JPWO2019004261A1 - Ethylene-vinyl alcohol copolymer composition, pellets and multilayer structure - Google Patents
Ethylene-vinyl alcohol copolymer composition, pellets and multilayer structure Download PDFInfo
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- JPWO2019004261A1 JPWO2019004261A1 JP2018534190A JP2018534190A JPWO2019004261A1 JP WO2019004261 A1 JPWO2019004261 A1 JP WO2019004261A1 JP 2018534190 A JP2018534190 A JP 2018534190A JP 2018534190 A JP2018534190 A JP 2018534190A JP WO2019004261 A1 JPWO2019004261 A1 JP WO2019004261A1
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- Prior art keywords
- evoh resin
- resin composition
- ethylene
- compound
- present
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- 229920000219 Ethylene vinyl alcohol Polymers 0.000 title claims abstract description 157
- 239000000203 mixture Substances 0.000 title claims abstract description 22
- 239000008188 pellet Substances 0.000 title claims description 27
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims abstract description 150
- -1 quinone compound Chemical class 0.000 claims abstract description 76
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 49
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 claims abstract 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 abstract description 96
- 238000010438 heat treatment Methods 0.000 abstract description 21
- 238000004040 coloring Methods 0.000 abstract description 13
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 abstract description 2
- 229920006026 co-polymeric resin Polymers 0.000 abstract 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 142
- 229920005989 resin Polymers 0.000 description 95
- 239000011347 resin Substances 0.000 description 95
- 238000000034 method Methods 0.000 description 49
- 239000010410 layer Substances 0.000 description 45
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 239000002585 base Substances 0.000 description 19
- 229920001567 vinyl ester resin Polymers 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 14
- 229920006223 adhesive resin Polymers 0.000 description 13
- 239000004840 adhesive resin Substances 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 229920005672 polyolefin resin Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 238000007127 saponification reaction Methods 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000005022 packaging material Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000000071 blow moulding Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 150000004053 quinones Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- MBGGFXOXUIDRJD-UHFFFAOYSA-N 4-Butoxyphenol Chemical compound CCCCOC1=CC=C(O)C=C1 MBGGFXOXUIDRJD-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 239000004278 EU approved seasoning Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 240000008415 Lactuca sativa Species 0.000 description 2
- 244000294411 Mirabilis expansa Species 0.000 description 2
- 235000015429 Mirabilis expansa Nutrition 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 2
- 235000021107 fermented food Nutrition 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000398 iron phosphate Inorganic materials 0.000 description 2
- 229910000358 iron sulfate Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
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- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
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- 150000004808 allyl alcohols Chemical class 0.000 description 1
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- 150000001413 amino acids Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- ITMIAZBRRZANGB-UHFFFAOYSA-N but-3-ene-1,2-diol Chemical compound OCC(O)C=C ITMIAZBRRZANGB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 230000002950 deficient Effects 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- 159000000014 iron salts Chemical class 0.000 description 1
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- 150000002576 ketones Chemical group 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 230000014759 maintenance of location Effects 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
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 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
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- VYQNWZOUAUKGHI-UHFFFAOYSA-N monobenzone Chemical compound C1=CC(O)=CC=C1OCC1=CC=CC=C1 VYQNWZOUAUKGHI-UHFFFAOYSA-N 0.000 description 1
- 229960000990 monobenzone Drugs 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- QEALYLRSRQDCRA-UHFFFAOYSA-N myristamide Chemical compound CCCCCCCCCCCCCC(N)=O QEALYLRSRQDCRA-UHFFFAOYSA-N 0.000 description 1
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GJQRYIOSVPEUQJ-UHFFFAOYSA-N n-[3-(prop-2-enoylamino)propyl]prop-2-enamide Chemical class C=CC(=O)NCCCNC(=O)C=C GJQRYIOSVPEUQJ-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 239000011129 pharmaceutical packaging material Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
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- 239000004431 polycarbonate resin Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 150000004291 polyenes Polymers 0.000 description 1
- 229920005678 polyethylene based resin Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920005673 polypropylene based resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 239000000376 reactant Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
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- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 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
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/11—Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
- C08K5/08—Quinones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
Abstract
加熱後の着色が抑制されたエチレン−ビニルアルコール系共重合体組成物および多層構造体として、エチレン−ビニルアルコール系共重合体(A)、キノン化合物(B)および鉄化合物(C)を含有するエチレン−ビニルアルコール系共重合体組成物であって、上記鉄化合物(C)の含有量がエチレン−ビニルアルコール系共重合体組成物の重量あたり、金属換算にて0.01〜20ppmであるエチレン−ビニルアルコール系共重合体樹脂組成物を提供する。An ethylene-vinyl alcohol-based copolymer composition and a multilayer structure in which coloring after heating is suppressed, containing an ethylene-vinyl alcohol-based copolymer (A), a quinone compound (B) and an iron compound (C). An ethylene-vinyl alcohol-based copolymer composition, wherein the content of the iron compound (C) is 0.01 to 20 ppm in terms of metal, based on the weight of the ethylene-vinyl alcohol-based copolymer composition. -Providing a vinyl alcohol-based copolymer resin composition.
Description
本発明は、エチレン−ビニルアルコール系共重合体(以下、「EVOH樹脂」と略記することがある。)を主成分とするEVOH樹脂組成物、EVOH樹脂組成物からなるペレットおよび多層構造体に関するものであり、さらに詳しくは、加熱後の着色が抑制されたEVOH樹脂組成物、EVOH樹脂組成物からなるペレットおよび、かかるEVOH樹脂組成物からなる層を備える多層構造体に関するものである。 TECHNICAL FIELD The present invention relates to an EVOH resin composition containing an ethylene-vinyl alcohol copolymer (hereinafter sometimes abbreviated as “EVOH resin”) as a main component, a pellet made of the EVOH resin composition, and a multilayer structure. More specifically, the present invention relates to an EVOH resin composition in which coloring after heating is suppressed, a pellet made of the EVOH resin composition, and a multilayer structure including a layer made of the EVOH resin composition.
EVOH樹脂は、透明性、酸素等のガスバリア性、保香性、耐溶剤性、耐油性、機械強度等に優れており、フィルム、シート、ボトル等に成形され、食品包装材料、医薬品包装材料、工業薬品包装材料、農薬包装材料等の各種包装材料として広く用いられている。 EVOH resin is excellent in transparency, gas barrier properties against oxygen, etc., aroma retention, solvent resistance, oil resistance, mechanical strength, etc., and is molded into films, sheets, bottles, etc., and used as food packaging materials, pharmaceutical packaging materials, It is widely used as various packaging materials such as industrial chemical packaging materials and agricultural chemical packaging materials.
しかし、EVOH樹脂は分子内に比較的活性な水酸基を有するため、熱により劣化しやすい傾向がある。したがって、溶融成形時に着色の問題が起こりやすい傾向がある。 However, the EVOH resin has a relatively active hydroxyl group in the molecule and therefore tends to be deteriorated by heat. Therefore, coloring problems tend to occur during melt molding.
一方、溶融成形時のフィッシュアイやゲル、ストリーク等の欠点の発生を抑制することができるため、外観性に優れる容器、フィルム等の成形品を形成することができる樹脂組成物として、EVOH樹脂(A)及び不飽和アルデヒド(B)を含有し、上記不飽和アルデヒド(B)のEVOH樹脂組成物に対する含有量が0.01ppm以上100ppm以下である樹脂組成物が知られている(例えば、特許文献1参照)。かかる樹脂組成物には、共役ポリエン化合物をさらに含有することにより、溶融成形時の酸化劣化を抑制することができる。これにより、当該樹脂組成物は、フィッシュアイ等の欠点の発生および着色をより抑制し、成形品の外観性を向上させることができると共に、ロングラン性にもより優れると記載されている。 On the other hand, since EVOH resin (a resin composition capable of suppressing defects such as fish eyes, gels, streaks and the like during melt molding) to form molded articles such as containers and films having excellent appearance, There is known a resin composition containing A) and an unsaturated aldehyde (B), and the content of the unsaturated aldehyde (B) in the EVOH resin composition is 0.01 ppm or more and 100 ppm or less (for example, Patent Document 1). 1). When such a resin composition further contains a conjugated polyene compound, oxidative deterioration during melt molding can be suppressed. As a result, it is described that the resin composition can further suppress the occurrence and coloring of defects such as fish eyes, improve the appearance of molded articles, and have excellent long-run properties.
しかしながら、上記不飽和アルデヒドのようなアルデヒド化合物は、微量であっても悪臭の原因となることがあり、特に高温に晒される成形工程にて揮発し作業環境の悪化が懸念されるため採用し難い。そこで、加熱後に着色しにくく、高品質な成形物が得られるEVOH樹脂が求められていた。 However, an aldehyde compound such as the above unsaturated aldehyde may cause a bad odor even in a small amount, and it is particularly difficult to employ because it may be volatilized in the molding step exposed to high temperature and deteriorate the working environment. .. Therefore, there has been a demand for an EVOH resin that is less likely to be colored after heating and that provides a high-quality molded product.
本発明者らは、上記実情に鑑み鋭意検討した結果、微量の鉄化合物とキノン化合物を併用する場合に上記課題が解決することを見出した。従来、キノン化合物を微量の鉄化合物と併用することでEVOH樹脂の成形物の熱安定性が向上することは知られていない。しかし、本発明では、予想外にも、特定微量の鉄化合物とキノン化合物とを併用する場合に、EVOH樹脂組成物の加熱後の着色が抑制されることを見出し、高品質な成形物が得られることを見出した。 As a result of intensive studies in view of the above circumstances, the present inventors have found that the above problem can be solved when a small amount of an iron compound and a quinone compound are used in combination. Conventionally, it has not been known that the thermal stability of a molded EVOH resin is improved by using a quinone compound together with a small amount of an iron compound. However, in the present invention, unexpectedly, it was found that the coloring of the EVOH resin composition after heating was suppressed when a specific trace amount of the iron compound and the quinone compound were used in combination, and a high quality molded product was obtained. I found that I can be.
すなわち、本発明は、EVOH樹脂(A)、キノン化合物(B)および鉄化合物(C)を含有するEVOH樹脂組成物であって、上記鉄化合物(C)の含有量がEVOH樹脂組成物の重量あたり、金属換算にて0.01〜20ppmであることを特徴とするEVOH樹脂組成物を第1の要旨とする。また、本発明は、上記EVOH樹脂組成物からなるペレットを第2の要旨とする。また、本発明は、上記EVOH樹脂組成物からなる層を有する多層構造体を第3の要旨とする。 That is, the present invention is an EVOH resin composition containing an EVOH resin (A), a quinone compound (B) and an iron compound (C), wherein the content of the iron compound (C) is the weight of the EVOH resin composition. Therefore, the first gist is an EVOH resin composition having a metal content of 0.01 to 20 ppm. The second aspect of the present invention is a pellet made of the EVOH resin composition. A third aspect of the present invention is a multilayer structure having a layer made of the above EVOH resin composition.
