WO2015031879A1 - Container and process for making the same - Google Patents

Container and process for making the same Download PDF

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Publication number
WO2015031879A1
WO2015031879A1 PCT/US2014/053665 US2014053665W WO2015031879A1 WO 2015031879 A1 WO2015031879 A1 WO 2015031879A1 US 2014053665 W US2014053665 W US 2014053665W WO 2015031879 A1 WO2015031879 A1 WO 2015031879A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
core
parison
hdpe
formulation
Prior art date
Application number
PCT/US2014/053665
Other languages
French (fr)
Inventor
Jeffrey C. Minnette
David D. SUN
Phillip A. DRISKILL
Birju A. SURTI
Anthony R. GUARNERA
Jonathan K. Williams
Original Assignee
Berry Plastics Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Berry Plastics Corporation filed Critical Berry Plastics Corporation
Priority to CN201480047978.1A priority Critical patent/CN105517775A/en
Priority to JP2016537930A priority patent/JP2016529141A/en
Priority to RU2016111549A priority patent/RU2016111549A/en
Priority to AU2014311990A priority patent/AU2014311990A1/en
Priority to MX2016002493A priority patent/MX2016002493A/en
Priority to EP14838960.4A priority patent/EP3038810A4/en
Priority to CA2918134A priority patent/CA2918134A1/en
Publication of WO2015031879A1 publication Critical patent/WO2015031879A1/en
Priority to HK16105361.2A priority patent/HK1217315A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/22Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00Making preforms
    • B29B11/06Making preforms by moulding the material
    • B29B11/10Extrusion moulding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001Combinations of extrusion moulding with other shaping operations
    • B29C48/0017Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion 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
    • B29C48/09Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/49Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using two or more extruders to feed one die or nozzle
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04Extrusion blow-moulding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/46Component parts, details or accessories; Auxiliary operations characterised by using particular environment or blow fluids other than air
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/46Component parts, details or accessories; Auxiliary operations characterised by using particular environment or blow fluids other than air
    • B29C2049/4602Blowing fluids
    • B29C2049/4605Blowing fluids containing an inert gas, e.g. helium
    • B29C2049/4608Nitrogen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/62Venting means
    • B29C2049/622Venting means for venting air between preform and cavity, e.g. using venting holes, gaps or patterned moulds
    • B29C2049/627Venting means for venting air between preform and cavity, e.g. using venting holes, gaps or patterned moulds using vacuum means
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00Shaping characteristics in general
    • B29C2791/004Shaping under special conditions
    • B29C2791/006Using vacuum
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2791/00Shaping characteristics in general
    • B29C2791/004Shaping under special conditions
    • B29C2791/007Using fluid under pressure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2949/00Indexing scheme relating to blow-moulding
    • B29C2949/30Preforms or parisons made of several components
    • B29C2949/3041Preforms or parisons made of several components having components being extruded
    • B29C2949/3042Preforms or parisons made of several components having components being extruded having two or more components being extruded
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/4252Auxiliary operations prior to the blow-moulding operation not otherwise provided for
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/42Component parts, details or accessories; Auxiliary operations
    • B29C49/48Moulds
    • B29C49/4802Moulds with means for locally compressing part(s) of the parison in the main blowing cavity
    • B29C49/4817Moulds with means for locally compressing part(s) of the parison in the main blowing cavity with means for closing off parison ends
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04Polymers of ethylene
    • B29K2023/06PE, i.e. polyethylene
    • B29K2023/0608PE, i.e. polyethylene characterised by its density
    • B29K2023/065HDPE, i.e. high density polyethylene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037Other properties
    • B29K2995/0063Density
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00Other particular articles
    • B29L2031/712Containers; Packaging elements or accessories, Packages

Definitions

  • the present disclosure relates to containers, and in particular to containers made from polymeric materials. More particularly, the present disclosure relates containers made using a blow-molding process.
  • a container is formed to include an interior region adapted to store products therein.
  • the container is made using a container-molding process in which a tube of polymeric materials is extruded and then blow molded.
  • a container-molding process is used to establish a multi-layer container from a multi-layer tube.
  • the container-molding process includes an extruding operation, a blow-molding operation, and a trimming operation.
  • a co-extrusion system co-extrudes a multi-layer tube that comprises an inner layer, an outer layer spaced apart from the inner layer, and a core layer located therebetween.
  • the core layer is made from relatively low-density insulative cellular non-aromatic polymeric materials.
  • the multi-layer tube is located in a mold and pressurized gas is pumped into a spaced formed in the multi-layer tube to cause the multi-layer tube to expand and take on a shape of the mold so that a vessel is established.
  • excess materials are removed from the vessel to establish the multi-layer container.
  • the multi-layer container includes an inner layer, an outer layer spaced apart from the inner layer, and a compressed core layer located therebetween.
  • the compressed core layer is made from relatively low-density insulative cellular non-aromatic polymeric material which has been compressed during the blow-molding operation.
  • the multi-layer container has a relatively low density while stack strength, rigidity, and top load performance are maximized.
  • the low density of the multi-layer container also minimizes an amount of polymeric material used to form the multi-layer container.
  • FIG. 1 is a diagrammatic and perspective view of a container-molding process in accordance with the present disclosure showing that the container-molding process includes an extruding operation in which a multi-layer tube is extruded from a co-extrusion system, a closing operation in which a mold is closed around the multi-layer tube, an inserting operation in which a blow needle is inserted into a tube space formed in the multi-layer tube while vacuum is applied to the mold, a pumping operation in which pressurized gas is pumped into tube space, an expanding operation in which the pressurized gas expands the multi-layer tube against an inner surface of the mold, an opening operation in which the mold is opened and a vessel is released, and a trimming operation in which excess material is trimmed from the vessel to establish a multi-layer container in accordance with the present disclosure as suggested in Fig. 13;
  • FIG. 2 is a diagrammatic view of the container-molding process of Fig. 2 showing that the container-molding process includes a series of operations which produce the multi-layer tube and form the multi-layer container;
  • Fig. 3 is a perspective and diagrammatic view of the co-extrusion system used to make the multi-layer tube showing that the co-extrusion system includes an outer-layer extruder configured to receive an outer-layer formulation and provide an outer-layer parison, an inner- layer extruder configured to receive an inner-layer formulation and provide an inner-layer parison, a core-layer extruder configured to receive a core-layer formulation and provide a core- layer parison, and a co-extrusion die coupled to each of the extruders to receive the associated parisons and configured to extrude the inner-layer, core-layer, and outer-layer parisons to establish the multi-layer tube;
  • the co-extrusion system includes an outer-layer extruder configured to receive an outer-layer formulation and provide an outer-layer parison, an inner- layer extruder configured to receive an inner-layer formulation and provide an inner-layer parison, a core-layer extruder configured to receive a core-layer formulation and provide a core-
  • Fig. 4 is a partial perspective view taken from below the co-extrusion die of the co-extrusion system showing that the co-extrusion die includes an annular aperture configured to extrude the multi-layer tube;
  • Fig. 5 is a view similar to Fig. 4 after co-extrusion of the multi-layer tube has begun with portions of the multi-layer tube broken away to reveal that the inner layer is spaced apart from the outer layer and that the core layer is located therebetween;
  • FIG. 6 is an enlarged partial perspective view of Fig. 1 showing that prior to the closing operation, the multi-layer tube is located between two mold halves and that a vacuum source coupled to the mold is turned off so that atmospheric pressure exists in a mold cavity formed between the two mold halves when the mold is in a closed position;
  • FIG. 7 is an enlarged partial perspective view of Fig. 1 showing that after the closing operation, the vacuum source is turned on and pressure inside the mold cavity decreases to establish a vacuum in the mold cavity which minimizes loss of cell structure in the core layer during the blowing and expanding operations;
  • Fig. 8A is a sectional view taken along line 8A-8A of Fig. 7 showing that prior to the blowing operation, the multi-layer tube has an outer tube surface which establishes a preform radius and an inner surface of the mold has a relatively greater mold radius;
  • Fig. 8B is a view similar to Fig. 8A taken along line 8B-8B of Fig. 1 showing that the multi-layer tube has expanded to engage the inner surface of the mold after the expanding operation is complete and that the vessel includes an outer container surface which establishes a relatively greater container radius which is about equal to the mold radius;
  • Fig. 9 is a view similar to Fig. 7 showing the mold and multi-layer tube after the inserting operation in which the blow needle is inserted through the mold and into the tube space of the multi-layer tube and that a pressurized source of gas is turned off so that a pressure in the space is about atmospheric;
  • Fig. 10 is sectional view taken along line 10-10 of Fig. 9 showing that prior to the blowing operation, the core layer of the multi-layer tube includes a plurality of expanded cells filled with gas which cause a density of the core layer to be minimized so that a density of the of the multi-layer container is also minimized;
  • Fig. 11 is view similar to Fig. 9 showing the mold and multi-layer tube during the expanding operation in which the source of pressurized gas has been turned on causing pressure in the tube space to increase to P BLOW which is above atmospheric pressure so that the multilayer tube expands outwardly toward the inner surface of the mold;
  • Fig. 12 is a view similar to Fig. 10 taken along line 12-12 of Fig. 11 showing that during the expanding operation, the plurality of expanded cells remain intact in the core layer so that the density of the vessel is minimized;
  • Fig. 13 is a perspective view of the multi-layer container formed from the container-molding process of Figs. 1 and 2 after the trimming operation has completed;
  • Fig. 14 is a sectional view taken along line 14-14 of Fig. 13 showing that the multi-layer container includes a side wall including the inner layer, the outer layer spaced apart from the inner layer, and a compressed core layer located therebetween and showing that some of the expanded cells have collapsed along the inner and outer layers to cause the compressed core layer to have a relatively greater density than the core layer of the multi-form tube;
  • Fig. 15 is a partial perspective view of the multi-layer container of Fig. 13 coupled to a top-load testing device undergoing top-load testing;
  • Fig. 16 is a photograph of the multi-layer container of Fig. 13 coupled to a rigidity testing device undergoing rigidity testing;
  • Fig. 17 is a perspective view of an unassembled density determination apparatus showing the components (clockwise starting in the upper left) gem holder, platform, suspension bracket, and suspension spacer.
  • Multi-layer container 10 is suggested in Fig. 1 and shown in Fig. 13.
  • Multi-layer container 10 is formed by a container-molding process 100 in accordance with the present disclosure as shown in Fig. 1 and suggested in Fig. 2.
  • Container-molding process 100 begins with extruding 102 a multi-layer tube 12 that includes a core layer 12B made from relatively low-density insulative cellular non-aromatic polymeric material.
  • Container-molding process 100 proceeds by molding multi-layer tube 12 into multilayer container 10 which may cause core layer 12B of multi-layer tube 12 to compress and establish a compressed core layer 10B included in multi-layer container 10.
  • compressed core layer 10B being made from relatively low-density insulative cellular non- aromatic polymeric material, a density of multi-layer container 10 is minimized while stack strength, rigidity, and top-load performance of multi-layer container 10 are maximized.
  • Container-molding process 100 begins with an extruding operation 102 in which multi-layer tube 12 is extruded from a co-extrusion system 16 as suggested in Fig. 1 and shown in Fig. 3.
  • Container- molding process 100 then proceeds to a closing operation 104 in which a mold 18 is closed around multi-layer tube 12 as shown in Fig. 1.
  • Container-molding process then moves onto an inserting operation 106 in which a blow needle 20 is inserted into a tube space 22 formed in multi-layer tube 12 while vacuum from a vacuum source 24 is applied to mold 18.
  • Container-molding process 100 then proceeds to a pumping operation 108 in which pressurized gas 26 is pumped into tube space 22 as suggested in Fig. 1.
  • Container-molding process 100 then moves on to simultaneous operations including a vacuuming operation 109 in which vacuum is applied to mold 18 and an expanding operation 110 in which pressurized gas 26 expands multi-layer tube 12 against an inner surface 28 of mold 18 and establishes a vessel 30.
  • An opening operation 112 then occurs in which mold 18 opens to reveal vessel 30.
  • a removing operation 114 occurs in which vessel 30 is separated from mold 18 and released from blow needle 20.
  • Container-molding process 100 then ends with a trimming operation 116 in which excess materials 62, 64 are trimmed from multi-layer container 10 to establish multi-layer container 10 as suggested in Fig. 1 and shown in Fig. 13.
  • Multi-layer container 10 is made during container-molding process 100 using multi-layer tube 12 as shown in Fig. 1.
  • Multi-layer tube 12 is provided during extruding operation 102 of container-molding process 100.
  • Extruding operation 102 is performed using co-extrusion system 16 as shown in Fig. 3.
  • Extruding operation 102 includes a preparing stage 102A in which various material formulations are provided to co-extrusion system 16, an extrusion stage 102B in which the various material formulations are processed by co-extrusion system 16 to provide associated parisons, and a co-extruding stage 102C in which the various parisons are extruded to provide multi-layer tube 12 as shown in Fig. 1 and suggested in Fig. 3.
  • Extruding operation 102 is performed on co-extrusion system 16 which includes an inner-layer extruder 32, an outer-layer extruder 34, a core-layer extruder 36, and a co- extrusion die 38 as shown in Fig. 3.
  • Inner-layer extruder 32 receives an inner-layer formulation 40 of a relatively high-density polymeric material and processes inner-layer formulation 40 to provide an inner-layer parison 42 to co-extrusion die 38 as shown in Fig. 3.
  • Outer-layer extruder 34 receives an outer-layer formulation 44 of a relatively high-density polymeric material and processes outer-layer formulation 44 to provide an outer-layer parison 46 to co- extrusion die 38 as shown in Fig. 3.
  • Core-layer extruder 36 receives a core-layer formulation 48 of a relatively low-density insulative cellular non-aromatic polymeric material and processes core-layer formulation 48 to provide a core-layer parison 50 to co-extrusion die 38 as shown in Fig. 3.
  • Co-extrusion die 38 receives the various parisons 42, 46, 50 and extrudes multi-layer tube 12 through an annular aperture 39 as suggested in Figs. 1 and 3 and shown in Figs. 4 and 5.
  • extruding operation 102 is shown forming multi-layer tube 12 having three layers, any number of layers may be formed during the extruding operation. Additional layers may include relatively low-density layers, tie layers, thermoplastic polyurethane (TPU), other olefins, combinations thereof, or any other suitable alternatives and combinations.
  • TPU thermoplastic polyurethane
  • Molding system 52 includes, for example, mold 18 formed to include a mold cavity 54 defined by inner surface 28 of mold 18, a vacuum system 56 configured to provide a vacuum pressure to mold cavity 54 during molding of multi-layer container 10, a blowing system 58 configured to provide pressurized gas 26 to tube space 22, and a trimming system 60 configured to remove excess materials 62, 64 from vessel 30 as shown in Fig. 1.
  • Container-molding process 100 proceeds to closing operation 104 after multilayer tube 12 has been established as shown in Figs. 1 and 2.
  • First and second mold halves 18A, 18B included in mold 18 begin in an opened position in which mold halves 18 A, 18B are spaced apart from one another as shown in Fig. 1.
  • mold halves 18A, 18B move toward one another to achieve a closed position in which multi-layer tube 12 is located in mold cavity 54 formed therebetween.
  • a vacuum source 66 included in vacuum system 56 remains off and pressure in mold cavity 54 remains at about atmospheric pressure as measured by a mold-cavity pressure gauge 68 as shown in Fig. 1.
  • container-molding process 100 proceeds to inserting operation 106 as shown in Figs. 1 and 2.
  • inserting operation 106 mold 18 moves away from co-extrusion die 38 and aligns with blow needle 20 included in blowing system 58.
  • Blow needle 20 then moves downwardly through mold 18 into tube space 22 included in multi-layer tube 12 as shown in Figs. 1 and 2.
  • vacuum source 66 is turned on causing pressure in mold cavity 54 to decrease to P VAC which is below atmospheric pressure. Vacuum is applied at a pressure in a range of about 5 mmHg to about 25 mmHg. In another example vacuum is applied at a pressure of about 20 mmHg.
  • P VAC is greater than the vacuum applied and less than atmospheric pressure.
  • P VAC may be in a range of about 5 inches Hg to about 20 inches Hg. In another example, P VAC is in a range of about 10 inches Hg to about 20 inches Hg. In still yet another example, P VAC is about 10 inches Hg.
  • a source 70 of pressurized gas 26 included in blowing system 58 may be communicated into tube space 22 to expand a size of multi-layer tube 12 in subsequent operations.
  • source 70 of pressurized gas 26 is turned off and pressure in tube space 22 is measured by a tube pressure gauge 72 to be at about atmospheric pressure (P ATM ).
  • Pressurized gas may be, for example, standard air, nitrogen, carbon dioxide, combinations thereof, or any other suitable alternative.
  • container-molding process 100 proceeds to pumping operation 108 as shown in Figs. 1 and 2.
  • source 70 of pressurized gas 26 is turned on and pressure inside tube space 22 increases to a relatively higher pressure (P BLOW) -
  • P BLOW is in a range of about 30 pounds per square inch and about 120 pounds per square inch.
  • P BLOW is in a range of about 10 pounds per square inch to about 130 pounds per square inch.
  • P BLOW is in a range of about 35 pounds per square inch to about 45 pounds per square inch.
  • P BLOW is about 40 pounds per square inch.
  • source 70 of pressurized gas 26 may be configured to deliver pressurized gas 26 at a temperature to tube space 22.
  • the temperature is in a range of about 35 degrees Fahrenheit to about 75 degrees Fahrenheit.
  • the temperature is in a range of about 40 degrees Fahrenheit to about 70 degrees Fahrenheit.
  • the temperature is in a range of about 50 degrees to about 75 degrees Fahrenheit.
  • the temperature is about room temperature.
  • the temperature is about 40 degrees Fahrenheit.
  • the temperature is about 50 degrees Fahrenheit.
  • container-molding process 100 proceeds to both vacuuming operation 109 and expanding operation 110 as shown in Figs. 1 and 2.
  • vacuuming operation 109 vacuum is applied to mold cavity 54.
  • expanding operation 110 commences.
  • pressurized gas 26 continues to flow through blow needle 20 causing multi-layer tube 12 to expand and engage inner surface 28 of mold 18 and fill mold cavity 54 as suggested in Fig. 1 and Fig. 11.
  • Expanding operation 110 is complete once multi-layer tube 12 has substantially the same shape as mold cavity 54.
  • vacuum source 66 remains on and pressure in mold cavity 54 remains below atmospheric pressure to minimize collapse and damage of expanded cells 69 included in core layer 12B of multi-layer tube 12 as shown in Fig. 12.
  • Pumping operation 108, vacuuming operation, and expanding operation 110 cause multi-layer tube 12 to expand from a pre-expansion shape as shown in Figs. 8A and 9 to a post-expansion shape shown in Figs. 1 and 8B which is substantially similar to a shape of vessel 30.
  • An outer tube surface 76 of multi-layer tube 12 has a pre-form radius 78 as shown in Fig. 8 A.
  • Inner surface 28 of mold 18 has a relatively greater mold radius 80 as shown in Fig. 8 A.
  • vessel 30 has an outer container surface 82 which has a relatively greater container radius 84. Relatively greater container radius 84 is about equal to relatively greater mold radius 80 after expanding operation 110 is complete.
  • a blow-up ratio for mold 18 and multi-layer tube 12 is calculated by dividing mold radius 80 by pre-form radius 78.
  • the blow-up ratio is in a range of about 100% to about 300%.
  • the blow-up ratio is in a range of about 150% to about 200%.
  • the blow-up ratio is about 200%. The blow-up ratio may be adjusted to suit various sizes of containers.
  • vessel 30 After expanding operation 110 is complete, vessel 30 is established. Vessel 30 includes multi-layer container 10 and excess material 62 coupled to an upper end of multi-layer container 10 and excess material 64 coupled to a lower end of multi-layer container 10.
  • Container-molding process 100 then proceeds to opening operation 112 as shown in Figs. 1 and 2.
  • opening operation 112 source 70 of pressurized gas 26 is turned off and mold 18 moves from the closed position to the opened position as shown in Fig. 1.
  • Vessel 30 is then ready for removal from mold 18 and while remaining coupled to blow needle 20 as suggested in Fig. 1.
  • Container-molding process 100 then proceeds to removing operation 114 in which vessel 30 is separated from mold 18 and released from blow needle 20.
  • source 70 of pressurized gas 26 briefly turns on blowing vessel 30 off of blow needle 20.
  • container-molding process 100 proceeds to trimming operation 116. During trimming operation 116, excess material 62, 64 is cut using one or more knives 86 or blades to provide multi-layer container 10 as shown in Fig. 1.
  • Molding system 52 is used in cooperation with a continuous extrusion process such as extruding operation 102.
  • molding system 52 may be a shuttle blow-molding machine.
  • mold 18 begins in the opened position and moves on a track toward co-extrusion die 38 to locate multi-layer tube 12 between mold halves 18 A, 18B. Mold 18 then moves to the closed position. Mold 18 then slides away from co-extrusion die 18 while another multi-layer tube 12 is extruded.
  • inserting operation 106, pumping operation 108, and expanding operation 110 are performed. Opening operation 112 and removing operations 114 are then performed which cause vessel 30 to be ejected from mold 18.
  • Mold 18 is now in the opened position ready to slide back toward co-extrusion die 30 and begin the process again.
  • One example molding machine 52 is a shuttle blow-molding machine available from Graham Engineering Corporation of York, Pennsylvania. In another example of a shuttle blow-molding machine, more than one mold may be used to minimize cycle time and increase an extrusion rate of co-extrusion system 16.
  • molding machine 52 may be a rotary blow molding machine.
  • a continuous multi-layer tube is extruded and a series of molds included in the rotary blow-molding machine rotate relative to the multi-layer tube. As molds approach co- extrusion die 38 forming the multi-layer tube 10, they begin to move from an opened
  • Container-molding process 100 has a cycle time defined as an amount of time between closing operation 104 and opening operation 112. This cycle time is defined the same way whether molding machine 52 is a shuttle blow-molding machine or a rotary extrusion blow- molding machine.
  • Multi-layer containers including core layer 12B made from relatively low- density insulative cellular non-aromatic polymeric material may have decreased cycle time due to reduced mass of the container resulting from the use of core-layer 12B.
  • the cycle time for container- molding process 100 and multi-layer container 10 on a shuttle blow-molding machine is in a range of about 5% to about 40% faster than molding operations and containers lacking a layer made from relatively low-density insulative cellular non-aromatic polymeric material.
  • cycle time may be in a range of about 5% to about 30% faster than molding operations and containers lacking a layer made from relatively low-density insulative cellular non-aromatic polymeric material.
  • the cycle time of container-molding process 100 and multi-layer container 10 was about 16 seconds.
  • Container-molding process 100 uses multi-layer tube 12 to establish multi-layer container 10 as shown, for example, in Figs. 1 and 13.
  • Multi-layer container 10 includes a floor 88, a sidewall 90, and neck 92 as shown in Fig. 13.
  • Sidewall 90 is relatively straight and vertical and provides outer container surface 82.
  • Floor 88 is coupled to a lower end of sidewall 90 and cooperates with sidewall 90 to define an interior product-storage region 94 therebetween.
  • Neck 92 is coupled to an opposite upper end of sidewall 90 and defines an open mouth 96 that is arranged to open into interior product-storage region 94.
  • Neck 92 has a neck radius 98 which is relatively smaller than container radius 84 as shown in Fig. 13.
  • Multi-layer container 10 was subjected to a series of performance tests which include drop testing, top load testing, rigidity testing, and metrology testing.
  • Drop testing determines a likelihood of container survival due to a drop or impact to the container.
  • Top load testing determines how much force a container can withstand before the container fails or necks in to form an hourglass shape.
  • Rigidity testing determines how resistant containers are to deformation.
  • Metrology testing determines dimensions of multi-layer container 10 in comparison to specifications for the container.
  • Multi-layer container 10 was subjected to drop testing according to one of the
  • the drop test may be performed according to the following procedure.
  • the container is filled with water and closed off with, for example, a lid.
  • the sample container is then held at about 73 degrees Fahrenheit (22.8 degrees Celsius) and about 50% relative humidity.
  • the filled, capped containers are then subjected to the following procedure: (a) the filled, capped container is located at about five feet above a hard surface such as concrete or tile; (b) the filled, capped container is then oriented such that a bottom of the filled, capped container is arranged to lie in a substantially parallel relation to the hard surface; (c) each of ten capped, filled containers are dropped; (d) upon impact, each filled, capped container is examined for any break or shattering of the wall that causes water to leak out of the bottle; and (d) the total number of bottles showing any sign of leakage after the drop test are counted as failures. Results for various different trial runs of multi-layer container 10 are shown below in Table. 1.
  • Instron tester 202 is used to determine top load performance as suggested in Fig. 15. Multi-layer containers 10 were tested until they failed or necked in to form an hourglass shape. Once failure or necking was observed, the value shown on Instron tester 202 was recorded. Table 2 shows the performance of several multi-layer containers including compressed core layer 10B tested vs. several high density polyethylene containers (excluding a core layer). Both types of containers had a total mass of about 56 grams.
  • FIG. 16 Various multi-layer containers 10 in accordance with the present disclosure were subjected to rigidity testing. Each multi-layer container was placed in a rigidity tester as shown in Fig. 16 and tested to determine rigidity as shown below in Table 3. Testing involves placing a multi-layer container in a rigidity tester 300 as shown in Fig. 16 in two orientations.
  • the rigidity tester includes a stationary cylindrical stop 302 on a left side and a movable anvil 304 and force gauge 306 on a right side.
  • the movable anvil is generally T-shaped as shown in Fig. 16. For each orientation, sidewall 90 of multi-layer container 10 is deformed about midway between floor 88 and neck 92 of multi-layer container 10.
  • Sidewall 90 is deformed about 0.25 inches over a 10 second interval and the force required to do so is recorded in pounds-Force.
  • the first orientation places a mold seam of multi-layer container in alignment to engage movable anvil 304 (0 Degrees).
  • the second orientation rotates multi-layer container 10 so that the seam is about 90 degrees away from the movable anvil (90 Degrees).
  • Table 4 shows a neck diameter 204 measured at different points along a multi-layer container for several multi-layer containers along with the specified values and limits for each multi-layer container. The measurements were taken at 0 degrees (part line of the mold), 90 degrees (counter-clockwise from the part line), 45 degrees (counter-clockwise from the part line), 135 degrees (counter-clockwise from the part line), average neck diameter, and ovality of the neck. Ovality is the difference between highest and lowest neck diameter measurements.
  • Various multi-layer containers 10 were subjected to metrology measurements to determine accuracy and repeatability of container-molding process 100 to manufacture multilayer containers 10 to specification.
  • Table 5 shows a thread diameter 206 measured at different points along a multi-layer container for several multi-layer containers along with the specified values and limits for each multi-layer container. The measurements were taken at 0 degrees (part line of the mold), 90 degrees (counter-clockwise from the part line), 45 degrees (counter-clockwise from the part line), 135 degrees (counter-clockwise from the part line), average neck diameter, and ovality of the neck. Ovality is the difference between highest and lowest thread diameter measurements.
  • Various multi-layer containers 10 were subjected to metrology measurements to determine accuracy and repeatability of container-molding process 100 to manufacture multilayer containers 10 to specification.
  • Table 6 shows various measurements taken for several multi-layer containers along with the specified values and limits for each multi-layer container. The measurements taken were an Overall Height (OAH) of the container, an outside diameter of the sidewall taken at 0 degrees (part line of the mold) and 90 degrees (counterclockwise from the part line), an average outside diameter, ovality of the diameter, weight of the container, OFC.
  • OFC is an overflow capacity of multi-layer container 10 and measured in cubic centimeters (cc).
  • Various multi-layer containers 10 were subjected to metrology measurements to determine accuracy and repeatability of container-molding process 100 to manufacture multilayer containers 10 to specification.
  • Table 7 below shows various thicknesses for each inner, outer, and core layer for several multi-layer containers.
  • Table 8 shows various layer thicknesses as a percent of a total thickness for each inner, outer, and core layer and a layer distribution between solid (inner and outer layer) cellular (core layer) for several multi-layer containers.
  • a total solid phase distribution of inner and outer layers is targeted at about 12- 15% while a cellular phase distribution is targeted about 85-88% as suggested in Table 8 below.
  • Multi-layer container 10 is made using container- molding process 100 which begins with an extruding operation 102 as shown in Figs. 1-3.
  • Extruding operation 102 includes several stages that each comprise several operations which cooperate to provide multi-layer tube 12.
  • extruding operation 102 includes a preparing stage 102A in which various material formulations are prepared and provided to each associated extruder to provide the associated layer of multi-layer tube 12.
  • Extruding operation 102 further includes an extrusion stage 102B in which the various formulations are processed by associated extruders to provide associated parisons which are communicated to co-extrusion die 38 as shown in Figs. 1 and 3.
  • extruding operation 102 ends with a co-extruding stage 102C in which the various parisons are aligned and co-extruded together to establish multi-layer tube 12.
  • preparing stage 102A of extruding operation 102 includes a first preparing operation 102A1 in which an inner-layer formulation 40 is prepared and provided to inner-layer extruder 32 as shown in Fig. 3.
  • inner-layer formulation 40 comprises at least one polymeric material.
  • the polymeric material may include one or more resins.
  • inner-layer formulation 40 includes a relatively high-density polymeric material.
  • inner-layer formulation 40 comprises relatively high-density polymeric material.
  • inner-layer formulation 40 is FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation).
  • inner-layer formulation 40 comprises a relatively high- density polymeric material and a colorant.
  • the relatively high-density polymeric material may be FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation) and the colorant may be COLORTECH® 11933-19 Titanium Oxide Colorant (available from COLORTECH® a PPM Company).
