WO2015020132A1 - 多層成形体 - Google Patents
多層成形体 Download PDFInfo
- Publication number
- WO2015020132A1 WO2015020132A1 PCT/JP2014/070826 JP2014070826W WO2015020132A1 WO 2015020132 A1 WO2015020132 A1 WO 2015020132A1 JP 2014070826 W JP2014070826 W JP 2014070826W WO 2015020132 A1 WO2015020132 A1 WO 2015020132A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- polyester resin
- multilayer
- multilayer molded
- acid
- Prior art date
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- 238000000465 moulding Methods 0.000 title claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 300
- 239000011347 resin Substances 0.000 claims abstract description 300
- 229920001225 polyester resin Polymers 0.000 claims abstract description 252
- 239000004645 polyester resin Substances 0.000 claims abstract description 251
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 72
- 150000002009 diols Chemical group 0.000 claims abstract description 70
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims abstract description 47
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 43
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 39
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000004985 diamines Chemical class 0.000 claims abstract description 23
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001361 adipic acid Substances 0.000 claims abstract description 14
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 14
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 14
- 239000010410 layer Substances 0.000 claims description 155
- 239000002344 surface layer Substances 0.000 claims description 100
- 238000001125 extrusion Methods 0.000 claims description 80
- 238000000034 method Methods 0.000 claims description 50
- 238000002347 injection Methods 0.000 claims description 42
- 239000007924 injection Substances 0.000 claims description 42
- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
- 239000012792 core layer Substances 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 238000000071 blow moulding Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 17
- 238000006068 polycondensation reaction Methods 0.000 claims description 17
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 12
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 10
- 229920005992 thermoplastic resin Polymers 0.000 claims description 10
- 125000002723 alicyclic group Chemical group 0.000 claims description 9
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 9
- 239000007790 solid phase Substances 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000001746 injection moulding Methods 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 5
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 5
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- HXEWWQYSYQOUSD-UHFFFAOYSA-N 2-[5-ethyl-5-(hydroxymethyl)-1,3-dioxan-2-yl]-2-methylpropan-1-ol Chemical compound CCC1(CO)COC(C(C)(C)CO)OC1 HXEWWQYSYQOUSD-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- BPZIYBJCZRUDEG-UHFFFAOYSA-N 2-[3-(1-hydroxy-2-methylpropan-2-yl)-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropan-1-ol Chemical compound C1OC(C(C)(CO)C)OCC21COC(C(C)(C)CO)OC2 BPZIYBJCZRUDEG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 abstract 1
- -1 polyethylene terephthalate Polymers 0.000 description 52
- 230000004888 barrier function Effects 0.000 description 31
- 238000011156 evaluation Methods 0.000 description 27
- 239000007789 gas Substances 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 22
- 235000014113 dietary fatty acids Nutrition 0.000 description 21
- 239000000194 fatty acid Substances 0.000 description 21
- 229930195729 fatty acid Natural products 0.000 description 21
- 150000004665 fatty acids Chemical group 0.000 description 21
- 238000002156 mixing Methods 0.000 description 20
- 230000002087 whitening effect Effects 0.000 description 20
- 239000002184 metal Substances 0.000 description 19
- 230000032798 delamination Effects 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000004952 Polyamide Substances 0.000 description 13
- 229920002647 polyamide Polymers 0.000 description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 description 13
- 239000005020 polyethylene terephthalate Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 125000004437 phosphorous atom Chemical group 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 235000013305 food Nutrition 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 8
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 238000010102 injection blow moulding Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 150000001869 cobalt compounds Chemical class 0.000 description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 6
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 238000007112 amidation reaction Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 230000001976 improved effect Effects 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- 235000021357 Behenic acid Nutrition 0.000 description 3
- 239000004278 EU approved seasoning Substances 0.000 description 3
- 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 3
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 235000014171 carbonated beverage Nutrition 0.000 description 3
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- 150000002148 esters Chemical class 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 2
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- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
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- 150000007942 carboxylates Chemical class 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
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- 150000004820 halides Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- 235000015110 jellies Nutrition 0.000 description 2
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- 229910052744 lithium Inorganic materials 0.000 description 2
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- 239000006210 lotion Substances 0.000 description 2
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 2
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- 230000007774 longterm Effects 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013536 miso Nutrition 0.000 description 1
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- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- CHDRADPXNRULGA-UHFFFAOYSA-N naphthalene-1,3-dicarboxylic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC(C(O)=O)=C21 CHDRADPXNRULGA-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 235000015927 pasta Nutrition 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- CGNKSELPNJJTSM-UHFFFAOYSA-N phenylphosphonous acid Chemical compound OP(O)C1=CC=CC=C1 CGNKSELPNJJTSM-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 235000020991 processed meat Nutrition 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 235000011962 puddings Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical compound [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 description 1
- 235000019992 sake Nutrition 0.000 description 1
- 235000015175 salami Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 235000013580 sausages Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 235000020083 shōchū Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- IYYIUOWKEMQYNV-UHFFFAOYSA-N sodium;ethoxy-oxido-oxophosphanium Chemical compound [Na+].CCO[P+]([O-])=O IYYIUOWKEMQYNV-UHFFFAOYSA-N 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N trans-decahydronaphthalene Natural products C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
Classifications
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- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/04—Extrusion blow-moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/06—Injection blow-moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
-
- 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
- B32B1/00—Layered products having a non-planar shape
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- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
- B65D1/0215—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C2049/023—Combined blow-moulding and manufacture of the preform or the parison using inherent heat of the preform, i.e. 1 step blow moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3032—Preforms or parisons made of several components having components being injected
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/3041—Preforms or parisons made of several components having components being extruded
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/08—Biaxial stretching during blow-moulding
- B29C49/16—Biaxial stretching during blow-moulding using pressure difference for pre-stretching, e.g. pre-blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/42—Component parts, details or accessories; Auxiliary operations
- B29C49/64—Heating or cooling preforms, parisons or blown articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/003—PET, i.e. poylethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/25—Solid
- B29K2105/253—Preform
- B29K2105/258—Tubular
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7158—Bottles
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
-
- 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
- B32B2439/00—Containers; Receptacles
-
- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/40—Closed containers
-
- 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
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Definitions
- the present invention relates to a multilayer molded body, and in particular, improves interlayer adhesion between a surface layer and a core layer when the multilayer molded body is subjected to an impact during transportation or dropping to prevent delamination of the multilayer molded body.
- the present invention relates to a multilayer molded body that can avoid delamination without having a shape with few concavo-convex portions and bent portions, and has a high degree of design freedom.
- plastic containers such as bottles
- plastic containers mainly composed of polyester such as polyethylene terephthalate (PET)
- PET polyethylene terephthalate
- the proportion of small plastic bottles in plastic containers is increasing year by year. Since the ratio of the surface area per unit volume increases as the bottle becomes smaller, the shelf life of the contents tends to be shorter when the bottle is made smaller.
- the containers have been made thinner and lighter, and further improvements in barrier properties are required.
- carbon coating, vapor deposition, and barrier resin coating are applied to multilayer bottles, blend bottles, and thermoplastic polyester resin single-layer bottles using thermoplastic polyester resin and gas barrier resin as a method for imparting gas barrier properties to containers.
- Barrier coating bottles, multilayer sheets, blend sheets, multilayer containers and the like have been developed.
- thermoplastic polyester resin such as PET that forms the surface layer
- thermoplastic gas barrier resin such as polymetaxylylene adipamide (polyamide MXD6)
- a resin having an oxygen scavenging function that traps oxygen inside the container while blocking oxygen from outside the container has been developed and applied to multilayer bottles.
- the oxygen scavenging bottle a multilayer bottle using polyamide MXD6 mixed with a transition metal catalyst as a gas barrier layer is preferable in terms of oxygen absorption rate, transparency, strength, moldability, and the like.
- the multilayer bottles are used for containers such as beer, tea and carbonated drinks because of their good gas barrier properties. Multilayer bottles are used in these applications to maintain the quality of contents and improve shelf life, while delamination occurs between different resins, for example, the outer surface layer and between the inner surface layer and the core layer. There is a problem that damages the value of the product.
- Patent Document 1 As a method for improving such a problem, when a resin constituting the surface layer is finally injected into the mold cavity, a backflow control device capable of allowing a certain amount of backflow to the gas barrier layer side is used. It is disclosed that the delamination resistance is improved by interposing a coarsely mixed resin (Patent Document 1).
- Patent Documents 2 and 3 Also disclosed is a method of suppressing delamination by using a mixed layer made of a polyester resin and a gas barrier resin as a core layer.
- Patent Document As an example of a multilayer sheet and a multilayer container obtained by molding the multilayer sheet, a laminate in which an adhesive layer is provided between a polyester resin layer and a gas barrier resin layer is known (Patent Document). 4).
- Patent Document 1 discloses improving the delamination resistance of a multilayer bottle has a problem of requiring a special device.
- the method of using a mixed layer composed of a polyester resin and a gas barrier resin for the core layer has a problem that not only the transparency is lowered but also a gas barrier property is lowered by adding a large amount of polyester resin.
- the object of the present invention is to solve the above-mentioned problems, and to provide a multilayer molded body that not only hardly peels off due to dropping or impact, but also has excellent transparency and excellent gas barrier properties. It is in.
- the present inventors have found that a multilayer molded article in which at least one resin layer in contact with a layer formed by mixing polyamide and a specific polyester contains a predetermined amount of polyester resin.
- the present inventors have found that a multi-layer molded article having improved interlayer adhesion at the time of dropping or impact and having excellent transparency and a gas barrier can be obtained.
- a resin multilayer molded body including two or more resin layers, At least one resin layer of the multilayer molded body comprises a polyamide resin (C) obtained by polymerizing a diamine component containing 70 mol% or more of metaxylylenediamine and a dicarboxylic acid component containing 70 mol% or more of adipic acid;
- a polyester resin (D) containing an acid unit and a diol unit, wherein 1 to 80 mol% of the diol unit is a diol unit having a cyclic acetal skeleton, (C) / (D) 99/1 to 10/90 Consists of mixed resin (B) contained in a weight ratio, Thermoplastic obtained by polymerizing a dicarboxylic acid component containing 80 mol% or more of terephthalic acid and a diol component containing 80 mol% or more of ethylene glycol in at least one resin layer in contact with the layer composed of the mixed resin
- the diol unit having a cyclic acetal skeleton of the polyester resin (D) is represented by the general formula (1): (Wherein R 1 and R 2 are each independently a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, and carbon.
- general formula (2): (Wherein R 1 is as defined above, R 3 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 6 to 10 carbon atoms) Represents a hydrocarbon group selected from the group consisting of aromatic hydrocarbon groups of The multilayer molded body according to ⁇ 1> or ⁇ 2>, which is a diol unit derived from a diol represented by ⁇ 4>
- the diol unit having a cyclic acetal skeleton of the polyester resin (D) is 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.
- the diol unit other than the diol unit having a cyclic acetal skeleton of the polyester resin (D) is selected from the group consisting of ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol.
- Units derived from dicarboxylic acid having 1 to 100 mol% in the dicarboxylic acid unit of the polyester resin (D) are derived from dicarboxylic acid having a benzene skeleton, and units from 0 to 99 mol% are derived from dicarboxylic acid having a naphthalene skeleton.
- the dicarboxylic acid unit of the polyester resin (D) is terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid.
- a polyamide resin obtained by subjecting the polyamide resin (C) to melt polycondensation with a diamine component containing 70 mol% or more of metaxylylenediamine and a dicarboxylic acid component containing 70 mol% or more of adipic acid is further solidified.
- the mixed resin (B) further contains 0.01 to 0.10% by weight of one or more metal elements selected from the group consisting of transition metals of Group VIII of the periodic table, manganese, copper and zinc
- ⁇ 10> The multilayer molded body according to any one of ⁇ 1> to ⁇ 9>, wherein the weight ratio of the mixed resin (B) to the total weight of the multilayer molded body is 1 to 30% by weight.
