CA2573057A1 - Delamination-resistant multilayer container, preform and method of manufacture - Google Patents
Delamination-resistant multilayer container, preform and method of manufacture Download PDFInfo
- Publication number
- CA2573057A1 CA2573057A1 CA002573057A CA2573057A CA2573057A1 CA 2573057 A1 CA2573057 A1 CA 2573057A1 CA 002573057 A CA002573057 A CA 002573057A CA 2573057 A CA2573057 A CA 2573057A CA 2573057 A1 CA2573057 A1 CA 2573057A1
- Authority
- CA
- Canada
- Prior art keywords
- coupling agent
- blends
- evoh
- set forth
- barrier resin
- 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.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 230000032798 delamination Effects 0.000 title description 16
- 230000004888 barrier function Effects 0.000 claims abstract description 115
- 229920005989 resin Polymers 0.000 claims abstract description 89
- 239000011347 resin Substances 0.000 claims abstract description 89
- 239000007822 coupling agent Substances 0.000 claims abstract description 88
- 229920001225 polyester resin Polymers 0.000 claims abstract description 34
- 239000004645 polyester resin Substances 0.000 claims abstract description 34
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 32
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 29
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 21
- 229920000728 polyester Polymers 0.000 claims abstract description 19
- 229920003023 plastic Polymers 0.000 claims abstract description 17
- 239000004033 plastic Substances 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 15
- 150000004645 aluminates Chemical class 0.000 claims abstract description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 74
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 49
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 48
- 239000004677 Nylon Substances 0.000 claims description 36
- 229920001778 nylon Polymers 0.000 claims description 36
- 229920001577 copolymer Polymers 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 13
- 229920000954 Polyglycolide Polymers 0.000 claims description 11
- 239000004633 polyglycolic acid Substances 0.000 claims description 11
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 10
- 239000004713 Cyclic olefin copolymer Substances 0.000 claims description 10
- 239000004927 clay Substances 0.000 claims description 10
- 229920000554 ionomer Polymers 0.000 claims description 10
- 239000002114 nanocomposite Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 230000005540 biological transmission Effects 0.000 claims description 8
- 238000001746 injection moulding Methods 0.000 claims description 5
- 238000000071 blow moulding Methods 0.000 claims description 4
- 239000000796 flavoring agent Substances 0.000 claims description 4
- 235000019634 flavors Nutrition 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 2
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 claims 32
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 claims 20
- 239000010410 layer Substances 0.000 description 44
- 238000012360 testing method Methods 0.000 description 26
- 239000005020 polyethylene terephthalate Substances 0.000 description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 description 17
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 16
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 15
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 15
- 239000011112 polyethylene naphthalate Substances 0.000 description 8
- RIDDLDUJQDKUIH-UHFFFAOYSA-N 2-(2-aminoethylamino)ethanolate 2,2-bis(prop-2-enoxymethyl)butan-1-olate titanium(4+) Chemical compound [Ti+4].NCCNCC[O-].NCCNCC[O-].NCCNCC[O-].CCC(C[O-])(COCC=C)COCC=C RIDDLDUJQDKUIH-UHFFFAOYSA-N 0.000 description 7
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 7
- 230000000007 visual effect Effects 0.000 description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 206010034701 Peroneal nerve palsy Diseases 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003348 petrochemical agent Substances 0.000 description 2
- 239000000341 volatile oil Substances 0.000 description 2
- RUJFFQKEGVXJKJ-UHFFFAOYSA-K 3-aminophenolate 2,2-bis(prop-2-enoxymethyl)butan-1-olate titanium(4+) Chemical compound [Ti+4].Nc1cccc([O-])c1.Nc1cccc([O-])c1.Nc1cccc([O-])c1.CCC(C[O-])(COCC=C)COCC=C RUJFFQKEGVXJKJ-UHFFFAOYSA-K 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910000078 germane Inorganic materials 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- UPRXAOPZPSAYHF-UHFFFAOYSA-N lithium;cyclohexyl(propan-2-yl)azanide Chemical compound CC(C)N([Li])C1CCCCC1 UPRXAOPZPSAYHF-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/06—Making preforms by moulding the material
- B29B11/08—Injection moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B11/00—Making preforms
- B29B11/14—Making preforms characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0078—Measures or configurations for obtaining anchoring effects in the contact areas between layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/071—Preforms or parisons characterised by their configuration, e.g. geometry, dimensions or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D22/00—Producing hollow articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D22/00—Producing hollow articles
- B29D22/003—Containers for packaging, storing or transporting, e.g. bottles, jars, cans, barrels, tanks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B1/00—Layered products having a non-planar shape
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
-
- 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
- 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
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- 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
-
- 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
- B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2949/00—Indexing scheme relating to blow-moulding
- B29C2949/07—Preforms or parisons characterised by their configuration
- B29C2949/0715—Preforms or parisons characterised by their configuration the preform having one end closed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2009/00—Layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/42—Alternating layers, e.g. ABAB(C), AABBAABB(C)
-
- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/105—Metal
-
- 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
- B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
- B32B2307/7242—Non-permeable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/738—Thermoformability
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Geometry (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
A plastic container or preform includes a multilayer wall having at least one layer of polyester resin, at least one layer of barrier resin, and an adhesion-promoting material blended with the barrier resin and/or the polyester resin to promote bonding between the barrier and polyester layers. The adhesion-promoting material includes an organometallic coupling agent based upon titanium, zirconium or aluminum. The organometallic coupling agent preferably has an amino end group with an affinity for carboxylic end groups in the polyester, and preferably is selected from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamino) ethyl titanate, zirconate and aluminate. Coupling agents based upon titanium and zirconium are particularly preferred for containers and preforms having a clear (non-colored) wall.
Description
DELAMINATION-RESISTANT MULTILAYER CONTAINER PREFORM AND
METHOD OF MANUFACTURE
The present invention is directed to multilayer plastic containers and preforms, and to methods of manufacturing such containers and preforms.
Background and Summary of the Invention Multilayer plastic containers and preforms typically include one or more layers of plastic resin such as polyethylene terephthalate (PET) alternating with one or more layers of bai7ier resin such as nylon or ethylene vinyl alcohol (EVOH) to resist transmission of gas, water vapor and/or flavorants, including odorants and essential oils, through the container wall. An important property of containers of this type is interlaminar adhesion to resist delamination between or among the various layers during filling and handling of the containers by the container manufacturer and the product paclcager, and during use of the container by the consumer. Various tecluziques have been proposed for increasing interlaminar adhesion, which generally result in a decrease in barrier properties, an increase in manufacturing cost and/or an increase in other undesirable container properties such as haze in the -container wall. It is therefore a general object of the present invention to provide a multilayer container, a container preform and a method of manufacture having improved adhesion characteristics between the layers of the container (and preform) wall without significantly affecting container cost or other parameters of manufacture.
A plastic container in accordance with one presently preferred aspect of the invention includes a multilayer wall having at least one layer ofpolyester resin, at least one layer of barrier resin, and an adhesion-promoting material blended with the barrier resin and/or the polyester resin to promote bonding between the barrier and polyester layers.
In the preferred embodiments of the invention, the adhesion-promoting material is blended with the barrier resin.
The adhesion-promoting material includes an organometallic coupling agent based upon titanium, zirconium or aluminum. The organometallic coupling agent preferably has an amino end group with an affinity for the carboxylic end group of the polyester, and preferably is selected from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamino) ethyl titanate, zirconate and aluminate. Coupling agents based upon titanium and zirconium are particularly preferred for containers having a clear (non-colored) wall.
