CN101360601A - 多层瓶 - Google Patents
多层瓶 Download PDFInfo
- Publication number
- CN101360601A CN101360601A CNA2007800018060A CN200780001806A CN101360601A CN 101360601 A CN101360601 A CN 101360601A CN A2007800018060 A CNA2007800018060 A CN A2007800018060A CN 200780001806 A CN200780001806 A CN 200780001806A CN 101360601 A CN101360601 A CN 101360601A
- Authority
- CN
- China
- Prior art keywords
- polyamide
- weight
- barrier layer
- multilayer bottle
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002647 polyamide Polymers 0.000 claims abstract description 158
- 239000004952 Polyamide Substances 0.000 claims abstract description 157
- 230000004888 barrier function Effects 0.000 claims abstract description 117
- 229920000728 polyester Polymers 0.000 claims abstract description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 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 26
- 150000002009 diols Chemical class 0.000 claims abstract description 6
- -1 m-xylene diamines Chemical class 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 16
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 150000004665 fatty acids Chemical class 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000002216 antistatic agent Substances 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- 239000004416 thermosoftening plastic Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- NAYYNDKKHOIIOD-UHFFFAOYSA-N phthalamide Chemical compound NC(=O)C1=CC=CC=C1C(N)=O NAYYNDKKHOIIOD-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 abstract description 18
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 abstract description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 10
- 150000004985 diamines Chemical class 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 229920006230 thermoplastic polyester resin Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 123
- 238000000034 method Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 21
- 238000001746 injection moulding Methods 0.000 description 21
- 238000010521 absorption reaction Methods 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 238000002156 mixing Methods 0.000 description 15
- 229920005989 resin Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 238000000071 blow moulding Methods 0.000 description 13
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 10
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 8
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 238000007493 shaping process Methods 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 229920002292 Nylon 6 Polymers 0.000 description 5
- 229920002302 Nylon 6,6 Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 241001122767 Theaceae Species 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 235000021357 Behenic acid Nutrition 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 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
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 235000013405 beer Nutrition 0.000 description 3