本発明のEVOH樹脂組成物は、EVOH樹脂(A)、キノン化合物(B)および鉄化合物(C)を含有するEVOH樹脂組成物であって、上記鉄化合物(C)の含有量がEVOH樹脂組成物の重量あたり、金属換算にて0.01〜20ppmであるため、加熱後の着色を抑制することができる。 The EVOH resin composition of the present invention is an EVOH resin composition containing an EVOH resin (A), a quinone compound (B) and an iron compound (C), wherein the content of the iron compound (C) is an EVOH resin composition. Since it is 0.01 to 20 ppm in terms of metal per weight of the product, coloring after heating can be suppressed.
また、本発明のなかでも、特に、上記キノン化合物(B)の含有量がEVOH樹脂組成物の重量あたり1〜10000ppmであると、より加熱後の着色が抑制されたものとすることができる。 Moreover, especially in the present invention, when the content of the quinone compound (B) is 1 to 10000 ppm based on the weight of the EVOH resin composition, the coloring after heating can be further suppressed.
さらに、本発明のなかでも、特に、上記鉄化合物(C)の金属換算含有量に対する、上記キノン化合物(B)の含有量の重量比が、0.2〜50000であると、より一層加熱後の着色が抑制されたものとすることができる。 Furthermore, in the present invention, in particular, when the weight ratio of the content of the quinone compound (B) to the metal-converted content of the iron compound (C) is 0.2 to 50,000, it is further heated. Can be suppressed.
また、本発明のEVOH樹脂組成物からなるペレットは、加熱後の着色が抑制されていることから、各種成形物として、例えば、食品、薬品、農薬等の包装材料に好適に用いることができる。 Further, since the pellets made of the EVOH resin composition of the present invention are suppressed from being colored after being heated, they can be suitably used as various molded products, for example, as packaging materials for foods, chemicals, agricultural chemicals and the like.
そして、本発明のEVOH樹脂組成物からなる層を備える多層構造体は、品質が良好であるため、例えば、食品、薬品、農薬等の包装材料として特に有用である。 Since the multilayer structure provided with the layer made of the EVOH resin composition of the present invention has good quality, it is particularly useful as a packaging material for foods, medicines, agricultural chemicals and the like.
以下、本発明の構成につき詳細に説明するが、これらは望ましい実施態様の一例を示すものであり、これらの内容に限定されるものではない。 Hereinafter, the configuration of the present invention will be described in detail, but these show examples of preferred embodiments and are not limited to these contents.
本発明のEVOH樹脂組成物は、EVOH樹脂(A)を主成分とし、キノン化合物(B)および鉄化合物(C)を含有するものである。本発明のEVOH樹脂組成物は、ベース樹脂がEVOH樹脂(A)である。すなわち、EVOH樹脂組成物におけるEVOH樹脂(A)の含有量は、通常70重量%以上であり、好ましくは80重量%以上であり、より好ましくは90重量%以上であり、特に好ましくは95重量%以上である。
以下に各成分について説明する。The EVOH resin composition of the present invention contains an EVOH resin (A) as a main component, and contains a quinone compound (B) and an iron compound (C). In the EVOH resin composition of the present invention, the base resin is EVOH resin (A). That is, the content of the EVOH resin (A) in the EVOH resin composition is usually 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight. That is all.
Each component will be described below.
[EVOH樹脂(A)]
本発明で用いるEVOH樹脂(A)は、通常、エチレンとビニルエステル系モノマーとの共重合体であるエチレン−ビニルエステル系共重合体をケン化させることにより得られる樹脂であり、非水溶性の熱可塑性樹脂である。上記ビニルエステル系モノマーとしては、経済的な面から、一般的には酢酸ビニルが用いられる。[EVOH resin (A)]
The EVOH resin (A) used in the present invention is usually a resin obtained by saponifying an ethylene-vinyl ester copolymer, which is a copolymer of ethylene and a vinyl ester monomer, and is water-insoluble. It is a thermoplastic resin. From the economical viewpoint, vinyl acetate is generally used as the vinyl ester-based monomer.
エチレンとビニルエステル系モノマーとの重合法としては、公知の任意の重合法、例えば、溶液重合、懸濁重合、エマルジョン重合等を用いて行うことができるが、一般的にはメタノールを溶媒とする溶液重合が用いられる。得られたエチレン−ビニルエステル系共重合体のケン化も公知の方法で行い得る。 As a polymerization method of ethylene and a vinyl ester-based monomer, any known polymerization method, for example, solution polymerization, suspension polymerization, emulsion polymerization or the like can be used. Generally, methanol is used as a solvent. Solution polymerization is used. Saponification of the obtained ethylene-vinyl ester copolymer can also be performed by a known method.
このようにして製造されるEVOH樹脂(A)は、エチレン由来の構造単位とビニルアルコール構造単位を主とし、ケン化されずに残存する若干量のビニルエステル構造単位を含むものである。 The EVOH resin (A) thus produced is mainly composed of ethylene-derived structural units and vinyl alcohol structural units, and contains a small amount of vinyl ester structural units remaining without being saponified.
上記ビニルエステル系モノマーとしては、市場入手性や製造時の不純物処理効率がよい点から、代表的には酢酸ビニルが用いられる。他のビニルエステル系モノマーとしては、例えば、ギ酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、バーサチック酸ビニル等の脂肪族ビニルエステル、安息香酸ビニル等の芳香族ビニルエステル等があげられ、通常炭素数3〜20、好ましくは炭素数4〜10、特に好ましくは炭素数4〜7の脂肪族ビニルエステルを用いることができる。これらは通常単独で用いるが、必要に応じて複数種を同時に用いてもよい。 As the vinyl ester-based monomer, vinyl acetate is typically used from the viewpoint of market availability and efficiency of treating impurities during production. Other vinyl ester-based monomers include, for example, vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl versatate, etc. Examples thereof include aromatic vinyl esters, aromatic vinyl esters such as vinyl benzoate, and the like. Use of an aliphatic vinyl ester having usually 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, and particularly preferably 4 to 7 carbon atoms. You can These are usually used alone, but if necessary, a plurality of types may be used simultaneously.
EVOH樹脂(A)におけるエチレン構造単位の含有量は、ビニルエステル系モノマーとエチレンとを共重合させる際のエチレンの圧力によって制御することができ、通常20〜60モル%、好ましくは25〜50モル%、特に好ましくは25〜35モル%である。かかる含有量が低すぎる場合は、高湿下のガスバリア性、溶融成形性が低下する傾向があり、逆に高すぎる場合は、ガスバリア性が低下する傾向がある。
なお、かかるエチレン構造単位の含有量は、ISO14663に基づいて測定することができる。The content of the ethylene structural unit in the EVOH resin (A) can be controlled by the pressure of ethylene at the time of copolymerizing the vinyl ester-based monomer and ethylene, and is usually 20 to 60 mol%, preferably 25 to 50 mol. %, Particularly preferably 25 to 35 mol%. If the content is too low, the gas barrier property under high humidity and the melt moldability tend to be lowered, and conversely, if it is too high, the gas barrier property tends to be lowered.
The content of the ethylene structural unit can be measured based on ISO14663.
EVOH樹脂(A)におけるビニルエステル成分のケン化度は、エチレン−ビニルエステル系共重合体をケン化する際のケン化触媒(通常、水酸化ナトリウム等のアルカリ性触媒が用いられる)の量、温度、時間などによって制御でき、通常90〜100モル%、好ましくは95〜100モル%、特に好ましくは99〜100モル%である。かかるケン化度が低すぎる場合にはガスバリア性、熱安定性、耐湿性等が低下する傾向がある。
かかるEVOH樹脂(A)のケン化度は、JIS K6726(ただし、EVOH樹脂は水/メタノール溶媒に均一に溶解した溶液として用いる)に基づいて測定することができる。The degree of saponification of the vinyl ester component in the EVOH resin (A) depends on the amount and temperature of the saponification catalyst (usually an alkaline catalyst such as sodium hydroxide is used) when saponifying the ethylene-vinyl ester copolymer. The amount is usually 90 to 100 mol%, preferably 95 to 100 mol%, particularly preferably 99 to 100 mol%. If the degree of saponification is too low, the gas barrier properties, thermal stability, moisture resistance, etc. tend to deteriorate.
The degree of saponification of the EVOH resin (A) can be measured based on JIS K6726 (however, the EVOH resin is used as a solution uniformly dissolved in a water / methanol solvent).
また、該EVOH樹脂(A)のメルトフローレート(MFR)(210℃、荷重2160g)は、通常0.5〜100g/10分であり、好ましくは1〜50g/10分、特に好ましくは3〜35g/10分である。かかるMFRが大きすぎる場合には、製膜時の安定性が損なわれる傾向があり、小さすぎる場合には粘度が高くなり過ぎて溶融押出しが困難となる傾向がある。
かかるMFRは、EVOH樹脂の重合度の指標となるものであり、エチレンとビニルエステル系モノマーを共重合する際の重合開始剤の量や、溶媒の量によって調整することができる。The melt flow rate (MFR) (210 ° C., load 2160 g) of the EVOH resin (A) is usually 0.5 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes, particularly preferably 3 to. It is 35 g / 10 minutes. If the MFR is too large, the stability during film formation tends to be impaired, and if it is too small, the viscosity tends to be too high and melt extrusion tends to be difficult.
The MFR is an index of the degree of polymerization of the EVOH resin and can be adjusted by the amount of the polymerization initiator and the amount of the solvent when the ethylene and the vinyl ester monomer are copolymerized.
本発明で用いられるEVOH樹脂(A)には、本発明の効果を阻害しない範囲(例えば、EVOH樹脂(A)の10モル%以下)で、以下に示すコモノマーに由来する構造単位が、さらに含まれていてもよい。 The EVOH resin (A) used in the present invention further contains structural units derived from the following comonomer within a range that does not impair the effects of the present invention (for example, 10 mol% or less of the EVOH resin (A)). It may be.
