CA1221318A - Multi-layer drawn polyester bottle and process for preparation thereof - Google Patents
Multi-layer drawn polyester bottle and process for preparation thereofInfo
- Publication number
- CA1221318A CA1221318A CA000452999A CA452999A CA1221318A CA 1221318 A CA1221318 A CA 1221318A CA 000452999 A CA000452999 A CA 000452999A CA 452999 A CA452999 A CA 452999A CA 1221318 A CA1221318 A CA 1221318A
- Authority
- CA
- Canada
- Prior art keywords
- layer
- pipe
- bottle
- ethylene
- polyester
- 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.)
- Expired
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000008569 process Effects 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000010410 layer Substances 0.000 claims abstract description 176
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 60
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 239000012790 adhesive layer Substances 0.000 claims abstract description 21
- 230000004888 barrier function Effects 0.000 claims abstract description 21
- 238000000071 blow moulding Methods 0.000 claims abstract description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- 229920001225 polyester resin Polymers 0.000 claims abstract description 14
- 239000004645 polyester resin Substances 0.000 claims abstract description 14
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000004927 fusion Effects 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 238000007664 blowing Methods 0.000 claims abstract description 4
- 238000005520 cutting process Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 45
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 42
- -1 polyethylene terephthalate Polymers 0.000 claims description 25
- 229920001634 Copolyester Polymers 0.000 claims description 17
- 239000002344 surface layer Substances 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 150000002148 esters Chemical group 0.000 claims description 9
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical group C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- 230000035699 permeability Effects 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 241000282320 Panthera leo Species 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 208000037062 Polyps Diseases 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 235000013405 beer Nutrition 0.000 description 3
- 235000019987 cider Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- VTDMBRAUHKUOON-UHFFFAOYSA-N 4-[(4-carboxyphenyl)methyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C=C1 VTDMBRAUHKUOON-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 235000016795 Cola Nutrition 0.000 description 1
- 235000011824 Cola pachycarpa Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 235000017899 Spathodea campanulata Nutrition 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229920001109 fluorescent polymer Polymers 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004890 malting Methods 0.000 description 1
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
- 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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals 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
-
- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- 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
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- 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
- B32B2439/60—Bottles
Landscapes
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Laminated Bodies (AREA)
Abstract
Abstract of the Disclosure Disclosed is a multi-layer drawn polyester bottle comprising a neck portion having an opening on the top end and a fitted or screwed part on the periphery, a bottom portion formed by fusion bonding and closing of a pipe and a barrel portion biaxially molecularly oriented by draw-blowing of the pipe, wherein the pipe is composed of a co-extrudate comprising inner and outer surface base layers of a polyester consisting essentially of ethylene terephthalate units and an intermediate layer of an ethylene-vinyl alcohol copolymer having an ethylene content lower than 50 mole %.
This multi layer drawn polyester bottle is prepared according to a process which comprises forming by co-extrusion a multi-layer pipe by using an ethylene-vinyl alcohol copolymer having an ethylene content lower than 50 mole % as an intermediate layer acting as a gas barrier resin layer and a polyester resin as inner and outer base layer and, if necessary, interposing an adhesive layer between the two resin layers, cutting the pipe into a redetermined length, closing one end of the cut pipe by fusion bonding to form a bottom portion, forming the other end of the cut pipe into a neck portion having an opening on the top end and a fitted or screwed part on the periphery, pre-heating the so-obtained preform at a drawing temperature of 85 to 120°C and subjecting the preform to draw-blow-forming biaxially in the axial direction and circumferential direction in a blow-forming mold.
This multi layer drawn polyester bottle is prepared according to a process which comprises forming by co-extrusion a multi-layer pipe by using an ethylene-vinyl alcohol copolymer having an ethylene content lower than 50 mole % as an intermediate layer acting as a gas barrier resin layer and a polyester resin as inner and outer base layer and, if necessary, interposing an adhesive layer between the two resin layers, cutting the pipe into a redetermined length, closing one end of the cut pipe by fusion bonding to form a bottom portion, forming the other end of the cut pipe into a neck portion having an opening on the top end and a fitted or screwed part on the periphery, pre-heating the so-obtained preform at a drawing temperature of 85 to 120°C and subjecting the preform to draw-blow-forming biaxially in the axial direction and circumferential direction in a blow-forming mold.
Description
SPECIFICATION
MULTI LAYER DRAWN POLYESTER BOTTLE AND PROCESS
OR PREPARATION THEREOF -(1) Field of the Invention:
The present invention relates to a multiolayer drawn polyester bottle and a process for the preparation thereof.
More particularly the present invention relates to a bottle hazing a wall biaxially molecularly oriented by drawing and an improved gas barrier property, which comprises a gas barrier layer of an e~hylene-vinyl alcohol copolymer and a base layer ox a polyester, and a process or to preparation of this bottle
MULTI LAYER DRAWN POLYESTER BOTTLE AND PROCESS
OR PREPARATION THEREOF -(1) Field of the Invention:
The present invention relates to a multiolayer drawn polyester bottle and a process for the preparation thereof.
More particularly the present invention relates to a bottle hazing a wall biaxially molecularly oriented by drawing and an improved gas barrier property, which comprises a gas barrier layer of an e~hylene-vinyl alcohol copolymer and a base layer ox a polyester, and a process or to preparation of this bottle
(2) Description of the Prior Art:
At the present, formation of drawn polyester bottles is very popular, and since drawn polyester bottles have an excellent transparency and an appropriate gas barrier property, they are widely used as vessels for liquid products such as liquid detergents shampoos, cosmetics, soys and sauces and also for carbonated drinks such as beer, cola and cider and refreshing drinks such as fruit juice and mineral water.
However since a drawn polyester bottle is a kind ox a plastic bottle, the drawn polyester bottle has a per mobility to oxygen or carbon dioxide gas though the permeability is very low, while the gas permeability of a completely sealed vessel such as a glass bottle or a metal can is substantially zero. Therefore, the drawn polyester bottle is inferior to a can or glass bottle in the preservability of a filled food, and when the drawn polyester bottle is used for a carbon dioxide gas incorporated drink, loss of carbon dioxide gas is caused
At the present, formation of drawn polyester bottles is very popular, and since drawn polyester bottles have an excellent transparency and an appropriate gas barrier property, they are widely used as vessels for liquid products such as liquid detergents shampoos, cosmetics, soys and sauces and also for carbonated drinks such as beer, cola and cider and refreshing drinks such as fruit juice and mineral water.
However since a drawn polyester bottle is a kind ox a plastic bottle, the drawn polyester bottle has a per mobility to oxygen or carbon dioxide gas though the permeability is very low, while the gas permeability of a completely sealed vessel such as a glass bottle or a metal can is substantially zero. Therefore, the drawn polyester bottle is inferior to a can or glass bottle in the preservability of a filled food, and when the drawn polyester bottle is used for a carbon dioxide gas incorporated drink, loss of carbon dioxide gas is caused
3 8 and in case ox beer cola or cider, the shell life is apparently limited.
As means for improving the gas barrier property of a drawn polyester bottle, there has been proposed a method in which a drawn polyester bottle is coated with a polyvinylidene chloride resin and a coated bottle of thy type has been put into practical use. In order to improve a drawn polyester bottle having inherently an appropriate gas barrier property it is ox no significance to laminate or coat the drawn polyester bottle with a gas - barrier resin which is tenor to the polyester in the gas barrier property. Namely, a resin having a higher gas barrier property than that ox the polyester should be used for lamination or coating. Therefore, use of thermoplastic resins such as a vinylidene chloride rosin, an acrylonitrile resin or a vinyl alcohol resin is expected but an appropriate resin should be selected while taking the properties and process ability ox the resin into con-side ration.
We found that in the preparation of a multi-layer drawn polyester bottle comprising a base layer ox a polyester and a gas barrier layer ox an ethylene-vinyl alcohol copolymer, if ~ormatlon of a pipe by co-extrusion~
cutting ox the pipe) hot formation ox a bottom and biaxial draw-blow formation are combined in this order, a multi-layer drawn polyester bottle excellent in the interlaminar adhesion, gas barrier property and molecular orientation can be obtained. We have now completed the present invention based on this lending More specifically, in accordance with one fund amen tat aspect ox the present invention, there is provided a multi-layer drawn polyester bottle comprising a neck portion having an opening on the top end and a pitted or screwed part on the periphery, a bottom portion formed by fusion bonding and closing of a pipe and a barrel portion biaxially molecularly oriented by draw-blowing ox the pipe, wherein the pipe is composed ox a co extradite comprising inner and outer surface base layers of a polyester consisting essentially of ethylene terephtha-lute units and an intermediate layer ox an ethylene-vinyl alcohol copolymer having an ethylene content lower than 50 mole %.
In accordance with another fundamental aspect ox the present invention, there is provided a process or the preparation of a multi layer polyester bottle which comprises forming by co extrusion a multi-layer pipe by using an ethylene-vinyl alcohol copolymer having an ethylene intent lower than 50 mole % as an intermediate layer acting as a gas barrier resin layer and a polyester resin as inner and outer base layer and, if necessary, interposing an adhesive layer between the two resin layers, cutting the pipe into a predator-mined length, closing one end of the cut pipe by fusion bonding to form a bottom portion, worming the other end ox the cut pipe into a neck portion hazing an opening on the top end and a fitted or screwed part on the periphery preheating the so-obtained preform at a drawing temperature of 85 to 120C and subjecting the preform to draw-blow-~orming biaxially in the axial direction and circumferential direction in a blow forming mold.
Fig. 1 is a sectional view showing a multi-layer pipe used in carrying out the present invention.
Figs. 2 and 3 are sectional views showing a preform in which a bottom portion and a neck portion are formed.
Figs. 4 and 5 are sectional views showing a preform
As means for improving the gas barrier property of a drawn polyester bottle, there has been proposed a method in which a drawn polyester bottle is coated with a polyvinylidene chloride resin and a coated bottle of thy type has been put into practical use. In order to improve a drawn polyester bottle having inherently an appropriate gas barrier property it is ox no significance to laminate or coat the drawn polyester bottle with a gas - barrier resin which is tenor to the polyester in the gas barrier property. Namely, a resin having a higher gas barrier property than that ox the polyester should be used for lamination or coating. Therefore, use of thermoplastic resins such as a vinylidene chloride rosin, an acrylonitrile resin or a vinyl alcohol resin is expected but an appropriate resin should be selected while taking the properties and process ability ox the resin into con-side ration.