- 229940116226 behenic acid Drugs 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical class NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 3
- 230000003116 impacting effect Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 3
- 235000003441 saturated fatty acids Nutrition 0.000 description 3
- 150000004671 saturated fatty acids Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- PWLXTFFHCFWCGG-UHFFFAOYSA-N Heneicosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCC(O)=O PWLXTFFHCFWCGG-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- OETHQSJEHLVLGH-UHFFFAOYSA-N metformin hydrochloride Chemical compound Cl.CN(C)C(=N)N=C(N)N OETHQSJEHLVLGH-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
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- 230000003068 static effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
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- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
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- JCUZDQXWVYNXHD-UHFFFAOYSA-N 2,2,4-trimethylhexane-1,6-diamine Chemical compound NCCC(C)CC(C)(C)CN JCUZDQXWVYNXHD-UHFFFAOYSA-N 0.000 description 1
- HJUJJQFGSUPBPQ-UHFFFAOYSA-N 2-(azepane-1-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC=C1C(=O)N1CCCCCC1 HJUJJQFGSUPBPQ-UHFFFAOYSA-N 0.000 description 1
- JINGUCXQUOKWKH-UHFFFAOYSA-N 2-aminodecanoic acid Chemical compound CCCCCCCCC(N)C(O)=O JINGUCXQUOKWKH-UHFFFAOYSA-N 0.000 description 1
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
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- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 239000002537 cosmetic Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
- Packages (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
本发明的多层瓶包括最外层和最内层、以及位于该最外层和最内层之间的至少一层阻隔层,其中,该最外层和最内层主要由聚酯(A)形成,该聚酯(A)为由含有80摩尔%以上的对苯二甲酸的二羧酸成分和含有80摩尔%以上的乙二醇的二醇成分聚合而成的热塑性聚酯树脂;而且,该阻隔层含有聚酰胺(B)和聚酰胺(C),所述聚酰胺(B)由含有70摩尔%以上的间苯二甲胺的二胺成分和含有70摩尔%以上的碳原子数为4-20的α,ω-直链脂肪族二羧酸的二羧酸成分缩聚而成,所述聚酰胺(C)在23℃、50%RH、1atm下测定的饱和水分率比聚酰胺(B)高,且相对于阻隔层的重量,所述聚酰胺(C)的重量为20重量%以下。该多层瓶由于在落下或冲击时不容易发生层间剥离,因此没有必要为了防止层间剥离而形成凹凸部、弯曲部较少的形状,设计自由度大。
Description
技术领域
本发明是关于气体阻隔性良好的多层瓶的防止层间剥离的发明,具体地说是关于如下所述的多层瓶:该多层瓶改进了最内层以及最外层与中间层之间的层间紧密性,防止在多层瓶中填充内容物时、多层瓶的运输时、或者落下时受到冲击的多层瓶的层间剥离,同时所述多层瓶即使不是凹凸部和弯曲部较少的形状,也能避免层间剥离,设计自由度较大。
背景技术
目前,以聚对苯二甲酸乙二酯(PET)等聚酯为主体的塑料容器(瓶等)广泛用于装茶、果汁饮料、碳酸饮料等中。另外,在塑料容器中,小型塑料瓶所占的比例逐年增长。随着瓶子的小型化,内容物的单位体积的表面积的比例增大,所以在瓶子变小时,内容物的保质期变短。另外,近年来,随着将容易受到氧气和光的影响的啤酒装在塑料瓶中进行销售以及塑料瓶装茶的热卖,塑料容器的应用范围变广,对氧气和二氧化碳等的气体阻隔性的要求进一步提高。
作为具有气体阻隔性的瓶子,已开发出对使用热塑性聚酯树脂和气体阻隔性树脂的多层瓶、混合瓶、热塑性聚酯树脂单层瓶实施碳涂层、蒸镀、阻隔性树脂的涂布的阻隔涂层瓶等。
作为多层瓶的一例,将形成最内层以及最外层的PET等热塑性聚酯树脂和聚己二酰间苯二甲胺(聚酰胺MXD6)等热塑性气体阻隔性树脂喷射填满模具腔得到具有三层或五层结构的预塑形坯(型坯),并将该预塑形坯双轴延伸吹塑成形得到瓶子。
并且,已开发出了阻断从容器外进入的氧气的同时具有捕捉容器内氧气的氧气捕捉功能的树脂,该树脂在多层瓶中得到了应用。作为氧气捕捉性瓶,考虑到氧气吸收速度、透明性、强度、成形性等方面,将混合有过渡金属类催化剂的聚酰胺MXD6用作气体阻隔层的多层瓶较为合适。
上述多层瓶由于具有良好的气体阻隔性,可用作啤酒、茶、碳酸饮料等的容器。多层瓶用于这些用途时,可以保持内容物的质量且能延长保质期,但是另一方面在不同树脂之间,例如在最内层以及最外层与中间层之间会发生层间剥离,影响商品价值。