上記コモノマーとしては、プロピレン、1−ブテン、イソブテン等のオレフィン類、3−ブテン−1−オール、3−ブテン−1,2−ジオール、4−ペンテン−1−オール、5−ヘキセン−1,2−ジオール等のヒドロキシ基含有α−オレフィン類やそのエステル化物、アシル化物等の誘導体;2−メチレンプロパン−1,3−ジオール、3−メチレンペンタン−1,5−ジオール等のヒドロキシアルキルビニリデン類;1,3−ジアセトキシ−2−メチレンプロパン、1,3−ジプロピオニルオキシ−2−メチレンプロパン、1,3−ジブチリルオキシ−2−メチレンプロパン等のヒドロキシアルキルビニリデンジアセテート類;アクリル酸、メタクリル酸、クロトン酸、(無水)フタル酸、(無水)マレイン酸、(無水)イタコン酸等の不飽和酸類あるいはその塩あるいは炭素数1〜18のモノまたはジアルキルエステル類;アクリルアミド、炭素数1〜18のN−アルキルアクリルアミド、N,N−ジメチルアクリルアミド、2−アクリルアミドプロパンスルホン酸あるいはその塩、アクリルアミドプロピルジメチルアミンあるいはその酸塩あるいはその4級塩等のアクリルアミド類;メタアクリルアミド、炭素数1〜18のN−アルキルメタクリルアミド、N,N−ジメチルメタクリルアミド、2−メタクリルアミドプロパンスルホン酸あるいはその塩、メタクリルアミドプロピルジメチルアミンあるいはその酸塩あるいはその4級塩等のメタクリルアミド類;N−ビニルピロリドン、N−ビニルホルムアミド、N−ビニルアセトアミド等のN−ビニルアミド類;アクリルニトリル、メタクリルニトリル等のシアン化ビニル類;炭素数1〜18のアルキルビニルエーテル、ヒドロキシアルキルビニルエーテル、アルコキシアルキルビニルエーテル等のビニルエーテル類;塩化ビニル、塩化ビニリデン、フッ化ビニル、フッ化ビニリデン、臭化ビニル等のハロゲン化ビニル化合物類;トリメトキシビニルシラン等のビニルシラン類;酢酸アリル、塩化アリル等のハロゲン化アリル化合物類;アリルアルコール、ジメトキシアリルアルコール等のアリルアルコール類;トリメチル−(3−アクリルアミド−3−ジメチルプロピル)−アンモニウムクロリド、アクリルアミド−2−メチルプロパンスルホン酸等のコモノマーがあげられる。これらは単独でもしくは2種以上併せて用いることができる。 Examples of the comonomer include olefins such as propylene, 1-butene and isobutene, 3-butene-1-ol, 3-butene-1,2-diol, 4-penten-1-ol, 5-hexene-1,2. -Hydroxy group-containing α-olefins such as diols and derivatives thereof such as esterified products and acylated products; hydroxyalkylvinylidenes such as 2-methylenepropane-1,3-diol and 3-methylenepentane-1,5-diol; Hydroxyalkyl vinylidene diacetates such as 1,3-diacetoxy-2-methylenepropane, 1,3-dipropionyloxy-2-methylenepropane and 1,3-dibutyryloxy-2-methylenepropane; acrylic acid, methacrylic acid , Crotonic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, etc. Saturated acids or salts thereof or mono- or dialkyl esters having 1 to 18 carbon atoms; acrylamide, N-alkyl acrylamide having 1 to 18 carbon atoms, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or salt thereof, acrylamidopropyl Acrylamides such as dimethylamine or acid salts thereof or quaternary salts thereof; methacrylamide, N-alkylmethacrylamides having 1 to 18 carbon atoms, N, N-dimethylmethacrylamide, 2-methacrylamidopropanesulfonic acid or salts thereof, Methacrylamides such as methacrylamidopropyldimethylamine or its acid salts or quaternary salts thereof; N-vinylamides such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide; Vinyl cyanides such as tolyl and methacrylonitrile; vinyl ethers such as alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers and alkoxyalkyl vinyl ethers; vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl bromide, etc. Halogenated vinyl compounds; vinylsilanes such as trimethoxyvinylsilane; allyl halides such as allyl acetate and allyl chloride; allyl alcohols such as allyl alcohol and dimethoxyallyl alcohol; trimethyl- (3-acrylamido-3-dimethyl) Examples thereof include comonomers such as propyl) -ammonium chloride and acrylamido-2-methylpropanesulfonic acid. These may be used alone or in combination of two or more.
特に、側鎖に1級水酸基を有するEVOH樹脂は、ガスバリア性を保持しつつ二次成形性が良好になる点で好ましく、なかでも、ヒドロキシ基含有α−オレフィン類を共重合したEVOH樹脂が好ましく、特には、1,2−ジオール構造を側鎖に有するEVOH樹脂が好ましい。
特に、側鎖に1級水酸基を有するEVOH樹脂である場合、当該1級水酸基を有するモノマー由来の構造単位の含有量は、EVOH樹脂の通常0.1〜20モル%、さらには0.5〜15モル%、特には1〜10モル%のものが好ましい。In particular, an EVOH resin having a primary hydroxyl group in the side chain is preferable in that the secondary moldability is improved while maintaining the gas barrier property, and among them, an EVOH resin in which a hydroxy group-containing α-olefin is copolymerized is preferable. Particularly, EVOH resin having a 1,2-diol structure in its side chain is preferable.
Particularly, in the case of an EVOH resin having a primary hydroxyl group in the side chain, the content of the structural unit derived from the monomer having a primary hydroxyl group is usually 0.1 to 20 mol% of the EVOH resin, further 0.5 to It is preferably 15 mol%, particularly preferably 1 to 10 mol%.
また、本発明で用いるEVOH樹脂(A)としては、ウレタン化、アセタール化、シアノエチル化、オキシアルキレン化等の「後変性」されたEVOH系樹脂を用いることもできる。 Further, as the EVOH resin (A) used in the present invention, an EVOH-based resin which has been “post-modified” such as urethanated, acetalized, cyanoethylated or oxyalkylenated can also be used.
さらに、本発明で用いるEVOH樹脂(A)は、異なる他のEVOH樹脂との混合物であってもよく、かかる他のEVOH樹脂としては、エチレン構造単位の含有量が異なるもの、ケン化度が異なるもの、重合度が異なるもの、共重合成分が異なるもの等をあげることができる。 Further, the EVOH resin (A) used in the present invention may be a mixture with other EVOH resins different from each other, and such other EVOH resins having different ethylene structural unit contents and different saponification degrees. Examples thereof include those having different degrees of polymerization, those having different copolymerization components, and the like.
[キノン化合物(B)]
本発明で用いるキノン化合物(B)は、ラジカルを共鳴安定化し捕捉する能力を有するキノン骨格を有する化合物またはその誘導体を意味する。キノン骨格を有する化合物とは、具体的には炭素骨格としてベンゼン環の、1位および4位、もしくは、1位および2位にケトン構造を有する環状ジケトン化合物である。キノン化合物(B)としては、例えば、キノン類、ハイドロキノン類等があげられる。[Quinone compound (B)]
The quinone compound (B) used in the present invention means a compound having a quinone skeleton or a derivative thereof having an ability to resonance-stabilize and trap radicals. The compound having a quinone skeleton is specifically a cyclic diketone compound having a ketone structure at the 1-position and 4-position or the 1-position and 2-position of the benzene ring as a carbon skeleton. Examples of the quinone compound (B) include quinones and hydroquinones.
上記キノン類としては、例えば、o−ベンゾキノン、p−ベンゾキノン、ジフェノキノン、1,4−ナフトキノン、アントラキノン等があげられ、なかでも、p−ベンゾキノンが好ましい。ハイドロキノン類としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、ジペンチルハイドロキノン、p−メトキシフェノール、p−ブトキシフェノール、p−ペントキシフェノール、モノベンゾン等があげられる。なかでも、生産性の点でハイドロキノン類が好ましく、特にはハイドロキノンを用いることが好ましい。また、これらは単独でもしくは2種以上併せて用いることができる。 Examples of the quinones include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, and the like, and among them, p-benzoquinone is preferable. Examples of hydroquinones include hydroquinone, hydroquinone monomethyl ether, dipentylhydroquinone, p-methoxyphenol, p-butoxyphenol, p-pentoxyphenol, and monobenzone. Among them, hydroquinones are preferable in terms of productivity, and hydroquinone is particularly preferable. Moreover, these can be used individually or in combination of 2 or more types.
上記キノン化合物(B)の分子量は、通常100〜100000、好ましくは100〜10000、特に好ましくは100〜1000、殊更に好ましくは100〜300である。分子量が上記範囲である場合、本発明の効果がより効果的に得られる傾向がある。 The molecular weight of the above quinone compound (B) is usually 100 to 100,000, preferably 100 to 10,000, particularly preferably 100 to 1,000, and particularly preferably 100 to 300. When the molecular weight is in the above range, the effect of the present invention tends to be more effectively obtained.
また、上記キノン化合物(B)の含有量は、本発明のEVOH樹脂組成物の重量あたり、通常1〜10000ppm、好ましくは5〜1000ppm、特に好ましくは10〜500ppm、殊に好ましくは20〜100ppmである。キノン化合物(B)の含有量が多すぎる場合は、生産性が低下する傾向があり、少なすぎる場合は、熱安定性が低下する傾向がある。
なお、上記キノン化合物(B)として、構造、組成、分子量等の異なるキノン化合物(B)を2種類以上併せて用いる場合は、その総重量(総含有量)が上記の範囲にあればよい。The content of the quinone compound (B) is usually 1 to 10000 ppm, preferably 5 to 1000 ppm, particularly preferably 10 to 500 ppm, and particularly preferably 20 to 100 ppm, based on the weight of the EVOH resin composition of the present invention. is there. If the content of the quinone compound (B) is too large, the productivity tends to decrease, and if it is too small, the thermal stability tends to decrease.
When two or more quinone compounds (B) having different structures, compositions, molecular weights and the like are used together as the quinone compound (B), the total weight (total content) thereof may be in the above range.
上記キノン化合物(B)の、EVOH樹脂組成物の重量あたりの含有量は、つぎのようにして測定することができる。まず、EVOH樹脂組成物を凍結粉砕したサンプル1gを、抽出溶媒にて抽出し、かかる抽出液を定容し、液体クロマトグラフ−紫外分光検出器を用いて測定する。別途、キノン化合物(B)の標準溶液から検量線を作成し、絶対検量線法によって、キノン化合物(B)の含有量を定量することができる。 The content of the quinone compound (B) per weight of the EVOH resin composition can be measured as follows. First, 1 g of a sample obtained by freeze-grinding an EVOH resin composition is extracted with an extraction solvent, the volume of the extract is fixed, and the measurement is performed using a liquid chromatograph-ultraviolet spectroscopic detector. Separately, a calibration curve is prepared from a standard solution of the quinone compound (B), and the content of the quinone compound (B) can be quantified by the absolute calibration curve method.
[鉄化合物(C)]
本発明は、EVOH樹脂(A)、キノン化合物(B)および鉄化合物(C)を含有し、かつ鉄化合物(C)の含有量が特定微量であることを特徴とする。かかる構成を採用することにより、得られる樹脂組成物が加熱後の着色が抑制されることを見出した。[Iron compound (C)]
The present invention is characterized by containing an EVOH resin (A), a quinone compound (B), and an iron compound (C), and the content of the iron compound (C) is a specific trace amount. It has been found that by adopting such a constitution, the obtained resin composition is suppressed from being colored after heating.