We found that in the preparation of a multi-layer drawn polyester bottle comprising a base layer ox a polyester and a gas barrier layer ox an ethylene-vinyl alcohol copolymer, if ~ormatlon of a pipe by co-extrusion~
cutting ox the pipe) hot formation ox a bottom and biaxial draw-blow formation are combined in this order, a multi-layer drawn polyester bottle excellent in the interlaminar adhesion, gas barrier property and molecular orientation can be obtained. We have now completed the present invention based on this lending More specifically, in accordance with one fund amen tat aspect ox the present invention, there is provided a multi-layer drawn polyester bottle comprising a neck portion having an opening on the top end and a pitted or screwed part on the periphery, a bottom portion formed by fusion bonding and closing of a pipe and a barrel portion biaxially molecularly oriented by draw-blowing ox the pipe, wherein the pipe is composed ox a co extradite comprising inner and outer surface base layers of a polyester consisting essentially of ethylene terephtha-lute units and an intermediate layer ox an ethylene-vinyl alcohol copolymer having an ethylene content lower than 50 mole %.
In accordance with another fundamental aspect ox the present invention, there is provided a process or the preparation of a multi layer polyester bottle which comprises forming by co extrusion a multi-layer pipe by using an ethylene-vinyl alcohol copolymer having an ethylene intent lower than 50 mole % as an intermediate layer acting as a gas barrier resin layer and a polyester resin as inner and outer base layer and, if necessary, interposing an adhesive layer between the two resin layers, cutting the pipe into a predator-mined length, closing one end of the cut pipe by fusion bonding to form a bottom portion, worming the other end ox the cut pipe into a neck portion hazing an opening on the top end and a fitted or screwed part on the periphery preheating the so-obtained preform at a drawing temperature of 85 to 120C and subjecting the preform to draw-blow-~orming biaxially in the axial direction and circumferential direction in a blow forming mold.
Fig. 1 is a sectional view showing a multi-layer pipe used in carrying out the present invention.
Figs. 2 and 3 are sectional views showing a preform in which a bottom portion and a neck portion are formed.
Figs. 4 and 5 are sectional views showing a preform
- 4 - %
held in a blow mold before and after blow forming 9 respectively.
Fig. 6 is a view showing a multi layer drawn bottle prepared according to the process ox the present invention As pointed out hereinbe~ore, it is a primmer object of the present invention to improve a gas baffler property of a drawn polyester bottle, and an ethylene vinyl alcohol copolymer, especially an ethylene-vinyl alcohol - copolymer having an ethylene content lower than 50 mole %, is selected and used among vinyl alcohol type resins.
As is known to those skilled in the art, polyvinyl alcohol is not thermoplastic unless it is modified by a special treatment, but in an ethylene-vinyl alcohol copolymer 9 with inquiry ox the ethylene content, the melting point is reduced and the thermoplastic characteristic is increased. Since the ethylene-vinyl alcohol copolymer is drawn together with a polyester resin, as described hereinafter, it is ordinarily considered that an ethylene-vinyl alcohol copolymer hazing a lower melting point and a lower drawable temperature should be selected and used.
However, in the present invention, an ethylene-vinyl alcohol copolymer having a higher malting point and a higher drawable temperature is selected and used.
The first reason is that it the ethylene content exceeds 50 mole %, the melting point and drawable Tom;
portray are lowered and co-drawing with a polyester resin is advantageously carried out, but with increase of the ethylene content 9 the gas barrier property is drastically reduced and lamination of the polyester resin with the ethylene vinyl alcohol copolymer becomes insignificant. The second reason is that since it ~Z~3~3 has been found that if the process of the present invention is adopted even an ethylene vinyl alcohol copolyrner having a high vinyl alcohol content can be drawn in the form of a multi-layer structure with a polyester resin at a temperature suitable for drawing of the polyester resin For these reasons, an ethylene-vinyl alcohol copolymer having an ethylene context lower than 50 mole Jo that is, a high vinyl alcohol content, is selected as the ethylene-vinyl alcohol copolymer to be laminated with the polyester resin.
As means or draw-blow-forming ox plastics such as polyesters, there are known process in which a bottomed prison preform ox a plastic material is formed by injection and the bottomed prison is blow-drawn while drawing it in the axial direction by a drawing rod, and a process in which a plastic material is extruded into a pipe, the pipe is gripped by a pair ox clamps and drawn in the axial direction and a fluid is blown into the pipe to effect blow-drawingl When these processes are applied to a multi layer prison comprising a polyester layer and an ethylene vinyl alcohol copolymer layer, natal defects arise with respect to the drawability and interlaminar adhesion.
In the first place, when the temperature exceeds a certain level for example, 140C, a polyester is readily crystallized and drawing becomes difficult; and the polyester is whitened and the formed vessel becomes opaque. In order to prepare a multi-layer prison by injection; it is necessary to inject a polyester resin and then inject an ethylene-vinyl alcohol copolymer on the preliminarily injection-~orm~d polyester resin.
Since it is necessary to control the temperature ox the preliminarily injection formed polyester to a level much lower than the above mentioned critical temperature heat boning of both the resins in the interface is incomplete and it sometimes happens that interlaminar peeling is caused or the ethylene-vinyl alcohol copolymer layer is broken in the peeled portion.
In the second place, the drawability, especially the biaxial drawabilityjof -the ethylene-vinyl alcohol copolymer is especially poor at a temperature suitable for drawing of a polyester. More speciflcally9 when a co-extruded multi-layer pipe comprising a polyester layer and an ethylene-vinyl alcohol ccpolymer layer is drawn in the axial direction in the state gripped by clamps and is then subjected to blow-drawing, many clefts and latent cracks are readily formed in the axial direction in the ethylene vinyl alcohol copolymer layer.
It is considered that a phenomenon resembling fibrila-lion will be caused in the ethylene-vinyl alcohol copolymer layer by drawing in the axial direction and clefts or cracks will be wormed by subsequent blow--drawing.
The first characteristic feature of the present invention is that a polyester and an ethylene-~inyl alcohol copolymer is co-extruded into a pipe. This co-extrusion is accomplished by joining a molten polyp ester and a molten ethylene-vinyl alcohol copolymer in a die and extruding them through an annular ring.
Since both the resins are contacted with each other in the molten state for a certain time good mingling of both the resins is caused in the interface between the two resins and the degree of heat bonding is much higher than in case of multi-layer injection forming.
This effect is attained quite similarly also in the case where an adhesive resin is interposed between the polyester and the ethylene-vinyl alcohol copolymer.
The second characteristic feature of -the present :~22~
-invention is that the co-extruded multi-layer pipe is cut into a predetermined length and one end is closed by fusion bonding to form a bottom portion. If this bottomed preform is prepared, it is possible to perform blow-drawing of this preform simultaneously or sub-staunchly simultaneously with axial drawing by pressing a drawing rod to the preform which has been preliminarily heated. If this simultaneous drawing is adopted, format lion of clefts or latent cracks, which is often observed 10 in case of sequential drawing, can be prevented.
In the present invention, a copolymer obtained by saponifying a copolymer of ethylene with a vinyl ester such as vinyl acetate is used as the ethylene-vinyl alcohol copolymer. It view of the adaptability to the forming operation and the gas barrier propriety it is preferred that an ethylene-vinyl alcohol copolymer having an ethylene content ox 15 to 50 mole %, espy-Shelley 25 to 45 mole Jo and a saponification degree of at least 96 % be used. The molecular weight ox the copolymer is not particularly critical so far as the copolymer has a film-forming property.
Polyethylene terephthalate or a copolyester consisting essentially of ethylene terephthalate units and containing a small amount of known modifying ester units is used as the polyester for attaining the object of the present invention. The molecular weight of the polyester is not particularly critical if -the polyester has a film forming property.
In order to enhance the adhesion between -the polyp 3 ester layer and the ethylene-vinyl alcohol copolymer layer, a known adhesive may be used though use of the adhesive is not indispensably necessary. A copolyester type adhesive, a polyester-ether type adhesive, an epoxy-modified thermoplastic resin and an acid-modified thermoplastic resin may be used as the adhesive.
Various lamination structures may be adopted for a polyester base layer (PET) 9 an ethylene vinyl alcohol copolymer layer (EVA) and an adhesive layer (AD).
For example, there may be adopted structures ox PET/EVAC/
PET, POETIC + AD/PEI' and PET/AD/EVAC/AD/PET, in which the inner layer is indicated on the right side and the outer layer is indicated on -the left side The thicknesses ox the respective layers may be changed in broad ranges, but it is preferred that the PET/EVAC thickness ratio be in the range ox prom 2/1 to 30/1, especially from 4/1 to 15/1. In the case where the adhesive layer is used, it is preferred that the PET/
AD thickness Roy be in the range of from 5/1 to 100/17 especially from 10/1 to 50/1 Fig. 1 shows a multi-layer pipe especially pro-fireball used in carrying out the prevent invention This multi layer pipe 1 comprises inner and outer layers 2 and 3 ox a polyester, an intermediate gas-barrier layer 4 of an ethylene-vinyl alcohol copolymer and interposed adhesive layers pa and 5b.
As pointed out hereinbe~ore, it is important that this pipe should be prepared by co-extrusion.
In order to prevent crystallization of the polyester I it is important that the extruded pipe should be quenched by water immersion or the like It the extruded multi-layer pipe is thus quenched, the polyester layer in the outer surface of the pipe is easily fixed in the amorphous state where -the density 3 is in the range ox 1.331 to 1.~39 g/cc as measured at 20C. Incidentally, the density referred to in the instant specification means a value measured at 20C by using an n-heptane/carbon tetrachloride liquid mixture density gradient tube. However, the polyester resin located on 9_ I
-the inner wall surface of the pipe apart from the cooled outer wall surface is maintained for a long time at a temperature higher than the temperature of the polyp ester resin of the outer surface layer. Even in the molten state, the ethylene vinyl alcohol copolymer has a thermal conductivity coefficient corresponding to from about 1/2 to about 1/4 of that of the polyester.
By dint of this characteristic, the ethylene-vinyl alcohol copolymer intermediate layer acts as a heat insulation layer in the multi-layer pope being cooled and solidified. Therefore, the inner surface polyester layer is maintained at a high emperor for a long time and crystallization is advanced in the polyester of the inner surface layer, and the density is increased to a level as high as 1,355 g/cc. As the result the polyester of the inner surface layer is whitened t the transparency is lost and drawing of the inner surface layer becomes difficult. In the present invention) the polyester of the inner surface layer is forcibly cooled by passing a cold medium through the interior of the co-extruded pipe so that the density of the final multi-layer preform is controlled to a level equal to or higher by unto 0.015 g/cc than the density of the polyester of the outer surface layer, whereby whitening of the polyester of the inner surface layer is prevented and the drawability of the polyester ox the inner surface layer is improved.
The pipe is cut in a predetermined length, and one end of the cut pipe is heated and used and is pressed by male and female molds having a cavity and projections corresponding to a desired bottom shape, for example, a semi-spherical shape, to form a bottom portion 6 as shown in Fig 2.
