JP6411705B1 - 樹脂組成物、その製造方法及びそれを用いた成形体 - Google Patents
樹脂組成物、その製造方法及びそれを用いた成形体 Download PDFInfo
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- JP6411705B1 JP6411705B1 JP2018540481A JP2018540481A JP6411705B1 JP 6411705 B1 JP6411705 B1 JP 6411705B1 JP 2018540481 A JP2018540481 A JP 2018540481A JP 2018540481 A JP2018540481 A JP 2018540481A JP 6411705 B1 JP6411705 B1 JP 6411705B1
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- Prior art keywords
- resin composition
- ethylene
- nonionic surfactant
- vinyl alcohol
- alcohol copolymer
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 115
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 98
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 60
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005977 Ethylene Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 238000007127 saponification reaction Methods 0.000 claims abstract description 10
- -1 alkenyl ether Chemical compound 0.000 claims description 99
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 22
- 229920005992 thermoplastic resin Polymers 0.000 claims description 19
- 125000005907 alkyl ester group Chemical group 0.000 claims description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 17
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 150000004665 fatty acids Chemical class 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 150000005215 alkyl ethers Chemical class 0.000 claims description 9
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 150000001408 amides Chemical class 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000002216 antistatic agent Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- SBOJXQVPLKSXOG-UHFFFAOYSA-N o-amino-hydroxylamine Chemical compound NON SBOJXQVPLKSXOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 abstract description 24
- 238000004898 kneading Methods 0.000 abstract description 7
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 76
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 76
- 239000010410 layer Substances 0.000 description 36
- 238000000034 method Methods 0.000 description 24
- 239000008188 pellet Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 229920000098 polyolefin Polymers 0.000 description 12
- 238000004040 coloring Methods 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 239000002356 single layer Substances 0.000 description 9