The polyester resin preferably is selected from the group consisting of PET, polyethylene naphthalate (PEN), blends and copolymers of PET and PEN, and process regrind that consists essentially of PET, PEN, or blends or copolymers of PET and PEN.
The barrier resin preferably is selected from the group consisting of EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid (PGA), and blends thereof.
EVOH and m eta-xylylenediamine (MXD) nylon are p articularly p referred. A
ctive o xygen absorbing barrier resins also may be employed in coinbination with or in place of the listed passive barrier resins.
Other aspects of the invention include a plastic container preform, methods of malcing a plastic container and a preform, a barrier resin blend, a method of processing a bairi.er resin and a multilayer article in accordance with the invention.
METHOD OF MANUFACTURE
The present invention is directed to multilayer plastic containers and preforms, and to methods of manufacturing such containers and preforms.
Background and Summary of the Invention Multilayer plastic containers and preforms typically include one or more layers of plastic resin such as polyethylene terephthalate (PET) alternating with one or more layers of bai7ier resin such as nylon or ethylene vinyl alcohol (EVOH) to resist transmission of gas, water vapor and/or flavorants, including odorants and essential oils, through the container wall. An important property of containers of this type is interlaminar adhesion to resist delamination between or among the various layers during filling and handling of the containers by the container manufacturer and the product paclcager, and during use of the container by the consumer. Various tecluziques have been proposed for increasing interlaminar adhesion, which generally result in a decrease in barrier properties, an increase in manufacturing cost and/or an increase in other undesirable container properties such as haze in the -container wall. It is therefore a general object of the present invention to provide a multilayer container, a container preform and a method of manufacture having improved adhesion characteristics between the layers of the container (and preform) wall without significantly affecting container cost or other parameters of manufacture.
A plastic container in accordance with one presently preferred aspect of the invention includes a multilayer wall having at least one layer ofpolyester resin, at least one layer of barrier resin, and an adhesion-promoting material blended with the barrier resin and/or the polyester resin to promote bonding between the barrier and polyester layers.
In the preferred embodiments of the invention, the adhesion-promoting material is blended with the barrier resin.
The adhesion-promoting material includes an organometallic coupling agent based upon titanium, zirconium or aluminum. The organometallic coupling agent preferably has an amino end group with an affinity for the carboxylic end group of the polyester, and preferably is selected from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamino) ethyl titanate, zirconate and aluminate. Coupling agents based upon titanium and zirconium are particularly preferred for containers having a clear (non-colored) wall.
The polyester resin preferably is selected from the group consisting of PET, polyethylene naphthalate (PEN), blends and copolymers of PET and PEN, and process regrind that consists essentially of PET, PEN, or blends or copolymers of PET and PEN.
The barrier resin preferably is selected from the group consisting of EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid (PGA), and blends thereof.
EVOH and m eta-xylylenediamine (MXD) nylon are p articularly p referred. A
ctive o xygen absorbing barrier resins also may be employed in coinbination with or in place of the listed passive barrier resins.
Other aspects of the invention include a plastic container preform, methods of malcing a plastic container and a preform, a barrier resin blend, a method of processing a bairi.er resin and a multilayer article in accordance with the invention.
Brief Description of the Drawings The invention, together with additional objects, features, advantages and aspects thereof, will be best understood from the following description, the appended claims and the accompanying drawings, in which:
FIGS. 1 to 4 are graplhic illustrations of test results on containers fabricated in accordance with exemplary einbodiments of the invention, FIGS. 5A and 5B are schematic diagrams of a container preform in accordance with one aspect of the invention, and FIGS. 6A and 6B are schematic diagrams of aplastic container in accordance with another aspect of the invention.
Detailed Description of Preferred Embodiments The Ken-React Reference Manual, published by Kenrich Petrochemicals, 2"a edition 1993, Bulletin KR 0401, is incorporated herein by reference.
Containers and preforms in accordance with the present invention have a multilayer wall with at least one layer of polyester resin alternating with at least one layer of barrier resin. (Additional layers not germane to the present invention may also be included, such as post consumer resin layers.) For example, a three-layer container or preform may have a wall with layers in the sequence polyester/barrier/polyester. A five-layer container or preform may have wall layers in the sequence polyester/barrier/polyester/barrier/polyester. The barrier layer or layers may extend throughout the bottom wall and the sidewall of the container or preform, or may be confined to a portion of the sidewall, for exanlple. The barrier layers may or may not extend into the fmish of the container or preform. FIGS. 6A and 6B are schematic illustrations of a five-layer container in accordance with the invention, the size and geometry being for illustrative purposes only. All exemplary test containers (and preforms) are five-layer containers (and preforms) of the type illustrated in FIGS. 6A and 6B (and FIGS. 5A and 5B), In accordance with one aspect of the present invention, an organometallic coupling agent based upon titanium, zirconium or aluminum is blended in each barrier layer and/or each polyester layer to promote adhesion between the barrier and polyester layers.
The polyester resin preferably is selected from the group consisting ofPET, PEN, blends and copolymers of PET and PEN, and process regrind that consists essentially of PET, PEN, or blends or copolymers of PET and PEN. In the examples discussed in the present application, the polyester resin was PET.
The barrier resin is a thermoplastic material that has a low gas and/or water vapor transmission rate, and/or exhibits a high barrier to transmission of flavorants including odorants and essential oils. The following materials are preferred: EVOH, nylon (including amorphous nylon and semicrystalline nylon such as MXD6), acrylonitrile copolymers, blends ofEVOH and nylon, blends of EVOH and an ionomer, cyclic olefin copolymers, PGA, nanocomposites of EVOH or nylon and clay, and blends thereof. EVOH and nylon are particularly preferred.
MXD6 nylon and EVOH were employed as bairier resins in the examples discussed in this application.
The organometallic coupling agents employed in the present invention preferably, although not necessarily, are marlceted by Kenrich Petrochemicals Inc. of Bayonne, New Jersey.
Coupling ageiits that are amino functionalized - i.e., that include. an amino end group - are ZO preferred. Such amino end groups in the coupling agent have an affmity for polyester, carbonyl and acid end groups in the structural resin layers. Neopentyl(diallyl)oxy, tri(N-ethylenediamino) ethyl titanate marlceted under the trade designation LICA-44 and neopentyl(diallyl)oxy, tri(N-ethylenediamino) ethyl zirconate marlceted under the trade designation NZ-44 are.particularly preferred. Corresponding organometallic coupling agents based upon aluminum can tint the wall of a clear (non-colored) plastic container, but may be employed where the container is intentionally colored and such tinting would not be an issue. Other coupling agents marketed by Kenrich and having amino end groups include isopropyl tri(N-ethylenediamino) ethyl titanate (KR-44), neopentyl (diallyl)oxy, tri(m-amino) phenyl titanate (LICA-97), dineopentyl(diallyl)oxy, diparamino beneoyl zirconate (NZ-37) andneopentyl(diallyl)oxy, tri(m-amino)phenyl zirconate (NZ-97). NZ-44 and LICA- 44 coupling agents were employed in the examples discussed in this application.
It is currently preferred that the coupling agent be blended with the barrier resin.
Because the barrier resin layers form a relatively small percentage by weight of the overall preform or container, a lesser quantity of coupling agent is required than if the coupling agent were blended with the polyester resin. However, the coupling agent could be blended with the polyester resin, or with both the polyester resin and the barrier resin, in accordance with the broadest aspects of the invention.
The organometallic coupling agent typically is in the form of a liquid, and preferably is blended witli the barrier resin material prior to forming the multilayer container.