  • Preparing stage 102 A of extruding operation 102 further includes a second preparing operation 102A2.
  • outer-layer formulation 44 is prepared and provided to outer-layer extruder 34 as shown in Fig. 3.
  • outer-layer formulation 44 comprises at least one polymeric material.
  • the polymeric material may include one or more resins.
  • inner-layer formulation 40 includes a relatively high-density polymeric material.
  • inner-layer formulation 40 comprises relatively high-density polymeric material.
  • inner-layer formulation 40 is FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation).
  • outer-layer formulation 44 comprises a relatively high- density polymeric material and a colorant.
  • the relatively high-density polymeric material may be FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation) and the colorant may be COLORTECH® 11933-19 Titanium Oxide Colorant (available from COLORTECH® a PPM Company).
  • inner-layer formulation 40 and outer-layer formulation 44 may be the same. In other examples, inner-layer formulation 40 and outer-layer formulation 44 may be different. In still yet other example, additional layers may be included and configured to be an oxygen barrier such as Ethylene Vinyl Alcohol (EVOH), a ultra-violet light barrier, and the like.
  • EVOH Ethylene Vinyl Alcohol
  • the additional layers or alternative layers may include other relatively low-density layers, tie layers, TPU layers, other olefins, combinations thereof, or any other suitable combinations and alternatives.
  • Preparing stage 102 A of extruding operation 102 further includes a third preparing operation 102A3 in which core-layer formulation 48 is prepared and provided to core- layer extruder 36 as shown in Fig. 3.
  • Core-layer formulation 48 is an insulative cellular non- aromatic polymeric material.
  • core-layer formulation 48 comprises a polyethylene base resin and one or more cell-forming agents.
  • Core-layer formulation 48 uses a polyethylene-based formulation to produce insulative cellular non-aromatic polymeric material after being processed through core-layer extruder 36.
  • Core-layer formulation 48 is heated in in core-layer extruder 36 where a cell-forming agent is introduced into the molten core-layer formulation prior to moving the materials from core-layer extruder 36 to co-extrusion die 38.
  • molten core-layer formulation 48 exits co-extrusion die 38 between inner and outer layers 12A, 12C, cells nucleate in the molten material and the material expands to form core layer 12B made from insulative cellular non-aromatic polymeric material.
  • core-layer formulation 48 used to produce the insulative cellular non-aromatic polymeric material includes at least one polymeric material.
  • the polymeric material may include one or more base resins.
  • the base resin is High Density Polyethylene (HDPE).
  • the base resin is a unimodal HDPE.
  • the base resin is unimodal, high-melt strength HDPE.
  • the base resin is unimodal, high-melt strength HDPE such as DOW®
  • DOWLEXTM IP 41 HDPE available from The Dow Chemical Company that has been electron beam modified to provide long chain branching and a melt index of about 0.25 g/10 min.
  • a unimodal, high-melt strength HDPE is EQUISTAR® ALATHON® H5520 HDPE copolymer (available from Lyondell Chemical Company) which has been electron beam modified to have long-chain branching and a melt index of about 0.25 g/10 min.
  • FORMOLENE® HB5502F HDPE hexene copolymer available from Formosa Plastics Corporation.
  • core-layer formulation 48 may include two base resins that are HDPE.
  • core-layer formulation 48 includes a first base resin of FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation) and a second base resin of EQUISTAR® ALATHON® H5520 HDPE copolymer (available from Lyondell Chemical Company).
  • first base resin of FORMOLENE® HB5502F HDPE hexene copolymer available from Formosa Plastics Corporation
  • EQUISTAR® ALATHON® H5520 HDPE copolymer available from Lyondell Chemical Company
  • different HDPE copolymers can be used depending on the attributes desired in the formulation.
  • core-layer formulation 48 may include both e-beam modified EQUISTAR® ALATHON® H5520 and FORMOLENE® HB5502F HDPE.
  • the EQUISTAR® ALATHON® H5520 provides higher melt strength which increases foaming potential, and has less flexural modulus or brittleness.
  • the FORMOLENE® HB5502F HDPE provides wide unimodal polydispersity index or distribution and maximizes economic advantage.
  • core-layer formulation 48 includes about 50% e-beam modified EQUISTAR® ALATHON® H5520 and about 50% FORMOLENE® HB5502F HDPE. Together the combination provides a film having drop resistance capability associated with a non-modified HDPE resin and increased melt strength of an e-beam modified long-chain branched HDPE.
  • the percentage of two HDPE copolymers may be varied, e.g., 25%/75%, 30%/70%, 35%/65%, 40%/60%, 45%/55%,
  • core-layer formulation 48 includes three HDPE copolymers in the base resin. Again, depending on the desired characteristics, the percentage of three HDPE copolymers can be varied, 33%/33%/33%, 30%/30%/40%, 25%/25%/50%, etc.
  • a core-layer formulation can include one or more base resins. The amount of
  • HDPE base resin may be one of several different values or fall within one of several different ranges. It is within the scope of the present disclosure to select an amount of HDPE base resin and be one of the following values: about 85%, 90%, 95%, 97%, 98%, 99%, 99.5%, and 99.9% of the total formulation by weight percentage. It is within the scope of the present disclosure for the amount of HDPE base resin in the formulation to fall within one of many different ranges.
  • the range of HDPE base resin is one of the following ranges: about 85% to 99.9%, 86% to 99.9%, 87% to 99.9%, 87.5% to 99.9%, 88% to 99.9%, 89% to 99.9%, 90% to 99.9%, 91% to 99.9%, 92% to 99.9%, 93% to 99.9%, 94% to 99.9%, 95% to 99.9%, 96% to 99.9%, 96.5% to 99.9%, 97% to 99.9%, and 98% to 99.9% of the total formulation by weight percentage.
  • the range of HDPE base resin is one of the following ranges: about 85% to 99.5%, 85% to 99%, 85% to 98%, 85% to 97%, 85% to 96%, 85% to 96.5%, 85% to 95%, 85% to 94%, 85% to 93%, 85% to 92%, 85% to 91%, 85% to 90%, 85% to 89%, 85% to 88%, 85% to 87%, and 85% to 86% of the total formulation by weight percentage.
  • the range of HDPE base resin is one of the following ranges: about 87.5% to 96.5%, 87.5% to 96%, 87.5% to 95.5%, 87.5% to 95%, 95% to 99%, 95.5% to 99%, 96% to 99%, and 96.5% to 99% of the total formulation by weight percentage.
  • ranges are embodied in the Examples.
  • Long chain branching refers to the presence of polymer side chains (branches) that have a length that is comparable or greater than a length of the backbone to which the polymer side chains are coupled to. Long chain branching creates viscoelastic chain
  • the strain hardening phenomenon may be observed through two analytical methods.
  • the second analytical method used to observe the presence of long chain branching is evaluating melt strength data as tested per ISO 16790 which is incorporated by reference herein in its entirety.
  • An amount of melt strength is known to be directly related to the presence of long chain branching when compared to similar virgin polymers lacking long chain branching.
  • Borealis DAPLOYTM WB140HMS Polypropylene (PP) (available from Borealis AG) is compared to other polymers having similar molecular weight, polydispersity index, and other physical characteristics.
  • the DAPLOYTM WB140HMS PP has a melt strength which exceeds about 36 centi-Newton while other similar PP resins lacking long chain branching have a melt strength of less than about 10 centi-Newton.
  • Core-layer formulation 48 used to produce the insulative cellular non-aromatic polymeric material may further include one or more cell-forming agents.
  • Cell-forming agents include nucleating agents and blowing agents.
  • a nucleating agent is used to provide and control nucleation sites within a molten formulation to promote formation of cells, bubbles, or voids in the molten formulation during extrusion.
  • a blowing agent is used to grow cells in the molten material at nucleation sites. Blowing agents may be used alone in the formulation or with nucleating agents.
  • Nucleating agent means a chemical or physical material that provides sites for cells to form in a molten formulation mixture.
  • Nucleating agents may include chemical nucleating agents and physical nucleating agents.
  • the nucleating agent may be blended with the formulation that is introduced into the hopper of the extruder. Alternatively, the nucleating agent may be added to the molten resin mixture in the extruder.
  • Suitable physical nucleating agents have desirable particle size, aspect ratio, and top-cut properties. Examples include, but are not limited to, talc, CaC0 3 , mica, and mixtures of at least two of the foregoing.
  • talc talc
  • CaC0 3 CaC0 3
  • mica talc
  • One representative example is Heritage Plastics HT6000 Linear Low Density Polyethylene (LLDPE) Based Talc Concentrate.
  • a core-layer formulation can include a physical nucleating agent.
  • the amount of a physical nucleating agent may be one of several different values or fall within one of several different ranges. It is within the scope of the present disclosure to select an amount of a physical nucleating agent and be one of the following values: about 0%, 0.1%, 0.25%, 0.5%, 0.75%, 1.0%, 1.25%, 1.5%, 1.75%, 2%, 2.25%, 2.5%, 3%, 4%, 5%, 6%, and 7% of the total formulation by weight percentage. It is within the scope of the present disclosure for the amount of a physical nucleating agent in the formulation to fall within one of many different ranges.
  • the range of a physical nucleating agent is one of the following ranges: about 0% to 7%, 0.1% to 7%, 0.25% to 7%, 0.5% to 7%, 0.75% to 7%, 1% to 7%, 1.25% to 7%, about 1.5% to 7%, 1.75% to 7%, 2.0% to 7%, 2.25% to 7%, 2.5% to 7%, 3% to 7%, 4% to 7%, 5% to 7%, and 6% to 7% of the total formulation by weight percentage.
  • the range of a physical nucleating agent is one of the following ranges: about 0% to 6%, 0% to 5%, 0% to 4%, 0% to 3%, 0% to 2.5%, 0% to 2.25%, 0% to 2%, 0% to 1.75%, 0% to 1.5%, 0% to 1.25%, 0% to 1%, 0% to 0.75%, and 0% to 0.5% of the total formulation by weight percentage.
  • the range of a physical nucleating agent is one of the following ranges: about 0.1% to 6%, 0.1% to 5%, 0.1% to 4%, 0.1% to 3.5%, 0.1% to 3%, 0.1% to 2.5%, 0.1% to 2.25%, 0.1% to 2%, 0.1% to 1.75%, 0.1% to 1.5%, 0.1% to 1.25%, 0.1% to 1%, 0.1% to 0.75%, and 0.1% to 0.5% of the total formulation by weight percentage.
  • each of these values and ranges is embodied in the Examples.
  • the formulation lacks talc.
  • Suitable chemical nucleating agents decompose to create cells in the molten formulation when a chemical reaction temperature is reached. These small cells act as nucleation sites for larger cell growth from a physical or other type of blowing agent.
  • the chemical nucleating agent is citric acid or a citric acid-based material.
  • HYDROCEROLTM CF-40E available from Clariant Corporation, which contains citric acid and a crystal nucleating agent.
  • a core-layer formulation can include a nucleating agent.
  • the amount of a nucleating agent may be one of several different values or fall within one of several different ranges. It is within the scope of the present disclosure to select an amount of a nucleating agent and be one of the following values: about 0.1%, 0.25%, 0.5%, 0.75%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 5%, 10%, and 15% of the total formulation by weight percentage. It is within the scope of the present disclosure for the amount of a nucleating agent in the formulation to fall within one of many different ranges.
  • the range of a nucleating agent is one of the following ranges: about 0.1% to 15%, 0.25% to 15%, 0.5% to 15%, 1% to 15%, 1.5% to 15%, 2% to 15%, 2.5% to 15%, 3% to 15%, 3.5% to 15%, 4% to 15%, 4.5% to 15%, and 5% to 15% of the total formulation by weight percentage.
  • the range of a nucleating agent is one of the following ranges: about 0.1% to 10%, 0.25% to 10%, 0.5% to 10%, 0.75% to 10%, 1% to 10%, 1.5% to 10%, 2% to 10%, 2.5% to 10%, 3% to 10%, 3.5% to 10%, 4% to 10%, 4.5% to 10%, and 5% to 10% of the total formulation by weight percentage.
  • the range of a nucleating agent is one of the following ranges: about 0.1% to 5%, 0.25% to 5%, 0.5% to 5%, 0.75% to 5%, 1% to 5%, 1.5% to 5%, 2% to 5%, 2.5% to 5%, 3% to 5%, 3.5% to 5%, 4% to 5%, and 4.5% to 5% of the total formulation by weight percentage.
  • ranges about 0.1% to 5%, 0.25% to 5%, 0.5% to 5%, 0.75% to 5%, 1% to 5%, 1.5% to 5%, 2% to 5%, 2.5% to 5%, 3% to 5%, 3.5% to 5%, 4% to 5%, and 4.5% to 5% of the total formulation by weight percentage.
  • a blowing agent refers to a physical or a chemical material (or combination of materials) that acts to expand nucleation sites. Blowing agents may include only chemical blowing agents, only physical blowing agents, combinations thereof, or several types of chemical and physical blowing agents. The blowing agent acts to reduce density by forming cells in the molten formulation at the nucleation sites. The blowing agent may be added to the molten resin mixture in the extruder.
  • Chemical blowing agents are materials that degrade or react to produce a gas.
  • Chemical blowing agents may be endo thermic or exothermic. Chemical blowing agents typically degrade at a certain temperature to decompose and release gas.
  • a chemical blowing agent is citric acid or citric-based material.
  • One representative example is HYDROCEROLTM CF-40E (available from Clariant Corporation), which contains citric acid and a crystal nucleating agent.
  • the citric acid decomposes at the appropriate temperature in the molten formulation and forms a gas which migrates toward the nucleation sites and grows cells in the molten formulation. If sufficient chemical blowing agent is present, the chemical blowing agent may act as both the nucleating agent and the blowing agent.
  • chemical blowing agents may be selected from the group consisting of azodicarbonamide; azodiisobutyro-nitrile; benzenesulfonhydrazide; 4,4- oxybenzene sulfonylsemicarbazide; p-toluene sulfonyl semi-carbazide; barium
  • dichlorotetrafluoroethane chloroheptafluoropropane; dichlorohexafluoropropane; methanol; ethanol; n-propanol; isopropanol; sodium bicarbonate; sodium carbonate; ammonium
  • bicarbonate ammonium carbonate; ammonium nitrite; N,N'-dimethyl-N,N'- dinitrosoterephthalamide; ⁇ , ⁇ '-dinitrosopentamethylene tetramine; azodicarbonamide; azobisisobutylonitrile; azocyclohexylnitrile; azodiaminobenzene; bariumazodicarboxylate;
  • benzene sulfonyl hydrazide toluene sulfonyl hydrazide; p,p'-oxybis(benzene sulfonyl hydrazide); diphenyl sulfone-3,3'-disulfonyl hydrazide; calcium azide; 4,4'-diphenyl disulfonyl azide; p-toluene sulfonyl azide, and combinations thereof.
  • the chemical blowing agent may be introduced into the material formulation that is added to the hopper.
  • N 2 nitrogen
  • the N 2 is pumped into the molten formulation via a port in the extruder as a supercritical fluid.
  • the molten material with the N 2 in suspension then exits the extruder via a die where a pressure drop occurs.
  • N 2 moves out of suspension toward the nucleation sites where cells grow. Excess gas blows off after extrusion with the remaining gas trapped in the cells formed in the extrudate.
  • Other suitable examples of physical blowing agents include, but are not limited to, carbon dioxide (C0 2 ), helium, argon, air, pentane, butane, or other alkane mixtures of the foregoing and the like.
  • a physical blowing agent may be introduced at a rate of about 0.02 pounds per hour to about 0.15 pounds per hour. In still yet another illustrative example, the physical blowing agent may be introduced at a rate of about 0.05 pounds per hours to about 0.15 pounds per hour.
  • At least one slip agent may be any slip agent.
  • Slip agent also known as a process aid
  • slip agent is a term used to describe a general class of materials which are added to the formulation and provide surface lubrication to the polymer during and after conversion. Slip agents may also reduce or eliminate die drool.
  • Representative examples of slip agent materials include amides of fats or fatty acids, such as, but not limited to, erucamide and oleamide. In one exemplary aspect, amides from oleyl (single unsaturated C-18) through erucyl (C-22 single unsaturated) may be used.
  • Other representative examples of slip agent materials include low molecular weight amides and fluoroelastomers. Combinations of two or more slip agents can be used. Slip agents may be provided in a master batch pellet form and blended with the resin formulation.
  • a suitable slip agent is Ampacet 102823 Process Aid PE MB LLDPE.
  • a core-layer formulation can include a slip agent.
  • the amount of a slip agent may be one of several different values or fall within one of several different ranges. It is within the scope of the present disclosure to select an amount of a slip agent and be one of the following values: about 0%, 0.1%, 0.25%, 0.5%, 0.75%, 1%, 1.25%, 1.5%, 1.75%, 2%, 2.25%, 2.5%, and 3% of the total formulation by weight percentage. It is within the scope of the present disclosure for the amount of a slip agent in the formulation to fall within one of many different ranges.
  • the range of a slip agent is one of the following ranges: about 0% to 3%, 0.1% to 3%, 0.25% to 3%, 0.5% to 3%, 1% to 3%, 1.25% to 3%, 1.5% to 3%, 1.75% to 3%, 2% to 3%, 2.25% to 3%, and 2.5% to 3% of the total formulation by weight percentage.
  • the range of a slip agent is one of the following ranges: about 0% to 2.5%, 0% to 2%, 0% to 1.75%, 0% to 1.5%, 0% to 1.25%, 0% to 1%, 0% to 0.75%, 0% to 0.5%, and 0.1% to 2.5% of the total formulation by weight percentage.
  • the range of a slip agent is one of the following ranges: about 0.1% to 2.5%, 0.1% to 2%, 0.1% to 1.75%, 0.1% to 1.5%, 0.1% to 1.25%, 0.1% to 1%, 0.1% to 0.75%, and 0.1% to 0.5% of the total formulation by weight percentage.
  • an impact modifier may be incorporated into the formulation to minimize fracturing of the insulative cellular non-aromatic polymeric material when subjected to an impact such as a drop test.
  • a suitable impact modifier is DOW® AFFINITYTM PL 1880G polyolefin plastomer.
  • a colorant can be about 0% to about 4% (w/w), about 0.1% to about 4%, about 0.25% to about 4%, about 0.5% to about 4%, about 0.75% to about 4%, about 1.0% to about 4%, about 1.25% to about 4%, about 1.5% to about 4%, about 1.75% to about 4%, about 2.0% to about 4%, about 2.25% to about 4%, about 2.5% to about 4%, about 3% to about 4%, about 0% to about 3.0%, about 0% to about 2.5%, about 0% to about 2.25%, about 0% to about 2.0%, about 0% to about 1.75%, about 0% to about 1.5%, about 0% to about 1.25%, about 0% to about 1.0%, about 0% to about 0.75%, about 0% to about 0.5%, about 0.1% to about 3.5%, about 0.1% to about 3.0%, about 0.1% to about 2.5%, about 0.1% to about 2.25%, about 0.1% to about 2.0%, about 0.1%
  • a core-layer formulation can include a colorant.
  • the amount of a colorant may be one of several different values or fall within one of several different ranges. It is within the scope of the present disclosure to select an amount of a colorant and be one of the following values: about 0%, 0.1%, 0.25%, 0.5%, 0.75%, 1%, 1.25%, 1.5%, 1.75%, 2%, 2.25%, 2.5%, 3%, and 4% of the total formulation by weight percentage. It is within the scope of the present disclosure for the amount of a slip agent in the formulation to fall within one of many different ranges.
  • the range of a colorant is one of the following ranges: about 0% to 4%, 0.1% to 4%, 0.25% to 4%, 0.5% to 4%, 1% to 4%, 1.25% to 4%, 1.5% to 4%, 1.75% to 4%, 2% to 4%, 2.25% to 4%, 2.5% to 4%, and 3% to 4% of the total formulation by weight percentage.
  • the range of a colorant is one of the following ranges: about 0% to 3%, 0% to 2.5%, about 0% to 2.25%, 0% to 2%, 0% to 1.75%, 0% to 1.5%, 0% to 1.25%, 0% to 1%, 0% to 0.75%, and 0% to 0.5% of the total formulation by weight percentage.
  • the range of a slip agent is one of the following ranges: about 0.1% to 3.5%, 0.1% to 3.0%, 0.1% to 2.5%, 0.1% to 2.25%, 0.1% to 2%, 0.1% to 1.75%, 0.1% to 1.5%, 0.1% to 1.25%, 0.1% to 1%, 0.1% to 0.75%, and 0.1% to 0.5% of the total formulation by weight percentage.
  • ranges about 0.1% to 3.5%, 0.1% to 3.0%, 0.1% to 2.5%, 0.1% to 2.25%, 0.1% to 2%, 0.1% to 1.75%, 0.1% to 1.5%, 0.1% to 1.25%, 0.1% to 1%, 0.1% to 0.75%, and 0.1% to 0.5% of the total formulation by weight percentage.
  • step (b) the multi-later parison is extruded in the form of a multi-layer tube in which the core parison surrounds the inner parison and the outer parison surrounds the core parison.
  • step (b) the inner parison core parison, and outer parison from step (a) are aligned such that the core parison is located between the inner parison and the outer parison and the aligned parisons are then co-extruded to form the multilayer tube.
  • the outer and inner parisons each comprise a high density polymeric material.
  • the high-density polymeric material is high density polyethylene or polypropylene.
  • the polypropylene used in either of the skin layers is a high stiffness polypropylene. More suitably, the polypropylene used in either of the skin layers is a high impact polypropylene. Even more suitably, the polypropylene used in either of the skin layers is DOW® D 207.03 developmental performance polypropylene resin or DOW® DC 7067.00 polypropylene impact copolymer. Reference is hereby made to U.S. Patent Application Serial No. 14/468,789, filed August 26, 2014 and titled POLYMERIC MATERIAL FOR
  • CONTAINER for disclosure relating to polypropylene used in either of the skin layers in accordance with the present disclosure, which application is hereby incorporated herein by reference in its entirety.
  • both of the outer and inner parisons are a formed from a polypropylene selected from DOW® D 207.03 developmental performance
  • polypropylene resin and/or DOW® DC 7067.00 polypropylene impact copolymer are examples of polypropylene resin and/or DOW® DC 7067.00 polypropylene impact copolymer.
  • the polyethylene used in either of the inner and outer parisons is a high density ethylene hexane- 1 copolymer.
  • the high density polyethylene is a HDPE hexene copolymer.
  • the high density polyethylene is FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics
  • the polyethylene used in either of the inner and outer parisons may be Chevron Phillips MARLEX® HHM 5502 BN.
  • one or both of the inner and outer layers comprise a high- density polymeric material as hereinbefore defined and a colorant.
  • one or both of the inner and outer layers may comprise 95 - 99.9% (w/w) of a high-density polymeric material as hereinbefore defined and 0.1 to 5% (w/w) a colorant.
  • one or both of the inner and outer layers may comprise 97 - 99.9% (w/w) of a high-density polymeric material as hereinbefore defined and 0.1 to 3% (w/w) a colorant.
  • one or both of the inner and outer layers may comprise 98 - 99.5% (w/w) of a high-density polymeric material as hereinbefore defined and 0.5 to 2% (w/w) a colorant.
  • the relatively high-density polymeric material may be FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation) and the colorant may be COLORTECH® 11933-19 Titanium Oxide Colorant (available from COLORTECH® a PPM Company).
  • inner-layer formulation and outer-layer formulation may be the same. In other examples, inner-layer formulation and outer-layer formulation may be different.
  • the core formulation is suitably as defined hereinbefore.
  • the core formulation comprises:
  • HDPE high density polyethylene
  • nucleating agent as defined herein;
  • the core formulation comprises:
  • HDPE high density polyethylene
  • the core formulation comprises:
  • HDPE high density polyethylene
  • step (d) the expansion of the multilayer tube is achieved by blow molding the multi-layer tube using techniques known in the art.
  • a multilayer vessel obtainable, obtained, or directly obtained by a process defined herein.
  • the core parison comprises an insulative cellular non-aromatic polymeric material.
  • a method of producing a multilayer container comprising:
  • molding the multilayer tube to form a multilayer container in a molding system comprising a mold, a vacuum system providing a vacuum pressure to a mold cavity of the mold during molding, a blowing system providing pressurized gas to tube space, and a trimming system removing excess material from the container following the molding.
  • Clause 3 The method of any other clause, further comprising the step of applying a vacuum in a range of about 5 millimeters Hg to about 25 millimeters Hg to the mold cavity during the expanding step whereby the outer parison engages with the inner surface of the mold.
  • Clause 6. The method of any other clause, wherein the pressurized gas has a pressure in a range of about 30 pounds per square inch to about 50 pounds per square inch.
  • Clause 7. The method of any other clause, wherein the pressurized gas has a pressure of about 40 pounds per square inch.
  • Clause 8 The method of any other clause, wherein the expanding step includes inserting a blow needle into the interior region of the multi-layer tube and pumping pressurized gas into interior region at a temperature up to about 200 degrees Fahrenheit.
  • Clause 14 The method of any other clause, wherein the multi-layer container has an average collapse force of in a range of about 50 pounds-Force to about 400 pounds-Force.
  • Clause 32 The method of any other clause, wherein the pressurized gas is delivered at a temperature of about 0° F to about 200 0 F.
  • Clause 33 The method of any other clause, wherein the pressurized gas is delivered at a temperature of about 30° F to about 80 0 F.
  • Clause 34 The method of any other clause, wherein the pressurized gas is delivered at a temperature of about 40° F to about 50 0 F.
  • Clause 36 The method of any other clause, wherein the pressurized gas is delivered at a temperature of about 50° F.
  • Clause 37 The method of any other clause, wherein the pressurized gas is delivered at a temperature of about room temperature.
  • Clause 50 The method of any other clause, wherein the inner-layer formulation further comprises a colorant.
  • Clause 55 The method of any other clause, further comprising extruding a core-layer formulation to form the core parison, wherein the core-layer formulation comprises a high-density polymeric material.
  • nucleating agent is about 0.1% to 15% (w/w) of the core-layer formulation.
  • nucleating agent is a chemical nucleating agent, a physical nucleating agent, or both a chemical nucleating agent and a physical nucleating agent.
  • Clause 70 The method of any other clause, wherein the physical nucleating agent is about 0% to 7% (w/w) of the core-layer formulation.
  • blowing agent is citric acid or a citric acid-based material.
  • Clause 76 The method of any other clause, wherein the chemical blowing agent is a citric acid and a crystal nucleating agent.
  • benzenesulfonhydrazide 4,4-oxybenzene sulfonylsemicarbazide; p-toluene sulfonyl semi- carbazide; barium azodicarboxylate; N,N'-dimethyl-N,N'-dinitrosoterephthalamide;
  • trihydrazino triazine methane; ethane; propane; n-butane; isobutane; n-pentane; isopentane; neopentane; methyl fluoride; perfluoromethane; ethyl fluoride; 1,1-difluoroethane; 1,1,1- trifluoroethane; 1,1,1,2-tetrafluoro-ethane; pentafluoroethane; perfluoroethane; 2,2- difluoropropane; 1,1,1-trifluoropropane; perfluoropropane; perfluorobutane;
  • perfluorocyclobutane methyl chloride; methylene chloride; ethyl chloride; 1,1,1- trichloroethane; 1,1-dichloro-l-fluoroethane; 1-chloro- 1,1-difluoroethane; l,l-dichloro-2,2,2- trifluoroethane; 1 -chloro- 1 ,2,2,2-tetrafluoroethane; trichloromonofluoromethane;
  • dichlorodifluoromethane trichlorotrifluoroethane ; dichlorotetrafluoroethane ; chloroheptafluoropropane; dichlorohexafluoropropane; methanol; ethanol; n-propanol;
  • azocyclohexylnitrile azodiaminobenzene; bariumazodicarboxylate; benzene sulfonyl hydrazide; toluene sulfonyl hydrazide; p,p'-oxybis(benzene sulfonyl hydrazide); diphenyl sulfone-3,3'- disulfonyl hydrazide; calcium azide; 4,4' -diphenyl disulfonyl azide; and p-toluene sulfonyl azide.
  • Clause 78 The method of any other clause, wherein the core-layer formulation further comprises a physical blowing agent.
  • Clause 88 The method of any other clause, wherein the colorant is about 0% to 4% (w/w) of the core-layer formulation.
  • Clause 89 The method of any other clause, wherein the multilayer tube further comprises an additional layer selected from the group consisting of an oxygen barrier layer, an oxygen scavenging layer, a UV barrier layer, a tie layer, an additional structural layer, and combinations thereof.
  • Inner-layer formulation 40 comprises about 100% FORMOSA PLASTICS®
  • Outer-layer formulation 44 comprises about 99% FORMOSA PLASTICS® FORMOLENE® HB5502F HDPE hexene copolymer and about 1% COLORTECH® 11933-19.
  • Core-layer formulation 48 comprises FORMOSA PLASTICS® FORMOLENE®
  • HB5502F HDPE hexene copolymer which was used as polyethylene base resin.
  • the polyethylene base resin was used in various percentages from about 97.95% to about 100% of the formulation. In some examples, the polyethylene base resin was blended with
  • HYDROCEROL® CF 40E as a nucleating agent and Heritage Plastics HT6000 LLDPE talc as another nucleating agent, and N2 as a blowing agent.
  • the blowing agent was used at levels between about 0.05 lbs/hr to about 0.15 lbs/hour.
  • COLORTECH® 11933-19 was added as a colorant in some examples.
  • Table 9 The various formulations and resulting multi-layer tube densities are shown below in Table 9.
