GB2141970A - Multi-layer drawn polyester bottle - Google Patents
Multi-layer drawn polyester bottle Download PDFInfo
- Publication number
- GB2141970A GB2141970A GB08410835A GB8410835A GB2141970A GB 2141970 A GB2141970 A GB 2141970A GB 08410835 A GB08410835 A GB 08410835A GB 8410835 A GB8410835 A GB 8410835A GB 2141970 A GB2141970 A GB 2141970A
- Authority
- GB
- United Kingdom
- Prior art keywords
- layer
- bottle
- pipe
- polyester
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 70
- 239000010410 layer Substances 0.000 claims abstract description 170
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 68
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 230000004888 barrier function Effects 0.000 claims abstract description 22
- 239000012790 adhesive layer Substances 0.000 claims abstract description 21
- 238000000071 blow moulding Methods 0.000 claims abstract description 19
- 229920001225 polyester resin Polymers 0.000 claims abstract description 15
- 239000004645 polyester resin Substances 0.000 claims abstract description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- 238000007664 blowing Methods 0.000 claims abstract description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 48
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 48
- -1 polyethylene terephthalate Polymers 0.000 claims description 26
- 229920001634 Copolyester Polymers 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 239000002344 surface layer Substances 0.000 claims description 13
- 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 description 11
- 238000002360 preparation method Methods 0.000 claims description 6
- 150000002148 esters Chemical group 0.000 claims description 5
- 230000004927 fusion Effects 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000004715 ethylene vinyl alcohol Substances 0.000 abstract description 3
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 24
- 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
- 230000035699 permeability Effects 0.000 description 12
- 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
- 229920001577 copolymer Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 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
- 239000004698 Polyethylene 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
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 235000016795 Cola Nutrition 0.000 description 3
- 235000011824 Cola pachycarpa Nutrition 0.000 description 3
- 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
- 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
- 239000011521 glass Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 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 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-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
- 230000000694 effects Effects 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QTDSLDJPJJBBLE-PFONDFGASA-N octyl (z)-octadec-9-enoate Chemical compound CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC QTDSLDJPJJBBLE-PFONDFGASA-N 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 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
- DFYQRCOZAAHDOU-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;2-[2-(2-hydroxyethoxy)ethoxy]ethanol Chemical compound OCCOCCO.OCCOCCOCCO DFYQRCOZAAHDOU-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
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- XKACUVXWRVMXOE-UHFFFAOYSA-N 4-[2-(4-carboxyphenyl)propan-2-yl]benzoic acid Chemical compound C=1C=C(C(O)=O)C=CC=1C(C)(C)C1=CC=C(C(O)=O)C=C1 XKACUVXWRVMXOE-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
- 241000282326 Felis catus Species 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
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-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
- 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
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 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
- 238000005304 joining Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 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
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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—Rigid or semi-rigid 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 or 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
- B32B27/06—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
A multi-layer drawn polyester bottle 16 comprises a neck portion having an opening 7 on the top end and a screwed part 8 on the periphery, a bottom portion formed by closing of a pipe and a barrel portion biaxially molecularly oriented by draw-blowing of the pipe, the pipe being composed of inner and outer base layers 2,3 of a polyester consisting of ethylene terephthalate and an intermediate layer 4 of ethylene-vinyl alcohol having an ethylene content lower than 50 mole %. This bottle is prepared by coextruding a multi-layer pipe using ethylene-vinyl alcohol as an intermediate gas barrier layer and polyester resin as inner and outer base layers and, if necessary, interposing adhesive layers 5a,5b between the resin layers, closing one end of the pipe to form a bottom portion, pre-heating the so- obtained preform at a temperature of 85 to 120 DEG C and draw-blow- forming biaxially in the axial and circumferential directions in a blow- forming mold. <IMAGE>
Description
SPECIFICATION
Multi-layer drawn polyester bottle and process for preparation thereof
Background of the Invention (1) Field of the Invention:
The present invention relates to a multi-layer drawn polyester bottle and a process for the preparation thereof. More particularly, the present invention relates to a bottle having a wall biaxially molecularly oriented by drawing and an improved gas barrier property, which comprises a gas barrier layer of an ethylene-vinyl alcohol copolymer and a base layer of a polyester, and a process for the 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 of a plastic bottle, the drawn polyester bottle has a permeability 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 and in case of beer, cola or cider the shelf 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 this type has been put into practical use. In order to improve a drawn polyester bottle having inherently an appropriate gas barrier property, it is of no significance to laminate or coat the drawn polyester bottle with a gas barrier resin which is inferior to the polyester in the gas barrier property. Namely, a resin having a higher gas barrier property than that of the polyester should be used for lamination or coating.Therefore, use of thermoplastic resins such as a vinylidene chloride resin, an acrylonitrile resin or a vinyl alcohol resin is expected, but an appropriate resin should be selected while taking the properties and processability of the resin into consideration.
