CN112384367A - 多层结构体 - Google Patents
多层结构体 Download PDFInfo
- Publication number
- CN112384367A CN112384367A CN201980047913.XA CN201980047913A CN112384367A CN 112384367 A CN112384367 A CN 112384367A CN 201980047913 A CN201980047913 A CN 201980047913A CN 112384367 A CN112384367 A CN 112384367A
- Authority
- CN
- China
- Prior art keywords
- ethylene
- vinyl alcohol
- alcohol copolymer
- multilayer structure
- vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005977 Ethylene Substances 0.000 claims abstract description 122
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 120
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 110
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 96
- 238000007127 saponification reaction Methods 0.000 claims abstract description 38
- 239000007864 aqueous solution Substances 0.000 claims abstract description 37
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 9
- 229920001225 polyester resin Polymers 0.000 claims abstract description 9
- 239000004645 polyester resin Substances 0.000 claims abstract description 9
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 26
- 239000005022 packaging material Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 37
- 239000001301 oxygen Substances 0.000 abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 abstract description 37
- 230000004888 barrier function Effects 0.000 abstract description 36
- 230000007774 longterm Effects 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 229920001567 vinyl ester resin Polymers 0.000 description 83
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 75
- 238000003756 stirring Methods 0.000 description 47
- 239000000243 solution Substances 0.000 description 45
- 238000000034 method Methods 0.000 description 36
- 239000010410 layer Substances 0.000 description 35
- -1 polypropylene Polymers 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000007789 gas Substances 0.000 description 26
- 239000007788 liquid Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 239000005038 ethylene vinyl acetate Substances 0.000 description 9
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 7
- 229920002292 Nylon 6 Polymers 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910001882 dioxygen Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 229920002302 Nylon 6,6 Polymers 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 239000005033 polyvinylidene chloride Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 150000002148 esters Chemical group 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000003507 refrigerant Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 2
- CJSBUWDGPXGFGA-UHFFFAOYSA-N 4-methylpenta-1,3-diene Chemical compound CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XZKRXPZXQLARHH-XVNBXDOJSA-N [(1e)-buta-1,3-dienyl]benzene Chemical compound C=C\C=C\C1=CC=CC=C1 XZKRXPZXQLARHH-XVNBXDOJSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004334 sorbic acid Substances 0.000 description 2