  • the apparatus also included a thermometer to measure the suspension liquid temperature.
  • a suspension liquid is a fluid with a density lower than that of the sample to be measured.
  • the sample must sink in the suspension fluid to determine the sample density.
  • a Mettler AT400 balance (Mettler- Toledo LLC, Columbus, OH) was also used.
  • the density of a limestone-filled HDPE bottle was measured. After taring the balance to zero, the dry solid sample was weighed after placing it in the cup of the Mettler balance. The dry weight was 0.3833 g. After weighing the dry sample and before removing the sample from the cup, the balance was tared again. The sample was removed from the cup and placed on the gem holder in the suspension fluid. The sample was weighed providing the weight with a negative number (-0.3287 g). The number was converted to its absolute value (0.3287 g); the positive value is the sample buoyancy. The sample density was calculated by multiplying the dry weight (0.3833 g) by the suspension fluid density (0.8808 g/cc) and dividing by the sample buoyancy (0.3287 g), which equaled 1.0272 g/cc.
  • Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
  • core-formulation 48 comprised Versalite (A) or Versalite (B).
  • A Versalite
  • B Versalite
  • LLDPE comprised DOW® DOWLEXTM 2045G LLDPE (available from The Dow Chemical Company), electron beam modified to have long-chain branching and a melt index of about 0.2 or 0.13 g/lOmin.
  • the polyethylene base resin was blended with
  • HYDROCEROL® CF 40E as a chemical blowing agent and Heritage Plastics HT6000 LLDPE talc as another nucleating agent.
  • N 2 was used as a blowing agent.
  • the blowing agent was used at levels between about 0.02 lbs/hr to about 0.15 lbs/hour.
  • the molding machine 52 was a rotary extrusion blow-molding machine available from Wilmington Machinery of Wilmington, North Carolina. The RPM speed of this machine was at levels between about 5 RPM to about 75 RPM.
  • the various formulations are shown below in Table 10.
  • the blowing agent, N 2 was injected into the molten formulation to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent.
  • the resulting expanded formulation was then extruded through a die head to establish a core-layer parison.
  • the core-layer parison was molded to form a container according to the present disclosure.
  • Containers formed according to Table 10 were subjected to a series of
  • Table 11 Parison densities, container densities, weights, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 3.
  • Core layer 48 comprised FORMOSA PLASTICS® FORMOLENE® HB5502F
  • HDPE hexene copolymer as a polyethylene base resin.
  • the polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent, Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent.
  • N2 was used as a blowing agent. The percentages were about:
  • a mold was closed around the tube and a blow needle was inserted into a space formed in the tube. During inserting the needle, the mold moved away from the die head. In some examples, vacuum was applied to the mold and in others no vacuum was applied to the mold. Vacuum caused the pressure to decrease to P VAC , which is between about 0 inches Hg and about 29 inches Hg. Pressurized gas, in some examples air, was pumped into a space formed in the tube to cause the tube to expand and take on the shape of the mold. In the next step, the mold was opened to reveal a container.
  • Cycle time is defined as an amount of time between closing the mold around the tube and opening the mold to reveal a container.
  • cycle time was varied between 14 and 18 seconds.
  • gas pressure varied between about 40 psi and about 60 psi.
  • pressurized gas was about room temperature.
  • Drop testing determines a likelihood of container survival due to a drop or impact to the container.
  • Containers were subjected to a drop testing procedure based on ASTM D2463 (Standard Test Method for Drop Impact Resistance of Blow-Molded Thermoplastic Containers), which is incorporated by reference herein in its entirety.
  • the drop test was performed according to the following procedure.
  • a bucket was filled with tap water.
  • the water in the bucket was allowed to condition for at least 24 hours at about room temperature and about 75% relative humidity.
  • the container was filled with water from the bucket and closed off with, for example, a lid.
  • the filled, capped containers were then subjected to the following procedure: (a) the filled, capped container was located at about five feet above a hard surface such as concrete or tile; (b) the filled, capped container was then oriented such that a bottom of the filled, capped container was arranged to lie in a substantially parallel relation to the hard surface; (c) each of ten capped, filled containers were dropped; (d) upon impact, each filled, capped container was examined for any break or shattering of the wall that causes water to leak out of the bottle; and (d) the total number of bottles showing any sign of leakage after the drop test were counted as failures.
  • Top load testing determines how much force a container can withstand before the container fails or necks in to form an hourglass shape.
  • Various containers 10 were subjected to top load testing.
  • An Instron tester such as and generally consistent with an Instron Series 5500 Load Frame, may be used to determine top load performance as suggested in Fig. 15.
  • the top load test was generally performed according to the following procedure.
  • a container was placed on a flat surface such that the floor of the container was arranged to lie in a substantially parallel relation to the flat surface.
  • a crosshead of the Instrom tester applied a compressive force to the top of the neck of the container.
  • a load transducer mounted in series with the container, measured the applied load.
  • Containers 10 were tested until they failed or necked in to form an hourglass shape. Once failure or necking was observed, the value shown on Instron tester was recorded.
  • Containers formed according to Table 12 were subjected to a series of
  • measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force performance measurements, and drop testing. The results are shown below in Table 13.
  • Table 13 Parison densities, bottle densities, weight, top load performance, bottle sidewall thicknesses, and drop test results of different insulative cellular non-aromatic polymeric material formulations of Example 5.
  • Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
  • HB5502F HDPE hexene copolymer as a first material of a polyethylene base resin.
  • EQUISTAR® ALATHON® H5520 HDPE copolymer (available from Lyondell Chemical Company), electron beam modified to have long-chain branching and a melt index of about 0.75 g/lOmin, was used as a second material of the polyethylene base resin.
  • the polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent.
  • N 2 was used as a blowing agent.
  • the blowing agent was used at levels between about 0.03 lbs/hr to about 0.11 lbs/hour.
  • the blowing agent, N 2 was injected into the molten formulation to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent.
  • the resulting expanded formulation was then extruded through a die head to establish a core-layer parison.
  • the core-layer parison, also called tube, was molded to form a container according to the present disclosure.
  • Containers formed according to Table 12 were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, and top load force performance measurements. The results are shown below in Table 13.
  • Table 15 Parison densities, bottle densities, weight, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 9.
  • Core-layer formulation 48 comprises FORMOSA PLASTICS® FORMOLENE®
  • HB5502F HDPE hexene copolymer as a first material of a polyethylene base resin.
  • DOW® DOWLEXTM 2045G LLDPE available from The Dow Chemical Company
  • electron beam modified to have long-chain branching and a melt index of about 0.15 g/lOmin is used as a second material of a second polyethylene base resin.
  • the polyethylene base resin is blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent and Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent.
  • N 2 is used as a blowing agent.
  • the blowing agent, N 2 is injected into the molten formulation to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent.
  • the resulting expanded formulation is then extruded through a die head to establish a core-layer parison.
  • the tube is molded to form a container according to the present disclosure.
  • Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
  • HB5502F HDPE hexene copolymer as a first material of a polyethylene base resin.
  • the FORMOSA PLASTICS® FORMOLENE® HB5502F HDPE hexene copolymer comprises various amounts of virgin and regrind materials.
  • the polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent and Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent. N2 was used as a blowing agent. The percentages were about:
  • a mold was closed around the tube and a blow needle was inserted into a space formed in the tube. During inserting the needle, the mold moved away from the die head.
  • Vacuum was applied to the mold and caused the pressure to decrease to P VAC , which is between about 0 inches Hg and about 29 inches Hg.
  • Pressurized gas in some examples air, was pumped into a space formed in the tube to cause the tube to expand and take on the shape of the mold.
  • the pressurized gas in this example was about 40 psi and about room temperature.
  • the mold was opened to reveal a container.
  • Cycle time is defined as an amount of time between closing the mold around the tube and opening the mold to reveal a container.
  • the cycle time in this example was between 14 and 16 second. In one example, cycle time was 15 seconds.
  • Containers formed according to Table 17 were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force performance measurements, and drop testing. The results are shown below in Table 18.
  • Table 18 Parison densities, bottle densities, weights, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 12.
  • Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
  • HB5502F HDPE hexene copolymer as a first material of a polyethylene base resin.
  • DOW® DOWLEXTM 2045G LLDPE available from The Dow Chemical Company
  • electron beam modified to have long-chain branching and a melt index of about 0.15 g/lOmin was used as a second material of a second polyethylene base resin.
  • the polyethylene base resin was blended with HYDROCEROL® CF 40E as a Chemical Blowing Agent (CBA) and nucleating agent and Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent.
  • N 2 was used as a blowing agent.
  • the blowing agent, N 2 was injected into the molten formulation at a rate between about 0.03 and 0.11 lbs/hr to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent.
  • the resulting expanded formulation was then extruded through a die head to establish a core-layer parison.
  • a mold was closed around the tube and a blow needle was inserted into a space formed in the tube. During inserting the needle, the mold moved away from the die head.
  • Vacuum was applied to the mold and caused the pressure to decrease to P VAC , which is between about 0 inches Hg and about 29 inches Hg.
  • Pressurized gas in some examples air, was pumped into a space formed in the tube to cause the tube to expand and take on the shape of the mold.
  • the pressurized gas in this example was about 40 psi and about room temperature.
  • the mold was opened to reveal a container.
  • Cycle time is defined as an amount of time between closing the mold around the tube and opening the mold to reveal a container.
  • the cycle time in this example was between 14 and 16 second. In one example, cycle time was 15 seconds.
  • Thickness for Formulations of Example 14 [00299] Containers formed according to Table 19 were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force performance measurements, and drop testing. The results are shown below in Table 20.
  • Table 20 Parison densities, bottle Densities, weight, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 14.
  • Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
  • the FORMOSA PLASTICS® FORMOLENE® HB5502F HDPE hexene copolymer comprises various amounts of virgin and second pass regrind material.
  • Second pass regrind material may be, for example, material prepared previously in Table 17 which included first pass regrind.
  • the polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent and Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent. N2 was used as a blowing agent. The percentages were about:
  • the HDPE and nucleating agents were added to an extruder hopper and blended to provide a formulation.
  • the formulation was then heated in the extruder to form a molten formulation.
  • the blowing agent was then added to the molten formulation at a rate of about:
  • blowing agent, N 2 was injected into the molten formulation to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent.
  • the resulting expanded formulation was then extruded through a die head to establish a parison.
  • a mold was closed around the tube and a blow needle was inserted into a space formed in the tube. During inserting the needle, the mold moved away from the die head.
  • Vacuum was applied to the mold and caused the pressure to decrease to P VAC , which is between about 0 inches Hg and about 29 inches Hg.
  • Pressurized gas in some examples air, was pumped into a space formed in the tube to cause the tube to expand and take on the shape of the mold.
  • the pressurized gas in this example was about 40 psi and about room temperature.
  • the mold was opened to reveal a container.
  • Cycle time is defined as an amount of time between closing the mold around the tube and opening the mold to reveal a container.
  • the cycle time in this example was between 14 and 16 second. In one example, cycle time was 15 seconds.
  • Table 21 Virgin/second pass regrind percentages and molding parameters used to form containers of Example 16. Table 17 formulations were run through Table 21.
  • Containers formed according to Table 21 were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force measurements, and drop testing. The results are shown below in Table 22.
  • Table 22 Parison densities, bottle densities, weight, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 16.
  • Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
  • HB5502F HDPE hexene copolymer as a first material of a polyethylene base resin.
  • the FORMOSA PLASTICS® FORMOLENE® HB5502F HDPE hexene copolymer comprises various amounts of virgin and second pass regrind material.
  • the polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent and Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent. N2 was used as a blowing agent. The percentages were about:
  • the HDPE and nucleating agents were added to an extruder hopper and blended to provide a formulation.
  • the formulation was then heated in the extruder to form a molten formulation.
  • the blowing agent was then added to the molten formulation at a rate of about:
  • Containers were prepared according to the present disclosure.
  • the molding machine 52 was a rotary extrusion blow-molding machine available from Wilmington
  • the RPM speed of this machine was at levels between about 5 RPM to about 75 RPM.
  • Containers were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force measurements, and drop testing. The results are shown below in Table 23.
  • Outer-layer formulation 44 comprised about 95% to about 100% Marlex® HHM
  • Inner-layer formulation 40 comprised about 100% Marlex® HHM 5502BN HDPE (available from Chevron Phillips Chemical Company).
  • Core-layer formulation 48 comprised about 100% Marlex® HHM 5502BN HDPE
  • polyethylene base resin (available from Chevron Phillips Chemical Company) as a first material of a polyethylene base resin.
  • EQUISTAR® ALATHON® H5520 HDPE copolymer (available from Lyondell Chemical Company), electron beam modified to have long-chain branching and a melt index of about 0.75 g/10 min , was used as a second material of the polyethylene base resin.
  • the polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and Heritage Plastics HT6000 LLDPE talc as another nucleating agent. N 2 was used as a blowing agent.
  • the blowing agent, N 2 was injected into the molten formulation at levels between about 0.02 lbs/hr to about 0.15 lbs/hour to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent.
  • the resulting expanded formulation was then extruded through a die head to establish a core-layer parison. Inner and outer layers were extruded through the die head, locating the expanded formulation therebetween, to form a multi-layer tube.
  • the multi-layer tube was molded to form a container according to the present disclosure.
  • Table 24 Comparison of different insulative cellular non-aromatic polymeric material formulations of Example 19.
  • Multi-layer containers formed according to Table 24 were subjected to a series of measurements including container the average of several density measurements, weight measurements (p), and thickness measurements. The results are shown below in Table 25.
  • Table 25 Densities, weights, top load performance, and layer thicknesses of insulative cellular non-aromatic polymeric material formulations of Example 19.
  • Rigidity testing determines how resistant containers are to deformation.
  • Various multi-layer containers 10 in accordance with the present disclosure were subjected to rigidity testing. Each multi-layer container was placed in a rigidity tester as shown in Fig. 16 and tested to determine rigidity as shown below in Table 3. Testing involved placing a multi-layer container in a rigidity tester 300 as shown in Fig. 16 in two orientations.
  • the rigidity tester included a stationary cylindrical stop 302 on a left side and a movable anvil 304 and force gauge 306 on a right side.
  • the movable anvil was generally T-shaped as shown in Fig. 16. For each orientation, sidewall 90 of multi-layer container 10 was deformed about midway between floor 88 and neck 92 of multi-layer container 10.
  • Multi-layer containers formed according to Table 24 were subjected to a series of measurements and performance tests including top load force performance measurements, rigidity measurements, and drop testing. The results are shown below in Table 25.
  • Outer-layer formulation 44 comprised about 75% to about 100% Marlex® HHM
  • COLORTECH® 11933-19 Titanium Oxide Colorant available from COLORTECH® a PPM Company
  • Hyperform® HPR-803i available from Milliken
  • Inner-layer formulation 40 comprised about 85% to 100% Marlex® HHM 5502BN HDPE (available from Chevron Phillips Chemical Company) and about 0% to about 20% Hyperform® HPR-803i (available from Milliken Chemical) as a reinforcing fiber.
  • Core-layer formulation 48 comprised about 98% to about 100 Marlex® HHM
  • HDPE available from Chevron Phillips Chemical Company
  • the polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent and Heritage Plastics HT6000 LLDPE talc as another nucleating agent.
  • N 2 was used as a blowing agent.
  • the blowing agent, N 2 was injected into the molten formulation at levels between about 11 kg/hour to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent.
  • the resulting expanded formulation was then extruded through a die head to establish a core-layer parison. Inner and outer layers were extruded through the die head, locating the expanded formulation therebetween, to form a multilayer tube.
  • the multi-layer tube was molded to form a container according to the present disclosure.
  • Table 27 Comparison of different insulative cellular non-aromatic polymeric material formulations of Example 23.
  • DOE 1-1 100% 0.10% 0.30% 95% 5% 0% 100% 0%
  • DOE 1-2 100% 0.10% 0.30% 95% 5% 0% 100% 0%
  • DOE 1-3 100% 0.10% 0.30% 95% 5% 0% 100% 0%
  • DOE 1-4 98.4% 0.10% 1.50% 95% 5% 0% 100% 0%
  • DOE 1-5 98.4% 0.10% 1.50% 95% 5% 0% 100% 0%
  • DOE 1-8 99.2% 0.50% 0.30% 95% 5% 0% 100% 0%
  • DOE 1-10 98.0% 0.50% 1.50% 95% 5% 0% 100% 0% E 1-lOA (Dual Fiber) 98.0% 0.50% 1.50% 80% 5% 15% 85% 15%
  • DOE 1-11 98.0% 0.50% 1.50% 95% 5% 0% 100% 0%
  • DOE 1-12 98.0% 0.50% 1.50% 95% 5% 0% 100% 0%
  • DOE 1-1 10% 99.6% 0.10% 0.30% 85% 5% 10% 100% 0%
  • DOE 1-1 15% 99.6% 0.10% 0.30% 80% 5% 15% 100% 0%
  • DOE 1-1 20% 99.6% 0.10% 0.30% 75% 5% 20% 100% 0%
  • Multi-layer containers formed according to Table 27 were subjected to a series of measurements including visual score (determined according to Example 30), container density (p) measurements, weight measurements, and thickness measurements. The results are shown below in Table 28.
  • Table 28 Visual score, densities, Weight, Top Load Performance, and Layer
  • Thicknesses of insulative cellular non-aromatic polymeric material formulations of Example 23 were obtained by insulative cellular non-aromatic polymeric material formulations of Example 23.
  • DOE 1-1 11.35 17.1 0.710 0.039 0.025 0.062
  • DOE 1-4 11.4 17.7 0.644 0.036 0.025 0.064
  • DOE 1-5 11.35 17.2 0.685 0.033 0.022 0.057
  • DOE 1-6 11.5 16.8 0.744 0.030 0.020 0.050
  • DOE 1-7 10.35 17.4 0.612 0.037 0.025 0.065
  • DOE 1-8 10.8 17.3 0.697 0.034 0.023 0.059
  • DOE 1-9 10.9 17.1 0.760 0.030 0.021 0.052 Physical Wall Thickness
  • DOE 1-10 10.7 17.0 0.625 0.038 0.024 0.060
  • DOE 1-11 10.5 17.1 0.693 0.032 0.021 0.051
  • DOE 1-12 11.6 17.5 0.784 0.029 0.022 0.044
  • DOE 1-1 10% 10.8 17.0 0.624 0.040 0.018 0.063
  • DOE 1-1 20% 9 17.1 0.665 0.034 0.023 0.055
  • Multi-layer containers formed according to Table 27 were subjected to a series of measurements and performance tests including top load force performance measurements, rigidity measurements, drop testing, and cap application and removal. The results are shown below in Table 29.
  • Example 6 Drop tests were conducted by methods described in Example 6. In some examples, the method described in Example 6 was followed with the exception of replacing water with shampoo. Top load performance was measured by methods described in Example 7. In some examples, the method described in Example 7 was performed with a container that was closed with a cap. In other examples, the method in Example 7 was performed with a container without a cap. Rigidity was measured by methods described in Example 21. The forces required to remove and apply caps to the containers were measured.
  • Containers having caps were subjected to application and removal testing based on ASTM D3473-88 (Standard Test Methods for Lifting Force Required to Remove Certain Child-Resistant Snap Caps) and ASTM D3480-88 (Standard Test Methods for Downward Force Required to Open or Activate Child-Resistant Snap-Engagement Packages), each of which is incorporated by reference herein in its entirety.
  • Containers were given scores based on a set of twelve observable factors. Each time a container lacked an observable factor, one point was awarded. Thus, a container lacking all observable factors obtained a best score of 12.
  • the observable factors included: 1) presence of holes, 2) the presence of foreign material, 3) whether the container was malformed, 4)

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Abstract

A vessel is configured to hold a product in an interior region formed in the vessel. The vessel includes an inner layer arranged to define the interior region and an outer layer. The vessel is formed using a blow-molding process in which a multiple layer parison is blow molded to form the vessel. The multiple layer parison is formed in an extrusion process in which a number of extruders are arranged to co-extrude associated.

Description

CONTAINER AND PROCESS FOR MAKING THE SAME
PRIORITY CLAIM
[0001] This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional
Application Serial No. 61/872,260, filed August 30, 2013, U.S. Provisional Application Serial No. 61/872,368, filed August 30, 2013, and U.S. Provisional Application Serial No. 61/872,183, filed August 30, 2013, each of which is expressly incorporated by reference herein.
BACKGROUND
[0002] The present disclosure relates to containers, and in particular to containers made from polymeric materials. More particularly, the present disclosure relates containers made using a blow-molding process.
SUMMARY
[0003] According to the present disclosure, a container is formed to include an interior region adapted to store products therein. The container is made using a container-molding process in which a tube of polymeric materials is extruded and then blow molded.
[0004] In illustrative embodiments, a container-molding process is used to establish a multi-layer container from a multi-layer tube. The container-molding process includes an extruding operation, a blow-molding operation, and a trimming operation. During the extruding operation, a co-extrusion system co-extrudes a multi-layer tube that comprises an inner layer, an outer layer spaced apart from the inner layer, and a core layer located therebetween. The core layer is made from relatively low-density insulative cellular non-aromatic polymeric materials. During the blow-molding operation, the multi-layer tube is located in a mold and pressurized gas is pumped into a spaced formed in the multi-layer tube to cause the multi-layer tube to expand and take on a shape of the mold so that a vessel is established. During the trimming operation, excess materials are removed from the vessel to establish the multi-layer container.
[0005] In illustrative embodiments, the multi-layer container includes an inner layer, an outer layer spaced apart from the inner layer, and a compressed core layer located therebetween. The compressed core layer is made from relatively low-density insulative cellular non-aromatic polymeric material which has been compressed during the blow-molding operation. As a result, the multi-layer container has a relatively low density while stack strength, rigidity, and top load performance are maximized. The low density of the multi-layer container also minimizes an amount of polymeric material used to form the multi-layer container.
[0006] Additional features of the present disclosure will become apparent to those skilled in the art upon consideration of illustrative embodiments exemplifying the best mode of carrying out the disclosure as presently perceived.
BRIEF DESCRIPTIONS OF THE DRAWINGS
[0007] The detailed description particularly refers to the accompanying figures in which:
[0008] Fig. 1 is a diagrammatic and perspective view of a container-molding process in accordance with the present disclosure showing that the container-molding process includes an extruding operation in which a multi-layer tube is extruded from a co-extrusion system, a closing operation in which a mold is closed around the multi-layer tube, an inserting operation in which a blow needle is inserted into a tube space formed in the multi-layer tube while vacuum is applied to the mold, a pumping operation in which pressurized gas is pumped into tube space, an expanding operation in which the pressurized gas expands the multi-layer tube against an inner surface of the mold, an opening operation in which the mold is opened and a vessel is released, and a trimming operation in which excess material is trimmed from the vessel to establish a multi-layer container in accordance with the present disclosure as suggested in Fig. 13;
[0009] Fig. 2 is a diagrammatic view of the container-molding process of Fig. 2 showing that the container-molding process includes a series of operations which produce the multi-layer tube and form the multi-layer container;
[0010] Fig. 3 is a perspective and diagrammatic view of the co-extrusion system used to make the multi-layer tube showing that the co-extrusion system includes an outer-layer extruder configured to receive an outer-layer formulation and provide an outer-layer parison, an inner- layer extruder configured to receive an inner-layer formulation and provide an inner-layer parison, a core-layer extruder configured to receive a core-layer formulation and provide a core- layer parison, and a co-extrusion die coupled to each of the extruders to receive the associated parisons and configured to extrude the inner-layer, core-layer, and outer-layer parisons to establish the multi-layer tube;
[0011] Fig. 4 is a partial perspective view taken from below the co-extrusion die of the co-extrusion system showing that the co-extrusion die includes an annular aperture configured to extrude the multi-layer tube; [0012] Fig. 5 is a view similar to Fig. 4 after co-extrusion of the multi-layer tube has begun with portions of the multi-layer tube broken away to reveal that the inner layer is spaced apart from the outer layer and that the core layer is located therebetween;
[0013] Fig. 6 is an enlarged partial perspective view of Fig. 1 showing that prior to the closing operation, the multi-layer tube is located between two mold halves and that a vacuum source coupled to the mold is turned off so that atmospheric pressure exists in a mold cavity formed between the two mold halves when the mold is in a closed position;
[0014] Fig. 7 is an enlarged partial perspective view of Fig. 1 showing that after the closing operation, the vacuum source is turned on and pressure inside the mold cavity decreases to establish a vacuum in the mold cavity which minimizes loss of cell structure in the core layer during the blowing and expanding operations;
[0015] Fig. 8A is a sectional view taken along line 8A-8A of Fig. 7 showing that prior to the blowing operation, the multi-layer tube has an outer tube surface which establishes a preform radius and an inner surface of the mold has a relatively greater mold radius;
[0016] Fig. 8B is a view similar to Fig. 8A taken along line 8B-8B of Fig. 1 showing that the multi-layer tube has expanded to engage the inner surface of the mold after the expanding operation is complete and that the vessel includes an outer container surface which establishes a relatively greater container radius which is about equal to the mold radius;
[0017] Fig. 9 is a view similar to Fig. 7 showing the mold and multi-layer tube after the inserting operation in which the blow needle is inserted through the mold and into the tube space of the multi-layer tube and that a pressurized source of gas is turned off so that a pressure in the space is about atmospheric;
[0018] Fig. 10 is sectional view taken along line 10-10 of Fig. 9 showing that prior to the blowing operation, the core layer of the multi-layer tube includes a plurality of expanded cells filled with gas which cause a density of the core layer to be minimized so that a density of the of the multi-layer container is also minimized;
[0019] Fig. 11 is view similar to Fig. 9 showing the mold and multi-layer tube during the expanding operation in which the source of pressurized gas has been turned on causing pressure in the tube space to increase to PBLOW which is above atmospheric pressure so that the multilayer tube expands outwardly toward the inner surface of the mold; [0020] Fig. 12 is a view similar to Fig. 10 taken along line 12-12 of Fig. 11 showing that during the expanding operation, the plurality of expanded cells remain intact in the core layer so that the density of the vessel is minimized;
[0021] Fig. 13 is a perspective view of the multi-layer container formed from the container-molding process of Figs. 1 and 2 after the trimming operation has completed;
[0022] Fig. 14 is a sectional view taken along line 14-14 of Fig. 13 showing that the multi-layer container includes a side wall including the inner layer, the outer layer spaced apart from the inner layer, and a compressed core layer located therebetween and showing that some of the expanded cells have collapsed along the inner and outer layers to cause the compressed core layer to have a relatively greater density than the core layer of the multi-form tube;
[0023] Fig. 15 is a partial perspective view of the multi-layer container of Fig. 13 coupled to a top-load testing device undergoing top-load testing;
[0024] Fig. 16 is a photograph of the multi-layer container of Fig. 13 coupled to a rigidity testing device undergoing rigidity testing;
[0025] Fig. 17 is a perspective view of an unassembled density determination apparatus showing the components (clockwise starting in the upper left) gem holder, platform, suspension bracket, and suspension spacer.
DETAILED DESCRIPTION
[0026] A multi-layer container 10 in accordance with the present disclosure is suggested in Fig. 1 and shown in Fig. 13. Multi-layer container 10 is formed by a container-molding process 100 in accordance with the present disclosure as shown in Fig. 1 and suggested in Fig. 2. Container-molding process 100 begins with extruding 102 a multi-layer tube 12 that includes a core layer 12B made from relatively low-density insulative cellular non-aromatic polymeric material. Container-molding process 100 proceeds by molding multi-layer tube 12 into multilayer container 10 which may cause core layer 12B of multi-layer tube 12 to compress and establish a compressed core layer 10B included in multi-layer container 10. As a result of compressed core layer 10B being made from relatively low-density insulative cellular non- aromatic polymeric material, a density of multi-layer container 10 is minimized while stack strength, rigidity, and top-load performance of multi-layer container 10 are maximized.
[0027] Container-molding process 100 begins with an extruding operation 102 in which multi-layer tube 12 is extruded from a co-extrusion system 16 as suggested in Fig. 1 and shown in Fig. 3. Container- molding process 100 then proceeds to a closing operation 104 in which a mold 18 is closed around multi-layer tube 12 as shown in Fig. 1. Container-molding process then moves onto an inserting operation 106 in which a blow needle 20 is inserted into a tube space 22 formed in multi-layer tube 12 while vacuum from a vacuum source 24 is applied to mold 18. Container-molding process 100 then proceeds to a pumping operation 108 in which pressurized gas 26 is pumped into tube space 22 as suggested in Fig. 1. Container-molding process 100 then moves on to simultaneous operations including a vacuuming operation 109 in which vacuum is applied to mold 18 and an expanding operation 110 in which pressurized gas 26 expands multi-layer tube 12 against an inner surface 28 of mold 18 and establishes a vessel 30. An opening operation 112 then occurs in which mold 18 opens to reveal vessel 30. Next, a removing operation 114 occurs in which vessel 30 is separated from mold 18 and released from blow needle 20. Container-molding process 100 then ends with a trimming operation 116 in which excess materials 62, 64 are trimmed from multi-layer container 10 to establish multi-layer container 10 as suggested in Fig. 1 and shown in Fig. 13.