Then, the other end of the pipe 1 is heated and subjected to pressing, drawing and blow forming in a desired mold to form a preform 10 having an opening 7 on the top end and a pitted, screwed or anchoring portion for a lid, such as a screw 8 or a neck ring support ring) I on the periphery, as shown in Fig. 3 The order of the steps for preparing the above-mentioned preform is not particularly critical. Namely the steps may be conducted in the above-mentioned order or in the reverse order.
If the above mentioned process is adopted, no super-flus resin portion is formed in preparing a preform prom a multi-layer pipe.
At the subsequent step the preform is heated by hot elf, an infrared ray heater or high frequency induction heating to a temperature suitable for drawing of the multi-layer preform. Namely, the preform is heated to a drawn temperature or the polyester resin ordain-aridly 85 to 120C, preferably 95 to 110C.
Referring to Figs. 4 and 5 illustrating the draw-blow-forming operation, a mandrel 11 it inserted into the opening ox the preform 10 and the opening is gripped by a pair ox split molds aye and 12b. A
vertically movable drawing rod 13 is arranged coccal with the mandrel 11, and fluid blowing annular passage 14 is wormed between the drawing rod 13 and the mandrel 11 .
In the present involution? the top end 15 of the drawing rod 13 is applied to the inner side of the bottom 6 ox the preform 10 and the drawing rod 13 is moved downward whereby the preform 10 is drawn in the axial direction Simultaneously, a fluid is blown into the preform 10 through the passage 14, whereby the preform 10 is expanded and drawn in the circumferential direction by the pressure of the fluid I
According to the present invention, it has been found that by performing drawing in the axial direction and drawing in the circumferential direction simultaneously or substantially simultaneously even a layer of an ethylene-vinyl alcohol copolymer having a high vinyl alcohol content can be drawn at a relatively low temperature.
This finding is quite surprising in view ox the fact that drawing of an ethylene vinyl alcohol copolymer is very difficult and even when a film ox this copolymer is drawn sequentially in the longitudinal direction and in the lateral direction even at a temperature suitable or drawing the film is ruptured during the drawing operation, as pointed out herein before.
Furthermore 9 it it is taken into consideration that in draw-blow-forming ox a multi layer pipe of a polypropylene layer and an ethylene-vinyl alcohol copolymrr layer, the ethylene-vinyl alcohol copolymer in the multi-layer structure can be drawn only at a con-siderably high temperature ox 140 to 165C, it is quite surprising that according to the present invent lion, the ethylene vinyl alcohol copolymer can be biaxially drawn at a drawing temperature for a polyester resin, that is such a low temperature as 85 to 120C, especially 95 to 110C.
The reason is considered to be that co-extrusion is carried out in the state where the e~hylene-vinyl alcohol copolymer layer is placed on the polyester layer inter-luminary peeling is controlled between both the resin layers and biaxial drawing is simultaneously effected in the well-balanced state.
Thus, a multi layer drawn polyester bottle 16 as shown in Fig. 6 is obtained. In the multi-layer draw-blown bottle of the present invention, the layer structure is molecularly oriented so that the density of the polyester layer constituting the outer surface is at least 1 345 g/cc, especially at least 1.348 gag as in case of an ordinary draw-blown polyester bottle.
One of the characteristic features of the bottle of the present invention is that the polyester layer con-stituting the inner surface, as well as the outer sun-race layer, is molecularly oriented so that the density of the inner surface layer is at least 1.345 gag especially at least 1.348 g/cc.
Moreover, this bottle is characterized in that also the ethylene-vinyl alcohol copol~mer constituting the intermediate layer is biaxially molecularly oriented so that the orientation coefficient (~) in the axial direction of the bottle and the orientation coefficient em) in the circumferential direction, determined accord ding to the polarized fluorimetry, satisfy the following requirements: the value of + m is at least 0.2, especially at least 0.3~ and the value of Jo - ml is smaller than 0.1, especially smaller than 0 07.
The two-dimensional orientation of the vessel wall (orientation in the plane of the vessel wall) can be determined according to the polarized fluorimetry.
As described in, for example, Yasunori Nishijima, Polymers, 15, No. 175, page 868 (published by the Japanese Polymer Association in 1966), the two-dimensianal orientation coefficients can be determined according to -the method in which -the degree or mode of the mole-cuter orientation of a thermoplastic resin as a polymer by solid deformation or by flowing in the form of a solution or melt is qualitatively and quantitatively determined by utilizing the optical an isotropy of a fluorescent polymer. If the -two-dimensional orientation in the wall plane of the draw-formed vessel of the ~22~3~
present invention is considered in -the light of the teaching of -the above-mentioned -technical report the twowdimensional orientation may be quantitatively expressed by the following formula:
It = Casey msin4W + I- n) wherein It stands or the intensity of the pole-rimed component of the fluorescence of a thermos plastic resin system as a sample, " indicates that the vibration direction of the incident polarized light is in parallel to the direction of the measured polarized light, stands for the rotation angle of the sample to the vibration direction of the fluorescence K stands for the maximum excitation probability when the molecular axis of the sample is in parallel to the vibration direction of the excited fluorescence, indicates the molecular fluorescence contraction, stands for the proportion of the molecular orientation in the axial direction in -the wall plane of the final formed vessel, m stands for the proportion of the molecular orientation in the direction rectangular to the axial direction (that is, the circumferential direction), n stands for the proportion ox non-orientation in the plane, and m -I n is 1.
The above-mentioned value ox B m indicates that the ethylene-vinyl alcohol copolymer is effectively biaxially molecularly oriented. By this in-plane molecular orientation, the bottle of the present invent lion is highly improved in the oxygen barrier property and transparency over a bottle in which the ethylene-vinyl alcohol copolymer is not oriented.
The absolute value ox the difference between and m, that is the value of lo - m I , has a relation to 14 ~2~3~3 the balance between the molecular orientation in the axial direction of the bottle and the molecular orientate ion in the circumferential direction of the bottle in the ethylene vinyl alcohol copolymer. In the vessel of the present invention, since the value of lo ; ml is smaller than 0.1~ the molecular orientation in the axial direction is well balanced with the molecular orientation in the circumferential direction.
A bottle in which in the intermediate layer of the central part of the barrel portion the value of + m is at least 0.2 and the value of I - ml is smaller than 0.1 is obtained for the firs-t time according to the process of the present invention Namely, in the present invention, by forming a pipe by co extruding inner and outer layers of polyethylene terephthalate and an intermediate layer of an ethylene-vinyl alcohol copolymer, it is made possible to perform draw blow forming so -that the value of a + m is at least 2, and by blow-drawing the preform in the circumferential direction simultane-ouzel or substantially simultaneously with drawing in the axial direction, it is made possible to maintain the orientation balance lo - ml below 0.1, whereby formation of cracks or pinholes in the ethylene vinyl alcohol copolymer layer can be prevented According to the sequential biaxial draw-blow-forming process in which a multi-layer pipe is drawn in the axial direction and is then blow-drawn in the circumferential direction, the value of the orientation coe~icient (B) in the axial direction is increased but the value of the orientation coefficient (m) in the air-cumferential direction is drastically lessened, resulting in reduction of the shock resistance and oxygen barrier property.
In the bottle of the present invention even the ~L2~L3~
intermediate layer composed of an ethylene vinyl alcohol copolymer is molecularly oriented in the well balanced state in both -the axial direction and the circumferential direction; and the oxygen permea~
lion coefficient is maintained at a very low level and the transparency it improved. Furthermore; these excellent characteristics can be maintained even if shocks are given to the bottle by falling or vibration or if the bottle is thermally set so as Jo improve the dimensional stability.
In accordance with another embodiment of the present invention, polyethylene terephthalate is used for the outer surface layer of a bottle or a pipe to be formed into a bottle, and a copolyester consisting essentially of ethylene terephthalate units, which has a lower crystallization speed than that of polyethylene terephthalate, is used for the inner surface layer.
This embodiment is to overcome the above-mentioned : defect concerning the heat conduction, which is caused when an ethylene-vinyl alcohol copolymer excellent in the gas barrier property is used as the intermediate layer of a multi-layer polyester bottle Namely, by using, instead of conventional polyethylene terephtha-late (PET) 9 a copolyester having a lower crystallization speed than that of PET for the inner layer, crystallize-lion of the resin of the inner resin, which is caused at the forming step, can be prevented as much as possible, and the adaptability of the inner layer resin to the drawing operation is improved and the transparency of the bottle is improved, and various properties can be improved by the drawing orientation.
Known polyethylene terephthalate can be used as the polyethylene terephthalate, and it is sufficient if polyethylene terephthalate has a ~ilm-forming - 16 - ~2~3~3 molecular weight. Polyethylene terephthalate having an intrinsic viscosity ox at least 0.89 especially at least 1.0~ is preferably used.
A copolyester composed mainly ox ethylene lore-phthalate units, which contains ester units in Wichita least one of the acid and alcohol components is an acid other than terephthalic acid or an alcohol other than ethylene glycol, is used as the copolyester keenest-tuning the inner layer. Since this copolyester is composed mainly ox ethylene terephthalate units, the copolyester can be draw~blow-formed under the same condo-lions as those or PET constituting the outer layer and also the inner layer per so can be biaxially molecularly oriented. Furthermore, since the Capella-I ester contains ester units other than ethylene lore-phthalate units, an advantage ox reduction of the cry-talllzation speed below that of PET can be attained.
The reason why different polyesters are used for the outer and inner layers in the present invention is that since polyethylene terephthalate of the outer layer is rapidly cooled by external cooling, as pointed out hereinbe~ore, and the resin layer is quenched, crystallization is inhibited even in polyethylene terephthalate for which the crystallization time is short and the transparency is maintained, and that the copolyester of the inner layer on the inner side of the intermediate layer is not crystallized because of a long crystallization time even if the cooling speed is low and hence the transparency is maintained.
I In the copolyester used in the present invention, as the acid component other than terephthalic acid, Thea can be mentioned isophthalic acid, naphthalene-dlcarboxylic acid, diphenyl~dicarboxylic acid, 232 ~is(4-carboxyphenyl)propane 9 bis(4-carboxyphenyl)methane, cyclohexane-dicarboxylic acid (hexahydroterephthalic acid and hexahydroisophthalic acidly adipic acid, sebacic acid, succinic acid and dodecane~dicarboxylic acid As the alcohol component other than ethylene glycol, there can be mentioned propylene glycol, butane-diol, neopentyl glycol, hexane-di.ol 3 glycerol, diethylene glycol) triethylene glycol, tetraethylene glycol, dibutylene glycol and tributylene glycol~ These acid components and/or alcohol components may be used singly or in the form ox a mixture of two or more of them.