Summary of the Invention
We found that in the preparation of a multilayer drawn polyester bottle comprising a base layer of a polyester and a gas barrier layer of an ethylene-vinyl alcohol copolymer, if formation of a pipe by co-extrusion, cutting of the pipe, hot formation of 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 finding.
More specifically, in accordance with one fundamental aspect of 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 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 ethylenevinyl alcohol copolymer having an ethylene content lower than 50 mole %.
In accordance with another fundamental aspect of the present invention, there is provided a process for the preparation of a multilayer 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, preheating the so-obtained preform at a drawing temperature of 85 to 1 20 C and subjecting the preform to draw-blow-forming biaxially in the axial direction and circumferential direction in a blow-forming mold.
Brief Description of the Drawings
Fig. 1 is a sectional view showing a multilayer 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 held in a blow mold before and after blow forming, respectively.
Fig. 6 is a view showing a multi-layer drawn bottle prepared according to the process of the present invention.
Detailed Description of the Preferred Embodiments
As pointed out hereinbefore, it is a primary object of the present invention to improve a gas barrier 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, with increase of the ethylene content, the melting point is reduced and the thermoplastic characteristic is increased.Since the ethylenevinyl alcohol copolymer is drawn together with a polyester resin, as described hereinafter, it is ordinarily considered that an ethylene-vinyl alcohol copolymer having 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 melting point and a higher drawable temperature is selected and used. The first reason is that if the ethylene content exceeds 50 mole %, the melting point and drawable temperature are lowered and co-drawing with a polyester resin is advantageously carried out, but with increase of the ethylene content, 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 has been found that if the process of the present invention is adopted, even an ethylene-vinyl alcohol copolymer having a high vinyl alcohol content can be drawn in the form of a multilayer structure with a polyester resin at a temperature suitable for drawing of the polyester resin.For these reasons, an ethylenevinyl alcohol copolymer having an ethylene content lower than 50 mole %, that is, a high vinyl alcohol content, is selected as the ethylene-vinyl alcohol copolymer to be laminated with the polyester resin.
As means for draw-blow-forming of plastics such as polyesters, there are known a process in which a bottomed parison (preform) of a plastic material is formed by injection and the bottomed parison 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 of clamps and drawn in the axial direction and a fluid is blown into the pipe to effect blow-drawing.
When these processes are applied to a multi-layer parison comprising a polyester layer and an ethylenevinyl alcohol copolymer layer, fatal defects arise with respect to the drawability and interlaminar adhesion.
In the first place, when the temperature exceeds a certain level, for example, 1 40'C, 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 parison by injection, it is necessary to inject a polyester resin and then inject an ethylene-vinyl alcohol copolymer on the preliminarily injectionformed polyester resin. Since it is necessary to control the temperature of the preliminarily injection-formed polyester to a level much lower than the above-mentioned critical temperature, heat bonding 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 drawability, of the ethylenevinyl alcohol copolymer is especially poor at a temperature suitable for drawing of a polyester. More specifically, when a co-extruded multi-layer pipe comprising a polyester layer and an ethylene-vinyl alcohol copolymer 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 fibrilation will be caused in the ethylene-vinyl alcohol copolymer layer by drawing in the axial direction and clefts or cracks will be formed by subsequent blowdrawing.