In the tests described in this application, the liquid coupling agent additive was blended with particles ofthe barrier material (MXD6 or EVOH) at room temperature before feeding the blend to the extruder. This blending could also be done by master batch concentration by the barrier material supplier: The coupling agent acts as a melt phase modifier during the manufacturing process, w hich c an 1 ower t he p rocessing t emperature a nd/or p ermit u se o f h igher i ntrinsic viscosity (IV) barrier resins. Higher IV barrier resins tend to have better barrier properties, and thus the present invention facilitates improved barrier properties of the resin without increasing the thiclcness of the barrier resin layer. The following Table 1 shows plaque screening test results on MXD6 barrier material without coupling agent (control), or blended with either LICA-44 or NZ-44 coupling agent, or blended with LICA-12 (neopentyl(diallyl)oxy, tri(dioctyl)phosphato titanate) or NZ- 12 (neopentyl(diallyl)oxy, tri(dioctyl)phosphato zirconate) coupling agents also supplied by Kenrich:
Table 1 Additive Additive Processing Test Resin RV Resin IV Plaque Plaque IV
% Temp ( C) (dl/g) RV (dl/g) Control - 260 IV & Visual 1.8795 1.41 1.837 1.35 LICA-12 0.35 230 IV & Visual 1.8795 1.41 1.836 1.35 LICA-44 0.35 230 IV & Visual 1.8795 1.41 1.832 1.35 NZ-12 0.35 230 IV & Visual 1.8795 1.41 1.834 1.35 NZ-44 0.35 230 IV & Visual 1.8795 1.41 1.825 1.34 The plaques were made by injection molding at the processing temperatures indicated in the Table. The plaques were stepped plaques 6.25 in (15 8.75 mni) long by 1.75 in (44.45 mm) wide.
The plaques had five equal sections of stepped thicknesses of 0.16 in (4.06 mm), 0.13 in (3.3 mm), 0.10 in (2.54 inm), 0.07 in (1.78 nun) and 0.04 in (1 mm). The visual tests consisted of observation whether the plaque mold had completely filled. The control sanlple required a processing temperature of 260 C to fill the plaque mold completely, while the samples with coupling agents required a processing temperature of only, 230 C to fill the plaque mold completely. It will also be noted that LICA-12 and NZ-12 coupling agents, which have phosphate end groups rather than amino end groups, also achieved the reduced processing temperature, although these additives would not be preferred forpromoting adhesion to polyester layers because of the absence of the amino end groups.
Table 1 also indicates the relative viscosities (RV) and intrinsic viscosities (IV) of the base resin and the plaques. These viscosities were measured in a Viscotek model Y501 C
FIGS. 1 to 4 are graplhic illustrations of test results on containers fabricated in accordance with exemplary einbodiments of the invention, FIGS. 5A and 5B are schematic diagrams of a container preform in accordance with one aspect of the invention, and FIGS. 6A and 6B are schematic diagrams of aplastic container in accordance with another aspect of the invention.
Detailed Description of Preferred Embodiments The Ken-React Reference Manual, published by Kenrich Petrochemicals, 2"a edition 1993, Bulletin KR 0401, is incorporated herein by reference.
Containers and preforms in accordance with the present invention have a multilayer wall with at least one layer of polyester resin alternating with at least one layer of barrier resin. (Additional layers not germane to the present invention may also be included, such as post consumer resin layers.) For example, a three-layer container or preform may have a wall with layers in the sequence polyester/barrier/polyester. A five-layer container or preform may have wall layers in the sequence polyester/barrier/polyester/barrier/polyester. The barrier layer or layers may extend throughout the bottom wall and the sidewall of the container or preform, or may be confined to a portion of the sidewall, for exanlple. The barrier layers may or may not extend into the fmish of the container or preform. FIGS. 6A and 6B are schematic illustrations of a five-layer container in accordance with the invention, the size and geometry being for illustrative purposes only. All exemplary test containers (and preforms) are five-layer containers (and preforms) of the type illustrated in FIGS. 6A and 6B (and FIGS. 5A and 5B), In accordance with one aspect of the present invention, an organometallic coupling agent based upon titanium, zirconium or aluminum is blended in each barrier layer and/or each polyester layer to promote adhesion between the barrier and polyester layers.
The polyester resin preferably is selected from the group consisting ofPET, PEN, blends and copolymers of PET and PEN, and process regrind that consists essentially of PET, PEN, or blends or copolymers of PET and PEN. In the examples discussed in the present application, the polyester resin was PET.
The barrier resin is a thermoplastic material that has a low gas and/or water vapor transmission rate, and/or exhibits a high barrier to transmission of flavorants including odorants and essential oils. The following materials are preferred: EVOH, nylon (including amorphous nylon and semicrystalline nylon such as MXD6), acrylonitrile copolymers, blends ofEVOH and nylon, blends of EVOH and an ionomer, cyclic olefin copolymers, PGA, nanocomposites of EVOH or nylon and clay, and blends thereof. EVOH and nylon are particularly preferred.
MXD6 nylon and EVOH were employed as bairier resins in the examples discussed in this application.
The organometallic coupling agents employed in the present invention preferably, although not necessarily, are marlceted by Kenrich Petrochemicals Inc. of Bayonne, New Jersey.
Coupling ageiits that are amino functionalized - i.e., that include. an amino end group - are ZO preferred. Such amino end groups in the coupling agent have an affmity for polyester, carbonyl and acid end groups in the structural resin layers. Neopentyl(diallyl)oxy, tri(N-ethylenediamino) ethyl titanate marlceted under the trade designation LICA-44 and neopentyl(diallyl)oxy, tri(N-ethylenediamino) ethyl zirconate marlceted under the trade designation NZ-44 are.particularly preferred. Corresponding organometallic coupling agents based upon aluminum can tint the wall of a clear (non-colored) plastic container, but may be employed where the container is intentionally colored and such tinting would not be an issue. Other coupling agents marketed by Kenrich and having amino end groups include isopropyl tri(N-ethylenediamino) ethyl titanate (KR-44), neopentyl (diallyl)oxy, tri(m-amino) phenyl titanate (LICA-97), dineopentyl(diallyl)oxy, diparamino beneoyl zirconate (NZ-37) andneopentyl(diallyl)oxy, tri(m-amino)phenyl zirconate (NZ-97). NZ-44 and LICA- 44 coupling agents were employed in the examples discussed in this application.
It is currently preferred that the coupling agent be blended with the barrier resin.
Because the barrier resin layers form a relatively small percentage by weight of the overall preform or container, a lesser quantity of coupling agent is required than if the coupling agent were blended with the polyester resin. However, the coupling agent could be blended with the polyester resin, or with both the polyester resin and the barrier resin, in accordance with the broadest aspects of the invention.
The organometallic coupling agent typically is in the form of a liquid, and preferably is blended witli the barrier resin material prior to forming the multilayer container.
