight of maleic anhydride was dissolved were continuously added to this IF solution over 2.0 hours while stirring.
それと同時にクメンヒドロパーオキサイド１．０重量部
を溶解した精製トルエン溶１１！１００重量部を２．０
時間で連続的に添加した。添加終了後も引続き３０分の
後反応をおこなった。冷却後大量のメチルアルコール中
に反応液を投入してポリマーを析出きせた。得られたポ
リマーを精製トルエンを溶剤とし、メチルアルコールを
非溶剤として再沈精製を行なった。このものは無水マレ
イン酸成分を１．５重量％含有し、ＭＩは４．３８７１
０分であった。At the same time, 1.0 parts by weight of cumene hydroperoxide was dissolved in purified toluene solution 11!100 parts by weight was added to 2.0 parts by weight.
It was added continuously over time. After the addition was completed, the reaction was continued for 30 minutes. After cooling, the reaction solution was poured into a large amount of methyl alcohol to precipitate a polymer. The obtained polymer was purified by reprecipitation using purified toluene as a solvent and methyl alcohol as a non-solvent. This product contains 1.5% by weight of maleic anhydride component and has an MI of 4.3871.
It was 0 minutes.
このようにして得られたポリマーに所定量の水酸化ナト
リウム（ＮａＯＨ）を含有する水溶液を均一に添加し、
一部乾燥後に、ベントつき押し出し機で減圧下に揮発物
を追い出しながら溶融混練ベレット化し、変性共重合体
からなる接着性樹脂組成物を得た。An aqueous solution containing a predetermined amount of sodium hydroxide (NaOH) is uniformly added to the thus obtained polymer,
After partially drying, the mixture was melt-kneaded into pellets while expelling volatile matter under reduced pressure using a vented extruder to obtain an adhesive resin composition comprising a modified copolymer.
上記に得た変性共重合接着***樹脂組成物の所定量を上
記のエチレン−アクリル酸エチルエステル共重合体とト
ライブレンドし、次いで押し出し機で溶融混練ペレット
化し、接着性樹脂ブレンド組成物を得た。A predetermined amount of the modified copolymer adhesive adhesive resin composition obtained above was triblended with the above ethylene-acrylic acid ethyl ester copolymer, and then melt-kneaded into pellets using an extruder to obtain an adhesive resin blend composition. .
酢酸ビニル成分の含有率が６７モル％であるエチレン−
酢酸ビニル共重合体の酢酸ビニル成分の９９．６％をけ
ん化する事によって得た［ｎ］＝１．１１ （フェノ
ール／水＝８５／１５混合溶液中、３０℃、ｄｌ／ｇ）
のエチレン−酢酸ビニル共重合体けん化物樹脂をガスバ
リヤ−性樹脂とし、ジカルボン酸成分としてテレフター
ル酸を用い、ジオール成分としてエチレングリコールを
用いて縮重合して得られた［ｎ］ ＝０．６７ （フェ
ノール／テトラクロルエタン＝ ５０１５０−合溶液中
、３０℃、ｄｉ／ｇ）の飽和ポリエステルを疎水性熱可
塑性樹脂としてつぎのような方法で積層体を得た。Ethylene containing 67 mol% of vinyl acetate component
Obtained by saponifying 99.6% of the vinyl acetate component of vinyl acetate copolymer [n] = 1.11 (in phenol/water = 85/15 mixed solution, 30°C, dl/g)
[n] = 0.67 (obtained by condensation polymerization using a saponified ethylene-vinyl acetate copolymer resin as a gas barrier resin, terephthalic acid as a dicarboxylic acid component, and ethylene glycol as a diol component) A laminate was obtained in the following method using a saturated polyester (di/g) as a hydrophobic thermoplastic resin in a mixed solution of phenol/tetrachloroethane=50150 at 30°C.