- thermoplastic polyester resin (A) A resin containing 70% by weight or more of the thermoplastic polyester resin (A) is injected from the surface layer side injection cylinder, then the mixed resin (B) is injected from the core side injection cylinder, and the thermoplastic resin is injected from the surface layer side injection cylinder. It is obtained by simultaneously injecting the polyester resin (A) and further blow molding a parison having a three-layer structure formed by injecting the thermoplastic polyester resin (A) from the surface layer side injection cylinder to fill the mold cavity. It is a multilayer molded object as described in said ⁇ 11> which is a hollow container.
- thermoplastic polyester resin (A) is injected from the surface layer side injection cylinder, then the mixed resin (B) is injected from the core side injection cylinder, and further from the surface layer side injection cylinder.
- the multilayer molded article according to the above ⁇ 11> which is a hollow container obtained by blow molding a parison having a five-layer structure formed by injecting a thermoplastic polyester resin (A) to fill a mold cavity.
- a multilayer molded body comprising A resin containing 70% by weight or more of the thermoplastic polyester resin (A) is extruded from the surface layer side extrusion cylinder or from at least one of the surface layer side extrusion cylinder and the core side extrusion cylinder.
- the multilayer molded article according to any one of ⁇ 1> to ⁇ 10> which is a resulting multilayer sheet having a thickness of 100 to 2000 ⁇ m.
- ⁇ 16> A multilayer sheet having a three-layer structure obtained by extruding a resin containing 70% by weight or more of the thermoplastic polyester resin (A) from the surface layer side extrusion cylinder and extruding the mixed resin (B) from the core side extrusion cylinder.
- Extruded resin, extruded mixed resin (B) from intermediate layer side extrusion cylinder or central layer side extrusion cylinder, and extruded thermoplastic resin from intermediate layer side extrusion cylinder or central layer side extrusion cylinder that did not extrude mixed resin (B) The multilayer molded article according to ⁇ 15>, which is a multilayer sheet having a five-layer structure obtained by extruding a resin containing 70% by weight or more of (A).
- the multilayer sheet container according to any one of the above ⁇ 15> to ⁇ 17> which is a multilayer sheet container obtained by rapidly heating and softening the surface of the multilayer sheet to 90 to 250 ° C. and then molding with a mold having a desired shape It is a multilayer molded object of description.
- the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
- the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
- the present invention can be implemented with appropriate modifications within the scope of the gist thereof.
- At least one resin layer is obtained by polymerizing a diamine component containing 70 mol% or more of metaxylylenediamine and a dicarboxylic acid component containing 70 mol% or more of adipic acid.
- Thermoplastic polyester resin (A) (hereinafter referred to as “polyester resin”) obtained by polymerizing a component and a diol component containing 80 mol% or more of ethylene glycol Composed of resin containing abbreviated as A) ”) 70 wt% or more.
- a more preferable configuration of the resin multilayer molded body of the present embodiment is a multilayer molded body including three or more resin layers, and the resin layers forming the surfaces on both sides of the molded body are made of 70% of the polyester resin (A). It is composed of a resin containing at least wt%. Use of a resin containing 70% by weight or more of the polyester resin (A) for the resin layer forming the surface is advantageous in terms of transparency, mechanical strength, and moldability.
- the polyester resin (A) used in the multilayer molded article of the present embodiment comprises 80 mol% or more, preferably 90 mol% or more of a dicarboxylic acid component that is terephthalic acid, and 80 mol% or more, preferably 90 mol% or more. It is a polyester obtained by polymerizing a diol component that is ethylene glycol.
- the molded object excellent in aroma retention can be obtained by using a polyester resin (A) for an inner surface layer.
- Polyethylene terephthalate is preferably used as the polyester resin (A). It becomes possible to exhibit excellent properties in all of transparency, mechanical strength, injection moldability, and stretch blow moldability of polyethylene terephthalate.
- dicarboxylic acid components other than terephthalic acid include isophthalic acid, diphenyl ether-4,4-dicarboxylic acid, naphthalene-1,4 or 2,6-dicarboxylic acid, adipic acid, sebacic acid, decane-1,10-carboxylic acid. Acid, hexahydroterephthalic acid can be used.
- other diol components include propylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis. (4-hydroxyethoxyphenyl) propane or the like can be used.
- oxyacids such as p-oxybenzoic acid can also be used as a raw material monomer for the polyester resin (A).
- the intrinsic viscosity of the polyester resin (A) is 0.55 to 1.50 (dL / g), preferably 0.65 to 1.40 (dL / g).
- the intrinsic viscosity is 0.55 (dL / g) or more, the multilayer parison can be obtained in a transparent amorphous state, and the mechanical strength of the obtained multilayer molded article is also satisfied.
- the intrinsic viscosity is 1.50 (dL / g) or less, molding troubles due to an increase in viscosity can be avoided.
- thermoplastic resins can be blended with the polyester resin (A) within a range not impairing the characteristics of the present invention.
- examples of other thermoplastic resins include thermoplastic polyester resins such as polyethylene-2,6-naphthalene dicarboxylate, polyolefin resins, polycarbonate, polyacrylonitrile, polyvinyl chloride, polystyrene, and the like.
- the end material generated in the process of producing the multilayer molded body of the present invention can be used as another thermoplastic resin.
- the blending amount of the other thermoplastic resin is less than 30% by weight of the resin constituting the resin layer containing the polyester resin (A), preferably 20% by weight or less, and more preferably 10% by weight or less. preferable.
- At least one layer is formed of a mixed resin (B) of the following polyamide resin (C) and a specific polyester resin (D).
- the polyamide resin (C) is obtained by polymerizing a diamine component containing 70 mol% or more of metaxylylenediamine and a dicarboxylic acid component containing 70 mol% or more of adipic acid.
- the amount of metaxylylenediamine in the diamine component is 70 mol% or more, excellent gas barrier properties can be maintained.
- the adipic acid in the dicarboxylic acid component is 70 mol% or more, it is possible to prevent a decrease in gas barrier properties and a decrease in crystallinity.
- Polyamide resin (C) exhibits excellent properties in co-injection moldability and co-stretch blow moldability with polyethylene resin (A) (polyethylene terephthalate), and as polyamide resin (C), polymetaxylylene adipamide (hereinafter referred to as polyamide MXD6) Are preferably used.
- diamine components that can be used in addition to metaxylylenediamine, tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, Aliphatic diamines such as 2,2,4-trimethylhexamethylenediamine and 2,4,4-trimethylhexamethylenediamine; 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1 , 3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminomethyl) decalin, bis (a Nomethyl) tricyclodecane
- dicarboxylic acid components that can be used in addition to adipic acid include suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and the like. Is not to be done.
- the polyamide resin (C) may contain a small amount of monoamine or monocarboxylic acid used as a molecular weight regulator during production.
- the above-mentioned polyamide resin (C) is produced by a melt polycondensation (melt polymerization) method or by further solid-phase polymerization after melt polycondensation.
- melt polycondensation method for example, there is a method in which a nylon salt composed of a diamine component and a dicarboxylic acid component is heated in the presence of water under pressure, and polymerized in a molten state while removing added water and condensed water. It can also be produced by a method in which a diamine component is directly added to a molten dicarboxylic acid component and polycondensed.
- the diamine component is continuously added to the dicarboxylic acid component, and the reaction system is heated up so that the reaction temperature does not fall below the melting point of the generated oligoamide and polyamide.
- polycondensation proceeds.
- a phosphorus atom-containing compound may be added in order to obtain an effect of promoting an amidation reaction and an effect of preventing coloration during polycondensation.
- phosphorus atom-containing compounds include dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, ethyl hypophosphite, phenylphosphonous acid, Sodium phenylphosphonite, potassium phenylphosphonite, lithium phenylphosphonite, ethyl phenylphosphonite, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, phenylphosphonic acid Examples include diethyl, sodium ethylphosphonate, potassium ethylphosphonate, phosphorous acid
- hypophosphorous Hypophosphite metal salts such as sodium, potassium hypophosphite, lithium hypophosphite and the like are preferably used because they have a high effect of promoting amidation reaction and are excellent in anti-coloring effect, especially sodium hypophosphite.
- the phosphorus atom-containing compounds that can be used in the present invention are not limited to these compounds.
- the amount of the phosphorus atom-containing compound added to the polycondensation system of the polyamide resin (C) is preferably 1 to 500 ppmm, more preferably 5 to 450 ppm in terms of the phosphorus atom concentration in the polyamide resin (C). Yes, more preferably 10 to 400 ppm.
- an alkali metal compound in combination with the phosphorus atom-containing compound.
- a sufficient amount of phosphorus atom-containing compound needs to be present, but in some cases it may promote gelation of the polyamide, so the amidation reaction rate is adjusted. Therefore, it is preferable to coexist an alkali metal compound or an alkaline earth metal compound.
- lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide and other alkali metal / alkaline earth metal hydroxides lithium acetate
- Examples include sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, barium acetate, and other alkali metal / alkaline earth metal acetates, etc., but these compounds can be used without limitation. .
- the value obtained by dividing the number of moles of the compound by the number of moles of the phosphorus atom-containing compound should be 0.5 to 2.0. Is more preferably 0.6 to 1.8, and still more preferably 0.7 to 1.5. By setting it as the above-mentioned range, it becomes possible to suppress the formation of gel while obtaining the amidation reaction promoting effect by the phosphorus atom-containing compound.
- the polyamide resin (C) obtained by melt polycondensation is once taken out, pelletized, and dried before use.
- solid phase polymerization may be performed.
- a heating device used in drying or solid phase polymerization a continuous heating drying device, a rotary drum type heating device called a tumble dryer, a conical dryer, a rotary dryer or the like, and a rotary blade inside a nauta mixer are used.
- a conical heating apparatus provided with can be used suitably, a well-known method and apparatus can be used without being limited to these.
- a batch heating apparatus is preferably used because it can seal the inside of the system and easily proceed with polycondensation in a state where oxygen that causes coloring is removed. It is done.
- the polyamide resin (C) obtained through the above-described steps is less colored and less gelled.
- b in the color difference test of JIS-K-7105 is used among the polyamides obtained through the above-mentioned steps.
- a value of 5 or less is preferably used, particularly preferably 3 or less, and more preferably 1 or less.
- the relative viscosity is generally used.
- a preferred relative viscosity is 1.5 to 4.2, more preferably 1.6 to 4.0, and still more preferably 1.7 to 3.8.
- the terminal amino group concentration of the polyamide resin (C) used in the present embodiment is preferably 10 to 40 ⁇ eq / g, more preferably 12 to 35 ⁇ eq / g, and still more preferably 15 to 30 ⁇ eq / g. is there.
- the terminal amino group concentration is preferably 10 to 40 ⁇ eq / g, more preferably 12 to 35 ⁇ eq / g, and still more preferably 15 to 30 ⁇ eq / g. is there.
- Means for bringing the terminal amino group concentration within the above range include a method of proceeding the polymerization so that the molar ratio of the diamine component to the dicarboxylic acid component is slightly excessive, or a monocarboxylic acid compound or dicarboxylic acid after the reaction is completed.
- a method of proceeding the polymerization so that the molar ratio of the diamine component to the dicarboxylic acid component is slightly excessive, or a monocarboxylic acid compound or dicarboxylic acid after the reaction is completed.
- the content of metaxylylenediamine remaining in the polyamide resin (C) is preferably 10 ppm or less, more preferably 5 ppm or less, and further preferably 1 ppm.
- the residual amount of metaxylylenediamine is 10 ppm or less, yellowing of the appearance caused by the reaction between acetaldehyde generated from the polyester resin (A) and the terminal amino group is suppressed.
- the means for reducing the content of metaxylylenediamine to 10 ppm or less include a method of heating the polyamide after polymerization under reduced pressure, a method of melting it with an extruder and the like, and reducing the pressure inside the system. Various methods can be used without being limited to the above.
- an oligomer composed of a dicarboxylic acid component and a diamine component may be mixed.
- a monomer (cyclic monomer) obtained by cyclization of metaxylylenediamine and adipic acid may float on the surface of the molded body during melt processing and impair the appearance of the molded body.