一般的にEVOH樹脂は、熱劣化によって着色が発生する。これは、熱によりEVOH樹脂が劣化してラジカルが発生し、EVOH樹脂が有する水酸基が脱水し、EVOH樹脂の主鎖に二重結合が生成し、かかる部位が反応起点となり脱水が促進され、共役ポリエン構造を形成するためと考えられる。
一方、本発明のEVOH樹脂組成物が、優れた耐劣化性を備えるのは、つぎのような理由によるものと推測される。通常、鉄は、2価および3価のイオンとして存在することが可能である。そして、本発明では、特定微量の鉄化合物(C)とともに上記キノン化合物(B)を併用することにより、キノン化合物(B)がしばしば3価の鉄イオンを還元して、2価の鉄イオンが生成し、かかる2価の鉄イオンが、既にラジカルを捕捉したキノン化合物(B)を再び還元することにより上記キノン化合物(B)の活性を取り戻すというサイクルが生起しているためと推測される。Generally, EVOH resin is colored due to thermal deterioration. This is because the EVOH resin is deteriorated by heat and radicals are generated, the hydroxyl group of the EVOH resin is dehydrated, a double bond is generated in the main chain of the EVOH resin, and such a site serves as a reaction starting point to promote dehydration, and the conjugation It is considered to form a polyene structure.
On the other hand, it is presumed that the EVOH resin composition of the present invention has excellent deterioration resistance for the following reasons. Normally, iron can exist as divalent and trivalent ions. In the present invention, the quinone compound (B) is often used in combination with the specific trace amount of the iron compound (C), so that the quinone compound (B) often reduces the trivalent iron ion and the divalent iron ion. It is speculated that this divalent iron ion is generated and a cycle occurs in which the activity of the quinone compound (B) is restored by reducing the quinone compound (B) that has already trapped the radicals.
また、鉄化合物(C)を含有する場合、鉄イオンにより製品が着色すると考えられるため、通常、当業者であれば上記鉄化合物の使用は避けることが技術常識である。しかしながら、本発明では、そのような技術常識に反して、特定微量の鉄化合物(C)とキノン化合物(B)とを併用する場合に、加熱後の着色が抑制されたEVOH樹脂組成物が得られることを見出したのである。 Further, when the iron compound (C) is contained, it is considered that the product is colored by iron ions, and therefore, it is a common general technical knowledge for those skilled in the art to avoid using the above iron compound. However, in the present invention, contrary to such common general knowledge, an EVOH resin composition in which coloring after heating is suppressed is obtained when a specific trace amount of an iron compound (C) and a quinone compound (B) are used in combination. I found that I could be done.
上記鉄化合物(C)は、EVOH樹脂組成物中で、例えば、酸化物、水酸化物、塩化物、鉄塩として存在する場合の他、イオン化した状態、あるいは樹脂や他の配位子と相互作用した錯体の状態で存在していてもよい。上記酸化物としては、例えば、酸化第二鉄、四三酸化鉄、亜酸化鉄等があげられる。上記塩化物としては、例えば、塩化第一鉄、塩化第二鉄等があげられる。上記水酸化物としては、例えば、水酸化第一鉄、水酸化第二鉄等があげられる。上記鉄塩としては、例えば、リン酸鉄、硫酸鉄等の無機塩やカルボン酸(酢酸、酪酸、ステアリン酸等)鉄等の有機塩があげられる。これらは単独でもしくは2種以上併せて用いることができる。 The iron compound (C) may be present in the EVOH resin composition as, for example, an oxide, a hydroxide, a chloride, or an iron salt, or in an ionized state, or may interact with a resin or another ligand. It may exist in the state of the complex that has acted. Examples of the oxide include ferric oxide, ferric tetroxide, iron suboxide, and the like. Examples of the chloride include ferrous chloride and ferric chloride. Examples of the hydroxide include ferrous hydroxide, ferric hydroxide and the like. Examples of the iron salt include inorganic salts such as iron phosphate and iron sulfate, and organic salts such as iron carboxylic acid (acetic acid, butyric acid, stearic acid, etc.). These may be used alone or in combination of two or more.
EVOH樹脂組成物における分散性の点で、鉄化合物(C)は水溶性であることが好ましい。また、分散性と生産性の観点から、その分子量は通常100〜10000、好ましくは100〜1000、特に好ましくは100〜500である。 From the viewpoint of dispersibility in the EVOH resin composition, the iron compound (C) is preferably water-soluble. From the viewpoint of dispersibility and productivity, the molecular weight is usually 100 to 10,000, preferably 100 to 1,000, and particularly preferably 100 to 500.
本発明のEVOH樹脂組成物は、鉄化合物(C)の含有量が、EVOH樹脂組成物の重量あたり金属換算にて0.01〜20ppmであることを特徴とするものである。かかる鉄化合物の含有量は、好ましくは0.03〜15ppmであり、より好ましくは0.05〜3ppm、特に好ましくは0.05〜1.5ppmである。
鉄化合物の含有量が少なすぎると着色防止効果が低下する傾向があり、逆に多すぎると成形物が着色する傾向がある。The EVOH resin composition of the present invention is characterized in that the content of the iron compound (C) is 0.01 to 20 ppm in terms of metal based on the weight of the EVOH resin composition. The content of such iron compound is preferably 0.03 to 15 ppm, more preferably 0.05 to 3 ppm, and particularly preferably 0.05 to 1.5 ppm.
If the content of the iron compound is too small, the anti-coloring effect tends to decrease, and if it is too large, the molded product tends to be colored.
ここで、鉄化合物(C)の含有量は、EVOH樹脂組成物を凍結粉砕した測定用サンプル0.5gを赤外線加熱炉で灰化処理(酸素気流中650℃、1時間)後、残った灰分を酸溶解し純水で定容したものを試料溶液として、ICP−MS(Agilent Technologies社製、7500ce型;標準添加法)で測定することにより求めることができる。 Here, the content of the iron compound (C) is determined by ashing 0.5 g of a measurement sample obtained by freeze-milling an EVOH resin composition in an infrared heating furnace (650 ° C. in an oxygen stream for 1 hour), and then removing the remaining ash content. Can be determined by measuring with ICP-MS (7500ce type; standard addition method, manufactured by Agilent Technologies) using a sample solution prepared by dissolving acid in acid and adjusting the volume with pure water.
本発明のEVOH樹脂組成物における上記鉄化合物(C)の金属換算含有量に対する、前記キノン化合物(B)の含有量の重量比は、通常0.2〜50000であり、好ましくは1〜10000であり、特に好ましくは5〜5000、殊に好ましくは50〜1000である。かかる値が大きすぎる場合、加熱後の着色抑制を妨げる傾向があり、小さすぎる場合成形物が着色する傾向がある。 The weight ratio of the content of the quinone compound (B) to the metal equivalent content of the iron compound (C) in the EVOH resin composition of the present invention is usually 0.2 to 50,000, preferably 1 to 10000. , Particularly preferably 5 to 5,000, particularly preferably 50 to 1,000. If this value is too large, the suppression of coloration after heating tends to be hindered, and if it is too small, the molded product tends to be colored.
[その他の熱可塑性樹脂]
本発明のEVOH樹脂組成物には、EVOH樹脂(A)以外の熱可塑性樹脂を、本発明の効果を阻害しない範囲(例えば、EVOH樹脂組成物の通常30重量%以下、好ましくは20重量%以下、特に好ましくは10重量%以下)にて含有することができる。[Other thermoplastic resins]
The EVOH resin composition of the present invention contains a thermoplastic resin other than the EVOH resin (A) in a range that does not impair the effects of the present invention (for example, usually 30% by weight or less, preferably 20% by weight or less of the EVOH resin composition). , Particularly preferably 10% by weight or less).
他の熱可塑性樹脂としては、公知の熱可塑性樹脂を用いることができる。例えば、具体的には、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリスチレン系樹脂、ポリ塩化ビニル系樹脂、ポリカーボネート系樹脂、ポリアクリル系樹脂、アイオノマー、エチレン−アクリル酸共重合体、エチレン−アクリル酸エステル共重合体、エチレン−メタクリル酸共重合体、エチレン−メタクリル酸エステル共重合体、ポリ塩化ビニリデン、ビニルエステル系樹脂、ポリエステルエラストマー、ポリウレタンエラストマー、塩素化ポリエチレン、塩素化ポリプロピレン等があげられる。これらは単独でもしくは2種以上併せて用いることができる。 As the other thermoplastic resin, a known thermoplastic resin can be used. For example, specifically, polyolefin resin, polyester resin, polystyrene resin, polyvinyl chloride resin, polycarbonate resin, polyacrylic resin, ionomer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer Examples thereof include polymers, ethylene-methacrylic acid copolymers, ethylene-methacrylic acid ester copolymers, polyvinylidene chloride, vinyl ester resins, polyester elastomers, polyurethane elastomers, chlorinated polyethylene, chlorinated polypropylene and the like. These may be used alone or in combination of two or more.