The first characteristic feature of the present invention is that a polyester and an ethylenevinyl alcohol copolymer is co-extruded into a pipe. This co-extrusion is accomplished by joining a molten polyester 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 invention is that the co-extruded multilayer 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 substantially simultaneously with axial drawing by pressing a drawing rod to the preform which has been preliminarily heated.
If this simultaneous drawing is adopted, formation of clefts or latent cracks, which is often observed 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. In view of the adaptability to the forming operation and the gas barrier property, it is preferred that an ethylene-vinyl alcohol copolymer having an ethylene content of 1 5 to 50 mole %, especially 25 to 45 mole %, and a saponification degree of at least 96% be used. The molecular weight of 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 polyester 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), an ethylene-vinyl alcohol copolymer layer (EVAC) and an adhesive layer (AD). For example, there may be adopted structures of PET/E
VAC/ PET, PET/EVAC + AD/PET and PE
T/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 of the respective layers may be changed in broad ranges, but it is preferred that the PET/EVAC thickness ratio be in the range of from 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 ratio be in the range of from 5/1 to 100/1, especially from 10/1 to 50/1.
Fig. 1 shows a multi-layer pipe especially preferably used in carrying out the present invention. This multi-layer pipe 1 comprises inner and outer layers 2 and 3 of a polyester, an intermediate gas-barrier layer 4 of an ethylene-vinyl alcohol copolymer and interposed adhesive layers 5a and 5b.
As pointed out herein before, it is important that this pipe should be prepared by coextrusion. In order to prevent crystallization of the polyester, it is important that the extruded pipe should be quenched by water immersion or the like.
If 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 is in the range of 1.331 to 1.339 g/cc as measured at 20"C. Incidentally, the density referred to in the instant specification means a value measured at 20"C by using an n-heptane/carbon tetrachloride liquid mixture density-gradient tube. However, the polyester resin located on 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 polyester 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 pipe being cooled and solidified. Therefore, the inner surface polyester layer is maintained at a high temperature 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, 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 upto 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 of the inner surface layer is improved.
The pipe is cut in a predetermined length, and one end of the cut pipe is heated and fused 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 blowforming in a desired mold to form a preform 10 having an opening 7 on the top end and a fitted, screwed or anchoring portion for a lid, such as a screw 8 or a neck ring (support ring) 9, 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 superffluous resin portion is formed in preparing a preform from a multi-layer pipe.
At the subsequent step, the preform is heated by hot air, 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 drawing temperature for the polyester resin, ordinarily 85 to 1 20 C, preferably 95 to 1 10'C.
Referring to Figs. 4 and 5 illustrating the drawblow-forming operation, a mandrel 11 is inserted into the opening of the preform 10 and the opening is gripped by a pair of split molds 1 2a and 1 2b. A vertically movable drawing rod 1 3 is arranged coaxially with the mandrel 11, and a fluid blowing annular passage 1 4 is formed between the drawing rod 1 3 and the mandrel 11.
In the present invention, the top end 1 5 of the drawing rod 1 3 is applied to the inner side of the bottom 6 of the preform 10 and the drawing rod 1 3 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.
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 ethylenevinyl aclohol copolymer having a high vinyl alcohol content can be drawn at a relatively low temperature.
This finding is quite surprising in view of the fact that drawing of an ethylene-vinyl alcohol copolymer is very difficult and even when a film of this copolymer is drawn sequentially in the longitudinal direction and in the lateral direction even at a temperature suitable for drawing, the film is ruptured during the drawing operation, as pointed out hereinbefore.
Furthermore, if it is taken into consideration that in draw-blow-forming of 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 considerably high temperature of 140 to 165"C, it is quite surprising that according to the present invention, 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 1 20 C, especially 95 to 1 10'C.
The reason is considered to be that coextrusion is carried out in the state where the ethylene-vinyl alcohol copolymer layer is placed on the polyester layer, interlaminar 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 1 6 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 g/cc, 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 constituting the inner surface, as well as the outer surfface layer, is molecularly oriented so that the density of the inner surface layer is at least 1.345 g/cc, especially at least 1.348 g/cc.