- the amount of the cyclic monomer contained in the polyamide resin (C) is preferably 1% by weight or less, more preferably 0.8% by weight or less, and further preferably 0.5% by weight or less. is there. By adjusting the content of the cyclic monomer to 1% by weight or less, a molded product having a good appearance can be continuously molded for a long time.
- a method of washing the polyamide resin (C) with water, a method of treating under high temperature and high vacuum, or removing the inside of the extrusion apparatus by reducing the pressure during melt extrusion is not limited to these methods, and known methods for removing low molecular weight or volatile components can be appropriately employed.
- the method for measuring the content of the cyclic monomer in the present invention can be obtained by pulverizing polyamide by freeze pulverization, extracting it at 80 ° C. for 1 hour with methanol as a solvent, and analyzing it by liquid chromatography. .
- Polyamide resin (C) includes antioxidants, matting agents, heat stabilizers, weather stabilizers, ultraviolet absorbers, nucleating agents, plasticizers, flame retardants, antistatic agents, as long as the effects of the present invention are not impaired. Additives such as anti-coloring agents, lubricants, anti-gelling agents, clays such as layered silicates, nanofillers, and the like can also be added. If necessary, nylon 6 and nylon 66, various polyamides such as amorphous nylon using aromatic dicarboxylic acid as a monomer, modified resins thereof, polyolefin and modified resins thereof, elastomers having styrene in the skeleton, etc.
- the polyamide resin (C) can be added as needed for the purpose of modification, but the present invention is not limited to those shown above, and various materials may be mixed. Furthermore, it can also be set as the multilayer molded object which has an oxygen absorption function by inducing the oxidation reaction of a polyamide resin (C) by making cobalt metal exist in the multilayer molded object of this invention.
- polyester resin (A) and / or polyester resin (D) using a cobalt compound as one of polymerization catalysts may be used, or polyester resin (A).
- / or a polyester compound (D) and / or a polyamide resin (C) may be previously melt-mixed with a cobalt compound and used, or a polyester resin to which a cobalt compound is added in the production of a multilayer molded article ( A) and / or polyester resin (D) and / or polyamide resin (C) may be mixed.
- cobalt compound cobalt carboxylates such as cobalt octoate, cobalt naphthenate, cobalt acetate, and cobalt stearate are preferably used.
- the addition amount of the cobalt compound is preferably 10 to 1000 ppm, more preferably 30 to 600 ppm, and still more preferably 50 to 400 ppm as the concentration of cobalt metal with respect to the weight of the multilayer molded body. By setting it within this range, an effective oxygen absorbing function can be imparted to the multilayer molded body.
- the cobalt compound mentioned above functions not only as a polyamide resin (C) but also as an oxidation reaction catalyst of an organic compound having an unsaturated carbon bond, in order to further enhance the oxygen absorption function of the multilayer molded body, Compounds exemplified by polymers of unsaturated hydrocarbons such as polyisoprene or oligomers thereof, compounds having a functional group added to improve compatibility, and the like can also be added.
- the polyester resin (D) used in this embodiment is a polyester containing a dicarboxylic acid unit and a diol unit and a diol unit having a cyclic acetal skeleton as a diol unit.
- the diol unit having a cyclic acetal skeleton is preferably a unit derived from a compound represented by the following general formula (1) or (2).
- R 1 and R 2 are each independently a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 6 to 6 carbon atoms.
- 10 represents a divalent hydrocarbon group selected from the group consisting of 10 divalent aromatic hydrocarbon groups.
- R 3 is selected from the group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms. Represents a hydrocarbon group.
- Examples of the compounds of the general formulas (1) and (2) include 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, Or 5-methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane is particularly preferred.
- the diol unit other than the diol unit having a cyclic acetal skeleton is not particularly limited, but ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol Aliphatic diols such as propylene glycol and neopentyl glycol; polyether diols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2- Decahydronaphthalene diethanol, 1,3-decahydronaphthalene diethanol, 1,4-decahydronaphthalene diethanol, 1,5-decahydronaphthalene diethanol, 1,6-decahydronaphtha Cycloaliphatic diols such as didimethanol, 2,7-decahydronaphthalene diethanol,
- the unit is preferably a unit derived from ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol.
- a unit derived from ethylene glycol is preferred.
- the exemplified diol units can be used alone or in combination.
- the ratio of the diol unit having a cyclic acetal skeleton in the diol unit in the polyester resin (D) of the present embodiment is 1 to 80 mol%, preferably 2 to 60 mol%, more preferably 5 to 50 mol%. is there.
- the delamination can be improved by setting the ratio of the diol unit having a cyclic acetal skeleton to 1 mol% or more.
- the ratio exceeds 80 mol%, the molding temperature is high and problems such as yellowing occur.
- the dicarboxylic acid unit of the polyester resin (D) of the present embodiment is not particularly limited, but succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclohexane Aliphatic dicarboxylic acids such as dicarboxylic acid, decanedicarboxylic acid, norbornane dicarboxylic acid, tricyclodecanedicarboxylic acid, pentacyclododecanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, 1,3-naphthalenedicarboxylic Derived from aromatic dicarboxylic acids such as acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedi
- terephthalic acid isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7-
- a unit derived from an aromatic dicarboxylic acid such as naphthalenedicarboxylic acid is preferable, and terephthalic acid, 2,6-naphthalenedicarboxylic acid, and isophthalic acid are particularly preferable.
- the unit is preferably derived from terephthalic acid, and transparency and gas barrier properties can be improved by using 2,6-naphthalenedicarboxylic acid.
- the illustrated dicarboxylic acids can be used alone or in combination.
- 1 to 100 mol% of the dicarboxylic acid unit of the polyester resin (D) is a unit derived from a dicarboxylic acid having a benzene skeleton, and 0 to 99 mol% is a unit derived from a dicarboxylic acid having a naphthalene skeleton. Is preferred. More preferably, 45 to 100 mol% in the dicarboxylic acid unit of the polyester resin (D) is a unit derived from a dicarboxylic acid having a benzene skeleton, and 0 to 55 mol% is derived from a dicarboxylic acid having a naphthalene skeleton.
- 70 to 100 mol% of the dicarboxylic acid unit of the polyester resin (D) is a unit derived from a dicarboxylic acid having a benzene skeleton, and 0 to 30 mol% is a dicarboxylic acid having a naphthalene skeleton. It is a unit derived from an acid.
- the polyester resin (D) is derived from a monoalcohol unit such as butyl alcohol, hexyl alcohol or octyl alcohol or a trihydric or higher polyhydric alcohol such as trimethylolpropane, glycerin or pentaerythritol within the range not impairing the object of the present invention.
- Units derived from monocarboxylic acids such as benzoic acid, propionic acid and butyric acid, and units derived from trivalent or higher polyvalent carboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can also be introduced.
- a conventionally well-known method is applicable. Examples thereof include a melt polymerization method such as a transesterification method and a direct esterification method, a solution polymerization method, and a solid phase polymerization method.
- the glass transition temperature (Tg 2 ) of the polyester resin (D) is preferably a temperature difference (
- the intrinsic viscosity of the polyester resin (D) is preferably 0.3 to 1.2 (dL / g), more preferably 0.5 to 1.0 (dL / g), still more preferably 0.6 to 0.00.
- the range is 8 (dL / g).
- the mixed resin (B) used in the present embodiment is a dry blend method in which pellets of the polyamide resin (C) and the polyester resin (D) are mixed in a dry manner, or the polyamide resin (C) and the polyester resin (D) are melt-extruded. And can be produced by any of the melt blending methods for re-pelletizing. An appropriate formulation is selected according to the application, use conditions, mechanical performance, and the like.
- the weight ratio ((C) / (D)) of the polyamide resin (C) and the polyester resin (D) in the mixed resin (B) is 99/1 to 10/90, preferably 97/3 to 20 / 80, more preferably 95/5 to 30/70, still more preferably 92/8 to 50/50, and particularly preferably 88/12 to 70/30.
- the weight ratio of the polyester resin (D) is less than 1%, the peel resistance improving effect cannot be obtained.
- the weight ratio of the polyester resin (D) exceeds 90%, an effect is seen in improving the peel resistance, but the good barrier properties of the polyamide resin (C) are not contributed to the multilayer molded article and are not practical.
- the mixed resin (B) can be used by blending other thermoplastic resins in addition to the polyamide resin (C) and the polyester resin (D) as long as the characteristics of the present invention are not impaired.
- other thermoplastic resins include thermoplastic polyester resins such as polyethylene-2,6-naphthalene dicarboxylate, polyolefin resins, polycarbonate, polyacrylonitrile, polyvinyl chloride, polystyrene, and the like.
- the blending amount of the other thermoplastic resin is preferably 30% by weight or less, more preferably 20% by weight or less, and still more preferably 10% by weight or less of the entire mixed resin (B).
- the mixed resin (B) may contain one or more metal elements selected from the group consisting of group VIII transition metals of the periodic table, manganese, copper and zinc. By containing the metal element, the oxidation of the mixed resin (B) is promoted and an oxygen absorbing function is exhibited.
- the metal element is preferably added to the polyamide resin (C) as a low acid number inorganic acid salt, organic acid salt or complex salt (hereinafter collectively referred to as a metal catalyst compound) of the metal element.
- inorganic acid salts include halides such as chlorides and bromides, sulfates, nitrates, phosphates, silicates, and the like.
- organic acid salt include a carboxylate, a sulfonate, and a phosphonate.
- complex salts include transition metal complexes with ⁇ -diketone, ⁇ -keto acid ester and the like.
- the oxygen absorption function is good, it is preferable to use a carboxylate, halide or acetylacetonate complex of the metal element, and it is more preferable to use a stearate, acetate or acetylacetonate complex.
- the metal element cobalt is particularly preferable because of its excellent oxygen absorption function.
- the said metal catalyst compound can add 1 type (s) or 2 or more types.
- the addition amount of the metal element is preferably 0.01 to 0.10% by weight, more preferably 0.02 to 0.08% by weight, based on the total amount of the polyamide resin (C) and the polyester resin (D). .
- the addition amount is less than 0.01% by weight, the oxygen absorbing function is not sufficiently exhibited, and the effect of improving the oxygen barrier property of the multilayer molded article is also lowered.
- the oxygen barrier effect of a multilayer molded object does not improve any more, and it is uneconomical.
- a portion having a low draw ratio (1 to 2.5 times) may be generated depending on the shape.
- the layer made of the mixed resin (B) in the low draw ratio part absorbs water, it may whiten.
- the whitening inhibitor used in this embodiment is a fatty acid metal salt having 18 to 50 carbon atoms, preferably 18 to 34 carbon atoms. With 18 or more carbon atoms, whitening prevention can be expected. Further, when the carbon number is 50 or less, uniform dispersion in the mixed resin (B) is good. Fatty acids may have side chains and double bonds, but linear saturated such as stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28), triacontanoic acid (C30) Fatty acids are preferred.
- the metal that forms a salt with the fatty acid is not particularly limited, but sodium, potassium, lithium, calcium, barium, magnesium, strontium, aluminum, zinc, etc. are exemplified, and sodium, potassium, lithium, calcium, aluminum, and zinc are particularly preferable.
- the particle diameter of the fatty acid metal salt is not particularly limited. However, since the smaller particle diameter facilitates uniform dispersion in the mixed resin (B), the particle diameter is preferably 0.2 mm or less. .
- the addition amount of the fatty acid metal salt is preferably 0.005 to 1.0 part by weight, more preferably 0.05 to 0.5 part per 100 parts by weight of the total amount of the polyamide resin (C) and the polyester resin (D). Part by weight, particularly preferably 0.12 to 0.5 part by weight. Addition of 0.005 part by weight or more with respect to 100 parts by weight of the total amount can be expected to prevent whitening. Moreover, it becomes possible to keep the fog value of the obtained multilayer molded article low when the addition amount is 1.0 part by weight or less with respect to the total amount of 100 parts by weight.
- a compound selected from the following diamide compounds and diester compounds may be added as a whitening inhibitor.
- One or two or more diamide compounds may be added, one or two or more diester compounds may be added, one or two or more diamide compounds and one or two or more types These diester compounds may be used in combination.
- the diamide compound is obtained from a fatty acid having 8 to 30 carbon atoms and a diamine having 2 to 10 carbon atoms.