内径１２０ｍｍΦの押し出し機１１内径６０ｍｍΦの押
し出し機１１、内径９０ｍｍΦの押し出し機１１１を備
え、押し出し機１１１１にあっては溶融材料が各々二層
に分岐後、押し出し機１１１より溶融押し出しされた樹
脂層に押し出し機＋１よりの樹脂、押し出し機Ｉよりの
樹脂と順次合流されるタイプのフィードブロック式の三
種五層共押し出し装置を用い、押し出し機Ｉには（Ｃ）
疎水性熱化塑性樹脂を、押し出し機ＩＩには（Ｂ）接着
性樹脂組成物を、押し出し機■には（Ａ）ガスバリヤ−
性樹脂を供給し、ダイ温度２６０℃、引取り速度４ｍ／
分で共押し出しを行ない、Ｃ／Ｂ／Ａ／Ｂ／Ｃ（４００
ｕ ／ ５０ ｕ ／ ５０ ｕ ／ ５０ ａ ／
４００μ）の三種五層のシートを作成し、次いで赤外線
で加熱するタイプの真空圧空成形機を用いて絞り比＝１
．１の型枠で深絞りを行ない、得られたカップの外観及
び剥離強度を測定した。An extruder 11 with an inner diameter of 120 mmΦ, an extruder 11 with an inner diameter of 90 mmΦ, and an extruder 111 with an inner diameter of 90 mmΦ.In the extruder 1111, the molten material is divided into two layers, and then transferred to the resin layer melted and extruded by the extruder 111. A feed block type three-type, five-layer co-extrusion device is used in which the resin from extruder +1 and the resin from extruder I are sequentially combined, and extruder I is (C).
A hydrophobic thermoplastic resin was placed in extruder II, (B) an adhesive resin composition was placed in extruder II, and (A) a gas barrier was placed in extruder II.
supply resin, die temperature 260℃, take-off speed 4m/
Perform coextrusion in minutes, C/B/A/B/C (400
u / 50 u / 50 u / 50 a /
A sheet of three types and five layers of 400μ) was created, and then a drawing ratio of 1 was created using a vacuum-pressure forming machine that heats with infrared rays.
．． Deep drawing was performed using the mold No. 1, and the appearance and peel strength of the resulting cup were measured.
グラフトした無水マレイン酸に対してＮａＯＨを０．０
５当量添加した実施例１および実施例２は良好な外観の
成形物が得られ、また充分な接着力を有していた。また
ＮａＯＨを０．１当量添加した実施例３および実施例４
は極めて良好な外観の成形物が充分な接着力で得られた
。な、おブレンド組成物中の変性共重合接着性樹脂組成
物含有率が２０％であっても変性共重合接着性樹脂組単
独の時とくらべて剥離強度が殆ど低下しない。結果は第
１表に示す。0.0 of NaOH to grafted maleic anhydride
In Examples 1 and 2, in which 5 equivalents were added, molded products with good appearance were obtained and had sufficient adhesive strength. Further, Example 3 and Example 4 in which 0.1 equivalent of NaOH was added
A molded product with an extremely good appearance and sufficient adhesive strength was obtained. Incidentally, even if the content of the modified copolymer adhesive resin composition in the blend composition is 20%, the peel strength hardly decreases compared to when the modified copolymer adhesive resin composition is used alone. The results are shown in Table 1.
比較例１〜４
ＮａＯＨの添加量を変更する以外は実施例１〜４と同様
にした。ＮａＯＨを添加しない比較例１および比較例２
は成形物の表面には凸凹が数多く出来ており、商品価値
の乏しいものであった。Comparative Examples 1 to 4 Comparative Examples 1 to 4 were carried out in the same manner as Examples 1 to 4 except that the amount of NaOH added was changed. Comparative Example 1 and Comparative Example 2 without adding NaOH
The molded product had many irregularities on its surface and had poor commercial value.
Ｎ ａ ＯＨを１．０当量添加すると変性共重合体が褐
色に着色しく比較例３）該変性共重合体樹脂とエチレン
−アクリル酸エチルエステル共重合体ブレンド組成物は
均一な混合が不可能であり、多くの褐色のブツがあるだ
けでなく、全体に着色しており（比較例４）商品価値の
乏しいものであり、共押し出し成形は実施しなかった。When 1.0 equivalent of NaOH was added, the modified copolymer turned brown, and Comparative Example 3) The modified copolymer resin and the ethylene-acrylic acid ethyl ester copolymer blend composition could not be uniformly mixed. In addition to having many brown spots, the product was colored throughout (Comparative Example 4) and had poor commercial value, so coextrusion molding was not performed.
結果は第１表にあわせて示す。The results are also shown in Table 1.
比較例５
変性共重合接着性樹脂を配合することなくエチレン−ア
クリル酸エチルエステル共重合体のみをＢ層樹脂として
実施例１と同様にして共押し出し成形を実施した。得ら
れた成形物は良好な外観であったが、接着力が極めて弱
く容易に剥離し、商品価値の乏しいものであった。Comparative Example 5 Coextrusion molding was carried out in the same manner as in Example 1 using only the ethylene-acrylic acid ethyl ester copolymer as the B layer resin without blending the modified copolymer adhesive resin. Although the obtained molded product had a good appearance, its adhesive strength was extremely weak and it peeled off easily, resulting in poor commercial value.