[その他の配合剤]
また、本発明のEVOH樹脂組成物には、本発明の効果を阻害しない範囲において、一般にEVOH樹脂に配合する配合剤が含有されていてもよい。上記配合剤としては、例えば、無機複塩(例えば、ハイドロタルサイト等)、可塑剤(例えば、エチレングリコール、グリセリン、ヘキサンジオール等の脂肪族多価アルコール等)、酸素吸収剤[例えば、アルミニウム粉、亜硫酸カリウム、光触媒酸化チタン等の無機系酸素吸収剤;アスコルビン酸、さらにその脂肪酸エステルや金属塩等、没食子酸、水酸基含有フェノールアルデヒド樹脂等の多価フェノール類、ビス−サリチルアルデヒド−イミンコバルト、テトラエチレンペンタミンコバルト、コバルト−シッフ塩基錯体、ポルフィリン類、大環状ポリアミン錯体、ポリエチレンイミン−コバルト錯体等の含窒素化合物と鉄以外の遷移金属との配位結合体、テルペン化合物、アミノ酸類とヒドロキシル基含有還元性物質の反応物、トリフェニルメチル化合物等の有機化合物系酸素吸収剤;窒素含有樹脂と鉄以外の遷移金属との配位結合体(例えば、メチルキシリレンジアミン〔MXD〕ナイロンとコバルトの組合せ)、三級水素含有樹脂と鉄以外の遷移金属とのブレンド物(例えば、ポリプロピレンとコバルトの組合せ)、炭素−炭素不飽和結合含有樹脂と鉄以外の遷移金属とのブレンド物(例えば、ポリブタジエンとコバルトの組合せ)、光酸化崩壊性樹脂(例えば、ポリケトン)、アントラキノン重合体(例えば、ポリビニルアントラキノン)等や、さらにこれらの配合物に光開始剤(ベンゾフェノン等)や、上記以外の酸化防止剤や消臭剤(活性炭等)を添加したもの等の高分子系酸素吸収剤]、熱安定剤、光安定剤、紫外線吸収剤、着色剤、帯電防止剤、界面活性剤(ただし、滑剤として用いるものを除く)、抗菌剤、アンチブロッキング剤、充填材(例えば、無機フィラー等)等を配合してもよい。これらの化合物は、単独でもしくは2種以上併せて用いることができる。[Other compounding agents]
Further, the EVOH resin composition of the present invention may contain a compounding agent that is generally compounded with the EVOH resin within a range that does not impair the effects of the present invention. Examples of the compounding agent include inorganic double salts (eg, hydrotalcite), plasticizers (eg, aliphatic polyhydric alcohols such as ethylene glycol, glycerin, and hexanediol), oxygen absorbers [eg, aluminum powder. Inorganic oxygen absorbers such as potassium sulfite and photocatalytic titanium oxide; polyphenols such as ascorbic acid, its fatty acid esters and metal salts, gallic acid, hydroxyl group-containing phenol aldehyde resins, bis-salicylaldehyde-imine cobalt, Coordination bond between nitrogen-containing compounds such as tetraethylenepentaminecobalt, cobalt-Schiff base complex, porphyrins, macrocyclic polyamine complex, polyethyleneimine-cobalt complex and transition metals other than iron, terpene compounds, amino acids and hydroxyl Reactant of group-containing reducing substance, trif Organic compound-based oxygen absorbers such as nylmethyl compounds; coordination bonds of nitrogen-containing resins with transition metals other than iron (for example, a combination of methylxylylenediamine [MXD] nylon and cobalt), tertiary hydrogen-containing resins and iron Blends with transition metals other than (for example, a combination of polypropylene and cobalt), blends of carbon-carbon unsaturated bond-containing resin with transition metals other than iron (for example, a combination of polybutadiene and cobalt), photooxidative disintegration Resin (eg polyketone), anthraquinone polymer (eg polyvinyl anthraquinone), etc., and photoinitiators (benzophenone etc.) and antioxidants and deodorants (activated carbon etc.) other than the above to these compounds Polymeric oxygen absorbers such as those prepared, heat stabilizers, light stabilizers, ultraviolet absorbers, colorants, antistatic agents, surfactants ( However, except for those used as lubricants), antimicrobial agents, antiblocking agents, fillers (e.g., may be blended inorganic fillers and the like) and the like. These compounds can be used alone or in combination of two or more.
[EVOH樹脂組成物の製造方法]
本発明のEVOH樹脂組成物を製造する方法としては、例えば、ドライブレンド法、溶融混合法、溶液混合法、含浸法等の公知の方法があげられ、これらを任意に組み合わせることも可能である。[Method for producing EVOH resin composition]
Examples of the method for producing the EVOH resin composition of the present invention include known methods such as a dry blending method, a melt mixing method, a solution mixing method and an impregnation method, and these methods can be combined arbitrarily.
ドライブレンド法としては、例えば(i)EVOH樹脂(A)ペレットと、キノン化合物(B)および鉄化合物(C)をタンブラー等を用いてドライブレンドする方法等があげられる。
溶融混合法としては、例えば、(ii)EVOH樹脂(A)ペレットと、キノン化合物(B)および鉄化合物(C)のドライブレンド物を溶融混練し、ペレットや成形物を得る方法や、(iii)溶融状態のEVOH樹脂(A)にキノン化合物(B)や鉄化合物(C)を添加して溶融混練し、ペレットや成形物を得る方法等があげられる。Examples of the dry blending method include a method of dry blending (i) EVOH resin (A) pellets with a quinone compound (B) and an iron compound (C) using a tumbler or the like.
Examples of the melt-mixing method include (ii) a method in which EVOH resin (A) pellets and a dry blend of a quinone compound (B) and an iron compound (C) are melt-kneaded to obtain pellets or a molded article, or (iii) ) A method in which a quinone compound (B) or an iron compound (C) is added to a molten EVOH resin (A) and the mixture is melt-kneaded to obtain pellets or a molded product can be used.
溶液混合法としては、例えば、(iv)市販のEVOH樹脂(A)ペレットを用いて溶液を調製し、ここにキノン化合物(B)および鉄化合物(C)の少なくとも一方を配合し、凝固成形してペレット化し、固液分離して乾燥する方法や、(v)EVOH樹脂(A)の製造過程で、ケン化前のエチレン−ビニルエステル系共重合体溶液やEVOH樹脂の均一溶液(水/アルコール溶液等)にキノン化合物(B)および鉄化合物(C)の少なくとも一方を含有させた後、凝固成形してペレット化し、固液分離して乾燥する方法等があげられる。 As a solution mixing method, for example, (iv) a commercially available EVOH resin (A) pellet is used to prepare a solution, and at least one of a quinone compound (B) and an iron compound (C) is added to the solution and coagulated and molded. Pelletization, solid-liquid separation and drying, or (v) EVOH resin (A) production process, before the saponification ethylene-vinyl ester copolymer solution or EVOH resin homogeneous solution (water / alcohol). (Solution) and the like, at least one of the quinone compound (B) and the iron compound (C) is added, and then the mixture is solidified and molded into pellets, solid-liquid separated, and dried.
含浸法としては、例えば(vi)EVOH樹脂(A)ペレットを、キノン化合物(B)および鉄化合物(C)の少なくとも一方を含有する水溶液と接触させ、EVOH樹脂(A)ぺレット中にキノン化合物(B)および鉄化合物(C)の少なくとも一方を含有させた後、乾燥する方法等をあげることができる。 As the impregnation method, for example, (vi) EVOH resin (A) pellets are contacted with an aqueous solution containing at least one of a quinone compound (B) and an iron compound (C), and the EVOH resin (A) pellet is filled with the quinone compound. A method of adding at least one of (B) and the iron compound (C) and then drying it may be mentioned.
本発明においては、上記の異なる方法を組み合わせることが可能である。なかでも、生産性や本発明の効果がより顕著な樹脂組成物が得られる点で、溶融混合法が好ましく、特には(ii)の方法が好ましい。 In the present invention, it is possible to combine the different methods described above. Among them, the melt mixing method is preferable, and the method (ii) is particularly preferable from the viewpoint that a resin composition having more remarkable productivity and effects of the present invention can be obtained.
なお、上記各方法によって得られる本発明のEVOH樹脂組成物ペレット、各方法で用いられるEVOH樹脂(A)ペレットの形状は任意である。例えば、球形、オーバル形、円柱形、立方体形、直方体形等があるが、通常、オーバル形、または円柱形であり、その大きさは、後に成形材料として用いる場合の利便性の観点から、オーバル形の場合は短径が通常1〜10mm、好ましくは2〜6mmであり、更に好ましくは2.5〜5.5mmであり、長径は通常1.5〜30mm、好ましくは3〜20、更に好ましくは3.5〜10mmである。また、円柱形の場合は底面の直径が通常1〜6mm、好ましくは2〜5mmであり、長さは通常1〜6mm、好ましくは2〜5mmである。 The shape of the EVOH resin composition pellets of the present invention obtained by each of the above methods and the EVOH resin (A) pellets used in each method are arbitrary. For example, there are a spherical shape, an oval shape, a cylindrical shape, a cubic shape, a rectangular parallelepiped shape, etc., but usually, an oval shape or a cylindrical shape, the size of which is convenient for later use as a molding material. In the case of the shape, the minor axis is usually 1 to 10 mm, preferably 2 to 6 mm, more preferably 2.5 to 5.5 mm, and the major axis is usually 1.5 to 30 mm, preferably 3 to 20 and more preferably. Is 3.5 to 10 mm. In the case of a cylindrical shape, the diameter of the bottom surface is usually 1 to 6 mm, preferably 2 to 5 mm, and the length is usually 1 to 6 mm, preferably 2 to 5 mm.
また、上記の各方法で用いられる鉄化合物(C)としては、前述のとおり、好ましくは、水溶性の鉄化合物が用いられ、例えば、酸化第二鉄、四三酸化鉄、亜酸化鉄等の酸化物、塩化第一鉄、塩化第二鉄等の塩化物、水酸化第一鉄、水酸化第二鉄等の水酸化物、リン酸鉄、硫酸鉄等の無機塩やカルボン酸(酢酸、酪酸、ステアリン酸等)鉄等の有機塩等の鉄塩があげられる。なお、かかる鉄化合物(C)は、前述のとおり、EVOH樹脂組成物中で、上記の塩として存在する場合の他、イオン化した状態、あるいは樹脂や他の化合物を配位子とした錯体の状態で存在していてもよい。 Further, as the iron compound (C) used in each of the above-mentioned methods, as described above, a water-soluble iron compound is preferably used, and examples thereof include ferric oxide, ferric tetroxide, and iron suboxide. Oxides, chlorides such as ferrous chloride and ferric chloride, hydroxides such as ferrous hydroxide and ferric hydroxide, inorganic salts such as iron phosphate and iron sulfate, and carboxylic acids (acetic acid, Butyric acid, stearic acid, etc.) Iron salts such as iron organic salts. As described above, the iron compound (C) is present in the EVOH resin composition as the above-mentioned salt, in the ionized state, or in the complex state using the resin or another compound as a ligand. May exist in.
また、上記(vi)の方法で用いられる鉄化合物(C)を含有する水溶液としては、上記鉄化合物(C)の水溶液や、鉄鋼材料を各種薬剤を含む水に浸漬することで鉄イオンを溶出させたものを用いることができる。なお、その場合、EVOH樹脂組成物中の鉄化合物(C)の含有量(金属換算)は、EVOH樹脂(A)ペレットを浸漬する水溶液中の鉄化合物(C)の濃度や浸漬温度、浸漬時間等によって制御することが可能である。上記浸漬温度、浸漬時間としては、通常、0.5〜48時間、好ましくは1〜36時間であり、浸漬温度は通常10〜40℃、好ましくは20〜35℃である。
かかるEVOH樹脂組成物ペレットは公知の手法にて固液分離し、公知の乾燥方法にて乾燥する。かかる乾燥方法として、種々の乾燥方法を採用することが可能であり、静置乾燥、流動乾燥のいずれでもよい。また、これらを組み合わせて行うこともできる。Further, as the aqueous solution containing the iron compound (C) used in the method (vi), the iron compound is eluted by immersing the aqueous solution of the iron compound (C) or the steel material in water containing various chemicals. What was made to use can be used. In that case, the content of the iron compound (C) in the EVOH resin composition (as metal) is the concentration of the iron compound (C) in the aqueous solution in which the EVOH resin (A) pellets are immersed, the immersion temperature, and the immersion time. And the like. The immersion temperature and the immersion time are usually 0.5 to 48 hours, preferably 1 to 36 hours, and the immersion temperature is usually 10 to 40 ° C, preferably 20 to 35 ° C.
The EVOH resin composition pellets are solid-liquid separated by a known method, and dried by a known drying method. Various drying methods can be adopted as such a drying method, and either static drying or fluidized drying may be used. Moreover, it is also possible to combine these.
本発明のEVOH樹脂組成物ペレットの含水率は、通常、0.01〜0.5重量%であり、好ましくは0.05〜0.35重量%、特に好ましくは0.1〜0.3重量%である。 The water content of the EVOH resin composition pellets of the present invention is usually 0.01 to 0.5% by weight, preferably 0.05 to 0.35% by weight, particularly preferably 0.1 to 0.3% by weight. %.
なお、本発明におけるEVOH樹脂組成物ペレットの含水率は以下の方法により測定・算出されるものである。
EVOH樹脂組成物ぺレットの乾燥前重量(W1)を電子天秤にて秤量し、150℃の熱風乾燥機中で5時間乾燥させ、デシケーター中で30分間放冷後の重量(W2)を秤量し、下記式より算出する。
含水率(重量%)=[(W1−W2)/W1]×100The water content of the EVOH resin composition pellets in the present invention is measured and calculated by the following method.
The weight (W1) of the EVOH resin composition pellet before drying was weighed with an electronic balance, dried in a hot air dryer at 150 ° C. for 5 hours, and allowed to cool in a desiccator for 30 minutes, then weighed (W2). , Calculated from the following formula.
Moisture content (% by weight) = [(W1-W2) / W1] × 100
このようにして得られたEVOH樹脂組成物のペレットは、そのまま溶融成形に供することが可能であるが、溶融成形時のフィード性を安定させる点で、ペレットの表面に公知の滑剤を付着させることも好ましい。滑剤の種類としては、例えば、炭素数12以上の高級脂肪酸(例えばラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘニン酸、オレイン酸等)、高級脂肪酸エステル(高級脂肪酸のメチルエステル、イソプロピルエステル、ブチルエステル、オクチルエステル等)、高級脂肪酸アミド(例えば、ラウリン酸アミド、ミリスチン酸アミド、パルミチン酸アミド、ステアリン酸アミド、ベヘニン酸アミド等の飽和高級脂肪酸アミド;オレイン酸アミド、エルカ酸アミド等の不飽和高級脂肪酸アミド、エチレンビスステアリン酸アミド、エチレンビスオレイン酸アミド、エチレンビスエルカ酸アミド、エチレンビスラウリン酸アミド等のビス高級脂肪酸アミド等)、低分子量ポリオレフィン(例えば分子量500〜10000程度の低分子量ポリエチレン、または低分子量ポリプロピレン等、またはその酸変性品)、炭素数6以上の高級アルコール、エステルオリゴマー、フッ化エチレン樹脂等があげられる。これらの化合物は、単独でもしくは2種以上併せて用いることができる。また、かかる滑剤の含有量は、EVOH樹脂組成物の通常、5重量%以下、好ましくは1重量%以下である。 The pellets of the EVOH resin composition thus obtained can be directly subjected to melt molding, but in order to stabilize the feedability during melt molding, a known lubricant should be attached to the surface of the pellet. Is also preferable. Examples of the lubricant include higher fatty acids having 12 or more carbon atoms (for example, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, etc.), higher fatty acid esters (methyl ester of higher fatty acid, isopropyl ester, Butyl ester, octyl ester, etc.), higher fatty acid amides (eg, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, etc., saturated higher fatty acid amides; oleic acid amide, erucic acid amide, etc. Saturated higher fatty acid amides, bis higher fatty acid amides such as ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylene bis erucic acid amide, and ethylene bis lauric acid amide), low molecular weight polyolefins (for example, a molecular weight of about 500 to 10,000) Molecular weight polyethylene or low molecular weight polypropylene, or an acid modified products), the number 6 or higher alcohol carbon, ester oligomers, such as ethylene fluoride resins. These compounds may be used alone or in combination of two or more. The content of the lubricant is usually 5% by weight or less, preferably 1% by weight or less of the EVOH resin composition.
このようにして得られた本発明のEVOH樹脂組成物は、ペレット、あるいは粉末状や液体状といった、さまざまな形態のEVOH樹脂組成物として調製され、各種の成形物の成形材料として提供される。特に本発明においては、溶融成形用の材料として提供される場合、本発明の効果がより効率的に得られる傾向があり好ましい。なお、本発明のEVOH樹脂組成物には、本発明のEVOH樹脂組成物に用いられるEVOH樹脂(A)以外の樹脂を混合して得られる樹脂組成物も含まれる。 The EVOH resin composition of the present invention thus obtained is prepared as an EVOH resin composition in various forms such as pellets, powder or liquid, and provided as a molding material for various molded products. In particular, in the present invention, when provided as a material for melt molding, the effect of the present invention tends to be obtained more efficiently, which is preferable. The EVOH resin composition of the present invention also includes a resin composition obtained by mixing a resin other than the EVOH resin (A) used in the EVOH resin composition of the present invention.
そして、かかる成形物としては、本発明のEVOH樹脂組成物を用いて成形された単層フィルムをはじめとして、本発明のEVOH樹脂組成物を用いて成形された層を有する多層構造体として実用に供することができる。 Then, as such a molded product, a multilayer structure having a layer molded using the EVOH resin composition of the present invention, including a single-layer film molded using the EVOH resin composition of the present invention, is practically used. Can be offered.
[多層構造体]
本発明の多層構造体は、上記本発明のEVOH樹脂組成物からなる層を有するものである。本発明のEVOH樹脂組成物を含む層(以下、単に「EVOH樹脂組成物層」という)は、本発明のEVOH樹脂組成物以外の熱可塑性樹脂を主成分とする他の基材(以下、基材に用いられる樹脂を「基材樹脂」と略記することがある。)と積層することで、さらに強度を付与したり、EVOH樹脂組成物層を水分等の影響から保護したり、他の機能を付与することができる。[Multilayer structure]
The multilayer structure of the present invention has a layer formed of the EVOH resin composition of the present invention. The layer containing the EVOH resin composition of the present invention (hereinafter, simply referred to as “EVOH resin composition layer”) is formed of another base material (hereinafter, referred to as a base) containing a thermoplastic resin as a main component other than the EVOH resin composition of the present invention. The resin used for the material may be abbreviated as “base resin”.) To provide more strength, protect the EVOH resin composition layer from the influence of moisture, etc. Can be given.
上記基材樹脂としては、例えば、直鎖状低密度ポリエチレン、低密度ポリエチレン、超低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、エチレン−プロピレン(ブロックおよびランダム)共重合体、エチレン−α−オレフィン(炭素数4〜20のα−オレフィン)共重合体等のポリエチレン系樹脂、ポリプロピレン、プロピレン−α−オレフィン(炭素数4〜20のα−オレフィン)共重合体等のポリプロピレン系樹脂、ポリブテン、ポリペンテン、ポリ環状オレフィン系樹脂(環状オレフィン構造を主鎖および側鎖の少なくとも一方を有する重合体)等の(未変性)ポリオレフィン系樹脂や、これらのポリオレフィン類を不飽和カルボン酸又はそのエステルでグラフト変性した不飽和カルボン酸変性ポリオレフィン系樹脂等の変性オレフィン系樹脂を含む広義のポリオレフィン系樹脂、アイオノマー、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸共重合体、エチレン−アクリル酸エステル共重合体、ポリエステル系樹脂、ポリアミド系樹脂(共重合ポリアミドも含む)、ポリ塩化ビニル、ポリ塩化ビニリデン、アクリル系樹脂、ポリスチレン系樹脂、ビニルエステル系樹脂、ポリエステル系エラストマー、ポリウレタン系エラストマー、ポリスチレン系エラストマー、塩素化ポリエチレン、塩素化ポリプロピレン等のハロゲン化ポリオレフィン、芳香族または脂肪族ポリケトン類等があげられる。 Examples of the base resin include linear low density polyethylene, low density polyethylene, ultra low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-propylene (block and random) copolymer, ethylene-α-olefin. Polyethylene resin such as (C4-20 α-olefin) copolymer, polypropylene, polypropylene such as propylene-α-olefin (C4-20 α-olefin) copolymer, polybutene, polypentene , (Unmodified) polyolefin resins such as polycyclic olefin resins (polymers having a cyclic olefin structure having at least one of a main chain and side chains), and graft modification of these polyolefins with unsaturated carboxylic acids or their esters Unsaturated carboxylic acid modified polyolefin resin, etc. Broadly defined polyolefin resin including modified olefin resin, ionomer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer, polyester resin, polyamide resin (copolymerized polyamide (Including also), polyvinyl chloride, polyvinylidene chloride, acrylic resin, polystyrene resin, vinyl ester resin, polyester elastomer, polyurethane elastomer, polystyrene elastomer, chlorinated polyethylene, halogenated polyolefin such as chlorinated polypropylene, Examples thereof include aromatic or aliphatic polyketones.
これらのうち、疎水性樹脂である、ポリアミド系樹脂、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリスチレン系樹脂が好ましく、より好ましくは、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリ環状オレフィン系樹脂およびこれらの不飽和カルボン酸変性ポリオレフィン系樹脂等のポリオレフィン系樹脂である。 Of these, hydrophobic resins such as polyamide-based resins, polyolefin-based resins, polyester-based resins, and polystyrene-based resins are preferred, and more preferably polyethylene-based resins, polypropylene-based resins, polycyclic olefin-based resins, and unsaturated resins thereof. A polyolefin resin such as a carboxylic acid-modified polyolefin resin.
多層構造体の層構成は、本発明のEVOH樹脂組成物層をa(a1、a2、・・・)、基材樹脂層をb(b1、b2、・・・)とするとき、a/b、b/a/b、a/b/a、a1/a2/b、a/b1/b2、b2/b1/a/b1/b2、b2/b1/a/b1/a/b1/b2等、任意の組み合わせが可能である。また、該多層構造体を製造する過程で発生する端部や不良品等を再溶融成形して得られる、本発明のEVOH樹脂組成物と本発明のEVOH樹脂組成物以外の熱可塑性樹脂との混合物を含むリサイクル層をRとするとき、b/R/a、b/R/a/b、b/R/a/R/b、b/a/R/a/b、b/R/a/R/a/R/b等とすることも可能である。多層構造体の層の数はのべ数にて通常2〜15、好ましくは3〜10である。上記の層構成において、それぞれの層間には、必要に応じて接着性樹脂を含有する接着性樹脂層を介在させてもよい。 When the EVOH resin composition layer of the present invention is a (a1, a2, ...) And the base resin layer is b (b1, b2, ...), the layer structure of the multilayer structure is a / b. , B / a / b, a / b / a, a1 / a2 / b, a / b1 / b2, b2 / b1 / a / b1 / b2, b2 / b1 / a / b1 / a / b1 / b2, etc., Any combination is possible. In addition, the EVOH resin composition of the present invention and a thermoplastic resin other than the EVOH resin composition of the present invention, which are obtained by remelt-molding edges and defective products generated in the process of manufacturing the multilayer structure, When the recycled layer containing the mixture is R, b / R / a, b / R / a / b, b / R / a / R / b, b / a / R / a / b, b / R / a It is also possible to use / R / a / R / b or the like. The total number of layers of the multilayer structure is usually 2 to 15, preferably 3 to 10. In the above layer structure, an adhesive resin layer containing an adhesive resin may be interposed between the respective layers, if necessary.