As preferred examples of the copolyester; there can be mentioned polyethylene terephthalate/isophthalate, polyethylene terephthalate/adipate, polyethylene/
battalion terephthalate, polyethylene/butylene terephthalate/isophthalate, polyethylene/neopentylene terephthalate and polyethylene/neopentylene terephthalate/
: isophthalate, though copolyesters that can be used are not limited to those exemplified above It is preferred that the copolyester used in the present invention should contain ethylene terephthalate units in an amount of 85 to 96 mole %, especially 90 to 94 mole %, the balance being other ester units.
Of course, i-t is indispensable that -the copolyester should have a film-forming molecular weight.
In this embodiment of the present invention, it is preferred that the outer PET layer/inner copolyester layer thickness ratio be in the range of from 1/1 to
held in a blow mold before and after blow forming 9 respectively.
Fig. 6 is a view showing a multi layer drawn bottle prepared according to the process ox the present invention As pointed out hereinbe~ore, it is a primmer object of the present invention to improve a gas baffler property of a drawn polyester bottle, and an ethylene vinyl alcohol copolymer, especially an ethylene-vinyl alcohol - copolymer having an ethylene content lower than 50 mole %, is selected and used among vinyl alcohol type resins.
As is known to those skilled in the art, polyvinyl alcohol is not thermoplastic unless it is modified by a special treatment, but in an ethylene-vinyl alcohol copolymer 9 with inquiry ox the ethylene content, the melting point is reduced and the thermoplastic characteristic is increased. Since the ethylene-vinyl alcohol copolymer is drawn together with a polyester resin, as described hereinafter, it is ordinarily considered that an ethylene-vinyl alcohol copolymer hazing a lower melting point and a lower drawable temperature should be selected and used.
However, in the present invention, an ethylene-vinyl alcohol copolymer having a higher malting point and a higher drawable temperature is selected and used.
The first reason is that it the ethylene content exceeds 50 mole %, the melting point and drawable Tom;
portray are lowered and co-drawing with a polyester resin is advantageously carried out, but with increase of the ethylene content 9 the gas barrier property is drastically reduced and lamination of the polyester resin with the ethylene vinyl alcohol copolymer becomes insignificant. The second reason is that since it ~Z~3~3 has been found that if the process of the present invention is adopted even an ethylene vinyl alcohol copolyrner having a high vinyl alcohol content can be drawn in the form of a multi-layer structure with a polyester resin at a temperature suitable for drawing of the polyester resin For these reasons, an ethylene-vinyl alcohol copolymer having an ethylene context lower than 50 mole Jo that is, a high vinyl alcohol content, is selected as the ethylene-vinyl alcohol copolymer to be laminated with the polyester resin.
As means or draw-blow-forming ox plastics such as polyesters, there are known process in which a bottomed prison preform ox a plastic material is formed by injection and the bottomed prison is blow-drawn while drawing it in the axial direction by a drawing rod, and a process in which a plastic material is extruded into a pipe, the pipe is gripped by a pair ox clamps and drawn in the axial direction and a fluid is blown into the pipe to effect blow-drawingl When these processes are applied to a multi layer prison comprising a polyester layer and an ethylene vinyl alcohol copolymer layer, natal defects arise with respect to the drawability and interlaminar adhesion.
In the first place, when the temperature exceeds a certain level for example, 140C, a polyester is readily crystallized and drawing becomes difficult; and the polyester is whitened and the formed vessel becomes opaque. In order to prepare a multi-layer prison by injection; it is necessary to inject a polyester resin and then inject an ethylene-vinyl alcohol copolymer on the preliminarily injection-~orm~d polyester resin.
Since it is necessary to control the temperature ox the preliminarily injection formed polyester to a level much lower than the above mentioned critical temperature heat boning of both the resins in the interface is incomplete and it sometimes happens that interlaminar peeling is caused or the ethylene-vinyl alcohol copolymer layer is broken in the peeled portion.
In the second place, the drawability, especially the biaxial drawabilityjof -the ethylene-vinyl alcohol copolymer is especially poor at a temperature suitable for drawing of a polyester. More speciflcally9 when a co-extruded multi-layer pipe comprising a polyester layer and an ethylene-vinyl alcohol ccpolymer layer is drawn in the axial direction in the state gripped by clamps and is then subjected to blow-drawing, many clefts and latent cracks are readily formed in the axial direction in the ethylene vinyl alcohol copolymer layer.
It is considered that a phenomenon resembling fibrila-lion will be caused in the ethylene-vinyl alcohol copolymer layer by drawing in the axial direction and clefts or cracks will be wormed by subsequent blow--drawing.
The first characteristic feature of the present invention is that a polyester and an ethylene-~inyl alcohol copolymer is co-extruded into a pipe. This co-extrusion is accomplished by joining a molten polyp ester and a molten ethylene-vinyl alcohol copolymer in a die and extruding them through an annular ring.
Since both the resins are contacted with each other in the molten state for a certain time good mingling of both the resins is caused in the interface between the two resins and the degree of heat bonding is much higher than in case of multi-layer injection forming.
This effect is attained quite similarly also in the case where an adhesive resin is interposed between the polyester and the ethylene-vinyl alcohol copolymer.
The second characteristic feature of -the present :~22~
-invention is that the co-extruded multi-layer pipe is cut into a predetermined length and one end is closed by fusion bonding to form a bottom portion. If this bottomed preform is prepared, it is possible to perform blow-drawing of this preform simultaneously or sub-staunchly simultaneously with axial drawing by pressing a drawing rod to the preform which has been preliminarily heated. If this simultaneous drawing is adopted, format lion of clefts or latent cracks, which is often observed 10 in case of sequential drawing, can be prevented.
In the present invention, a copolymer obtained by saponifying a copolymer of ethylene with a vinyl ester such as vinyl acetate is used as the ethylene-vinyl alcohol copolymer. It view of the adaptability to the forming operation and the gas barrier propriety it is preferred that an ethylene-vinyl alcohol copolymer having an ethylene content ox 15 to 50 mole %, espy-Shelley 25 to 45 mole Jo and a saponification degree of at least 96 % be used. The molecular weight ox the copolymer is not particularly critical so far as the copolymer has a film-forming property.
Polyethylene terephthalate or a copolyester consisting essentially of ethylene terephthalate units and containing a small amount of known modifying ester units is used as the polyester for attaining the object of the present invention. The molecular weight of the polyester is not particularly critical if -the polyester has a film forming property.
In order to enhance the adhesion between -the polyp 3 ester layer and the ethylene-vinyl alcohol copolymer layer, a known adhesive may be used though use of the adhesive is not indispensably necessary. A copolyester type adhesive, a polyester-ether type adhesive, an epoxy-modified thermoplastic resin and an acid-modified thermoplastic resin may be used as the adhesive.
Various lamination structures may be adopted for a polyester base layer (PET) 9 an ethylene vinyl alcohol copolymer layer (EVA) and an adhesive layer (AD).
For example, there may be adopted structures ox PET/EVAC/
PET, POETIC + AD/PEI' and PET/AD/EVAC/AD/PET, in which the inner layer is indicated on the right side and the outer layer is indicated on -the left side The thicknesses ox the respective layers may be changed in broad ranges, but it is preferred that the PET/EVAC thickness ratio be in the range ox prom 2/1 to 30/1, especially from 4/1 to 15/1. In the case where the adhesive layer is used, it is preferred that the PET/
AD thickness Roy be in the range of from 5/1 to 100/17 especially from 10/1 to 50/1 Fig. 1 shows a multi-layer pipe especially pro-fireball used in carrying out the prevent invention This multi layer pipe 1 comprises inner and outer layers 2 and 3 ox a polyester, an intermediate gas-barrier layer 4 of an ethylene-vinyl alcohol copolymer and interposed adhesive layers pa and 5b.
As pointed out hereinbe~ore, it is important that this pipe should be prepared by co-extrusion.
In order to prevent crystallization of the polyester I it is important that the extruded pipe should be quenched by water immersion or the like It the extruded multi-layer pipe is thus quenched, the polyester layer in the outer surface of the pipe is easily fixed in the amorphous state where -the density 3 is in the range ox 1.331 to 1.~39 g/cc as measured at 20C. Incidentally, the density referred to in the instant specification means a value measured at 20C by using an n-heptane/carbon tetrachloride liquid mixture density gradient tube. However, the polyester resin located on 9_ I
-the inner wall surface of the pipe apart from the cooled outer wall surface is maintained for a long time at a temperature higher than the temperature of the polyp ester resin of the outer surface layer. Even in the molten state, the ethylene vinyl alcohol copolymer has a thermal conductivity coefficient corresponding to from about 1/2 to about 1/4 of that of the polyester.
By dint of this characteristic, the ethylene-vinyl alcohol copolymer intermediate layer acts as a heat insulation layer in the multi-layer pope being cooled and solidified. Therefore, the inner surface polyester layer is maintained at a high emperor for a long time and crystallization is advanced in the polyester of the inner surface layer, and the density is increased to a level as high as 1,355 g/cc. As the result the polyester of the inner surface layer is whitened t the transparency is lost and drawing of the inner surface layer becomes difficult. In the present invention) the polyester of the inner surface layer is forcibly cooled by passing a cold medium through the interior of the co-extruded pipe so that the density of the final multi-layer preform is controlled to a level equal to or higher by unto 0.015 g/cc than the density of the polyester of the outer surface layer, whereby whitening of the polyester of the inner surface layer is prevented and the drawability of the polyester ox the inner surface layer is improved.
The pipe is cut in a predetermined length, and one end of the cut pipe is heated and used and is pressed by male and female molds having a cavity and projections corresponding to a desired bottom shape, for example, a semi-spherical shape, to form a bottom portion 6 as shown in Fig 2.
Then, the other end of the pipe 1 is heated and subjected to pressing, drawing and blow forming in a desired mold to form a preform 10 having an opening 7 on the top end and a pitted, screwed or anchoring portion for a lid, such as a screw 8 or a neck ring support ring) I on the periphery, as shown in Fig. 3 The order of the steps for preparing the above-mentioned preform is not particularly critical. Namely the steps may be conducted in the above-mentioned order or in the reverse order.
If the above mentioned process is adopted, no super-flus resin portion is formed in preparing a preform prom a multi-layer pipe.
At the subsequent step the preform is heated by hot elf, an infrared ray heater or high frequency induction heating to a temperature suitable for drawing of the multi-layer preform. Namely, the preform is heated to a drawn temperature or the polyester resin ordain-aridly 85 to 120C, preferably 95 to 110C.
Referring to Figs. 4 and 5 illustrating the draw-blow-forming operation, a mandrel 11 it inserted into the opening ox the preform 10 and the opening is gripped by a pair ox split molds aye and 12b. A
vertically movable drawing rod 13 is arranged coccal with the mandrel 11, and fluid blowing annular passage 14 is wormed between the drawing rod 13 and the mandrel 11 .