In the tests described in this application, the liquid coupling agent additive was blended with particles ofthe barrier material (MXD6 or EVOH) at room temperature before feeding the blend to the extruder. This blending could also be done by master batch concentration by the barrier material supplier: The coupling agent acts as a melt phase modifier during the manufacturing process, w hich c an 1 ower t he p rocessing t emperature a nd/or p ermit u se o f h igher i ntrinsic viscosity (IV) barrier resins. Higher IV barrier resins tend to have better barrier properties, and thus the present invention facilitates improved barrier properties of the resin without increasing the thiclcness of the barrier resin layer. The following Table 1 shows plaque screening test results on MXD6 barrier material without coupling agent (control), or blended with either LICA-44 or NZ-44 coupling agent, or blended with LICA-12 (neopentyl(diallyl)oxy, tri(dioctyl)phosphato titanate) or NZ- 12 (neopentyl(diallyl)oxy, tri(dioctyl)phosphato zirconate) coupling agents also supplied by Kenrich:
Table 1 Additive Additive Processing Test Resin RV Resin IV Plaque Plaque IV
% Temp ( C) (dl/g) RV (dl/g) Control - 260 IV & Visual 1.8795 1.41 1.837 1.35 LICA-12 0.35 230 IV & Visual 1.8795 1.41 1.836 1.35 LICA-44 0.35 230 IV & Visual 1.8795 1.41 1.832 1.35 NZ-12 0.35 230 IV & Visual 1.8795 1.41 1.834 1.35 NZ-44 0.35 230 IV & Visual 1.8795 1.41 1.825 1.34 The plaques were made by injection molding at the processing temperatures indicated in the Table. The plaques were stepped plaques 6.25 in (15 8.75 mni) long by 1.75 in (44.45 mm) wide.
The plaques had five equal sections of stepped thicknesses of 0.16 in (4.06 mm), 0.13 in (3.3 mm), 0.10 in (2.54 inm), 0.07 in (1.78 nun) and 0.04 in (1 mm). The visual tests consisted of observation whether the plaque mold had completely filled. The control sanlple required a processing temperature of 260 C to fill the plaque mold completely, while the samples with coupling agents required a processing temperature of only, 230 C to fill the plaque mold completely. It will also be noted that LICA-12 and NZ-12 coupling agents, which have phosphate end groups rather than amino end groups, also achieved the reduced processing temperature, although these additives would not be preferred forpromoting adhesion to polyester layers because of the absence of the amino end groups.
Table 1 also indicates the relative viscosities (RV) and intrinsic viscosities (IV) of the base resin and the plaques. These viscosities were measured in a Viscotek model Y501 C
viscometer employing standard dilute solution viscometrytechniques. Relative viscosities were measured at the "low" range of the equipment. Intrinsic viscosities were measured as described in the equipment manual with use of the Solomon-Gatesman equation. Resin viscosities were measured at 30 C in 60:40 Phenol:1,1,2,2 Tetrachloroethane. Thus, as shown in Table 1, the coupling agents permitted the processing temperature to be lowered 30 C and still make good plaques. The control (MXD6 without coupling agent) could not be processed at temperatures below 260 C in the equipment employed. (The same Arburg Model 320-210-500 molding equipment was employed for all tests.) There were no significant differences among the intrinsic viscosities of the blends and the control, demonstrating that there was no degradation of the polymer molecular weight.
The following Table 2 demonstrates the increase in barrier properties employing an MXD6 barrier resin of higher intrinsic viscosity (IV), which was enabled by blending the barrier resin with the coupling agent. In test containers of Table 2, the containers with M]XD6 barrier resin were of the five-layer construction of FIGS, 6A and 6B, with the total weight percentages of barrier resin (blended with coupling agent) being 3%, such that each barrier layer was approximately 1.5 wt % of the total container weight. That is, the NZ-44 coupling agent was 0.5 wt % of the total barrier resin, and the blend of coupling agent and barrier resin was 3 wt%
of the containers.
The following Table 2 demonstrates the increase in barrier properties employing an MXD6 barrier resin of higher intrinsic viscosity (IV), which was enabled by blending the barrier resin with the coupling agent. In test containers of Table 2, the containers with M]XD6 barrier resin were of the five-layer construction of FIGS, 6A and 6B, with the total weight percentages of barrier resin (blended with coupling agent) being 3%, such that each barrier layer was approximately 1.5 wt % of the total container weight. That is, the NZ-44 coupling agent was 0.5 wt % of the total barrier resin, and the blend of coupling agent and barrier resin was 3 wt%
of the containers.
Table 2 Container Container Construction MXD6 IV* (dUg) NZ-44 % Transmission**
(cc-CO2/day) Monolayer PET N/A N/A 1.60 3% MXD6 1.41 0.5 1.00 3% MXD6 1.60 0.5 0.78 * Measured @ 30 C in 60:40 Phenol : 1,1,2,2 Tetrachloroethane en7ploying the Viscotek equipment and techniques discussed above.
28mm 500 ml beverage containers were filled at 3.0 gas volumes of C 02 b y c hemical carbonation techniques and were capped with 28 mm closures. These closures were polypropylene closures with ethylene vinyl acetate (EVA) liners as disclosed in U.S. Patent 5,306,542. After being allowed to equilibrate for 14 days at 68F/50% RH
storage, the total container CO2 transmission rate was measured by placing the container within a sealed vessel with a known capture volume. The sealed vessel had two ports through which nitrogen carrier gas flowed in through one of the ports and exited the vessel from the other port.. The exit port was directed to a Mocon C-IV CO2 test machine used for detecting the amount of COa. The quantity of COz was measured for a period of time, from which the COZ
transmission rate was deternzined.
The process of container manufacture preferably involves manufacture of a preform, followed by blow molding the preform to form the container. In the examples discussed in this application, the preform was fomzed in a sequential injection molding operation of a type illustrated in U.S. Patents 4,550,043, 4,609,516, 4,710,118 and 4,954,376.
FIGS. 5A and 5B are a schematic illustrations of a preform in accordance with the invention, the size and geometry being for illustrative purposes only. However, the preform can also be formed in a simultaneous injection molding operation of a type illustrated in U.S. Patents 4,990,301 and 5,098,274, an over-molding operation of a type illustrated in U.S. Patent 6,428,737, a compression molding operation of a type illustrated in U.S. published application 2002/0098310 using a mold cliarge that includes the polyester resin and the barrier resin/coupling agent blend, or in a coextrusion operation that produces a hollow tube having alternate layers ofpolyester resin and barrier resin blend. These specific citations are merely exemplary.
The amount of coupling agent blended with the barrier resin preferably does not exceed about 4% by weight of the blend. The amount of coupling agent more preferably does not exceed about 1.5% by weight of the blend. All percentages in this application are by weight unless otherwise indicated.
The presently preferred coupling agents identified above are well suited for the chemistries of the disclosed barrier and polyester resins. The chemical functionalities of the coupling agents do not affect the processability or barrier properties of the barrierinaterial, other than acting as a melt phase modifier as discussed above. The preferred organometallic coupling agents promote bonding between the polyester and barrier resin layers while the materials are in contact at elevated melt temperatures; it was difficult to separate the layers of a preform after the preform had cooled. While not being bound by any particular theory or mechanism, one theory is that the bonding between the polyester resin layers and the barrier resin layers promoted by the organometallic coupling agents includes covalent bonding, ionic bonding and/or polar bonding depending upon the type of barrier resin employed.
FIGS. 1-4 illustrate delamination test results on various container samples constructed in accordance with the present invention. Each container had a five-layer wall of PET/MXD6/PET/MXD6/PET configuration (FIGS. 1-3B) or PET/EVOH/PET/EVOH/PET
:0 configuration (FIG. 4). In all tests, the containers were experimental containers constructed for comparison purposes only. The tests were arbitrarily devised to obtain differentiation in data, and do not reflect anyperfom7ance specification or conditions ofuse. In each figure, the ordinate indicates the percentage of containers in which delamination was observed by visual inspection as a result of the test, while the abscissa indicates the container structure, specifically the total amount of barrier material by weight and the amount of NZ- 44 or LICA 44 coupling agent employed. With the exception of the amount and type of coupling agent (NZ-44 or LICA-44), and the type of barrier resin employed (EVOH or MXD6), all containers in each test were identical.