上記接着性樹脂としては、公知のものを使用でき、基材樹脂「b」に用いる熱可塑性樹脂の種類に応じて適宜選択すればよい。代表的には不飽和カルボン酸またはその無水物をポリオレフィン系樹脂に付加反応やグラフト反応等により化学的に結合させて得られるカルボキシル基を含有する変性ポリオレフィン系重合体をあげることができる。上記カルボキシル基を含有する変性ポリオレフィン系重合体としては、例えば、無水マレイン酸グラフト変性ポリエチレン、無水マレイン酸グラフト変性ポリプロピレン、無水マレイン酸グラフト変性エチレン−プロピレン(ブロックおよびランダム)共重合体、無水マレイン酸グラフト変性エチレン−エチルアクリレート共重合体、無水マレイン酸グラフト変性エチレン−酢酸ビニル共重合体、無水マレイン酸変性ポリ環状オレフィン系樹脂、無水マレイン酸グラフト変性ポリオレフィン系樹脂等があげられる。そして、これらから選ばれた1種または2種以上の混合物を用いることができる。 As the above adhesive resin, a known adhesive resin can be used and may be appropriately selected depending on the type of the thermoplastic resin used for the base resin “b”. Typically, a modified polyolefin polymer containing a carboxyl group obtained by chemically bonding an unsaturated carboxylic acid or an anhydride thereof to a polyolefin resin by an addition reaction or a graft reaction can be mentioned. Examples of the modified polyolefin polymer containing a carboxyl group include maleic anhydride graft-modified polyethylene, maleic anhydride graft-modified polypropylene, maleic anhydride graft-modified ethylene-propylene (block and random) copolymers, maleic anhydride. Examples thereof include graft-modified ethylene-ethyl acrylate copolymer, maleic anhydride graft-modified ethylene-vinyl acetate copolymer, maleic anhydride-modified polycyclic olefin-based resin, maleic anhydride graft-modified polyolefin-based resin, and the like. Then, one kind or a mixture of two or more kinds selected from these can be used.
多層構造体において、本発明のEVOH樹脂組成物層と基材樹脂層との間に、接着性樹脂層を用いる場合、接着性樹脂層がEVOH樹脂組成物層の両側に位置することから、疎水性に優れた接着性樹脂を用いることが好ましい。 When an adhesive resin layer is used between the EVOH resin composition layer of the present invention and the base resin layer in a multilayer structure, the adhesive resin layer is located on both sides of the EVOH resin composition layer, and It is preferable to use an adhesive resin having excellent properties.
上記基材樹脂、接着性樹脂には、本発明の趣旨を阻害しない範囲(例えば、樹脂全体に対して、30重量%以下、好ましくは10重量%以下)において、従来知られているような可塑剤、フィラー、クレー(モンモリロナイト等)、着色剤、酸化防止剤、帯電防止剤、滑剤、核材、ブロッキング防止剤、ワックス等を含んでいてもよい。これらは単独でもしくは2種以上併せて用いることができる。 The above-mentioned base resin and adhesive resin have plasticity as conventionally known within a range that does not impair the gist of the present invention (for example, 30% by weight or less, preferably 10% by weight or less based on the entire resin). Agents, fillers, clay (such as montmorillonite), colorants, antioxidants, antistatic agents, lubricants, core materials, antiblocking agents, and waxes may be included. These may be used alone or in combination of two or more.
本発明のEVOH樹脂組成物層と上記基材樹脂層との積層(接着性樹脂層を介在させる場合を含む)は、公知の方法にて行うことができる。例えば、本発明のEVOH樹脂組成物のフィルム、シート等に基材樹脂を溶融押出ラミネートする方法、基材樹脂層に本発明のEVOH樹脂組成物を溶融押出ラミネートする方法、EVOH樹脂組成物と基材樹脂とを共押出する方法、EVOH樹脂組成物(層)と基材樹脂(層)とを有機チタン化合物、イソシアネート化合物、ポリエステル系化合物、ポリウレタン化合物等の公知の接着剤を用いてドライラミネートする方法、基材樹脂上にEVOH樹脂組成物の溶液を塗工してから溶媒を除去する方法等があげられる。これらのなかでも、コストや環境の観点から考慮して共押出する方法が好ましい。 The EVOH resin composition layer of the present invention and the above-mentioned base resin layer may be laminated (including a case where an adhesive resin layer is interposed) by a known method. For example, a method of melt extrusion laminating a base resin on a film, sheet or the like of the EVOH resin composition of the present invention, a method of melt extrusion laminating the EVOH resin composition of the present invention on a base resin layer, an EVOH resin composition and a base. Method of co-extruding a material resin, and EVOH resin composition (layer) and base resin (layer) are dry-laminated using a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound or a polyurethane compound. Examples of the method include a method of applying a solution of the EVOH resin composition on the base resin and then removing the solvent. Among these, the coextrusion method is preferable from the viewpoints of cost and environment.
上記の如き多層構造体は、次いで必要に応じて(加熱)延伸処理が施される。延伸処理は、一軸延伸、二軸延伸のいずれであってもよく、二軸延伸の場合は同時延伸であっても逐次延伸であってもよい。また、延伸方法としてはロール延伸法、テンター延伸法、チューブラー延伸法、延伸ブロー法、真空圧空成形等のうち延伸倍率の高いものも採用できる。延伸温度は、多層構造体の融点近傍の温度で、通常40〜170℃、好ましくは60〜160℃程度の範囲から選ばれる。延伸温度が低すぎた場合は延伸性が不良となり、高すぎた場合は安定した延伸状態を維持することが困難となる。 The above-mentioned multilayer structure is then subjected to a (heating) stretching treatment, if necessary. The stretching treatment may be uniaxial stretching or biaxial stretching, and in the case of biaxial stretching, it may be simultaneous stretching or sequential stretching. As a stretching method, a roll stretching method, a tenter stretching method, a tubular stretching method, a stretching blow method, a vacuum pressure molding or the like having a high stretching ratio can be adopted. The stretching temperature is a temperature in the vicinity of the melting point of the multilayer structure and is usually selected from the range of 40 to 170 ° C, preferably about 60 to 160 ° C. If the stretching temperature is too low, the stretchability will be poor, and if it is too high, it will be difficult to maintain a stable stretched state.
なお、延伸後に寸法安定性を付与することを目的として、熱固定を行ってもよい。熱固定は周知の手段で実施可能であり、例えば上記延伸フィルムを緊張状態を保ちながら通常80〜180℃、好ましくは100〜165℃で通常2〜600秒間程度熱処理を行う。また、本発明のEVOH樹脂組成物から得られた多層延伸フィルムをシュリンク用フィルムとして用いる場合には、熱収縮性を付与するために、上記の熱固定を行わず、例えば延伸後のフィルムに冷風を当てて冷却固定するなどの処理を行えばよい。 In addition, heat setting may be performed for the purpose of imparting dimensional stability after stretching. The heat setting can be carried out by a well-known means. For example, the stretched film is usually heat-treated at 80 to 180 ° C., preferably 100 to 165 ° C. for usually 2 to 600 seconds while maintaining a tension state. When the multilayer stretched film obtained from the EVOH resin composition of the present invention is used as a shrink film, the above heat setting is not performed in order to impart heat shrinkability, and for example, the stretched film is cooled with cold air. It suffices to apply a process such as applying heat to fix it.
また、場合によっては、本発明の多層構造体を用いてカップやトレイ状の多層容器を得ることも可能である。その場合は、通常絞り成形法が採用され、具体的には真空成形法、圧空成形法、真空圧空成形法、プラグアシスト式真空圧空成形法等があげられる。更に多層パリソン(ブロー前の中空管状の予備成形物)からチューブやボトル状の多層容器(積層体構造)を得る場合はブロー成形法が採用される。具体的には、押出ブロー成形法(双頭式、金型移動式、パリソンシフト式、ロータリー式、アキュムレーター式、水平パリソン式等)、コールドパリソン式ブロー成形法、射出ブロー成形法、二軸延伸ブロー成形法(押出式コールドパリソン二軸延伸ブロー成形法、射出式コールドパリソン二軸延伸ブロー成形法、射出成形インライン式二軸延伸ブロー成形法等)などがあげられる。得られる積層体は必要に応じ、熱処理、冷却処理、圧延処理、印刷処理、ドライラミネート処理、溶液または溶融コート処理、製袋加工、深絞り加工、箱加工、チューブ加工、スプリット加工等を行うことができる。 In some cases, it is possible to obtain a cup-shaped or tray-shaped multilayer container by using the multilayer structure of the present invention. In that case, the draw forming method is usually adopted, and specific examples thereof include a vacuum forming method, a pressure forming method, a vacuum pressure forming method, a plug assist type vacuum pressure forming method and the like. Further, when a tube or bottle-shaped multilayer container (laminate structure) is obtained from a multilayer parison (a hollow tubular preform before being blown), a blow molding method is adopted. Specifically, extrusion blow molding method (double head type, mold moving type, parison shift type, rotary type, accumulator type, horizontal parison type, etc.), cold parison type blow molding method, injection blow molding method, biaxial stretching. Blow molding methods (extrusion cold parison biaxial stretching blow molding method, injection cold parison biaxial stretching blow molding method, injection molding in-line biaxial stretching blow molding method, etc.) can be mentioned. If necessary, the resulting laminate may be subjected to heat treatment, cooling treatment, rolling treatment, printing treatment, dry lamination treatment, solution or melt coating treatment, bag making processing, deep drawing processing, box processing, tube processing, split processing, etc. You can
多層構造体(延伸したものを含む)の厚み、更には多層構造体を構成するEVOH樹脂組成物層、基材樹脂層および接着性樹脂層の厚みは、層構成、基材樹脂の種類、接着性樹脂の種類、用途や包装形態、要求される物性等により一概にいえないが、多層構造体(延伸したものを含む)の厚みは、通常10〜5000μm、好ましくは30〜3000μm、特に好ましくは50〜2000μmである。EVOH樹脂組成物層は通常1〜500μm、好ましくは3〜300μm、特に好ましくは5〜200μmであり、基材樹脂層は通常5〜3000μm、好ましくは10〜2000μm、特に好ましくは20〜1000μmであり、接着性樹脂層は、通常0.5〜250μm、好ましくは1〜150μm、特に好ましくは3〜100μmである。 The thickness of the multilayer structure (including stretched ones), and further the thickness of the EVOH resin composition layer, the base resin layer and the adhesive resin layer forming the multilayer structure are the layer structure, the type of base resin, and the adhesion. The thickness of the multilayer structure (including stretched ones) is usually 10 to 5000 μm, preferably 30 to 3000 μm, and particularly preferably, though it cannot be generally stated depending on the type of the resin, the application, the packaging form, the required physical properties and the like. It is 50 to 2000 μm. The EVOH resin composition layer is usually 1 to 500 μm, preferably 3 to 300 μm, particularly preferably 5 to 200 μm, and the base resin layer is usually 5 to 3000 μm, preferably 10 to 2000 μm, particularly preferably 20 to 1000 μm. The adhesive resin layer has a thickness of usually 0.5 to 250 μm, preferably 1 to 150 μm, and particularly preferably 3 to 100 μm.