In the present involution? the top end 15 of the drawing rod 13 is applied to the inner side of the bottom 6 ox the preform 10 and the drawing rod 13 is moved downward whereby the preform 10 is drawn in the axial direction Simultaneously, a fluid is blown into the preform 10 through the passage 14, whereby the preform 10 is expanded and drawn in the circumferential direction by the pressure of the fluid I
According to the present invention, it has been found that by performing drawing in the axial direction and drawing in the circumferential direction simultaneously or substantially simultaneously even a layer of an ethylene-vinyl alcohol copolymer having a high vinyl alcohol content can be drawn at a relatively low temperature.
This finding is quite surprising in view ox the fact that drawing of an ethylene vinyl alcohol copolymer is very difficult and even when a film ox this copolymer is drawn sequentially in the longitudinal direction and in the lateral direction even at a temperature suitable or drawing the film is ruptured during the drawing operation, as pointed out herein before.
Furthermore 9 it it is taken into consideration that in draw-blow-forming ox a multi layer pipe of a polypropylene layer and an ethylene-vinyl alcohol copolymrr layer, the ethylene-vinyl alcohol copolymer in the multi-layer structure can be drawn only at a con-siderably high temperature ox 140 to 165C, it is quite surprising that according to the present invent lion, the ethylene vinyl alcohol copolymer can be biaxially drawn at a drawing temperature for a polyester resin, that is such a low temperature as 85 to 120C, especially 95 to 110C.
The reason is considered to be that co-extrusion is carried out in the state where the e~hylene-vinyl alcohol copolymer layer is placed on the polyester layer inter-luminary peeling is controlled between both the resin layers and biaxial drawing is simultaneously effected in the well-balanced state.
Thus, a multi layer drawn polyester bottle 16 as shown in Fig. 6 is obtained. In the multi-layer draw-blown bottle of the present invention, the layer structure is molecularly oriented so that the density of the polyester layer constituting the outer surface is at least 1 345 g/cc, especially at least 1.348 gag as in case of an ordinary draw-blown polyester bottle.
One of the characteristic features of the bottle of the present invention is that the polyester layer con-stituting the inner surface, as well as the outer sun-race layer, is molecularly oriented so that the density of the inner surface layer is at least 1.345 gag especially at least 1.348 g/cc.
Moreover, this bottle is characterized in that also the ethylene-vinyl alcohol copol~mer constituting the intermediate layer is biaxially molecularly oriented so that the orientation coefficient (~) in the axial direction of the bottle and the orientation coefficient em) in the circumferential direction, determined accord ding to the polarized fluorimetry, satisfy the following requirements: the value of + m is at least 0.2, especially at least 0.3~ and the value of Jo - ml is smaller than 0.1, especially smaller than 0 07.
The two-dimensional orientation of the vessel wall (orientation in the plane of the vessel wall) can be determined according to the polarized fluorimetry.
As described in, for example, Yasunori Nishijima, Polymers, 15, No. 175, page 868 (published by the Japanese Polymer Association in 1966), the two-dimensianal orientation coefficients can be determined according to -the method in which -the degree or mode of the mole-cuter orientation of a thermoplastic resin as a polymer by solid deformation or by flowing in the form of a solution or melt is qualitatively and quantitatively determined by utilizing the optical an isotropy of a fluorescent polymer. If the -two-dimensional orientation in the wall plane of the draw-formed vessel of the ~22~3~
present invention is considered in -the light of the teaching of -the above-mentioned -technical report the twowdimensional orientation may be quantitatively expressed by the following formula:
It = Casey msin4W + I- n) wherein It stands or the intensity of the pole-rimed component of the fluorescence of a thermos plastic resin system as a sample, " indicates that the vibration direction of the incident polarized light is in parallel to the direction of the measured polarized light, stands for the rotation angle of the sample to the vibration direction of the fluorescence K stands for the maximum excitation probability when the molecular axis of the sample is in parallel to the vibration direction of the excited fluorescence, indicates the molecular fluorescence contraction, stands for the proportion of the molecular orientation in the axial direction in -the wall plane of the final formed vessel, m stands for the proportion of the molecular orientation in the direction rectangular to the axial direction (that is, the circumferential direction), n stands for the proportion ox non-orientation in the plane, and m -I n is 1.
The above-mentioned value ox B m indicates that the ethylene-vinyl alcohol copolymer is effectively biaxially molecularly oriented. By this in-plane molecular orientation, the bottle of the present invent lion is highly improved in the oxygen barrier property and transparency over a bottle in which the ethylene-vinyl alcohol copolymer is not oriented.
The absolute value ox the difference between and m, that is the value of lo - m I , has a relation to 14 ~2~3~3 the balance between the molecular orientation in the axial direction of the bottle and the molecular orientate ion in the circumferential direction of the bottle in the ethylene vinyl alcohol copolymer. In the vessel of the present invention, since the value of lo ; ml is smaller than 0.1~ the molecular orientation in the axial direction is well balanced with the molecular orientation in the circumferential direction.
A bottle in which in the intermediate layer of the central part of the barrel portion the value of + m is at least 0.2 and the value of I - ml is smaller than 0.1 is obtained for the firs-t time according to the process of the present invention Namely, in the present invention, by forming a pipe by co extruding inner and outer layers of polyethylene terephthalate and an intermediate layer of an ethylene-vinyl alcohol copolymer, it is made possible to perform draw blow forming so -that the value of a + m is at least 2, and by blow-drawing the preform in the circumferential direction simultane-ouzel or substantially simultaneously with drawing in the axial direction, it is made possible to maintain the orientation balance lo - ml below 0.1, whereby formation of cracks or pinholes in the ethylene vinyl alcohol copolymer layer can be prevented According to the sequential biaxial draw-blow-forming process in which a multi-layer pipe is drawn in the axial direction and is then blow-drawn in the circumferential direction, the value of the orientation coe~icient (B) in the axial direction is increased but the value of the orientation coefficient (m) in the air-cumferential direction is drastically lessened, resulting in reduction of the shock resistance and oxygen barrier property.
In the bottle of the present invention even the ~L2~L3~
intermediate layer composed of an ethylene vinyl alcohol copolymer is molecularly oriented in the well balanced state in both -the axial direction and the circumferential direction; and the oxygen permea~
lion coefficient is maintained at a very low level and the transparency it improved. Furthermore; these excellent characteristics can be maintained even if shocks are given to the bottle by falling or vibration or if the bottle is thermally set so as Jo improve the dimensional stability.
In accordance with another embodiment of the present invention, polyethylene terephthalate is used for the outer surface layer of a bottle or a pipe to be formed into a bottle, and a copolyester consisting essentially of ethylene terephthalate units, which has a lower crystallization speed than that of polyethylene terephthalate, is used for the inner surface layer.
This embodiment is to overcome the above-mentioned : defect concerning the heat conduction, which is caused when an ethylene-vinyl alcohol copolymer excellent in the gas barrier property is used as the intermediate layer of a multi-layer polyester bottle Namely, by using, instead of conventional polyethylene terephtha-late (PET) 9 a copolyester having a lower crystallization speed than that of PET for the inner layer, crystallize-lion of the resin of the inner resin, which is caused at the forming step, can be prevented as much as possible, and the adaptability of the inner layer resin to the drawing operation is improved and the transparency of the bottle is improved, and various properties can be improved by the drawing orientation.
Known polyethylene terephthalate can be used as the polyethylene terephthalate, and it is sufficient if polyethylene terephthalate has a ~ilm-forming - 16 - ~2~3~3 molecular weight. Polyethylene terephthalate having an intrinsic viscosity ox at least 0.89 especially at least 1.0~ is preferably used.
A copolyester composed mainly ox ethylene lore-phthalate units, which contains ester units in Wichita least one of the acid and alcohol components is an acid other than terephthalic acid or an alcohol other than ethylene glycol, is used as the copolyester keenest-tuning the inner layer. Since this copolyester is composed mainly ox ethylene terephthalate units, the copolyester can be draw~blow-formed under the same condo-lions as those or PET constituting the outer layer and also the inner layer per so can be biaxially molecularly oriented. Furthermore, since the Capella-I ester contains ester units other than ethylene lore-phthalate units, an advantage ox reduction of the cry-talllzation speed below that of PET can be attained.
The reason why different polyesters are used for the outer and inner layers in the present invention is that since polyethylene terephthalate of the outer layer is rapidly cooled by external cooling, as pointed out hereinbe~ore, and the resin layer is quenched, crystallization is inhibited even in polyethylene terephthalate for which the crystallization time is short and the transparency is maintained, and that the copolyester of the inner layer on the inner side of the intermediate layer is not crystallized because of a long crystallization time even if the cooling speed is low and hence the transparency is maintained.
I In the copolyester used in the present invention, as the acid component other than terephthalic acid, Thea can be mentioned isophthalic acid, naphthalene-dlcarboxylic acid, diphenyl~dicarboxylic acid, 232 ~is(4-carboxyphenyl)propane 9 bis(4-carboxyphenyl)methane, cyclohexane-dicarboxylic acid (hexahydroterephthalic acid and hexahydroisophthalic acidly adipic acid, sebacic acid, succinic acid and dodecane~dicarboxylic acid As the alcohol component other than ethylene glycol, there can be mentioned propylene glycol, butane-diol, neopentyl glycol, hexane-di.ol 3 glycerol, diethylene glycol) triethylene glycol, tetraethylene glycol, dibutylene glycol and tributylene glycol~ These acid components and/or alcohol components may be used singly or in the form ox a mixture of two or more of them.
As preferred examples of the copolyester; there can be mentioned polyethylene terephthalate/isophthalate, polyethylene terephthalate/adipate, polyethylene/
battalion terephthalate, polyethylene/butylene terephthalate/isophthalate, polyethylene/neopentylene terephthalate and polyethylene/neopentylene terephthalate/
: isophthalate, though copolyesters that can be used are not limited to those exemplified above It is preferred that the copolyester used in the present invention should contain ethylene terephthalate units in an amount of 85 to 96 mole %, especially 90 to 94 mole %, the balance being other ester units.
Of course, i-t is indispensable that -the copolyester should have a film-forming molecular weight.
In this embodiment of the present invention, it is preferred that the outer PET layer/inner copolyester layer thickness ratio be in the range of from 1/1 to
5/1, especially from 2/1 to 3/1 Hereupon, it must be noted that the present invention includes an embody-mint where the thickness of the outer layer is increased and the thickness of the inner layer is reduced, whereby cooling of the inner layer is further promoted.
The bottle of the present invention has not only a high transparency but also a much higher gas barrier ~2~2~3~
property than -that of other plastic bottle or a bottle composed solely ox a polyester (drawn PET bottle).
Furthermore, the gas barrier property can optionally be adjusted; and the bottle has a high pressure nests-lance. Therefore, the filling preservability of carbon dioxide gas incorporated drinks such as beer cola and cider can be increased. Furthermore the bottle of the present invention is excellent from the sanitary viewpoint, and when the used bottle is subjected to incineration, generated gases are sub-staunchly carbon dioxide gas and water vapor and no harmful gas is produced. Therefore 3 the bottle of the present invention is excellent in the adaptability to the incineration treatment. Moreover the bottle ox the present invention is comparable to a glass bottle in the transparency, gas barrier property and pressure resistance and it also has a light weight and a high resistance to breakage, Accordingly, an ideal bottle is provided.
The present invention will now be described in detail with reverence to the following examples that by no means limit the scope ox the invention By using extrudes or inner and outer layers, provided with a full-flighted screw having a diameter of 65 mm and an effective length of 1430 mm, extrudes or an intermediate layer and adhesive layers, provided with a full-flighted screw having a diameter ox 50 mm and an effective length ox 1100 mm, and a 5-layer annular die, a three-kind five-layer laminate pipe comprising inner and outer layers of polyethylene terephthalate (PET) having an intrinsic viscosity ox 1.0) an intermediate layer of an ethylene-vinyl alcohol copolymer (ENACT) having a vinyl alcohol content _ 19 I
of 70 mole % and interposed adhesive layers of modified high density polyethylene grafted with malefic android, in which 10000 ppm of epoxidized octal owlet was in-corporate, was extruded into water from the die to cool the outer portion of the pipe and simultaneously, nitrogen gas was blown into the interior of the pipe to cool the inner portion of the pipe. This pipe had an outer diameter ox 30 mm and an inner diameter ox 22 mm, and the thicknesses of the inner layer outer layer adhesive layer and intermediate layer were 1.4 mm, 2 0 mm9 0~05 mm and 0.5 mm, respectively. The pipe was cut into a predetermined size (the length was 129 mm and the weight was 55 g). One end of the pipe was heated at 220C and fusion-closed to form a semi-spherical bottom. The other end of the pipe was heated at 150C to promote the crystallization of the neck portion and a screwed portion and a neck ring were formed to obtain a preform having a total height of 148 mm.
The preform was heated at 105C, and the preform was subjected to substantially simultaneous biaxial draw blow-~orming in a blow mold by stretching the preform a-t a draw ratio of 1.9 in the longitudinal direction and blow-drawing the preform at a draw ratio ox 3.0 in the lateral direction, whereby a multi layer drawn bottle having an inner volume of 1550 cc was prepared.
In the barrel portion of this bottle, the density of PET of the outer layer was 1.355 g/cc and the density of PET of the inner layer was 1.365 gag and in the intermediate EVA layer, the orientation coefficients and m were 0.34 and 0.38, respectively. The oxygen permeability of the bottle was about 1.5 cc/m 24 hours-elm (37C), and the bottle was excellent in the trays-; patency. When the bottle was let to fall down on a . .
concrete floor from a height of 120 cm, the bottle was not broken, and no interlaminar peeling was caused Since the neck portion of this bottle was considerably crystallized, even if the bottle was willed with a liquid maintained a 9~C and sealed no deformation of the neck portion was caused.
By using the same apparatus as used in Example 1, a two-kind three-layer laminate pipe comprising inner and outer layers of polyethylene terephthalate PET) having an intrinsic viscosity of 0.9 and an intermediate layer of an ethylene-vinyl alcohol copolymer (EKE) having a vinyl alcohol content of 58 mole % was extruded into water to cool the outer portion of the pipe, and simultaneously, air was blown into the interior of the pipe to cool the inner portion of the pipe. The pipe had an outer diameter ox 22 mm and an inner die meter ox 16 mm. The thicknesses of -the outer layer, inner layer and intermediate layer were 1.6 mm9 1.2 mm and 0.2 mm, respectively The pipe was cut into a predetermined size (the length was 85 mm and the weight was 20 g). One end of the pipe was heated at about 230C and fusion-closed to Norm a semi-spherical bottom and in order to prevent crystallization of the neck portion, the other end was preliminarily heated at about 110C and a screw and a neck ring were formed to obtain a preform.
The preform was heated at 100C and was subjected to substantially simultaneous biaxial draw-blow-forming at a draw ratio of 1 8 in the longitudinal direction and at a draw ratio of 2.5 in the lateral direction to obtain a multl;layer drawn bottle having an inner volume of 500 cc.
In the barrel portion of this bottle, the density I
of PET of the outer layer was 1.352 g/cc and the density of PET of the inner layer was 1.357 g/cc, and the orient station coefficients and m of EVA were 0,31 and 0,35, respectively. The oxygen permeability of the bottle was 2.0 c~/m2~24 hours~atm (37C), When the bottle was let to Hall down on a concrete floor prom a height ox 120 cm, the bottle was not broken.
A three-kind 5-layer laminate pipe was prepared in the same manner as described in Example 1 except that only the outer portion was cooled.
The pipe was subjected to substantially simultaneous biaxial draw~blow-~orming under the same conditions as adopted in Example 1 to obtain a multi-layer drawn bottle having an inner volume of 1550 cc, The inner layer ox the bottle was milky white and the bottle was slightly interior to the bottle obtained in Example 1 in the transparency.
A laminate pipe and then a preform were prepared under -the same conditions as described in Example 1.
'rho preform was heated at 105C9 sod the preform was drawn at a draw ratio of 1.7 in the longitudinal direction. Then, the preform was drawn at a draw ratio of 3.0 in the lateral direction in a blow mold. A
multi-layer drawn bottle having an inner volume of 1550 cc was obtained by this sequential draw blow-~orming.
Cracks were formed in the intermediate EVA layer, and the oxygen permeability of the bottle was 3.1 cc/m2-24 hours-atm (37C)~ and the appearance was inferior to that ox the bottle obtained in Example 1.
Exam By using extrudes or outer and inner layers, provided with a full-flighted screw having a diameter ; 22 -ox 65 mm and an effective length of 1430 mm, extrudes for an intermediate layer and adhesive layers, provided with a full-flighted screw having a diameter of 50 mm and an effective length of 1100 mm, and a five-layer annular die, a 4-kind awry laminate pipe comprising an outer layer of polyethylene tereph~halate PUT
having an intrinsic viscosity ox 1,0, an inner layer of an ethylene terephthalate copolymer having an isoph thalic acid content of 8 mole % and an intrinsic viscosity of 1.1, an intermediate layer of an ethylene-vinyl alcohol copolymer (EVA) having a vinyl alcohol content of 70 mole % an adhesive layers of a polyester-ether block copolymer interposed between the outer layer and the intermediate layer and between the inner layer and the intermediate layer was co-extruded into a water-cooling type cooling tank from the multi layer die.
Toe pipe had an outer diameter of 30.0 mm and a thick-news of 3.8 mm, and the outer layer/adhesive layer/
intermediate layer/adhesive layer/inner layer thickness ratio was 100/5/15/5/40. The lower end of the obtained transparent pipe was fusion closed to form a semi-, .... ..
spherical bottom and the upper end of the pipe was formed into a neck portion having a screw. The so-obtained preform was preliminarily heated at 98C
and was subjected in a blow-forming mold to sub Stan-tidally simultaneous biaxial draw-blow-forming at a draw ratio of 1.9 in the longitudinal direction and at a draw ratio of 3.0 in the lateral direction to obtain a multi-layer drawn polyester bottle having an inner volume of 1550 cc.
In the barrel portion of the so-obtained bottle 7 the density of PET was 1.360 gag and the orientation coefficients and m of EVA were 0.32 and 0.35, respectively. The haze of the barrel portion of the - 23 ~l22~
bottle was 10 to 12. When the bottle was let to fall down on a concrete floor from a height of 120 cm, the bottle was not broken. The oxygen permeability of the bottle was 1.7 cc/m2-24 hours-atm as measured at 37C
at a relative humidity of ~100 % in the bottle and a relate humidity of 20 % outside the bottle. The oxygen permeability of a bottle composed 501ely of polyethylene terephthalate ) which had the same weight and shape as described above, was 9.8 cc/m~-24 hours~atm. Namely, the oxygen permeability of the bottle of -the present invention was about 1/5 of the oxygen permeability of the bottle composed solely of PET.
By using the same apparatus as used in Example 5, a Canada 5-layer laminate pipe comprising an outer layer of polyethylene -tereph-thalate PET) having an intrinsic viscosity of 0.9, an inner layer of an ethylene terephthalate copolymer having an isophthalic acid content ox 8 mole % and an intrinsic viscosity of 1.1, an intermediate layer of an ethylene-vinyl alcohol copolymer tEVAC~ having a vinyl alcohol content of 70 mole % and adhesive layers ox modified high density polyethylene grated with malefic ~nhydride, in which 10000 ppm of epoxidized octal owlet were incorporated, was extruded into water from the die to cool the pipe. The pipe had an outer diameter of I mm and an inner diameter 22 mm, and -the thicknesses of the inner layer, outer layer, adhesive layer and intermediate layer were 1.4 mm, 2 0 em, 0.05 mm and 0~5 mm, respect lively. The pipe was cut into a predetermined size the length was 129 mm and the weight was 55 go, and one end of the pipe was heated at about 220C and fusion-closed to form a semi-spherical bottom. The other end of the pipe was heated at 150C to promote the crystallization of the neck portion, and a screw and a neck ring were formed to obtain a preform having a total height of 148 mm.
m e preform was heated at 105C and was subjected in a blow mold to substantially simultaneous biaxial draw~blow-forming while stretching the preform at a draw ratio ox 1.9 in the longitudinal direction and blow-drawing the preform at a draw ratio of 3.0 in the lateral directions whereby a multi-layer drawn bottle having an inner volume of 1550 cc was obtained.
In the barrel portion ox the bottle, the density of PET was 1.~55 g/cc, and the orientation coefficients and m ox EVA were 0.34 and 0.38, respectively. The haze of the bottle was 9 and the oxygen permeability was about 1,5 cc/m2 24 hours-atm (37C). When the bottle was let to fall down on a concrete floor from a height of 120 cm, the bottle was not broken and no interlaminar peeling was caused. Since the neck portion ox the bottle was considerably crystallized, even it the bottle was filled with a liquid maintained at 93C and sealed, deformation of the neck portion was not caused.
I
By using the same apparatus as used in Example 5, a 4-kind 5-layer laminate pipe comprising an outer layer I polyethylene terephthalate (PET) having an intrinsic viscosity of 1 0, an intermediate layer of an ethylene terephthalate copolymer (Kodar~PETG5 763) in which a part of the glycol component was 1,4-cyclohexane-dim ethanol, an intermediate layer ox an ethylene-vinyl alcohol copolymer EVOKE) having a vinyl alcohol content ox 70 mole % and adhesive layers ox malefic android-grated polyethylene the malefic android content was 0.8 % by weight) interposed between the outer and intermediate layers and between the inner and intermediate ye York layers was extruded end cooled in water.