FIG. 1 illustrates the results of drop tests performed on twenty-four ounce non-round containers having a rounded rectangular cross section. The containers were filled with water, in which a blue dye was added to facilitate visual identification of delaminations where they occurred. The barrier layers totaled 1.5% of the containers by weight, with the percentages of NZ-44 or LICA-44 indicated in FIG. 1 (and in FIGS. 2A-4) being percentages of the total barrier layers -e.g., 0.20% of the 1.5% barrier layer or 0.003 % coupling agent based upon the total weight of the container. The filled containers were dropped onto a cement base from a height of three feet so that the containers iinpacted on their bottoms, and then were examined for delamination. As shown in FIG. 1, approximately 22% of the containers showed delainination without the NZ-44 or LICA-44 coupling agent in the barrier layers. The containers 1.5 having MXD6 blended with 0.2 % LICA-44 showed delamination in 10% ofthe containers. The percentage of containers showing delainination progressively decreased in container have 0.20%, 0,35% and 0.50% NZ-44. The last column in FIG. 1 shows delamination in 5% of containers when NZ-44 in the amount of 0.50% by weight was mixed with the MXD6 barrier material. This percentage ofNZ-44 zirconate coupling agent was then employed in subsequent tests (FIGS. 2A-4).
FIGS. 2A and 2B illustrate side-impact test results on 400 ml cylindrical carbonated beverage containers. This side-impact testing involved a single impact against the container sidewall with a steel wedge and with the container clamped in stationary position. The energy of the impact was approximately 3.3 joules. FIG. 2A illustrates test results with the containers filled with water, and FIG. 2B illustrates test results with the containers filled with water and carbonated at 3.0 GV (gas volumes). The barrier resin layers totaled 3% by weight of the containers. In the sa.inples having a coupling agent, the coupling agent was in the amount of 0.50% of the total barrier resin layers. Both FIGS. 2A and 2B show significant percentages of containers without the coupling agents of the present invention exhibiting delainination after testing, while containers in which the coupling agent was blended with the barrier resin exhibited no delamination after testing.
FIGS. 3A and 3B illustrate the results of drop tests on higllly embossed 500 ml cylindrical beverage containers. These embossments were decorative design details molded into the container walls, and tend to act as stress concentrators and promote delamination in the container walls. In both of the tests ofFIG. 3A and 3B, the containers were filled with water and dropped onto a ceinent base to iinpact on their bottoms. FIG. 3A illustrates the results of a three-foot drop. The containers containing MXD6 barrier material exhibited delamination in 6% of the containers, while the containers having NIXD6 with 0.50% NZ-44 in the barrier layers exhibited no delamination. The drop height was then increased to six feet, with the results being illustrated in FIG. 3B. The containers without coupling agents exhibited delamination in 42%
of the containers, while the containers with coupling agent exhibited delamination in only about 8% ofthe containers. The coupling agent/barrier resin blend constituted 3% of the total container weight in the tests of FIGS. 3A and 3B.
FIG. 4 illustrates the results of a three-foot drop test on eight ounce cylindrical containers having 5% EVOH (or EVOH blended with coupling agent) as the barrier layer. In the three-foot drop test, in which the water-filled container was dropped onto its base as described above in connection with FIG. 1, FIG. 4 shows that there was a 20% reduction in delamination when the coupling agent was blended with the barrier material. In a side-iinpact test, in which the water-filled container was impacted on its sidewall as described above in connection with FIG. 2A, the containers showed no delamination both with and without the coupling agent.
There have thus been disclosed a multilayer container, a multilayer preform, a barrier resin blend for use in a multilayer container, a method of making a multilayerprefonn or container, and a multilayer plastic article of manufacture that fully satisfy all of the objects and aims previously set forth. The container, barrier blend and method of manufacture have been disclosed in conjunction with a number of exemplary embodiments thereof, and several niodifications and variations have been discussed. Other modifications and variations will readily suggest themselves to persons of ordinary skill in the art. For example, the invention in its broadest aspects can also be applied to other articles of manufacture having multilayer walls, particularly walls with one or more barrier layers, such as container closures and liners, or films or sheets for later thermoforming, without departing from the scope of the invention in its broadest aspects. The invention is intended to embrace all such modifications and variations as fall within the spirit and broad scope of the appended claims.
(cc-CO2/day) Monolayer PET N/A N/A 1.60 3% MXD6 1.41 0.5 1.00 3% MXD6 1.60 0.5 0.78 * Measured @ 30 C in 60:40 Phenol : 1,1,2,2 Tetrachloroethane en7ploying the Viscotek equipment and techniques discussed above.
28mm 500 ml beverage containers were filled at 3.0 gas volumes of C 02 b y c hemical carbonation techniques and were capped with 28 mm closures. These closures were polypropylene closures with ethylene vinyl acetate (EVA) liners as disclosed in U.S. Patent 5,306,542. After being allowed to equilibrate for 14 days at 68F/50% RH
storage, the total container CO2 transmission rate was measured by placing the container within a sealed vessel with a known capture volume. The sealed vessel had two ports through which nitrogen carrier gas flowed in through one of the ports and exited the vessel from the other port.. The exit port was directed to a Mocon C-IV CO2 test machine used for detecting the amount of COa. The quantity of COz was measured for a period of time, from which the COZ
transmission rate was deternzined.
The process of container manufacture preferably involves manufacture of a preform, followed by blow molding the preform to form the container. In the examples discussed in this application, the preform was fomzed in a sequential injection molding operation of a type illustrated in U.S. Patents 4,550,043, 4,609,516, 4,710,118 and 4,954,376.
FIGS. 5A and 5B are a schematic illustrations of a preform in accordance with the invention, the size and geometry being for illustrative purposes only. However, the preform can also be formed in a simultaneous injection molding operation of a type illustrated in U.S. Patents 4,990,301 and 5,098,274, an over-molding operation of a type illustrated in U.S. Patent 6,428,737, a compression molding operation of a type illustrated in U.S. published application 2002/0098310 using a mold cliarge that includes the polyester resin and the barrier resin/coupling agent blend, or in a coextrusion operation that produces a hollow tube having alternate layers ofpolyester resin and barrier resin blend. These specific citations are merely exemplary.
The amount of coupling agent blended with the barrier resin preferably does not exceed about 4% by weight of the blend. The amount of coupling agent more preferably does not exceed about 1.5% by weight of the blend. All percentages in this application are by weight unless otherwise indicated.
The presently preferred coupling agents identified above are well suited for the chemistries of the disclosed barrier and polyester resins. The chemical functionalities of the coupling agents do not affect the processability or barrier properties of the barrierinaterial, other than acting as a melt phase modifier as discussed above. The preferred organometallic coupling agents promote bonding between the polyester and barrier resin layers while the materials are in contact at elevated melt temperatures; it was difficult to separate the layers of a preform after the preform had cooled. While not being bound by any particular theory or mechanism, one theory is that the bonding between the polyester resin layers and the barrier resin layers promoted by the organometallic coupling agents includes covalent bonding, ionic bonding and/or polar bonding depending upon the type of barrier resin employed.
FIGS. 1-4 illustrate delamination test results on various container samples constructed in accordance with the present invention. Each container had a five-layer wall of PET/MXD6/PET/MXD6/PET configuration (FIGS. 1-3B) or PET/EVOH/PET/EVOH/PET
:0 configuration (FIG. 4). In all tests, the containers were experimental containers constructed for comparison purposes only. The tests were arbitrarily devised to obtain differentiation in data, and do not reflect anyperfom7ance specification or conditions ofuse. In each figure, the ordinate indicates the percentage of containers in which delamination was observed by visual inspection as a result of the test, while the abscissa indicates the container structure, specifically the total amount of barrier material by weight and the amount of NZ- 44 or LICA 44 coupling agent employed. With the exception of the amount and type of coupling agent (NZ-44 or LICA-44), and the type of barrier resin employed (EVOH or MXD6), all containers in each test were identical.