さらに、多層構造体におけるEVOH樹脂組成物層の基材樹脂層に対する厚みの比(EVOH樹脂組成物層/基材樹脂層)は、各層が複数ある場合は最も厚みの厚い層同士の比にて、通常1/99〜50/50、好ましくは5/95〜45/55、特に好ましくは10/90〜40/60である。また、多層構造体におけるEVOH樹脂組成物層の接着性樹脂層に対する厚み比(EVOH樹脂組成物層/接着性樹脂層)は、各層が複数ある場合は最も厚みの厚い層同士の比にて、通常10/90〜99/1、好ましくは20/80〜95/5、特に好ましくは50/50〜90/10である。 Furthermore, the thickness ratio of the EVOH resin composition layer to the base resin layer in the multilayer structure (EVOH resin composition layer / base resin layer) is the ratio of the thickest layers when there are multiple layers. , Usually 1/99 to 50/50, preferably 5/95 to 45/55, particularly preferably 10/90 to 40/60. Further, the thickness ratio of the EVOH resin composition layer to the adhesive resin layer in the multilayer structure (EVOH resin composition layer / adhesive resin layer) is the ratio between the thickest layers when there are a plurality of layers, It is usually 10/90 to 99/1, preferably 20/80 to 95/5, particularly preferably 50/50 to 90/10.
上記の如く得られたフィルム、シート、延伸フィルムからなる袋およびカップ、トレイ、チューブ、ボトル等からなる容器や蓋材は、一般的な食品の他、マヨネーズ、ドレッシング等の調味料、味噌等の発酵食品、サラダ油等の油脂食品、飲料、化粧品、医薬品等の各種の包装材料容器として有用である。 The film and sheet obtained as described above, a bag and a cup made of a stretched film, a tray, a tube, a container made of a bottle or the like, a general food, mayonnaise, seasonings such as dressing, miso, etc. It is useful as a packaging material container for fermented foods, oil and fat foods such as salad oil, beverages, cosmetics, pharmaceuticals, and the like.
以下、実施例をあげて本発明を具体的に説明するが、本発明はその要旨を超えない限り、実施例の記載に限定されるものではない。
尚、例中「部」とあるのは、断りのない限り重量基準を意味する。Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the description of the examples as long as the gist thereof is not exceeded.
In addition, "part" in the examples means weight basis unless otherwise specified.
実施例に先立って以下のEVOH樹脂(A)のペレットを準備し、そのEVOH樹脂(A)に含まれている鉄化合物(C)の含有量を測定した。
・EVOH樹脂(A):エチレン構造単位の含有量29モル%、ケン化度99.6モル%、MFR3.9g/10分(210℃、荷重2160g)のエチレン−ビニルアルコール共重合体Prior to the examples, the following EVOH resin (A) pellets were prepared, and the content of the iron compound (C) contained in the EVOH resin (A) was measured.
EVOH resin (A): ethylene structural unit content 29 mol%, saponification degree 99.6 mol%, MFR 3.9 g / 10 min (210 ° C., load 2160 g) ethylene-vinyl alcohol copolymer.
[鉄化合物(C)の含有量の測定]
上記EVOH樹脂(A)のペレットを粉砕したサンプル0.5gを赤外線加熱炉で灰化処理(酸素気流中650℃、1時間)し、灰分を酸溶解して純水で定容したものを試料溶液とした。この溶液を下記のICP−MS(Agilent Technologies社製 ICP質量分析装置 7500ce型)を用いて標準添加法で測定した。その結果、鉄化合物(C)の含有量は、金属換算にて0ppmであった。[Measurement of Content of Iron Compound (C)]
0.5g sample of crushed pellets of the EVOH resin (A) was ashed in an infrared heating furnace (650 ° C in an oxygen stream for 1 hour), and the ash was acid-dissolved to give a fixed volume with pure water. It was a solution. The solution was measured by the standard addition method using the following ICP-MS (ICP mass spectrometer 7500ce type manufactured by Agilent Technologies). As a result, the content of the iron compound (C) was 0 ppm in terms of metal.
〔実施例1〕
上記EVOH樹脂(A)ペレット100部、キノン化合物(B)としてハイドロキノン0.003部(EVOH樹脂組成物の重量あたり30ppm)、鉄化合物(C)としてリン酸鉄(III)n水和物(和光純薬工業社製、230℃乾燥減量20.9重量%)0.000034部(EVOH樹脂組成物の重量あたり金属換算にて0.1ppm)をプラストグラフ(ブラベンダー社製)にて、230℃において5分間予熱したのち5分間溶融混練し、EVOH樹脂組成物を得た。得られたEVOH樹脂組成物を、粉砕機(ソメタニ産業社製 型式:SKR16−240)にて650rpmにて粉砕して粉砕物を得た。かかる粉砕物は、1〜5mm角の小片であった。[Example 1]
100 parts of the EVOH resin (A) pellets, 0.003 parts of hydroquinone as the quinone compound (B) (30 ppm based on the weight of the EVOH resin composition), and iron (III) phosphate n-hydrate as the iron compound (C) (sum Koujunyaku Kogyo Co., Ltd., 230 ° C dry weight loss 20.9% by weight) 0.000034 parts (0.1 ppm in terms of metal based on the weight of the EVOH resin composition) at 230 ° C with a plastograph (Bravender Co., Ltd.) After preheating for 5 minutes, the mixture was melt-kneaded for 5 minutes to obtain an EVOH resin composition. The obtained EVOH resin composition was pulverized with a pulverizer (Sometan Sangyo Co., Ltd. model: SKR16-240) at 650 rpm to obtain a pulverized product. The pulverized product was a small piece of 1 to 5 mm square.
〔実施例2〕
実施例1において、リン酸鉄(III)n水和物の配合量を0.00034部(EVOH樹脂組成物の重量あたり金属換算にて1ppm)に変更した以外は、実施例1と同様にしてEVOH樹脂組成物およびその粉砕物を得た。[Example 2]
In the same manner as in Example 1 except that the amount of the iron (III) phosphate n-hydrate mixed was changed to 0.00034 parts (1 ppm in terms of metal per weight of the EVOH resin composition). An EVOH resin composition and a pulverized product thereof were obtained.
〔実施例3〕
実施例1において、リン酸鉄(III)n水和物の配合量を0.0034部(EVOH樹脂組成物の重量あたり金属換算にて10ppm)に変更した以外は、実施例1と同様にしてEVOH樹脂組成物およびその粉砕物を得た。[Example 3]
In the same manner as in Example 1 except that the amount of the iron (III) phosphate n-hydrate blended was changed to 0.0034 parts (10 ppm in terms of metal per weight of the EVOH resin composition). An EVOH resin composition and a pulverized product thereof were obtained.
〔比較例1〕
実施例1において、リン酸鉄(III)n水和物を配合しなかった。それ以外は実施例1と同様にしてEVOH樹脂組成物およびその粉砕物を得た。[Comparative Example 1]
In Example 1, iron (III) phosphate n-hydrate was not added. An EVOH resin composition and a pulverized product thereof were obtained in the same manner as in Example 1 except for the above.
つぎに、下記に示す方法により実施例1〜3および比較例1にて得られたEVOH樹脂組成物の着色評価を行なった。その結果を下記の表1に示す。 Next, the EVOH resin compositions obtained in Examples 1 to 3 and Comparative Example 1 were evaluated for coloring by the method described below. The results are shown in Table 1 below.
[着色評価]
上記のEVOH樹脂組成物の粉砕物をサンプルとし、日本電色工業社製 分光色差計 SE6000にてYI値を測定した。このとき、内径32mm高さ30mmの円筒にサンプルを充填し擦りきった状態で測定に供した。また、かかるサンプルを空気雰囲気下のオーブン内で150℃、5時間加熱処理したサンプルについても同様に測定した。かかる加熱前のYI値に対する加熱後のYI値の比を算出した。かかる値が大きいほど、樹脂組成物が加熱後に黄色く着色していることを意味する。[Coloring evaluation]
The pulverized product of the above EVOH resin composition was used as a sample, and the YI value was measured by a spectral color difference meter SE6000 manufactured by Nippon Denshoku Industries Co., Ltd. At this time, the sample was filled in a cylinder having an inner diameter of 32 mm and a height of 30 mm, and the sample was rubbed and used for the measurement. Further, a sample obtained by heating the sample at 150 ° C. for 5 hours in an oven under an air atmosphere was similarly measured. The ratio of the YI value after heating to the YI value before heating was calculated. The larger the value, the more the resin composition is colored yellow after heating.
上記結果、鉄化合物(C)を含有しない、キノン化合物(B)のみ配合された比較例1品は、加熱前後のYI値の比が1.9であった。これに対してキノン化合物(B)および特定微量の鉄化合物(C)を含有する実施例1〜3では加熱前後のYI値の比が比較例1品よりも全て低い値となり、加熱後の着色が抑制されていることがわかる。 As a result, in the product of Comparative Example 1 containing no iron compound (C) and containing only the quinone compound (B), the YI value ratio before and after heating was 1.9. On the other hand, in Examples 1 to 3 containing the quinone compound (B) and the specific trace amount of the iron compound (C), the ratio of YI values before and after heating was lower than that of the product of Comparative Example 1, and coloring after heating. It can be seen that is suppressed.
上記実施例においては、本発明における具体的な形態について示したが、上記実施例は単なる例示にすぎず、限定的に解釈されるものではない。当業者に明らかな様々な変形は、本発明の範囲内であることが企図されている。 Although specific embodiments of the present invention have been shown in the above embodiments, the above embodiments are merely examples and should not be construed as limiting. Various modifications apparent to those skilled in the art are intended to be within the scope of the present invention.
本発明のEVOH樹脂組成物は、加熱後の着色が抑制されることから、各種食品の他、マヨネーズ、ドレッシング等の調味料、味噌等の発酵食品、サラダ油等の油脂食品、飲料、化粧品、医薬品等の各種の包装材料として有用である。 Since the EVOH resin composition of the present invention suppresses coloring after heating, in addition to various foods, seasonings such as mayonnaise and dressings, fermented foods such as miso, oil and fat foods such as salad oil, beverages, cosmetics, and pharmaceuticals It is useful as various packaging materials such as.
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