- 239000004840 adhesive resin Substances 0.000 description 8
- 229920006223 adhesive resin Polymers 0.000 description 8
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 239000000446 fuel Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229920000092 linear low density polyethylene Polymers 0.000 description 7
- 239000004707 linear low-density polyethylene Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920001567 vinyl ester resin Polymers 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- 229920000223 polyglycerol Polymers 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 235000012055 fruits and vegetables Nutrition 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241000251468 Actinopterygii Species 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 2
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 2
- 239000004147 Sorbitan trioleate Substances 0.000 description 2
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229940070765 laurate Drugs 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229940035044 sorbitan monolaurate Drugs 0.000 description 2
- 239000001570 sorbitan monopalmitate Substances 0.000 description 2
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 2
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 2
- 235000019337 sorbitan trioleate Nutrition 0.000 description 2
- 229960000391 sorbitan trioleate Drugs 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- WZUNUACWCJJERC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CC)(CO)CO WZUNUACWCJJERC-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XHALKWMTKWHQLO-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxyphenyl)sulfanylphenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(SC=2C=C(C(O)=CC=2)C(C)(C)C)=C1 XHALKWMTKWHQLO-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- POZWNWYYFQVPGC-UHFFFAOYSA-N 3-methoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[SiH2]CCCOC(=O)C(C)=C POZWNWYYFQVPGC-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N Butanol Natural products CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
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Abstract
【選択図】なし
Description
本発明の樹脂組成物は、エチレン−ビニルアルコール共重合体及び非イオン界面活性剤を含有するものであって、前記エチレン−ビニルアルコール共重合体のエチレン単位含有量が15〜60モル%であり、ケン化度が90モル%以上であり、前記エチレン−ビニルアルコール共重合体を主成分として含有し、前記非イオン界面活性剤を3〜400ppm含有するものである。