Moreover, this bottle is characterized in that also the ethylene-vinyl alcohol copolymer constituting the intermediate layer is biaxially molecularly oriented so that the orientation coefficient (I) in the axial direction of the bottle and the orientation coefficient (m) in the circumferential direction, determined according to the polarized fluorimetry, satisfy the following requirements: the value of I + m is at least 0.2, especially at least 0.3, and the value of II - 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-dimensional orientation coefficients can be determined according to the method in which the degree or mode of the molecular 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 anisotropy of a fluorescent polymer.If the two-dimensional orientation in the wall plane of the draw-formed vessel of the present invention is considered in the light of the teaching of the above-mentioned technical report, the two-dimensional orientation may be quantitatively expressed by the following formula: I,,(w) = K+(lcos4 + msin4 + 3/8n) wherein I, ,(co) stands for the intensity of the polarized component of the fluorescence of a thermoplastic 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, w 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, (b indicates the molecular fluorescence contraction, I 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 of nonorientation in the plane, and
I + m + n is 1.
The above-mentioned value of I + m indi cates that the ethylene-vinyl alcohol copolymer is effectively biaxially molecularly oriented. By this in-plane molecular orientation, the bottle of the present invention is highly improved in the oxygen barrier property and transparency over a bottle in which the ethylenevinyl alcohol copolymer is not oriented.
The absolute value of the difference between I and m, that is, the value of II - ml, has a relation to the balance between the molecular orientation in the axial direction of the bottle and the molecular orientation in the circumferential direction of the bottle in the ethylene-vinyl alcohol copolymer. In the vessel of the present invention, since the value of II - 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 I + m is at least 0.2 and the value of II - m | is smaller than 0.1 is obtained for the first 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 I + m is at least 2, and by blowdrawing the preform in the circumferential direction simultaneously or substantially simultaneously with drawing in the axial direction, it is made possible to maintain the orientation balance II - 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 drawblow-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 coefficient (I) in the axial direction is increased but the value of the orientation coefficient (m) in the circumferential direction is drastically lessened, resulting in reduction of the shock resistance and oxygen barrier property.
In the bottle of the present invention, even the 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 permeation coefficient is maintained at a very low level and the transparency is 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 to 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 abovementioned 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 terephthalate (PET), a copolyester having a lower crystallization speed than that of PET for the inner layer, crystallization 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 film-forming molecular weight. Polyethylene terephthalate having an intrinsic viscosity of at least 0.8, especially at least 1.0, is preferably used.
A copolyester composed mainly of ethylene terephthalate units, which contains ester units in which at 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 constituting the inner layer. Since this copolyester is composed mainly of ethylene terephthalate units, the copolyester can be draw-blow-formed under the same conditions as those for PET constituting the outer layer, and also the inner layer per se can be biaxially molecularly oriented. Furthermore, since the copolyester contains ester units other than ethylene terephthalate units, an advantage of reduction of the crystallization 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 hereinbefore, 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.
In the copolyester used in the present invention, as the acid component other than terephthalic acid, there can be mentioned isophthalic acid, naphthalenedicarboxylic acid, diphenyl-dicarboxylic acid, 2,2bis(4-carboxyphenyl)propane, bis(4-carboxyphenyl)meth ane, cyclohexane-dicarboxylic acid (hexahydroterephthalic acid and hexahydroisophthalic acid), 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-diol, 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 of 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/ butylene 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, it 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 embodiment 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 property than that of other plastic bottle or a bottle composed solely of a polyester (drawn PET bottle). Furthermore, the gas barrier property can optionally be adjusted, and the bottle has a high pressure resistance. 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 substantially carbon dioxide gas and water vapor and no harmful gas is produced. Therefore, the bottle of the present invention is excellent in the adaptability to the incineration treatment.
Moreover, the bottle of 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 reference to the following examples that by no means limit the scope of the invention.