- 229940075582 sorbic acid Drugs 0.000 description 2
- 235000010199 sorbic acid Nutrition 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- CGMDPTNRMYIZTM-NKYSMPERSA-N (2e,4e,6e)-octa-2,4,6-triene Chemical compound C\C=C\C=C\C=C\C CGMDPTNRMYIZTM-NKYSMPERSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- ICCVOKMKWYGITK-UHFFFAOYSA-N 1-(2-methylprop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C(C)=C ICCVOKMKWYGITK-UHFFFAOYSA-N 0.000 description 1
- IAUGBVWVWDTCJV-UHFFFAOYSA-N 1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CCC(S(O)(=O)=O)NC(=O)C=C IAUGBVWVWDTCJV-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PGYJSURPYAAOMM-UHFFFAOYSA-N 2-ethenoxy-2-methylpropane Chemical compound CC(C)(C)OC=C PGYJSURPYAAOMM-UHFFFAOYSA-N 0.000 description 1
- GNUGVECARVKIPH-UHFFFAOYSA-N 2-ethenoxypropane Chemical compound CC(C)OC=C GNUGVECARVKIPH-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical compound CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- CGMDPTNRMYIZTM-UHFFFAOYSA-N Sarohornene Natural products CC=CC=CC=CC CGMDPTNRMYIZTM-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 229920010346 Very Low Density Polyethylene (VLDPE) Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- GNQWHYWLSGTMSL-OUKQBFOZSA-N [(e)-3-phenylbut-1-enyl]benzene Chemical compound C=1C=CC=CC=1C(C)\C=C\C1=CC=CC=C1 GNQWHYWLSGTMSL-OUKQBFOZSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
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Abstract
多层结构体,其具有层(A)和层(B),所述层(A)含有乙烯‑乙烯醇共聚物,所述乙烯‑乙烯醇共聚物的乙烯单元的含有率为1摩尔%以上且小于20摩尔%、粘均聚合度为200~5000、皂化度为80~99.7摩尔%、乙烯单元的嵌段特性为0.90~0.99,所述层(B)含有选自聚烯烃树脂、聚酯树脂和聚酰胺树脂中的至少1种树脂。这样的多层结构体的氧气阻隔性优异。此外,含有前述乙烯‑乙烯醇共聚物的水溶液即使长时间保存后,粘度稳定性也优异。因此,即使从制备该水溶液起经过长时间后使用时,也可均匀地涂布在基材上,因此得到氧气阻隔性优异的多层结构体。
Description
技术领域
本发明涉及具有含有乙烯单元的嵌段特性为特定范围内的乙烯-乙烯醇共聚物的层的氧气阻隔性优异的多层结构体、其制造方法、和具备其的包装材料。
背景技术
氧气阻隔性优异的多层结构体被用作包装材料等。铝箔具有完美的氧气阻隔性,因此被用作这样的多层结构体的中间层。然而,将包含铝箔的多层结构体焚烧时会产生残渣,而且将该多层结构体用作包装材料时,不能看到内容物,而且也存在不能用金属探测器检查内容物的问题。
聚偏二氯乙烯(以下有时简称为“PVDC”)不易吸湿、即使在高湿下也具有良好的氧气阻隔性,因此将聚偏二氯乙烯涂布在各种基材上得到的多层结构体被用作包装材料等。作为前述基材,可使用双轴拉伸聚丙烯(以下有时简称为“OPP”)、双轴拉伸尼龙(以下有时简称为“ON”)、双轴拉伸聚对苯二甲酸乙二醇酯(以下有时简称为“OPET”)、赛璐酚等的膜。然而,存在焚烧包含PVDC的多层结构体的废弃物时会产生氯化氢气体的问题。
此外,已知完全皂化的未改性聚乙烯醇(以下有时将“聚乙烯醇”简称为“PVA”)的氧气阻隔性也优异。然而,该未改性PVA存在容易吸湿且在高湿度下氧气阻隔性降低的倾向。此外,该未改性PVA存在与用于基材的OPP、OPET的粘接性低的问题。作为抑制吸湿的方法,提出了在PVA膜的两面涂布PVDC的方法、使用含有20摩尔%以上的乙烯单元的乙烯-乙烯醇共聚物的方法。然而,存在焚烧包含PVDC的多层结构体时会产生氯气体的问题。此外,将含有20摩尔%以上的乙烯单元的乙烯-乙烯醇共聚物涂布在基材上时,有时所得多层结构体的涂膜的均一性变得不充分。
专利文献1中记载了包含含有3~19摩尔%的碳原子数4以下的α-烯烃单元的PVA的膜。并且,记载了该膜的耐水性优异,在高湿度下也具有优异的氧气阻隔性。然而,此外该膜有时氧气阻隔性不充分。包含前述PVA的水溶液的涂布剂的粘度稳定性差,因此有时难以将从制备起经过了长时间的涂布剂均匀地涂布在基材上,所得多层结构体的氧气阻隔性变得不充分。
现有技术文献
专利文献
【专利文献1】日本特开2000-119585号公报。
发明内容
发明要解决的问题
本发明是为了解决上述课题而进行的,目的在于提供制造中使用的含有乙烯-乙烯醇共聚物的水溶液的粘度稳定性即使在长时间保存后也良好、而且氧气阻隔性也优异的多层结构体。
用于解决问题的手段
上述课题通过多层结构体而解决,其具有层(A)和层(B),所述层(A)含有乙烯-乙烯醇共聚物,所述乙烯-乙烯醇共聚物的乙烯单元的含有率为1摩尔%以上且小于20摩尔%、粘均聚合度为200~5000、皂化度为80~99.7摩尔%、乙烯单元的嵌段特性为0.90~0.99,所述层(B)含有选自聚烯烃树脂、聚酯树脂和聚酰胺树脂中的至少1种树脂。
此时,优选层(A)的厚度为0.1~20μm。
优选层(A)进一步含有相对于前述乙烯-乙烯醇共聚物100质量份为0.000001~0.01质量份的具有共轭双键的分子量1000以下的化合物。