本発明の樹脂組成物に含有されるEVOHは、エチレン単位及びビニルアルコール単位を含有する共重合体である。前記EVOHは、公知の方法にて製造することができる。例えば、エチレンとビニルエステルを共重合させてエチレン−ビニルエステル共重合体を得た後、当該共重合体をアルカリ触媒等を用いてケン化することにより前記EVOHが得られる。前記ビニルエステルとしては、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル等の脂肪酸ビニルエステルが挙げられ、酢酸ビニルが好ましい。前記EVOHは、本発明の効果を阻害しない範囲であれば、エチレン及びビニルアルコール以外の共重合成分を含有していてもよい。そのような他の共重合成分として、例えばビニルシラン化合物に由来する単位が挙げられる。ここで、ビニルシラン化合物に由来する単位としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリ(β−メトキシ−エトキシ)シラン又はγ−メタクリルオキシプロピルメトキシシランに由来する単位が挙げられる。これらのなかでも、ビニルトリメトキシシラン又はビニルトリエトキシシランに由来する単位が好適である。さらに、前記EVOHは、他の共重合成分として、プロピレン、ブテン等のα−オレフィン;(メタ)アクリル酸や(メタ)アクリル酸メチルなどの不飽和カルボン酸又はそのエステル;及びN−ビニルピロリドンなどのビニルピロリドンに由来する単位を含有していてもよい。前記EVOH中のエチレン単位及びビニルアルコール単位以外の共重合成分の含有量は、10モル%以下が好ましく、5モル%以下がより好ましく、1モル%以下がさらに好ましい。
本発明の樹脂組成物は、非イオン界面活性剤を3〜400ppm含有する。前記樹脂組成物が所定量の非イオン界面活性剤を含有することによって、溶融成形する際の樹脂の吐出量を増加させることができる。特に、前記樹脂組成物が前記EVOH以外の他の成分を含有する場合でも、このような成分の影響を受けることなく、樹脂の吐出量を増加させることができるとともに、溶融した樹脂が低温である場合でも一定の吐出量を確保することができる。さらに、驚くべきことに、前記樹脂組成物が所定量の非イオン界面活性剤を含有することによって、溶融成形時における当該樹脂組成物の着色が抑制される。詳細は明らかではないが、以下のようなことが推察される。一般的に、EVOHに金属イオンが含有された場合、当該金属イオンとEVOHとが反応することによって、EVOHの熱劣化が促進されて、EVOHに黄変等の着色が生じることが知られている。このような反応を非イオン界面活性剤が阻害すること等により、EVOHの熱劣化が抑制されるものと推察される。
R−O−(AO)nH (1)
R−COO(AO)nH (2)
前記樹脂組成物は、さらにアルカリ金属塩を含むことが好適である。このようにアルカリ金属塩を含有する樹脂組成物とすることによって、他の樹脂に対する接着性が良好になる。特に、前記樹脂組成物からなる層と前記エチレン−ビニルアルコール共重合体以外の熱可塑性樹脂からなる層を有する多層構造体における、層間接着性が向上する。しかも、驚くべきことに、所定量の非イオン界面活性剤を用いることにより、アルカリ金属塩によるEVOHの熱劣化を抑制しつつ、接着性を向上させることができる。
前記樹脂組成物は、本発明の効果を阻害しない範囲であれば、前記EVOH及び非イオン界面活性剤以外の他の成分を含有していてもよい。前記樹脂組成物中の他の成分の含有量は0.005〜45質量%が好ましい。当該含有量は、20質量%以下がより好ましく、10質量%以下がさらに好ましく、5質量%以下が特に好ましく、1質量%以下が最も好ましい。ここで、2種以上の成分が用いられる場合には、合計含有量が前記範囲であればよい。
カルボン酸:シュウ酸、コハク酸、安息香酸、クエン酸、酢酸、乳酸等
リン酸化合物:リン酸、亜リン酸等の各種の酸やその塩等
ホウ素化合物:ホウ酸、ホウ酸エステル、ホウ酸塩、水素化ホウ素等
本発明の樹脂組成物の製造方法は特に限定されないが、前記EVOH、非イオン界面活性剤及び必要に応じて他の成分を含む混合物を溶融混練する方法が挙げられる。
こうして得られた樹脂組成物を含有する成形体が本発明の好適な実施態様である。当該成形体は、当該樹脂組成物のみからなるものであってもよいし、当該樹脂組成物からなる部分と当該樹脂組成物以外のものからなる部分とを有するものであってもよい。
(1)前記樹脂組成物と他の熱可塑性樹脂とを共押出する方法
(2)前記樹脂組成物からなる成形体上に他の熱可塑性樹脂を溶融押出する方法
(3)前記樹脂組成物と他の熱可塑性樹脂とを共射出する方法
(4)前記樹脂組成物からなる成形体と他の熱可塑性樹脂からなる成形体とを接着剤を用いて積層させる方法
(1)多層構造体(シート、フィルム等)を一軸又は二軸方向に延伸するとともに、熱処理することにより得られる多層延伸シート又は多層延伸フィルム
(2)多層構造体(シート、フィルム等)を圧延することにより得られる多層圧延シート又は多層圧延フィルム
(3)多層構造体(シート、フィルム等)を熱成形(真空成形、圧空成形、真空圧空成形等)することにより得られる多層トレー又は多層カップ状容器
(4)多層構造体(パイプ等)をストレッチブロー成形することにより得られる多層ボトル、多層カップ状容器等
(1)樹脂組成物ペレットの作製