- a fatty acid having 8 to 30 carbon atoms and a diamine having 2 to 10 carbon atoms When the fatty acid has 8 or more carbon atoms and the diamine has 2 or more carbon atoms, an effect of preventing whitening can be expected.
- the carbon number of the fatty acid is 30 or less and the carbon number of the diamine is 10 or less, uniform dispersion in the mixed resin (B) becomes good.
- the fatty acid may have a side chain or a double bond, but a linear saturated fatty acid is preferred.
- Examples of the fatty acid component of the diamide compound include stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28), and triacontanoic acid (C30).
- Examples of the diamine component of the diamide compound include ethylenediamine, butylenediamine, hexanediamine, xylylenediamine, and bis (aminomethyl) cyclohexane. A diamide compound obtained by combining these is used in the present invention.
- a diamide compound obtained from a diamine composed mainly of a fatty acid having 8 to 30 carbon atoms and mainly ethylenediamine, or a diamide compound obtained from a fatty acid mainly composed of montanic acid and a diamine having 2 to 10 carbon atoms is preferred.
- the diester compound is obtained from a fatty acid having 8 to 30 carbon atoms and a diol having 2 to 10 carbon atoms.
- the fatty acid has 8 or more carbon atoms and the diol has 2 or more carbon atoms, an effect of preventing whitening can be expected.
- the fatty acid has 30 or less carbon atoms and the diol has 10 or less carbon atoms, uniform dispersion in the mixed resin (B) becomes good.
- the fatty acid may have a side chain or a double bond, but a linear saturated fatty acid is preferred.
- Examples of the fatty acid component of the diester compound include stearic acid (C18), eicosanoic acid (C20), behenic acid (C22), montanic acid (C28), triacontanoic acid (C30) and the like.
- Examples of the diol component of the diester compound include ethylene glycol, propanediol, butanediol, hexanediol, xylylene glycol, and cyclohexanedimethanol. A diester compound obtained by combining these is used in the present invention. Particularly preferred are diester compounds obtained from fatty acids composed mainly of montanic acid and diols composed mainly of ethylene glycol and / or 1,3-butanediol.
- the addition amount of the diamide compound and / or diester compound is preferably 0.005 to 1.0 part by weight, more preferably 0.05 to 100 parts by weight of the total amount of the polyamide resin (C) and the polyamide resin (D). Is 0.5 to 0.5 part by weight, particularly preferably 0.12 to 0.5 part by weight. Addition of 0.005 part by weight or more with respect to 100 parts by weight of the total amount can be expected to prevent whitening. Further, when the addition amount is 1.0 part by weight or less with respect to the total amount of 100 parts by weight, it becomes possible to keep the haze value of the resulting multilayer molded article low.
- the layer made of the mixed resin (B) is produced by the molding method of the present invention. Moreover, it can prevent that the layer which consists of mixed resin (B) whitens after storing a multilayer molded object for a long term on the conditions which do not whiten or increase whitening. That is, even if a whitening inhibitor is not added, the multilayer molded body is exposed to high humidity, water or boiling after being stored for a long time in a condition where whitening does not increase or whitening does not increase, for example, at a temperature of 23 ° C. and a humidity of 50% RH. Even if it is brought into contact with water or heated to the glass transition temperature or higher, whitening is suppressed as in the case immediately after molding.
- the shape of the multilayer molded body in the present embodiment is not particularly limited, and examples thereof include a container shape, a sheet shape, and a stretched film shape.
- a hollow container, a tray, and a container can be illustrated as a container-shaped molded object.
- Examples of the hollow container include a hollow container by injection blow molding and a hollow container by direct blow molding depending on the molding method.
- a multilayer molded body by injection blow molding usually has a layer structure of three or more layers.
- the multilayer molded body is formed by using an injection molding machine having two injection cylinders to mold the polyester resin (A) and the mixed resin (B) having gas barrier properties from the injection cylinders on the surface layer side and the core side respectively.
- the multilayer parison obtained by injecting into a mold cavity through a hot runner is further biaxially stretch blow molded.
- the blow molding of the multilayer parison may be performed by a conventionally known method.
- the method of blow molding after heating the surface of the multilayer parison to 80 to 120 ° C., crystallizing the mouth of the multilayer parison by heat treatment A method of blow molding in a mold of 90 to 150 ° C. after heating to 80 to 120 ° C. is employed.
- the blow pressure is usually 0.5 to 4 MPa.
- the polyester resin (A) constituting the outer surface layer and the inner surface layer from the surface layer side injection cylinder and injecting the mixed resin (B) constituting the core layer from the core side injection cylinder first the polyester resin ( A) is injected, then mixed resin (B) and polyester resin (A) are injected simultaneously, then the required amount of polyester resin (A) is injected to fill the mold cavity (polyester resin) A multilayer parison of (A) / mixed resin (B) / polyester resin (A)) can be produced.
- the polyester resin (A) constituting the outer surface layer and the inner surface layer from the surface layer side injection cylinder and injecting the mixed resin (B) constituting the core layer from the core side injection cylinder first the polyester resin ( A) is injected, then the mixed resin (B) is injected alone, and finally the polyester resin (A) is injected to fill the mold cavity, thereby forming a five-layer structure (polyester resin (A) / mixed resin).
- a multilayer parison of (B) / polyester resin (A) / mixed resin (B) / polyester resin (A)) can be produced.
- the method for producing the multilayer parison is not limited to the above method.
- the thickness of the surface layer containing the polyester resin (A) in the hollow container by injection blow molding of this embodiment is preferably 0.01 to 1.0 mm, and the thickness of the core layer made of the mixed resin (B) The thickness is preferably 0.005 to 0.2 mm.
- the thickness of the hollow container does not need to be constant throughout the container, and is usually in the range of 0.2 to 1.0 mm.
- the gas barrier performance can be exhibited if at least the core layer made of the mixed resin (B) is present in the body of the hollow container.
- the gas barrier performance is better when the core layer is extended.
- the weight of the layer made of the mixed resin (B) is preferably 1 to 30% by weight, more preferably 2 to 20% by weight with respect to the total weight of the hollow container. It is. If the weight of the layer made of the mixed resin (B) is less than 1% by weight, the gas barrier property of the hollow container may not be sufficient, which is not preferable. Further, if the weight of the layer made of the mixed resin (B) is more than 30% by weight, it may be difficult to form the precursor multi-layer parison into a hollow container.
- the hollow container by injection blow molding of this embodiment is less likely to delaminate due to dropping or impact. Further, even if the shape includes an uneven portion and a bent portion, delamination does not easily occur. Therefore, the shape of the hollow container is not limited to a shape having few uneven portions and a bent portion, and the degree of freedom in design is increased.
- the hollow container of the present invention is excellent in perfume retention, for example, carbonated drinks, juice, water, milk, sake, whiskey, shochu, coffee, tea, jelly drinks, liquid drinks such as health drinks, seasonings Storage and storage of various items such as liquids, sauces, soy sauce, dressings, seasonings such as liquid soup, liquid foods such as liquid soup, liquid pharmaceuticals, lotions, lotions, hair conditioners, hair dyes, shampoos, etc. It is suitable for.
- the multilayer molded body in the present embodiment is a multilayer sheet
- the method for producing the multilayer sheet is not particularly limited, and conventionally known multilayering techniques such as extrusion molding, coextrusion, lamination, and vapor deposition can be used.
- extrusion molding a single screw or a twin screw can be used as the extruder, and the temperature of the extruder is preferably 200 to 290 ° C. More preferably, it is 210 to 280 ° C.
- the multilayer sheet in this embodiment has at least a core layer made of the above-described mixed resin (B) and a layer made of a resin containing 70% by weight or more of the polyester resin (A) in contact therewith.
- Polyester resin excluding polyester resin (A) and polyester resin (D), acrylic resin, polystyrene resin, polycarbonate resin, methyl methacrylate-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, vinyl chloride resin, and alicyclic You may have the layer which consists of 1 or more types of transparent resin (E) chosen from the group which consists of polyolefin resin.
- Polyester resins other than the polyester resin (A) and the polyester resin (D) are preferably polyethylene naphthalate, isophthalic acid-modified polyethylene terephthalate, 1,4-cyclohexanedimethanol-modified polyethylene terephthalate, and polyarylate.
- the resin layer is formed by extruding a resin containing 70% by weight or more of the thermoplastic polyester resin (A) from the surface layer side extrusion cylinder and at least one of the core side extrusion cylinders. It can be obtained by extruding the mixed resin (B) from the two core-side extrusion cylinders to form at least one core layer in contact with the resin layer made of the resin containing the polyester resin (A).
- thermoplastic polyester resin (A) used for the multilayer sheet is used by blending the end material generated when the multilayer sheet container obtained by molding the multilayer sheet end or the multilayer sheet described later is used. I can do it.
- a resin obtained by blending a polyester resin (A) and an end material of a multilayer sheet is referred to as a polyester resin (A ′).
- the end material generated when manufacturing the said multilayer sheet edge part and a multilayer sheet container can also be blended and used for the said transparent resin (E).
- a resin obtained by blending the transparent resin (E) and the end material of the multilayer sheet is referred to as a transparent resin (E ′).
- Particularly preferred configurations of the multilayer sheet in the present embodiment are polyester resin (A) / mixed resin (B) / polyester resin (A), two types and three layers, polyester resin (A) / mixed resin (B) / polyester.
- the multilayer sheet is a two-layer / three-layer sheet of polyester resin (A) / mixed resin (B) / polyester resin (A), for example, 70 weight of the thermoplastic polyester resin (A) from the surface layer side extrusion cylinder. % Or more of the resin, and the mixed resin (B) can be extruded from the core layer side extrusion cylinder.
- the multilayer sheet is a three-layered three-layer sheet of polyester resin (A) / mixed resin (B) / polyester resin (A ′), for example, two surface layer side extrusion cylinders and a core layer side extrusion cylinder are provided.
- a resin containing 70% by weight or more of the thermoplastic polyester resin (A) is extruded from one surface layer side extrusion cylinder, and the thermoplastic polyester (A ′) is extruded from the other surface layer side extrusion cylinder.
- the mixed resin (B) is extruded from the core layer side extrusion cylinder.
- the multilayer sheet is a sheet of two types and five layers of polyester resin (A) / mixed resin (B) / polyester resin (A) / mixed resin (B) / polyester resin (A), for example, surface layer side extrusion
- a resin containing 70% by weight or more of the thermoplastic polyester resin (A) is extruded from the surface layer side extrusion cylinder and the center layer extrusion cylinder, It can be produced by extruding the mixed resin (B) from the intermediate layer side extrusion cylinder.
- the multilayer sheet is a sheet of a three-kind five-layer structure of polyester resin (A) / polyester resin (A ′) / mixed resin (B) / polyester resin (A ′) / polyester resin (A), for example, a surface layer
- a resin containing 70% by weight or more of the thermoplastic polyester resin (A) is extruded from the surface layer side extrusion cylinder. It can be produced by extruding the thermoplastic polyester resin (A ′) from the extrusion cylinder and extruding the mixed resin (B) from the center layer extrusion cylinder.
- the multilayer sheet is a three-layer five-layer sheet of polyester resin (A) / mixed resin (B) / polyester resin (A ′) / mixed resin (B) / polyester resin (A), for example, the surface layer side
- a resin containing 70% by weight or more of the thermoplastic polyester resin (A) is extruded from the surface layer extrusion cylinder, and the intermediate layer side extrusion It can be produced by extruding the mixed resin (B) from the cylinder and extruding the thermoplastic polyester resin (A ′) from the center layer extrusion cylinder.
- each layer of the multilayer sheet in this embodiment may be appropriately selected depending on the use, but the layer thickness of the mixed resin (B) is preferably 1 to 150 ⁇ m, more preferably 10 to 100 ⁇ m, The thickness is preferably 20 to 80 ⁇ m.
- the thickness of the surface layer containing the polyester resin (A) is preferably 50 to 1000 ⁇ m, more preferably 100 to 800 ⁇ m, and further preferably 200 to 600 ⁇ m.