上述课题通过多层结构体的制造方法而解决,其具有制备含有前述乙烯-乙烯醇共聚物的水溶液而得到涂布剂的步骤、以及将该涂布剂涂布在包含选自聚烯烃树脂、聚酯树脂和聚酰胺树脂中的至少1种树脂的基材的表面的步骤。此时,优选从制备前述涂布剂起经过1~30天后,将该涂布剂涂布在前述基材的表面。
具备前述多层结构体的包装材料是本发明的适合实施方式。
发明效果
包含含有乙烯单元的嵌段特性为规定范围内的本发明的乙烯-乙烯醇共聚物的层的多层结构体的氧气阻隔性优异。此外,含有前述乙烯-乙烯醇共聚物的水溶液即使在长时间保存后粘度稳定性也优异。因此,即使从制备该水溶液起经过长时间后使用的情况,也可均匀地涂布在基材上,因此可得到氧气阻隔性优异的多层结构体。
附图说明
[图1] 实施例中使用的聚合装置的示意图。
[图2] 本发明中使用的宽桨叶片的例子的示意图。
具体实施方式
[层(A)]
构成本发明的多层结构体的层(A)含有乙烯单元的嵌段特性满足规定条件的乙烯-乙烯醇共聚物。
(乙烯-乙烯醇共聚物)
层(A)中含有的乙烯-乙烯醇共聚物是乙烯单元的含有率为1摩尔%以上且小于20摩尔%、粘均聚合度为200~5000、皂化度为80~99.7摩尔%的乙烯-乙烯醇共聚物,该乙烯-乙烯醇共聚物中的乙烯单元的嵌段特性为0.90~0.99。
(乙烯单元的嵌段特性)
乙烯单元的嵌段特性为0.90~0.99是本发明中使用的乙烯-乙烯醇共聚物的明显特征。通过使前述嵌段特性在这样的范围,所得多层结构体的氧气阻隔性提高。乙烯单元的嵌段特性优选为0.93以上,更优选为0.95以上。另一方面,乙烯单元的嵌段特性小于0.90时,疏水性变得过高,从制备这样的乙烯-乙烯醇共聚物的水溶液起经过长时间后使用的情况下,将该水溶液均匀地涂布在基材上变得困难,因此所得多层结构体的氧气阻隔性降低。乙烯单元的嵌段特性超过0.99时,亲水性变高,因此所得多层结构体的氧气阻隔性降低。因此,嵌段特性在适当的范围内是重要的。
需要说明的是,嵌段特性是表示乙烯单元与通过乙烯基酯单元的皂化而产生的乙烯醇单元的分布的数值,采取0~2之间的值。0表示乙烯单元或乙烯醇单元完全分布成嵌段,随着值的增加而交替性逐渐增加,1表示乙烯单元和乙烯醇单元完全无规地存在,2表示乙烯单元和乙烯醇单元完全交替地存在。嵌段特性通过13C-NMR如下那样地求出。首先,将乙烯-乙烯醇共聚物皂化至皂化度为99.9摩尔%以上后,用甲醇充分进行清洗,以90℃减压干燥2天。使所得完全皂化乙烯-乙烯醇共聚物溶解于DMSO-d6后,使用500MHz的13C-NMR(JEOLGX-500)以80℃对所得试样进行测定。
使用根据所得光谱谱图并利用T.Moritani and H.Iwasaki,11,1251-1259,Macromolecules(1978)中记载的方法进行归属、计算而得的乙烯醇-乙烯的二单元组链的摩尔分数(AE)、乙烯醇单元的摩尔分数(A)、乙烯单元的摩尔分数(E),由下述式求出乙烯单元的嵌段特性(η)。
具有上述规定的乙烯单元的嵌段特性的乙烯-乙烯醇共聚物可通过包括后述聚合工序和皂化工序的特殊制造方法来获得。本发明人等经深入研究的结果,通过采用这种制造方法而成功地控制乙烯单元的嵌段特性。并且发现:通过使乙烯单元的嵌段特性为上述范围,能够获得上述效果。以下,针对本发明中使用的乙烯-乙烯醇共聚物,更详细地进行说明。
(乙烯基酯)
本发明中使用的乙烯-乙烯醇共聚物通过将乙烯与乙烯基酯共聚而得到乙烯-乙烯基酯共聚物后,将该乙烯-乙烯基酯共聚物进行皂化来获得。作为所用的乙烯基酯,可列举出甲酸乙烯酯、乙酸乙烯酯、丙酸乙烯酯、戊酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、苯甲酸乙烯酯、特戊酸乙烯酯和叔碳酸乙烯酯等,其中优选为乙酸乙烯酯。
(乙烯单元的含有率)
本发明中使用的乙烯-乙烯醇共聚物的乙烯单元的含有率为1摩尔%以上且小于20摩尔%。乙烯单元的含有率小于1摩尔%时,所得多层结构体的氧气阻隔性变得不充分。乙烯单元的含有率优选为1.5摩尔%以上,更优选为2摩尔%以上。另一方面,乙烯单元的含有率为20摩尔%以上时,乙烯-乙烯醇共聚物变得不溶于水,难以制备水溶液。乙烯单元的含有率优选为15摩尔%以下,更优选为10摩尔%以下,进一步优选为8.5摩尔%以下。
乙烯单元的含有率通过例如以下的方法由乙烯-乙烯醇共聚物的前体或再皂化物、即乙烯-乙烯基酯共聚物的1H-NMR来求出。使用正己烷与丙酮的混合溶液进行3次以上的试样乙烯-乙烯基酯共聚物的再沉淀提纯后,以80℃减压干燥3天来制作分析用的乙烯-乙烯基酯共聚物。将所得乙烯-乙烯基酯共聚物溶解于DMSO-d6,以80℃进行1H-NMR(500MHz)测定。使用源自乙烯基酯的主链次甲基的峰(4.7~5.2ppm)以及源自乙烯和乙烯基酯的主链亚甲基的峰(0.8~1.6ppm),能够算出乙烯单元的含有率。
(皂化度)
本发明中使用的乙烯-乙烯醇共聚物的皂化度为80~99.7摩尔%。皂化度小于80摩尔%时,所得多层结构体的氧气阻隔性变得不充分。皂化度优选为85摩尔%以上,更优选为90摩尔%以上。另一方面,皂化度超过99.7摩尔%时,无法稳定地制造乙烯-乙烯醇共聚物。皂化度优选为99.5摩尔%以下。乙烯-乙烯醇共聚物的皂化度可按照JIS K6726(1994年)进行测定。
(粘均聚合度)
本发明中使用的乙烯-乙烯醇共聚物的粘均聚合度为200~5000。粘均聚合度小于200时,多层结构体的制造变得困难。粘均聚合度优选为250以上,更优选为300以上,进一步优选为400以上。另一方面,粘均聚合度超过5000时,乙烯-乙烯醇共聚物的水溶液的粘度变得过高,难以处理。粘均聚合度优选为4500以下,更优选为4000以下,进一步优选为3500以下。粘均聚合度P可按照JIS K6726(1994年)进行测定。即,可以将本发明中使用的乙烯-乙烯醇共聚物再皂化至皂化度为99.5摩尔%以上并提纯后,在30℃的水中进行测定,根据由此得到的特性粘度[η](L/g)利用下式来求出。
(其它单体单元)
本发明中使用的乙烯-乙烯醇共聚物中,只要是不损害本发明效果的范围,则可以含有除了乙烯醇单元、乙烯单元和乙烯基酯单元之外的其它单体单元。作为这种其它单体单元,可列举出丙烯、正丁烯、异丁烯等α-烯烃;丙烯酸及其盐;丙烯酸酯;甲基丙烯酸及其盐;甲基丙烯酸酯;丙烯酰胺;N-甲基丙烯酰胺、N-乙基丙烯酰胺、N,N-二甲基丙烯酰胺、二丙酮丙烯酰胺、丙烯酰胺丙磺酸及其盐、丙烯酰胺丙基二甲基胺及其盐或其季铵盐、N-羟甲基丙烯酰胺及其衍生物等丙烯酰胺衍生物;甲基丙烯酰胺;N-甲基甲基丙烯酰胺、N-乙基甲基丙烯酰胺、甲基丙烯酰胺丙磺酸及其盐、甲基丙烯酰胺丙基二甲基胺及其盐或其季铵盐、N-羟甲基甲基丙烯酰胺及其衍生物等甲基丙烯酰胺衍生物;甲基乙烯基醚、乙基乙烯基醚、正丙基乙烯基醚、异丙基乙烯基醚、正丁基乙烯基醚、异丁基乙烯基醚、叔丁基乙烯基醚、十二烷基乙烯基醚、硬脂基乙烯基醚等乙烯基醚;丙烯腈、甲基丙烯腈等腈;氯乙烯、氟乙烯等卤代乙烯;偏二氯乙烯、偏二氟乙烯等偏二卤代乙烯;乙酸烯丙酯、烯丙基氯等烯丙基化合物;马来酸、衣康酸、富马酸等不饱和二羧酸及其盐或其酯;乙烯基三甲氧基硅烷等乙烯基甲硅烷基化合物;源自乙酸异丙烯酯的单元等。这些其它单体单元的含有率因使用目的、用途等而异,优选为10摩尔%以下,更优选小于5摩尔%,进一步优选小于1摩尔%,特别优选小于0.5摩尔%。
(乙烯-乙烯醇共聚物的制造方法)
本发明中使用的乙烯-乙烯醇共聚物的优选制造方法是在使乙烯与乙烯基酯反应而得到乙烯-乙烯基酯共聚物后,将该乙烯-乙烯基酯共聚物进行皂化来制造乙烯-乙烯醇共聚物的方法,在获得乙烯-乙烯基酯共聚物时,包括如下工序:(a)在聚合槽内,使用宽桨叶片,以每单位体积的搅拌动力Pv达到0.5~10kW/m3、弗劳德数Fr达到0.05~0.2的方式,一边搅拌包含乙烯基酯的溶液一边使其接触含乙烯的气体的工序。
通过利用这种方法使包含乙烯基酯的溶液与含乙烯的气体相接触,能够使乙烯-乙烯醇共聚物的乙烯单元的嵌段特性为上述范围。以下,针对前述制造方法,详细进行说明。
(聚合工序)
在聚合工序中,通过使乙烯与乙烯基酯发生反应(共聚)而得到乙烯-乙烯基酯共聚物。作为使乙烯与乙烯基酯发生共聚的方法,优选为将乙烯与乙烯基酯在醇等有机溶剂中进行聚合的溶液聚合法。作为上述醇,可列举出甲醇、乙醇等低级醇,特别优选为甲醇。作为聚合中使用的引发剂,可列举出2,2'-偶氮双(异丁腈)、2,2’-偶氮双(4-甲氧基-2,4-二甲基戊腈)、2,2’-偶氮双(2,4-二甲基戊腈)、过氧化苯甲酰、过氧化二碳酸正丙酯等偶氮系引发剂或过氧化物系引发剂等公知引发剂。
在聚合工序中,为了调节所得乙烯-乙烯基酯共聚物的粘均聚合度等,也可以共存有链转移剂。作为链转移剂,可列举出乙醛、丙醛、丁醛、苯甲醛等醛;丙酮、甲乙酮、己酮、环己酮等酮;2-羟基乙硫醇等硫醇;硫代乙酸等硫代羧酸;三氯乙烯、全氯乙烯等卤代烃等。其中,优选使用醛和酮。链转移剂的添加量根据所添加的链转移剂的链转移常数和目标乙烯-乙烯基酯共聚物的粘均聚合度来决定,通常相对于所使用的乙烯基酯100质量份为0.1~10质量份。
在聚合操作时,也可以采用连续法、半间歇法和间歇法中的任意聚合方式,优选为连续法。作为聚合反应器,可列举出连续槽型反应器、间歇反应器、管型反应器等,优选为连续槽型反应器。
以下,针对具体的聚合装置和使用了其的聚合工序,参照附图来进行说明。图1是实施例1中使用的聚合装置的示意图。该装置是连续槽型反应器,聚合槽1借助导管3、4而与换热器2相连。乙烯基酯与乙烯能够在前述换热器2内发生对流接触。
多个导管5、6、7连接于聚合槽1。导管的根数、配置不限定于图示的形态。通过这些导管,向聚合槽1中供给乙烯、聚合引发剂和有机溶剂。关于每单元时间向聚合槽内导入的原料比例,优选的是:相对于乙烯基酯100质量份,乙烯为0.1~20质量份、有机溶剂为1~100质量份、聚合引发剂为0.00001~1质量份。根据情况,也能够通过这些导管来供给乙烯基酯、其它单体。聚合槽1内的反应液从与聚合槽1的底部相连的反应液导出管9连续排出。
在聚合槽1内设置了具有宽桨叶片作为搅拌叶片的搅拌机8。通过使用前述宽桨叶片,一边搅拌包含乙烯基酯的溶液一边使其接触含乙烯的气体,使乙烯与乙烯基酯发生反应而得到乙烯-乙烯基酯共聚物。
作为对包含乙烯基酯的溶液进行搅拌的搅拌叶片,优选使用宽桨叶片。图2中示出本发明所使用的宽桨叶片的例子的示意图。如图2所示那样,具有宽度b的宽桨是宽桨叶片的特征。宽桨叶片的宽度b可根据聚合槽1的容量等来适当调整,如后所述优选为1~10m。通过使用这种桨,溶液从底部到液面为止被均匀混合,且乙烯被包含乙烯基酯的溶液有效地吸收。前述宽桨叶片可以为单段(例如MAXBLEND叶片),也可以为多段(例如FULLZONE叶片)。从乙烯被乙烯基酯更有效地吸收的观点出发,在包含乙烯基酯的溶液的搅拌中,该溶液的液面优选处于搅拌叶片的上端部附近。作为宽桨叶片,具体而言,可列举出MAXBLEND叶片(住友重机械工艺机器公司)、FULLZONE叶片(神钢环境ソリューション公司)、SANMELER叶片(三菱重工业公司)、Hi-Fi MIXER叶片(综研化学公司)、SUPERMIX叶片(佐竹化学机械工业公司、SUPERMIX MR203、SUPERMIX MR205)、BENDLEAF叶片(八光产业公司)等。
聚合时的聚合槽内的乙烯压力优选为0.01~0.9MPa,更优选为0.05~0.8MPa,进一步优选为0.1~0.7MPa。聚合槽出口处的乙烯基酯的聚合率没有特别限定,通常优选为10~90%,更优选为15~85%。
聚合温度没有特别限定,通常优选为0~180℃,更优选为20~160℃,进一步优选为30~150℃。
使乙烯与乙烯基酯发生反应时,优选的是:在聚合槽内,以包含乙烯基酯的溶液的每单位体积的搅拌动力Pv达到0.5~10kW/m3的方式搅拌该溶液。搅拌动力小于0.5kW/m3时,向乙烯基酯中混入的乙烯量变得不充分,且反应液的均匀性也变得不充分,无法获得乙烯单元的嵌段特性为上述范围的乙烯-乙烯醇共聚物。搅拌动力更优选为1kW/m3以上,进一步优选为1.5kW/m3以上。另一方面,搅拌动力超过10kW/m3时,运转所使用的动力变得非常大,工业上不优选。搅拌动力更优选为7kW/m3以下,进一步优选为5kW/m3以下。包含乙烯基酯的溶液的每单位体积的搅拌动力Pv通过后述实施例中记载的方法进行测定。
弗劳德数Fr是通过下式而定义的惯性力与重力之比,成为液体表面的漩涡形状的指标。
n:搅拌叶片的转速(rps)
d:搅拌叶片直径(m)
g:重力加速度(m/s2)。
使乙烯与乙烯基酯发生反应时,优选的是:在聚合槽内,以弗劳德数Fr达到0.05~0.2的方式,对包含乙烯基酯的溶液进行搅拌。可以认为:通过将弗劳德数Fr调整至上述范围来控制液体表面的漩涡形状,乙烯会被乙烯基酯适度地吸收,因此,能够容易地获得乙烯单元的嵌段特性处于上述范围的乙烯-乙烯醇共聚物。弗劳德数Fr更优选为0.06以上,进一步优选为0.07以上。另一方面,弗劳德数Fr更优选为0.18以下,进一步优选为0.15以下。为了使弗劳德数Fr为上述范围,适当变更搅拌叶片的转速或搅拌叶片直径即可。
宽桨叶片的搅拌叶片直径d以搅拌动力Pv和弗劳德数Fr达到上述范围内的方式进行调整即可,没有特别限定,从提高乙烯吸收效率的观点出发,优选为0.5~5m。搅拌叶片直径d更优选为0.75m以上。另一方面,搅拌叶片直径d更优选为4m以下。搅拌叶片直径d是将从旋转轴起至叶片前端(距离旋转轴最远的点)为止的距离翻倍而得的值。
宽桨叶片(桨)的宽度b(高度方向的长度)根据聚合槽1的容量等来调整即可,没有特别限定,从提高乙烯吸收效率的观点出发,优选为1~10m。宽度b更优选为1.5m以上。另一方面,宽度b更优选为8m以下。
宽桨叶片的宽度(桨的宽度)b相对于搅拌叶片直径d的比值(b/d)根据聚合槽1的形状等来决定即可,没有特别限定,从提高乙烯吸收效率的观点出发,优选为1以上。前述比值(b/d)更优选为1.5以上。另一方面,前述比值(b/d)通常为2.5以下。
聚合槽1的形状没有特别限定,通常使用大致圆柱状的聚合槽。此时,宽桨叶片以聚合槽1的旋转轴与宽桨叶片的旋转轴在大致圆柱状的聚合槽1内保持一致的方式进行配置。搅拌叶片直径d(m)相对于聚合槽的内径D(m)的比值(d/D)只要是不损害本发明效果的范围,就没有特别限定,根据所使用的聚合槽来适当调整即可,通常为0.4~0.9。聚合槽的容量没有特别限定,通常为1~200kl。
搅拌叶片的转速n只要以搅拌动力Pv和弗劳德数Fr达到上述范围内的方式进行调整即可,没有特别限定,优选为0.5~1.35rps。转速n小于0.5rps时,在导热面附近容易发生聚合溶液的过冷却,因此,有时在聚合槽的内壁生成凝胶状物,难以长期运转。另一方面,若转速n超过1.35rps,则使用粘度低的聚合溶液时,有时该溶液弹跳而附着于聚合槽的气相部的内壁。若这种附着物发生固化而混入至聚合溶液中,则形成异物,因此,有时无法稳定运转。
以往,在制造乙烯-乙烯醇共聚物时,对搅拌强度的指标、即每单位体积的搅拌动力进行控制。然而,搅拌动力受到反应液的容量、粘度和密度、聚合槽的形状、以及搅拌叶片的形状和转速等的各种影响。因此,仅控制搅拌动力时难以严格控制乙烯单元的嵌段性,作为结果,导致乙烯链的扩链(乙烯单元的嵌段化),所得乙烯-乙烯醇共聚物中的乙烯单元的嵌段特性小于0.90。并且,因乙烯链的扩链而导致分子间的疏水性相互作用变强,因此,所得多层结构体的氧气阻隔性不能说充分。发明人等对于该问题进行深入研究的结果发现:通过在特定条件下进行聚合反应,能够得到与以往相比乙烯链短(乙烯单元的位置随机的)共聚物,从而成功地提高所得多层结构体的氧气阻隔性。
从能够更严格地控制乙烯单元的嵌段特性的观点出发,在前述制造方法中,优选的是:在聚合工序中使用的前述聚合槽借助配管而与换热器相连,在获得乙烯-乙烯基酯共聚物时,还包括如下工序:(b)将存在于前述聚合槽的气相部的含乙烯的气体导入至前述换热器中的工序;(c)向前述换热器中供给乙烯基酯的工序;(d)在前述换热器中,使乙烯基酯与含乙烯的气体相接触的工序;以及(e)从前述换热器中导出溶解有乙烯的乙烯基酯,并导入至前述聚合槽内的工序。可以将乙烯基酯直接供给至聚合槽而不经由换热器,但通过这样地预先在换热器中使乙烯基酯吸收乙烯后,再供给至聚合槽,从而使乙烯被乙烯基酯有效地吸收,因此,乙烯单元的嵌段特性得以严格控制。也可以使供给至聚合槽的一部分乙烯基酯在换热器中与含乙烯的气体接触,但优选使所供给的全部乙烯基酯在换热器中与含乙烯的气体接触。
所使用的换热器没有特别限定,从乙烯的有效吸收的观点出发,优选为表面积大的换热器。可列举出例如立式湿壁式换热器、立式湿壁多管式换热器、在填充塔式或者多孔板或泡罩式吸收器中设有夹套和/或线圈的换热器等。其中,更优选为立式湿壁多管式换热器。
在图1所示的装置中,作为换热器2而使用立式湿壁多管式换热器。该换热器2与乙烯基酯导入管10相连,通过其向换热器2的上部供给乙烯基酯。作为原料的乙烯基酯,可以单独使用乙烯基酯,也可以使用包含上述有机溶剂和乙烯基酯的混合液,优选为后者。
图1所示的换热器2与制冷剂管11、12相连。管的位置不限定于图示的形态,优选制冷剂从与换热器2的下部相连的制冷剂管12供给,并从与换热器2的上部相连的制冷剂管11排出。通过这样地连接,能够将乙烯基酯有效地冷却,乙烯吸收效率良好。冷却介质没有特别限定,可以使用甲醇、乙醇、乙二醇、甘油等醇水溶液;食盐、氯化钙的水溶液、氟利昂等。从处理容易度、成本等理由出发,适合使用醇水溶液,特别适合使用甲醇水溶液。
用于从换热器2排出气体的气体排出管13与换热器2的上部相连。该气体排出管13可以连接有雾沫分离器(未图示)。所排出的气体中的液滴被雾沫分离器去除,能够回收或释放无雾沫的乙烯。雾沫分离器是利用重力・离心力・静电力之类的外力或者屏蔽或筛效果将浮游在气体中的液滴进行分离的装置。作为雾沫分离器,可列举出重力沉降器、旋风分离器、电集尘机、洗涤器、袋式除尘器、填充层。其中,优选为旋风分离器。
在换热器2中,使乙烯基酯与含乙烯的气体接触的方法没有特别限定。可列举出例如下述方法:使乙烯基酯从换热器2的上部流下,且向换热器的下部供给已加压的含乙烯的气体,在该换热器2中,使两者发生对流接触的方法;使乙烯基酯从换热器2的上部流下,且向换热器的上部供给已加压的含乙烯的气体,在该换热器2中,使两者发生并流接触的方法等。从有效的乙烯吸收的观点出发,优选为前者。
在图1所示的装置中,2根导管3、4将聚合槽1与换热器2进行连接。含乙烯的气体从聚合槽1通过导管3被导入至换热器2的下部,吸收有乙烯的乙烯基酯从换热器2的下部通过导管4被导入至聚合槽1。
乙烯基酯通过导入管10被供给至换热器2。向换热器2的上部导入的乙烯基酯一边通过换热器2一边吸收乙烯。
含乙烯的气体通过与换热器2的下部相连的导管3被导入至换热器2。换热器侧的导管3与换热器2的下部相连,另一方面,乙烯基酯导入管10与换热器2的上部相连。含乙烯的气体一边与乙烯基酯对流接触一边在换热器2内逐渐上升。其结果,气体中的乙烯溶解于乙烯基酯。
吸收有乙烯的乙烯基酯通过导管4而被导入至聚合槽1。在连续制造的情况下,乙烯在聚合槽1、换热器2和导管3、4中发生循环。一部分乙烯包含于乙烯基酯并从反应液导出管9被排出,因此,从与聚合槽1相连的乙烯供给源借助导管5、6、7中的至少一者而进行补充。
(皂化工序)
通过将聚合工序中得到的乙烯-乙烯基酯共聚物进行皂化而得到乙烯-乙烯醇共聚物。此时,优选将前述乙烯-乙烯基酯共聚物在有机溶剂中在催化剂的存在下通过醇解或水解反应进行皂化。作为皂化工序中使用的催化剂,可列举出氢氧化钠、氢氧化钾、甲醇钠等碱性催化剂;或者硫酸、盐酸、对甲苯磺酸等酸性催化剂。皂化工序中使用的有机溶剂没有特别限定,可列举出甲醇、乙醇等醇;乙酸甲酯、乙酸乙酯等酯;丙酮、甲乙酮等酮;苯、甲苯等芳香族烃等。它们可单独使用1种或组合使用2种以上。其中,将甲醇或者甲醇与乙酸甲酯的混合溶液用作溶剂,在作为碱性催化剂的氢氧化钠的存在下进行皂化反应是简便的,故而优选。皂化催化剂的用量以相对于乙烯-乙烯基酯共聚物中的乙烯基酯单元的摩尔比计优选为0.001~0.5。该摩尔比更优选为0.002以上。另一方面,该摩尔比更优选为0.4以下,进一步优选为0.3以下。
在进行皂化工序后,可以进行粉碎工序和干燥工序。进而,粉碎工序可以被分为预粉碎工序和主粉碎工序。在进行皂化工序后,可以进一步根据需要进行用于去除乙酸钠等杂质的清洗工序。
(具有共轭双键的化合物)
从氧气阻隔性的观点出发,层(A)优选包含下述物质:含有前述乙烯-乙烯醇共聚物和具有共轭双键且分子量为1000以下的化合物,且前述化合物的含量相对于前述乙烯-乙烯醇共聚物100质量份为0.000001~0.01质量份的乙烯-乙烯醇共聚物组合物。氧气阻隔性的提高机理尚未确定,推测其原因是共轭双键部位与乙烯-乙烯醇共聚物的乙烯单元适度地发生相互作用。