実施例５〜８
アクリル酸エチルエステル成分の含有率が３０重量％、
ＭＩが（１９０℃、２１６０ｇ）１１．２ｇ／１０分、
密度が０．９３８ｇ／ａｍ３、融点が８０℃であるエチ
レン−アクリル酸エチルエステル共重合体を用い無水マ
レイン酸およびクメンヒドロパーオキサイドの使用量を
変更しＮａＯＨを０．０８当量用いる以外は実施例１の
方法と同様にして接着性樹脂組成物を得た。Examples 5 to 8 The content of the acrylic acid ethyl ester component is 30% by weight,
MI (190℃, 2160g) 11.2g/10min,
Example except that an ethylene-acrylic acid ethyl ester copolymer having a density of 0.938 g/am3 and a melting point of 80°C was used, the amounts of maleic anhydride and cumene hydroperoxide were changed, and 0.08 equivalent of NaOH was used. An adhesive resin composition was obtained in the same manner as in Method 1.
上記に得た接着性樹脂組成物とアクリル酸エチルエステ
ル成分の含有率が３０重量％、ＭＩ（１９０℃、２１６
０ｇ）が１１．２ｇ／１０分、密度が０．９４ｇ／ａｍ
３、融点が８０℃であルエチレンーアクリル酸エチルエ
ステル共重合体と１０：９０にトライブレンドしくＢ）
層樹脂とした。The content of the adhesive resin composition obtained above and the acrylic acid ethyl ester component was 30% by weight, MI (190°C, 216°C).
0g) is 11.2g/10min, density is 0.94g/am
3. Tri-blend at 10:90 with ethylene-acrylic acid ethyl ester copolymer with a melting point of 80°C B)
It was made into a layered resin.
酢酸ビニル成分の含有率が５６モル％であるエチレン−
酢酸ビニル共重合体の酢酸ビニル成分の９９．５％をけ
ん化する事によって得た［ｎ］＝０．９６ （フェノー
ル／水＝８５／１５混合溶液中、３０℃、ｄｉ／ｇ）の
エチレン−酢酸ビニル共重合体けん化物樹脂を（Ａ）ガ
スバリヤ−性樹脂とし、ポリカーボネート（［Ｎ０ＶＡ
ＲＥＸ７０３０Ａ］三菱化成工業社製）を（Ｃ）疎水性
熱可塑性樹脂として次のような方法で積層体を得た。Ethylene containing 56 mol% of vinyl acetate component
[n] = 0.96 (phenol/water = 85/15 mixed solution, 30°C, di/g) obtained by saponifying 99.5% of the vinyl acetate component of the vinyl acetate copolymer. Saponified vinyl acetate copolymer resin was used as (A) gas barrier resin, and polycarbonate ([N0VA
REX7030A] manufactured by Mitsubishi Chemical Industries, Ltd.) was used as the hydrophobic thermoplastic resin (C) to obtain a laminate in the following manner.
内径６０ｍｍΦの押し出し機１１内径４０ｍｍΦの押し
出し機１１ 、内径９０ｍｍΦの押し出し機１１１を備
え、各押し出し機からの溶融材料がひとつのダイ内で各
々のマニホールによって広げられた後、当該ダイ内で合
流し多層化されるタイプのフラットダイ式の三種三層共
押し出し装置を用い、押し出し機■には（Ｃ）疎水性熱
化塑性樹脂を、押し出し機＋Ｉには（Ｂ）接着性樹脂組
成物を、押し出し機Ｉ１１には（Ａ）ガスバリヤ−性樹
脂を供給し、引取り速度４ｍ／分で共押し出しを行ない
、Ｃ／ Ｂ ／ Ａ （２００ｕ ／ ５０ ｕ ／
５０ ｕ ）の三層構成のシートを作成した。得られた
シートのは良好な外観であり、剥離強度を測定したとこ
ろ、いずれも十分な接着力であった。An extruder 11 with an inner diameter of 60 mmΦ, an extruder 111 with an inner diameter of 90 mmΦ, and the molten material from each extruder is spread by each manihole in one die and then merged in the die. Using a multi-layer type flat die type three-layer co-extrusion device, (C) a hydrophobic thermoplastic resin was placed in the extruder ■, (B) an adhesive resin composition was placed in the extruder +I, (A) gas barrier resin was supplied to the extruder I11, and co-extrusion was performed at a take-up speed of 4 m/min, resulting in C/B/A (200u/50u/
A sheet with a three-layer structure of 50 u) was prepared. The obtained sheets had a good appearance, and when their peel strength was measured, they all had sufficient adhesive strength.