Example 1
By using extruders for inner and outer layers, provided with a full-flighted screw having a diameter of 65 mm and an effective length of 1430 mm, extruders 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 5-layer annular die. a three-kind five-layer laminate pipe comprising inner and outer layers of polyethylene terephthalate (PET) having an intrinsic viscosity of 1.0, an intermediate layer of an ethylene-vinyl alcohol copolymer (EVAC) having a vinyl alcohol content of 70 mole % and interposed adhesive layers of modified high density polyethylene grafted with maleic anhydride, in which 10000 ppm of epoxidized octyl oleate was incorporated.
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 of 30 mm and an inner diameter of 22 mm, and the thicknesses of the inner layer, outer layer, adhesive layer and intermediate layer were 1.4 mm, 2.0 mm, 0.05 mm and 0.5 mm, respectively. The pipe was cut into a predetermined size (the length was 1 29 mm and the weight was 55 g). One end of the pipe was heated at 220"C and fusion-closed to form a semispherical bottom. The other end of the pipe was heated at 150do 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 105"C, and the preform was subjected to substantially simultaneous biaxial draw-blow-forming in a blow mold by stretching the preform at a draw ratio of 1.9 in the longitudinal direction and blowdrawing the preform at a draw ratio of 3.0 in the lateral direction, whereby a multi-layer drawn bottle having an inner volume of 1 550 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 g/cc, and in the intermediate
EVAC layer, the orientation coefficients I and m were 0.34 and 0.38, respectively. The oxygen permeability of the bottle was about 1.5 cc/m2.24 hours. atm (37'C), and the bottle was excellent in the transparency.
When the bottle was let to fall down on a concrete floor from a height of 1 20 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 filled with a liquid maintained at 93"C and sealed, no deformation of the neck portion was caused.
Example 2
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 (EVAC) 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 of 22 mm and an inner diameter of 1 6 mm. The thicknesses of the outer layer, inner layer and intermediate layer were 1.6 mm, 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 230"C and fusion-closed to form a semi-spherical bottom, and in order to prevent crystallization of the neck portion, the other end was preliminarily heated at about 110"C and a screw and a neck ring were formed to obtain a preform.
The preform was heated at 100"C 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 multi-layer drawn bottle having an inner volume of 500 cc.
In the barrel portion of this bottle, the density 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 orientation coefficients 1 and m of EVAC were 0.31 and 0.35, respectively. The oxygen permeability of the bottle was 2.0 cc/m224 hours atom (37"C).
When the bottle was let to fall down on a concrete floor from a height of 1 20 cm, the bottle was not broken.
Example 3
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-forming under the same conditions as adopted in Example 1 to obtain a multi-layer drawn bottle having an inner volume of 1 550 cc.
The inner layer of the bottle was milky white and the bottle was slightly inferior to the bottle obtained in Example 1 in the transparency.
Example 4
A laminate pipe and then a preform were prepared under the same conditions as described in Example 1. The preform was heated at 105"C, and 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 1 550 cc was obtained by this sequential draw-blow-forming.
Cracks were formed in the intermediate
EVAC layer, and the oxygen permeability of the bottle was 3.1 cc/m2 24 hours atom (37"C), and the appearance was inferior to that of the bottle obtained in Example 1.
Example 5
By using extruders for outer and inner layers, provided with a full-flighted screw having a diameter of 65 mm and an effective length of 1 430 mm, extruders 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 5-layer laminate pipe comprising an outer layer of polyethylene terephthalate (PET) having an intrinsic viscosity of 1.0, an inner layer of an ethylene terephthalate copolymer having an isophthalic acid content of 8 mole % and an intrinsic viscosity of
1.1, an intermediate layer of an ethylenevinyl alcohol copolymer (EVAC) having a vinyl alcohol content of 70 mole % and adhesive layers of a polyesterether 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 watercooling type cooling tank from the multi-layer die. The pipe had an outer diameter of 30.0 mm and a thickness 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 semispherical 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 98"C and was subjected in a blow-forming mold to substantially 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 1 550 cc.