The pipe had an outer diameter of 22 mm and an inner diameter ox 16 my and the thicknesses of the Quoter layer inner layer and intermediate layer were 1~6 my 1.2 mm and 0.2 mm, respectively. The pipe was cut into a predetermined size (the length was 85 mm and the weight was 29 g). One end of the pipe was heated at about 230C and fusion-closed to form a semi-spherical bottom, In order to prevent crystallization ox the neck portion, the other end was preliminarily heated at about 110C 5 and a screw and a neck ring were formed to obtain a preform.
The preform was heated at 100C and was subjected to substantially simultaneous biaxial draw-blow-forming at a draw ratio of 1.8 in the longitudinal direction and at a draw ratio of 205 in the lateral direction to obtain a multi-layer drawn bottle having an inner volume of 500 cc.
In the barrel portion of the bottle 7 the density of PET was 1.353 g/cc, and the orientation coefficients and m of EVA were 0.32 and 0~33, respectively. The haze of the bottle was 8 and the oxygen permeability was 2.0 cc/m2.24 hours-atm (37C). When the bottle was let to fall down on a concrete floor prom a height ox 120 cm, -the bottle was not broken.
The bottle of the present invention has not only a high transparency but also a much higher gas barrier ~2~2~3~
property than -that of other plastic bottle or a bottle composed solely ox a polyester (drawn PET bottle).
Furthermore, the gas barrier property can optionally be adjusted; and the bottle has a high pressure nests-lance. Therefore, the filling preservability of carbon dioxide gas incorporated drinks such as beer cola and cider can be increased. Furthermore the bottle of the present invention is excellent from the sanitary viewpoint, and when the used bottle is subjected to incineration, generated gases are sub-staunchly carbon dioxide gas and water vapor and no harmful gas is produced. Therefore 3 the bottle of the present invention is excellent in the adaptability to the incineration treatment. Moreover the bottle ox the present invention is comparable to a glass bottle in the transparency, gas barrier property and pressure resistance and it also has a light weight and a high resistance to breakage, Accordingly, an ideal bottle is provided.
The present invention will now be described in detail with reverence to the following examples that by no means limit the scope ox the invention By using extrudes or inner and outer layers, provided with a full-flighted screw having a diameter of 65 mm and an effective length of 1430 mm, extrudes or an intermediate layer and adhesive layers, provided with a full-flighted screw having a diameter ox 50 mm and an effective length ox 1100 mm, and a 5-layer annular die, a three-kind five-layer laminate pipe comprising inner and outer layers of polyethylene terephthalate (PET) having an intrinsic viscosity ox 1.0) an intermediate layer of an ethylene-vinyl alcohol copolymer (ENACT) having a vinyl alcohol content _ 19 I
of 70 mole % and interposed adhesive layers of modified high density polyethylene grafted with malefic android, in which 10000 ppm of epoxidized octal owlet was in-corporate, was extruded into water from the die to cool the outer portion of the pipe and simultaneously, nitrogen gas was blown into the interior of the pipe to cool the inner portion of the pipe. This pipe had an outer diameter ox 30 mm and an inner diameter ox 22 mm, and the thicknesses of the inner layer outer layer adhesive layer and intermediate layer were 1.4 mm, 2 0 mm9 0~05 mm and 0.5 mm, respectively. The pipe was cut into a predetermined size (the length was 129 mm and the weight was 55 g). One end of the pipe was heated at 220C and fusion-closed to form a semi-spherical bottom. The other end of the pipe was heated at 150C to promote the crystallization of the neck portion and a screwed portion and a neck ring were formed to obtain a preform having a total height of 148 mm.
The preform was heated at 105C, and the preform was subjected to substantially simultaneous biaxial draw blow-~orming in a blow mold by stretching the preform a-t a draw ratio of 1.9 in the longitudinal direction and blow-drawing the preform at a draw ratio ox 3.0 in the lateral direction, whereby a multi layer drawn bottle having an inner volume of 1550 cc was prepared.
In the barrel portion of this bottle, the density of PET of the outer layer was 1.355 g/cc and the density of PET of the inner layer was 1.365 gag and in the intermediate EVA layer, the orientation coefficients and m were 0.34 and 0.38, respectively. The oxygen permeability of the bottle was about 1.5 cc/m 24 hours-elm (37C), and the bottle was excellent in the trays-; patency. When the bottle was let to fall down on a . .
concrete floor from a height of 120 cm, the bottle was not broken, and no interlaminar peeling was caused Since the neck portion of this bottle was considerably crystallized, even if the bottle was willed with a liquid maintained a 9~C and sealed no deformation of the neck portion was caused.
By using the same apparatus as used in Example 1, a two-kind three-layer laminate pipe comprising inner and outer layers of polyethylene terephthalate PET) having an intrinsic viscosity of 0.9 and an intermediate layer of an ethylene-vinyl alcohol copolymer (EKE) having a vinyl alcohol content of 58 mole % was extruded into water to cool the outer portion of the pipe, and simultaneously, air was blown into the interior of the pipe to cool the inner portion of the pipe. The pipe had an outer diameter ox 22 mm and an inner die meter ox 16 mm. The thicknesses of -the outer layer, inner layer and intermediate layer were 1.6 mm9 1.2 mm and 0.2 mm, respectively The pipe was cut into a predetermined size (the length was 85 mm and the weight was 20 g). One end of the pipe was heated at about 230C and fusion-closed to Norm a semi-spherical bottom and in order to prevent crystallization of the neck portion, the other end was preliminarily heated at about 110C and a screw and a neck ring were formed to obtain a preform.
The preform was heated at 100C and was subjected to substantially simultaneous biaxial draw-blow-forming at a draw ratio of 1 8 in the longitudinal direction and at a draw ratio of 2.5 in the lateral direction to obtain a multl;layer drawn bottle having an inner volume of 500 cc.
In the barrel portion of this bottle, the density I
of PET of the outer layer was 1.352 g/cc and the density of PET of the inner layer was 1.357 g/cc, and the orient station coefficients and m of EVA were 0,31 and 0,35, respectively. The oxygen permeability of the bottle was 2.0 c~/m2~24 hours~atm (37C), When the bottle was let to Hall down on a concrete floor prom a height ox 120 cm, the bottle was not broken.
A three-kind 5-layer laminate pipe was prepared in the same manner as described in Example 1 except that only the outer portion was cooled.
The pipe was subjected to substantially simultaneous biaxial draw~blow-~orming under the same conditions as adopted in Example 1 to obtain a multi-layer drawn bottle having an inner volume of 1550 cc, The inner layer ox the bottle was milky white and the bottle was slightly interior to the bottle obtained in Example 1 in the transparency.
A laminate pipe and then a preform were prepared under -the same conditions as described in Example 1.
'rho preform was heated at 105C9 sod the preform was drawn at a draw ratio of 1.7 in the longitudinal direction. Then, the preform was drawn at a draw ratio of 3.0 in the lateral direction in a blow mold. A
multi-layer drawn bottle having an inner volume of 1550 cc was obtained by this sequential draw blow-~orming.
Cracks were formed in the intermediate EVA layer, and the oxygen permeability of the bottle was 3.1 cc/m2-24 hours-atm (37C)~ and the appearance was inferior to that ox the bottle obtained in Example 1.
Exam By using extrudes or outer and inner layers, provided with a full-flighted screw having a diameter ; 22 -ox 65 mm and an effective length of 1430 mm, extrudes for an intermediate layer and adhesive layers, provided with a full-flighted screw having a diameter of 50 mm and an effective length of 1100 mm, and a five-layer annular die, a 4-kind awry laminate pipe comprising an outer layer of polyethylene tereph~halate PUT
having an intrinsic viscosity ox 1,0, an inner layer of an ethylene terephthalate copolymer having an isoph thalic acid content of 8 mole % and an intrinsic viscosity of 1.1, an intermediate layer of an ethylene-vinyl alcohol copolymer (EVA) having a vinyl alcohol content of 70 mole % an adhesive layers of a polyester-ether block copolymer interposed between the outer layer and the intermediate layer and between the inner layer and the intermediate layer was co-extruded into a water-cooling type cooling tank from the multi layer die.
Toe pipe had an outer diameter of 30.0 mm and a thick-news of 3.8 mm, and the outer layer/adhesive layer/
intermediate layer/adhesive layer/inner layer thickness ratio was 100/5/15/5/40. The lower end of the obtained transparent pipe was fusion closed to form a semi-, .... ..
spherical bottom and the upper end of the pipe was formed into a neck portion having a screw. The so-obtained preform was preliminarily heated at 98C
and was subjected in a blow-forming mold to sub Stan-tidally simultaneous biaxial draw-blow-forming at a draw ratio of 1.9 in the longitudinal direction and at a draw ratio of 3.0 in the lateral direction to obtain a multi-layer drawn polyester bottle having an inner volume of 1550 cc.
In the barrel portion of the so-obtained bottle 7 the density of PET was 1.360 gag and the orientation coefficients and m of EVA were 0.32 and 0.35, respectively. The haze of the barrel portion of the - 23 ~l22~
bottle was 10 to 12. When the bottle was let to fall down on a concrete floor from a height of 120 cm, the bottle was not broken. The oxygen permeability of the bottle was 1.7 cc/m2-24 hours-atm as measured at 37C
at a relative humidity of ~100 % in the bottle and a relate humidity of 20 % outside the bottle. The oxygen permeability of a bottle composed 501ely of polyethylene terephthalate ) which had the same weight and shape as described above, was 9.8 cc/m~-24 hours~atm. Namely, the oxygen permeability of the bottle of -the present invention was about 1/5 of the oxygen permeability of the bottle composed solely of PET.
By using the same apparatus as used in Example 5, a Canada 5-layer laminate pipe comprising an outer layer of polyethylene -tereph-thalate PET) having an intrinsic viscosity of 0.9, an inner layer of an ethylene terephthalate copolymer having an isophthalic acid content ox 8 mole % and an intrinsic viscosity of 1.1, an intermediate layer of an ethylene-vinyl alcohol copolymer tEVAC~ having a vinyl alcohol content of 70 mole % and adhesive layers ox modified high density polyethylene grated with malefic ~nhydride, in which 10000 ppm of epoxidized octal owlet were incorporated, was extruded into water from the die to cool the pipe. The pipe had an outer diameter of I mm and an inner diameter 22 mm, and -the thicknesses of the inner layer, outer layer, adhesive layer and intermediate layer were 1.4 mm, 2 0 em, 0.05 mm and 0~5 mm, respect lively. The pipe was cut into a predetermined size the length was 129 mm and the weight was 55 go, and one end of the pipe was heated at about 220C and fusion-closed to form a semi-spherical bottom. The other end of the pipe was heated at 150C to promote the crystallization of the neck portion, and a screw and a neck ring were formed to obtain a preform having a total height of 148 mm.
m e preform was heated at 105C and was subjected in a blow mold to substantially simultaneous biaxial draw~blow-forming while stretching the preform at a draw ratio ox 1.9 in the longitudinal direction and blow-drawing the preform at a draw ratio of 3.0 in the lateral directions whereby a multi-layer drawn bottle having an inner volume of 1550 cc was obtained.
In the barrel portion ox the bottle, the density of PET was 1.~55 g/cc, and the orientation coefficients and m ox EVA were 0.34 and 0.38, respectively. The haze of the bottle was 9 and the oxygen permeability was about 1,5 cc/m2 24 hours-atm (37C). When the bottle was let to fall down on a concrete floor from a height of 120 cm, the bottle was not broken and no interlaminar peeling was caused. Since the neck portion ox the bottle was considerably crystallized, even it the bottle was filled with a liquid maintained at 93C and sealed, deformation of the neck portion was not caused.
I
By using the same apparatus as used in Example 5, a 4-kind 5-layer laminate pipe comprising an outer layer I polyethylene terephthalate (PET) having an intrinsic viscosity of 1 0, an intermediate layer of an ethylene terephthalate copolymer (Kodar~PETG5 763) in which a part of the glycol component was 1,4-cyclohexane-dim ethanol, an intermediate layer ox an ethylene-vinyl alcohol copolymer EVOKE) having a vinyl alcohol content ox 70 mole % and adhesive layers ox malefic android-grated polyethylene the malefic android content was 0.8 % by weight) interposed between the outer and intermediate layers and between the inner and intermediate ye York layers was extruded end cooled in water.
The pipe had an outer diameter of 22 mm and an inner diameter ox 16 my and the thicknesses of the Quoter layer inner layer and intermediate layer were 1~6 my 1.2 mm and 0.2 mm, respectively. The pipe was cut into a predetermined size (the length was 85 mm and the weight was 29 g). One end of the pipe was heated at about 230C and fusion-closed to form a semi-spherical bottom, In order to prevent crystallization ox the neck portion, the other end was preliminarily heated at about 110C 5 and a screw and a neck ring were formed to obtain a preform.
The preform was heated at 100C and was subjected to substantially simultaneous biaxial draw-blow-forming at a draw ratio of 1.8 in the longitudinal direction and at a draw ratio of 205 in the lateral direction to obtain a multi-layer drawn bottle having an inner volume of 500 cc.
In the barrel portion of the bottle 7 the density of PET was 1.353 g/cc, and the orientation coefficients and m of EVA were 0.32 and 0~33, respectively. The haze of the bottle was 8 and the oxygen permeability was 2.0 cc/m2.24 hours-atm (37C). When the bottle was let to fall down on a concrete floor prom a height ox 120 cm, -the bottle was not broken.
Claims (7)
1. A multi-layer drawn polyester bottle comprising a neck portion having an opening on the top end and a fitted or screwed part on the periphery, a bottom portion formed by fusion bonding and closing of a pipe and a barrel portion biaxially molecularly oreinted by draw-blowing of the pipe, wherein the pipe is composed of a co-extrudate comprising inner and outer surface base layers of a polyester consisting essentially of ethylene terephthalate units and an intermediate layer of an ethylene-vinyl alcohol copolymer having an ethylene content lower than 50 mole %.
2. A multi-layer drawn polyester bottle as set forth in claim 1, wherein the inner surface and outer surface base layers of the polyester are biaxially molecularly oriented so that at the central part of the barrel portion of the bottle, the density (20°C) of each of said inner surface and outer surface base layers was at least 1.345 g/cc, and the intermediate layer of the ethylene-vinyl alcohol copolymer is biaxially molecularly oriented so that the orientation coefficient (?) in the axial direction of the bottle and the orientation coefficient (m) in the circumferential direction of the bottle, each being determined according to the polarized fluorimetry, satisfy such requirements that the value of ? + m is at least 0.2 and the value of ¦? - m¦ is smaller than 0.1.
3. A process for the preparation of a multi-layer polyester bottle, which comprises forming by co-extrusion a multi-layer pipe by using an ethylene-vinyl alcohol copolymer having an ethylene content lower than 50 mole % as an intermediate layer acting as a gas barrier resin layer and a polyester resin as inner and outer base layer and, if necessary, interposing an adhesive layer between the two resin layers, cutting the pipe into a predetermined length, closing one end of the cut pipe by fusion bonding to form a bottom portion, forming the other end of the cut pipe into a neck portion having an opening on the top end and a fitted or screwed part on the periphery, pre-heating the so-obtained preform at a drawing temperature of 85 to 120°C and subjecting the preform to draw-blow-forming biaxially in the axial direction and circumferential direction in a blow-forming mold.
4. A process according to claim 3, wherein the outer surface polyester layer of the preform has a density (20°C) of 1.331 to 1.339 g/cc and the inner surface polyester layer has a density (20°C) equal to or higher by upto 0.015 g/cc than the density of the outer surface polyester layer.
5. A process according to claim 3, wherein a draw-ing rod is pressed to the bottom portion of the prelimi-narily heated preform to draw the preform in the axial direction, and blow-drawing of the preform is carried out substantially simultaneous with said drawing in the axial direction
6 A multi-layer drawn polyester bottle as set forth in claim 1, wherein the outer surface layer is composed of polyethylene terephthalate and the inner surface layer is composed of a copolyester consisting essentially of ethylene terephthalate units, which has a lower crystallization speed than that of poly-ethylene terephthalate.
7. A multi-layer drawn polyester bottle as set forth in claim 6, wherein the copolyester comprises 85 to 96 mole % of ethylene terephthalate units, the balance being ester units other than ethylene tere-phthalate units.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP73893/83 | 1983-04-28 | ||
| JP58073893A JPS59199237A (en) | 1983-04-28 | 1983-04-28 | Manufacture of multilayer stretched polyester bottle |
| JP58197580A JPS6089362A (en) | 1983-10-24 | 1983-10-24 | Multilayer stretched polyester bottle and manufacture thereof |
| JP197580/83 | 1983-10-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1221318A true CA1221318A (en) | 1987-05-05 |
Family
ID=26415038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000452999A Expired CA1221318A (en) | 1983-04-28 | 1984-04-27 | Multi-layer drawn polyester bottle and process for preparation thereof |
Country Status (4)
| Country | Link |
|---|---|
| AU (1) | AU571223B2 (en) |
| CA (1) | CA1221318A (en) |
| GB (1) | GB2141970B (en) |
| SE (1) | SE468381B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4649004A (en) * | 1983-12-27 | 1987-03-10 | Toyo Seikan Kaisha, Ltd. | Process for production of multi-layer pipes for draw-forming |
| JPS6160436A (en) * | 1984-08-23 | 1986-03-28 | 東洋製罐株式会社 | Multilayer gas barrier property oriented polyester vessel |
| JPH0617136B2 (en) * | 1985-02-15 | 1994-03-09 | 日精エ−・エス・ビ−機械株式会社 | Biaxially oriented container with excellent gas barrier properties |
| GB2188272B (en) * | 1986-02-28 | 1990-10-10 | Toyo Seikan Kaisha Ltd | A process for preparation of a biaxially drawn polyester vessel having resistance to heat distortion and gas barrier properties. |
| US4764403A (en) * | 1986-11-10 | 1988-08-16 | Owens-Illinois Plastic Products Inc. | Multilayer biaxially oriented heat set articles |
| US5599495A (en) * | 1995-06-07 | 1997-02-04 | Owens-Brockway Plastic Products Inc. | Method for molding hollow plastic container having a finish with a smaller diameter than the body of the container |
| SE9802313D0 (en) * | 1998-06-29 | 1998-06-29 | Plm Ab | Biaxially oriented container of plastic material |
| GB2360077B (en) * | 1999-11-22 | 2004-07-28 | Chemisar Lab Inc | Impervious, chemically stable thermoplastic tubing and film |
| US6626324B1 (en) * | 2000-06-30 | 2003-09-30 | Schmalbach-Lubeca Ag | Plastic container having a crystallinity gradient |
| GB2366781A (en) * | 2000-09-19 | 2002-03-20 | Shya Hsin Plastic Works Co Ltd | Three-layer moulded container |
| JP3896524B2 (en) | 2000-12-20 | 2007-03-22 | 株式会社吉野工業所 | Synthetic resin biaxial stretch blow molding |
| DE102005049718A1 (en) * | 2005-10-14 | 2007-04-19 | Degussa Gmbh | By welding in electromagnetic alternating field available plastic composite molding |
| US8124202B2 (en) | 2006-09-15 | 2012-02-28 | The Coca-Cola Company | Multilayer container for enhanced gas barrier properties |
| CH715533A1 (en) * | 2018-11-09 | 2020-05-15 | Alpla Werke Alwin Lehner Gmbh & Co Kg | Plastic container with a container neck with a pouring opening and method for producing a plastic container made from a preform. |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4261473A (en) * | 1975-12-17 | 1981-04-14 | Toyo Seikan Kaisha Limited | Molded container having wall composed of oriented resin blend |
| JPS5449285A (en) * | 1977-09-24 | 1979-04-18 | Toyo Seikan Kaisha Ltd | Automatically filled liquid food bottle |
| JPS5951889B2 (en) * | 1979-08-31 | 1984-12-17 | 固 青木 | Injection stretch blow molding method |
| JPS5677143A (en) * | 1979-11-30 | 1981-06-25 | Yoshino Kogyosho Co Ltd | Polyethylene terephthalate resin product |
| AU549286B2 (en) * | 1981-01-22 | 1986-01-23 | Toyo Boseki K.K. | Blow moulded multiply vessel |
| ATE29237T1 (en) * | 1981-10-05 | 1987-09-15 | Ball Corp | MULTI-LAYER PIPE BODY WITH AN OFF-CENTRE BARRIER LAYER. |
| GB2131739B (en) * | 1982-10-14 | 1986-03-26 | Toyo Seikan Kaisha Ltd | Multi-layer drawn plastic vessel |
-
1984
- 1984-04-27 GB GB08410835A patent/GB2141970B/en not_active Expired
- 1984-04-27 SE SE8402336A patent/SE468381B/en not_active IP Right Cessation
- 1984-04-27 AU AU27438/84A patent/AU571223B2/en not_active Ceased
- 1984-04-27 CA CA000452999A patent/CA1221318A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU571223B2 (en) | 1988-04-14 |
| GB2141970B (en) | 1986-10-08 |
| AU2743884A (en) | 1984-11-01 |
| SE8402336D0 (en) | 1984-04-27 |
| SE468381B (en) | 1993-01-11 |
| GB2141970A (en) | 1985-01-09 |
| SE8402336L (en) | 1984-10-29 |
| GB8410835D0 (en) | 1984-06-06 |
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| MKEX | Expiry |