FIG. 1 illustrates the results of drop tests performed on twenty-four ounce non-round containers having a rounded rectangular cross section. The containers were filled with water, in which a blue dye was added to facilitate visual identification of delaminations where they occurred. The barrier layers totaled 1.5% of the containers by weight, with the percentages of NZ-44 or LICA-44 indicated in FIG. 1 (and in FIGS. 2A-4) being percentages of the total barrier layers -e.g., 0.20% of the 1.5% barrier layer or 0.003 % coupling agent based upon the total weight of the container. The filled containers were dropped onto a cement base from a height of three feet so that the containers iinpacted on their bottoms, and then were examined for delamination. As shown in FIG. 1, approximately 22% of the containers showed delainination without the NZ-44 or LICA-44 coupling agent in the barrier layers. The containers 1.5 having MXD6 blended with 0.2 % LICA-44 showed delamination in 10% ofthe containers. The percentage of containers showing delainination progressively decreased in container have 0.20%, 0,35% and 0.50% NZ-44. The last column in FIG. 1 shows delamination in 5% of containers when NZ-44 in the amount of 0.50% by weight was mixed with the MXD6 barrier material. This percentage ofNZ-44 zirconate coupling agent was then employed in subsequent tests (FIGS. 2A-4).
FIGS. 2A and 2B illustrate side-impact test results on 400 ml cylindrical carbonated beverage containers. This side-impact testing involved a single impact against the container sidewall with a steel wedge and with the container clamped in stationary position. The energy of the impact was approximately 3.3 joules. FIG. 2A illustrates test results with the containers filled with water, and FIG. 2B illustrates test results with the containers filled with water and carbonated at 3.0 GV (gas volumes). The barrier resin layers totaled 3% by weight of the containers. In the sa.inples having a coupling agent, the coupling agent was in the amount of 0.50% of the total barrier resin layers. Both FIGS. 2A and 2B show significant percentages of containers without the coupling agents of the present invention exhibiting delainination after testing, while containers in which the coupling agent was blended with the barrier resin exhibited no delamination after testing.
FIGS. 3A and 3B illustrate the results of drop tests on higllly embossed 500 ml cylindrical beverage containers. These embossments were decorative design details molded into the container walls, and tend to act as stress concentrators and promote delamination in the container walls. In both of the tests ofFIG. 3A and 3B, the containers were filled with water and dropped onto a ceinent base to iinpact on their bottoms. FIG. 3A illustrates the results of a three-foot drop. The containers containing MXD6 barrier material exhibited delamination in 6% of the containers, while the containers having NIXD6 with 0.50% NZ-44 in the barrier layers exhibited no delamination. The drop height was then increased to six feet, with the results being illustrated in FIG. 3B. The containers without coupling agents exhibited delamination in 42%
of the containers, while the containers with coupling agent exhibited delamination in only about 8% ofthe containers. The coupling agent/barrier resin blend constituted 3% of the total container weight in the tests of FIGS. 3A and 3B.
FIG. 4 illustrates the results of a three-foot drop test on eight ounce cylindrical containers having 5% EVOH (or EVOH blended with coupling agent) as the barrier layer. In the three-foot drop test, in which the water-filled container was dropped onto its base as described above in connection with FIG. 1, FIG. 4 shows that there was a 20% reduction in delamination when the coupling agent was blended with the barrier material. In a side-iinpact test, in which the water-filled container was impacted on its sidewall as described above in connection with FIG. 2A, the containers showed no delamination both with and without the coupling agent.
There have thus been disclosed a multilayer container, a multilayer preform, a barrier resin blend for use in a multilayer container, a method of making a multilayerprefonn or container, and a multilayer plastic article of manufacture that fully satisfy all of the objects and aims previously set forth. The container, barrier blend and method of manufacture have been disclosed in conjunction with a number of exemplary embodiments thereof, and several niodifications and variations have been discussed. Other modifications and variations will readily suggest themselves to persons of ordinary skill in the art. For example, the invention in its broadest aspects can also be applied to other articles of manufacture having multilayer walls, particularly walls with one or more barrier layers, such as container closures and liners, or films or sheets for later thermoforming, without departing from the scope of the invention in its broadest aspects. The invention is intended to embrace all such modifications and variations as fall within the spirit and broad scope of the appended claims.
Claims (44)
1.
A plastic container having a multilayer wall that includes:
at least one layer of polyester resin, at least one layer of barrier resin, and an adhesion-promoting material blended with said barrier resin and/or said polyester resin to promote bonding between said barrier and polyester layers, said adhesion-promoting material including an organometallic coupling agent based upon titanium, zirconium or aluminum.
A plastic container having a multilayer wall that includes:
at least one layer of polyester resin, at least one layer of barrier resin, and an adhesion-promoting material blended with said barrier resin and/or said polyester resin to promote bonding between said barrier and polyester layers, said adhesion-promoting material including an organometallic coupling agent based upon titanium, zirconium or aluminum.
2.
The container set forth in claim 1 wherein said organometallic coupling agent includes an amino end group.
The container set forth in claim 1 wherein said organometallic coupling agent includes an amino end group.
3.
The container set forth in claim 2 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
The container set forth in claim 2 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
4.
The container set forth in claim 3 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
The container set forth in claim 3 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
5.
The container set forth in claim 1 wherein said polyester resin is selected from the group consisting of: PET, PEN, blends or copolymers of PET and PEN, and process regrind consisting essentially of PET, PEN, or blends or copolymers of PET and PEN.
The container set forth in claim 1 wherein said polyester resin is selected from the group consisting of: PET, PEN, blends or copolymers of PET and PEN, and process regrind consisting essentially of PET, PEN, or blends or copolymers of PET and PEN.
6.
The container set forth in claim 1 wherein said barrier resin is selected from the group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.
The container set forth in claim 1 wherein said barrier resin is selected from the group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.
7.
A plastic container having a multilayer wall that includes:
at least one layer of polyester resin selected from the, group consisting of PET, PEN, blends or copolymers of PET and PEN, and process regrind that consists essentially of PET, PEN, or blends or copolymers of PET and PEN, at least one layer of barrier resin selected from the group consisting of EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof, and an organometallic coupling agent blended in said at least one layer of barrier resin to promote bonding between said barrier and polyester layers, said organometallic coupling agent having an amino end group that has an affinity for carboxylic end groups in the polyester resin and being selected from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
A plastic container having a multilayer wall that includes:
at least one layer of polyester resin selected from the, group consisting of PET, PEN, blends or copolymers of PET and PEN, and process regrind that consists essentially of PET, PEN, or blends or copolymers of PET and PEN, at least one layer of barrier resin selected from the group consisting of EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof, and an organometallic coupling agent blended in said at least one layer of barrier resin to promote bonding between said barrier and polyester layers, said organometallic coupling agent having an amino end group that has an affinity for carboxylic end groups in the polyester resin and being selected from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
8.
The container set forth in claim 7 wherein said coupling agent is selected from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
The container set forth in claim 7 wherein said coupling agent is selected from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
9.
The container set forth in claim 8 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
The container set forth in claim 8 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
10.
A barrier resin blend for use in a layered plastic container, said barrier resin blend including:
a barrier resin to resist transmission of gas, water vapor or flavorants, and an organometallic coupling agent based on titanium, zirconium or aluminum, said coupling agent having an amino end group to promote bonding between said barrier resin and adjacent layers in a container.