本发明中,具有共轭双键且分子量为1000以下的化合物为具有脂肪族双键彼此的共轭双键的化合物、或者具有脂肪族双键与芳香环的共轭双键的化合物。从氧气阻隔性的提高效果更高的观点出发,优选为前者。此外,分子量为1000以下,优选为800以下,更优选为500以下。
具有脂肪族双键彼此的共轭双键的化合物是具有碳-碳双键与碳-碳单键交替连接而成的结构,且碳-碳双键的数量为2个以上的具有共轭双键的化合物。具体而言,可列举出具有2个碳-碳双键、1个碳-碳单键交替连接而成的共轭结构的共轭二烯化合物;具有3个碳-碳双键、2个碳-碳单键交替连接而成的共轭结构的共轭三烯化合物(例如2,4,6-辛三烯);以及具有上述以上的数量的碳-碳双键与碳-碳单键交替连接而成的共轭结构的共轭多烯化合物等。其中,从氧气阻隔性的提高效果更高的观点出发,优选为共轭二烯化合物。本发明中使用的具有共轭双键且分子量为1000以下的化合物中,可以在1分子中独立地组合有多个共轭双键,例如,还包括桐油那样地在同一分子内具有3个共轭三烯的化合物。
具有共轭双键且分子量为1000以下的化合物可以具有除了共轭双键之外的其它官能团。作为其它官能团,可列举出例如羧基及其盐、羟基、酯基、羰基、醚基、氨基、二烷基氨基、亚氨基、酰胺基、氰基、重氮基、硝基、巯基、磺基、亚砜基、硫醚基、硫醇基、磺酸基及其盐、磷酸基及其盐、卤原子等极性基团;苯基等非极性基团。从氧气阻隔性的提高效果更高的观点出发,作为其它官能团,优选为极性基团,更优选为羧基及其盐、以及羟基。其它官能团可以直接键合于共轭双键中的碳原子,也可以键合于远离共轭双键的位置。其它官能团中的多键可以位于能够与前述共轭双键共轭的位置,例如,具有苯基的1-苯基-1,3-丁二烯、具有羧基的山梨酸等也可用作前述具有共轭双键的化合物。此外,前述具有共轭双键且分子量为1000以下的化合物可以具有非共轭双键、非共轭三键。
作为前述具有共轭双键且分子量为1000以下的化合物,具体而言,可列举出2,3-二甲基-1,3-丁二烯、4-甲基-1,3-戊二烯、1-苯基-1,3-丁二烯、山梨酸、香叶烯等具有脂肪族双键彼此的共轭双键的化合物;2,4-二苯基-4-甲基-1-戊烯、α-甲基苯乙烯聚合物、1,3-二苯基-1-丁烯等具有脂肪族双键与芳香环的共轭双键的化合物。
前述乙烯-乙烯醇共聚物组合物中的具有共轭双键且分子量为1000以下的化合物的含量相对于前述乙烯-乙烯醇共聚物100质量份优选为0.000001~0.01质量份。该含量更优选为0.000002质量份以上,进一步优选为0.000003质量份以上。另一方面,前述含量更优选为0.0075质量份以下,进一步优选为0.005质量份以下,特别优选为0.0025质量份以下。
本发明中,具有共轭双键且分子量为1000以下的化合物的添加方法没有特别限定。可列举出例如下述方法:1)向所得乙烯-乙烯基酯共聚物中添加前述化合物后,进行皂化的方法;2)将乙烯-乙烯基酯共聚物皂化时,添加前述化合物的方法;3)对于乙烯-乙烯醇共聚物,喷雾包含前述化合物的液体的方法;4)将乙烯-乙烯醇共聚物浸渗于包含前述化合物的液体后,使其干燥的方法;5)制备含有乙烯-乙烯醇共聚物和上述化合物的水溶液后,使其干燥的方法;6)制备含有乙烯-乙烯醇共聚物和上述化合物的水溶液,将该水溶液混合的方法等。其中,从容易调整上述化合物的含量的观点出发,优选为方法6)。
前述乙烯-乙烯醇共聚物组合物中的前述乙烯-乙烯醇共聚物的含量适合为50质量%以上,更适合为80质量%以上,进一步适合为95质量%以上。此外,前述乙烯-乙烯醇共聚物组合物中,优选前述乙烯-乙烯醇共聚物相对于全部聚合物成分的质量比(乙烯-乙烯醇共聚物/全部聚合物成分)为0.9以上,更优选前述乙烯-乙烯醇共聚物组合物中包含的聚合物成分实质上仅为前述乙烯-乙烯醇共聚物。
[层(B)]
层(B)含有选自聚烯烃树脂、聚酯树脂和聚酰胺树脂中的至少1种树脂。层(B)的厚度(拉伸时的最终厚度)优选为5~100μm。
作为聚烯烃树脂,可列举例如聚乙烯[高密度聚乙烯(HDPE)、低密度聚乙烯(LDPE)、直链状低密度聚乙烯(LLDPE)、超低密度聚乙烯(VLDPE)等]、聚丙烯、共聚聚丙烯、乙烯-乙酸乙烯酯共聚物、乙烯-(甲基)丙烯酸酯共聚物等。其中,优选为聚乙烯和聚丙烯。
作为聚酯树脂,可列举出聚对苯二甲酸乙二醇酯(以下有时简称为“PET”)、聚萘二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸乙二醇酯/聚间苯二甲酸乙二醇酯等。其中,优选为聚对苯二甲酸乙二醇酯(PET)。
作为聚酰胺树脂,可列举出例如聚己酰胺(尼龙-6)、聚十一碳酰胺(尼龙-11)、聚月桂基内酰胺(尼龙-12)、聚六亚甲基己二酰胺(尼龙-6,6)、聚六亚甲基癸二酰胺(尼龙-6,12)等均聚物;己内酰胺/月桂基内酰胺共聚物(尼龙-6/12)、己内酰胺/氨基十一酸聚合物(尼龙-6/11)、己内酰胺/ω-氨基壬烷酸聚合物(尼龙-6,9)、己内酰胺/己二酸六亚甲基二铵共聚物(尼龙-6/6,6)、己内酰胺/己二酸六亚甲基二铵/己二酸六亚甲基二铵共聚物(尼龙-6/6,6/6,12)、己二酸与间苯二甲酰二胺的聚合物、和六亚甲基二胺与间,对-邻苯二甲酸的聚合物即芳族系尼龙等共聚物。其中,优选为聚己酰胺(尼龙-6)和聚六亚甲基己二酰胺(尼龙-6,6)。
(多层结构体)
本发明的多层结构体具有层(A)和层(B)。前述多层结构体的透氧量适合为150cc/m2・day・atm以下,更适合为100cc/m2・day・atm以下,进一步适合为50cc/m2・day・atm以下。本发明中,多层结构体的透氧量可利用实施例记载的方法求出。
以气体阻隔性的提高、强度提高、操作性改善为目的,本发明的多层结构体中的各层可含有无机层状化合物。作为无机层状化合物,可列举出例如云母类、滑石、蒙脱石、高岭石、蛭石等,它们可以为天然产出的物质,也可以是合成的物质。
本发明的多层结构体中的各层可以以提高耐水性的目的而含有交联剂。作为交联剂,可列举出环氧化合物、异氰酸酯化合物、醛化合物、钛系化合物、二氧化硅化合物、铝化合物、锆化合物、硼化合物等。其中,优选为胶体二氧化硅、烷基硅酸酯等二氧化硅化合物。
本发明的多层结构体的制造方法没有特别限定,优选具有制备含有前述乙烯-乙烯醇共聚物的水溶液而得到涂布剂的步骤、以及将该涂布剂涂布在包含选自聚烯烃树脂、聚酯树脂和聚酰胺树脂中的至少1种树脂的基材的表面的步骤。
作为前述基材,可列举出包含聚烯烃树脂的膜、包含聚酯树脂的膜、包含聚酰胺树脂的膜。该基材形成层(B)。
前述水溶液中的前述乙烯-乙烯醇共聚物的含量没有特别限制,优选为5~50质量%。浓度小于5质量%时,干燥负荷变大,超过50质量%时,水溶液粘度变高而涂布性降低。将包含前述水溶液的涂布剂涂布在前述基材表面上后进行干燥,从而形成层(A)。此时的蒸发速度适合为2~2000g/m2・min,更适合为50~500g/m2・min。
此外,本发明的制造方法中,从制备前述涂布剂起,优选在30天以内涂布在前述基材的表面上,更优选为20天以内,进一步优选为10天以内,特别优选为7天以内。含有前述乙烯-乙烯醇共聚物的水溶液即使长时间保存后,粘度稳定性也优异。因此,即使从制备该水溶液起经过长时间后使用时,也可在基材均匀地涂布该水溶液,因此可得到氧气阻隔性优异的多层结构体。从该观点出发,优选从制备前述涂布剂起经过1天以上后在前述基材的表面涂布。
前述水溶液可含有表面活性剂、流平剂等。此外,从涂布性的观点出发,前述水溶液可含有甲醇、乙醇、异丙醇等低级脂肪族醇。此时,前述水溶液中的低级脂肪族醇的含量相对于水100质量份适合为100质量份以下,更适合为50质量份以下,进一步适合为20质量份以下。从操作环境的观点出发,优选前述水溶液中包含的液体介质仅为水。此外,前述水溶液可含有防霉剂、防腐剂等。前述水溶液的涂布时的温度优选为20~80℃。涂布方法适合使用凹版辊涂法、反式凹版涂布法、反式辊涂法、线式棒涂法。可以对涂布涂布剂前的基材、所得多层结构体进行拉伸、热处理。此时,考虑到操作性时,优选在对前述基材进行一段拉伸后、在该基材上涂布涂布剂、然后再进行二段拉伸、在该二段拉伸中或二段拉伸后进行热处理的方法。
前述热处理可在空气中等进行。热处理温度根据前述基材的种类调整即可,通常聚烯烃膜时为140℃~170℃,聚酯膜和聚酰胺膜时为140℃~240℃。进行层(A)的热处理时,通常与层(B)同时进行。
层(A)的厚度(拉伸时的最终厚度)适合为0.1~20μm,更适合为0.1~9μm。
前述多层结构体中的层(A)相对于层(B)的厚度比(A/B)适合为0.9以下,更适合为0.5以下。
在层(A)与层(B)之间,以提高粘接性为目的,可形成粘接性成分层。作为粘接成分,可列举出锚固剂等。涂布前述乙烯-乙烯醇共聚物的水溶液前,可通过在前述基材的表面涂布粘接性成分的方法等而形成前述粘接剂层。
本发明的多层结构体中,层(A)的未与层(B)相接的面上可进一步形成热封树脂层。热封树脂层通常可利用挤出层压法或者干式层压法形成。作为热封树脂,可使用HDPE、LDPE、LLDPE等聚乙烯树脂、聚丙烯树脂、乙烯-乙酸乙烯酯共聚物、乙烯・α-烯烃无规共聚物、离聚物树脂等。
[包装材料]
具备本发明的多层结构体的包装材料也是本申请发明的适合实施方式。该包装材料通过具备本发明的多层结构体,氧气阻隔性优异。
该包装材料可用于包装例如食品;饮料物;农药、医药等药品;医疗器材;机械部件、精密材料等产业资材;衣料等。特别是该包装材料优选用于需要对氧的阻隔性的用途、和包装材料的内部被各种功能性气体置换的用途。
作为该包装材料的形态,可列举出例如立式袋填充密封袋、真空包装袋、带嘴袋、层压管容器、容器用盖材料等。
实施例
接着,列举出实施例,更具体地说明本发明,但本发明完全不限定于这些实施例。需要说明的是,在以下的实施例和比较例中,“份”和“%”只要没有特别记载,则以质量为基准。
针对通过下述实施例和比较例而得到的乙烯-乙烯醇共聚物的物性值,按照以下的方法进行测定。
[乙烯-乙烯醇共聚物的粘均聚合度和皂化度]
乙烯-乙烯醇共聚物的粘均聚合度和皂化度通过JIS K6726(1994年)中记载的方法来求出。
[乙烯-乙烯醇共聚物的乙烯单元的嵌段特性]
将乙烯-乙烯醇共聚物皂化至皂化度为99.9摩尔%以上后,用甲醇充分进行清洗,接着,以90℃减压干燥2天,将由此得到的共聚物溶解于DMSO-d6,使用600MHz的13C-NMR,以80℃进行测定。使用根据所得光谱谱图并利用T.Moritani and H.Iwasaki,11,1251-1259,Macromolecules(1978)中记载的方法进行归属、计算而得的乙烯醇-乙烯的二单元组链的摩尔分数(AE)、乙烯醇单元的摩尔分数(A)、乙烯单元的摩尔分数(E),由下述式求出乙烯单元的嵌段特性(η)。
每单元体积的搅拌动力Pv(kW/m3)由下述式进行计算。此处,Pt为聚合反应中的搅拌动力(kW),Pe为无负荷时(聚合槽是空的)的搅拌动力(kW),V为聚合反应器中的聚合溶液量(m3)。
上述式中的Pe、Pt通过下述式由搅拌机的电流值(A)和电压值(V)分别计算。
Pe(或Pt)=31/2×电压×电流值×功率因数×效率/1000。
[氧气阻隔性]
将实施例和比较例中得到的多层结构体在温度20℃、85%RH的状态下调湿5天,然后使用透氧量测定装置(モダンコントロール公司制MOCON OX-TRAN2/21)测定透氧量(cc/m2・day・atm)。
[实施例1]
(共聚物1的制造)
将所使用的聚合装置的示意图示于图1。向作为搅拌叶片8而具备FULLZONE叶片[神钢环境ソリューション公司制、搅拌叶片直径(直径)d:1.1m、叶片(桨)宽度b:1.5m]的大致圆柱状的聚合槽1[容量:7kL、槽内径D:1.8m]中,分别以槽内乙烯压力达到0.23MPa的方式从导管5导入乙烯,并以3L/hr的速度从导管6导入作为聚合引发剂的2,2’-偶氮双-(4-甲氧基-2,4-二甲基戊腈)的1质量%甲醇溶液。此外,借助导入管10和换热器2,将含有乙酸乙烯酯的液体(乙酸乙烯酯:777L/hr、甲醇:170L/hr)导入至聚合槽1中。此外,将含乙烯的气体从聚合槽1借助导管3而导入至换热器2中。含有乙酸乙烯酯的液体通过沿着管的表面流下而吸收乙烯,借助导管4而注入至聚合槽1中,与反应液混合,并供于其与乙烯的连续聚合。以聚合槽1内的液面达到恒定的方式从导管9连续地取出聚合液。以聚合槽1出口处的乙酸乙烯酯的聚合率达到30%的方式进行调整。此外,每单位体积的搅拌动力Pv为3.1kW/m3,以弗劳德数Fr达到0.15的方式进行调整。叶片(桨)整体浸渍于反应液中,且在液面与叶片(桨)的上端邻近的状态下搅拌反应液。聚合槽中的反应液的滞留时间为5小时。聚合槽出口的温度为60℃。通过向连续取出的聚合液中导入甲醇蒸气而进行未反应的乙酸乙烯酯单体的去除,得到乙烯-乙酸乙烯酯共聚物的甲醇溶液(浓度为32%)。
将作为皂化催化剂的氢氧化钠的甲醇溶液(浓度为4质量%)以氢氧化钠相对于前述乙烯-乙酸乙烯酯共聚物中的乙酸乙烯酯单元的摩尔比达到0.012的方式添加至通过前述聚合工序而得到的乙烯-乙酸乙烯酯共聚物的甲醇溶液(浓度为32质量%)中。将乙烯-乙酸乙烯酯共聚物溶液和皂化催化剂溶液用静态混合器进行混合后,将所得混合物载置在带上,以40℃保持18分钟来进行皂化反应。其后,进行粉碎、干燥,得到乙烯-乙烯醇共聚物。所得共聚物的乙烯单元的含有率为2摩尔%,粘均聚合度为1700,皂化度为98.5摩尔%,乙烯单元的嵌段特性为0.95。
(多层结构体的制造)
将所得乙烯-乙烯醇共聚物100质量份和作为具有共轭双键的分子量1000以下的化合物的2,4-二苯基-4-甲基-1-戊烯(DPMP)0.004质量份添加在水中,制备乙烯-乙烯醇共聚物浓度7质量%的水溶液(涂布剂)后,在20℃、60%RH下静置1小时。将锚固剂(粘接剂)涂布在厚度15μm的层(B)拉伸聚对苯二甲酸乙二醇酯(OPET)膜(基材)上,在OPET膜的表面形成粘接剂层。使用凹版涂布机,在40℃下在粘接剂层的表面涂布上述得到的涂布剂,然后在120℃下干燥而形成层(A)。为了促进锚固剂的反应,将前述膜进一步在160℃下进行120秒的热处理,由此得到多层结构体。层(A)的厚度为2μm。将所得多层结构体的透氧量X示于表2。此外,将所制备的涂布剂静置5天,除此以外,与上述同样地得到多层结构体后,测定透氧量Y。将结果示于表2。
[实施例2~6和8~9、以及比较例2、3和5]
(乙烯-乙酸乙烯酯共聚物的制造)
如表1所示那样地变更聚合时的乙烯、乙酸乙烯酯、甲醇和引发剂的进料量、聚合率、搅拌动力Pv、弗劳德数Fr、以及皂化时的乙烯-乙烯基酯共聚物溶液的浓度和氢氧化钠的摩尔比,并且,作为搅拌叶片8而使用MAXBLEND叶片[住友重机械工艺机器公司制、搅拌叶片直径(直径)d:1m、叶片(桨)宽度b:2m],除此之外,与实施例1同样操作,制造乙烯-乙烯醇共聚物。
(多层结构体的制造)
变更所使用的乙烯-乙烯醇共聚物、具有共轭双键且分子量为1000以下的化合物、基材的种类、热处理温度等,除此之外,与实施例1同样操作,得到多层结构体后,测定透氧量。将结果示于表2。
弗劳德数Fr过低时(比较例2、Fr为0.02),得到乙烯单元的嵌段特性为0.88的乙烯单元的嵌段性高的乙烯-乙烯醇共聚物。并且,使用所得乙烯-乙烯醇共聚物而制备涂布剂,5天后制作多层结构体,所得多层结构体的氧气阻隔性不充分。另一方面,弗劳德数Fr过高时(比较例3、Fr为0.21),得到乙烯单元的嵌段特性为1.01的乙烯单元的无规性极高的乙烯-乙烯醇共聚物。并且,使用该乙烯-乙烯醇共聚物而得到的的多层结构体不管涂布剂的静置时间如何,其氧气阻隔性都不充分。另一方面,皂化度过高时(比较例5、皂化度为99.9摩尔%),制备后静置5天的涂布剂发生凝胶化而无法制作多层结构体,无法进行评价。
[实施例7]
(乙烯-乙酸乙烯酯共聚物的制造)
向作为搅拌叶片8而具备MAXBLEND叶片[住友重机械工艺机器公司制、搅拌叶片直径(直径)d:1m、叶片(桨)宽度b:2m]的聚合槽1中,分别以槽内乙烯压力达到0.27MPa的方式从导管5导入乙烯,并以1.8L/hr的速度从导管6导入作为聚合引发剂的2,2’-偶氮双-(4-甲氧基-2,4-二甲基戊腈)的1质量%甲醇溶液。此外,将含有乙酸乙烯酯的液体(乙酸乙烯酯:906L/hr、甲醇:42L/hr)从导入管7导入至聚合槽1中。以聚合槽1内的液面达到恒定的方式从导管9连续取出聚合液。以聚合槽1出口的聚合率达到24%的方式进行调整。此外,搅拌动力Pv为4kW/m3,以弗劳德数Fr达到0.16的方式进行调整。聚合槽中的反应液的滞留时间为5小时。聚合槽出口的温度为60℃。通过向连续取出的聚合液中导入甲醇蒸气而进行未反应的乙酸乙烯酯单体的去除,得到乙烯-乙酸乙烯酯共聚物的甲醇溶液(浓度为25%)。
将作为皂化催化剂的氢氧化钠的甲醇溶液(浓度为4质量%)以氢氧化钠相对于前述乙烯-乙烯基酯共聚物中的乙酸乙烯酯单元的摩尔比达到0.022的方式添加至通过前述聚合工序而得到的乙烯-乙酸乙烯酯共聚物的甲醇溶液(浓度为25质量%)中。将乙烯-乙烯基酯共聚物溶液和皂化催化剂溶液用静态混合器进行混合后,将所得混合物静置在带上,以40℃保持18分钟来进行皂化反应。其后,进行粉碎、干燥,得到乙烯-乙烯醇共聚物。所得共聚物的乙烯单元的含有率为2摩尔%,粘均聚合度为2800,皂化度为99.5摩尔%,乙烯单元的嵌段特性为0.93。
(多层结构体的制造)
变更所使用的乙烯-乙烯醇共聚物、和具有共轭双键且分子量为1000以下的化合物,除此之外,与实施例1同样操作,得到多层结构体,测定20℃、85%RH下的透氧量。将结果示于表2。
[比较例1]
如表1所示那样地变更聚合时的乙烯、乙酸乙烯酯、甲醇和引发剂的进料量和聚合率、每单位体积的搅拌动力Pv、弗劳德数Fr、以及皂化时的乙烯-乙烯基酯共聚物溶液的浓度和氢氧化钠的摩尔比,并且,作为搅拌叶片8而使用两段倾斜桨叶片[搅拌叶片直径(直径)d:1.5m、叶片(桨)宽度b:0.88m],除此之外,利用与实施例7相同的方法,制造各种乙烯-乙烯醇共聚物。需要说明的是,前述两段倾斜桨叶片因叶片(桨)宽度b小而不符合宽桨叶片。
(多层结构体的制造)
变更所使用的乙烯-乙烯醇共聚物、和具有共轭双键且分子量为1000以下的化合物,除此之外,与实施例1同样操作,得到多层结构体后,测定透氧量。将结果示于表2。
比较例1中,使用不是宽桨叶片的2段倾斜桨叶片时,得到乙烯单元的嵌段特性为0.85的乙烯单元的嵌段性高的乙烯-乙烯醇共聚物。并且,从使用所得乙烯-乙烯醇共聚物制备涂布剂起5天后制作的多层结构体的氧气阻隔性不充分。
[比较例4]
如表1所示那样地变更聚合时的乙烯、乙酸乙烯酯、甲醇和引发剂的进料量和聚合率、每单位体积的搅拌动力Pv、弗劳德数Fr、以及皂化时的乙烯-乙烯基酯共聚物溶液的浓度和氢氧化钠的摩尔比,并且,作为搅拌叶片8而使用锚式叶片[搅拌叶片直径(直径)d:1.7m、叶片(桨)宽度b:0.85m],除此之外,利用与实施例1相同的方法,制造各种乙烯-乙烯醇共聚物。需要说明的是,前述锚式叶片因叶片(桨)宽度b小而不符合宽桨叶片。
(多层结构体的制造)
乙烯单元的含量(22摩尔%)过多、乙烯-乙烯醇共聚物不溶于水,因此无法进行多层结构体的制造和评价。
如实施例中所示,使用乙烯单元的嵌段特性为规定范围内的乙烯-乙烯醇共聚物而得到的本发明的多层结构体的氧气阻隔性优异。此外,含有前述乙烯-乙烯醇共聚物的水溶液即使长时间保存后粘度稳定性也优异。因此,即使从制备该水溶液起经过长时间后使用时,也可均匀地涂布在基材上,因此可得到氧气阻隔性优异的多层结构体。
附图标记说明
1 聚合槽
2 换热器
3~7 导管
8 搅拌机
9 反应液导出管
10 乙烯基酯导入管
11、12 制冷剂管
13 气体排出管
21 MAXBLEND叶片
22 SUPERMIX MR203
23 SUPERMIX MR205
24 FULLZONE叶片
Claims (6)
1.多层结构体,其具有层(A)和层(B),所述层(A)含有乙烯-乙烯醇共聚物,所述乙烯-乙烯醇共聚物的乙烯单元的含有率为1摩尔%以上且小于20摩尔%、粘均聚合度为200~5000、皂化度为80~99.7摩尔%、乙烯单元的嵌段特性为0.90~0.99,所述层(B)含有选自聚烯烃树脂、聚酯树脂和聚酰胺树脂中的至少1种树脂。
2.根据权利要求1所述的多层结构体,其中,层(A)的厚度为0.1~20μm。
3.根据权利要求1或2所述的多层结构体,其中,层(A)进一步含有相对于前述乙烯-乙烯醇共聚物100质量份为0.000001~0.01质量份的具有共轭双键的分子量1000以下的化合物。
4.权利要求1~3中任一项所述的多层结构体的制造方法,其具有制备含有前述乙烯-乙烯醇共聚物的水溶液而得到涂布剂的步骤、以及将该涂布剂涂布在包含选自聚烯烃树脂、聚酯树脂和聚酰胺树脂中的至少1种树脂的基材的表面的步骤。
5.根据权利要求4所述的制造方法,其中,从制备前述涂布剂起经过1~30天后,将该涂布剂涂布在前述基材的表面。
6.包装材料,其具备权利要求1~3中任一项所述的多层结构体。
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