作为解决这些问题的方法,已公开了通过在聚酰胺MXD6中混合尼龙6和尼龙6I/6T来抑制阻隔层的结晶化,形成结晶化速度慢的、或者不结晶化的聚酰胺,从而改善层间剥离的方法(参考专利文献1)。但是,该方法中,在抑制聚酰胺MXD6的结晶化,使结晶速度变慢时,相对聚酰胺MXD6,必须添加相当量的气体阻隔性相对差的尼龙6和尼龙6I/6T。因此,与只使用聚酰胺MXD6的多层瓶相比,气体阻隔性差,存在无法充分改善保质期的问题。此外,为了补充氧气阻隔性的降低而混合过渡金属类催化剂时,存在添加催化剂,使得成本提高的问题。而且,即使添加过渡金属类催化剂也无法改善二氧化碳阻隔性,因此,存在不适合用于啤酒或碳酸饮料等的容器的问题。此外,根据公开的方法,这些聚酰胺在形成瓶之前,必须通过挤出机进行熔融混合,存在制备成本增高的问题。
专利文献1:美国专利申请公开2005/0009976号说明书
发明内容
本发明的目的是为了解决上述问题,提供在落下或冲击时不容易产生剥离,且没有必要为了防止剥离而形成凹凸部、弯曲部较少的形状,设计自由度大、气体阻隔性优良的廉价的多层瓶。
本发明人对多层瓶的耐层间剥离性进行了深入研究,其结果发现,通过使阻隔层为特定的组成,可以使阻隔层变得柔软,改善层间的紧密性,防止落下等时的层间剥离,从而完成本发明。
即,本发明涉及一种多层瓶,该多层瓶包括最外层和最内层、以及位于该最外层和最内层之间的至少一层阻隔层,其中,该最外层和最内层主要由聚酯(A)形成,(I)该聚酯(A)为由含有80摩尔%以上的对苯二甲酸的二羧酸成分和含有80摩尔%以上的乙二醇的二醇成分聚合而成的热塑性聚酯树脂;而且,(II)该阻隔层含有聚酰胺(B)和聚酰胺(C),所述聚酰胺(B)由含有70摩尔%以上的间苯二甲胺的二胺成分和含有70摩尔%以上的碳原子数为4-20的α,ω-直链脂肪族二羧酸的二羧酸成分缩聚而成,所述聚酰胺(C)在23℃、50%RH、1atm下测定的饱和水分率比聚酰胺(B)高,且相对于该阻隔层的重量,所述聚酰胺(C)的重量为20重量%以下。
具体实施方式
形成本发明的多层瓶的最外层、最内层、以及根据情况存在的中间层的热塑性聚酯树脂是将含有80摩尔%以上、优选90摩尔%以上(包括100摩尔%)的对苯二甲酸的二羧酸成分和含有80摩尔%以上、优选90摩尔%以上(包括100摩尔%)的乙二醇的二醇成分进行聚合反应而得到的聚酯树脂(以下简称为“聚酯(A)”)。
聚酯(A)适合使用聚对苯二甲酸乙二酯。这样就可以发挥聚对苯二甲酸乙二酯具有的良好的透明性、机械强度、注塑成形性、延伸吹塑成形性等所有特性。
对苯二甲酸以外的其他二羧酸成分可以使用间苯二甲酸、二苯醚-4,4’-二羧酸、萘-1,4-二羧酸、萘-2,6-二羧酸、己二酸、癸二酸、癸烷-1,10-羧酸、六氢对苯二甲酸。另外,乙二醇以外的其他二醇成分可以使用丙二醇、1,4-丁二醇、季戊二醇、一缩二乙二醇、环己烷二甲醇、2,2-双(4-羟基苯基)丙烷、2,2-双(4-羟基乙氧基苯基)丙烷等。而且,作为聚酯(A)的原料单体,也可以使用对羟基苯甲酸等含氧酸。
聚酯(A)的固有粘度优选为0.55-1.30dl/g,更优选为0.65-1.20dl/g。当固有粘度为0.55dl/g以上时,可以得到透明的非晶体状态的多层预塑形坯,且得到的多层瓶的机械强度也良好。另外,当固有粘度为1.30dl/g以下时,不会影响成形时的流动性,容易实现瓶的成形。
上述最外层或最内层主要由聚酯(A)构成,但是在不影响本发明特征的范围内,可以混合使用其它的热塑性树脂和各种添加剂。此时,优选最外层或最内层的90重量%以上(包括100重量%)为聚酯(A)。上述其它热塑性树脂可以举出聚2,6-萘二羧酸乙二酯等热塑性聚酯树脂、聚烯烃类树脂、聚碳酸酯、聚丙烯腈、聚氯乙烯、聚苯乙烯等。另外,上述添加剂可举出紫外线吸收剂、氧气吸收剂、着色剂、用于促进预塑形坯的加热并使成形时的循环时间变短的红外线吸收剂(再热添加剂)等。
本发明的多层瓶的阻隔层在温度23℃、相对湿度50%RH的条件下的氧气透过系数(OTR)优选满足OTR(平均值)≤0.15cc·mm/(m2·day·atm)。所述OTR更优选满足OTR≤0.12cc·mm/(m2·day·atm),进一步优选满足OTR≤0.10cc·mm/(m2·day·atm),特别优选满足OTR≤0.08cc·mm/(m2·day·atm)。本发明的阻隔层显示为这样的氧气阻隔性,因此,得到的瓶的气体阻隔性优良,可以延长保存的内容物的保质期。
本发明的多层瓶的阻隔层至少含有聚酰胺(B)和聚酰胺(C)。聚酰胺(B)由含有70摩尔%以上(包括100摩尔%)的间苯二甲胺的二胺成分和含有70摩尔%以上(包括100摩尔%)的碳原子数为4-20的α,ω-直链脂肪族二羧酸的二羧酸成分缩聚而成。聚酰胺(C)在23℃、50%RH、1atm下的饱和水分率比聚酰胺(B)高。
通常,聚酰胺具有吸水性,该饱和水分率根据聚酰胺的种类而不同。此外,聚酰胺通过吸水,各种物理性质发生变化,例如变软。聚酰胺(B)吸水后也变软,在作为多层瓶的阻隔层时,该吸水率越高,耐层间剥离性越好。但是,聚酰胺(B)与其它聚酰胺相比,饱和水分率和吸收速度低,因此,作为多层瓶的阻隔层时,无法达到充分的吸水率,耐层间剥离性较差。
另外,为了提高多层瓶中的聚酰胺(B)的吸水量,在瓶成形时使用水分率高的聚酰胺MXD6时,在成形中加入的热量使水分蒸发并起泡,从而无法获得产品。通常在成形时为了抑制起泡,聚酰胺(B)干燥至数百ppm以下来使用。
因此,通过混合饱和水分率比聚酰胺(B)高的聚酰胺(C),使得瓶成形后的阻隔层的吸水率增高,从而改善了柔软性、层间的紧密性,得到良好的耐层间剥离性能。
本发明中,聚酰胺(B)和聚酰胺(C)的饱和水分率通过如下方法在23℃、50%RH、1atm下进行测定。
(1)以面积倍率计,将聚酰胺(B)或聚酰胺(C)的单层薄膜双轴延伸8-13倍(无热固定)。
(2)将得到的延伸薄膜在23℃、50%RH、1atm的条件下保存4周。
(3)根据卡尔-费歇法,在235℃、30分钟的条件下测定保存后的延伸薄膜的水分率,将该测定值作为饱和水分率。
聚酰胺(B)在23℃、50%RH、1atm下的饱和水分率优选为2.5-5重量%,更优选为3-4重量%。聚酰胺(C)在23℃、50%RH、1atm下的饱和水分率优选为3-13重量%,更优选为3.5-11重量%。聚酰胺(C)的饱和水分率比聚酰胺(B)的高,而且,在上述范围内时,可以从聚酰胺(C)向聚酰胺(B)供给水分,聚酰胺(B)变软,对瓶施加冲击时阻隔层相对最外层以及最内层的随动性良好,因此对于耐层间剥离性具有优良的效果。
本发明中使用的聚酰胺(B)具有高阻隔性,此外,与聚酯(A)(优选为聚对苯二甲酸乙二酯)共注塑成形时能发挥优良的性能。
聚酰胺(B)的二胺成分优选含有70摩尔%以上的间苯二甲胺,更优选含有75摩尔%以上,进一步优选含有80摩尔%以上(包括100摩尔%)。二胺成分中的间苯二甲胺的量比70摩尔%少时,聚酰胺(B)的气体阻隔性降低,因此不优选。本发明中,除间苯二甲胺之外可使用的二胺成分可举出,四亚甲基二胺、五亚甲基二胺、2-甲基戊二胺、六亚甲基二胺、七亚甲基二胺、八亚甲基二胺、九亚甲基二胺、十亚甲基二胺、十二亚甲基二胺、2,2,4-三甲基六亚甲基二胺、2,4,4-三甲基六亚甲基二胺等脂肪族二胺;1,3-双(氨甲基)环己烷、1,4-双(氨甲基)环己烷、1,3-二氨基环己烷、1,4-二氨基环己烷、双(4-氨基环己基)甲烷、2,2-双(4-氨基环己基)丙烷、双(氨甲基)萘烷、双(氨甲基)三环癸烷等脂环族二胺;双(4-氨基苯基)醚、对苯二胺、对苯二甲胺、双(氨甲基)萘等具有芳环的二胺类等,但是并不限定在这些。
聚酰胺(B)的二羧酸成分优选含有70摩尔%以上的碳原子数为4-20的α,ω-直链脂肪族二羧酸,更优选含有75摩尔%以上,进一步优选含有80摩尔%以上(包括100摩尔%)。在上述范围时,阻隔性以及成形性优良。本发明中使用的碳原子数为4-20的α,ω-直链脂肪族二羧酸可举出,琥珀酸、戊二酸、庚二酸、辛二酸、壬二酸、己二酸、癸二酸、十一烷二酸、十二烷二酸等脂肪族二羧酸,其中优选为己二酸。
此外,本发明中作为除上述α,ω-直链脂肪族二羧酸之外的二羧酸,也可以添加对苯二甲酸、间苯二甲酸、2,6-萘二羧酸等芳香族二羧酸类。并且,在使用芳香族二羧酸时,其添加量优选为二羧酸成分的0.5-30摩尔%。而且,在聚酰胺的缩聚过程中,也可以添加少量的单胺、单羧酸来作为分子量调节剂。本发明中,优选使用含有100-70摩尔%的碳原子数为4-20的α,ω-直链脂肪族二羧酸、和0-30摩尔%的芳香族二羧酸的二羧酸成分。
聚酰胺(B)可以通过熔融缩聚法制备。例如,由间苯二甲胺和己二酸制成的尼龙盐通过在水存在下在加压状态下加热,一边除去加入的水以及缩合水,一边在熔融状态下进行聚合的方法来制备。另外,也可以通过将间苯二甲胺直接加入到熔融状态的己二酸中,在常压下进行缩聚的方法来制备。此时,为了将反应体系保持在均匀的液体状态,在将间苯二甲胺连续加入到己二酸中时,对反应体系进行加热,使反应温度不低于生成的低聚酰胺以及聚酰胺的熔点地来进行缩聚。
另外,也可以将通过熔融聚合法制得的聚酰胺(B)进行固相聚合。聚酰胺(B)的制备方法没有特别的限定,可以通过以往公知的方法以及聚合条件来制备。
聚酰胺(B)的数均分子量优选为18000-43500,更优选为20000-30000。在该范围内时,多层瓶的成形性良好,得到的多层瓶具有优良的耐层间剥离性。另外,聚酰胺(B)的数均分子量为18000-43500时,聚酰胺(B)的相对粘度大概为2.3-4.2,聚酰胺(B)的数均分子量为20000-30000时,聚酰胺(B)的相对粘度大概为2.44-3.19。这里,所谓的相对粘度是指将1g的聚酰胺溶解在100ml的96%硫酸中,在25℃下利用卡农芬斯克型粘度计等测定得到的值。
作为聚酰胺(C),从饱和水分率高的方面考虑,优选使用脂肪族聚酰胺和/或无定形半芳香族聚酰胺。如上所述,本发明中,关于脂肪族聚酰胺以及无定形半芳香族聚酰胺两者的饱和水分率比聚酰胺(B)的高这一点很重要。
作为脂肪族聚酰胺(聚酰胺(C1))可举出,例如,作为聚(己内酰胺)已知的聚(6-氨基己酸)(PA-6)、聚(六亚甲基己二酰胺)(PA-6,6)、聚(7-氨基庚酸)(PA-7)、聚(10-氨基癸酸)(PA-10)、聚(11-氨基十一烷酸)(PA-11)、聚(六亚甲基癸二酰胺)(PA-6,10)、聚(六亚甲基壬二酰胺)(PA-6,9)、聚(四亚甲基己二酰胺)(PA-4,6)等均聚物、己内酰胺/六亚甲基己二酰胺共聚物(PA-6,6/6)、六亚甲基己二酰胺/己内酰胺共聚物(PA-6/6,6)等脂肪族聚酰胺。其中,优选使用PA-6、PA-6,6。聚酰胺(C1)的数均分子量优选为10000-30000,更优选为12500-25000。
作为无定形半芳香族聚酰胺(聚酰胺(C2)),可以举出聚(六亚甲基间苯二甲酰胺)(PA-6I)、六亚甲基间苯二甲酰胺/六亚甲基对苯二甲酰胺共聚物(PA-6I/6T)、聚(间苯二甲酰间苯二甲胺)(PA-MXDI)、己内酰胺/间苯二甲酰间苯二甲胺共聚物(PA-6/MXDI)、己内酰胺/六亚甲基间苯二甲酰胺共聚物(PA-6/6I)等。其中,特别优选使用PA-6I/6T。聚酰胺(C2)的数均分子量优选为5000-40000,更优选为10000-30000。
聚酰胺(C1)和聚酰胺(C2)各自可以使用一种物质或多种物质。在聚酰胺(B)中只添加聚酰胺(C1)时,根据聚酰胺(C1)的种类和用量,结晶化速度提高,瓶在成形时可能发生不良情况。此外,在聚酰胺(B)中只添加聚酰胺(C2)时,根据聚酰胺(C2)的种类和用量,结晶化速度降低,瓶在成形时可能发生不良情况。因此,作为聚酰胺(C)优选并用聚酰胺(C1)和聚酰胺(C2)。
聚酰胺(C)(聚酰胺(C1)和聚酰胺(C2))的吸水速度优选比聚酰胺(B)的大。本发明中,吸水速度是在23℃、50%RH、1atm下通过以下方法测定。
(1)将预先干燥得到的颗粒在23℃、50%RH、1atm的条件下保存24小时。
(2)根据卡尔-费歇法,在235℃、30分钟的条件下测定保存前后的颗粒的水分率,将吸水后的水分率和吸水前的水分率除以(T)1/2(T为保存时间,为24小时)得到的值作为吸水速度。
另外,除以(T)1/2的目的是由于吸水开始后的吸水速度会逐渐变慢,并时刻在变化,因此通过除以(T)1/2来将该影响平均化。另外,即使除以T,其值也不同,但实际上的意义没有变。
聚酰胺(B)在23℃、50%RH、1atm下的吸水速度优选为100-500ppm/hr1/2,更优选为150-400ppm/hr1/2。
另外,聚酰胺(C)在23℃、50%RH、1atm下的吸水速度优选为250-1500ppm/hr1/2,更优选为300-1300ppm/hr1/2,进一步优选为500-1200ppm/hr1/2。聚酰胺(C)的吸水速度在上述范围内时,在将瓶子吹塑成形后,可以快速地将水分从迅速吸收了水分的聚酰胺(C)供给到聚酰胺(B),聚酰胺(B)变软,向瓶子施加冲击时,阻隔层相对最外层以及最内层的随动性优良,因此,对耐层间剥离性具有优良的效果。
聚酰胺(B)和聚酰胺(C)的混合方法没有特别的限定,在制作瓶的预塑形坯时,可以进行干混,也可以在制作预塑形坯时预先通过单轴挤出机或双轴挤出机等熔融混合,也可以通过熔融混合制作母体胶料来使用,但是,单纯的熔融混合在混合上成本较高,因此,从廉价的方面考虑,优选干混或者通过熔融混合来制作母体胶料。
本发明中,相对于阻隔层的重量,聚酰胺(C)的重量为20重量%以下,优选为1-20重量%,更优选为1.5-15重量%,进一步优选为2-10重量%。在该范围内时,多层瓶的成形性良好,得到的多层瓶的耐层间剥离性优良,阻隔性良好。
所述阻隔层优选主要由聚酰胺(B)形成,从阻隔性能的观点考虑,聚酰胺(B)优选含有阻隔层的70重量%以上,更优选含有阻隔层的80重量%以上,进一步优选含有阻隔层的90重量%以上(各自的上限均为99重量%)。根据在聚酰胺(B)中添加的树脂等的种类,聚酰胺(B)中添加的树脂等在超过阻隔层的30重量%时,所述的OTR超过0.15cc·mm/(m2·day·atm),阻隔性能变差。
脂肪族聚酰胺(聚酰胺(C1))和无定形半芳香族聚酰胺(聚酰胺(C2))并用时,相对于1重量份的聚酰胺(C1),聚酰胺(C2)优选使用0.25-4重量份,更优选使用0.35-2.9重量份,进一步优选使用0.45-2.2重量份。在上述范围内时,瓶容易成形,在实际中阻隔性不会降低,且耐层间剥离性得到改善。
所述阻隔层中,在不影响目的的范围内,可以混合聚酯、烯烃、苯氧树脂等其它树脂中的一种或多种。另外,也可以添加如下添加剂:玻璃纤维、碳纤维等的无机填充剂;玻璃片、滑石粉、高岭土、云母、蒙脱石、有机化粘土等板状无机填充剂;弹性体类等的耐冲击性改良剂;晶核剂;脂肪酰胺类、脂肪酸金属盐类、脂肪酰胺基类化合物等的润滑剂;铜化合物、有机或无机卤素类化合物、受阻酚类、受阻胺类、肼类、硫类化合物、磷类化合物等的抗氧剂;热稳定剂;防止着色剂;苯并三唑类等的紫外线吸收剂;脱模剂;增塑剂;着色剂;阻燃剂;含钴金属的化合物等的捕氧剂;碱金属化合物等的防凝胶剂等的添加剂。
本发明的多层瓶中,根据预塑形坯和瓶的形状而可能产生低延伸倍率(1-2.5倍)的部分。低延伸倍率部分的阻隔层吸水后会白化,而且,添加饱和水分率比聚酰胺(B)高的聚酰胺(C)后,能促进吸水。因此,根据需要,在阻隔层中添加防止白化剂来抑制白化,从而得到透明性良好的多层瓶。
本发明中使用的防止白化剂优选碳原子数为18-50、更优选碳原子数为18-34的脂肪酸金属盐。碳原子数为18以上时,可得到防止白化的效果。另外,碳原子数为50以下时,在阻隔层中的均匀分散性良好。脂肪酸可以具有侧链或双键,优选为硬脂酸(C18)、二十烷酸(C20)、二十二烷酸(C22)、褐煤酸(C28)、三十烷酸(C30)等直链饱和脂肪酸。与脂肪酸形成盐的金属没有特别限制,可举出钠、钾、锂、钙、钡、镁、锶、铝、锌等,特别优选钠、钾、锂、钙、铝、以及锌。
脂肪酸金属盐可以使用一种,也可以使用两种以上。本发明中对脂肪酸金属盐的粒径没有特别限定,粒径越小,越容易在阻隔层中均匀分散,所以粒径优选为0.2mm以下。
脂肪酸金属盐的添加量相对100重量份的阻隔层的合计量,优选为0.005-1.0重量份,更优选为0.05-0.5重量份,进一步优选为0.12-0.5重量份。脂肪酸金属盐的添加量相对100重量份的阻隔层的合计量为0.005重量份以上时,可以得到防止白化的效果。此外,添加量相对100重量份的合计量为1.0重量份以下时,可以保持多层瓶的低雾度。
作为防止白化剂,也可以添加选自下述二酰胺化合物和二酯化合物中的化合物来代替上述脂肪酸金属盐。可以添加一种或两种以上的二酰胺化合物,也可以添加一种或两种以上的二酯化合物,还可以并用一种或两种以上的二酰胺化合物和一种或两种以上的二酯化合物。
二酰胺化合物可以从碳原子数为8-30的脂肪酸和碳原子数为2-10的二胺得到。脂肪酸的碳原子数为8以上且二胺的碳原子数为2以上时,可得到防止白化的效果。另外,脂肪酸的碳原子数为30以下且二胺的碳原子数为10以下时,在阻隔层中的均匀分散性良好。脂肪酸可以具有侧链或双键,优选为直链饱和脂肪酸。
二酰胺化合物的脂肪酸成分可举出,硬脂酸(C18)、二十烷酸(C20)、二十二烷酸(C22)、褐煤酸(C28)、三十烷酸(C30)。二酰胺化合物的二胺成分可举出,乙撑二胺、丁撑二胺、己撑二胺、苯二甲胺、双(氨甲基)环己烷等。将它们组合得到的二酰胺化合物可以在本发明中使用。优选从碳原子数为8-30的脂肪酸和主要由乙撑二胺形成的二胺得到的二酰胺化合物、或者从主要由褐煤酸形成的脂肪酸和碳原子数为2-10的二胺得到的二酰胺化合物。
二酯化合物可以从碳原子数为8-30的脂肪酸和碳原子数为2-10的二醇得到。脂肪酸的碳原子数为8以上且二醇的碳原子数为2以上时,可得到防止白化的效果。另外,脂肪酸的碳原子数为30以下且二醇的碳原子数为10以下时,在阻隔层中的均匀分散性良好。脂肪酸可以具有侧链或双键,优选为直链饱和脂肪酸。
二酯化合物的脂肪酸成分可举出,硬脂酸(C18)、二十烷酸(C20)、二十二烷酸(C22)、褐煤酸(C28)、三十烷酸(C30)等。二酯化合物的二醇成分可举出,乙二醇、丙二醇、丁二醇、己二醇、苯二甲醇、环己烷二甲醇等。将它们组合得到的二酯化合物可以在本发明中使用。特别优选从主要由褐煤酸形成的脂肪酸和主要由乙二醇和/或1,3-丁二醇形成的二醇得到的二酯化合物。
二酰胺化合物和/或二酯化合物的添加量相对100重量份的阻隔层的合计量,优选为0.005-1.0重量份,更优选为0.05-0.5重量份,进一步优选为0.12-0.5重量份。相对100重量份的合计量为0.005重量份以上时,能充分发挥防止白化的效果。此外,相对100重量份的合计量为1.0重量份以下时,可以保持多层瓶的低雾度。
在聚酰胺(阻隔层)中添加防止白化剂的方法可以适当采用以往公知的混合方法。例如,可以在旋转中空容器内投入聚酰胺树脂的颗粒、防止白化剂进行混合来使用。另外,可以采用在制备得到含有高浓度防止白化剂的聚酰胺树脂组合物后,利用不含防止白化剂的聚酰胺树脂颗粒稀释到指定浓度,并将其熔融混合的方法,以及熔融混合后继续通过注塑成形等进行成形的方法等。
使用防止白化剂时,可防止刚制作多层瓶后阻隔层白化的现象。另外,在不白化或白化不会增大的条件下长期保存多层瓶后,也能防止阻隔层白化。也就是说,在不添加防止白化剂也不会白化或白化不会增大的条件、例如温度23℃、湿度50%RH的环境下长期保存后,即使将多层瓶暴露在高湿度下,或使多层瓶与水或沸腾水接触,或者加热到玻璃化温度以上,也能与刚成形时一样抑制白化。
本发明中,可以在由聚酰胺(B)和聚酰胺(C)形成的混合物中添加1-1000ppm的防静电剂。在将聚酰胺(B)和聚酰胺(C)干混时,由于它们的介电常数等不同,根据使用环境产生的静电,聚酰胺(B)和聚酰胺(C)会分离、分级,从而在成形物的不同部位中,配比不均匀,成形的瓶无法得到规定的性能。因此,根据需要通过在阻隔层中添加防静电剂,从而聚酰胺(B)和聚酰胺(C)能够均匀混合,得到性能良好的多层瓶。
本发明中,可以使用非离子表面活性剂、阴离子表面活性剂、阳离子表面活性剂等的公知的防静电剂。作为非离子表面活性剂,可以列举出酯型、醚型、烷基酚型的聚乙二醇系表面活性剂;山梨糖醇酐酯型的多元醇部分酯系表面活性剂;聚氧乙烯山梨糖醇酐酯型的酯醚系表面活性剂等,但是并不限定在这些表面活性剂。本发明中,从聚酰胺(B)和聚酰胺(C)具有相对优良的防静电效果的方面考虑,优选作为聚氧乙烯山梨糖醇酐酯型的酯醚系表面活性剂中的一种的聚氧乙烯山梨糖醇酐单月桂酸酯。
防静电剂可以使用一种,也可以两种以上并用。防静电剂的添加量相对于阻隔层的合计量优选为1-1000ppm,更优选为10-500ppm,进一步优选为20-100ppm。在该范围内时,聚酰胺(B)和聚酰胺(C)可以均匀混合,制备得到质量稳定的瓶。
本发明的多层瓶使用具有两个注塑气缸的注塑成形机,将聚酯(A)以及聚酰胺(B)和聚酰胺(C)的混合物从外壳侧、中心侧各自的注塑气缸,通过热浇道模,在模具腔内注塑,将得到的多层预塑形坯通过双轴延伸吹塑成形来制作。
通常,多层预塑形坯的吹塑成形有所谓的冷型坯法或者热型坯法等以往公知的方法。例如有,将多层预塑形坯的表面加热到80-120℃后,通过插入芯棒等的机械方法在轴向上进行延伸,然后,通常喷吹2-4MPa的高压空气,在横向延伸来吹塑成形的方法;使多层预塑形坯的口部结晶化,将表面加热至80-120℃后,在90-150℃的模具内进行吹塑成形的方法等。
本发明中,预塑形坯的加热温度优选为90-110℃,更优选为95-108℃。预塑形坯的加热温度低于90℃时,加热不充分,阻隔层或聚酯(A)层就会冷延伸,存在白化。当高于110℃时,阻隔层就会结晶化,产生白化,所以不优选。而且,也会降低耐层间剥离性能。
本发明中,从阻隔性、成形性等优良的方面考虑,多层瓶优选具有聚酯(A)层/阻隔层/聚酯(A)层的三层结构,或者聚酯(A)层/阻隔层/聚酯(A)层/阻隔层/聚酯(A)层的五层结构。
三层结构或者五层结构的多层瓶是通过将对应的三层结构或者五层结构的多层预塑形坯通过公知的方法双轴延伸吹塑成形得到的。三层结构或五层结构的多层预塑形坯的制备方法没有特别的限定,可以利用公知的方法。例如,首先从外壳侧注塑气缸注塑用于形成最内层和最外层的聚酯(A),然后从中心侧注塑气缸注塑用于形成阻隔层的树脂、以及同时从外壳侧注塑气缸注塑聚酯(A),然后从外壳侧注塑气缸注塑必要量的聚酯(A),充满模具腔,从而制备得到三层结构(聚酯(A)层/阻隔层/聚酯(A)层)的多层预塑形坯。
此外,首先将聚酯(A)从外壳侧注塑气缸注塑,然后将形成阻隔层的树脂单独从中心侧注塑气缸注塑,最后将聚酯(A)从外壳侧注塑气缸注塑,充满模具腔,从而制备得到五层结构(聚酯(A)层/阻隔层/聚酯(A)层/阻隔层/聚酯(A)层)的多层预塑形坯。
另外,多层预塑形坯的制备方法并不仅限于上述方法。
在多层瓶中,聚酯(A)层的厚度优选为0.01-1.0mm,阻隔层的厚度优选为0.005-0.2mm(5-200μm)。此外,多层瓶的厚度没有必要整体一致,通常在0.2-1.0mm的范围内即可。
在将多层预塑形坯双轴延伸吹塑成形得到的多层瓶中,至少在多层瓶的本体部上存在阻隔层,即可发挥气体阻隔性能,但是,阻隔层延伸到多层瓶的开口部顶端附近,气体阻隔性能更好。
本发明的多层瓶中,阻隔层的重量相对于多层瓶的总重量优选为1-20重量%,更优选为2-15重量%,进一步优选为3-10重量%。阻隔层的重量在上述范围内时,可以得到气体阻隔性良好的多层瓶,同时,使得作为前驱体的多层预塑形坯容易成形为多层瓶。
本发明中,优选将聚酰胺(B)和聚酰胺(C)的干混合物供给到成形机中来制备多层预塑形坯。通过供给干混合物,可以减少熔融混合的费用,能廉价地制备瓶子。此外,在熔融混合中,由于条件的不同会在聚酰胺(B)或聚酰胺(C)中施加过量的热,聚酰胺会劣化,从而在一定条件下难以制备预塑形坯,或者聚酰胺会变成黄色。此外,聚酰胺(B)和聚酰胺(C)在干混时,优选添加防静电剂。
聚酰胺(B)和/或聚酰胺(C)中,为了提高熔融成形时的加工稳定性,或者防止着色,优选添加磷化合物。作为磷化合物,优选使用含碱金属或碱土类金属的磷化合物,例如,可以举出钠、镁、钙等的碱金属或碱土类金属的磷酸盐、次磷酸盐、亚磷酸盐,但是,碱金属或碱土类金属的次磷酸盐由于在防止着色上效果优良,因此特别优选使用。聚酰胺(B)和/或聚酰胺(C)中的磷化合物的浓度以磷原子计,优选为1-500ppm,更优选为350ppm以下,进一步优选为200ppm以下。磷原子浓度即使超过500ppm,防止着色的效果也不会更好,而且得到的薄膜的雾度升高,因此不优选。
本发明的多层瓶难以引起因落下或冲击而产生的层间剥离,不像以往的多层瓶那样,为了改善层间剥离而牺牲阻隔性能。另外,即使具有凹凸部、弯曲部的形状,也难以引起层间剥离,所以多层瓶的形状不必限定在凹凸部、弯曲部少的形状,设计自由度变大。本发明的多层瓶适合用于容纳、保存例如碳酸饮料、果汁、水、牛奶、日本酒、威士忌、烧酒、咖啡、茶、果冻饮料、健康饮料等液体饮料,调味液、酱、酱油、调味剂、液体汤料等调味料,液体汤等液体类食品,液状医药品,化妆水,化妆乳液,定发剂等的化妆料,染发剂,洗发液等的护发品等的各种产品。
实施例
下面通过实施例以及比较例,进一步详细说明本发明,但是本发明并不限定在这些实施例。多层瓶的评价按如下方法进行。
(1)层间剥离高度
根据ASTM D2463-95步骤B(ProcedureB),通过瓶的落下试验,求出层间剥离高度。层间剥离高度越高,表示耐层间剥离性越好。首先,多层容器中装满水并盖紧盖子后,将多层容器落下,目视判断有没有层间剥离。多层容器垂直落下,使得多层容器的底部与地板接触。落下高度以15cm为间隔进行增减,并重复测试。试验瓶数量为30个。
(2)氧气透过率/氧气透过系数
在23℃、瓶内部100%RH、瓶外部50%RH的环境下,根据ASTM D3985测定瓶的氧气透过率。使用モダンコントロ一ルズ公司制OX-TRAN 2/61进行测定。测定值越低,表示氧气阻隔性越好。此外,瓶阻隔层的氧气透过系数(OTR)是小心地将瓶解体后,仅取出阻隔层,在60%RH、23℃的条件下进行测定得到的。测定中使用モダンコントロ一ルズ公司制OX-TRAN2/61。
(3)二氧化碳阻隔性(CO2损耗)
瓶(内容积:500ml)中填充含有4G.V.(气体体积:瓶内容积的4倍(标准状态))的二氧化碳的碳酸水。将其保存在23℃、50%RH的环境下,继续测定瓶内部压力随时间的变化。瓶内部的二氧化碳随时间变化而从瓶壁面透过,因此,压力也随时间变化而降低。将初期的压力设定为100%,将减少到90%时的天数作为保存期来评价瓶的二氧化碳阻隔性。保存期的值越大,表示二氧化碳阻隔性越好。
(4)饱和水分率
在23℃、50%RH、1atm的条件下将聚酰胺的延伸薄膜(面积倍率为10倍)保存4周,使用平沼产业(株)制AQ-2000,根据卡尔-费歇法测定水分率。将测定值作为饱和水分率。测定温度为235℃,测定时间为30分钟。此外,小心地将瓶解体,取出阻隔层,同样地测定阻隔层的饱和水分率。
实施例1
通过下述条件,注塑成形由聚酯(A)层/阻隔层/聚酯(A)层形成的3层预塑形坯(27g),冷却后,加热预塑形坯,进行双轴延伸吹塑成形,得到多层瓶。
聚酯(A)层
聚对苯二甲酸乙二酯(日本ユニペツト制RT543C)
固有粘度:0.75dl/g(使用苯酚/四氯乙烷=6/4(重量比)的混合溶剂,在30℃下测定)。
阻隔层
聚酰胺(B):聚己二酰间苯二甲胺(三菱瓦斯化学株式会社制MX尼龙S6007)95重量%
聚酰胺(C):尼龙6(宇部兴产株式会社制1015B)5重量%
在树脂混合时,添加50ppm的作为防静电剂的聚氧乙烯山梨糖醇酐单月桂酸酯(日本油脂制ノニオンLT-221),在滚筒中干混30分钟。预塑形坯成形时,不会发生由颗粒的分级、静电引起的在漏斗壁面上的颗粒粘附等,可以得到质量稳定的预塑形坯。相对于得到的多层瓶的总重量,阻隔层的重量为5重量%。多层瓶的评价结果如表1所示。
三层预塑形坯的形状
全长为95mm
外径为22mm
厚度为4.2mm
在三层预塑形坯的制备中使用名机制作所(株)制的注塑成形机(型号:M200,使用4个)。
三层预塑形坯的成形条件
外壳侧注塑气缸温度:280℃
中心侧注塑气缸温度:250℃
模具内树脂流路温度:280℃
模具冷却水温度:15℃
预塑形坯中的阻隔层树脂的比例:5重量%
多层瓶的形状
全长为223mm
外径为65mm
内容积为500ml
底部形状:香槟瓶型
本体部凹凸部:没有
双轴延伸吹塑成形使用フロンテイア公司制吹塑成形机(型号:EFB1000ET)。
双轴延伸吹塑成形的条件
预塑形坯加热温度:103℃
延伸杆用压力:0.5MPa
一次吹塑压力:1.0MPa
二次吹塑压力:2.5MPa
一次吹塑延迟时间:0.35秒
一次吹塑时间:0.28秒
二次吹塑时间:2.0秒
吹塑排气时间:0.6秒
模具温度:30℃
实施例2-5、比较例1-3
除了将阻隔层组成变成如表1所示之外,与实施例1相同进行,得到多层瓶。多层瓶的评价结果如表1所示。
另外,表1中记载的聚酰胺的省略符号如下所示。
(1)S6007:聚己二酰间苯二甲胺(三菱瓦斯化学株式会社制MX尼龙S6007,固相聚合品)
数均分子量:23500
相对粘度:2.70(1g树脂/100ml的96%硫酸,测定温度25℃,以下相同)
饱和水分率:3.4重量%
吸水速度:280ppm/hr1/2
(2)S6121:聚己二酰间苯二甲胺(三菱瓦斯化学株式会社制MX尼龙S6121,固相聚合品)
数均分子量:40000
相对粘度:3.94
饱和水分率:3.4重量%
吸水速度:270ppm/hr1/2
(3)1015B:尼龙6(宇部兴产株式会社制,等级:1015B)
数均分子量:15000
饱和水分率:7.1重量%
吸水速度:1090ppm/hr1/2
(4)1020B:尼龙6(宇部兴产株式会社制,等级:1020B)
数均分子量:20000
饱和水分率:7.1重量%
吸水速度:1070ppm/hr1/2
(5)2020B:尼龙66(宇部兴产株式会社制,等级:2020B)
数均分子量:20000
饱和水分率:6.3重量%
吸水速度:1000ppm/hr1/2
(6)X21F07:尼龙6I/6T(三菱エンジニアリングプラスチツクス社制,等级:ノバミツドX21F07)
饱和水分率:11重量%
吸水速度:910ppm/hr1/2
(7)3024:尼龙12(宇部兴产株式会社制,等级:3024NUX)
饱和水分率:1.2重量%
吸水速度:100ppm/hr1/2
如以上的实施例所示,阻隔层满足特定的饱和水分率的、由不同的聚酰胺形成的、本发明的瓶兼具非常优良的耐层间剥离性和良好的气体阻隔性,相对于此,不满足本发明的要点的瓶的耐层间剥离性或者气体阻隔性差。
表1
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | |
聚酰胺(B) | S6007 | S6007 | S6007 | S6007 | S6121 |
阻隔层中的配比(重量%) | 95 | 85 | 90 | 90 | 90 |
聚酰胺(C) | |||||
脂肪族聚酰胺 | 1015B | - | 1015B | 1020B | 2020B |
阻隔层中的配比(重量%) | 5 | - | 6.7 | 5 | 4 |
无定形半芳香族聚酰胺 | - | X21F07 | X21F07 | X21F07 | X21F07 |
阻隔层中的配比(重量%) | - | 15 | 3.3 | 5 | 6 |
层间剥离高度(cm) | 250 | 270 | 319 | 308 | 310 |
阻隔层的OTR[cc·mm/(m2·day·atm)] | 0.06 | 0.08 | 0.07 | 0.07 | 0.06 |
瓶的氧气透过率(cc/bottle·day·0.21atm) | 0.011 | 0.013 | 0.012 | 0.012 | 0.011 |
CO2损耗(天) | 120 | 105 | 115 | 112 | 119 |
阻隔层的饱和水分率(重量%) | 3.6 | 4.5 | 3.8 | 4.0 | 4.0 |
表2
比较例1 | 比较例2 | 比较例3 | |
聚酰胺(B) | S6007 | S6007 | S6007 |
阻隔层中的配比(重量%) | 100 | 50 | 80 |
聚酰胺(C) | |||
脂肪族聚酰胺 | - | 1015B | 3024 |
阻隔层中的配比(重量%) | - | 40 | 20 |
无定形半芳香族聚酰胺 | - | X21F07 | - |
阻隔层中的配比(重量%) | - | 10 | - |
层间剥离高度(cm) | 150 | 302 | 180 |
阻隔层的OTR[cc·mm/(m2·day·atm)] | 0.06 | 0.19 | 0.16 |
瓶的氧气透过率(cc/bottle·day·0.21atm) | 0.011 | 0.02 | 0.019 |
CO2损耗(天) | 120 | 63 | 70 |
阻隔层的饱和水分率(重量%) | 3.4 | 5.6 | 3.0 |
工业实用性
根据本发明,由于难以引起层间剥离,因此提高了容器形状的自由度,而且由于可以廉价地得到气体阻隔性优良的多层瓶,因此,本发明的工业意义重大。
Claims (15)
1、一种多层瓶,该多层瓶包括最外层和最内层、以及位于该最外层和最内层之间的至少一层阻隔层,其中,该最外层和最内层主要由聚酯(A)形成,该聚酯(A)为由含有80摩尔%以上的对苯二甲酸的二羧酸成分和含有80摩尔%以上的乙二醇的二醇成分聚合而成的热塑性聚酯树脂;而且,该阻隔层含有聚酰胺(B)和聚酰胺(C),所述聚酰胺(B)由含有70摩尔%以上的间苯二甲胺的二胺成分和含有70摩尔%以上的碳原子数为4-20的α,ω-直链脂肪族二羧酸的二羧酸成分缩聚而成,所述聚酰胺(C)在23℃、50%RH、1atm下测定的饱和水分率比聚酰胺(B)高,且相对于该阻隔层的重量,所述聚酰胺(C)的重量为20重量%以下。
2、根据权利要求1所述的多层瓶,其中,所述聚酰胺(B)的饱和水分率为2.5-5重量%。
3、根据权利要求1所述的多层瓶,其中,所述聚酰胺(C)的饱和水分率为3-13重量%。
4、根据权利要求1所述的多层瓶,其中,相对于所述阻隔层的重量,所述聚酰胺(C)的含量为1-20重量%。
5、根据权利要求1所述的多层瓶,其中,所述聚酰胺(C)为选自脂肪族聚酰胺和无定形半芳香族聚酰胺中的至少一种的聚酰胺。
6、根据权利要求5所述的多层瓶,其中,所述聚酰胺(C)为脂肪族聚酰胺和无定形半芳香族聚酰胺的组合。
7、根据权利要求5所述的多层瓶,其中,所述脂肪族聚酰胺为聚(6-氨基己酸)和/或聚(六亚甲基己二酰胺);所述无定形半芳香族聚酰胺为六亚甲基间苯二甲酰胺/六亚甲基对苯二甲酰胺共聚物。
8、根据权利要求5所述的多层瓶,其中,相对于1重量份的所述脂肪族聚酰胺,所述无定形半芳香族聚酰胺的含量为0.25-4重量份。
9、根据权利要求1所述的多层瓶,其中,相对于100重量份的所述阻隔层的合计量,所述阻隔层含有0.005-1.0重量份的碳原子数为18-50的脂肪酸金属盐。
10、根据权利要求1所述的多层瓶,其中,所述阻隔层含有1-1000ppm的防静电剂。
11、根据权利要求1所述的多层瓶,其中,所述聚酰胺(B)的数均分子量为18000-43500。
12、根据权利要求1所述的多层瓶,其中,所述多层瓶具有聚酯(A)层/阻隔层/聚酯(A)层的三层结构。
13、根据权利要求1所述的多层瓶,其中,所述多层瓶具有聚酯(A)层/阻隔层/聚酯(A)层/阻隔层/聚酯(A)层的五层结构。
14、根据权利要求1所述的多层瓶,其中,所述阻隔层相对于多层瓶的总重量的重量比为1-20重量%。
15、根据权利要求1所述的多层瓶,其中,所述阻隔层为由聚酰胺(B)和聚酰胺(C)的干混合物形成的层。
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JP2004181628A (ja) * | 2002-11-29 | 2004-07-02 | Mitsubishi Gas Chem Co Inc | 多層チューブ |
CN1550326B (zh) * | 2003-05-06 | 2010-08-25 | 三菱瓦斯化学株式会社 | 多层容器 |
JP4720102B2 (ja) | 2003-05-06 | 2011-07-13 | 三菱瓦斯化学株式会社 | 多層容器 |
JP4561965B2 (ja) * | 2003-05-06 | 2010-10-13 | 三菱瓦斯化学株式会社 | 多層容器 |
JP4206299B2 (ja) * | 2003-05-27 | 2009-01-07 | 大倉工業株式会社 | 熱水処理用包装袋 |
US20050009976A1 (en) * | 2003-07-10 | 2005-01-13 | Honeywell International, Inc. | Delamination-resistant, barrier polyamide compositions for 3-layer pet beverage bottles |
JP4821353B2 (ja) | 2006-02-09 | 2011-11-24 | 三菱瓦斯化学株式会社 | 多層ボトル |
-
2007
- 2007-01-15 KR KR1020087016226A patent/KR101330500B1/ko active IP Right Grant
- 2007-01-15 JP JP2007554880A patent/JP5104318B2/ja not_active Expired - Fee Related
- 2007-01-15 RU RU2008133600/05A patent/RU2415015C2/ru active
- 2007-01-15 UA UAA200810449A patent/UA96437C2/ru unknown
- 2007-01-15 AT AT07706754T patent/ATE525295T1/de not_active IP Right Cessation
- 2007-01-15 US US12/160,469 patent/US8778470B2/en active Active
- 2007-01-15 EP EP07706754A patent/EP1974901B1/en active Active
- 2007-01-15 ES ES07706754T patent/ES2373372T3/es active Active
- 2007-01-15 CN CN2007800018060A patent/CN101360601B/zh not_active Expired - Fee Related
- 2007-01-15 WO PCT/JP2007/050420 patent/WO2007083598A1/ja active Application Filing
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN112041163A (zh) * | 2018-04-24 | 2020-12-04 | 三菱瓦斯化学株式会社 | 多层体和多层容器 |
CN112041163B (zh) * | 2018-04-24 | 2023-04-25 | 三菱瓦斯化学株式会社 | 多层体和多层容器 |
US11872788B2 (en) | 2018-04-24 | 2024-01-16 | Mitsubishi Gas Chemical Company, Inc. | Multilayered article and multilayered container |
US12017433B2 (en) | 2018-04-24 | 2024-06-25 | Mitsubishi Gas Chemical Company, Inc. | Multilayered article and multilayered container |
CN114981081A (zh) * | 2020-02-14 | 2022-08-30 | 三菱瓦斯化学株式会社 | 多层容器、其制造方法和再生聚酯的制造方法 |
CN115243891A (zh) * | 2020-03-06 | 2022-10-25 | 三菱瓦斯化学株式会社 | 多层容器、其制造方法、和再生聚酯的制造方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20080083655A (ko) | 2008-09-18 |
JPWO2007083598A1 (ja) | 2009-06-11 |
RU2008133600A (ru) | 2010-02-27 |
UA96437C2 (ru) | 2011-11-10 |
KR101330500B1 (ko) | 2013-11-15 |
RU2415015C2 (ru) | 2011-03-27 |
US20100233401A1 (en) | 2010-09-16 |
WO2007083598A1 (ja) | 2007-07-26 |
EP1974901A4 (en) | 2009-12-16 |
EP1974901A1 (en) | 2008-10-01 |
ATE525295T1 (de) | 2011-10-15 |
JP5104318B2 (ja) | 2012-12-19 |
EP1974901B1 (en) | 2011-09-21 |
CN101360601B (zh) | 2012-05-09 |
ES2373372T3 (es) | 2012-02-02 |
US8778470B2 (en) | 2014-07-15 |
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