A barrier resin blend for use in a layered plastic container, said barrier resin blend including:
a barrier resin to resist transmission of gas, water vapor or flavorants, and an organometallic coupling agent based on titanium, zirconium or aluminum, said coupling agent having an amino end group to promote bonding between said barrier resin and adjacent layers in a container.
11.
The barrier resin blend set forth in claim 10 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
The barrier resin blend set forth in claim 10 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
12.
The barrier resin blend set forth in claim 11 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
The barrier resin blend set forth in claim 11 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
13.
The barrier resin blend set forth in claim 10 wherein said barrier resin is selected from the group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.
The barrier resin blend set forth in claim 10 wherein said barrier resin is selected from the group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.
14.
A method of making a multilayer plastic container that includes:
(a) blending an organometallic coupling agent based on titanium, zirconium or aluminum with a barrier resin, and (b) forming a preform in which the blend formed in step (a) is in layers alternating with layers of polyester resin, and in which said coupling agent promotes bonding between said barrier resin and said polyester resin.
A method of making a multilayer plastic container that includes:
(a) blending an organometallic coupling agent based on titanium, zirconium or aluminum with a barrier resin, and (b) forming a preform in which the blend formed in step (a) is in layers alternating with layers of polyester resin, and in which said coupling agent promotes bonding between said barrier resin and said polyester resin.
15.
The process set forth in claim 14 further including: (c) blow molding the preform formed in step (b) into a hollow plastic container.
The process set forth in claim 14 further including: (c) blow molding the preform formed in step (b) into a hollow plastic container.
16.
The method set forth in claim 14 wherein said step (b) is carried out while said blend formed in said step (a) and said polyester resin are in melt phase.
The method set forth in claim 14 wherein said step (b) is carried out while said blend formed in said step (a) and said polyester resin are in melt phase.
17.
The method set forth in claim 16 wherein said step (b) is carried out by a process selected from the group consisting of simultaneously injection molding said polyester resin and said barrier resin blend, sequentially injection molding said polyester resin and said barrier resin blend, overmolding sequential layers of said polyester resin and said barrier resin blend, compression molding a mold charge that includes said polyester resin and said barrier resin blend, and extruding a hollow tube that includes alternate layers of said polyester resin and said barrier resin blend.
The method set forth in claim 16 wherein said step (b) is carried out by a process selected from the group consisting of simultaneously injection molding said polyester resin and said barrier resin blend, sequentially injection molding said polyester resin and said barrier resin blend, overmolding sequential layers of said polyester resin and said barrier resin blend, compression molding a mold charge that includes said polyester resin and said barrier resin blend, and extruding a hollow tube that includes alternate layers of said polyester resin and said barrier resin blend.
18.
The method set forth in claim 14 wherein said coupling agent has an amino end group.
The method set forth in claim 14 wherein said coupling agent has an amino end group.
19.
The method set forth in claim 18 wherein said organometallic coupling agent is.
selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
The method set forth in claim 18 wherein said organometallic coupling agent is.
selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
20.
The method set forth in claim 19 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
The method set forth in claim 19 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
21.
The method set forth in claim 18 wherein said polyester resin is selected from the group consisting of: PET, PEN, blends or copolymers of PET and PEN, and process regrind consisting essentially of PET, PEN, or blends or copolymers of PET and PEN.
The method set forth in claim 18 wherein said polyester resin is selected from the group consisting of: PET, PEN, blends or copolymers of PET and PEN, and process regrind consisting essentially of PET, PEN, or blends or copolymers of PET and PEN.
22.
The method set forth in claim 18 wherein said barrier resin is selected from the group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.
The method set forth in claim 18 wherein said barrier resin is selected from the group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.
23.
A preform for blow molding a plastic container having a multilayer wall, which includes:
at least one layer of polyester resin, at least one layer of barrier resin, and an adhesion-promoting material blended with said barrier resin and/or said polyester resin to promote bonding between said barrier and polyester layers, said adhesion-promoting material including an organometallic coupling agent based upon titanium, zirconium or, aluminum.
A preform for blow molding a plastic container having a multilayer wall, which includes:
at least one layer of polyester resin, at least one layer of barrier resin, and an adhesion-promoting material blended with said barrier resin and/or said polyester resin to promote bonding between said barrier and polyester layers, said adhesion-promoting material including an organometallic coupling agent based upon titanium, zirconium or, aluminum.
24.
The preform set forth in claim 23 wherein said organometallic coupling agent includes an amino end group.
The preform set forth in claim 23 wherein said organometallic coupling agent includes an amino end group.
25.
The preform set forth in claim 24 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
The preform set forth in claim 24 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
26.
The preform set forth in claim 25 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
The preform set forth in claim 25 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
27.
The preform set forth in claim 23 wherein said polyester resin is selected from the group consisting of: PET, PEN, blends or copolymers of PET and PEN, and process regrind consisting essentially of PET, PEN, or blends or copolymers of PET and PEN.
The preform set forth in claim 23 wherein said polyester resin is selected from the group consisting of: PET, PEN, blends or copolymers of PET and PEN, and process regrind consisting essentially of PET, PEN, or blends or copolymers of PET and PEN.
28.
The preform set forth in claim 23 wherein said barrier resin is selected from the group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.
The preform set forth in claim 23 wherein said barrier resin is selected from the group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.
29.
A preform for blow molding a plastic container having a multilayer wall, which includes:
at least one layer of polyester resin selected from the group consisting of PET, PEN, blends or copolymers of PET and PEN, and process regrind that consists essentially of PET, PEN, or blends or copolymers of PET and PEN, at least one layer of barrier resin selected from the group consisting of EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof, and an organometallic coupling agent blended in said at least one layer of barrier resin to promote bonding between said barrier and polyester layers, said organometallic coupling agent having an amino end group that has an affinity for carboxylic end groups in the polyester resin and being selected from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
A preform for blow molding a plastic container having a multilayer wall, which includes:
at least one layer of polyester resin selected from the group consisting of PET, PEN, blends or copolymers of PET and PEN, and process regrind that consists essentially of PET, PEN, or blends or copolymers of PET and PEN, at least one layer of barrier resin selected from the group consisting of EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof, and an organometallic coupling agent blended in said at least one layer of barrier resin to promote bonding between said barrier and polyester layers, said organometallic coupling agent having an amino end group that has an affinity for carboxylic end groups in the polyester resin and being selected from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
30.
The preform set forth in claim 29 wherein said coupling agent is selected from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
The preform set forth in claim 29 wherein said coupling agent is selected from the group consisting of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
31.
The preform set forth in claim 30 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
The preform set forth in claim 30 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
32.
A barrier resin blend for use in a layered plastic container, said barrier resin blend including:
a barrier resin to resist transmission of gas, water vapor or flavorants, and an organometallic coupling agent based on titanium, zirconium or aluminum, said coupling agent functioning as a melt phase modifier to said barrier resin and lowering the temperature required to process said barrier resin in melt phase.
A barrier resin blend for use in a layered plastic container, said barrier resin blend including:
a barrier resin to resist transmission of gas, water vapor or flavorants, and an organometallic coupling agent based on titanium, zirconium or aluminum, said coupling agent functioning as a melt phase modifier to said barrier resin and lowering the temperature required to process said barrier resin in melt phase.
33.
The barrier resin blend set forth in claim 32 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
The barrier resin blend set forth in claim 32 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
34.
The barrier resin blend set forth in claim 33 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
The barrier resin blend set forth in claim 33 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
35.
The barrier resin blend set forth in claim 32 wherein said barrier resin is selected from the group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.