- the total thickness of the multilayer sheet is preferably 100 to 2000 ⁇ m, more preferably 200 to 1600 ⁇ m, and still more preferably 400 to 1200 ⁇ m.
- the weight of the layer made of the mixed resin (B) is preferably 1 to 30% by weight, more preferably 2 to 20% by weight, based on the total weight of the multilayer sheet. If the weight of the layer made of the mixed resin (B) is less than 1% by weight, the gas barrier property of the multilayer sheet may not be sufficient, which is not preferable. Moreover, when the layer which consists of mixed resin (B) is more than 30 weight%, when forming a container etc. using a multilayer sheet, it may become difficult to shape
- the multilayer molded body in this embodiment is a tray and a container shape is demonstrated below.
- the multilayer sheet is subjected to a sheet surface temperature of 90 to 90 using a compressed air molding machine, a vacuum molding machine, a compressed air vacuum molding machine, or the like.
- a container multilayer sheet container
- the sheet surface temperature is lower than 90 ° C., the sheet is not sufficiently softened, so that molding becomes difficult.
- drawdown will become intense and it cannot shape
- the thickness of the multilayer sheet container in this embodiment is preferably 5 to 2000 ⁇ m, more preferably 20 to 1800 ⁇ m, and further preferably 30 to 1500 ⁇ m.
- the haze value of the multilayer sheet container in this embodiment is preferably 15% or less.
- the weight of the layer made of the mixed resin (B) is preferably 1 to 30% by weight, more preferably 2 to 20% by weight, based on the total weight of the multilayer sheet container. If the weight of the layer made of the mixed resin (B) is less than 1% by weight, the gas barrier property of the multilayer sheet container may not be sufficient, which is not preferable. Further, if the weight of the layer made of the mixed resin (B) is more than 30% by weight, it may be difficult to form the precursor multilayer sheet into a multilayer sheet container, which is not preferable.
- a polyethylene terephthalate product recovered product a modified polyethylene terephthalate product recovered containing a small amount of isophthalic acid component units, a polyamide product recovered product, and / or a molded product are within the range not impairing the effects of the present invention.
- the contents filled in the multilayer sheet container in the present embodiment are not particularly limited, and examples thereof include food, cosmetics, pharmaceuticals, toiletries, mechanical / electrical / electronic parts, oil, and resins.
- the multilayer molded article of this embodiment can be suitably used particularly as a container for storing food. .
- the multilayer sheet container in this embodiment is less likely to delaminate due to dropping or impact. Further, even when the shape includes an uneven portion and a bent portion, delamination does not easily occur. Therefore, the shape of the multilayer molded body is not limited to a shape having few uneven portions and a bent portion, and the degree of freedom in design is increased.
- the multilayer molded article of the present invention includes, for example, gel foods such as tofu, egg tofu, jelly, pudding, water gourd, mousse, yogurt, apricot tofu; jam, miso, pickles, and spices Spices; processed meat products such as salami, ham, sausage, yakitori, meatballs, hamburger, grilled pork, beef jerky; Processed rice products such as cheese, butter, cream and condensed milk; processed egg products such as boiled eggs and hot spring eggs; cooked vegetables, boiled beans, fried foods, steamed foods, fried foods, boiled foods, grilled foods, etc. Pickles; noodles and pasta such as udon, soba and spaghetti; suitable for storage and storage of various items such as pickled fruit syrup.
- gel foods such as tofu, egg tofu, jelly, pudding, water gourd, mousse, yogurt, apricot tofu
- jam, miso, pickles, and spices Spices processed meat products such as salami, ham, sausage, yakitori,
- Thickness of hollow container After the hollow container was cut out and delaminated, the thickness at a position of 75 mm from the bottom surface of the hollow container was measured using a micrometer. In addition, three places (0 °, 120 °, 240 °) in the circumferential direction were measured, and the thickness was calculated by the arithmetic average of the measured values.
- Thickness of multilayer sheet After the multilayer sheet was delaminated, the thicknesses of the surface layer and the core layer were measured using a micrometer. The thickness of the surface layer was calculated as the average of both sides of the surface layer. The number of measurements was 3 for each layer, and the thickness was calculated by the arithmetic average.
- Thickness of multilayer sheet container The multilayer sheet container was cut out, the total thickness of the container bottom face and the container bottom face was measured using a micrometer, and after delamination, the thickness of the core layer was measured.
- Oxygen transmission rate and oxygen transmission coefficient of multilayer molded body Measurement was performed according to ASTM D3985 in an atmosphere of a temperature of 23 ° C, a relative humidity of 100% inside the multilayer molded body, and an external relative humidity of 50%. The measurement used OX-TRAN 10 / 50A made by Modern Controls.
- Methyl 2,6-naphthalenedicarboxylate, dimethyl terephthalate, ethylene glycol, and 3,9-bis (1,1-dimethyl-2-hydroxyethethyl) -2,4,8,10-tetraoxaspiro [5.5 Undecane (SPG)) was charged, and transesterification was carried out by raising the temperature to 215 ° C. in a nitrogen atmosphere in the presence of 0.03 mol of manganese acetate tetrahydrate per 100 mol of the dicarboxylic acid component.
- polyester resin (D) [Other resins] In Examples 1 to 9 and Comparative Examples 1 to 4, the following resins were used as resins other than the polyester resin (D). Table 3 shows the composition and physical properties of the resin.
- Polyester resin (A) Polyethylene terephthalate (Nihon Unipet BK2180)
- the hollow containers used in Examples 1 to 5 and Comparative Examples 1 and 2 were produced by the following method.
- Three-layer parison shape total length 95 mm, outer diameter 22 mm, wall thickness 4.2 mm.
- an injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. (model: SE-130DU-CI, 2 pcs) was used.
- Example 1 A three-layer hollow container was formed using the following materials.
- Outer surface layer and inner surface layer Polyester resin (A) Core layer Mixed resin (B): Resin obtained by dry blending polyamide resin (C) and polyester resin (D1) at (C) / (D1) 80/20 (weight ratio) Table 4 shows the evaluation results.
- a multilayer sheet having a three-layer structure was formed, and a cup-shaped multilayer sheet container was further formed.
- Table 6 shows the evaluation results of the obtained multilayer sheet
- Table 7 shows the evaluation results of the multilayer sheet container.
- a multilayer sheet having a three-layer structure was formed, and a cup-shaped multilayer sheet container was further formed.
- Table 6 shows the evaluation results of the obtained multilayer sheet
- Table 7 shows the evaluation results of the multilayer sheet container.
- a multilayer sheet having a three-layer structure was formed, and a cup-shaped multilayer sheet container was further formed.
- Table 6 shows the evaluation results of the obtained multilayer sheet
- Table 7 shows the evaluation results of the multilayer sheet container.
- a multilayer sheet having a three-layer structure was formed, and a cup-shaped multilayer sheet container was further formed.
- Table 6 shows the evaluation results of the obtained multilayer sheet
- Table 7 shows the evaluation results of the multilayer sheet container.
- Example 4 A multilayer sheet having a three-layer structure was formed in the same manner as in Example 6 except that the polyamide resin (C) was used as the resin constituting the core layer, and a cup-shaped multilayer sheet container was further formed.
- Table 6 shows the evaluation results of the obtained multilayer sheet
- Table 7 shows the evaluation results of the multilayer sheet container.
- the multilayer molded article of the present invention is unlikely to peel off due to dropping or impact, and is excellent in transparency and gas barrier properties. Therefore, containers for various articles such as liquid beverages, seasonings, liquid foods, liquid pharmaceuticals, cosmetics, etc. Is preferably used.
- a resin multilayer molded body comprising two or more resin layers, wherein 70% by weight or more of the resin constituting the resin layer forming at least one surface of the multilayer molded body contains 80 mol of terephthalic acid.
- thermoplastic polyester resin (A) obtained by polymerizing a dicarboxylic acid component containing at least 80% and a diol component containing at least 80 mol% ethylene glycol, and the resin layer in contact with the resin layer forming the surface is metaxylylenediamine 1 to 80 mol% of the diol unit comprising a polyamide resin (C) obtained by polymerizing a diamine component containing 70 mol% or more and a dicarboxylic acid component containing 70 mol% or more of adipic acid, a dicarboxylic acid unit and a diol unit.
- a multilayer molded article comprising (B).
- a resin multilayer molded body composed of three or more resin layers, wherein 70% by weight or more of the resin constituting the resin layer forming the surfaces on both sides of the multilayer molded body is the thermoplastic polyester resin (
- the diol unit having the cyclic acetal skeleton of the polyester resin (D) is represented by the general formula (1): (Wherein R 1 and R 2 are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 6 to 10 carbon atoms) Represents a hydrocarbon group selected from the group consisting of aromatic hydrocarbon groups.) Or general formula (2): (Wherein R 1 is as defined above, R 3 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 6 to 10 carbon atoms) Represents a hydrocarbon group selected from the group consisting of aromatic hydrocarbon groups of The multilayer molded article according to ⁇ 1> or ⁇ 2>, which is a diol unit derived from a diol represented by the formula: ⁇ 4> The diol unit having the cyclic acetal skeleton of the polyester resin (
- the diol unit other than the diol unit having a cyclic acetal skeleton of the polyester resin (D) is selected from the group consisting of ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol.
- ⁇ 6> 1 to 100 mol% of the dicarboxylic acid unit of the polyester resin (D) is a unit derived from a dicarboxylic acid having a benzene skeleton, and 0 to 99 mol% is a unit derived from a dicarboxylic acid having a naphthalene skeleton.
- the dicarboxylic acid unit of the polyester resin (D) is terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid.
- a polyamide resin obtained by subjecting the polyamide resin (C) to melt polycondensation with a diamine component containing 70 mol% or more of metaxylylenediamine and a dicarboxylic acid component containing 70 mol% or more of adipic acid is further solidified.
- the mixed resin (B) further contains 0.01 to 0.10% by weight of one or more metal elements selected from the group consisting of transition metals of Group VIII of the periodic table, manganese, copper and zinc
- the multilayer molded article according to any one of ⁇ 1> to ⁇ 8> is a polyamide resin obtained by subjecting the polyamide resin (C) to melt polycondensation with a diamine component containing 70 mol% or more of metaxylylenediamine and a dicarboxylic acid component containing 70 mol% or more of a
- An outer surface layer, an inner surface layer, and at least one layer located between the outer surface layer and the inner surface layer manufactured using an injection molding machine having a surface layer side injection cylinder and a core side injection cylinder A multilayer molded body comprising a core layer, wherein a resin containing 70% by weight or more of a thermoplastic polyester resin (A) is injected from a surface layer side injection cylinder to form an outer surface layer and an inner surface layer, and the core side injection
- thermoplastic polyester resin (A) A resin containing 70% by weight or more of the thermoplastic polyester resin (A) is injected from the surface layer side injection cylinder, and then the mixed resin (B) is injected from the core side injection cylinder to the thermoplastic polyester resin from the surface layer side injection cylinder.
- a hollow container obtained by simultaneously injecting (A) and further blow molding a parison having a three-layer structure formed by injecting a thermoplastic polyester resin (A) from a surface layer side injection cylinder to fill a mold cavity ⁇ 11> is the multilayer molded article.
- thermoplastic polyester resin (A) is injected from the surface layer side injection cylinder, then the mixed resin (B) is injected from the core side injection cylinder, and further from the surface layer side injection cylinder.
- the multilayer molded article according to ⁇ 11> which is a hollow container obtained by blow molding a parison having a five-layer structure formed by injecting a thermoplastic polyester resin (A) to fill a mold cavity.
- thermoplastic polyester resin (A) is 70 from the surface layer side extrusion cylinder and the intermediate layer side extrusion cylinder.
- the multilayer molded article according to ⁇ 15> which has a five-layer structure obtained by extruding a resin containing at least wt% and extruding the mixed resin (B) from a central layer side extrusion cylinder.
- the multilayer molding according to ⁇ 15> to ⁇ 17> which is a multilayer sheet container obtained by rapidly heating and softening the surface of the multilayer sheet to 90 to 250 ° C. and then molding with a mold having a desired shape body.