In the barrel portion of the so-obtained bottle, the density of PET was 1.360 g/cc, and the orientation coefficients I and m of
EVAC were 0.32 and 0.35, respectively. The haze of the barrel portion of the bottle was 10 to 1 2. When the bottle was let to fall down on a concrete floor from a height of 1 20 cm, the bottle was not broken. The oxygen permeability of the bottle was 1.7 cc/m224 hours'atom as measured at 37"C at a relative humidity of 100% in the bottle and a relative humidity of 20% outside the bottle.The oxygen permeability of a bottle composed solely of polyethylene terephthalate, which had the same weight and shape as described above, was 9.8 cc/m2-24 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.
Example 6
By using the same apparatus as used in
Example 5, a 4-kind 5-layer laminate pipe comprising an outer layer of polyethylene terephthalate (PET) having an intrinsic viscosity of 0.9, an inner layer of an ethylene terephthalate copolymer having an isophthalic acid content of 8 mole % and an intrinsic viscosity of 1.1, an intermediate layer of an ethylene-vinyl alcohol copolymer (EVAC) having a vinyl alcohol content of 70 mole % and adhesive layers of modified high density polyethylene grafted with maleic anhydride, in which 10000 ppm of epoxidized octyl oleate were incorporated, was extruded into water from the die to cool the pipe. The pipe had an outer diameter of 30 mm and an inner diameter of 22 mm, and the thicknesses of the inner layer, outer layer, adhesive layer and intermediate layer were 1.4 mm, 2.0 mm, 0.05 mm and 0.5 mm, respectively.The pipe was cut into a predetermined size (the length was 1 29 mm and the weight was 55 g), and one end of the pipe was heated at about 220'C and fusion-closed to form a semi-spherical bottom. The other end of the pipe was heated at 150 C 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.
The preform was heated at 105"C and was subjected in a blow mold to substantially simultaneous biaxial draw-blow-forming while stretching the preform at a draw ratio of 1.9 in the longitudinal direction and blow-drawing the preform at a draw ratio of 3.0 in the laterial direction, whereby a multi-layer drawn bottle having an inner volume of 1 550 cc was obtained.
In the barrel portion of the bottle, the density of PET was 1.355 g/cc, and the orientation coefficients I and m of EVAC were 0.34 and 0.38, respectively. The haze of the bottle was 9 and the oxygen permeability was about 1.5 cc/m2-4 hours atom (37"C). When the bottle was let to fall down on a concrete floor from a height of 1 20 cm, the bottle was not broken and no interlaminar peeling was caused. Since the neck portion of the bottle was considerably crystallized, even if the bottle was filled with a liquid maintained at 93"C and sealed, deformation of the neck portion was not caused.
Example 7
By using the same apparatus as used in
Example 5, a 4-kind 5-layer laminate pipe comprising an outer layer of 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-cyclohexanedimethanol, an intermediate layer of an ethylene-vinyl alcohol copolymer (EVAC) having a vinyl alcohol content of 70 mole % and adhesive layers of maleic anhydride-grafted polyethylene (the maleic anhydride content was 0.8% by weight) interposed between the outer and intermediate layers and between the inner and intermediate layers was extruded and cooled in water.
The pipe had an outer diameter of 22 mm and an inner diameter of 1 6 mm, and the thicknesses of the outer layer, inner layer and intermediate layer were 1.6 mm, 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 230"C and fusionclosed to form a semispherical bottom. In order to prevent crystallization of the neck portion, the other end was preliminarily heated at about 110"C, and a screw and a neck ring were formed to obtain a preform.
The preform was heated at 100 C 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 multi-layer drawn bottle having an inner volume of 500 cc.
In the barrel portion of the bottle, the density of PET was 1.353 g/cc, and the orientation coefficients 1 and m of EAC 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 atom (37"C). When the bottle was let to fall down on a concrete floor from a height of 1 20 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 ethylenevinyl 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 bi axially molecularly oriented so that the orientation coefficient (I) 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 I + m is at least 0.2 and the value of II - ml is smaller than 0.1.
3. A process for the preparation of a multilayer 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, preheating 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 drawing rod is pressed to the bottom portion of the preliminarily 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 polyethylene 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 terephthalate units.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8410835D0 GB8410835D0 (en) | 1984-06-06 |
| GB2141970A true GB2141970A (en) | 1985-01-09 |
| GB2141970B GB2141970B (en) | 1986-10-08 |
Family
ID=26415038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08410835A Expired GB2141970B (en) | 1983-04-28 | 1984-04-27 | Multi-layer drawn polyester bottle |
Country Status (4)
| Country | Link |
|---|---|
| AU (1) | AU571223B2 (en) |
| CA (1) | CA1221318A (en) |
| GB (1) | GB2141970B (en) |
| SE (1) | SE468381B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2153739A (en) * | 1983-12-27 | 1985-08-29 | Toyo Seikan Kaisha Ltd | Process for production of multi-layer polyethylene terephthalate pipes for (stretch) blow moulding |
| FR2595067A1 (en) * | 1986-02-28 | 1987-09-04 | Toyo Seikan Kaisha Ltd | PROCESS FOR MANUFACTURING A BIAXIALLY STRETCHED CONTAINER AND CONTAINER MANUFACTURED THEREBY |
| EP0747290A1 (en) * | 1995-06-07 | 1996-12-11 | Owens-Brockway Plastic Products Inc. | Hollow plastic container having a finish with a smaller diameter than the body of the container |
| GB2360077A (en) * | 1999-11-22 | 2001-09-12 | Chemisar Lab Inc | Impervious chemically stable thermoplastic tubing and film |
| GB2366781A (en) * | 2000-09-19 | 2002-03-20 | Shya Hsin Plastic Works Co Ltd | Three-layer moulded container |
| WO2002002417A3 (en) * | 2000-06-30 | 2002-05-30 | Schmalbach Lubeca | Plastic container having a crystallinity gradient |
| AU2002216375B2 (en) * | 2000-12-20 | 2006-08-17 | Yoshino Kogyosho Co., Ltd. | Synthetic resin biaxial oriented blow formed preform for forming bottle body |
| WO2008033765A2 (en) | 2006-09-15 | 2008-03-20 | The Coca-Cola Company | Multilayer container for enhanced gas barrier properties |
| US8524342B2 (en) * | 2005-10-14 | 2013-09-03 | Evonik Degussa Gmbh | Plastic composite moulded bodies obtainable by welding in an electromagnetic alternating field |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US4764403A (en) * | 1986-11-10 | 1988-08-16 | Owens-Illinois Plastic Products Inc. | Multilayer biaxially oriented heat set articles |
| SE9802313D0 (en) * | 1998-06-29 | 1998-06-29 | Plm Ab | Biaxially oriented container of plastic material |
| 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. |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1545096A (en) * | 1975-12-17 | 1979-05-02 | Toyo Seikan Kaisha Ltd | Moulded plastic container |
| GB2006108A (en) * | 1977-09-24 | 1979-05-02 | Toyo Seikan Kaisha Ltd | Bottle for liquid foodstuffs |
| GB2057962A (en) * | 1979-08-31 | 1981-04-08 | Aoki K | Stretch-blow moulding a two layer article |
| GB2067131A (en) * | 1979-11-30 | 1981-07-22 | Yoshino Kogyosho Co Ltd | Articles of polyethylene terephthalate resin |
| GB2091629A (en) * | 1981-01-22 | 1982-08-04 | Toyo Boseki | Blow-molded multiply vessel |
| EP0076366A2 (en) * | 1981-10-05 | 1983-04-13 | Ball Corporation | Multilayer tubular body with uncentered barrier layer |
| GB2131739A (en) * | 1982-10-14 | 1984-06-27 | Toyo Seikan Kaisha Ltd | Multi-layer drawn plastic vessel |
-
1984
- 1984-04-27 SE SE8402336A patent/SE468381B/en not_active IP Right Cessation
- 1984-04-27 GB GB08410835A patent/GB2141970B/en not_active Expired
- 1984-04-27 CA CA000452999A patent/CA1221318A/en not_active Expired
- 1984-04-27 AU AU27438/84A patent/AU571223B2/en not_active Ceased
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1545096A (en) * | 1975-12-17 | 1979-05-02 | Toyo Seikan Kaisha Ltd | Moulded plastic container |
| GB2006108A (en) * | 1977-09-24 | 1979-05-02 | Toyo Seikan Kaisha Ltd | Bottle for liquid foodstuffs |
| GB2057962A (en) * | 1979-08-31 | 1981-04-08 | Aoki K | Stretch-blow moulding a two layer article |
| GB2067131A (en) * | 1979-11-30 | 1981-07-22 | Yoshino Kogyosho Co Ltd | Articles of polyethylene terephthalate resin |
| GB2091629A (en) * | 1981-01-22 | 1982-08-04 | Toyo Boseki | Blow-molded multiply vessel |
| EP0076366A2 (en) * | 1981-10-05 | 1983-04-13 | Ball Corporation | Multilayer tubular body with uncentered barrier layer |
| GB2131739A (en) * | 1982-10-14 | 1984-06-27 | Toyo Seikan Kaisha Ltd | Multi-layer drawn plastic vessel |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2153739A (en) * | 1983-12-27 | 1985-08-29 | Toyo Seikan Kaisha Ltd | Process for production of multi-layer polyethylene terephthalate pipes for (stretch) blow moulding |
| FR2595067A1 (en) * | 1986-02-28 | 1987-09-04 | Toyo Seikan Kaisha Ltd | PROCESS FOR MANUFACTURING A BIAXIALLY STRETCHED CONTAINER AND CONTAINER MANUFACTURED THEREBY |
| EP0747290A1 (en) * | 1995-06-07 | 1996-12-11 | Owens-Brockway Plastic Products Inc. | Hollow plastic container having a finish with a smaller diameter than the body of the container |
| GB2360077B (en) * | 1999-11-22 | 2004-07-28 | Chemisar Lab Inc | Impervious, chemically stable thermoplastic tubing and film |
| GB2360077A (en) * | 1999-11-22 | 2001-09-12 | Chemisar Lab Inc | Impervious chemically stable thermoplastic tubing and film |
| WO2002002417A3 (en) * | 2000-06-30 | 2002-05-30 | Schmalbach Lubeca | Plastic container having a crystallinity gradient |
| AU2001273100B2 (en) * | 2000-06-30 | 2004-10-21 | Amcor Limited | Plastic container having a crystallinity gradient |
| GB2366781A (en) * | 2000-09-19 | 2002-03-20 | Shya Hsin Plastic Works Co Ltd | Three-layer moulded container |
| AU2002216375B2 (en) * | 2000-12-20 | 2006-08-17 | Yoshino Kogyosho Co., Ltd. | Synthetic resin biaxial oriented blow formed preform for forming bottle body |
| US7115309B2 (en) * | 2000-12-20 | 2006-10-03 | Yoshino Kogyosho Co., Ltd. | Synthetic resin preform to be biaxially stretched and blow molded into a bottle |
| US7964257B2 (en) | 2000-12-20 | 2011-06-21 | Yoshino Kogyosho Co., Ltd. | Synthetic resin preform to be biaxially stretched and blow molded into a bottle |
| US8524342B2 (en) * | 2005-10-14 | 2013-09-03 | Evonik Degussa Gmbh | Plastic composite moulded bodies obtainable by welding in an electromagnetic alternating field |
| WO2008033765A2 (en) | 2006-09-15 | 2008-03-20 | The Coca-Cola Company | Multilayer container for enhanced gas barrier properties |
| WO2008033765A3 (en) * | 2006-09-15 | 2009-07-30 | Coca Cola Co | Multilayer container for enhanced gas barrier properties |
| RU2446952C2 (en) * | 2006-09-15 | 2012-04-10 | Дзе Кока-Кола Компани | Multilayer container with improved gas-barrier properties |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2141970B (en) | 1986-10-08 |
| SE8402336L (en) | 1984-10-29 |
| AU2743884A (en) | 1984-11-01 |
| SE468381B (en) | 1993-01-11 |
| SE8402336D0 (en) | 1984-04-27 |
| GB8410835D0 (en) | 1984-06-06 |
| AU571223B2 (en) | 1988-04-14 |
| CA1221318A (en) | 1987-05-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19950427 |