The barrier resin blend set forth in claim 32 wherein said barrier resin is selected from the group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.
36.
A method of processing a barrier resin having a predetermined intrinsic viscosity, which includes:
(a) processing said barrier resin in melt phase, and (b) blending said barrier resin prior to or during said step (a) with a melt phase modifier that includes an organometallic coupling agent based upon titanium, zirconium or aluminum to reduce the temperature required in said step (a) to process said barrier resin in melt phase.
A method of processing a barrier resin having a predetermined intrinsic viscosity, which includes:
(a) processing said barrier resin in melt phase, and (b) blending said barrier resin prior to or during said step (a) with a melt phase modifier that includes an organometallic coupling agent based upon titanium, zirconium or aluminum to reduce the temperature required in said step (a) to process said barrier resin in melt phase.
37.
The method set forth in claim 36 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate, and neopentyl(diallyl)oxy, tri(dioctyl)phosphato titanate, zirconate and aluminate.
The method set forth in claim 36 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate, and neopentyl(diallyl)oxy, tri(dioctyl)phosphato titanate, zirconate and aluminate.
38.
The method set forth in claim 30 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate, and neopentyl(diallyl)oxy, tri(dioctyl)phosphato zirconate or titanate.
The method set forth in claim 30 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate, and neopentyl(diallyl)oxy, tri(dioctyl)phosphato zirconate or titanate.
39.
A plastic article of manufacture having a multilayer wall that includes:
at least one layer of polyester resin, at least one layer of barrier resin, and an adhesion-promoting material blended with said barrier resin to promote bonding between said barrier and polyester layers, said adhesion-promoting material including an organometallic coupling agent based upon titanium, zirconium or aluminum.
A plastic article of manufacture having a multilayer wall that includes:
at least one layer of polyester resin, at least one layer of barrier resin, and an adhesion-promoting material blended with said barrier resin to promote bonding between said barrier and polyester layers, said adhesion-promoting material including an organometallic coupling agent based upon titanium, zirconium or aluminum.
40.
The article set forth in claim 39 wherein said organometallic coupling agent includes an amino end group.
The article set forth in claim 39 wherein said organometallic coupling agent includes an amino end group.
41.
The article set forth in claim 40 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
The article set forth in claim 40 wherein said organometallic coupling agent is selected from the group consisting of: neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate, zirconate and aluminate.
42.
The article set forth in claim 41 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
The article set forth in claim 41 wherein said coupling agent consists essentially of neopentyl(diallyl)oxy, tri(N-ethylenediamine) ethyl titanate or zirconate.
43.
The article set forth in claim 39 wherein said polyester resin is selected from the group consisting of: PET, PEN, blends or copolymers of PET and PEN, and process regrind consisting essentially of PET, PEN, or blends or copolymers of PET and PEN.
The article set forth in claim 39 wherein said polyester resin is selected from the group consisting of: PET, PEN, blends or copolymers of PET and PEN, and process regrind consisting essentially of PET, PEN, or blends or copolymers of PET and PEN.
44.
The article set forth in claim 39 wherein said barrier resin is selected from the group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.
The article set forth in claim 39 wherein said barrier resin is selected from the group consisting of: EVOH, nylon, acrylonitrile copolymers, blends of EVOH and nylon, nanocomposites of EVOH or nylon and clay, blends of EVOH and an ionomer, acrylonitrile, cyclic olefin copolymers, polyglycolic acid, and blends thereof.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2004/022212 WO2006016875A1 (en) | 2004-07-09 | 2004-07-09 | Delamination-resistant multilayer container, preform and method of manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2573057A1 true CA2573057A1 (en) | 2006-02-16 |
Family
ID=34958279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002573057A Abandoned CA2573057A1 (en) | 2004-07-09 | 2004-07-09 | Delamination-resistant multilayer container, preform and method of manufacture |
Country Status (6)
| Country | Link |
|---|---|
| AU (1) | AU2004322268B2 (en) |
| BR (1) | BRPI0418947A (en) |
| CA (1) | CA2573057A1 (en) |
| DE (1) | DE112004002912T5 (en) |
| GB (1) | GB2430912B (en) |
| WO (1) | WO2006016875A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016168306A2 (en) * | 2015-04-15 | 2016-10-20 | Invista North America S.A.R.L. | Hydrophobic thermoplastic nylon compositions, articles and methods for making |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8192811B2 (en) * | 2003-03-14 | 2012-06-05 | Graham Packaging Pet Technologies Inc. | Delamination-resistant multilayer container, preform and method of manufacture |
-
2004
- 2004-07-09 DE DE112004002912T patent/DE112004002912T5/en not_active Withdrawn
- 2004-07-09 WO PCT/US2004/022212 patent/WO2006016875A1/en active Application Filing
- 2004-07-09 CA CA002573057A patent/CA2573057A1/en not_active Abandoned
- 2004-07-09 BR BRPI0418947-7A patent/BRPI0418947A/en not_active IP Right Cessation
- 2004-07-09 GB GB0701187A patent/GB2430912B/en not_active Expired - Fee Related
- 2004-07-09 AU AU2004322268A patent/AU2004322268B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006016875A1 (en) | 2006-02-16 |
| DE112004002912T5 (en) | 2007-07-12 |
| GB2430912B (en) | 2009-11-25 |
| GB2430912A (en) | 2007-04-11 |
| AU2004322268B2 (en) | 2010-08-26 |
| GB0701187D0 (en) | 2007-02-28 |
| BRPI0418947A (en) | 2007-12-04 |
| AU2004322268A1 (en) | 2006-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7807270B2 (en) | Multilayered package with barrier properties | |
| US20090136760A1 (en) | Delamination-resistant multilayer container, preform, article and method of manufacture | |
| EP0277350B1 (en) | Multilayered container | |
| US5540878A (en) | Method for producing blow molded multilayer plastic articles | |
| US20070110933A1 (en) | Multilayered package with barrier properties | |
| EP2272912A3 (en) | Container having barrier properties and method of manufacturing the same | |
| CA1265457A (en) | Injection stretch blow container | |
| EP1651527B1 (en) | Composition for making a packaging article having oxygen-scavenging properties and low haze | |
| US20070218304A1 (en) | Active oxygen barrier compositions of poly(hydroxyalkanoates) and articles made thereof | |
| EP2305751A1 (en) | Multi-layered article | |
| AU2013320646A1 (en) | Oxygen scavenging plastic material | |
| AU2004242605B2 (en) | Oxygen barrier formulations | |
| US8192811B2 (en) | Delamination-resistant multilayer container, preform and method of manufacture | |
| JP2008307846A (en) | Coinjection-molded container and its manufacturing method | |
| CN101001750A (en) | Containers incorporating polyester-containing multilayer structures | |
| AU2004322268B2 (en) | Delamination-resistant multilayer container, preform and method of manufacture | |
| JP2004043022A (en) | Co-injection stretch blow-molded container | |
| AU2015230363A1 (en) | Oxygen scavenging composition for plastic material | |
| JPS6279258A (en) | Polyester bottle and production thereof | |
| JP2009173033A (en) | Multi-layer container with gas barrier property | |
| MXPA06004062A (en) | Delimitation-resistant multilayer container, preform, article and method of manufacture | |
| JP2010500940A (en) | Oxygen scavenging dry blends and their use to make single layer packaging articles | |
| KR20070031265A (en) | Delimitation-resistant multilayer container, preform, article and method of manufacture | |
| EP4019249A1 (en) | Resin layered body | |
| CZ16323U1 (en) | Mixed barrier resin intended for use in a multilayer product, the multilayer product, particularly plastic product per se, plastic container and blank thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |