CN1914030A - 中空容器及其制造方法 - Google Patents
中空容器及其制造方法 Download PDFInfo
- Publication number
- CN1914030A CN1914030A CN200580003626.7A CN200580003626A CN1914030A CN 1914030 A CN1914030 A CN 1914030A CN 200580003626 A CN200580003626 A CN 200580003626A CN 1914030 A CN1914030 A CN 1914030A
- Authority
- CN
- China
- Prior art keywords
- resin
- polyglycolic acid
- container
- acid resin
- weight
- 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
- 238000000034 method Methods 0.000 title claims description 25
- 230000008569 process Effects 0.000 title description 3
- 229920005989 resin Polymers 0.000 claims abstract description 116
- 239000011347 resin Substances 0.000 claims abstract description 116
- 229920000954 Polyglycolide Polymers 0.000 claims abstract description 91
- 239000004633 polyglycolic acid Substances 0.000 claims abstract description 91
- 239000004645 polyester resin Substances 0.000 claims abstract description 30
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 229920001225 polyester resin Polymers 0.000 claims abstract description 22
- 230000004888 barrier function Effects 0.000 claims description 45
- 239000007789 gas Substances 0.000 claims description 39
- 238000003475 lamination Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 230000009477 glass transition Effects 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 230000005540 biological transmission Effects 0.000 claims description 10
- 229920003232 aliphatic polyester Polymers 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 230000003252 repetitive effect Effects 0.000 claims description 6
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- 230000035699 permeability Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 30
- 238000000071 blow moulding Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 7
- -1 alkyl glycolate ester Chemical class 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical class CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005457 optimization Methods 0.000 description 5
- 230000008602 contraction Effects 0.000 description 4
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 3
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 3