[0028] Multi-layer container 10 is made during container-molding process 100 using multi-layer tube 12 as shown in Fig. 1. Multi-layer tube 12 is provided during extruding operation 102 of container-molding process 100. Extruding operation 102 is performed using co-extrusion system 16 as shown in Fig. 3. Extruding operation 102 includes a preparing stage 102A in which various material formulations are provided to co-extrusion system 16, an extrusion stage 102B in which the various material formulations are processed by co-extrusion system 16 to provide associated parisons, and a co-extruding stage 102C in which the various parisons are extruded to provide multi-layer tube 12 as shown in Fig. 1 and suggested in Fig. 3. Reference is hereby made to U.S. Provisional Application Serial No. 61/872,260, filed August 30, 2013 and titled MULTI-LAYER TUBE AND PROCESS FOR MAKING THE SAME and
U.S. Application Serial No. , filed September 2, 2014 and titled
MULTI-LAYER TUBE AND PROCESS FOR MAKING THE SAME for disclosure relating to an extruding operation, which application is hereby incorporated in its entirety.
[0029] Extruding operation 102 is performed on co-extrusion system 16 which includes an inner-layer extruder 32, an outer-layer extruder 34, a core-layer extruder 36, and a co- extrusion die 38 as shown in Fig. 3. Inner-layer extruder 32 receives an inner-layer formulation 40 of a relatively high-density polymeric material and processes inner-layer formulation 40 to provide an inner-layer parison 42 to co-extrusion die 38 as shown in Fig. 3. Outer-layer extruder 34 receives an outer-layer formulation 44 of a relatively high-density polymeric material and processes outer-layer formulation 44 to provide an outer-layer parison 46 to co- extrusion die 38 as shown in Fig. 3. Core-layer extruder 36 receives a core-layer formulation 48 of a relatively low-density insulative cellular non-aromatic polymeric material and processes core-layer formulation 48 to provide a core-layer parison 50 to co-extrusion die 38 as shown in Fig. 3. Co-extrusion die 38 receives the various parisons 42, 46, 50 and extrudes multi-layer tube 12 through an annular aperture 39 as suggested in Figs. 1 and 3 and shown in Figs. 4 and 5.
[0030] While extruding operation 102 is shown forming multi-layer tube 12 having three layers, any number of layers may be formed during the extruding operation. Additional layers may include relatively low-density layers, tie layers, thermoplastic polyurethane (TPU), other olefins, combinations thereof, or any other suitable alternatives and combinations.
[0031] Once extruding operation 102 is complete and multi-layer tube 12 is provided, container- molding process 100 proceeds to establish multi-layer container 10 using a molding system 52 as shown in Fig. 1. Molding system 52 includes, for example, mold 18 formed to include a mold cavity 54 defined by inner surface 28 of mold 18, a vacuum system 56 configured to provide a vacuum pressure to mold cavity 54 during molding of multi-layer container 10, a blowing system 58 configured to provide pressurized gas 26 to tube space 22, and a trimming system 60 configured to remove excess materials 62, 64 from vessel 30 as shown in Fig. 1.
[0032] Container-molding process 100 proceeds to closing operation 104 after multilayer tube 12 has been established as shown in Figs. 1 and 2. First and second mold halves 18A, 18B included in mold 18 begin in an opened position in which mold halves 18 A, 18B are spaced apart from one another as shown in Fig. 1. During closing operation 104, mold halves 18A, 18B move toward one another to achieve a closed position in which multi-layer tube 12 is located in mold cavity 54 formed therebetween. During closing operation 104, a vacuum source 66 included in vacuum system 56 remains off and pressure in mold cavity 54 remains at about atmospheric pressure as measured by a mold-cavity pressure gauge 68 as shown in Fig. 1.
[0033] Once mold 18 is in the closed position, container-molding process 100 proceeds to inserting operation 106 as shown in Figs. 1 and 2. During inserting operation 106, mold 18 moves away from co-extrusion die 38 and aligns with blow needle 20 included in blowing system 58. Blow needle 20 then moves downwardly through mold 18 into tube space 22 included in multi-layer tube 12 as shown in Figs. 1 and 2. At the same time, vacuum source 66 is turned on causing pressure in mold cavity 54 to decrease to PVAC which is below atmospheric pressure. Vacuum is applied at a pressure in a range of about 5 mmHg to about 25 mmHg. In another example vacuum is applied at a pressure of about 20 mmHg. As a result, PVAC is greater than the vacuum applied and less than atmospheric pressure. PVAC may be in a range of about 5 inches Hg to about 20 inches Hg. In another example, PVAC is in a range of about 10 inches Hg to about 20 inches Hg. In still yet another example, PVAC is about 10 inches Hg.
[0034] As a result of blow needle 20 being inserted into tube space 22, pressurized gas
(e.g., air) provided by a source 70 of pressurized gas 26 included in blowing system 58 may be communicated into tube space 22 to expand a size of multi-layer tube 12 in subsequent operations. However, during inserting operation 106, source 70 of pressurized gas 26 is turned off and pressure in tube space 22 is measured by a tube pressure gauge 72 to be at about atmospheric pressure (PATM). Pressurized gas may be, for example, standard air, nitrogen, carbon dioxide, combinations thereof, or any other suitable alternative.
[0035] After blow needle 20 has been inserted into tube space 22, container-molding process 100 proceeds to pumping operation 108 as shown in Figs. 1 and 2. During pumping operation 108, source 70 of pressurized gas 26 is turned on and pressure inside tube space 22 increases to a relatively higher pressure (PBLOW)- In one example, PBLOW is in a range of about 30 pounds per square inch and about 120 pounds per square inch. In another example, PBLOW is in a range of about 10 pounds per square inch to about 130 pounds per square inch. In yet another example, PBLOW is in a range of about 35 pounds per square inch to about 45 pounds per square inch. In still yet another example, PBLOW is about 40 pounds per square inch.
[0036] In another illustrative example, source 70 of pressurized gas 26 may be configured to deliver pressurized gas 26 at a temperature to tube space 22. In one example, the temperature is in a range of about 35 degrees Fahrenheit to about 75 degrees Fahrenheit. In another example, the temperature is in a range of about 40 degrees Fahrenheit to about 70 degrees Fahrenheit. In yet another example, the temperature is in a range of about 50 degrees to about 75 degrees Fahrenheit. In another example, the temperature is about room temperature. In another example, the temperature is about 40 degrees Fahrenheit. In still yet another example, the temperature is about 50 degrees Fahrenheit.
[0037] After pressurized gas 26 has begun to enter tube space 22 through blow needle
20, container-molding process 100 proceeds to both vacuuming operation 109 and expanding operation 110 as shown in Figs. 1 and 2. During vacuuming operation 109, vacuum is applied to mold cavity 54. At the same time vacuuming operation 109 is ongoing, expanding operation 110 commences. During expanding operation 110, pressurized gas 26 continues to flow through blow needle 20 causing multi-layer tube 12 to expand and engage inner surface 28 of mold 18 and fill mold cavity 54 as suggested in Fig. 1 and Fig. 11. Expanding operation 110 is complete once multi-layer tube 12 has substantially the same shape as mold cavity 54. While expanding operation 110 is ongoing, vacuum source 66 remains on and pressure in mold cavity 54 remains below atmospheric pressure to minimize collapse and damage of expanded cells 69 included in core layer 12B of multi-layer tube 12 as shown in Fig. 12.
[0038] Pumping operation 108, vacuuming operation, and expanding operation 110 cause multi-layer tube 12 to expand from a pre-expansion shape as shown in Figs. 8A and 9 to a post-expansion shape shown in Figs. 1 and 8B which is substantially similar to a shape of vessel 30. An outer tube surface 76 of multi-layer tube 12 has a pre-form radius 78 as shown in Fig. 8 A. Inner surface 28 of mold 18 has a relatively greater mold radius 80 as shown in Fig. 8 A. As shown, for example, in Fig. 8B, vessel 30 has an outer container surface 82 which has a relatively greater container radius 84. Relatively greater container radius 84 is about equal to relatively greater mold radius 80 after expanding operation 110 is complete.
[0039] A blow-up ratio for mold 18 and multi-layer tube 12 is calculated by dividing mold radius 80 by pre-form radius 78. In one example, the blow-up ratio is in a range of about 100% to about 300%. In another example, the blow-up ratio is in a range of about 150% to about 200%. In still yet another example, the blow-up ratio is about 200%. The blow-up ratio may be adjusted to suit various sizes of containers.
[0040] After expanding operation 110 is complete, vessel 30 is established. Vessel 30 includes multi-layer container 10 and excess material 62 coupled to an upper end of multi-layer container 10 and excess material 64 coupled to a lower end of multi-layer container 10.
Container-molding process 100 then proceeds to opening operation 112 as shown in Figs. 1 and 2. During opening operation 112, source 70 of pressurized gas 26 is turned off and mold 18 moves from the closed position to the opened position as shown in Fig. 1. Vessel 30 is then ready for removal from mold 18 and while remaining coupled to blow needle 20 as suggested in Fig. 1.
[0041] Container-molding process 100 then proceeds to removing operation 114 in which vessel 30 is separated from mold 18 and released from blow needle 20. In one example, source 70 of pressurized gas 26 briefly turns on blowing vessel 30 off of blow needle 20. [0042] Once vessel 30 is separated form mold 18 and blow needle 20, container-molding process 100 proceeds to trimming operation 116. During trimming operation 116, excess material 62, 64 is cut using one or more knives 86 or blades to provide multi-layer container 10 as shown in Fig. 1.
[0043] Molding system 52 is used in cooperation with a continuous extrusion process such as extruding operation 102. As suggested in Fig. 1, molding system 52 may be a shuttle blow-molding machine. In this example, mold 18 begins in the opened position and moves on a track toward co-extrusion die 38 to locate multi-layer tube 12 between mold halves 18 A, 18B. Mold 18 then moves to the closed position. Mold 18 then slides away from co-extrusion die 18 while another multi-layer tube 12 is extruded. At the same time, inserting operation 106, pumping operation 108, and expanding operation 110 are performed. Opening operation 112 and removing operations 114 are then performed which cause vessel 30 to be ejected from mold 18. Mold 18 is now in the opened position ready to slide back toward co-extrusion die 30 and begin the process again. One example molding machine 52 is a shuttle blow-molding machine available from Graham Engineering Corporation of York, Pennsylvania. In another example of a shuttle blow-molding machine, more than one mold may be used to minimize cycle time and increase an extrusion rate of co-extrusion system 16.
[0044] In another example, molding machine 52 may be a rotary blow molding machine.
In this example, a continuous multi-layer tube is extruded and a series of molds included in the rotary blow-molding machine rotate relative to the multi-layer tube. As molds approach co- extrusion die 38 forming the multi-layer tube 10, they begin to move from an opened
arrangement to a closed arrangement trapping a portion of the multi-layer tube 10 in a mold cavity formed in the mold. As the molds move away from the co-extrusion die forming the multi-layer tube, pressurized gas is injected in the tube space expanding the multi-layer container. The molds then move from the closed position to an opened position where the vessel 30 is ejected from the mold cavity. One example of a rotary extrusion blow-molding machine is available from Wilmington Machinery of Wilmington, North Carolina.
[0045] Container-molding process 100 has a cycle time defined as an amount of time between closing operation 104 and opening operation 112. This cycle time is defined the same way whether molding machine 52 is a shuttle blow-molding machine or a rotary extrusion blow- molding machine. Multi-layer containers including core layer 12B made from relatively low- density insulative cellular non-aromatic polymeric material may have decreased cycle time due to reduced mass of the container resulting from the use of core-layer 12B.
[0046] In one example, the cycle time for container- molding process 100 and multi-layer container 10 on a shuttle blow-molding machine is in a range of about 5% to about 40% faster than molding operations and containers lacking a layer made from relatively low-density insulative cellular non-aromatic polymeric material. However, it is believed that similar cycle time improvements also occur when using a rotary extrusion blow-molding machine. In another example, cycle time may be in a range of about 5% to about 30% faster than molding operations and containers lacking a layer made from relatively low-density insulative cellular non-aromatic polymeric material. The cycle time of container-molding process 100 and multi-layer container 10 was about 16 seconds.
[0047] Container-molding process 100 uses multi-layer tube 12 to establish multi-layer container 10 as shown, for example, in Figs. 1 and 13. Multi-layer container 10 includes a floor 88, a sidewall 90, and neck 92 as shown in Fig. 13. Sidewall 90 is relatively straight and vertical and provides outer container surface 82. Floor 88 is coupled to a lower end of sidewall 90 and cooperates with sidewall 90 to define an interior product-storage region 94 therebetween. Neck 92 is coupled to an opposite upper end of sidewall 90 and defines an open mouth 96 that is arranged to open into interior product-storage region 94. Neck 92 has a neck radius 98 which is relatively smaller than container radius 84 as shown in Fig. 13.
[0048] Multi-layer container 10 was subjected to a series of performance tests which include drop testing, top load testing, rigidity testing, and metrology testing. Drop testing determines a likelihood of container survival due to a drop or impact to the container. Top load testing determines how much force a container can withstand before the container fails or necks in to form an hourglass shape. Rigidity testing determines how resistant containers are to deformation. Metrology testing determines dimensions of multi-layer container 10 in comparison to specifications for the container.
[0049] Multi-layer container 10 was subjected to drop testing according to one of the
Plastic Bottle Institute Test for Drop Impact Resistance of Plastic Bottles, PBI 4-1968, Rev. 2- 1988 test method and the Rigid Plastics Container Division of the Society of Plastics Industry, Inc. RPCD-7-1991 test method. Various runs of multi-layer container 10 were tested according to Rigid Plastics Container Division of the Society of Plastics Industry, Inc. RPCD-7-1991 test method and the results are shown below in Table 1. [0050] In another example, the drop test may be performed according to the following procedure. The container is filled with water and closed off with, for example, a lid. The sample container is then held at about 73 degrees Fahrenheit (22.8 degrees Celsius) and about 50% relative humidity. The filled, capped containers are then subjected to the following procedure: (a) the filled, capped container is located at about five feet above a hard surface such as concrete or tile; (b) the filled, capped container is then oriented such that a bottom of the filled, capped container is arranged to lie in a substantially parallel relation to the hard surface; (c) each of ten capped, filled containers are dropped; (d) upon impact, each filled, capped container is examined for any break or shattering of the wall that causes water to leak out of the bottle; and (d) the total number of bottles showing any sign of leakage after the drop test are counted as failures. Results for various different trial runs of multi-layer container 10 are shown below in Table. 1.
[0051] Table 1. Drop Test Results for Various Multi-Layer Containers
Trial Run Failure Total Quantity
Number Quantity Tested
1 3 5
2 5 5
3 3 5
4 3 5
5 5 5
6 4 5
7 4 5
8 4 5
9 4 5
10 2 5
11 4 5
12 4 5
13 5 5
14 5 5
15 4 5
16 5 5 [0052] Various multi-layer containers 10 were also subjected to top load testing. An
Instron tester 202 is used to determine top load performance as suggested in Fig. 15. Multi-layer containers 10 were tested until they failed or necked in to form an hourglass shape. Once failure or necking was observed, the value shown on Instron tester 202 was recorded. Table 2 shows the performance of several multi-layer containers including compressed core layer 10B tested vs. several high density polyethylene containers (excluding a core layer). Both types of containers had a total mass of about 56 grams.
[0053] Table 2. Top Load Test Results for Various Multi-Layer Containers
Figure imgf000014_0001
*High density polyethylene container lacking a core layer made from relatively low-density insulative cellular non-aromatic polymeric material [0054] Various types of multi-layer containers 10 in accordance with the present disclosure survived top loads in a range of about 115 pounds-Force to about 170 pounds-Force. In another example, various types of multi-layer containers 10 in accordance with the present disclosure performed about 6% to about 55% better than comparable containers lacking the core layer.
[0055] Various multi-layer containers 10 in accordance with the present disclosure were subjected to rigidity testing. Each multi-layer container was placed in a rigidity tester as shown in Fig. 16 and tested to determine rigidity as shown below in Table 3. Testing involves placing a multi-layer container in a rigidity tester 300 as shown in Fig. 16 in two orientations. The rigidity tester includes a stationary cylindrical stop 302 on a left side and a movable anvil 304 and force gauge 306 on a right side. The movable anvil is generally T-shaped as shown in Fig. 16. For each orientation, sidewall 90 of multi-layer container 10 is deformed about midway between floor 88 and neck 92 of multi-layer container 10. Sidewall 90 is deformed about 0.25 inches over a 10 second interval and the force required to do so is recorded in pounds-Force. The first orientation places a mold seam of multi-layer container in alignment to engage movable anvil 304 (0 Degrees). The second orientation rotates multi-layer container 10 so that the seam is about 90 degrees away from the movable anvil (90 Degrees).
302
[0056] Table 3. Rigidity Test Results for Various Multi-Layer Containers
Sidewall Rigidity -
Trial Run Sidewall Rigidity - Sidewall Rigidity - 0 Degrees 90 Degrees Average
Number
(pounds-Force) (pounds-Force) (pounds-Force)
XI* 1.703 0.887 1.295
1 2.286 1.836 2.061
2 2.298 2.253 2.2755
3 2.231 1.741 1.986
4 2.309 1.857 2.083
5 2.555 1.845 2.2
6 2.25 1.841 2.0455
7 2.424 1.904 2.164
8 2.421 1.928 2.1745 Sidewall Rigidity -
Trial Run Sidewall Rigidity - Sidewall Rigidity - 0 Degrees 90 Degrees Average
Number
(pounds-Force) (pounds-Force) (pounds-Force)
9 2.203 1.775 1.989
X2* 2.081 0.974 1.5275
15 2.192 1.698 1.945
16 2.624 2.009 2.3165
17 3.029 2.551 2.79
18 2.765 2.434 2.5995
19 2.731 2.585 2.658
20 2.104 1.707 1.9055
*High density polyethylene container lacking a core layer made from relatively low-density insulative cellular non-aromatic polymeric material
[0057] Various multi-layer containers 10 were also subjected to metrology
measurements to determine accuracy and repeatability of container- molding process 100 to manufacture multi-layer containers 10 to specification. Table 4 below shows a neck diameter 204 measured at different points along a multi-layer container for several multi-layer containers along with the specified values and limits for each multi-layer container. The measurements were taken at 0 degrees (part line of the mold), 90 degrees (counter-clockwise from the part line), 45 degrees (counter-clockwise from the part line), 135 degrees (counter-clockwise from the part line), average neck diameter, and ovality of the neck. Ovality is the difference between highest and lowest neck diameter measurements.
[0058] Table 4. Neck Diameter Values for Various Runs of Multi-Layer Containers
0 Degree 90 Degree 45 Degree 135 Degree Average
Trial Run
Value Value Value Value Value Ovality Number
(inches) (inches) (inches) (inches) (inches)
Spec.
.090
3.4940 3.4940 3.4940 3.4940 3.4940 Dimension Max.
Spec.
+/-.017 +/-.017 +/-.017 +/-.017 +/-.017 Tolerance
1 3.5719 3.5605 3.4200 3.4337 3.4965 0.1534
2 3.4603 3.4181 3.4669 3.5091 3.4636 0.0964 0 Degree 90 Degree 45 Degree 135 Degree Average
Trial Run
Value Value Value Value Value Ovality Number
(inches) (inches) (inches) (inches) (inches)
Spec.
.090
3.4940 3.4940 3.4940 3.4940 3.4940 Dimension Max.
Spec.
+/-.017 +/-.017 +/-.017 +/-.017 +/-.017 Tolerance
3 3.5697 3.5657 3.4261 3.4332 3.4987 0.1442
4 3.5675 3.5667 3.4159 3.4110 3.4903 0.1609
5 3.5700 3.5671 3.4136 3.4085 3.4898 0.1721
6 3.5658 3.5636 3.4105 3.4121 3.4880 0.1583
7 3.5655 3.5729 3.4129 3.4030 3.4886 0.1701
8 3.5847 3.5599 3.3980 3.4136 3.4890 0.1866
9 3.4960 3.4951 3.5072 3.5054 3.5009 0.0169
14 3.5949 3.5315 3.3871 3.4449 3.4896 0.2078
15 3.5941 3.5441 3.3895 3.4362 3.4910 0.2046
17 3.5739 3.5332 3.3857 3.4135 3.4766 0.1882
18 3.4864 3.4774 3.4559 3.4557 3.4689 0.0425
19 3.4551 3.4126 3.4997 3.5088 3.4690 0.1032
20 3.5039 3.4888 3.4710 3.4749 3.4846 0.0392
21 3.5661 3.4777 3.4235 3.5062 3.4934 0.1427
[0059] Various multi-layer containers 10 were subjected to metrology measurements to determine accuracy and repeatability of container-molding process 100 to manufacture multilayer containers 10 to specification. Table 5 below shows a thread diameter 206 measured at different points along a multi-layer container for several multi-layer containers along with the specified values and limits for each multi-layer container. The measurements were taken at 0 degrees (part line of the mold), 90 degrees (counter-clockwise from the part line), 45 degrees (counter-clockwise from the part line), 135 degrees (counter-clockwise from the part line), average neck diameter, and ovality of the neck. Ovality is the difference between highest and lowest thread diameter measurements.
[0060] Table 5. Thread Diameter Values for Various Runs of Multi-Layer Containers 0 Degree 90 Degree 45 Degree 135 Degree Average
Trial Run
Value Value Value Value Value Ovality Number
(inches) (inches) (inches) (inches) (inches)
Spec.
.090
3.3740 3.3740 3.3740 3.3740 3.3740 Dimension Max.
Spec.
+/-.017 +/-.017 +/-.017 +/-.017 +/-.017 Tolerance
1 3.4508 3.4409 3.2993 3.3196 3.3777 0.1528
2 3.3417 3.3075 3.3447 3.3946 3.3471 0.0954
3 3.4504 3.4483 3.3063 3.3209 3.3815 0.1455
4 3.4477 3.4484 3.2963 3.2991 3.3729 0.1566
5 3.4485 3.4479 3.2946 3.2970 3.3720 0.1652
6 3.4462 3.4455 3.2911 3.3005 3.3708 0.1573
7 3.4448 3.4530 3.2942 3.2910 3.3708 0.1644
8 3.4651 3.4401 3.2785 3.3021 3.3715 0.1867
9 3.3822 3.3808 3.3840 3.3914 3.3846 0.0133
14 3.4732 3.4141 3.2679 3.3318 3.3717 0.2054
15 3.4732 3.4273 3.2706 3.3239 3.3737 0.2026
17 3.4530 3.4135 3.2667 3.3001 3.3583 0.1863
18 3.3667 3.3620 3.3333 3.3415 3.3509 0.0422
19 3.3330 3.2997 3.3778 3.3882 3.3497 0.0954
20 3.3841 3.3712 3.3483 3.3586 3.3656 0.0384
21 3.4449 3.3594 3.3025 3.3900 3.3742 0.1423
[0061] Various multi-layer containers 10 were subjected to metrology measurements to determine accuracy and repeatability of container-molding process 100 to manufacture multilayer containers 10 to specification. Table 6 below shows various measurements taken for several multi-layer containers along with the specified values and limits for each multi-layer container. The measurements taken were an Overall Height (OAH) of the container, an outside diameter of the sidewall taken at 0 degrees (part line of the mold) and 90 degrees (counterclockwise from the part line), an average outside diameter, ovality of the diameter, weight of the container, OFC. OFC is an overflow capacity of multi-layer container 10 and measured in cubic centimeters (cc).
[0062] Table 6. Metrology Body Values for Various Runs of Multi-Layer Containers O Deg. 90 Deg. Average OFC
Trial Run OAH Weight
Value Value Value Ovality (cc) Number (inches) (g)
(inches) (inches) (inches)
Spec.
.090
7.5970 3.7110 3.7110 3.7110 80.0000 1225.3000 Dimension Max.
Spec.
+/-.047 +/-.047 +/-.047 +/-.047 +/- 3.500 +/- 12.900 Tolerance
1 7.5387 3.7282 3.6762 3.7022 0.0520 55.5033 1217.4150
2 7.5083 3.6977 3.6602 3.6790 0.0375 55.5000 *
3 7.5518 3.7333 3.6668 3.7001 0.0665 56.0433 1233.1400
4 7.5482 3.7303 3.6628 3.6966 0.0675 57.2567 1224.2700
5 7.5372 3.7277 3.6534 3.6906 0.0743 57.9767 1218.6800
6 7.5415 3.7321 3.6537 3.6929 0.0784 56.3967 1216.5367
7 7.5394 3.7301 3.6577 3.6939 0.0724 57.5567 1210.1567
8 7.5431 3.7365 3.6518 3.6942 0.0847 56.9300 1216.0400
9 7.5814 3.7240 3.7028 3.7134 0.0212 54.3667 1259.6100
14 7.5309 3.7276 3.6700 3.6988 0.0576 55.4033 1212.4733
15 7.5307 3.7306 3.6666 3.6986 0.0640 56.0200 1216.4100
17 7.5197 3.7317 3.6905 3.7111 0.0520 56.7133 1190.3700
18 7.5157 3.7132 3.7110 3.7121 0.0754 55.7967 *
19 7.5263 3.7236 3.6370 3.6803 0.0866 56.4967 1165.9950
20 7.5438 3.7457 3.6322 3.6890 0.1135 53.5700 1219.2850
21 7.5469 3.7351 3.6617 3.6984 0.0734 56.8267 1222.3133
Value not available as multi-layer container leaked
[0063] Various multi-layer containers 10 were subjected to metrology measurements to determine accuracy and repeatability of container-molding process 100 to manufacture multilayer containers 10 to specification. Table 7 below shows various thicknesses for each inner, outer, and core layer for several multi-layer containers. Table 8 shows various layer thicknesses as a percent of a total thickness for each inner, outer, and core layer and a layer distribution between solid (inner and outer layer) cellular (core layer) for several multi-layer containers. In one example, a total solid phase distribution of inner and outer layers is targeted at about 12- 15% while a cellular phase distribution is targeted about 85-88% as suggested in Table 8 below.
[0064] Table 7. Layer Thicknesses for Various Runs of Multi-Layer Containers
Trial Run Inner Layer Compressed Core Outer Layer
Number (mils) Layer (mils) (mils)
1 3.6 48.8 1.6
2 3.0 50.6 1.9 Trial Run Inner Layer Compressed Core Outer Layer
Number (mils) Layer (mils) (mils)
3 3.6 42.2 1.6
4 3.7 49.3 1.3
5 3.9 49.3 7.9
6 4.4 46.8 3.6
7 5.9 45.5 2.1
8 5.1 52.2 2.1
9 2.7 51.5 1.7
14 4.1 46.1 3.4
15 4.4 50.4 1.9
17 5.4 51.4 2.9
18 5.6 65.6 5.0
19 6.7 72.3 5.8
20 5.9 48.1 6.4
21 5.4 43.6 5.1
[0065] Table 8. Layer Analysis for Various Runs of Multi-Layer Containers
Figure imgf000020_0001
[0066] Multi-layer container 10 is made using container- molding process 100 which begins with an extruding operation 102 as shown in Figs. 1-3. Extruding operation 102 includes several stages that each comprise several operations which cooperate to provide multi-layer tube 12. As suggested in Fig. 3, extruding operation 102 includes a preparing stage 102A in which various material formulations are prepared and provided to each associated extruder to provide the associated layer of multi-layer tube 12. Extruding operation 102 further includes an extrusion stage 102B in which the various formulations are processed by associated extruders to provide associated parisons which are communicated to co-extrusion die 38 as shown in Figs. 1 and 3. Finally, extruding operation 102 ends with a co-extruding stage 102C in which the various parisons are aligned and co-extruded together to establish multi-layer tube 12.
[0067] As suggested in Fig. 3, preparing stage 102A of extruding operation 102 includes a first preparing operation 102A1 in which an inner-layer formulation 40 is prepared and provided to inner-layer extruder 32 as shown in Fig. 3. In one example, inner-layer formulation 40 comprises at least one polymeric material. The polymeric material may include one or more resins. In one example, inner-layer formulation 40 includes a relatively high-density polymeric material. In another example, inner-layer formulation 40 comprises relatively high-density polymeric material. In yet another example, inner-layer formulation 40 is FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation).
[0068] In another example, inner-layer formulation 40 comprises a relatively high- density polymeric material and a colorant. The relatively high-density polymeric material may be FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation) and the colorant may be COLORTECH® 11933-19 Titanium Oxide Colorant (available from COLORTECH® a PPM Company).
[0069] Preparing stage 102 A of extruding operation 102 further includes a second preparing operation 102A2. During second preparing operation 102A2, outer-layer formulation 44 is prepared and provided to outer-layer extruder 34 as shown in Fig. 3. In one example, outer-layer formulation 44 comprises at least one polymeric material. The polymeric material may include one or more resins. In one example, inner-layer formulation 40 includes a relatively high-density polymeric material. In another example, inner-layer formulation 40 comprises relatively high-density polymeric material. In yet another example, inner-layer formulation 40 is FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation).
[0070] In another example, outer-layer formulation 44 comprises a relatively high- density polymeric material and a colorant. The relatively high-density polymeric material may be FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation) and the colorant may be COLORTECH® 11933-19 Titanium Oxide Colorant (available from COLORTECH® a PPM Company).
[0071] In some examples, inner-layer formulation 40 and outer-layer formulation 44 may be the same. In other examples, inner-layer formulation 40 and outer-layer formulation 44 may be different. In still yet other example, additional layers may be included and configured to be an oxygen barrier such as Ethylene Vinyl Alcohol (EVOH), a ultra-violet light barrier, and the like. The additional layers or alternative layers may include other relatively low-density layers, tie layers, TPU layers, other olefins, combinations thereof, or any other suitable combinations and alternatives.
[0072] Preparing stage 102 A of extruding operation 102 further includes a third preparing operation 102A3 in which core-layer formulation 48 is prepared and provided to core- layer extruder 36 as shown in Fig. 3. Core-layer formulation 48 is an insulative cellular non- aromatic polymeric material. Reference is hereby made to U.S. Application Serial No.
14/331,066, filed July 14, 2014 and titled POLYMERIC MATERIAL FOR CONTAINER for disclosure relating to possible material formulations.
[0073] In one example, core-layer formulation 48 comprises a polyethylene base resin and one or more cell-forming agents. Core-layer formulation 48 uses a polyethylene-based formulation to produce insulative cellular non-aromatic polymeric material after being processed through core-layer extruder 36. Core-layer formulation 48 is heated in in core-layer extruder 36 where a cell-forming agent is introduced into the molten core-layer formulation prior to moving the materials from core-layer extruder 36 to co-extrusion die 38. As molten core-layer formulation 48 exits co-extrusion die 38 between inner and outer layers 12A, 12C, cells nucleate in the molten material and the material expands to form core layer 12B made from insulative cellular non-aromatic polymeric material.
[0074] In one exemplary embodiment, core-layer formulation 48 used to produce the insulative cellular non-aromatic polymeric material includes at least one polymeric material. The polymeric material may include one or more base resins. In one example, the base resin is High Density Polyethylene (HDPE). In another example, the base resin is a unimodal HDPE. In yet another example, the base resin is unimodal, high-melt strength HDPE. In still yet another example, the base resin is unimodal, high-melt strength HDPE such as DOW®
DOWLEX™ IP 41 HDPE (available from The Dow Chemical Company) that has been electron beam modified to provide long chain branching and a melt index of about 0.25 g/10 min.
Another example a unimodal, high-melt strength HDPE is EQUISTAR® ALATHON® H5520 HDPE copolymer (available from Lyondell Chemical Company) which has been electron beam modified to have long-chain branching and a melt index of about 0.25 g/10 min. Another example of a suitable unimodal HDPE is FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation).
[0075] In certain exemplary embodiments, core-layer formulation 48 may include two base resins that are HDPE. One illustrative example of core-layer formulation 48 includes a first base resin of FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation) and a second base resin of EQUISTAR® ALATHON® H5520 HDPE copolymer (available from Lyondell Chemical Company). In embodiments with more than one HDPE copolymer, different HDPE copolymers can be used depending on the attributes desired in the formulation. For example, core-layer formulation 48 may include both e-beam modified EQUISTAR® ALATHON® H5520 and FORMOLENE® HB5502F HDPE. In such an embodiment the EQUISTAR® ALATHON® H5520 provides higher melt strength which increases foaming potential, and has less flexural modulus or brittleness. The FORMOLENE® HB5502F HDPE provides wide unimodal polydispersity index or distribution and maximizes economic advantage.
[0076] In another example, core-layer formulation 48 includes about 50% e-beam modified EQUISTAR® ALATHON® H5520 and about 50% FORMOLENE® HB5502F HDPE. Together the combination provides a film having drop resistance capability associated with a non-modified HDPE resin and increased melt strength of an e-beam modified long-chain branched HDPE. Depending on the desired characteristics, the percentage of two HDPE copolymers may be varied, e.g., 25%/75%, 30%/70%, 35%/65%, 40%/60%, 45%/55%,
50%/50%, etc. In an embodiment, core-layer formulation 48 includes three HDPE copolymers in the base resin. Again, depending on the desired characteristics, the percentage of three HDPE copolymers can be varied, 33%/33%/33%, 30%/30%/40%, 25%/25%/50%, etc.
[0077] A core-layer formulation can include one or more base resins. The amount of
HDPE base resin may be one of several different values or fall within one of several different ranges. It is within the scope of the present disclosure to select an amount of HDPE base resin and be one of the following values: about 85%, 90%, 95%, 97%, 98%, 99%, 99.5%, and 99.9% of the total formulation by weight percentage. It is within the scope of the present disclosure for the amount of HDPE base resin in the formulation to fall within one of many different ranges. In a first set of ranges, the range of HDPE base resin is one of the following ranges: about 85% to 99.9%, 86% to 99.9%, 87% to 99.9%, 87.5% to 99.9%, 88% to 99.9%, 89% to 99.9%, 90% to 99.9%, 91% to 99.9%, 92% to 99.9%, 93% to 99.9%, 94% to 99.9%, 95% to 99.9%, 96% to 99.9%, 96.5% to 99.9%, 97% to 99.9%, and 98% to 99.9% of the total formulation by weight percentage. In a second set of ranges, the range of HDPE base resin is one of the following ranges: about 85% to 99.5%, 85% to 99%, 85% to 98%, 85% to 97%, 85% to 96%, 85% to 96.5%, 85% to 95%, 85% to 94%, 85% to 93%, 85% to 92%, 85% to 91%, 85% to 90%, 85% to 89%, 85% to 88%, 85% to 87%, and 85% to 86% of the total formulation by weight percentage. In a third set of ranges, the range of HDPE base resin is one of the following ranges: about 87.5% to 96.5%, 87.5% to 96%, 87.5% to 95.5%, 87.5% to 95%, 95% to 99%, 95.5% to 99%, 96% to 99%, and 96.5% to 99% of the total formulation by weight percentage. Each of these values and ranges is embodied in the Examples.
[0078] Long chain branching refers to the presence of polymer side chains (branches) that have a length that is comparable or greater than a length of the backbone to which the polymer side chains are coupled to. Long chain branching creates viscoelastic chain
entanglements (polymer entanglements) that hamper flow during extensional or oriented stretching and provide for a strain hardening phenomenon. The strain hardening phenomenon may be observed through two analytical methods.
[0079] The first analytical method used to observe the presence of strain hardening on an extensional rheometer. During extensional or oriented flow on an extensional rheometer, strain hardening will occur when polymer entanglements do not allow the polymer to flow under Linear Viscoelastic (LVE) conditions. As a result, these polymer entanglements hamper flow and create a deviation from the LVE conditions as observed as a hook formation. The strain hardening phenomenon becomes more severe as strain and strain rate increase due to faster and more severe polymer chain entanglement motion. Virgin polymers without long chain branching will exhibit LVE flow characteristics. In comparison, long chain branched polymers will exhibit strain hardening and which causes a deviation from the LVE flow characteristics of the virgin polymer providing the hook formation under the same test conditions.
[0080] The second analytical method used to observe the presence of long chain branching is evaluating melt strength data as tested per ISO 16790 which is incorporated by reference herein in its entirety. An amount of melt strength is known to be directly related to the presence of long chain branching when compared to similar virgin polymers lacking long chain branching. By way of example, Borealis DAPLOY™ WB140HMS Polypropylene (PP) (available from Borealis AG) is compared to other polymers having similar molecular weight, polydispersity index, and other physical characteristics. The DAPLOY™ WB140HMS PP has a melt strength which exceeds about 36 centi-Newton while other similar PP resins lacking long chain branching have a melt strength of less than about 10 centi-Newton.
[0081] Core-layer formulation 48 used to produce the insulative cellular non-aromatic polymeric material may further include one or more cell-forming agents. Cell-forming agents include nucleating agents and blowing agents. A nucleating agent is used to provide and control nucleation sites within a molten formulation to promote formation of cells, bubbles, or voids in the molten formulation during extrusion. A blowing agent is used to grow cells in the molten material at nucleation sites. Blowing agents may be used alone in the formulation or with nucleating agents.
[0082] Nucleating agent means a chemical or physical material that provides sites for cells to form in a molten formulation mixture. Nucleating agents may include chemical nucleating agents and physical nucleating agents. The nucleating agent may be blended with the formulation that is introduced into the hopper of the extruder. Alternatively, the nucleating agent may be added to the molten resin mixture in the extruder.
[0083] Suitable physical nucleating agents have desirable particle size, aspect ratio, and top-cut properties. Examples include, but are not limited to, talc, CaC03, mica, and mixtures of at least two of the foregoing. One representative example is Heritage Plastics HT6000 Linear Low Density Polyethylene (LLDPE) Based Talc Concentrate.
[0084] A core-layer formulation can include a physical nucleating agent. The amount of a physical nucleating agent may be one of several different values or fall within one of several different ranges. It is within the scope of the present disclosure to select an amount of a physical nucleating agent and be one of the following values: about 0%, 0.1%, 0.25%, 0.5%, 0.75%, 1.0%, 1.25%, 1.5%, 1.75%, 2%, 2.25%, 2.5%, 3%, 4%, 5%, 6%, and 7% of the total formulation by weight percentage. It is within the scope of the present disclosure for the amount of a physical nucleating agent in the formulation to fall within one of many different ranges. In a first set of ranges, the range of a physical nucleating agent is one of the following ranges: about 0% to 7%, 0.1% to 7%, 0.25% to 7%, 0.5% to 7%, 0.75% to 7%, 1% to 7%, 1.25% to 7%, about 1.5% to 7%, 1.75% to 7%, 2.0% to 7%, 2.25% to 7%, 2.5% to 7%, 3% to 7%, 4% to 7%, 5% to 7%, and 6% to 7% of the total formulation by weight percentage. In a second set of ranges, the range of a physical nucleating agent is one of the following ranges: about 0% to 6%, 0% to 5%, 0% to 4%, 0% to 3%, 0% to 2.5%, 0% to 2.25%, 0% to 2%, 0% to 1.75%, 0% to 1.5%, 0% to 1.25%, 0% to 1%, 0% to 0.75%, and 0% to 0.5% of the total formulation by weight percentage. In a third set of ranges, the range of a physical nucleating agent is one of the following ranges: about 0.1% to 6%, 0.1% to 5%, 0.1% to 4%, 0.1% to 3.5%, 0.1% to 3%, 0.1% to 2.5%, 0.1% to 2.25%, 0.1% to 2%, 0.1% to 1.75%, 0.1% to 1.5%, 0.1% to 1.25%, 0.1% to 1%, 0.1% to 0.75%, and 0.1% to 0.5% of the total formulation by weight percentage. Each of these values and ranges is embodied in the Examples. Each of these values and ranges is embodied in the Examples. In an embodiment, the formulation lacks talc.
[0085] Suitable chemical nucleating agents decompose to create cells in the molten formulation when a chemical reaction temperature is reached. These small cells act as nucleation sites for larger cell growth from a physical or other type of blowing agent. In one example, the chemical nucleating agent is citric acid or a citric acid-based material. One representative example is HYDROCEROL™ CF-40E (available from Clariant Corporation), which contains citric acid and a crystal nucleating agent.
[0086] A core-layer formulation can include a nucleating agent. The amount of a nucleating agent may be one of several different values or fall within one of several different ranges. It is within the scope of the present disclosure to select an amount of a nucleating agent and be one of the following values: about 0.1%, 0.25%, 0.5%, 0.75%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 5%, 10%, and 15% of the total formulation by weight percentage. It is within the scope of the present disclosure for the amount of a nucleating agent in the formulation to fall within one of many different ranges. In a first set of ranges, the range of a nucleating agent is one of the following ranges: about 0.1% to 15%, 0.25% to 15%, 0.5% to 15%, 1% to 15%, 1.5% to 15%, 2% to 15%, 2.5% to 15%, 3% to 15%, 3.5% to 15%, 4% to 15%, 4.5% to 15%, and 5% to 15% of the total formulation by weight percentage. In a second set of ranges, the range of a nucleating agent is one of the following ranges: about 0.1% to 10%, 0.25% to 10%, 0.5% to 10%, 0.75% to 10%, 1% to 10%, 1.5% to 10%, 2% to 10%, 2.5% to 10%, 3% to 10%, 3.5% to 10%, 4% to 10%, 4.5% to 10%, and 5% to 10% of the total formulation by weight percentage. In a third set of ranges, the range of a nucleating agent is one of the following ranges: about 0.1% to 5%, 0.25% to 5%, 0.5% to 5%, 0.75% to 5%, 1% to 5%, 1.5% to 5%, 2% to 5%, 2.5% to 5%, 3% to 5%, 3.5% to 5%, 4% to 5%, and 4.5% to 5% of the total formulation by weight percentage. Each of these values and ranges is embodied in the Examples.
[0087] A blowing agent refers to a physical or a chemical material (or combination of materials) that acts to expand nucleation sites. Blowing agents may include only chemical blowing agents, only physical blowing agents, combinations thereof, or several types of chemical and physical blowing agents. The blowing agent acts to reduce density by forming cells in the molten formulation at the nucleation sites. The blowing agent may be added to the molten resin mixture in the extruder.
[0088] Chemical blowing agents are materials that degrade or react to produce a gas.
Chemical blowing agents may be endo thermic or exothermic. Chemical blowing agents typically degrade at a certain temperature to decompose and release gas. One example of a chemical blowing agent is citric acid or citric-based material. One representative example is HYDROCEROL™ CF-40E (available from Clariant Corporation), which contains citric acid and a crystal nucleating agent. Here, the citric acid decomposes at the appropriate temperature in the molten formulation and forms a gas which migrates toward the nucleation sites and grows cells in the molten formulation. If sufficient chemical blowing agent is present, the chemical blowing agent may act as both the nucleating agent and the blowing agent.
[0089] In another example, chemical blowing agents may be selected from the group consisting of azodicarbonamide; azodiisobutyro-nitrile; benzenesulfonhydrazide; 4,4- oxybenzene sulfonylsemicarbazide; p-toluene sulfonyl semi-carbazide; barium
azodicarboxylate; N,N'-dimethyl-N,N'-dinitrosoterephthalamide; trihydrazino triazine;
methane; ethane; propane; n-butane; isobutane; n-pentane; isopentane; neopentane; methyl fluoride; perfluoromethane; ethyl fluoride; 1,1-difluoroethane; 1,1,1-trifluoroethane; 1,1,1,2- tetrafluoro-ethane; pentafluoroethane; perfluoroethane; 2,2-difluoropropane; 1,1,1- trifluoropropane; perfluoropropane; perfluorobutane; perfluorocyclobutane; methyl chloride; methylene chloride; ethyl chloride; 1,1,1-trichloroethane; 1,1-dichloro-l-fluoroethane; 1-chloro- 1,1-difluoroethane; l,l-dichloro-2,2,2-trifluoroethane; 1-chloro- 1,2,2,2-tetrafluoroethane;
trichloromonofluoromethane ; dichlorodifluoromethane ; trichlorotrifluoroethane ;
dichlorotetrafluoroethane; chloroheptafluoropropane; dichlorohexafluoropropane; methanol; ethanol; n-propanol; isopropanol; sodium bicarbonate; sodium carbonate; ammonium
bicarbonate; ammonium carbonate; ammonium nitrite; N,N'-dimethyl-N,N'- dinitrosoterephthalamide; Ν,Ν'-dinitrosopentamethylene tetramine; azodicarbonamide; azobisisobutylonitrile; azocyclohexylnitrile; azodiaminobenzene; bariumazodicarboxylate;
benzene sulfonyl hydrazide; toluene sulfonyl hydrazide; p,p'-oxybis(benzene sulfonyl hydrazide); diphenyl sulfone-3,3'-disulfonyl hydrazide; calcium azide; 4,4'-diphenyl disulfonyl azide; p-toluene sulfonyl azide, and combinations thereof.
[0090] In one aspect of the present disclosure, where a chemical blowing agent is used, the chemical blowing agent may be introduced into the material formulation that is added to the hopper.
[0091] One example of a physical blowing agent is nitrogen (N2). The N2 is pumped into the molten formulation via a port in the extruder as a supercritical fluid. The molten material with the N2 in suspension then exits the extruder via a die where a pressure drop occurs. As the pressure drop happens, N2 moves out of suspension toward the nucleation sites where cells grow. Excess gas blows off after extrusion with the remaining gas trapped in the cells formed in the extrudate. Other suitable examples of physical blowing agents include, but are not limited to, carbon dioxide (C02), helium, argon, air, pentane, butane, or other alkane mixtures of the foregoing and the like. In an illustrative example, a physical blowing agent may be introduced at a rate of about 0.02 pounds per hour to about 0.15 pounds per hour. In still yet another illustrative example, the physical blowing agent may be introduced at a rate of about 0.05 pounds per hours to about 0.15 pounds per hour.
[0092] In one aspect of the present disclosure, at least one slip agent may be
incorporated into the formulation to aid in increasing production rates. Slip agent (also known as a process aid) is a term used to describe a general class of materials which are added to the formulation and provide surface lubrication to the polymer during and after conversion. Slip agents may also reduce or eliminate die drool. Representative examples of slip agent materials include amides of fats or fatty acids, such as, but not limited to, erucamide and oleamide. In one exemplary aspect, amides from oleyl (single unsaturated C-18) through erucyl (C-22 single unsaturated) may be used. Other representative examples of slip agent materials include low molecular weight amides and fluoroelastomers. Combinations of two or more slip agents can be used. Slip agents may be provided in a master batch pellet form and blended with the resin formulation. One example of a suitable slip agent is Ampacet 102823 Process Aid PE MB LLDPE.
[0093] A core-layer formulation can include a slip agent. The amount of a slip agent may be one of several different values or fall within one of several different ranges. It is within the scope of the present disclosure to select an amount of a slip agent and be one of the following values: about 0%, 0.1%, 0.25%, 0.5%, 0.75%, 1%, 1.25%, 1.5%, 1.75%, 2%, 2.25%, 2.5%, and 3% of the total formulation by weight percentage. It is within the scope of the present disclosure for the amount of a slip agent in the formulation to fall within one of many different ranges. In a first set of ranges, the range of a slip agent is one of the following ranges: about 0% to 3%, 0.1% to 3%, 0.25% to 3%, 0.5% to 3%, 1% to 3%, 1.25% to 3%, 1.5% to 3%, 1.75% to 3%, 2% to 3%, 2.25% to 3%, and 2.5% to 3% of the total formulation by weight percentage. In a second set of ranges, the range of a slip agent is one of the following ranges: about 0% to 2.5%, 0% to 2%, 0% to 1.75%, 0% to 1.5%, 0% to 1.25%, 0% to 1%, 0% to 0.75%, 0% to 0.5%, and 0.1% to 2.5% of the total formulation by weight percentage. In a third set of ranges, the range of a slip agent is one of the following ranges: about 0.1% to 2.5%, 0.1% to 2%, 0.1% to 1.75%, 0.1% to 1.5%, 0.1% to 1.25%, 0.1% to 1%, 0.1% to 0.75%, and 0.1% to 0.5% of the total formulation by weight percentage. Each of these values and ranges is embodied in the Examples.
[0094] In another aspect of the present disclosure, an impact modifier may be incorporated into the formulation to minimize fracturing of the insulative cellular non-aromatic polymeric material when subjected to an impact such as a drop test. One representative example of a suitable impact modifier is DOW® AFFINITY™ PL 1880G polyolefin plastomer.
[0095] In an embodiment, a colorant can be about 0% to about 4% (w/w), about 0.1% to about 4%, about 0.25% to about 4%, about 0.5% to about 4%, about 0.75% to about 4%, about 1.0% to about 4%, about 1.25% to about 4%, about 1.5% to about 4%, about 1.75% to about 4%, about 2.0% to about 4%, about 2.25% to about 4%, about 2.5% to about 4%, about 3% to about 4%, about 0% to about 3.0%, about 0% to about 2.5%, about 0% to about 2.25%, about 0% to about 2.0%, about 0% to about 1.75%, about 0% to about 1.5%, about 0% to about 1.25%, about 0% to about 1.0%, about 0% to about 0.75%, about 0% to about 0.5%, about 0.1% to about 3.5%, about 0.1% to about 3.0%, about 0.1% to about 2.5%, about 0.1% to about 2.25%, about 0.1% to about 2.0%, about 0.1% to about 1.75%, about 0.1% to about 1.5%, about 0.1% to about 1.25%, about 0.1% to about 1.0%, about 0.1% to about 0.75%, or about 0.1% to about 0.5%. In an embodiment, the formulation lacks a colorant.
[0096] A core-layer formulation can include a colorant. The amount of a colorant may be one of several different values or fall within one of several different ranges. It is within the scope of the present disclosure to select an amount of a colorant and be one of the following values: about 0%, 0.1%, 0.25%, 0.5%, 0.75%, 1%, 1.25%, 1.5%, 1.75%, 2%, 2.25%, 2.5%, 3%, and 4% of the total formulation by weight percentage. It is within the scope of the present disclosure for the amount of a slip agent in the formulation to fall within one of many different ranges. In a first set of ranges, the range of a colorant is one of the following ranges: about 0% to 4%, 0.1% to 4%, 0.25% to 4%, 0.5% to 4%, 1% to 4%, 1.25% to 4%, 1.5% to 4%, 1.75% to 4%, 2% to 4%, 2.25% to 4%, 2.5% to 4%, and 3% to 4% of the total formulation by weight percentage. In a second set of ranges, the range of a colorant is one of the following ranges: about 0% to 3%, 0% to 2.5%, about 0% to 2.25%, 0% to 2%, 0% to 1.75%, 0% to 1.5%, 0% to 1.25%, 0% to 1%, 0% to 0.75%, and 0% to 0.5% of the total formulation by weight percentage. In a third set of ranges, the range of a slip agent is one of the following ranges: about 0.1% to 3.5%, 0.1% to 3.0%, 0.1% to 2.5%, 0.1% to 2.25%, 0.1% to 2%, 0.1% to 1.75%, 0.1% to 1.5%, 0.1% to 1.25%, 0.1% to 1%, 0.1% to 0.75%, and 0.1% to 0.5% of the total formulation by weight percentage. Each of these values and ranges is embodied in the Examples.
[0097] According to an aspect of the present invention, there is provided a method of producing a multilayer vessel, the method comprising the steps of
(a) extruding an inner-layer formulation, a core-layer formulation, and an outer-layer formulation to form an inner parison, an outer parison, and a core parison configured to have a core-parison density different than each of an inner-parison density of the inner parison and an outer-parison density of the outer parison,
(b) aligning the inner parison, the core parison, and the outer parison to cause the core parison to be located between the inner parison and the outer parison to cause the core parison to surround the inner parison and to be surrounded by the outer parison to form a multilayer tube,
(c) placing the multilayer tube in a mold cavity formed in a mold,
(d) forming a multilayer vessel having an interior region formed therein by expanding the multilayer tube within the mold so that the outer parison engages an inner surface of the mold, and wherein the core parison of the multilayer tube is transformed into a core layer of the vessel having a core-layer density that enables cell collapse and damage within the core layer of multilayer vessel to be minimized.
[0098] It will be understood that the inner, core and outer parisons forming the multilayer parison are disposed one directly on top of the other, in the sense that the core parison is coupled to the inner parison on one side and the outer parison on the other side. It will also be understood that in step (b) the multi-later parison is extruded in the form of a multi-layer tube in which the core parison surrounds the inner parison and the outer parison surrounds the core parison.
[0099] In an embodiment, in step (b), the inner parison core parison, and outer parison from step (a) are aligned such that the core parison is located between the inner parison and the outer parison and the aligned parisons are then co-extruded to form the multilayer tube.
[00100] In an embodiment, the outer and inner parisons each comprise a high density polymeric material. Suitably, the high-density polymeric material is high density polyethylene or polypropylene.
[00101] Suitably, the polypropylene used in either of the skin layers is a high stiffness polypropylene. More suitably, the polypropylene used in either of the skin layers is a high impact polypropylene. Even more suitably, the polypropylene used in either of the skin layers is DOW® D 207.03 developmental performance polypropylene resin or DOW® DC 7067.00 polypropylene impact copolymer. Reference is hereby made to U.S. Patent Application Serial No. 14/468,789, filed August 26, 2014 and titled POLYMERIC MATERIAL FOR
CONTAINER for disclosure relating to polypropylene used in either of the skin layers in accordance with the present disclosure, which application is hereby incorporated herein by reference in its entirety.
[00102] In a particular embodiment, both of the outer and inner parisons are a formed from a polypropylene selected from DOW® D 207.03 developmental performance
polypropylene resin and/or DOW® DC 7067.00 polypropylene impact copolymer.
[00103] In an embodiment, the polyethylene used in either of the inner and outer parisons is a high density ethylene hexane- 1 copolymer. In an embodiment, the high density polyethylene is a HDPE hexene copolymer. In a particular embodiment, the high density polyethylene is FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics
Corporation).
[00104] Alternatively, the polyethylene used in either of the inner and outer parisons may be Chevron Phillips MARLEX® HHM 5502 BN.
[00105] In certain embodiment, one or both of the inner and outer layers comprise a high- density polymeric material as hereinbefore defined and a colorant. For example, one or both of the inner and outer layers may comprise 95 - 99.9% (w/w) of a high-density polymeric material as hereinbefore defined and 0.1 to 5% (w/w) a colorant. In an embodiment, one or both of the inner and outer layers may comprise 97 - 99.9% (w/w) of a high-density polymeric material as hereinbefore defined and 0.1 to 3% (w/w) a colorant. In a further embodiment, one or both of the inner and outer layers may comprise 98 - 99.5% (w/w) of a high-density polymeric material as hereinbefore defined and 0.5 to 2% (w/w) a colorant. The relatively high-density polymeric material may be FORMOLENE® HB5502F HDPE hexene copolymer (available from Formosa Plastics Corporation) and the colorant may be COLORTECH® 11933-19 Titanium Oxide Colorant (available from COLORTECH® a PPM Company).
[00106] In some examples, inner-layer formulation and outer-layer formulation may be the same. In other examples, inner-layer formulation and outer-layer formulation may be different.
[00107] The core formulation is suitably as defined hereinbefore. In an embodiment, the core formulation comprises:
85 - 99.9% (w/w) of a high density polyethylene (HDPE) as defined herein;
0.1 - 15% (w/w) of a nucleating agent as defined herein;
0 - 3% (w/w) of a slip agent as defined herein; and
0 - 4% (w/w) of a colorant as defined herein.
[00108] In a further embodiment, the core formulation comprises:
97 - 99.9% (w/w) of a high density polyethylene (HDPE) as defined herein; 0.1 - 3% (w/w) of a nucleating agent as defined herein;
0 - 3% (w/w) of a slip agent as defined herein; and
0 - 3% (w/w) of a colorant as defined herein.
[00109] In a further embodiment, the core formulation comprises:
98 - 99.9% (w/w) of a high density polyethylene (HDPE) as defined herein; 0.1 - 2% (w/w) of a nucleating agent as defined herein;
0 - 2% (w/w) of a slip agent as defined herein; and
0 - 2% (w/w) of a colorant as defined herein.
[00110] Suitably, in step (d) the expansion of the multilayer tube is achieved by blow molding the multi-layer tube using techniques known in the art.
[00111] According to another aspect of the present invention, there is provided a multilayer vessel obtainable, obtained, or directly obtained by a process defined herein.
[00112] The following numbered clauses include embodiments that are contemplated and non-limiting: [00113] Clause 1. A method of producing a multilayer vessel, the method comprising the steps of
[00114] extruding an inner parison, an outer parison, and a core parison,
[00115] aligning the inner parison, the core parison, and the outer parison to cause the core parison to be located between the inner parison and the outer parison to cause the core parison to surround the inner parison and to be surrounded by the outer parison to form a multilayer tube,
[00116] placing the multilayer tube in a mold cavity formed in a mold, and
[00117] expanding the multilayer tube to cause the outer parison to engage an inner surface of a mold and cause the multilayer tube to deform to create a multilayer vessel having an interior region,
[00118] wherein the core parison comprises an insulative cellular non-aromatic polymeric material.
[00119] Clause 2. A method of producing a multilayer container comprising:
[00120] extruding a multilayer tube from an inner parison, an outer parison, and a core parison and
[00121] molding the multilayer tube to form a multilayer container in a molding system comprising a mold, a vacuum system providing a vacuum pressure to a mold cavity of the mold during molding, a blowing system providing pressurized gas to tube space, and a trimming system removing excess material from the container following the molding.
[00122] Clause 3. The method of any other clause, further comprising the step of applying a vacuum in a range of about 5 millimeters Hg to about 25 millimeters Hg to the mold cavity during the expanding step whereby the outer parison engages with the inner surface of the mold.
[00123] Clause 4. The method of any other clause, wherein the vacuum is in a range of about 20 millimeters Hg to the mold cavity during the expanding step.
[00124] Clause 5. The method of any other clause, wherein the expanding step includes inserting a blow needle into the interior region of the multi-layer tube and pumping pressurized gas into interior region at a pressure in a range of about 10 pounds per square inch to about 130 pounds per square inch.
[00125] Clause 6. The method of any other clause, wherein the pressurized gas has a pressure in a range of about 30 pounds per square inch to about 50 pounds per square inch. [00126] Clause 7. The method of any other clause, wherein the pressurized gas has a pressure of about 40 pounds per square inch.
[00127] Clause 8. The method of any other clause, wherein the expanding step includes inserting a blow needle into the interior region of the multi-layer tube and pumping pressurized gas into interior region at a temperature up to about 200 degrees Fahrenheit.
[00128] Clause 9. The method of any other clause, wherein the pressurized gas has a temperature in a range of about 35 degrees Fahrenheit to about 75 degrees Fahrenheit.
[00129] Clause 10. The method of any other clause, wherein the pressurized gas has a temperature of about 50 degrees Fahrenheit.
[00130] Clause 11. The method of any other clause, wherein the mold has a blow-up ratio in a range of about 100% to about 400%.
[00131] Clause 12. The method of any other clause, wherein the blow-up ratio in a range of about 100% to about 300%.
[00132] Clause 13. The method of any other clause, wherein the blow-up ratio in a range of about 150% to about 200%.
[00133] Clause 14. The method of any other clause, wherein the multi-layer container has an average collapse force of in a range of about 50 pounds-Force to about 400 pounds-Force.
[00134] Clause 15. The method of any other clause, wherein the average collapse force is in a range of about 100 pounds-Force to about 250 pounds-Force.
[00135] Clause 16. The method of any other clause, wherein the average collapse force is in a range of about 115 pounds-Force to about 170 pounds-Force.
[00136] Clause 17. The method of any other clause, wherein the multilayer vessel comprises a compressed core-layer.
[00137] Clause 18. The method of any other clause, wherein the insulative cellular non-aromatic polymeric material is a low density insulative cellular non-aromatic polymeric material
[00138] Clause 19. The method of any other clause, wherein the inner parison is formed by extruding an inner-layer formulation of high-density polymeric material.
[00139] Clause 20. The method of any other clause, wherein the outer parison is formed by extruding an outer-layer formulation of high-density polymeric material.
[00140] Clause 21. The method of any other clause, wherein the core parison is formed by extruding a core-layer formulation of polymeric material. [00141] Clause 22. The method of any other clause, wherein the inner-layer formulation and the outer-layer formulation are the same formulation.
[00142] Clause 23. The method of any other clause, wherein the inner-layer formulation and the outer-layer formulation are different formulations.
[00143] Clause 24. The method of any other clause, wherein the blowing system comprises a blow needle.
[00144] Clause 25. The method of any other clause, wherein the vacuum pressure in the mold cavity during molding is below atmospheric pressure.
[00145] Clause 26. The method of any other clause, wherein the vacuum pressure is about 5 millimeters Hg to about 25 millimeters Hg.
[00146] Clause 27. The method of any other clause, wherein the vacuum pressure is about 15 millimeters Hg to about 25 millimeters Hg.
[00147] Clause 28. The method of any other clause, wherein the vacuum pressure is about 20 millimeters Hg.
[00148] Clause 29. The method of any other clause, wherein the pressurized gas expands the multilayer tube in size.
[00149] Clause 30. The method of any other clause, wherein the pressurized gas is up to about 130 pounds per square inch (psi).
[00150] Clause 31. The method of any other clause, wherein the pressurized gas is about 40 40 psi.
[00151] Clause 32. The method of any other clause, wherein the pressurized gas is delivered at a temperature of about 0° F to about 200 0 F.
[00152] Clause 33. The method of any other clause, wherein the pressurized gas is delivered at a temperature of about 30° F to about 80 0 F.
[00153] Clause 34. The method of any other clause, wherein the pressurized gas is delivered at a temperature of about 40° F to about 50 0 F.
[00154] Clause 35. The method of any other clause, wherein the pressurized gas is delivered at a temperature of about 40° F.
[00155] Clause 36. The method of any other clause, wherein the pressurized gas is delivered at a temperature of about 50° F.
[00156] Clause 37. The method of any other clause, wherein the pressurized gas is delivered at a temperature of about room temperature. [00157] Clause 38. The method of any other clause, wherein the multilayer tube expands in size until the multilayer tube has substantially the same shape as the mold cavity.
[00158] Clause 39. The method of any other clause, wherein the pressurized gas and the vacuum pressure are provided simultaneously.
[00159] Clause 40. The method of any other clause, wherein the blow-up ratio is about 100% to about 400%.
[00160] Clause 41. The method of any other clause, wherein the blow-up ratio is about 150% to about 200%.
[00161] Clause 42. The method of any other clause, wherein the trimming system comprises one or more knives or blades.
[00162] Clause 43. The method of any other clause, wherein the multi-layer container has an average collapse force of about 115 pounds-Force to about 170 pounds-Force.
[00163] Clause 44. The method of any other clause, further comprising extruding an inner-layer formulation and outer layer formulation to form the inner parison and outer parison, wherein both the inner-layer formulation and the outer-layer formulation comprise high-density polymeric material.
[00164] Clause 45. The method of any other clause, wherein the inner-layer formulation and the outer-layer formulation are the same formulation.
[00165] Clause 46. The method of any other clause, wherein the inner-layer formulation and the outer-layer formulation are different formulations.
[00166] Clause 47. The method of any other clause, wherein the inner-layer formulation comprises one or more base resins.
[00167] Clause 48. The method of any other clause, wherein the one or more base resins is a high density polyethylene (HDPE).
[00168] Clause 49. The method of any other clause, wherein the HDPE is a HDPE hexene copolymer.
[00169] Clause 50. The method of any other clause, wherein the inner-layer formulation further comprises a colorant.
[00170] Clause 51. The method of any other clause, wherein the outer-layer formulation comprises one or more base resins.
[00171] Clause 52. The method of any other clause, wherein the one or more base resins is a high density polyethylene (HDPE). [00172] Clause 53. The method of any other clause, wherein the HDPE is a HDPE hexene copolymer.
[00173] Clause 54. The method of any other clause, wherein the outer-layer formulation further comprises a colorant.
[00174] Clause 55. The method of any other clause, further comprising extruding a core-layer formulation to form the core parison, wherein the core-layer formulation comprises a high-density polymeric material.
[00175] Clause 56. The method of any other clause, wherein the core-layer formulation comprises one or more high density polyethylene base resins (HDPE).
[00176] Clause 57. The method of any other clause, wherein the HDPE is unimodal.
[00177] Clause 58. The method of any other clause, wherein the unimodal HDPE is a unimodal, high-melt strength HDPE.
[00178] Clause 59. The method of any other clause, wherein the unimodal, high-melt strength HDPE is electron beam modified.
[00179] Clause 60. The method of any other clause, wherein the electron beam modified unimodal, high-melt strength HDPE has long chain branching and a melt index of about 0.25 g/10 min.
[00180] Clause 61. The method of any other clause, wherein the one or more HDPE base resins is two HDPE base resins.
[00181] Clause 62. The method of any other clause, wherein the two HDPE base resins are 50% of a unimodal HDPE and 50% of an electron beam modified HDPE.
[00182] Clause 63. The method of any other clause, wherein the one or more HDPE resins comprises about 85% to 99.9% (w/w) HDPE base resin.
[00183] Clause 64. The method of any other clause, wherein the wherein the one or more HDPE resins comprises about 97% to about 99.9% HDPE base resin.
[00184] Clause 65. The method of any other clause, wherein the wherein the one or more HDPE resins comprises about 98% to about 99.9% HDPE base resin.
[00185] Clause 66. The method of any other clause, wherein the core-layer formulation further comprises a nucleating agent.
[00186] Clause 67. The method of any other clause, wherein the nucleating agent is about 0.1% to 15% (w/w) of the core-layer formulation. [00187] Clause 68. The method of any other clause, wherein the nucleating agent is a chemical nucleating agent, a physical nucleating agent, or both a chemical nucleating agent and a physical nucleating agent.
[00188] Clause 69. The method of any other clause, wherein the physical nucleating agent is selected from the group consisting of talc, calcium carbonate, mica, and mixtures thereof.
[00189] Clause 70. The method of any other clause, wherein the physical nucleating agent is about 0% to 7% (w/w) of the core-layer formulation.
[00190] Clause 71. The method of any other clause, wherein the physical nucleating agent is about 0.1% to 0.5% (w/w) of the core-layer formulation.
[00191] Clause 72. The method of any other clause, wherein the physical nucleating agent is talc.
[00192] Clause 73. The method of any other clause, wherein the core-layer formulation lacks talc.
[00193] Clause 74. The method of any other clause, wherein the chemical nucleating agent is a blowing agent.
[00194] Clause 75. The method of any other clause, wherein the blowing agent is citric acid or a citric acid-based material.
[00195] Clause 76. The method of any other clause, wherein the chemical blowing agent is a citric acid and a crystal nucleating agent.
[00196] Clause 77. The method of any other clause, wherein the chemical blowing agent is selected from the group consisting of azodicarbonamide; azodiisobutyro-nitrile;
benzenesulfonhydrazide; 4,4-oxybenzene sulfonylsemicarbazide; p-toluene sulfonyl semi- carbazide; barium azodicarboxylate; N,N'-dimethyl-N,N'-dinitrosoterephthalamide;
trihydrazino triazine; methane; ethane; propane; n-butane; isobutane; n-pentane; isopentane; neopentane; methyl fluoride; perfluoromethane; ethyl fluoride; 1,1-difluoroethane; 1,1,1- trifluoroethane; 1,1,1,2-tetrafluoro-ethane; pentafluoroethane; perfluoroethane; 2,2- difluoropropane; 1,1,1-trifluoropropane; perfluoropropane; perfluorobutane;
perfluorocyclobutane; methyl chloride; methylene chloride; ethyl chloride; 1,1,1- trichloroethane; 1,1-dichloro-l-fluoroethane; 1-chloro- 1,1-difluoroethane; l,l-dichloro-2,2,2- trifluoroethane; 1 -chloro- 1 ,2,2,2-tetrafluoroethane; trichloromonofluoromethane;
dichlorodifluoromethane ; trichlorotrifluoroethane ; dichlorotetrafluoroethane ; chloroheptafluoropropane; dichlorohexafluoropropane; methanol; ethanol; n-propanol;
isopropanol; sodium bicarbonate; sodium carbonate; ammonium bicarbonate; ammonium carbonate; ammonium nitrite; N,N'-dimethyl-N,N'-dinitrosoterephthalamide; Ν,Ν'- dinitrosopentamethylene tetramine; azodicarbonamide; azobisisobutylonitrile;
azocyclohexylnitrile; azodiaminobenzene; bariumazodicarboxylate; benzene sulfonyl hydrazide; toluene sulfonyl hydrazide; p,p'-oxybis(benzene sulfonyl hydrazide); diphenyl sulfone-3,3'- disulfonyl hydrazide; calcium azide; 4,4' -diphenyl disulfonyl azide; and p-toluene sulfonyl azide.
[00197] Clause 78. The method of any other clause, wherein the core-layer formulation further comprises a physical blowing agent.
[00198] Clause 79. The method of any other clause, wherein the physical blowing agent is selected from the group consisting of carbon dioxide, nitrogen, helium, argon, air, an alkane, and mixtures thereof.
[00199] Clause 80. The method of any other clause, wherein the alkane is pentane or butane.
[00200] Clause 81. The method of any other clause, wherein the core-layer formulation further comprises a slip agent.
[00201] Clause 82. The method of any other clause, wherein the slip agent is about
0% to 3% (w/w) of the core-layer formulation.
[00202] Clause 83. The method of any other clause, wherein the slip agent is an amide of fat or fatty acid, a low molecular weight amide, or fluoroelastomer.
[00203] Clause 84. The method of any other clause, wherein the fatty acid amide is a single unsaturated C18 to C22 amide.
[00204] Clause 85. The method of any other clause, wherein the fatty acid amide is erucamide or oleamide.
[00205] Clause 86. The method of any other clause, wherein the core-layer formulation further comprises a colorant.
[00206] Clause 87. The method of any other clause, wherein the colorant is titanium dioxide.
[00207] Clause 88. The method of any other clause, wherein the colorant is about 0% to 4% (w/w) of the core-layer formulation. [00208] Clause 89. The method of any other clause, wherein the multilayer tube further comprises an additional layer selected from the group consisting of an oxygen barrier layer, an oxygen scavenging layer, a UV barrier layer, a tie layer, an additional structural layer, and combinations thereof.
[00209] Clause 90. The method of any other clause, wherein the oxygen barrier layer comprises ethylene vinyl alcohol.
[00210] Clause 91. The method of any other clause, wherein the multilayer tube has a density of about 0.35 g/cm 3 or about 0.55 g/cm 3.
[00211] Clause 92. The method of any other clause, wherein the multilayer tube has a density of about 0.4 g/cm .
[00212] Example 1
[00213] Formulations and Test Results
[00214] Inner-layer formulation 40 comprises about 100% FORMOSA PLASTICS®
FORMOLENE® HB5502F HDPE hexene copolymer. Outer-layer formulation 44 comprises about 99% FORMOSA PLASTICS® FORMOLENE® HB5502F HDPE hexene copolymer and about 1% COLORTECH® 11933-19.
[00215] Core-layer formulation 48 comprises FORMOSA PLASTICS® FORMOLENE®
HB5502F HDPE hexene copolymer which was used as polyethylene base resin. The polyethylene base resin was used in various percentages from about 97.95% to about 100% of the formulation. In some examples, the polyethylene base resin was blended with
HYDROCEROL® CF 40E as a nucleating agent and Heritage Plastics HT6000 LLDPE talc as another nucleating agent, and N2 as a blowing agent. The blowing agent was used at levels between about 0.05 lbs/hr to about 0.15 lbs/hour. COLORTECH® 11933-19 was added as a colorant in some examples. The various formulations and resulting multi-layer tube densities are shown below in Table 9.
[00216] Table 9. Comparison of different insulative cellular non-aromatic polymeric material formulations to create various multi-layer parison and insulative container densities
Inner-Layer Outer-Layer
Core-Layer Formulation
Formulation Formulation Tube
Formosa Formosa CF- N2 Formosa Density
Trial Colortech HT6000 Colortech
5502F 5502F 40E [lbs/hr] 5502F [g/cm3]
1 100% 97.95 % 1% 0.75% 0.3% 0.1222 99% 1% *
2 100% 98% 0% 2% 0% 0.0529 99% 1% *
3 100% 99.25% 0% 0.75% 0% 0.0534 99% 1% *
4 100% 99% 0% 1.0% 0% 0.0511 99% 1% 0.4292
5 100% 98.7% 0% 1.0% 0.3% 0.0514 99% 1% 0.4272
6 100% 98.45% 0% 1.25% 0.3% 0.0521 99% 1% 0.4276
7 100% 98.75% 0% 1.25% 0% 0.0529 99% 1% 0.4236
8 100% 98.75% 0% 1.25% 0% 0.0522 99% 1% 0.4234
9 100% 98.75% 0% 1.25% 0% 0.0538 99% 1% 0.4304
10 0% 100% 0% 0% 0% 0.1468 0% 0% *
11 100% 100% 0% 0% 0% 0.1392 99% 1% *
12 100% 99.9% 0% 0% 0.1% 0.1393 99% 1% *
13 100% 99.5% 0% 0% 0.5% 0.0656 99% 1% *
14 100% 99.4% 0% 0.1% 0.5% 0.0702 99% 1% *
15 100% 99.3% 0% 0.2% 0.5% 0.0692 99% 1% *
16 100% 99.7% 0% 0.1% 0.2% 0.0673 99% 1% *
17 100% 99.7% 0% 0.1% 0.2% 0.0892 99% 1% *
18 100% 99.7% 0% 0.1% 0.2% 0.105 99% 1% *
19 100% 99.7% 0% 0.1% 0.2% 0.1188 99% 1% *
20 100% 99.7% 0% 0.1% 0.2% 0.0915 99% 1% *
21 100% 99.05% 0% 0.75% 0.2% 0.0906 99% 1% *
Data not available
[00217] Example 2
[00218] Density Measurements
[00219] This Example demonstrates the test used to measure the density of filled and unfilled polymer parts.
[00220] Procedure
[00221] The density was determined by the apparatus shown, unassembled, in Fig. 17.
Although not shown in Fig. 17, the apparatus also included a thermometer to measure the suspension liquid temperature. A suspension liquid is a fluid with a density lower than that of the sample to be measured. The sample must sink in the suspension fluid to determine the sample density. Water has a density of 1 g/cm3, so most unfilled polymers require some other suspension fluid such as isopropyl alcohol, density = .8808 g/cm3. A Mettler AT400 balance (Mettler- Toledo LLC, Columbus, OH) was also used.
[00222] The density of a limestone-filled HDPE bottle was measured. After taring the balance to zero, the dry solid sample was weighed after placing it in the cup of the Mettler balance. The dry weight was 0.3833 g. After weighing the dry sample and before removing the sample from the cup, the balance was tared again. The sample was removed from the cup and placed on the gem holder in the suspension fluid. The sample was weighed providing the weight with a negative number (-0.3287 g). The number was converted to its absolute value (0.3287 g); the positive value is the sample buoyancy. The sample density was calculated by multiplying the dry weight (0.3833 g) by the suspension fluid density (0.8808 g/cc) and dividing by the sample buoyancy (0.3287 g), which equaled 1.0272 g/cc.
[00223] Example 3
[00224] Formulations
[00225] Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
HB5502F HDPE hexene copolymer which was used as polyethylene base resin. In some examples, core-formulation 48 comprised Versalite (A) or Versalite (B). Reference is hereby made to U.S. Patent Application Serial No. 14/462,073, filed August 18, 2014 and titled
POLYMERIC MATERIAL FOR AN INSULATED CONTAINER for disclosure relating to various formulations of VERSALITE in accordance with the present disclosure, which application is hereby incorporated herein by reference in its entirety. In further examples, LLDPE comprised DOW® DOWLEX™ 2045G LLDPE (available from The Dow Chemical Company), electron beam modified to have long-chain branching and a melt index of about 0.2 or 0.13 g/lOmin. In still further examples, the polyethylene base resin was blended with
HYDROCEROL® CF 40E as a chemical blowing agent and Heritage Plastics HT6000 LLDPE talc as another nucleating agent. In still yet further examples, N2 was used as a blowing agent. The blowing agent was used at levels between about 0.02 lbs/hr to about 0.15 lbs/hour. The molding machine 52 was a rotary extrusion blow-molding machine available from Wilmington Machinery of Wilmington, North Carolina. The RPM speed of this machine was at levels between about 5 RPM to about 75 RPM. The various formulations are shown below in Table 10.
[00226] The blowing agent, N2, was injected into the molten formulation to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent. The resulting expanded formulation was then extruded through a die head to establish a core-layer parison. The core-layer parison was molded to form a container according to the present disclosure.
[00227] Table 10. Comparison of different insulative cellular non-aromatic polymeric material formulations of Example 3.
Trial [#] Formosa Ampacet Ampacet Versalite CF-40E HT6000 N2 Processing
5502F 102823 102823 [lbs/hr] [RPM]
[0.2MI] [0.13MI]
7.0.0 100% 0% 0% 0% 0% 0% 0 20
7.0.5 100% 0% 0% 0% 0% 0% 0.132 20
7.1.0 98.8% 0% 0% 0% 0.2% 1.0% 0.132 20
7.2.0 49.7% 49.7% 0% 0% 0.1% 0.5% 0.132 20
7.3.0 0% 0% 0% 100% (B) 0% 0% 0.132 12
7.3.1 0% 0% 0% 100% (B) 0% 0% 0.132 24
7.4.0 0% 0% 0% 100% (A) 0% 0% 0.132 12
7.4.1 0% 0% 0% 100% (A) 0% 0% 0.132 24
7.4.2 0% 0% 0% 100% (A) 0% 0% 0.132 36
7.4.3 0% 99.4% 0% 0% 0.1% 0.5% 0.132 18
7.4.4 0% 99.4% 0% 0% 0.1% 0.5% 0.132 36
7.5.0 0% 99.4% 0% 0% 0.1% 0.5% 0.132 20
7.5.1 0% 99.4% 0% 0% 0.1% 0.5% 0.132 75
7.6.0 0% 74.55% 0% 24.85% 0.1% 0.5% 0.132 20
7.7.0 0% 0% 99.4% 0% 0.1% 0.5% 0.07 20
7.7.1 0% 0% 99.4% 0% 0.1% 0.5% 0.07 20
Pre- 100% 0% 0% 0% 0% 0.07 20 7.8.0
Purge
7.8.0 99.4% 0% 0% 0% 0.1% 0.5% 0.07 11
7.8.1 99.4% 0% 0% 0% 0.1% 0.5% 0.035 11
7.9.0A 99.4% 0% 0% 0% 0.1% 0.5% 0.035 11
7.9.0B 99.4% 0% 0% 0% 0.1% 0.5% 0.035 19
7.9.1 99.4% 0% 0% 0% 0.1% 0.5% 0.07 18
7.9.2A 99.4% 0% 0% 0% 0.1% 0.5% 0.05 18
7.9.2B 99.4% 0% 0% 0% 0.1% 0.5% 0.05 11
7.10A 0% 0% 99.4% 0% 0.1% 0.5% 0.02 9
7.10B 0% 0% 99.4% 0% 0.1% 0.5% 0.02 25 Trial [#] Formosa Ampacet Ampacet Versalite CF-40E HT6000 N2 Processing 5502F 102823 102823 [lbs/hr] [RPM]
[0.2MI] [0.13MI]
7. IOC 0% 0% 99.4% 0% 0.1% 0.5% 0.05 25
7.11A 84.5% 0% 14.9% 0% 0.1% 0.5% 0.03 18
7.9 99% 0% 0% 0% *
1% 0% 0.05
7.10 *
98.7% 0% 0% 0% 1% 0.3% 0.05
7.11 98.45% 0% 0% 0% 1.25% 0.3% 0.05 *
7.12 98.75% 0% 0% 0% 1.25% 0% 0.05 *
7.20 99.4% 0% 0% 0% 0.10% 0.5% 0.07 *
7.21 99.3% 0% 0% 0% 0.20% 0.5% 0.07 *
Data not available
[00228] Example 4
[00229] Parison Densities, Bottle Densities, Weight, Top Load Performance, and
Thickness for Formulations of Example 3
[00230] Containers formed according to Table 10 were subjected to a series of
measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, and top load force performance measurements. The results are shown below in Table 11.
[00231] Density was determined by the apparatus and methods described in Example 2.
Top load performance was measured by methods described in Example 7.
[00232] Table 11. Parison densities, container densities, weights, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 3.
Trial [#] Parison Density Container Density Weight Top Load Thickness
[g/cc] [g/cc] [g] [lbs-F] [mils]
7.0.0 0.95 0.95 60.3 133 42.3
7.0.5 0.90 * * * *
7.1.0 0.70 * * * *
7.2.0 0.60 * * * *
7.3.0 0.70 * * * *
7.3.1 0.58 * * * *
7.4.0 0.56 * * * *
7.4.1 0.57 * * * *
7.4.2 0.57 * * * *
7.4.3 0.47 * * * *
7.4.4 0.42 * * * * Trial [#] Parison Density Container Density Weight Top Load Thickness [g/cc] [g/cc] [g] [lbs-F] [mils]
7.5.0 0.43 * * * *
7.5.1 0.51 * * * *
7.6.0 0.55 0.58 * * *
7.7.0 0.40 * * * *
7.7.1 0.41 0.64 * * *
Pre-7.8.0 * 0.62 * * * Purge
7.8.0 0.42 * * * *
7.8.1 0.42 * * * *
7.9.0A 0.41 0.62 30.7 31 38.1
7.9.0B 0.51 0.73 49.0 87 43.1
7.9.1 * * * * *
7.9.2A 0.43 0.68 41.9 56 40.4
7.9.2B * * * * *
7.1 OA 0.48 0.51 * * *
7.10B 0.61 0.81 * * *
7.10C 0.66 * * * *
7.11A 0.52 0.72 * * *
7.9 0.43 0.74 56 * *
7.10 0.43 0.73 56 * *
7.11 0.43 0.73 56 * *
7.12 0.42 0.73 56 * *
7.20 * 0.683 56 * *
7.21 * 0.701 56 * *
Data not available
[00233] Example 5
[00234] Molding parameters used to form containers
[00235] Core layer 48 comprised FORMOSA PLASTICS® FORMOLENE® HB5502F
HDPE hexene copolymer as a polyethylene base resin. The polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent, Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent. N2 was used as a blowing agent. The percentages were about:
[00236] 99.4% FORMOLENE® HB5502F HDPE hexene copolymer
[00237] 0.1% HYDROCEROL® CF 40E
[00238] 0.5% Heritage Plastics HT6000 LLDPE Based Talc Concentrate [00239] The HDPE and nucleating agents were added to an extruder hopper and blended to provide a formulation. The formulation was then heated in the extruder to form a molten formulation. The blowing agent was then added to the molten formulation at a rate of about:
[00240] 0.04 lbs/hr
[00241] The blowing agent, N2 was injected into the molten formulation to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent. The resulting expanded formulation was then extruded through a die head to establish a parison, also called tube.
[00242] A mold was closed around the tube and a blow needle was inserted into a space formed in the tube. During inserting the needle, the mold moved away from the die head. In some examples, vacuum was applied to the mold and in others no vacuum was applied to the mold. Vacuum caused the pressure to decrease to PVAC, which is between about 0 inches Hg and about 29 inches Hg. Pressurized gas, in some examples air, was pumped into a space formed in the tube to cause the tube to expand and take on the shape of the mold. In the next step, the mold was opened to reveal a container.
[00243] Parameters that were varied were cycle time, gas pressure, and vacuum. Cycle time is defined as an amount of time between closing the mold around the tube and opening the mold to reveal a container. In some examples, cycle time was varied between 14 and 18 seconds. In further examples, gas pressure varied between about 40 psi and about 60 psi. In still further examples, pressurized gas was about room temperature.
[00244] Table 12. Molding parameters used to form containers of Example 5.
Run [#] Cycle [s] Air [psi] Vacuum
8.1.1 14 40 Off
8.1.2 14 40 On
8.1.3 14 60 Off
8.1.4 14 60 On
8.1.5 15 40 Off
8.1.6 15 40 On
8.1.7 15 60 Off
8.1.8 15 60 On
8.1.9 16 40 Off
8.1.10 16 40 On
8.1.11 16 60 Off
8.1.12 16 60 On
8.1.13 17 40 Off Run [#] Cycle [s] Air [psi] Vacuum
8.1.1 17 40 On
8.1.2 17 60 Off
8.1.3 17 60 On
8.1.4 18 40 Off
8.1.5 18 40 On
8.1.6 18 60 Off
8.1.7 18 60 On
[00245] Example 6
[00246] Drop Test Measurements
[00247] General Procedure
[00248] Drop testing determines a likelihood of container survival due to a drop or impact to the container. Containers were subjected to a drop testing procedure based on ASTM D2463 (Standard Test Method for Drop Impact Resistance of Blow-Molded Thermoplastic Containers), which is incorporated by reference herein in its entirety.
[00249] The drop test was performed according to the following procedure. A bucket was filled with tap water. The water in the bucket was allowed to condition for at least 24 hours at about room temperature and about 75% relative humidity. The container was filled with water from the bucket and closed off with, for example, a lid. The filled, capped containers were then subjected to the following procedure: (a) the filled, capped container was located at about five feet above a hard surface such as concrete or tile; (b) the filled, capped container was then oriented such that a bottom of the filled, capped container was arranged to lie in a substantially parallel relation to the hard surface; (c) each of ten capped, filled containers were dropped; (d) upon impact, each filled, capped container was examined for any break or shattering of the wall that causes water to leak out of the bottle; and (d) the total number of bottles showing any sign of leakage after the drop test were counted as failures.
[00250] Example 7
[00251] Top Load Measurements
[00252] General Procedure
[00253] Top load testing determines how much force a container can withstand before the container fails or necks in to form an hourglass shape. Various containers 10 were subjected to top load testing. An Instron tester, such as and generally consistent with an Instron Series 5500 Load Frame, may be used to determine top load performance as suggested in Fig. 15.
[00254] The top load test was generally performed according to the following procedure.
A container was placed on a flat surface such that the floor of the container was arranged to lie in a substantially parallel relation to the flat surface. A crosshead of the Instrom tester applied a compressive force to the top of the neck of the container. A load transducer, mounted in series with the container, measured the applied load. Containers 10 were tested until they failed or necked in to form an hourglass shape. Once failure or necking was observed, the value shown on Instron tester was recorded.
[00255] Example 8
[00256] Parison Densities, Bottle Densities, Weight, Top Load Performance, Thickness, and Drop Test Results for Formulations of Example 5
[00257] Containers formed according to Table 12 were subjected to a series of
measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force performance measurements, and drop testing. The results are shown below in Table 13.
[00258] Density was determined by the apparatus and methods described in Example 2.
Drop tests were conducted by methods described in Example 6. Top load performance was measured by methods described in Example 7.
[00259] Table 13. Parison densities, bottle densities, weight, top load performance, bottle sidewall thicknesses, and drop test results of different insulative cellular non-aromatic polymeric material formulations of Example 5.
Run Parison Density Container Density Weight [g] Thickness Top Load [lbs-F] Drop Test [Pass]
[#] [g/cc] [g/cc] [mils]
.1.1 0.546 0.748 52.8 43.8 109.0 40% .1.2 0.570 0.795 53.8 44.6 107.5 80% .1.3 0.542 0.706 51.2 44.0 111.4 20% .1.4 0.538 0.724 51.8 46.6 105.3 20% .1.5 0.553 0.792 52.0 42.8 107.0 60% .1.6 0.559 0.789 52.4 42.9 107.5 40% .1.7 0.542 0.844 53.5 40.0 108.8 80% .1.8 0.550 0.798 52.6 39.1 106.8 100% .1.9 0.536 0.649 48.8 45.1 102.8 0%.1.10 0.549 0.788 51.4 42.3 102.7 60% 1.11 0.540 0.825 52.1 38.7 107.1 100%1.12 0.555 0.840 51.5 39.2 103.1 80%1.13 0.548 0.791 49.8 40.7 97.1 100%1.14 0.544 0.789 50.0 40.4 95.0 100%1.15 0.543 0.716 47.3 40.0 91.4 0%1.16 0.548 0.707 47.5 40.1 89.4 20%1.17 0.546 0.806 49.7 38.4 93.1 60%1.18 0.540 0.792 50.1 40.2 94.5 80%1.19 0.533 0.833 49.0 35.3 94.9 100%1.20 0.547 0.829 48.8 36.1 92.6 80%
[00260] Example 9
[00261] Formulations Comprising Electron Beam Modified HDPE
[00262] Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
HB5502F HDPE hexene copolymer as a first material of a polyethylene base resin.
EQUISTAR® ALATHON® H5520 HDPE copolymer (available from Lyondell Chemical Company), electron beam modified to have long-chain branching and a melt index of about 0.75 g/lOmin, was used as a second material of the polyethylene base resin. The polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent. N2 was used as a blowing agent. The blowing agent was used at levels between about 0.03 lbs/hr to about 0.11 lbs/hour.