比較例６〜９
ＮａＯＨの添加量を変更する以外は実施例５〜６と同様
にした。ＮａＯＨを添加しない比較例６および比較例７
は成形物の表面には凸凹が数多く出来ており、商品価値
の乏しいものであった。Comparative Examples 6-9 The same procedures as Examples 5-6 were carried out except that the amount of NaOH added was changed. Comparative Example 6 and Comparative Example 7 without adding NaOH
The molded product had many irregularities on its surface and had poor commercial value.
Claims (12)
酸無水物をグラフトしたエチレン−アクリル酸エステル
もしくはメタクリル酸エステル共重合体にエチレン性不
飽和カルボン酸もしくは該カルボン酸無水物成分に対し
０．０２〜０．６当量の周期律表第 I ａもしくはIIａ
族の金属の水酸化物を配合するか、または該金属水酸化
物とエチレン−アクリル酸エステルもしくはメタクリル
酸エステル共重合体を配合した接着性樹脂組成物。(1) Ethylene-acrylic ester or methacrylic ester copolymer grafted with ethylenically unsaturated carboxylic acid or carboxylic acid anhydride from 0.02 to 0.02 to 0.6 equivalent periodic table Ia or IIa
An adhesive resin composition containing a hydroxide of a group metal, or containing the metal hydroxide and an ethylene-acrylic acid ester or methacrylic acid ester copolymer.
ルがアクリル酸エチルエステルである特許請求の範囲第
１項に記載の接着性樹脂組成物。(2) The adhesive resin composition according to claim 1, wherein the acrylic ester or methacrylic ester is ethyl acrylate.
酸無水物が無水マレイン酸である特許請求の範囲第１項
もしくは第２項に記載の接着性樹脂組成物。(3) The adhesive resin composition according to claim 1 or 2, wherein the ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride is maleic anhydride.
物が水酸化ナトリウムである特許請求の範囲第１〜３項
のいずれかに記載の接着性樹脂組成物。(4) The adhesive resin composition according to any one of claims 1 to 3, wherein the hydroxide of a metal in group Ia or IIa of the periodic table is sodium hydroxide.
チレン性不飽和カルボン酸もしくは該カルボン酸無水物
をグラフトしたエチレン−アクリル酸エステルもしくは
メタクリル酸エステル共重合体にエチレン性不飽和カル
ボン酸もしくは該カルボン酸無水物成分に対し０．０２
〜０．６当量の周期律表第 I ａもしくはIIａ族の金属
の水酸化物を配合するか、または該金属水酸化物とエチ
レン−アクリル酸エステルもしくはメタクリル酸エステ
ル共重合体を配合した接着性樹脂組成物を介して積層し
た積層体。(5) A gas barrier resin and a hydrophobic thermoplastic resin are combined with an ethylene-acrylic ester or methacrylic ester copolymer grafted with an ethylenically unsaturated carboxylic acid or an ethylenically unsaturated carboxylic acid anhydride. 0.02 for the carboxylic anhydride component
Adhesive properties in which ~0.6 equivalent of a hydroxide of a metal in group Ia or IIa of the periodic table is blended, or the metal hydroxide is blended with an ethylene-acrylic acid ester or methacrylic acid ester copolymer. A laminate that is laminated with a resin composition interposed therebetween.
ルがアクリル酸エチルエステルである特許請求の範囲第
５項に記載の積層体。(6) The laminate according to claim 5, wherein the acrylic ester or methacrylic ester is ethyl acrylate.
酸無水物が無水マレイン酸である特許請求の範囲第５項
もしくは第６項に記載の積層体。(7) The laminate according to claim 5 or 6, wherein the ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride is maleic anhydride.
物が水酸化ナトリウムである特許請求の範囲第５〜７項
のいずれかに記載の積層体。(8) The laminate according to any one of claims 5 to 7, wherein the hydroxide of a metal of group Ia or IIa of the periodic table is sodium hydroxide.
５５モル％、けん化度９０％以上のエチレン−酢酸ビニ
ル共重合体けん化物樹脂である特許請求の範囲第５〜８
項のいずれかに記載の積層体。(9) Gas barrier resin has an ethylene component content of 20~
Claims 5 to 8 are saponified ethylene-vinyl acetate copolymer resins with a saponification degree of 55 mol% and a saponification degree of 90% or more.
The laminate according to any of paragraphs.
特許請求の範囲第５〜９項のいずれかに記載の積層体。(10) The laminate according to any one of claims 5 to 9, wherein the hydrophobic thermoplastic resin is a saturated polyester.
特許請求の範囲第５〜９項のいずれかに記載の積層体。(11) The laminate according to any one of claims 5 to 9, wherein the hydrophobic thermoplastic resin is polycarbonate.
第５〜１１項のいずれかに記載の積層体。(12) The laminate according to any one of claims 5 to 11, wherein the laminate is a coextrusion laminate.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61041038A JPH0684458B2 (en) | 1986-02-25 | 1986-02-25 | Adhesive resin composition |
| US07/013,827 US4810755A (en) | 1986-02-25 | 1987-02-12 | Adhesive resin composition, laminated material using it and resin composition containing it |
| AU69012/87A AU593885B2 (en) | 1986-02-25 | 1987-02-18 | Adhesive resin composition, laminated material using it and resin composition containing it |
| DK85987A DK85987A (en) | 1986-02-25 | 1987-02-19 | CLAIM |
| EP19870102595 EP0238870B1 (en) | 1986-02-25 | 1987-02-24 | Adhesive resin composition laminated material using it and resin composition containing it |
| DE8787102595T DE3783251T2 (en) | 1986-02-25 | 1987-02-24 | ADHESIVE COMPOSITION, LAMINATED ITEMS MADE THEREOF AND RESIN COMPOSITION CONTAINING THEM. |
| CA000530601A CA1270972A (en) | 1986-02-25 | 1987-02-25 | Adhesive resin composition, laminated material using it and resin composition containing it |
| US07/221,088 US4810581A (en) | 1986-02-25 | 1988-07-19 | Adhesive resin composition, laminated material using it and resin composition containing it |
| US07/221,663 US4977212A (en) | 1986-02-25 | 1988-07-20 | Adhesive resin composition, laminated material using it and resin composition containing it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61041038A JPH0684458B2 (en) | 1986-02-25 | 1986-02-25 | Adhesive resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62197436A true JPS62197436A (en) | 1987-09-01 |
| JPH0684458B2 JPH0684458B2 (en) | 1994-10-26 |
Family
ID=12597230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61041038A Expired - Fee Related JPH0684458B2 (en) | 1986-02-25 | 1986-02-25 | Adhesive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0684458B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015533683A (en) * | 2012-08-28 | 2015-11-26 | ダウ ブラジル インダストリア エコメルシオ デ プロダトス クイミコス エルティーディーエイ | Film containing functional ethylene polymer composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5852340A (en) * | 1981-09-24 | 1983-03-28 | Sumitomo Chem Co Ltd | Adhesive polyolefin resin composition |
| JPS59138252A (en) * | 1983-01-28 | 1984-08-08 | Sumitomo Chem Co Ltd | Easily adhesive resin composition |
| JPS59149943A (en) * | 1983-02-16 | 1984-08-28 | Sumitomo Chem Co Ltd | Adhesive resin composition |
| JPS59159843A (en) * | 1983-02-28 | 1984-09-10 | Sumitomo Chem Co Ltd | Bondable polyolefin resin composition |
| JPS61293247A (en) * | 1985-06-20 | 1986-12-24 | Nippon Yunikaa Kk | Modified resin composite material |
| JPS62177046A (en) * | 1986-01-31 | 1987-08-03 | Nippon Telegr & Teleph Corp <Ntt> | Acid-resistant flame-retardant resin composition |
-
1986
- 1986-02-25 JP JP61041038A patent/JPH0684458B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5852340A (en) * | 1981-09-24 | 1983-03-28 | Sumitomo Chem Co Ltd | Adhesive polyolefin resin composition |
| JPS59138252A (en) * | 1983-01-28 | 1984-08-08 | Sumitomo Chem Co Ltd | Easily adhesive resin composition |
| JPS59149943A (en) * | 1983-02-16 | 1984-08-28 | Sumitomo Chem Co Ltd | Adhesive resin composition |
| JPS59159843A (en) * | 1983-02-28 | 1984-09-10 | Sumitomo Chem Co Ltd | Bondable polyolefin resin composition |
| JPS61293247A (en) * | 1985-06-20 | 1986-12-24 | Nippon Yunikaa Kk | Modified resin composite material |
| JPS62177046A (en) * | 1986-01-31 | 1987-08-03 | Nippon Telegr & Teleph Corp <Ntt> | Acid-resistant flame-retardant resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015533683A (en) * | 2012-08-28 | 2015-11-26 | ダウ ブラジル インダストリア エコメルシオ デ プロダトス クイミコス エルティーディーエイ | Film containing functional ethylene polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0684458B2 (en) | 1994-10-26 |
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