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NPAXBRSUVYCZGM-UHFFFAOYSA-N carbonic acid;propane-1,2-diol Chemical compound OC(O)=O.CC(O)CO NPAXBRSUVYCZGM-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- ULKFLOVGORAZDI-UHFFFAOYSA-N 3,3-dimethyloxetan-2-one Chemical compound CC1(C)COC1=O ULKFLOVGORAZDI-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 description 1
- 229940006015 4-hydroxybutyric acid Drugs 0.000 description 1
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 235000020965 cold beverage Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 235000020400 fruit nectar Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000005340 laminated glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000011496 sports drink Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
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- 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
- B32B1/08—Tubular products
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- 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
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- 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
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/081—Specified dimensions, e.g. values or ranges
- B29C2949/0811—Wall thickness
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- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0861—Other specified values, e.g. values or ranges
- B29C2949/0872—Weight
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- 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
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/22—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at neck portion
-
- 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
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/24—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at flange portion
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- 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
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/26—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at body portion
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- 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
- B29C2949/20—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer
- B29C2949/28—Preforms or parisons whereby a specific part is made of only one component, e.g. only one layer at bottom portion
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- 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
- B29C2949/3008—Preforms or parisons made of several components at neck portion
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- 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
- B29C2949/3012—Preforms or parisons made of several components at flange portion
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/30—Preforms or parisons made of several components
- B29C2949/302—Preforms or parisons made of several components at bottom portion
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- 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
- B29C2949/3024—Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique
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- 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
- B29C2949/3024—Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique
- B29C2949/3026—Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique having two or more components
- B29C2949/3028—Preforms or parisons made of several components characterised by the number of components or by the manufacturing technique having two or more components having three or more components
-
- 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
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- 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
- B29C2949/3034—Preforms or parisons made of several components having components being injected having two or more components being injected
- B29C2949/3036—Preforms or parisons made of several components having components being injected having two or more components being injected having three or more components being injected
-
- 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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0065—Permeability to gases
- B29K2995/0067—Permeability to gases non-permeable
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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
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/244—All polymers belonging to those covered by group B32B27/36
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明的课题在于提供一种多层中空容器,是具有聚乙醇酸树脂与芳香族聚酯树脂等的共层压树脂的层压结构的中空容器,可以最大限度地发挥聚乙醇酸树脂层的阻气性、适合要求更大强度的阻气性的小容量瓶。本发明通过提供下述的多层中空容器而解决了上述课题,即,一种多层中空容器,其具有在含有60重量%以上的下式(1)-(O·CH2·CO)-……(1)所示的重复单元的聚乙醇酸树脂的层的至少一个面上层压芳香族聚酯树脂等的共层压树脂、并且进行共拉伸而成的多层的器壁结构,且满足下式(2),T×w/v≤0.8×10-3(2)这里,T为氧气透过率(ml/容器/天/气压),v是容器的容量(ml),w是聚乙醇酸树脂相对于容器的总重量的重量%。
Description
技术领域
本发明涉及一种通常被称作塑料瓶的树脂制中空容器,特别是阻气性得到改善的树脂制中空容器,及其制造方法。
背景技术
塑料瓶轻、耐冲击性也高,因此被广泛用作代替玻璃瓶的容器。其中,以聚对苯二甲酸乙二酯(以下有时简称为“PET”)为材料的统称的PET瓶,由于透明性、光泽性优良,所以作为碳酸饮料、果实饮料、运动饮料、茶类、咖啡饮料等的瓶而流通。一般使用单层PET瓶,但是由于PET的阻气性差,所以提出了为了延长保存期间、防止内容物的劣化,而配合了阻气性高的树脂层的多层瓶的方案(特开2001-106219号公报)。特别地,近年来瓶有小型化的倾向,瓶相对于内容量的表面积的比例变大,因此对瓶器壁材料的阻气性的要求逐渐提高。作为阻气性树脂,已知乙烯-乙烯酯共聚合皂化物(EVOH)、芳香族聚酰胺(MXD6尼龙)等,EVOH具有在低湿度下阻气性高,但是在高湿度下阻气性低的缺点,MXD6尼龙的阻气性不充分。作为代替它们的阻挡材料,作为脂肪族聚酯的聚乙醇酸(PGA)树脂具有MXD6尼龙的几倍以上的氧气阻挡性(几分之一以下的氧气透过系数),并且如EVOH那样的在高湿度下的阻气性的降低也很少,因此可以期待作为代替现有阻挡树脂的材料。通常来说,PET瓶的成型方法,一般采用下述方法,即,首先,通过注射成型来成型为称作预成型坯的试管状的成型物,加热该预成型坯,在利用棒进行纵向拉伸的同时,向内部吹入压缩空气,赋形为瓶状(吹塑成型),根据需要进行热固定(hot set)的方法,已知通过分2阶段进行吹塑成型的成型方法、热固定条件的最优化,可以改善耐热性、耐压性等。
但是,在以PGA树脂为阻气层的PET类或者聚酯树脂类瓶中,基本没有利用与成型条件的关系来使层压结构最优化、从而改善阻气性的尝试。
发明内容
因此,本发明的主要目的在于,利用与成型条件的关系,将层压结构最优化,来提供以阻气性改善了的PGA树脂为阻气层的多层中空容器。
即,本发明提供一种阻气性多层中空容器,其具有在含有60重量%以上的下式(1)
-(O·CH2·CO)- ……(1)
所示的重复单元的聚乙醇酸树脂的层的至少一个面上、层压含有芳香族聚酯树脂或聚乙醇酸树脂以外的脂肪族聚酯树脂的共层压树脂、并且进行共拉伸而成的多层的器壁结构,且满足下式(2),
T×w/v≤0.8×10-3 (2)
这里,T为氧气透过率(ml/容器/天/气压),v是容器的容量(ml),w是聚乙醇酸树脂相对于容器的总重量的重量%。
上述的规定本发明的多层中空容器的上式(2)的左边的T×w/v,是随着容器容量的减小、对作为阻挡树脂的PGA树脂的要求增大的阻气性的指标,其越小,则表示PGA树脂处于显示越大的阻气性的分子配列状态。
另外,本发明的阻气性多层中空容器的制造方法,其特征在于,对在含有60重量%以上的下式(1)
-(O·CH2·CO)- ……(1)
所示的重复单元的聚乙醇酸树脂的层的至少一个面上、层压玻璃化转变温度为70℃以上的由芳香族聚酯树脂或聚乙醇酸树脂以外的脂肪族聚酯树脂构成的共层压树脂得到的中空层压预成型坯进行加热成型,冷却,再加热后,进行共拉伸。
本发明者们基于上述目的进行了研究,对实现本发明的过程进行若干附加说明。
已知约1.5g/cm3以上的那样的高密度引起的致密的分子配列有利于PGA树脂显示的增大的阻气性。并且,PGA树脂的密度,随着拉伸和结晶化引起的分子配列的致密化而增大,其本身对于阻气性的增大很有效。但是,在为了拉伸PGA树脂与芳香族聚酯树脂等的层压预成型坯而进行的加热中,如果PGA树脂过度结晶化,则PGA分子不能追随拉伸时的分子再排列,发生分子链的破裂,结晶内或界面处的破坏,产生微小的缺欠(空隙),因此最终生成的中空容器(瓶)的PGA树脂的密度下降,PGA树脂层的阻气性当然也下降。本发明者们在层压预成型坯的拉伸之前,为了防止PGA树脂的过早结晶化,通过组合PGA树脂和芳香族聚酯树脂等的共层压树脂、并对再加热条件进行最优化,实现了上述式(2)左边T×w/v的极小化,即,PGA树脂层显示阻气性的极大化,从而实现了本发明。
具体实施方式
下面,依次说明本发明的多层中空容器的优选形态。
(聚乙醇酸树脂)
根据本发明制造的多层中空容器的主要构成层之一,由聚乙醇酸树脂(以下经常称作“PGA树脂”)组成。这里,作为PGA树脂,使用以60重量%以上的比例、具有下式(1)
-(O·CH2·CO)- ……(1)
所示的乙醇酸单元作为重复单元的均聚物或共聚物。上述乙醇酸单元可通过乙醇酸、乙醇酸烷基酯或乙醇酸盐的缩聚而获得,更优选通过乙交酯(GL)的开环聚合来获得,所述乙交酯是由2分子乙醇酸形成的环状酯。
另外,在本发明的多层中空容器中,聚乙醇酸树脂层优选以阻气性树脂层的形式含有。特别是在与芳香族聚酯树脂等形成的树脂层压体中,即使在以小于等于10重量%比例的层的形式含有的情况下,也优选用作有效的阻气性树脂层。为了形成如此优异的阻气性树脂,使用至少含有大于等于80重量%、更优选大于等于85重量%、特别优选大于等于90重量%、最优选大于等于95重量%的聚乙醇酸(PGA)聚合单元的共聚物(PGA共聚物),而为了获得最高的阻气性,应该选择均聚物(PGA均聚物)。
作为用于与乙醇酸一起形成PGA共聚物、且以较小的比例使用的共聚单体,可列举出例如,草酸乙二醇酯(即,1,4-二烷-2,3-二酮),丙交酯类,内酯类(例如β-丙内酯,β-丁内酯,新戊内酯,γ-丁内酯,δ-戊内酯,β-甲基-δ-戊内酯,ε-己内酯等),碳酸酯类(例如碳酸丙二醇酯等),醚类(例如1,3-二烷等),醚酯类(例如二氧环己酮等),酰胺类(ε-己内酰胺等)等环状单体;乳酸,3-羟基丙酸,3-羟基丁酸,4-羟基丁酸,6-羟基己酸等羟基羧酸或其烷基酯;乙二醇、1,4-丁二醇等脂肪族二元醇类与琥珀酸、己二酸等脂肪族二羧酸类或其烷基酯的实质上等摩尔的混合物;或是它们的两种以上的组合。其中,优选选自丙交酯(包括LA;L丙交酯(LLA)、D丙交酯(DLA)、DL丙交酯(DLLA)等的光学异构体)、碳酸丙二醇酯(TMC)和己内酯(CL)的共聚单体。
PGA树脂的通过使用六氟异丙醇溶剂的GPC测定所获得的重均分子量(聚甲基丙烯酸甲酯换算)优选在5万~80万的范围内。如果重均分子量过低,则强度弱,在拉伸等时容易产生皲裂或断裂。如果重均分子量过高,则在进行多层成型时,树脂层厚度变得不均匀,很难获得良好的拉伸成型物,熔融加工时螺杆的剪切力导致发热,在将PGA树脂加工成颗粒时或加工为成型物时,树脂着色被促进,另外,由于熔融不良而产生斑痕(成型物的流痕)等,外观变得不良。更优选重均分子量为15万~30万左右。
PGA树脂,优选使用具有以下为了顺利地实施拉伸而优选的热特性的树脂:Tg(玻璃化转变温度)为30~55℃,更优选为35~50℃;Tc1(升温过程的结晶化温度)为60~135℃,更优选为65~120℃;Tc2(降温过程的结晶化温度)为140~200℃,更优选为145~195℃;Tm(熔点)为150~230℃,更优选为180~225℃。
在聚乙醇酸树脂层中,除了上述PGA树脂之外,还可以配合其他热塑性树脂,在这种情况下,也优选由占构成聚乙醇酸树脂层的树脂的60重量%以上的尽可能高比例的PGA聚合单元构成。
可以根据需要,向PGA树脂中,相对于其100重量份,加入0.003~3重量份,优选加入0.005~1重量份的热稳定剂。
(共层压树脂)
在本发明的多层中空容器中,在PGA树脂层的至少一个面、优选2个面上层压有共层压树脂,所述共层压树脂含有芳香族聚酯树脂或聚乙醇酸树脂以外的脂肪族聚酯树脂。作为聚乙醇酸树脂以外的脂肪族聚酯树脂,使用聚乳酸等的可以与上述乙醇酸共聚合的共聚单体类的均聚物或共聚物。另外,芳香族聚酯树脂是构成聚酯的二元醇和二元羧酸的至少一方、优选二元羧酸为芳香族的聚酯,优选使用乙二醇与对苯二甲酸的酯、即对苯二甲酸乙二酯的聚合物。如果芳香族聚酯树脂等的共层压树脂相对于PGA树脂层的Tc1,具有过高的Tg(玻璃化转变温度),则在为了拉伸而进行再加热时,PGA树脂层的结晶化进展,因此是不优选的。芳香族聚酯树脂等的共层压树脂的Tg优选为70℃以下,更优选为50~60℃。如果要使用Tc1高的PGA树脂,则可以使用对苯二甲酸乙二酯的均聚物(Tg约等于75℃),但是更优选使用由CHDM(环己二醇)、二聚酸等,将乙二醇或对苯二甲酸的一方的一部分置换而得到的共聚合聚酯,也优选使用聚对苯二甲酸丁二酯。芳香族聚酯树脂等的共层压树脂,优选使用由乌氏粘度计测定出的IV(特性粘度)值为0.7~0.8的共层压树脂。
共层压树脂可以是为了循环利用而在这些纯树脂中混合下述树脂而成的再生树脂,所述树脂包括多层中空容器粉碎而得的颗粒状的树脂或它们再次进行颗粒加工而得的树脂等。另外,可以是例如通过用碱水、温水或酸水来洗涤颗粒上的树脂,从颗粒状的树脂中除去聚乙醇酸树脂,然后进行混合而得的物质。在共层压树脂中可以含有聚乙醇酸树脂,但是从多层中空容器的成型加工、透明性的观点出发,其量优选为10重量%以下,更优选为3重量%以下,最优选为1重量%以下。
(制造方法)
本发明的多层中空容器,优选使用下述方法:通过对PGA树脂与芳香族聚酯树脂等的共层压树脂形成的试管状的层压体,即层压预成型坯或有底型坯进行暂时加热成型,并进行冷却来形成,在再加热后,在利用棒进行纵向拉伸的同时,向内部吹入压缩空气,压附在模具上,赋形成瓶状(吹塑成型)的方法。
(层压预成型坯)
层压预成型坯中的聚乙醇酸树脂层的构成比例,以重量基准(基本等同于厚度基准)计,优选的比例为1~10%。如果超过10重量%,则有时在为了拉伸层压预成型坯而进行加热时,结晶化过度进行,为了拉伸而需要很大的应力,并且由于产生空隙,反而使阻气性下降。当小于1重量%时,所获得的多层中空容器的阻气性变差,很难实现所谓获得阻气性良好的多层中空容器的本发明的目的。
预成型坯通过共注射(co-injection)成型法来成型。在共注射成型法中,有逐次成型法和同时成型法,用任一种成型法都可以进行成型,但是在对以阻挡层为中间层的2种3层构成的预成型坯进行成型时,优选使用同时成型法。注射温度优选为250~280℃。这样获得的层压预成型坯通常具有2~10mm左右的厚度。
(层压预成型坯的拉伸前加热(再加热))
在层压预成型坯的拉伸吹塑成型之前,将层压预成型坯再加热至相对于PGA树脂的Tc1,不是过高的温度,优选90℃以下,更优选50~60℃。在红外线加热中,优选使用再加热30~110秒、更优选40~100秒的方法。如果再加热时间过短,则预成型坯的温度变得不均匀,吹塑成型时容易产生厚的斑,分子配列也变得不均匀。相反,如果再加热时间过长,则PGA结晶化,拉伸性受损。
(拉伸吹塑成型)
将进行了再加热的层压预成型坯放置在模具中,吹塑拉伸至纵向为1.5~4.0倍,横向为3.0~9.0倍,优选纵向为2.0~3.5倍,横向为3.5~5.0倍。如果拉伸倍率过低,则分子取向不充分,如果拉伸倍率过高,则分子链容易发生断裂。以面积倍率(纵向的拉伸倍率×横向的拉伸倍率)计,优选为9~12。
(热固定)
优选通过将拉伸吹塑成型的最终工序中形成的中空容器(瓶)在70~160℃,优选110~150℃的温度下保持1~10秒,优选3~7秒来进行热固定,从而改善成型的中空容器的尺寸稳定性。其优选通过在加热至上述温度的模具中保持已成型的中空容器来进行热固定。通过保持在这样的加热模具中来进行的热固定操作,在通常的PET瓶的拉伸吹塑成型中不进行,但是在使用玻璃化转变温度较低的聚酯作为优选的共层压树脂的本发明的中空容器的情况下,为了良好地保持加热销售机等中的50~60℃的高温环境下的尺寸稳定性,热固定起到有效作用。当没有热固定时,在55℃容易产生收缩变形,而通过热固定,可以抑制这样的收缩变形。
(多层中空容器)
通过上述各工序获得的本发明的多层中空容器,显示出以上式(2)左边的参数,即,T×w/v(这里,T为氧气透过率(ml/容器/天/气压),v是容器的容量(ml),w是聚乙醇酸树脂相对于容器的总重量的重量%)为0.8×10-3以下、优选0.5×10-3以下所代表的优异的阻气性,可以用作碳酸饮料水、清凉饮料水、食用油、果汁、酒类的容器,进而用作饮料水、洗涤剂、化妆品的容器,在现有PET瓶被应用的用途中,用作具有更优异的阻气性的中空容器。
本发明的多层中空容器,具有显示特别优异的阻气性的器壁结构,因此特别适合于单位容量的表面积大的内容量700ml以下,特别是300~550ml的小容量瓶。小容量瓶的多层成型一般很容易变得困难,但是为了良好地保持本发明的多层中容器的成型性,构成层压容器的聚乙醇酸树脂层的重量比例(基本等同于厚度比例),优选在1~10重量%的范围内。在本发明的多层中空容器中,即使是这样的比例小的(因此是薄的)聚乙醇酸树脂层,也可以作为良好的阻气层而起作用。
[实施例]
下面,列举实施例和比较例,来对本发明进行具体说明。物性等的测定方法,如下所示。
(1)玻璃化转变温度(Tg)
使用小型压缩成型机,在280℃制作厚度约200μm的片,从该片切下重量约5mg,作为样品。使用差示扫描量热仪(岛津制作所“DSC-60A”),使升温速度为20℃/min,对该样品进行测定,将由起始转变(on-set)温度和结束转变(end set)温度求出的中间点作为玻璃化转变温度。
(2)密度
从预成型坯或瓶的中间层中取出PGA,用密度梯度管,在23℃测定密度。预成型坯的再加热后的密度,在预成型坯通过吹塑成型机的再加热区之后,立即用液氮进行急速冷却,作为样品。
(3)氧气透过率
氧气透过率测定装置(モダンコントロ一ル社制“OX-TRAN 2/20”),在23℃和内部湿度80%RH、外部湿度50%RH的条件下,测定氧气透过率。
(4)再加热温度
在预成型坯刚通过吹塑成型机的再加热区之后,通过红外传感方式来测定预成型坯的温度。
(5)瓶容量
向形成的瓶中填充水,根据水的重量,求出瓶容量。
(6)收缩开始温度
沿高度方向切下瓶主体部分的表面层(外层),作为样品。使用热机械分析装置(セイコ一インスツルメンツ(株)制“EXSTER6000”),测定该样品在升温速度20℃/分钟的升温下的收缩开始温度(℃)。
(实施例1)
作为聚乙醇酸(PGA),使用在温度270℃、剪切速度120sec-1下测定出的熔融粘度为450Pa·s的均聚物。相对于100重量份的该聚乙醇酸,添加0.1重量份的亚磷酸盐类抗氧化剂(旭电化工业株式会社制“PET-8”),进行颗粒化。以该聚乙醇酸为中间层(7重量%)、在内外层中使用IV值为0.74,玻璃化转变温度为44℃的共聚合聚酯(カネボウ合织(株)、WPTS),使中间层和内外层的注射温度为270℃,获得重量为28g的预成型坯。使用Sidel社制的吹塑成型机(“SBO-1”),使成型循环为400BPH、再加热温度为60℃,使用容量为500ml的加热至40℃的瓶模具,对该预成型坯进行吹塑成型,在成型后,保持5秒,进行热固定。
(实施例2)
与实施例1同样操作,使用预成型坯,使模具温度为70℃,除此之外,与实施例1同样进行吹塑成型。
(实施例3)
与实施例1同样操作,使用预成型坯,使模具温度为110℃,除此之外,与实施例1同样进行吹塑成型。
(实施例4)
与实施例1同样操作,使用预成型坯,使模具温度为150℃,除此之外,与实施例1同样进行吹塑成型。
(比较例1)
使用实施例1中使用的加入了抗氧化剂的PGA颗粒,以该聚乙醇酸为中间层(8重量%)、在内外层中使用IV值为0.74,玻璃化转变温度为74℃的聚对苯二甲酸乙二酯,使中间层的注射温度为270℃,内外层的注射温度为280℃,获得重量为28g的预成型坯。使用Sidel社制的吹塑成型机(“SBO-1”),使成型循环为400BPH、再加热温度为93℃,与实施例1同样,在模具温度为40℃,保持时间为5秒的条件下,对该预成型坯进行吹塑成型。
(比较例2)
使用IV值为0.74,玻璃化转变温度为44℃的共聚合聚酯(与实施例1~4中使用的聚酯相同),在注射温度为270℃下,获得重量为28g的单层预成型坯。使用Sidel社制的吹塑成型机(“SBO-1”),使成型循环为400BPH、再加热温度为60℃,使用500ml的瓶模具,对该预成型坯进行成型。
(比较例3)
使用IV值为0.74,玻璃化转变温度为74℃的聚对苯二甲酸乙二酯(与比较例1中使用的聚酯相同),在注射温度为290℃下,获得重量为28g的单层预成型坯。使再加热温度为93℃,除此之外,与实施例1同样,将该预成型坯成型为500ml的瓶。
将对上述实施例和比较例分别求出的预成型坯和瓶物性以及PGA阻气性能系数T×w/v,一并记载在下表1中。
表1
预成型坯 | 瓶 | ||||||
PGA密度(g/cm3) | PGA密度(g/cm3) | 氧气透过率T(cc/瓶/天/气压) | 瓶容量v(ml) | PGA性能系数(T×w/v×104) | 收缩开始温度(℃) | ||
再加热前 | 再加热后 | ||||||
实施例1 | 1.515 | 1.515 | 1.538 | 0.02 | 524 | 3.1 | 55 |
实施例2 | 1.515 | 1.515 | 1.556 | 0.03 | 529 | 4.5 | 60 |
实施例3 | 1.515 | 1.515 | 1.563 | 0.02 | 492 | 3.3 | 72 |
实施例4 | 1.515 | 1.515 | 1.568 | 0.02 | 483 | 3.3 | 91 |
比较例1 | 1.515 | 1.563 | 1.557 | 0.07 | 533 | 10.5 | - |
比较例2 | - | - | - | 0.50 | 530 | - | - |
比较例3 | - | - | - | 0.29 | 531 | - | - |
由表1所示的结果可以清楚地看出,为了防止层压预成型坯的拉伸之前的PGA树脂的过早结晶化,对PGA树脂与芳香族聚酯树脂的组合以及再加热条件进行最优化而获得的本发明的实施例1~4(PGA比例w=7重量%)的瓶,不必说与不含有PGA树脂的单层PET瓶即比较例2和3的瓶相比较,与更大PGA比例(w=8重量%)的比较例1的瓶相比较,也显示30~40%的很低的氧气透过率(v)。另外,其PGA阻气性系数T×w/v与比较例1相比较,是显著小的,由此可以证明其改善了的氧气阻挡性。
工业可利用性
如上所述,根据本发明,可以提供了一种多层中空容器,其是具有PGA树脂与芳香族聚酯树脂等的共层压树脂的层压结构的中空容器,其最大限度地发挥了PGA树脂层的阻气性、适合要求更大强度的阻气性的小容量瓶。
Claims (14)
1.一种阻气性多层中空容器,具有在含有60重量%以上的下式(1)
-(O·CH2·CO)- ……(1)
所示的重复单元的聚乙醇酸树脂层的至少一个面上、层压含有芳香族聚酯树脂或聚乙醇酸树脂以外的脂肪族聚酯树脂的共层压树脂、并且进行共拉伸而成的多层的器壁结构,且满足下式(2),
T×w/v≤0.8×10-3 (2)
其中,T为氧气透过率(ml/容器/天/气压),v是容器的容量(ml),w是聚乙醇酸树脂相对于容器的总重量的重量%。
2.如权利要求1所述的多层中空容器,共层压树脂的玻璃化转变温度为70℃以下。
3.一种阻气性多层中空容器,具有在含有60重量%以上的下式(1)
-(O·CH2·CO)- ……(1)
所示的重复单元的聚乙醇酸树脂的层的至少一个面上、层压含有芳香族聚酯树脂或聚乙醇酸树脂以外的脂肪族聚酯树脂的共层压树脂、并且进行共拉伸而成的多层的器壁结构,且满足下式(2),
T×w/v≤0.8×10-3 (2)
其中,T为氧气透过率(ml/容器/天/气压),v是700ml以下的容器的容量(ml),w为聚乙醇酸树脂相对于容器的总重量的比例、在1~10重量%的范围内。
4.如权利要求1~3的任一项所述的多层中空容器,由聚乙醇酸树脂与芳香族聚酯树脂的层压体构成。
5.如权利要求1~3的任一项所述的多层中空容器,在聚乙醇酸树脂层的两侧层压有芳香族聚酯树脂或聚乙醇酸树脂以外的脂肪族聚酯树脂的任一方或两方的树脂的层,并进行了共拉伸。
6.如权利要求5所述的多层中空容器,在聚乙醇酸树脂层的两侧层压有芳香族聚酯树脂的层。
7.如权利要求4~6的任一项所述的多层中空容器,共层压树脂是再生树脂。
8.如权利要求7所述的多层中空容器,再生树脂中的聚乙醇酸树脂的量为10重量%以下。
9.如权利要求1~8的任一项所述的多层中空容器,其中聚乙醇酸树脂,作为其热性质,具有Tg(玻璃化转变温度)=30~55℃,Tc1(升温过程的结晶化温度)=60~135℃,Tc2(降温过程的结晶化温度)=140~200℃,Tm(熔点)=150~230℃。
10.一种阻气性多层中空容器的制造方法,对在含有60重量%以上的下式(1)
-(O·CH3·CO)- ……(1)
所示的重复单元的聚乙醇酸树脂的层的至少一个面上、层压由芳香族聚酯树脂或聚乙醇酸树脂以外的脂肪族聚酯树脂构成的玻璃化转变温度为70℃以下的共层压树脂得到的中空层压预成型坯进行加热成型,冷却,再加热后,进行共拉伸。
11.如权利要求10所述的制造方法,中空层压预成型坯通过共注射法来成型。
12.如权利要求10或11所述的制造方法,将冷却后的层压预成型坯用红外线加热器加热30~110秒,再加热至90℃以下的温度。
13.如权利要求10~12的任一项所述的制造方法,将再加热后的层压预成型坯放置在模具中,吹塑共拉伸至纵向为1.5~4.0倍、横向为3.0~9.0倍。
14.如权利要求10~13的任一项所述的制造方法,进一步具备将共拉伸后的容器在70~160℃的加热模具中保持1~10秒来进行热固定的工序。
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