[00263] The blowing agent, N2, was injected into the molten formulation to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent. The resulting expanded formulation was then extruded through a die head to establish a core-layer parison. The core-layer parison, also called tube, was molded to form a container according to the present disclosure.
[00264] Table 14. Comparison of different insulative cellular non-aromatic polymeric material formulations of Example 9.
Run [#] Formosa E-Beam HDPE Chemical Blowing Agent Nitrogen [lbs/hr]
8.2.1 25% 75% 0.1% 0.035
8.2.2 25% 75% 0.5% 0.07
8.2.3 25% 75% 1.0% 0.105
8.2.4 50% 50% 0.1% 0.07
8.2.5 50% 50% 0.5% 0.105
8.2.6 50% 50% 1.0% 0.035
8.2.7 75% 25% 0.1% 0.105 8.2.8 75% 25% 0.5% 0.035
8.2.9 75% 25% 1.0% 0.07
[00265] Example 10
[00266] Parison Densities, Bottle Densities, Weight, Top Load Performance, and
Thickness for Formulations of Example 9
[00267] Containers formed according to Table 12 were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, and top load force performance measurements. The results are shown below in Table 13.
[00268] Density was determined by the apparatus and methods described in Example 2.
Drop tests were conducted by methods described in Example 6. Top load performance was measured by methods described in Example 7.
[00269] Table 15. Parison densities, bottle densities, weight, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 9.
Figure imgf000050_0001
Data not available
[00270] Example 11
[00271] Formulations Comprising Electron Beam Modified LLDPE
[00272] Core-layer formulation 48 comprises FORMOSA PLASTICS® FORMOLENE®
HB5502F HDPE hexene copolymer as a first material of a polyethylene base resin. DOW® DOWLEX™ 2045G LLDPE (available from The Dow Chemical Company), electron beam modified to have long-chain branching and a melt index of about 0.15 g/lOmin, is used as a second material of a second polyethylene base resin. The polyethylene base resin is blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent and Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent. N2 is used as a blowing agent.
[00273] The blowing agent, N2, is injected into the molten formulation to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent. The resulting expanded formulation is then extruded through a die head to establish a core-layer parison. The tube is molded to form a container according to the present disclosure.
[00274] Table 16. Comparison of different insulative cellular non-aromatic polymeric material formulations of Example 11.
Figure imgf000051_0001
[00275] Example 12
[00276] Formulations Using Virgin and Regrind HDPE
[00277] Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
HB5502F HDPE hexene copolymer as a first material of a polyethylene base resin. In some examples, the FORMOSA PLASTICS® FORMOLENE® HB5502F HDPE hexene copolymer comprises various amounts of virgin and regrind materials. The polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent and Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent. N2 was used as a blowing agent. The percentages were about:
[00278] 99.4% FORMOLENE® HB5502F HDPE hexene copolymer
[00279] 0.1% HYDROCEROL® CF 40E
[00280] 0.5% Heritage Plastics HT6000 LLDPE Based Talc Concentrate [00281] The HDPE and nucleating agents were added to an extruder hopper and blended to provide a formulation. The formulation was then heated in the extruder to form a molten formulation. The blowing agent was then added to the molten formulation at a rate of about:
[00282] 0.04 lbs/hr
[00283] The blowing agent, N2 was injected into the molten formulation to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent. The resulting expanded formulation was then extruded through a die head to establish a parison.
[00284] A mold was closed around the tube and a blow needle was inserted into a space formed in the tube. During inserting the needle, the mold moved away from the die head.
Vacuum was applied to the mold and caused the pressure to decrease to PVAC, which is between about 0 inches Hg and about 29 inches Hg. Pressurized gas, in some examples air, was pumped into a space formed in the tube to cause the tube to expand and take on the shape of the mold. The pressurized gas in this example was about 40 psi and about room temperature. In the next step, the mold was opened to reveal a container. Cycle time is defined as an amount of time between closing the mold around the tube and opening the mold to reveal a container. The cycle time in this example was between 14 and 16 second. In one example, cycle time was 15 seconds.
[00285] Table 17. Virgin/re grind percentages and molding parameters used to form containers of Example 12.
Run [#] Virgin HDPE Regrind HDPE Cycle Time
9.1. Control 100% 0% 15
9.1.1 80% 20% 14
9.1.2 80% 20% 15
9.1.3 80% 20% 16
9.1.4 60% 40% 14
9.1.5 60% 40% 15
9.1.6 60% 40% 16
9.1.7 40% 60% 14
9.1.8 40% 60% 15
9.1.9 40% 60% 16
9.1.10 20% 80% 14
9.1.11 20% 80% 15
9.1.12 20% 80% 16 [00286] Example 13
[00287] Parison Densities, Bottle Densities, Weight, Top Load Performance, and
Thickness for Formulations of Example 12.
[00288] Containers formed according to Table 17 were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force performance measurements, and drop testing. The results are shown below in Table 18.
[00289] Density was determined by the apparatus and methods described in Example 2.
Drop tests were conducted by methods described in Example 6. Top load performance was measured by methods described in Example 7.
[00290] Table 18. Parison densities, bottle densities, weights, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 12.
Figure imgf000053_0001
[00291] Example 14
[00292] Formulations Using Virgin and Regrind HDPE
[00293] Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
HB5502F HDPE hexene copolymer as a first material of a polyethylene base resin. DOW® DOWLEX™ 2045G LLDPE (available from The Dow Chemical Company), electron beam modified to have long-chain branching and a melt index of about 0.15 g/lOmin, was used as a second material of a second polyethylene base resin. The polyethylene base resin was blended with HYDROCEROL® CF 40E as a Chemical Blowing Agent (CBA) and nucleating agent and Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent. N2 was used as a blowing agent.
[00294] The blowing agent, N2 was injected into the molten formulation at a rate between about 0.03 and 0.11 lbs/hr to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent. The resulting expanded formulation was then extruded through a die head to establish a core-layer parison.
[00295] A mold was closed around the tube and a blow needle was inserted into a space formed in the tube. During inserting the needle, the mold moved away from the die head.
Vacuum was applied to the mold and caused the pressure to decrease to PVAC, which is between about 0 inches Hg and about 29 inches Hg. Pressurized gas, in some examples air, was pumped into a space formed in the tube to cause the tube to expand and take on the shape of the mold. The pressurized gas in this example was about 40 psi and about room temperature. In the next step, the mold was opened to reveal a container. Cycle time is defined as an amount of time between closing the mold around the tube and opening the mold to reveal a container. The cycle time in this example was between 14 and 16 second. In one example, cycle time was 15 seconds.
[00296] Table 19. Comparison of different insulative cellular non-aromatic polymeric material formulations of Example 14.
Figure imgf000054_0001
[00297] Example 15
[00298] Parison Densities, Bottle Densities, Weight, Top Load Performance, and
Thickness for Formulations of Example 14 [00299] Containers formed according to Table 19 were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force performance measurements, and drop testing. The results are shown below in Table 20.
[00300] Density was determined by the apparatus and methods described in Example 2.
Drop tests were conducted by methods described in Example 6. Top load performance was measured by methods described in Example 7.
[00301] Table 20. Parison densities, bottle Densities, weight, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 14.
Figure imgf000055_0001
Data not available
[00302] Example 16
[00303] Formulations Using Virgin and Second Pass Re grind HDPE
[00304] Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
HB5502F HDPE hexene copolymer as a first material of a polyethylene base resin. In some examples, the FORMOSA PLASTICS® FORMOLENE® HB5502F HDPE hexene copolymer comprises various amounts of virgin and second pass regrind material. Second pass regrind material may be, for example, material prepared previously in Table 17 which included first pass regrind. The polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent and Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent. N2 was used as a blowing agent. The percentages were about:
[00305] 99.4% FORMOLENE® HB5502F HDPE hexene copolymer [00306] 0.1% HYDROCEROL® CF 40E
[00307] 0.5% Heritage Plastics HT6000 LLDPE Based Talc Concentrate
[00308] The HDPE and nucleating agents were added to an extruder hopper and blended to provide a formulation. The formulation was then heated in the extruder to form a molten formulation. The blowing agent was then added to the molten formulation at a rate of about:
[00309] 0.04 lbs/hr
[00310] The blowing agent, N2 was injected into the molten formulation to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent. The resulting expanded formulation was then extruded through a die head to establish a parison.
[00311] A mold was closed around the tube and a blow needle was inserted into a space formed in the tube. During inserting the needle, the mold moved away from the die head.
Vacuum was applied to the mold and caused the pressure to decrease to PVAC, which is between about 0 inches Hg and about 29 inches Hg. Pressurized gas, in some examples air, was pumped into a space formed in the tube to cause the tube to expand and take on the shape of the mold. The pressurized gas in this example was about 40 psi and about room temperature. In the next step, the mold was opened to reveal a container. Cycle time is defined as an amount of time between closing the mold around the tube and opening the mold to reveal a container. The cycle time in this example was between 14 and 16 second. In one example, cycle time was 15 seconds.
[00312] Table 21. Virgin/second pass regrind percentages and molding parameters used to form containers of Example 16. Table 17 formulations were run through Table 21.
Run [#] Virgin Second Pass Regrind Cycle Time
9.3.1 80% 20% 14
9.3.2 80% 20% 15
9.3.3 80% 20% 16
9.3.4 60% 40% 14
9.3.5 60% 40% 15
9.3.6 60% 40% 16
9.3.7 40% 60% 14
9.3.8 40% 60% 15
9.3.9 40% 60% 16
9.3.10 20% 80% 14
9.3.11 20% 80% 15
9.3.12 20% 80% 16
9.3.13 0% 100% 14 Run [#] Virgin Second Pass Regrind Cycle Time
9.3.14 0% 100% 15
9.3.15 0% 100% 16
[00313] Example 17
[00314] Parison Densities, Bottle Densities, Weight, Top Load Performance, and
Thickness for Formulations of Example 16.
[00315] Containers formed according to Table 21 were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force measurements, and drop testing. The results are shown below in Table 22.
[00316] Density was determined by the apparatus and methods described in Example 2.
Drop tests were conducted by methods described in Example 6. Top load performance was measured by methods described in Example 7.
[00317] Table 22. Parison densities, bottle densities, weight, top load performance, and bottle sidewall thicknesses of different insulative cellular non-aromatic polymeric material formulations of Example 16.
Figure imgf000057_0001
Data not available [00318] Example 18
[00319] Throughput Study
[00320] Core-layer formulation 48 comprised FORMOSA PLASTICS® FORMOLENE®
HB5502F HDPE hexene copolymer as a first material of a polyethylene base resin. In some examples, the FORMOSA PLASTICS® FORMOLENE® HB5502F HDPE hexene copolymer comprises various amounts of virgin and second pass regrind material. The polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent and Heritage Plastics HT6000 LLDPE Based Talc Concentrate as an additional nucleating agent. N2 was used as a blowing agent. The percentages were about:
[00321] 99.4% FORMOLENE® HB5502F HDPE hexene copolymer
[00322] 0.1% HYDROCEROL® CF 40E
[00323] 0.5% Heritage Plastics HT6000 LLDPE Based Talc Concentrate
[00324] The HDPE and nucleating agents were added to an extruder hopper and blended to provide a formulation. The formulation was then heated in the extruder to form a molten formulation. The blowing agent was then added to the molten formulation at a rate of about:
[00325] 0.04 lbs/hr
[00326] Containers were prepared according to the present disclosure. The molding machine 52 was a rotary extrusion blow-molding machine available from Wilmington
Machinery of Wilmington, North Carolina. The RPM speed of this machine was at levels between about 5 RPM to about 75 RPM.
[00327] Containers were subjected to a series of measurements and performance tests including core-layer parison density (p) measurements, container density (p) measurements, weight measurements, thickness measurements, top load force measurements, and drop testing. The results are shown below in Table 23.
[00328] Density was determined by the apparatus and methods described in Example 2.
Drop tests were conducted by methods described in Example 6. Top load performance was measured by methods described in Example 7. [00329] Table 23. Parison densities, bottle densities, weight, top load performance, and bottle sidewall thicknesses of insulative cellular non-aromatic polymeric material formulations formed at different RPM levels.
Figure imgf000059_0001
[00330] Example 19
[00331] Formulations
[00332] Outer-layer formulation 44 comprised about 95% to about 100% Marlex® HHM
5502BN HDPE (available from Chevron Phillips Chemical Company) and about 0% to about 5% COLORTECH® 11933-19 Titanium Oxide Colorant (available from COLORTECH® a PPM Company). Inner-layer formulation 40 comprised about 100% Marlex® HHM 5502BN HDPE (available from Chevron Phillips Chemical Company).
[00333] Core-layer formulation 48 comprised about 100% Marlex® HHM 5502BN HDPE
(available from Chevron Phillips Chemical Company) as a first material of a polyethylene base resin. EQUISTAR® ALATHON® H5520 HDPE copolymer (available from Lyondell Chemical Company), electron beam modified to have long-chain branching and a melt index of about 0.75 g/10 min , was used as a second material of the polyethylene base resin. The polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and Heritage Plastics HT6000 LLDPE talc as another nucleating agent. N2 was used as a blowing agent.
[00334] The blowing agent, N2, was injected into the molten formulation at levels between about 0.02 lbs/hr to about 0.15 lbs/hour to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent. The resulting expanded formulation was then extruded through a die head to establish a core-layer parison. Inner and outer layers were extruded through the die head, locating the expanded formulation therebetween, to form a multi-layer tube. The multi-layer tube was molded to form a container according to the present disclosure. [00335] Table 24. Comparison of different insulative cellular non-aromatic polymeric material formulations of Example 19.
Figure imgf000060_0001
[00336] Example 20
[00337] Densities, weights, and layer thicknesses for formulations of Example 19
[00338] Multi-layer containers formed according to Table 24 were subjected to a series of measurements including container the average of several density measurements, weight measurements (p), and thickness measurements. The results are shown below in Table 25.
[00339] Density was determined by the apparatus and methods described in Example 2.
[00340] Table 25. Densities, weights, top load performance, and layer thicknesses of insulative cellular non-aromatic polymeric material formulations of Example 19.
Figure imgf000060_0002
Data not available
[00341] Example 21
[00342] Rigidity Test
[00343] General Procedure
[00344] Rigidity testing determines how resistant containers are to deformation. Various multi-layer containers 10 in accordance with the present disclosure were subjected to rigidity testing. Each multi-layer container was placed in a rigidity tester as shown in Fig. 16 and tested to determine rigidity as shown below in Table 3. Testing involved placing a multi-layer container in a rigidity tester 300 as shown in Fig. 16 in two orientations. The rigidity tester included a stationary cylindrical stop 302 on a left side and a movable anvil 304 and force gauge 306 on a right side. The movable anvil was generally T-shaped as shown in Fig. 16. For each orientation, sidewall 90 of multi-layer container 10 was deformed about midway between floor 88 and neck 92 of multi-layer container 10. Sidewall 90 was deformed about 0.25 inches over a 10 second interval and the force required to do so was recorded in pounds-Force. The first orientation placed a mold seam of multi-layer container in alignment to engage movable anvil 304 (0 Degrees). The second orientation rotated multi-layer container 10 so that the seam was about 90 degrees away from the movable anvil (90 Degrees). The second orientation is reported for rigidity measurements herein.
[00345] Example 22
[00346] Top load performance, rigidity, and drop test results for formulations of Example
19
[00347] Multi-layer containers formed according to Table 24 were subjected to a series of measurements and performance tests including top load force performance measurements, rigidity measurements, and drop testing. The results are shown below in Table 25.
[00348] Drop tests were conducted by methods described in Example 6. Top load performance was measured by methods described in Example 7. Rigidity was measured by methods described in Example 21.
[00349] Table 26. Drop Test Results, Rigidity, and Top Load Performance of insulative cellular non-aromatic polymeric material formulations of Example 19.
Sample ID Drop [#/10] Rigidity [kg-F] Top Load [lbF]
10.A 100% 1.879 62.3
10.B 100% 1.145 63.0
10.C 100% 1.208 58.7
10.E 100% 1.096 104.4
10.F 100% 1.086 98.6
10.G 100% 0.817 58.6
10.H 100% 0.921 63.9 [00350] Example 23
[00351] Formulations
[00352] Outer-layer formulation 44 comprised about 75% to about 100% Marlex® HHM
5502BN HDPE (available from Chevron Phillips Chemical Company), about 5%
COLORTECH® 11933-19 Titanium Oxide Colorant (available from COLORTECH® a PPM Company), and about 0% to about 20% Hyperform® HPR-803i (available from Milliken
Chemical) as a reinforcing fiber. Inner-layer formulation 40 comprised about 85% to 100% Marlex® HHM 5502BN HDPE (available from Chevron Phillips Chemical Company) and about 0% to about 20% Hyperform® HPR-803i (available from Milliken Chemical) as a reinforcing fiber.
[00353] Core-layer formulation 48 comprised about 98% to about 100 Marlex® HHM
5502BN HDPE (available from Chevron Phillips Chemical Company) which was used as a polyethylene base resin. The polyethylene base resin was blended with HYDROCEROL® CF 40E as a chemical blowing agent and nucleating agent and Heritage Plastics HT6000 LLDPE talc as another nucleating agent. N2 was used as a blowing agent.
[00354] The blowing agent, N2, was injected into the molten formulation at levels between about 11 kg/hour to expand the molten formulation and reduce the density of the mixture of polymer and nucleating agent. The resulting expanded formulation was then extruded through a die head to establish a core-layer parison. Inner and outer layers were extruded through the die head, locating the expanded formulation therebetween, to form a multilayer tube. The multi-layer tube was molded to form a container according to the present disclosure.
[00355] Table 27. Comparison of different insulative cellular non-aromatic polymeric material formulations of Example 23.
Core Layer Outer Inside
Trial ID Chevron CBA HT6000 Chevron Color Fiber Chevron Fiber
Control 100% 0% 0% 95% 5% 0% 100% 0%
DOE 1-1 100% 0.10% 0.30% 95% 5% 0% 100% 0%
DOE 1-2 100% 0.10% 0.30% 95% 5% 0% 100% 0%
DOE 1-3 100% 0.10% 0.30% 95% 5% 0% 100% 0%
DOE 1-4 98.4% 0.10% 1.50% 95% 5% 0% 100% 0%
DOE 1-5 98.4% 0.10% 1.50% 95% 5% 0% 100% 0%
DOE 1-6 98.4% 0.10% 1.50% 95% 5% 0% 100% 0% Core Layer Outer Inside
Trial ID Chevron CBA HT6000 Chevron Color Fiber Chevron Fiber
DOE 1-7 99.2% 0.50% 0.30% 95% 5% 0% 100% 0%
DOE 1-8 99.2% 0.50% 0.30% 95% 5% 0% 100% 0%
DOE 1-9 99.2% 0.50% 0.30% 95% 5% 0% 100% 0%
DOE 1-10 98.0% 0.50% 1.50% 95% 5% 0% 100% 0% E 1-lOA (Dual Fiber) 98.0% 0.50% 1.50% 80% 5% 15% 85% 15%
DOE 1-11 98.0% 0.50% 1.50% 95% 5% 0% 100% 0%
DOE 1-12 98.0% 0.50% 1.50% 95% 5% 0% 100% 0%
DOE 1-1 10% 99.6% 0.10% 0.30% 85% 5% 10% 100% 0%
DOE 1-1 15% 99.6% 0.10% 0.30% 80% 5% 15% 100% 0%
DOE 1-1 20% 99.6% 0.10% 0.30% 75% 5% 20% 100% 0%
[00356] Example 24
[00357] Densities, weights, layer thicknesses, and visual scores for formulations of
Example 23
[00358] Multi-layer containers formed according to Table 27 were subjected to a series of measurements including visual score (determined according to Example 30), container density (p) measurements, weight measurements, and thickness measurements. The results are shown below in Table 28.
[00359] Density was determined by the apparatus and methods described in Example 2.
[00360] Table 28. Visual score, densities, Weight, Top Load Performance, and Layer
Thicknesses of insulative cellular non-aromatic polymeric material formulations of Example 23.
Physical Wall Thickness
Trial ID Average Weight [g] Density Avg. Min Max
Visual [g/cc] [mils] [mils] [mils] Score
Max 12
Control 12 23.0 0.934 0.032 0.019 0.044
DOE 1-1 11.35 17.1 0.710 0.039 0.025 0.062
DOE 1-2 11.65 16.9 0.734 0.032 0.021 0.056
DOE 1-3 11.25 17.1 0.760 0.030 0.022 0.055
DOE 1-4 11.4 17.7 0.644 0.036 0.025 0.064
DOE 1-5 11.35 17.2 0.685 0.033 0.022 0.057
DOE 1-6 11.5 16.8 0.744 0.030 0.020 0.050
DOE 1-7 10.35 17.4 0.612 0.037 0.025 0.065
DOE 1-8 10.8 17.3 0.697 0.034 0.023 0.059
DOE 1-9 10.9 17.1 0.760 0.030 0.021 0.052 Physical Wall Thickness
Trial ID Average Weight [g] Density Avg. Min Max
Visual [g/cc] [mils] [mils] [mils]
Score
Max 12
DOE 1-10 10.7 17.0 0.625 0.038 0.024 0.060
DOE 1-lOA 11.25 17.0 0.479 0.047 0.031 0.070
DOE 1-11 10.5 17.1 0.693 0.032 0.021 0.051
DOE 1-12 11.6 17.5 0.784 0.029 0.022 0.044
DOE 1-1 10% 10.8 17.0 0.624 0.040 0.018 0.063
DOE 1-1 15% 10.3 17.5 0.656 0.034 0.020 0.056
DOE 1-1 20% 9 17.1 0.665 0.034 0.023 0.055
[00361] Example 25
[00362] Top load performance, rigidity, drop test results, and cap application and removal for formulations of Example 23
[00363] Multi-layer containers formed according to Table 27 were subjected to a series of measurements and performance tests including top load force performance measurements, rigidity measurements, drop testing, and cap application and removal. The results are shown below in Table 29.
[00364] Drop tests were conducted by methods described in Example 6. In some examples, the method described in Example 6 was followed with the exception of replacing water with shampoo. Top load performance was measured by methods described in Example 7. In some examples, the method described in Example 7 was performed with a container that was closed with a cap. In other examples, the method in Example 7 was performed with a container without a cap. Rigidity was measured by methods described in Example 21. The forces required to remove and apply caps to the containers were measured. Containers having caps were subjected to application and removal testing based on ASTM D3473-88 (Standard Test Methods for Lifting Force Required to Remove Certain Child-Resistant Snap Caps) and ASTM D3480-88 (Standard Test Methods for Downward Force Required to Open or Activate Child-Resistant Snap-Engagement Packages), each of which is incorporated by reference herein in its entirety.
[00365] Table 29. Drop test results, rigidity, top load performance, and cap application and removal of insulative cellular non-aromatic polymeric material formulations of Example 23. Trial ID Water Rigidity Top Load Top Cap Cap Cap Cap Drop [kg-F] Uncapped Load Removal Removal Application Application
[N] Capped [lb-f] [N] [lb-f] [N]
[N]
Control 100% 1.82 343 495 26 117 20 91 OE 1-1 70% 1.43 184 * 17 74 20 89 OE 1-2 80% 1.04 162 * 16 73 27 118 OE 1-3 70% 0.90 149 * 18 79 25 113 OE 1-4 90% 1.28 194 * 17 76 22 100 OE 1-5 100% 1.01 167 243 17 77 25 109 OE 1-6 80% 0.88 150 * 18 79 28 125 OE 1-7 60% 1.16 180 * 18 81 26 114 OE 1-8 100% 1.07 167 239 18 79 28 125 OE 1-9 100% 0.88 151 * 17 74 21 95 OE 1-10 100% 1.32 197 271 18 79 24 107OE 1-lOA 60% 1.87 245 * 17 77 22 96 OE 1-11 100% 0.99 173 260 18 78 26 116 OE 1-12 100% 0.88 165 * 18 79 24 106E 1-1 10% 100% 1.34 209 309 18 79 26 116E 1-1 15% 90% 1.15 207 * 19 85 36 161E 1-1 20% 90% 1.15 212 * 19 85 26 117
Data not available
[00366] Example 30
[00367] Visual Score
[00368] General Procedure
[00369] Containers were given scores based on a set of twelve observable factors. Each time a container lacked an observable factor, one point was awarded. Thus, a container lacking all observable factors obtained a best score of 12. The observable factors included: 1) presence of holes, 2) the presence of foreign material, 3) whether the container was malformed, 4)
engraving on the container, 5) undesirable appearance of the container, 6) undesirable color of the container, 7) presence of odor in the container, 8) neck top of the container lacking
smoothness, 9) neck bore of the container lacking smoothness, 10) whether the container had a rocker bottom defect, 11) undesirable finish quality, and 12) undesirable parting line. In some examples, several containers were formed, tested, and the scores were averaged.

Claims

1. A method of producing a multilayer vessel, the method comprising the steps of
extruding an inner parison, an outer parison, and a core parison, aligning the inner parison, the core parison, and the outer parison to cause the core parison to be located between the inner parison and the outer parison to cause the core parison to surround the inner parison and to be surrounded by the outer parison to form a multilayer tube,
placing the multilayer tube in a mold cavity formed in a mold,
expanding the multilayer tube to cause the outer parison to engage an inner surface of a mold and cause the multilayer tube to deform to create a multilayer vessel having an interior region,
wherein the core parison comprises an insulative cellular non-aromatic polymeric material.
2. The method of claim 1, further comprising the step of applying a vacuum in a range of about 5 millimeters Hg to about 25 millimeters Hg to the mold cavity during the expanding step whereby the outer parison engages with the inner surface of the mold.
3. The method of claim 2, wherein the vacuum is in a range of about 20 millimeters Hg to the mold cavity during the expanding step.
4. The method of claim 1, wherein the expanding step includes inserting a blow needle into the interior region of the multi-layer tube and pumping pressurized gas into interior region at a pressure in a range of about 10 pounds per square inch to about 130 pounds per square inch.
5. The method of claim 4, wherein the pressurized gas has a pressure in a range of about 30 pounds per square inch to about 50 pounds per square inch.
6. The method of claim 5, wherein the pressurized gas has a pressure of about 40 pounds per square inch.
7. The method of claim 1, wherein the expanding step includes inserting a blow needle into the interior region of the multi-layer tube and pumping pressurized gas into interior region at a temperature up to about 200 degrees Fahrenheit.
8. The method of claim 7, wherein the pressurized gas has a temperature in a range of about 35 degrees Fahrenheit to about 75 degrees Fahrenheit.
9. The method of claim 8, wherein the pressurized gas has a temperature of about 50 degrees Fahrenheit.
10. The method of claim 1, wherein the mold has a blow-up ratio in a range of about 100% to about 400%.
11. The method of claim 10, wherein the blow-up ratio in a range of about 100% to about 300%.
12. The method of claim 11, wherein the blow-up ratio in a range of about 150% to about 200%.
13. The method of claim 1, wherein the multi-layer container has an average collapse force of in a range of about 50 pounds-Force to about 400 pounds-Force.
14. The method of claim 13, wherein the average collapse force is in a range of about 100 pounds-Force to about 250 pounds-Force.
15. The method of claim 14, wherein the average collapse force is in a range of about 115 pounds-Force to about 170 pounds-Force.
16. The method of claim 1, wherein the multilayer vessel comprises a compressed core-layer.
17. The method of claim 1, wherein the insulative cellular non-aromatic polymeric material is a low density insulative cellular non-aromatic polymeric material
18. The method of claim 1, wherein the inner parison is formed by extruding an inner-layer formulation of high-density polymeric material.
19. The method of claim 1, wherein the outer parison is formed by extruding an outer-layer formulation of high-density polymeric material.
20. The method of claim 1, wherein the core parison is formed by extruding a core-layer formulation of polymeric material.
21. The method of claim 20, wherein the inner-layer formulation and the outer-layer formulation are the same formulation.
22. The method of claim 20, wherein the inner-layer formulation and the outer-layer formulation are different formulations.
23. A method of producing a multilayer container comprising: extruding a multilayer tube from an inner parison, an outer parison, and a core parison and
molding the multilayer tube to form a multilayer container in a molding system comprising a mold, a vacuum system providing a vacuum pressure to a mold cavity of the mold during molding, a blowing system providing pressurized gas to tube space, and a trimming system removing excess material from the container following the molding.
24. The method of claim 23, wherein the blowing system comprises a blow needle.
25. The method of claim 24, wherein the vacuum pressure in the mold cavity during molding is below atmospheric pressure.
26. The method of claim 25, wherein the vacuum pressure is about 5 millimeters Hg to about 25 millimeters Hg.
27. The method of claim 26, wherein the vacuum pressure is about 15 millimeters Hg to about 25 millimeters Hg.
28. The method of claim 26, wherein the vacuum pressure is about 20 millimeters Hg.
29. The method of claim 23, wherein the pressurized gas expands the multilayer tube in size.
30. The method of claim 29, wherein the pressurized gas is up to about 130 pounds per square inch (psi).
31. The method of claim 30, wherein the pressurized gas is about 40 40 psi.
32. The method of claim 23, wherein the pressurized gas is delivered at a temperature of about 0° F to about 200 0 F.
33. The method of claim 32, wherein the pressurized gas is delivered at a temperature of about 30° F to about 80 0 F.
34. The method of claim 33, wherein the pressurized gas is delivered at a temperature of about 40° F to about 50 0 F.
35. The method of claim 32, wherein the pressurized gas is delivered at a temperature of about 40° F.
36. The method of claim 32, wherein the pressurized gas is delivered at a temperature of about 50° F.
37. The method of claim 23, wherein the pressurized gas is delivered at a temperature of about room temperature.
38. The method of claim 37, wherein the multilayer tube expands in size until the multilayer tube has substantially the same shape as the mold cavity.
39. The method of claim 38, wherein the pressurized gas and the vacuum pressure are provided simultaneously.
40. The method of claim 39, wherein the blow-up ratio is about 100% to about 400%.
41. The method of claim 40, wherein the blow-up ratio is about 150% to about 200%.
42. The method of claim 41, wherein the trimming system comprises one or more knives or blades.
43. The method of claim 42, wherein the multi-layer container has an average collapse force of about 115 pounds-Force to about 170 pounds-Force.
44. The method of claim 43 further comprising extruding an inner-layer formulation and outer layer formulation to form the inner parison and outer parison, wherein both the inner-layer formulation and the outer-layer formulation comprise high-density polymeric material.
45. The method of claim 44, wherein the inner-layer formulation and the outer-layer formulation are the same formulation.
46. The method of claim 44, wherein the inner-layer formulation and the outer-layer formulation are different formulations.
47. The method of claim 44, wherein the inner-layer formulation comprises one or more base resins.
48. The method of claim 47, wherein the one or more base resins is a high density polyethylene (HDPE).
49. The method of claim 48, wherein the HDPE is a HDPE hexene copolymer.
50. The method of claim 49, wherein the inner-layer formulation further comprises a colorant.
51. The method of claim 44, wherein the outer-layer formulation comprises one or more base resins.
52. The method of claim 51, wherein the one or more base resins is a high density polyethylene (HDPE).
53. The method of claim 52, wherein the HDPE is a HDPE hexene copolymer.
54. The method of claim 53, wherein the outer-layer formulation further comprises a colorant.
55. The method of claim 54, further comprising extruding a core-layer formulation to form the core parison, wherein the core-layer formulation comprises a high- density polymeric material.
56. The method of claim 55, wherein the core-layer formulation comprises one or more high density polyethylene base resins (HDPE).
57. The method of claim 56, wherein the HDPE is unimodal.
58. The method of claim 57, wherein the unimodal HDPE is a unimodal, high-melt strength HDPE.
59. The method of claim 58, wherein the unimodal, high-melt strength HDPE is electron beam modified.
60. The method of claim 59, wherein the electron beam modified unimodal, high-melt strength HDPE has long chain branching and a melt index of about 0.25 g/10 min.
61. The method of claim 56, wherein the one or more HDPE base resins is two HDPE base resins.
62. The method of claim 61, wherein the two HDPE base resins are 50% of a unimodal HDPE and 50% of an electron beam modified HDPE.
63. The method of claim 62, wherein the one or more HDPE resins comprises about 85% to 99.9% (w/w) HDPE base resin.
64. The method of claim 63, wherein the wherein the one or more HDPE resins comprises about 97% to about 99.9% HDPE base resin.
65. The method of claim 64, wherein the wherein the one or more HDPE resins comprises about 98% to about 99.9% HDPE base resin.
66. The method of claim 65, wherein the core-layer formulation further comprises a nucleating agent.
67. The method of claim 66, wherein the nucleating agent is about 0.1% to 15% (w/w) of the core-layer formulation.
68. The method of claim 66, wherein the nucleating agent is a chemical nucleating agent, a physical nucleating agent, or both a chemical nucleating agent and a physical nucleating agent.
69. The method of claim 68, wherein the physical nucleating agent is selected from the group consisting of talc, calcium carbonate, mica, and mixtures thereof.
70. The method of claim 66, wherein the physical nucleating agent is about 0% to 7% (w/w) of the core-layer formulation.
71. The method of claim 68, wherein the physical nucleating agent is about 0.1% to 0.5% (w/w) of the core-layer formulation.
72. The method of claim 71, wherein the physical nucleating agent is talc.
73. The method of claim 72, wherein the core-layer formulation lacks talc.
74. The method of claim 68, wherein the chemical nucleating agent is a blowing agent.
75. The method of claim 74, wherein the blowing agent is citric acid or a citric acid-based material.
76. The method of claim 74, wherein the chemical blowing agent is a citric acid and a crystal nucleating agent.
77. The method of claim 74, wherein the chemical blowing agent is selected from the group consisting of azodicarbonamide; azodiisobutyro-nitrile; benzenesulfonhydrazide; 4,4-oxybenzene sulfonylsemicarbazide; p-toluene sulfonyl semi-carbazide; barium
azodicarboxylate; N,N'-dimethyl-N,N'-dinitrosoterephthalamide; trihydrazino triazine;
methane; ethane; propane; n-butane; isobutane; n-pentane; isopentane; neopentane; methyl fluoride; perfluoromethane; ethyl fluoride; 1,1-difluoroethane; 1,1,1-trifluoroethane; 1,1,1,2- tetrafluoro-ethane; pentafluoroethane; perfluoroethane; 2,2-difluoropropane; 1,1,1- trifluoropropane; perfluoropropane; perfluorobutane; perfluorocyclobutane; methyl chloride; methylene chloride; ethyl chloride; 1,1,1-trichloroethane; 1,1-dichloro-l-fluoroethane; 1-chloro- 1,1-difluoroethane; l,l-dichloro-2,2,2-trifluoroethane; 1-chloro- 1,2,2,2-tetrafluoroethane;
trichloromonofluoromethane ; dichlorodifluoromethane ; trichlorotrifluoroethane ;
dichlorotetrafluoroethane; chloroheptafluoropropane; dichlorohexafluoropropane; methanol; ethanol; n-propanol; isopropanol; sodium bicarbonate; sodium carbonate; ammonium bicarbonate; ammonium carbonate; ammonium nitrite; N,N'-dimethyl-N,N'- dinitrosoterephthalamide; Ν,Ν' -dinitrosopentamethylene tetramine; azodicarbonamide;
azobisisobutylonitrile; azocyclohexylnitrile; azodiaminobenzene; bariumazodicarboxylate; benzene sulfonyl hydrazide; toluene sulfonyl hydrazide; p,p'-oxybis(benzene sulfonyl hydrazide); diphenyl sulfone-3,3'-disulfonyl hydrazide; calcium azide; 4,4'-diphenyl disulfonyl azide; and p-toluene sulfonyl azide.
78. The method of claim 77, wherein the core-layer formulation further comprises a physical blowing agent.
79. The method of claim 78, wherein the physical blowing agent is selected from the group consisting of carbon dioxide, nitrogen, helium, argon, air, an alkane, and mixtures thereof.
80. The method of claim 79, wherein the alkane is pentane or butane.
81. The method of claim 80, wherein the core-layer formulation further comprises a slip agent.
82. The method of claim 81, wherein the slip agent is about 0% to 3% (w/w) of the core-layer formulation.
83. The method of claim 82, wherein the slip agent is an amide of fat or fatty acid, a low molecular weight amide, or fluoroelastomer.
84. The method of claim 83, wherein the fatty acid amide is a single unsaturated C18 to C22 amide.
85. The method of claim 84, wherein the fatty acid amide is erucamide or oleamide.
86. The method of claim 85, wherein the core-layer formulation further comprises a colorant.
87. The method of claim 86, wherein the colorant is titanium dioxide.
88. The method of claim 87, wherein the colorant is about 0% to 4% (w/w) of the core-layer formulation.
89. The method of claim 23, wherein the multilayer tube further comprises an additional layer selected from the group consisting of an oxygen barrier layer, an oxygen scavenging layer, a UV barrier layer, a tie layer, an additional structural layer, and combinations thereof.
90. The method of claim 89, wherein the oxygen barrier layer comprises ethylene vinyl alcohol.
91. The method claim 22, wherein the multilayer tube has a density of about
0.35 g/cm 3 or about 0.55 g/cm 3.
92. The method of claim 91, wherein the multilayer tube has a density of about 0.4 g/cm .
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Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8263198B2 (en) * 2007-09-26 2012-09-11 Chevron Phillips Chemical Company Lp System and method for creating high gloss plastic items via the use of styrenic copolymers as a coextruded layer
JP2016518289A (en) 2013-03-14 2016-06-23 ベリー プラスチックス コーポレイション container
AU2014286957A1 (en) 2013-07-12 2016-01-21 Berry Plastics Corporation Polymeric material for container
TW201532782A (en) 2013-08-30 2015-09-01 Berry Plastics Corp Container and process for making the same
WO2016141179A1 (en) 2015-03-04 2016-09-09 Berry Plastics Corporation Polymeric material for container
FR3034340A1 (en) * 2015-04-03 2016-10-07 Inergy Automotive Systems Research Sa PROCESS FOR MANUFACTURING A PLASTIC RESERVOIR WITH ANTI-BALLOTING DEVICE
EP3283566A1 (en) * 2015-04-17 2018-02-21 Obrist Closures Switzerland GmbH Formulation
JP6785165B2 (en) * 2017-01-27 2020-11-18 株式会社クレハ Manufacturing method of molded product
CN106945314A (en) * 2017-03-06 2017-07-14 五行科技股份有限公司 A kind of noctilucence flexible pipe and its manufacture method for conveying fracturing fluid backwater
US10259155B2 (en) * 2017-06-29 2019-04-16 Discma Ag Preform for a blow molding operation
CN108582716B (en) * 2017-10-11 2020-06-23 江苏中鑫家居新材料股份有限公司 Method for manufacturing floor base material
TW201946763A (en) 2018-05-16 2019-12-16 日商琉Sok股份有限公司 Method for manufacturing measurement pipeline portion of ultrasonic flow meter
US11242180B2 (en) 2018-05-25 2022-02-08 Dart Container Corporation Drink lid for a cup
KR102561446B1 (en) * 2021-09-02 2023-08-01 소인철 Multi-layer hose and manufacturing method thereof
JP2024061511A (en) * 2022-10-21 2024-05-07 キョーラク株式会社 Manufacturing method of foamed molded article

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5037285A (en) * 1983-04-13 1991-08-06 American National Can Company Apparatus for injection molding and injection blow molding multi-layer articles
US6221925B1 (en) * 1996-12-05 2001-04-24 Mobil Oil Corporation Foamable high density polyethylene
US20030021927A1 (en) * 2001-07-30 2003-01-30 The Coleman Company, Inc. Method of blow and vacuum molding insulated containers
US20060142495A1 (en) * 2003-02-24 2006-06-29 Erkki Lalho Polypropylene compositions
US20120318859A1 (en) * 2011-06-17 2012-12-20 Berry Plastics Corporation Process for forming an insulated container having artwork
US20130026128A1 (en) * 2011-07-25 2013-01-31 Devtech Labs, Inc. Multi-gallon capacity blow molded container
US20130085244A1 (en) * 2011-10-04 2013-04-04 Mosha H. ZHAO Use of Temperature and Ethylene Partial Pressure to Introduce Long Chain Branching in High Density Polyethylene

Family Cites Families (130)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3221954A (en) * 1963-06-11 1965-12-07 Haveg Industries Inc Blow molded foamed plastic container
US3290198A (en) 1963-10-23 1966-12-06 Haveg Industries Inc Method of forming a series of unfilled containers from thermoplastic tubing
US3981412A (en) 1971-03-29 1976-09-21 Asmus Richard W Container closure
US3892828A (en) * 1973-06-07 1975-07-01 Continental Can Co Method of making plastic articles having easily severable flash
US4468435C1 (en) 1973-08-21 2001-06-12 Sumitomo Electric Industries Process for the production of highly expanded polyolefin insulated wires and cables
AU8393475A (en) 1974-09-30 1977-02-17 Bakelite Xylonite Ltd Polymer films
JPS5311994B2 (en) 1974-11-13 1978-04-26
US4047868A (en) * 1975-08-12 1977-09-13 Toppan Printing Co., Ltd. Multilayer parison extrusion molding machine for blow molding
US4220730A (en) 1978-10-16 1980-09-02 The Dow Chemical Company Crosslinked chlorinated polyethylene foam
JPS57110439A (en) 1980-12-29 1982-07-09 Nihon Dixie Co Ltd Vessel made of heat insulating paper and its manufacture
US4479989A (en) 1982-12-02 1984-10-30 Cutter Laboratories, Inc. Flexible container material
US4553999A (en) 1984-04-16 1985-11-19 Aga, A.B. Methods and apparatus for blow molding glass articles
US5079057A (en) 1986-12-29 1992-01-07 Owens-Illinois Plastic Products Inc. Plastic container with multilayer label applied by in-mold labeling
JPS63260418A (en) 1987-04-17 1988-10-27 Mazda Motor Corp Extrusion molding device for multi-layer parison
US4990382A (en) 1987-09-11 1991-02-05 Continental Plastic Containers, Inc. Plastic container with glass-like appearance, parison for and method of making same
JPH01286826A (en) 1988-02-19 1989-11-17 Furukawa Electric Co Ltd:The Manufacture of crosslinked polyolefin resin foam
US5037684A (en) 1989-07-19 1991-08-06 Graham Engineering Corporation Blow molded aseptic bottle and method
US5055022A (en) 1990-03-22 1991-10-08 Hoover Universal, Inc. Multiple parison extrusion device for producing laminar articles
US5301838A (en) 1991-01-23 1994-04-12 Continental Pet Technologies, Inc. Multilayer bottle with separable inner layer and method for forming same
JPH0694190B2 (en) 1991-03-06 1994-11-24 積水化成品工業株式会社 Laminated foam sheet suitable for vacuum forming
US5601200A (en) 1991-09-06 1997-02-11 Tri-Seal International, Inc. Cap liner for hot filled container and method
EP0611793A3 (en) 1993-02-19 1994-11-09 Mitsubishi Cable Ind Ltd Foamable organic polymer composition and production of foamed article.
US5328651A (en) 1993-03-05 1994-07-12 Davidson Textron Inc. Method for manufacturing an automobile trim component by blow molding and injection molding
US5464106A (en) 1994-07-06 1995-11-07 Plastipak Packaging, Inc. Multi-layer containers
US5575965A (en) 1995-05-19 1996-11-19 Union Carbide Chemicals & Plastics Technology Corporation Process for extrusion
BR9610557A (en) 1995-09-20 1999-12-21 Uponor Bv Oriented polymeric products
US5857572A (en) 1995-12-21 1999-01-12 Bird; Gerald C. Component carrier tape
US5628453A (en) 1996-01-16 1997-05-13 Packaging Resources, Inc. Cup with thermally insulated side wall
US6001439A (en) 1996-05-09 1999-12-14 Kureha Kagaku Kogyo K.K. Stretch blow molded container and production process thereof
DE69733286T2 (en) 1996-08-27 2006-01-19 Trexel, Inc., Woburn Process for extruding microcell polymers
CA2274070A1 (en) 1996-12-05 1998-06-11 Anthony Poloso Foamed high density polyethylene
US6884823B1 (en) 1997-01-16 2005-04-26 Trexel, Inc. Injection molding of polymeric material
SE508853C2 (en) 1997-03-10 1998-11-09 Perstorp Ab Foamed laminated plastic article and process for its manufacture
US5927525A (en) 1997-04-28 1999-07-27 Plastipak Packaging, Inc. Multi-layer containers and preforms
SE512309C2 (en) 1997-05-29 2000-02-28 Tetra Laval Holdings & Finance Extruded / mold blown bottle, whose wall structure includes a layer of cellular plastic
US5952423A (en) 1997-07-18 1999-09-14 Baxter International Inc. Plastic compositions for medical containers and methods for providing such containers and for storing red blood cells
WO1999028111A1 (en) 1997-11-28 1999-06-10 Jsp Corporation Blow-molded foam and process for producing the same
US6706223B1 (en) 1997-12-19 2004-03-16 Trexel, Inc. Microcelluar extrusion/blow molding process and article made thereby
CN1265955C (en) 1997-12-19 2006-07-26 特瑞塞尔公司 Microcellular foam extrusion/blow molding process and article made thereby
JP3501683B2 (en) * 1999-06-01 2004-03-02 株式会社ジェイエスピー Thermoplastic foam molded product with skin, container, and shock absorbing material for automobile
JP3646858B2 (en) 1999-08-09 2005-05-11 株式会社ジェイエスピー MULTILAYER POLYPROPYLENE RESIN FOAM MOLDED BODY, PROCESS FOR PRODUCING THE SAME, AND CONTAINER
US6323251B1 (en) 1999-09-24 2001-11-27 3M Innovative Properties Co Thermoplastic/thermoset hybrid foams and methods for making same
US20010048988A1 (en) 1999-09-28 2001-12-06 Glenn J. Forte Polyolefin bottles and method for making same
PL204201B1 (en) 2000-02-04 2009-12-31 Dow Global Technologies A process for producing thermoformable foam sheet using a physical blowing agent
EP1741744B1 (en) 2000-02-04 2017-06-21 Dow Global Technologies LLC A process for producing thermoformable foam sheet using a physical blowing agent
CN1255302C (en) 2000-04-26 2006-05-10 花王株式会社 Insulating container
US6593384B2 (en) 2000-05-25 2003-07-15 Trexel, Inc. Polymer foam processing with low blowing agent levels
EP1174261A1 (en) 2000-07-20 2002-01-23 Borcalis GmbH Single and multilayer polyolefin foam pipes
US6616434B1 (en) 2000-08-10 2003-09-09 Trexel, Inc. Blowing agent metering system
AU2002220024A1 (en) 2000-11-08 2002-05-21 Valspar Sourcing, Inc. Multilayered package with barrier properties
MY127292A (en) 2001-01-30 2006-11-30 Sumitomo Chemical Co Thermoplastic resin foam molding.
MY131000A (en) 2001-03-16 2007-07-31 Dow Global Technologies Inc High melt strength polymers and method of making same
US6811843B2 (en) 2001-04-05 2004-11-02 Appleton Papers Inc. Insulated beverage or food container
WO2002088233A1 (en) 2001-04-26 2002-11-07 Washington State University Research Foundation Low-density cellular wood plastic composite and process for formation
JP2004538177A (en) 2001-08-16 2004-12-24 イスパ インコーポレイテッド Extrusion composite compression injection method and apparatus
US6749914B2 (en) 2001-12-14 2004-06-15 Joseph M. Starita Melt blended high-density polyethylene compositions with enhanced properties and method for producing the same
US20030113496A1 (en) 2001-12-17 2003-06-19 Harris Michael G. Polyethylene melt blends for high density polyethylene applications
EP1472087B1 (en) 2002-02-04 2006-04-19 Colgate-Palmolive Company Container wall post-forming
JP4278340B2 (en) 2002-04-12 2009-06-10 Jsr株式会社 Rubber composition, method for producing the same, rubber molded article and fuel hose
US20030211350A1 (en) 2002-05-10 2003-11-13 Migliorini Robert A. Multilayer heat sealable polyolefin film comprising skin layer and transition layer of differing melting points
US8110260B2 (en) 2007-02-02 2012-02-07 Rick Merical Containers intended for moisture-sensitive products
US7871558B2 (en) 2002-06-20 2011-01-18 Alcan Global Pharmaceutical Packaging, Inc. Containers intended for moisture-sensitive products
US20060255049A1 (en) 2002-08-09 2006-11-16 Fort James Corporation Stretch blow-molded stackable tumbler
JP4257826B2 (en) 2002-09-30 2009-04-22 株式会社ジェイエスピー Method for producing polypropylene resin foam molding
JP2004137377A (en) 2002-10-17 2004-05-13 Kanegafuchi Chem Ind Co Ltd Polypropylene-based resin foamed sheet and molded form
US7588810B2 (en) * 2002-10-30 2009-09-15 Plastic Technologies, Inc. Container having foam layer
US8124203B2 (en) 2002-10-30 2012-02-28 Plastic Technologies, Inc. Container having a foamed wall
US9694515B2 (en) 2002-10-30 2017-07-04 Plastic Technologies, Inc. Overmolded container having an inner foamed layer
US7238765B2 (en) 2003-02-06 2007-07-03 Equistar Chemicals, Lp High density polyethylene and insulation compositions for wire and cable
JP4084209B2 (en) 2003-02-21 2008-04-30 株式会社ジェイエスピー Foam molded body and method for producing the same
US7704440B2 (en) 2003-12-02 2010-04-27 Ti Group Automotive Systems, L.L.C. Fuel system component and method of manufacture
US7557147B2 (en) 2004-03-17 2009-07-07 Dow Global Technologies Inc. Soft foams made from interpolymers of ethylene/alpha-olefins
CN1984763A (en) 2004-04-16 2007-06-20 先进塑料技术卢森堡有限公司 Mono and multi-layer articles and compression methods of making the same
AU2005235596A1 (en) 2004-04-16 2005-11-03 Advanced Plastics Technologies Luxembourg S.A. Preforms, bottles and methods of manufacturing the preforms and the bottles
US7226956B2 (en) 2004-06-30 2007-06-05 Gary Richard Wilkes Low density polymeric foam using a three-polymer blend
US7183005B2 (en) 2004-08-20 2007-02-27 Exxonmobil Chemical Patents Inc. Impact strength improvement of regrind
CN101044008A (en) 2004-10-19 2007-09-26 京洛株式会社 Blow molded article with surface skin and method for production thereof
US7727606B2 (en) 2004-11-02 2010-06-01 Jsp Corporation Polylactic acid resin foamed molding and process for manufacturing the same
EP1674238A1 (en) 2004-12-21 2006-06-28 Total Petrochemicals Research Feluy Bottles prepared from compositions of polypropylene and non-sorbitol nucleating agents
AR054010A1 (en) 2005-03-04 2007-05-30 Dow Global Technologies Inc IMPROVED POLYETHYLENE RESIN COMPOSITIONS WITH LOW FUSION INDEX AND HIGH FUSION RESISTANCE IMPROVED POLYETHYLENE RESIN COMPOSITIONS WITH LOW FUSION INDEX AND HIGH FUSION RESISTANCE
US20070013110A1 (en) 2005-07-13 2007-01-18 Graham Packaging Company, L.P. Two-stage blown air system and method for foamed articles
KR101233002B1 (en) 2005-07-13 2013-02-13 도요 세이칸 가부시키가이샤 Plastic container having pearl-like appearance and process for producing the same
US8535598B2 (en) 2005-08-04 2013-09-17 Jsp Corporation Method of forming hollow foam moldings
US7759267B2 (en) 2006-04-05 2010-07-20 Azdel, Inc. Lightweight composite thermoplastic sheets including reinforcing skins
JP4771315B2 (en) 2006-08-31 2011-09-14 株式会社吉野工業所 Multi-layer blow container
CN101511930B (en) 2006-09-12 2012-07-04 三井化学株式会社 Polypropylene resin and blown container
DE102007013273A1 (en) 2007-03-16 2008-09-18 Bayer Materialscience Ag Method for producing multilayer containers
GB0708493D0 (en) 2007-05-02 2007-06-06 Betts Uk Ltd Collapsible tube containers
SI2164893T1 (en) 2007-05-31 2013-11-29 Saudi Basic Industries Corporation Polyethylene foam
DE102007028881B4 (en) 2007-06-20 2014-07-10 Kautex Textron Gmbh & Co. Kg Process for the production of hollow bodies made of thermoplastic material
US8263198B2 (en) 2007-09-26 2012-09-11 Chevron Phillips Chemical Company Lp System and method for creating high gloss plastic items via the use of styrenic copolymers as a coextruded layer
US8061541B2 (en) 2007-11-15 2011-11-22 Conopco, Inc. Blow molded camouflage bottle
ES2719531T3 (en) 2008-04-15 2019-07-11 Palziv Ein Hanatziv Agricultural Co Operative Soc Ltd Crosslinked polyolefin foam sheet comprising cork particles
US20090269566A1 (en) 2008-04-23 2009-10-29 Berry Plastics Corporation Pre-stretched multi-layer stretch film
EP2141000B1 (en) 2008-06-30 2014-02-26 TI Automotive Technology Center GmbH Method of manufacturing an article and apparatus therefore
FR2934806A1 (en) 2008-08-07 2010-02-12 Inergy Automotive Systems Res METHOD FOR ATTACHING AN ACCESSORY IN A HOLLOW BODY OF PLASTIC MATERIAL
CN102202881B (en) 2008-10-31 2018-04-24 京洛株式会社 The manufacturing process of battenboard, the manufacturing process of core material for sandwich panel and battenboard
US8562885B2 (en) 2009-02-21 2013-10-22 Dow Global Technologies Inc. Multilayer structures having annular profiles and methods and apparatus of making the same
JP5371094B2 (en) 2009-04-15 2013-12-18 株式会社ジェイエスピー Hollow foam blow molding
MX2011011054A (en) 2009-05-05 2011-12-16 Meadwestvaco Corp Packaging materials with enhanced thermal-insulating performance.
CN102802914B (en) 2009-06-25 2016-01-20 Ti汽车技术中心有限责任公司 Vessel fabrication
US9023446B2 (en) 2009-09-22 2015-05-05 Graham Packaging Lc, L.P. PET containers with enhanced thermal properties and process for making same
DE202009015977U1 (en) 2009-11-23 2011-04-07 Optipack Gmbh packaging container
CN102762350A (en) 2009-11-24 2012-10-31 陶氏环球技术有限责任公司 Process for forming a double-sided shaped foam article
JP5602468B2 (en) * 2010-03-24 2014-10-08 株式会社ジェイエスピー Method for producing polypropylene resin foam blow molded article
EP2384984B8 (en) 2010-05-06 2013-09-25 Clariant Masterbatches (Italia) S.p.A. Process for the production of multilayer blow-molded hollow articles, and such a multilayer blow-molded hollow article
JP5552940B2 (en) 2010-07-27 2014-07-16 キョーラク株式会社 Method for producing multilayer foam
US9102093B2 (en) 2010-09-14 2015-08-11 Kyoraku Co., Ltd. Molding apparatus and molding method
CA2752335A1 (en) 2010-09-30 2012-03-30 Optipack Gmbh Method for producing a packaging container and packaging container
US8342420B2 (en) 2010-10-27 2013-01-01 Roberts Jr Richard W Recyclable plastic structural articles and method of manufacture
EP3272665A1 (en) 2011-06-17 2018-01-24 Berry Plastics Corporation Insulated container
BR112014004460A2 (en) * 2011-08-31 2017-03-21 Berry Plastics Corp polymeric material for an insulated container
CN102313084B (en) * 2011-09-02 2013-02-27 王井洋 Three-layer noise reduction drainage pipe and manufacture method thereof
US9175156B2 (en) 2011-09-21 2015-11-03 Polyone Corporation Sustainable thermoplastic compounds
WO2013082024A1 (en) 2011-11-29 2013-06-06 Revolutionary Plastics, Llc Low density high impact resistant composition and method of forming
US8648122B2 (en) 2011-12-01 2014-02-11 Sealed Air Corporation (Us) Method of foaming polyolefin using acrylated epoxidized fatty acid and foam produced therefrom
CN202691319U (en) * 2011-12-22 2013-01-23 神塑科技有限公司 Three layer co-extrusion polypropylene randon coplymer (PPR) water supply pipe
JP5863531B2 (en) 2012-03-28 2016-02-16 積水化成品工業株式会社 Polyethylene resin composition for foaming and polyethylene resin foam sheet
EP2877767B1 (en) 2012-07-26 2018-12-19 Saint-Gobain Performance Plastics Corporation Multilayer flexible tube
CN202895651U (en) * 2012-08-29 2013-04-24 通辽市津蒙线缆制造有限公司 Three-layer coextruding horizontal cable producing equipment
CN104769020B (en) 2012-10-31 2017-12-22 埃克森美孚化学专利公司 The product of the resin containing broad molecular weight distribution polypropylene
CN203125917U (en) * 2012-11-12 2013-08-14 佛山市海瑞嘉精密挤出机械有限公司 Three-layer tube extrusion die
MX2015008131A (en) 2012-12-21 2015-09-23 Dow Global Technologies Llc Polyolefin-based cable compound formulation for improved foamability and enhanced processability.
US20140272229A1 (en) 2013-03-13 2014-09-18 Raven Industries, Inc. Polyethylene foam and multilayered structure including the same
US20140377512A1 (en) 2013-06-24 2014-12-25 The Procter & Gamble Company Printed Foamed Film Packaging
AU2014286957A1 (en) 2013-07-12 2016-01-21 Berry Plastics Corporation Polymeric material for container
CN105592997A (en) 2013-08-16 2016-05-18 比瑞塑料公司 Polymeric material for an insulated container
TW201532782A (en) 2013-08-30 2015-09-01 Berry Plastics Corp Container and process for making the same
US20160089852A1 (en) 2014-09-29 2016-03-31 Mucell Extrusion, Llc Multi-layer thermoformed polymeric foam articles and methods
WO2016141179A1 (en) 2015-03-04 2016-09-09 Berry Plastics Corporation Polymeric material for container

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5037285A (en) * 1983-04-13 1991-08-06 American National Can Company Apparatus for injection molding and injection blow molding multi-layer articles
US6221925B1 (en) * 1996-12-05 2001-04-24 Mobil Oil Corporation Foamable high density polyethylene
US20030021927A1 (en) * 2001-07-30 2003-01-30 The Coleman Company, Inc. Method of blow and vacuum molding insulated containers
US20060142495A1 (en) * 2003-02-24 2006-06-29 Erkki Lalho Polypropylene compositions
US20120318859A1 (en) * 2011-06-17 2012-12-20 Berry Plastics Corporation Process for forming an insulated container having artwork
US20130026128A1 (en) * 2011-07-25 2013-01-31 Devtech Labs, Inc. Multi-gallon capacity blow molded container
US20130085244A1 (en) * 2011-10-04 2013-04-04 Mosha H. ZHAO Use of Temperature and Ethylene Partial Pressure to Introduce Long Chain Branching in High Density Polyethylene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3038810A4 *

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