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- Injection Moulding Of Plastics Or The Like (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
<1> 2層以上の樹脂層を含む樹脂製多層成形体であって、
該多層成形体の少なくとも一つの樹脂層が、メタキシリレンジアミンを70モル%以上含むジアミン成分およびアジピン酸を70モル%以上含むジカルボン酸成分を重合して得たポリアミド樹脂(C)と、ジカルボン酸単位とジオール単位とを含みジオール単位中1~80モル%が環状アセタール骨格を有するジオール単位であるポリエステル樹脂(D)とを、(C)/(D)=99/1~10/90の重量比で含有する混合樹脂(B)により構成され、
該混合樹脂(B)で構成される層に接する少なくとも一つの樹脂層が、テレフタル酸を80モル%以上含むジカルボン酸成分およびエチレングリコールを80モル%以上含むジオール成分を重合して得た熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂で構成されることを特徴とする多層成形体である。
<2> 3層以上の樹脂層を含む樹脂製多層成形体であって、
該多層成形体の両側の表面を形成する樹脂層が、テレフタル酸を80モル%以上含むジカルボン酸成分およびエチレングリコールを80モル%以上含むジオール成分を重合して得た熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂で構成されることを特徴とする上記<1>に記載の多層成形体である。
<3> ポリエステル樹脂(D)の環状アセタール骨格を有するジオール単位が、一般式(1):
または一般式(2):
で表されるジオールに由来するジオール単位である上記<1>または<2>に記載の多層成形体である。
<4> ポリエステル樹脂(D)の環状アセタール骨格を有するジオール単位が、3,9-ビス(1,1-ジメチル-2-ヒドロキシエチル)-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカンに由来するジオール単位、または5-メチロール-5-エチル-2-(1,1-ジメチル-2-ヒドロキシエチル)-1,3-ジオキサンに由来するジオール単位である上記<1>または<2>に記載の多層成形体である。
<5> ポリエステル樹脂(D)の環状アセタール骨格を有するジオール単位以外のジオール単位が、エチレングリコール、ジエチレングリコール、トリメチレングリコール、1,4-ブタンジオールおよび1,4-シクロヘキサンジメタノールからなる群から選ばれる1種以上のジオールに由来するジオール単位である上記<1>~<4>のいずれかに記載の多層成形体である。
<6> ポリエステル樹脂(D)のジカルボン酸単位中の1~100モル%が、ベンゼン骨格を有するジカルボン酸に由来する単位であり、0~99モル%がナフタレン骨格を有するジカルボン酸に由来する単位である上記<1>~<5>のいずれかに記載の多層成形体である。
<7> ポリエステル樹脂(D)のジカルボン酸単位が、テレフタル酸、イソフタル酸、1,4-ナフタレンジカルボン酸、1,5-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸および2,7-ナフタレンジカルボン酸からなる群から選ばれる1種以上のジカルボン酸に由来するジカルボン酸単位である上記<1>~<6>のいずれかに記載の多層成形体である。
<8> ポリアミド樹脂(C)が、メタキシリレンジアミンを70モル%以上含むジアミン成分とアジピン酸を70モル%以上含むジカルボン酸成分とを溶融重縮合して得られたポリアミド樹脂を、更に固相重合することにより得られた固相重合ポリアミド樹脂である上記<1>~<7>のいずれかに記載の多層成形体である。
<9> 混合樹脂(B)が、さらに、元素周期律表第VIII族の遷移金属、マンガン、銅及び亜鉛からなる群より選択された一種以上の金属元素を0.01~0.10重量%含有する上記<1>~<8>のいずれかに記載の多層成形体である。
<10> 多層成形体総重量に対する混合樹脂(B)の重量比が1~30重量%である上記<1>~<9>のいずれかに記載の多層成形体である。
<11> 表面層側射出シリンダーおよびコア側射出シリンダーを有する射出成形機を用いて製造される、外表面層、内表面層および外表面層と内表面層との間に位置する少なくとも1層のコア層を含む多層成形体であって、
表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を射出して外表面層および内表面層を形成し、該コア側射出シリンダーから、混合樹脂(B)を射出して該コア層の少なくとも1層を形成した多層パリソンを、ブロー成形して得られる中空容器である上記<1>~<10>のいずれかに記載の多層成形体である。
<12> 表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を射出し、次にコア側射出シリンダーから混合樹脂(B)を、そして表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を同時に射出し、更に表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を射出して金型キャビティーを満たして形成した3層構造を有するパリソンをブロー成形して得られる中空容器である上記<11>に記載の多層成形体である。
<13> 表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を射出し、次にコア側射出シリンダーから混合樹脂(B)を射出し、更に表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を射出して金型キャビティーを満たして形成した5層構造を有するパリソンをブロー成形して得られる中空容器である上記<11>に記載の多層成形体である。
<14> 前記パリソンの表面を80~120℃に加熱した後にブロー成形して得られる中空容器である上記<11>~<13>のいずれかに記載の多層成形体である。
<15> 少なくとも1つの表面層側押出シリンダーおよび少なくとも1つのコア側押出シリンダーを有する多層シート成形機を用いて製造される、両表面層および両表面層の間に位置する少なくとも1層のコア層を含む多層成形体であって、
該表面層側押出シリンダーから、または該表面層側押出シリンダーと該コア側押出シリンダーのうちの少なくとも1つの押出シリンダーとから、熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を押し出して樹脂層を形成し、少なくとも1つの該コア側押出シリンダーから混合樹脂(B)を押し出して、該熱可塑性ポリエステル樹脂(A)を含む樹脂からなる樹脂層と接するコア層の少なくとも1層を形成して得られる、厚さ100~2000μmの多層シートである上記<1>~<10>のいずれかに記載の多層成形体である。
<16> 表面層側押出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を押し出し、コア側押出シリンダーから混合樹脂(B)を押し出すことにより得られる3層構造を有する多層シートである上記<15>に記載の多層成形体である。
<17> 表面層側押出シリンダーと、中間層側押出シリンダー、及び中心層側押出シリンダーを有する多層シート成形機を用いて、表面層側押出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を押し出し、中間層側押出シリンダーまたは中心層側押出シリンダーから混合樹脂(B)を押し出し、混合樹脂(B)を押し出さなかった中間層側押出シリンダーまたは中心層側押出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を押し出すことにより得られる5層構造を有する多層シートである上記<15>に記載の多層成形体である。
<18> 前記多層シートの表面を90~250℃に急速加熱軟化した後に、所望の形状の金型にて成形して得られる多層シート容器である上記<15>~<17>のいずれかに記載の多層成形体である。
<19> 成形品の曇価が15%以下であることを特徴とする上記<18>に記載の多層成形体である。
ポリアミド樹脂(C)は、メタキシリレンジアミンを70モル%以上含むジアミン成分およびアジピン酸を70モル%以上含むジカルボン酸成分を重合して得られる。ジアミン成分中のメタキシリレンジアミンが70モル%以上であると、優れたガスバリア性が維持できる。ジカルボン酸成分中のアジピン酸が70モル%以上であると、ガスバリア性の低下や結晶性の低下を防止することができる。
また、ポリアミド樹脂(C)は、製造時に分子量調節剤として使用される少量のモノアミン、モノカルボン酸を含んでいても良い。
相対粘度=t/t0 … (イ)
上述の範囲内に末端アミノ基濃度を設定することにより、ポリアミド樹脂(C)の熱履歴増大によるゲル化が抑制され、かつポリエステル樹脂(A)から発生するアセトアルデヒドと末端アミノ基の反応により生じる外観の黄変が抑制される。末端アミノ基濃度を上述の範囲にするための手段としては、ジアミン成分とジカルボン酸成分のモル比をジカルボン酸が若干過剰になるように重合を進める方法や、反応終了後にモノカルボン酸化合物やジカルボン酸無水物等を添加することで末端アミノ基を封止する方法が挙げられるが、これらの方法に限定されることなく様々な方法を用いることができる。
ポリエステル樹脂(D)のジカルボン酸単位中の1~100モル%が、ベンゼン骨格を有するジカルボン酸に由来する単位であり、0~99モル%がナフタレン骨格を有するジカルボン酸に由来する単位であることが好ましい。より好ましくは、ポリエステル樹脂(D)のジカルボン酸単位中の45~100モル%が、ベンゼン骨格を有するジカルボン酸に由来する単位であり、0~55モル%がナフタレン骨格を有するジカルボン酸に由来する単位であり、更に好ましくは、ポリエステル樹脂(D)のジカルボン酸単位中の70~100モル%が、ベンゼン骨格を有するジカルボン酸に由来する単位であり、0~30モル%がナフタレン骨格を有するジカルボン酸に由来する単位である。
Tg1とTg2の温度差が50℃以上の場合、ブロー成形での厚みムラや白化等の外観不良などの問題が生じる恐れがある。
ジエステル化合物は、炭素数8~30の脂肪酸と炭素数2~10のジオールから得られる。脂肪酸の炭素数が8以上、ジオールの炭素数が2以上であると白化防止効果が期待できる。また、脂肪酸の炭素数が30以下、ジオールの炭素数が10以下であると混合樹脂(B)中への均一分散が良好となる。脂肪酸は側鎖や二重結合があってもよいが、直鎖飽和脂肪酸が好ましい。
該多層成形体は、2つの射出シリンダーを有する射出成形機を使用して、ポリエステル樹脂(A)とガスバリア性を有する混合樹脂(B)とを表面層側、コア側それぞれの射出シリンダーから金型ホットランナーを通して金型キャビティー内に射出して得られた多層パリソンを更に2軸延伸ブロー成形することにより得られる。多層パリソンのブロー成形は従来公知の方法で行えばよく、例えば、多層パリソンの表面を80~120℃に加熱した後にブロー成形する方法、多層パリソンの口部を加熱処理により結晶化させ、表面を80~120℃に加熱した後に90~150℃の金型内でブロー成形する方法が採用される。ブロー圧は、通常、0.5~4MPaである。
また、前記の多層シート端部や多層シート容器を製造する際に発生する端材は、前記透明樹脂(E)とブレンドして使用することも出来る。(以下、透明樹脂(E)と多層シートの端材をブレンドした樹脂を透明樹脂(E’)と記載する。)
シート表面温度が90℃を下回る場合、シート軟化が不十分なため、成形が困難となる。また、250℃を超えると、ドローダウンが激しくなり、成形ができない。
以下の実施例及び比較例で測定した特性の測定法を以下に示す。
(1)ポリエチレンテレフタレートの極限粘度
Viscotek社製 相対粘度計Y501により測定した。測定温度は25℃で、フェノール/テトラクロロエタン=6/4(重量比)の混合溶媒を使用した。サンプル/混合液を0.2、0.4、0.6g/dlの濃度で調整し、90℃/40分で溶解させ、比粘度ηspと濃度Cの比ηsp/Cを濃度Cでプロットした際の線形近似をとり、外挿した直線の切片の値をIV値とした。
固有粘度[η]=limC→0(ηsp/C)
(2)ポリアミドMXD6の相対粘度[ηrel]
ポリアミド樹脂1gを精秤し、96%硫酸100mlに20~30℃で撹拌溶解した。完全に溶解した後、速やかにキャノンフェンスケ型粘度計に溶液5ccを取り、25℃の恒温槽中で10分間放冷後、落下速度(t)を測定した。また、96%硫酸そのものの落下速度(t0)も同様に測定した。tおよびt0から次式(イ)により相対粘度を算出した。
相対粘度=t/t0(イ)
(3)樹脂組成
各構成単位の組成を1H-NMR測定にて算出した。測定はBRUKER製BRUKER AVANCE-500IIIを用い、500MHzで測定した。溶媒は、ポリエステル樹脂(A)及びポリアミド樹脂(C)の評価の際は重トリフルオロ酢酸を用い、ポリエステル樹脂(D)の評価の際は重クロロホルムを用いた。
(4)ガラス転移温度
島津製作所製の熱流束示差走査熱量計(型式:DSC-50)により測定した。昇温速度を20℃/minとした。
(5)溶融粘度
東洋精機製 Capirograph 1C(キャピログラフ)を用い、温度:260℃、予熱時間:1min、ノズル径:1mm、ノズル長:10mm、剪断速度:100(1/sec)で測定を行った。
(6)中空容器の厚み
中空容器を切り出し層間剥離させた後、マイクロメーターを使用して中空容器底面から75mmの位置の厚みを測定した。尚、周方向の3か所(0°、120°、240°)を測定し、その測定値の算術平均で厚みを算出した。
(7)多層シートの厚み
多層シートを層間剥離させた後、マイクロメーターを使用して表面層とコア層の厚みを測定した。表面層の厚みは表面層両側の平均で算出した。尚、測定数は各層3個とし、その算術平均で厚みを算出した。
(8)多層シート容器の厚み
多層シート容器を切り出し、マイクロメーターを使用して容器底面と容器底面の全厚を測定し、層間剥離させた後、コア層の厚みを測定した。
(9)全光線透過率、曇価、YI
日本電色工業社製の曇価測定装置(型式:COH-300A)を使用し、JIS-K-7105、ASTM D1003に準じ、測定を行った。
(10)中空容器の層間剥離性(容器の側面打撃試験による剥離評価)
試験方法:多層成形体に水を満たしキャップをした後、24時間静置した多層成形体の側面を、幅20mm、R1mmの突起を有する重さ1kgで回転軸から重心までの距離27cmの振り子式ハンマーを、持ち上げ角度90度から振り下ろして打撃させ、層間剥離の有無を目視で判定し、層間剥離が発生するまでの打撃回数を測定した。
(11)多層シートの層間強度
多層成形体を幅15mmに切り出し、東洋精機製ストログラフを用いて、速度50mm/minでTピール試験を行った。剥離するときの最大点荷重を測定し、これをTピール荷重とし、層間強度を評価した。尚、測定数は各10個とし、その測定値の算術平均で層間強度を算出した。
(12)多層シート容器の層間剥離性(落下試験による剥離評価)
容器内に、水50mlを充填後、ポリエチレンテレフタレートからなるフィルムでヒートシールした。その後、24時間、23℃50%RHの環境で静置後、地上200cmの高さからコンクリート面に水平落下させ、層間剥離の有無を目視で判定し、層間剥離が発生するまでの落下回数を測定した。
(13)多層成形体の酸素透過率、酸素透過係数
温度23℃、多層成形体内部の相対湿度100%、外部の相対湿度50%の雰囲気下にてASTM D3985に準じて測定した。測定は、モダンコントロールズ社製、OX-TRAN 10/50Aを使用した。
充填塔式精留塔、分縮器、全縮器、コールドトラップ、攪拌機、過熱装置、及び窒素導入管を備えた150リットルのポリエステル樹脂製造装置に、表1に記載量のテレフタル酸とエチレングリコールを仕込み、常法にてエステル化反応を行った。得られたエステルに表1に記載量の解重合用エチレングリコールと、二酸化ゲルマニウムを加え、225℃、窒素気流下で解重合を行なった。生成する水を留去しつつ3時間反応を行った後、215℃、13.3kPaでエチレングリコールを留去した。得られたエステルに表1に記載量のテトラ-n-ブチルチタネート、酢酸カリウム、リン酸トリエチル、及び3,9-ビス(1,1-ジメチル-2-ヒドロキシエテチル)-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカン(SPG)を添加し、225℃、13.3kPaで3時間反応を行った。得られたエステルを昇温、減圧し、最終的に270℃、高真空化(300Pa以下)で重縮合反応を行い、所定の溶融粘度となったところで反応を終了しポリエステル樹脂(D1)及び(D2)を得た。得られたポリエステル樹脂(D1)及び(D2)の評価結果を表1に示す。
充填塔式精留塔、分縮器、全縮器、コールドトラップ、撹拌機、加熱装置、及び窒素導入管を備えた150リットルのポリエステル製造装置に、表2に記載量の原料モノマー(即ち、2,6-ナフタレンジカルボン酸メチル、ジメチルテレフタレート、エチレングリコール、及び3,9-ビス(1,1-ジメチル-2-ヒドロキシエテチル)-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカン(SPG))を仕込み、ジカルボン酸成分100モルに対し酢酸マンガン四水和物0.03モルの存在下、窒素雰囲気下で215℃迄昇温してエステル交換反応を行った。メタノールの留出量が理論量に対して80%以上に達した後、表2に記載量の酸化アンチモン(III)と三酸化アンチモン・エチレングリコール溶液とリン酸トリエチルを加え、昇温と減圧を徐々に行い、最終的に280℃、100Pa以下で重合を行った。適度な溶融粘度になった時点で反応を終了し、ポリエステル樹脂(D3)、(D4)及び(D5)を得た。得られたポリエステル樹脂(D3)、(D4)及び(D5)の評価結果を表2に示す。
実施例1~9および比較例1~4では、ポリエステル樹脂(D)以外の樹脂として以下の樹脂を使用した。樹脂の組成及び物性を表3に示す。
・ポリエステル樹脂(A):ポリエチレンテレフタレート(日本ユニペット製 BK2180)
・ポリアミド樹脂(C):ポリアミドMXD6(三菱ガス化学製 MXナイロン S6011)
実施例1~5および比較例1、2に用いた中空容器は下記の方法で製造した。
3層パリソン形状:全長95mm、外径22mm、肉厚4.2mm。なお、3層パリソンの製造には、住友重機械工業(株)製の射出成形機(型式:SE-130DU-CI、2個取り)を使用した。
3層パリソン成形条件
表面層側射出シリンダー温度:285℃
コア層側射出シリンダー温度:275℃
金型内樹脂流路温度:285℃
金型冷却水温度:20℃
パリソン中の混合樹脂(B)の割合:5重量%
中空容器形状:全長223mm、外径65mm、内容積500ml、底部形状はペタロイドタイプ、ポリエステル樹脂(A)層/混合樹脂(B)層/ポリエステル樹脂(A)層の標準厚み0.18mm/0.038mm/0.21mm。なお、2軸延伸ブロー成形はブロー成形機(株式会社フロンティア製、型式:EFB1000ET)を使用した。
2軸延伸ブロー成形条件
プリフォーム加熱温度:105℃
延伸ロッド用圧力:0.7MPa
一次ブロー圧力:1MPa
二次ブロー圧力:2.6MPa
一次ブロー遅延時間:0.3sec
一次ブロー時間:0.3sec
二次ブロー時間:2sec
ブロー排気時間:0.6sec
金型温度:30℃
下記の材料を使用し、3層構成の中空容器を成形した。
外表面層および内表面層
ポリエステル樹脂(A)
コア層
混合樹脂(B):ポリアミド樹脂(C)とポリエステル樹脂(D1)とを(C)/(D1)=80/20(重量比)でドライブレンドした樹脂
評価結果を表4に示す。
混合樹脂(B)としてポリアミド樹脂(C)とポリエステル樹脂(D2)とを(C)/(D2)=80/20(重量比)で混合した樹脂を使用した以外は、実施例1と同様にして3層構成の中空容器を成形した。得られた3層容器の評価結果を表4に示す。
混合樹脂(B)としてポリアミド樹脂(C)とポリエステル樹脂(D3)とを(C)/(D3)=80/20(重量比)で混合した樹脂を使用した以外は、実施例1と同様にして3層構成の中空容器を成形した。得られた3層容器の評価結果を表4に示す。
混合樹脂(B)としてポリアミド樹脂(C)とポリエステル樹脂(D4)とを(C)/(D4)=80/20(重量比)で混合した樹脂を使用した以外は、実施例1と同様にして3層構成の中空容器を成形した。得られた3層容器の評価結果を表5に示す。
混合樹脂(B)としてポリアミド樹脂(C)とポリエステル樹脂(D5)とを(C)/(D5)=80/20(重量比)で混合した樹脂を使用した以外は、実施例1と同様にして3層構成の中空容器を成形した。得られた3層容器の評価結果を表5に示す。
コア層を構成する樹脂としてポリアミド樹脂(C)とポリエステル樹脂(A)とを(C)/(A)=80/20(重量比)で混合した樹脂を使用した以外は、実施例1と同様にして3層構成の中空容器を成形した。得られた3層容器の評価結果を表5に示す。
コア層を構成する樹脂としてポリアミド樹脂(C)を使用した以外は、実施例1と同様にして3層構成の中空容器を成形した。得られた3層容器の評価結果を表5に示す。
<実施例6>
3台の押出機、フィードブロック、Tダイ、冷却ロール、巻き取り機等を備えた多層シート製造装置を用い、1台目の押出機から混合樹脂(B)としてポリアミド樹脂(C)とポリエステル樹脂(D2)とを(C)/(D2)=80/20(重量比)で混合した樹脂を260℃で、2台目と3台目の押出機からスキン層としてポリエステル樹脂(A)を270℃でそれぞれ押し出し、フィードブロックを介して表面層(ポリエステル樹脂(A)、270μm)/ガスバリア層(混合樹脂(B)、60μm)/表面層(ポリエステル樹脂(A)、270μm)の層構成を有する2種3層の多層シートを製造した。
次いで、浅野研究所製のプラグアシストを備えた真空圧空成形機を使用して、シート表面温度が120℃に達した時点で熱成形を行い、開口部70x70mm、深さ26mm、容積100mlのカップ状容器を得た。得られた多層シートの評価結果を表6、カップ状の多層シート容器の評価結果を表7に示す。
混合樹脂(B)としてポリアミド樹脂(C)とポリエステル樹脂(D2)とを(C)/(D2)=60/40(重量比)で混合した樹脂を使用した以外は、実施例6と同様にして3層構成の多層シートを成形し、更にカップ状の多層シート容器を成形した。得られた多層シートの評価結果を表6、多層シート容器の評価結果を表7に示す。
混合樹脂(B)としてポリアミド樹脂(C)とポリエステル樹脂(D2)とを(C)/(D2)=90/10(重量比)で混合した樹脂を使用した以外は、実施例6と同様にして3層構成の多層シートを成形し、更にカップ状の多層シート容器を成形した。得られた多層シートの評価結果を表6、多層シート容器の評価結果を表7に示す。
混合樹脂(B)としてポリアミド樹脂(C)とポリエステル樹脂(D2)とを(C)/(D2)=85/15(重量比)で混合した樹脂を使用した以外は、実施例6と同様にして3層構成の多層シートを成形し、更にカップ状の多層シート容器を成形した。得られた多層シートの評価結果を表6、多層シート容器の評価結果を表7に示す。
混合樹脂(B)としてポリアミド樹脂(C)とポリエステル樹脂(A)とを(C)/(A)=80/20(重量比)で混合した樹脂を使用した以外は、実施例6と同様にして3層構成の多層シートを成形し、更にカップ状の多層シート容器を成形した。得られた多層シートの評価結果を表6、多層シート容器の評価結果を表7に示す。
コア層を構成する樹脂としてポリアミド樹脂(C)を使用した以外は、実施例6と同様にして3層構成の多層シートを成形し、更にカップ状の多層シート容器を成形した。得られた多層シートの評価結果を表6、多層シート容器の評価結果を表7に示す。
・PTA:テレフタル酸
・EG:エチレングリコール
・SPG:3,9-ビス(1,1-ジメチル-2-ヒドロキシエテチル)-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカン
・GeO2:二酸化ゲルマニウム
・TBT:テトラ-n-ブチルチタネート
・AcOK:酢酸カリウム
・TEP:リン酸トリエチル
・NDCM:2,6-ナフタレンジカルボン酸メチル
・DMT:ジメチルテレフタレート
・MnAc2:酢酸マンガン四水和物
・Sb2O3:三酸化アンチモン
・Sb2O3/EG:三酸化アンチモン・エチレングリコール溶液
<1> 2層以上の樹脂層からなる樹脂製多層成形体であって、該多層成形体の少なくとも一方の表面を形成する樹脂層を構成する樹脂の70重量%以上が、テレフタル酸を80モル%以上含むジカルボン酸成分およびエチレングリコールを80モル%以上含むジオール成分を重合して得た熱可塑性ポリエステル樹脂(A)であり、該表面を形成する樹脂層に接する樹脂層が、メタキシリレンジアミンを70モル%以上含むジアミン成分およびアジピン酸を70モル%以上含むジカルボン酸成分を重合して得たポリアミド樹脂(C)とジカルボン酸単位とジオール単位とを含みジオール単位中1~80モル%が環状アセタール骨格を有するジオール単位であるポリエステル樹脂(D)を99.5/0.5~2/98の重量比で含有する混合樹脂(B)により構成されることを特徴とする多層成形体。
<2> 3層以上の樹脂層からなる樹脂製多層成形体であって、該多層成形体の両側の表面を形成する樹脂層を構成する樹脂の70重量%以上が、前記熱可塑性ポリエステル樹脂(A)であり、該表面を形成する樹脂層に接するコア層の少なくとも1層が、前記混合樹脂(B)により構成されることを特徴とする<1>に記載の多層成形体。
<3> ポリエステル樹脂(D)の該環状アセタール骨格を有するジオール単位が、一般式(1):
または一般式(2):
で表されるジオールに由来するジオール単位である<1>または<2>に記載の多層成形体。
<4> ポリエステル樹脂(D)の該環状アセタール骨格を有するジオール単位が、3,9-ビス(1,1-ジメチル-2-ヒドロキシエチル)-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカンに由来するジオール単位、または5-メチロール-5-エチル-2-(1,1-ジメチル-2-ヒドロキシエチル)-1,3-ジオキサンに由来するジオール単位である<1>または<2>に記載の多層成形体。
<5> ポリエステル樹脂(D)の環状アセタール骨格を有するジオール単位以外のジオール単位が、エチレングリコール、ジエチレングリコール、トリメチレングリコール、1,4-ブタンジオールおよび1,4-シクロヘキサンジメタノールからなる群から選ばれる1種以上のジオールに由来するジオール単位である<1>~<4>のいずれかに記載の多層成形体。
<6> ポリエステル樹脂(D)のジカルボン酸単位中の1~100モル%がベンゼン骨格を有するジカルボン酸に由来する単位であり、0~99モル%がナフタレン骨格を有するジカルボン酸に由来する単位である<1>~<5>のいずれかに記載の多層成形体。
<7> ポリエステル樹脂(D)のジカルボン酸単位が、テレフタル酸、イソフタル酸、1,4-ナフタレンジカルボン酸、1,5-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸および2,7-ナフタレンジカルボン酸からなる群から選ばれる1種以上のジカルボン酸に由来するジカルボン酸単位である<1>~<6>のいずれかに記載の多層成形体。
<8> ポリアミド樹脂(C)が、メタキシリレンジアミンを70モル%以上含むジアミン成分とアジピン酸を70モル%以上含むジカルボン酸成分とを溶融重縮合して得られたポリアミド樹脂を、更に固相重合することにより得られた固相重合ポリアミド樹脂である<1>~<7>のいずれかに記載の多層成形体。
<9> 混合樹脂(B)が、さらに、元素周期律表第VIII族の遷移金属、マンガン、銅及び亜鉛からなる群より選択された一種以上の金属元素を0.01~0.10重量%含有する<1>~<8>のいずれかに記載の多層成形体。
<10> 多層成形体総重量に対する混合樹脂(B)の重量比が1~50重量%である<1>~<9>のいずれかに記載の多層成形体。
<11> 表面層側射出シリンダーおよびコア側射出シリンダーを有する射出成形機を用いて製造される、外表面層、内表面層および外表面層と内表面層との間に位置する少なくとも1層のコア層からなる多層成形体であって、表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を射出して外表面層および内表面層を形成し、該コア側射出シリンダーから、混合樹脂(B)を射出して該コア層の少なくとも1層を形成した多層パリソンを、ブロー成形して得られる中空容器である<1>~<10>に記載の多層成形体。
<12> 表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を射出し、次にコア側射出シリンダーから混合樹脂(B)を表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を同時に射出し、更に表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を射出して金型キャビティーを満たして形成した3層構造を有するパリソンをブロー成形して得られる中空容器である<11>に記載の多層成形体。
<13> 表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を射出し、次にコア側射出シリンダーから混合樹脂(B)を射出し、更に表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を射出して金型キャビティーを満たして形成した5層構造を有するパリソンをブロー成形して得られる中空容器である<11>に記載の多層成形体。
<14> 前記パリソンの表面を80~120℃に加熱した後にブロー成形して得られる中空容器である<11>~<13>のいずれかに記載の多層成形体。
<15> 少なくとも1つの表面層側押出シリンダーおよび少なくとも1つのコア側押出シリンダーを有する多層シート成形機を用いて製造される、両表面層および両表面層の間に位置する少なくとも1層のコア層からなる多層成形体であって、少なくとも1つの該表面層側押出シリンダーから、熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を押し出して該表面層を形成し、少なくとも1つの該コア側押出シリンダーから混合樹脂(B)を押し出して、ポリエステル樹脂(A)を含む樹脂からなる表面層と接するコア層の少なくとも1層を形成して得られる、厚さ100~2000μmの多層シートである<1>~<10>のいずれかに記載の多層成形体。
<16> 表面層側押出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を押し出し、コア側押出シリンダーから混合樹脂(B)を押し出すことにより得られる3層構造を有する<15>に記載の多層成形体。
<17> 表面層側押出シリンダーと中間層押出シリンダー、中心層側押出シリンダーを有する多層シート成形機を用いて、表面層側押出シリンダーと中間層側押出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を押し出し、中心層側押出シリンダーから混合樹脂(B)を押し出すことにより得られる5層構造を有する<15>に記載の多層成形体。
<18> 前記多層シートの表面を90~250℃に急速加熱軟化した後に、所望の形状の金型にて成形して得られる多層シート容器である<15>~<17>に記載の多層成形体。
<19> 成形品の曇価が15%以下であることを特徴とする<18>に記載の多層成形体。
Claims (19)
- 2層以上の樹脂層を含む樹脂製多層成形体であって、
該多層成形体の少なくとも一つの樹脂層が、メタキシリレンジアミンを70モル%以上含むジアミン成分およびアジピン酸を70モル%以上含むジカルボン酸成分を重合して得たポリアミド樹脂(C)と、ジカルボン酸単位とジオール単位とを含みジオール単位中1~80モル%が環状アセタール骨格を有するジオール単位であるポリエステル樹脂(D)とを、(C)/(D)=99/1~10/90の重量比で含有する混合樹脂(B)により構成され、
該混合樹脂(B)で構成される層に接する少なくとも一つの樹脂層が、テレフタル酸を80モル%以上含むジカルボン酸成分およびエチレングリコールを80モル%以上含むジオール成分を重合して得た熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂で構成されることを特徴とする多層成形体。 - 3層以上の樹脂層を含む樹脂製多層成形体であって、
該多層成形体の両側の表面を形成する樹脂層が、テレフタル酸を80モル%以上含むジカルボン酸成分およびエチレングリコールを80モル%以上含むジオール成分を重合して得た熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂で構成されることを特徴とする請求項1に記載の多層成形体。 - ポリエステル樹脂(D)の環状アセタール骨格を有するジオール単位が、3,9-ビス(1,1-ジメチル-2-ヒドロキシエチル)-2,4,8,10-テトラオキサスピロ〔5.5〕ウンデカンに由来するジオール単位、または5-メチロール-5-エチル-2-(1,1-ジメチル-2-ヒドロキシエチル)-1,3-ジオキサンに由来するジオール単位である請求項1または2に記載の多層成形体。
- ポリエステル樹脂(D)の環状アセタール骨格を有するジオール単位以外のジオール単位が、エチレングリコール、ジエチレングリコール、トリメチレングリコール、1,4-ブタンジオールおよび1,4-シクロヘキサンジメタノールからなる群から選ばれる1種以上のジオールに由来するジオール単位である請求項1~4のいずれか一項に記載の多層成形体。
- ポリエステル樹脂(D)のジカルボン酸単位中の1~100モル%が、ベンゼン骨格を有するジカルボン酸に由来する単位であり、0~99モル%がナフタレン骨格を有するジカルボン酸に由来する単位である請求項1~5のいずれか一項に記載の多層成形体。
- ポリエステル樹脂(D)のジカルボン酸単位が、テレフタル酸、イソフタル酸、1,4-ナフタレンジカルボン酸、1,5-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸および2,7-ナフタレンジカルボン酸からなる群から選ばれる1種以上のジカルボン酸に由来するジカルボン酸単位である請求項1~6のいずれか一項に記載の多層成形体。
- ポリアミド樹脂(C)が、メタキシリレンジアミンを70モル%以上含むジアミン成分とアジピン酸を70モル%以上含むジカルボン酸成分とを溶融重縮合して得られたポリアミド樹脂を、更に固相重合することにより得られた固相重合ポリアミド樹脂である請求項1~7のいずれか一項に記載の多層成形体。
- 混合樹脂(B)が、さらに、元素周期律表第VIII族の遷移金属、マンガン、銅及び亜鉛からなる群より選択された一種以上の金属元素を0.01~0.10重量%含有する請求項1~8のいずれか一項に記載の多層成形体。
- 多層成形体総重量に対する混合樹脂(B)の重量比が1~30重量%である請求項1~9のいずれか一項に記載の多層成形体。
- 表面層側射出シリンダーおよびコア側射出シリンダーを有する射出成形機を用いて製造される、外表面層、内表面層および外表面層と内表面層との間に位置する少なくとも1層のコア層を含む多層成形体であって、
表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を射出して外表面層および内表面層を形成し、該コア側射出シリンダーから、混合樹脂(B)を射出して該コア層の少なくとも1層を形成した多層パリソンを、ブロー成形して得られる中空容器である請求項1~10のいずれか一項に記載の多層成形体。 - 表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を射出し、次にコア側射出シリンダーから混合樹脂(B)を、そして表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を同時に射出し、更に表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を射出して金型キャビティーを満たして形成した3層構造を有するパリソンをブロー成形して得られる中空容器である請求項11に記載の多層成形体。
- 表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を射出し、次にコア側射出シリンダーから混合樹脂(B)を射出し、更に表面層側射出シリンダーから熱可塑性ポリエステル樹脂(A)を射出して金型キャビティーを満たして形成した5層構造を有するパリソンをブロー成形して得られる中空容器である請求項11に記載の多層成形体。
- 前記パリソンの表面を80~120℃に加熱した後にブロー成形して得られる中空容器である請求項11~13のいずれか一項に記載の多層成形体。
- 少なくとも1つの表面層側押出シリンダーおよび少なくとも1つのコア側押出シリンダーを有する多層シート成形機を用いて製造される、両表面層および両表面層の間に位置する少なくとも1層のコア層を含む多層成形体であって、
該表面層側押出シリンダーから、または該表面層側押出シリンダーと該コア側押出シリンダーのうちの少なくとも1つの押出シリンダーとから、熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を押し出して樹脂層を形成し、少なくとも1つの該コア側押出シリンダーから混合樹脂(B)を押し出して、該熱可塑性ポリエステル樹脂(A)を含む樹脂からなる樹脂層と接するコア層の少なくとも1層を形成して得られる、厚さ100~2000μmの多層シートである請求項1~10のいずれか一項に記載の多層成形体。 - 表面層側押出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を押し出し、コア側押出シリンダーから混合樹脂(B)を押し出すことにより得られる3層構造を有する多層シートである請求項15に記載の多層成形体。
- 表面層側押出シリンダーと、中間層側押出シリンダー、及び中心層側押出シリンダーを有する多層シート成形機を用いて、表面層側押出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を押し出し、中間層側押出シリンダーまたは中心層側押出シリンダーから混合樹脂(B)を押し出し、混合樹脂(B)を押し出さなかった中間層側押出シリンダーまたは中心層側押出シリンダーから熱可塑性ポリエステル樹脂(A)を70重量%以上含む樹脂を押し出すことにより得られる5層構造を有する多層シートである請求項15に記載の多層成形体。
- 前記多層シートの表面を90~250℃に急速加熱軟化した後に、所望の形状の金型にて成形して得られる多層シート容器である請求項15~17のいずれか一項に記載の多層成形体。
- 成形品の曇価が15%以下であることを特徴とする請求項18に記載の多層成形体。
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