エチレン単位含有量32モル%、ケン化度99.98モル%、MFR3.8g/10分(温度210℃、荷重2160g)、含水率0.2質量%、金属塩として酢酸ナトリウムをナトリウム換算で200ppm含有するEVOH1を準備した。また、非イオン界面活性剤としてポリオキシエチレン(7)ステアリルエーテル(非イオン界面活性剤の化合物名中の括弧内の数字は、ポリオキシエチレン単位の縮合度を表す。以下同様である。)が分散した水分散液(非イオン界面活性剤の含有量:10.0g/L)を準備した。100質量部のEVOH1と1質量部の前記水分散液とをブレンドした。得られた混合物を以下の条件で溶融混練した後、ペレット化してさらに乾燥させることにより、樹脂組成物ペレットを得た。
装置:25mmφ二軸押出機(東洋精機製作所製の「ラボプラストミル4C150」)
L/D:25
スクリュー:同方向完全噛合型
ダイスホール数:2ホール(3mmφ)
押出温度:C1=200℃、C2からC5=220℃、ダイ=220℃
乾燥:真空乾燥90℃/20hr
樹脂組成物ペレット10gを1,1,1,3,3,3−ヘキサフルオロ−2−プロパノールに溶解した後、当該溶液をメタノールに滴下した。この液体をフィルターでろ過して析出物を除去した後に濃縮した。得られた濃縮液をWaters社の「UPLC H−Class」を用いて測定することにより、EVOHペレット中の非イオン界面活性剤の含有量を算出した。なお、定量に際しては各非イオン界面活性剤を用いて作成した検量線を用いた。樹脂組成物ペレット中のポリオキシエチレン(7)ステアリルエーテルの含有量は100ppmであった。
樹脂組成物ペレットを、東洋精機製作所製の20mm押出機「D2020」(D=20mm、L/D=20、圧縮比=2.0、スクリュー:フルフライト)を用いて、以下の条件で厚み20μmの単層フィルムを得た。このときの1時間あたりの単層フィルムの生産量を樹脂組成物の吐出量として評価した。吐出量が0.5kg/hr以上であれば実用可能である。測定の結果、樹脂組成物の吐出量は1.6kg/hrであった。
単層フィルム作製条件
押出温度:供給部/圧縮部/計量部/ダイ
=160/180/210/210℃
スクリュー回転数:40rpm
引取りロール温度:80℃
上記方法で作製された単層フィルムを紙管に巻き取り、フィルム端面の着色を肉眼で以下の基準により評価した。その結果、フィルム端面の着色は確認されなかった。
A :着色は確認されなかった
B :わずかに黄変していた
C :黄変していたが実用可能な程度であった
D :激しく黄変して実用不可能であった
樹脂組成物ペレット、直鎖状低密度ポリエチレン(LLDPE:三井化学社製ウルトゼックス2022L)及び接着性樹脂(SUMICA.ATOCHEM Co.Ltd製Bondine TX8030、以下Adと略することがある)を用いて、以下のとおり、3種5層の多層フィルム(LLDPE/Ad/樹脂組成物/Ad/LLDPE=50μm/10μm/10μm/10μm/50μm)を得た。得られた多層フィルムを、多層製膜直後にMD方向に150mm、TD方向に10mmで切り出した後、直ちにオートグラフ(島津製作所社製DCS−50M)によりT型剥離モードで樹脂組成物層/Ad層間の剥離強度を測定して、以下の基準により評価した。その結果、接着強度は550g/15cmであった。
〈多層製膜条件〉
押出機:
EVOH用 :20mmφ押出機 ラボ機ME型CO−EXT(東洋精機社製)
Ad用 :25mmφ押出機 P25−18AC(大阪精機社製)
LLDPE用:32mmφ押出機 GF−32−A(プラスチック工学研究所社製)
EVOH押出温度 供給部/圧縮部/計量部/ダイ
=175/210/220/220℃
Ad押出温度 供給部/圧縮部/計量部/ダイ
=100/160/220/220℃
LLDPE押出温度 供給部/圧縮部/計量部/ダイ
=150/200/210/220℃
ダイ 300mm幅コートハンガーダイ(プラスチック工学研究所社製)
〈接着性の判定基準〉
A :600g/15cm以上
B :450g/15cm以上600g/15cm未満
C :300g/15cm以上450g/15cm未満
D :300g/15cm未満
表1及び2に示すように、EVOHの種類、非イオン界面活性剤の種類及び含有量を変更したこと以外は、実施例1と同様にして樹脂組成物のペレット、単層フィルム及び多層構造体を作製した後、それらの分析及び評価を行った。結果を表2に示す。
実施例1と同様にして、EVOH1及び非イオン界面活性剤の水分散液を準備した。100質量部のEVOH1、1質量部の前記水分散液及び酸化防止剤として0.5質量部のN,N’−ヘキサン−1,6−ジイルビス〔3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオナミド〕をブレンドした。こうして得られた混合物を用いたこと以外は実施例1と同様にして樹脂組成物ペレット、単層フィルム及び多層構造体を作製した後、それらの分析及び評価を行った。結果を表3に示す。
非イオン界面活性剤量並びに添加剤の種類及び添加量を表3に示すとおりに変更したこと以外は実施例34と同様にして樹脂組成物ペレット、単層フィルム及び多層構造体を作製した後、それらの分析及び評価を行った。結果を表3に示す。
100質量部のEVOH1の代わりに、85質量部のEVOH1及び15質量部のEVOH3(エチレン含量48モル%、ケン化度99.98モル%、MFR15g/10分(温度210℃、荷重2160g)、含水率0.2質量%)を用いたこと及び非イオン界面活性剤の含有量を表3に示すとおりとしたこと以外は実施例1と同様にして樹脂組成物のペレット、単層フィルム及び多層構造体を作製した後、それらの分析及び評価を行った。結果を表3に示す。
実施例1で得られた樹脂組成物ペレットを用い、3種5層共押出機を用いて、ポリプロピレン層(200μm)/接着性樹脂層(25μm)/樹脂組成物層(50μm)/接着性樹脂層(25μm)/ポリプロピレン層(200μm)の5層構成の多層フィルムを作製した。ここで、接着性樹脂として、無水マレイン酸変性ポリプロピレンを用いた。得られた多層フィルムの外観を実施例1と同様にして評価したところ、フィルム端面の着色は確認されなかった。
比較例1で得られた樹脂組成物ペレットを用いた以外は実施例51と同様にして多層フィルムの作製と外観の評価を行った。フィルム端面は激しく黄変して実用不可能であった。
Claims (11)
- エチレン−ビニルアルコール共重合体及び非イオン界面活性剤を含有する樹脂組成物であって、
前記エチレン−ビニルアルコール共重合体のエチレン単位含有量が15〜60モル%であり、ケン化度が90モル%以上であり、
前記エチレン−ビニルアルコール共重合体を主成分として含有し、
前記非イオン界面活性剤を3〜400ppm含有する、樹脂組成物。 - 前記非イオン界面活性剤が、エーテル型、アミノエーテル型、エステル型、エステル・エーテル型及びアミド型からなる群から選択される少なくとも一種である、請求項1に記載の樹脂組成物。
- 前記非イオン界面活性剤が、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルケニルエーテル、ポリオキシエチレンスチレン化フェニルエーテル、ポリオキシアルキレンアルキルアミン、ポリオキシアルキレンアルケニルアミン、ポリオキシアルキレンアルキルエステル、ポリオキシアルキレンアルケニルエステル、ソルビタンアルキルエステル、ソルビタンアルケニルエステル、ポリオキシエチレンソルビタンアルキルエステル、ポリオキシエチレンソルビタンアルケニルエステル、グリセロールアルキルエステル、グリセロールアルケニルエステル、ポリグリセリンアルキルエステル、ポリグリセリンアルケニルエステル及び高級脂肪酸アミドからなる群から選択される少なくとも一種である、請求項2に記載の樹脂組成物。
- さらに、アルカリ金属塩を金属元素換算で10〜500ppm含有する、請求項1〜3のいずれかに記載の樹脂組成物。
- さらに、酸化防止剤、紫外線吸収剤、可塑剤、帯電防止剤、滑剤及び充填剤からなる群から選択される少なくとも1種の添加剤を0.005〜1質量%含有する、請求項1〜4のいずれかに記載の樹脂組成物。
- 前記エチレン−ビニルアルコール共重合体として、エチレン単位含有量が異なるエチレン−ビニルアルコール共重合体を2種含有する、請求項1〜5のいずれかに記載の樹脂組成物。
- 請求項1〜6のいずれかに記載の樹脂組成物を含有する成形体。
- 請求項1〜6のいずれかに記載の樹脂組成物からなる層と前記エチレン−ビニルアルコール共重合体以外の熱可塑性樹脂からなる層を有する多層構造体。
- 前記非イオン界面活性剤、水及び前記エチレン−ビニルアルコール共重合体を含む混合物を溶融混練する請求項1〜6のいずれかに記載の樹脂組成物の製造方法。
- 前記混合物における、前記エチレン−ビニルアルコール共重合体100質量部に対する水の含有量が0.1〜50質量部である請求項9に記載の製造方法。
- 前記非イオン界面活性剤を含む水溶液又は水分散体を前記エチレン−ビニルアルコール共重合体に添加して前記混合物を得る請求項9又は10に記載の製造方法。
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JP2006249407A (ja) * | 2005-02-14 | 2006-09-21 | Nippon Synthetic Chem Ind Co Ltd:The | ポリビニルアルコール系フィルム、およびその製造方法 |
WO2011132592A1 (ja) * | 2010-04-20 | 2011-10-27 | 株式会社クラレ | ポリビニルアルコール系重合体フィルム |
JP2013193759A (ja) * | 2012-03-19 | 2013-09-30 | Sumitomo Bakelite Co Ltd | 青果物用包装袋及び青果物包装体 |
WO2013146458A1 (ja) * | 2012-03-30 | 2013-10-03 | 株式会社クラレ | ポリビニルアルコール系重合体フィルムおよび偏光フィルム |
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TW201842031A (zh) | 2018-12-01 |
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EP3597701A4 (en) | 2020-12-02 |
CN110603292B (zh) | 2022-04-19 |
CN110603292A (zh) | 2019-12-20 |
US20200385546A1 (en) | 2020-12-10 |
JPWO2018168903A1 (ja) | 2019-03-22 |
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