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WO2012078129A1 - Tube stratifié ayant une résilience améliorée par un copolymère bloc - Google Patents

Tube stratifié ayant une résilience améliorée par un copolymère bloc Download PDF

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Publication number
WO2012078129A1
WO2012078129A1 PCT/US2010/059071 US2010059071W WO2012078129A1 WO 2012078129 A1 WO2012078129 A1 WO 2012078129A1 US 2010059071 W US2010059071 W US 2010059071W WO 2012078129 A1 WO2012078129 A1 WO 2012078129A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
dispenser
outer layer
substance
impact resistance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2010/059071
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English (en)
Inventor
Jun Wang
Bob Li
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive Co
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
Priority to CN2010800705464A priority Critical patent/CN103249550A/zh
Priority to US13/991,938 priority patent/US20130260069A1/en
Priority to RU2013131000/12A priority patent/RU2013131000A/ru
Priority to MX2013006312A priority patent/MX2013006312A/es
Priority to PCT/US2010/059071 priority patent/WO2012078129A1/fr
Priority to JP2013539810A priority patent/JP2014504237A/ja
Priority to SG2013031406A priority patent/SG189521A1/en
Priority to AU2010365033A priority patent/AU2010365033B2/en
Priority to PH1/2013/501149A priority patent/PH12013501149A1/en
Priority to MYPI2013001866A priority patent/MY160320A/en
Priority to CA2818247A priority patent/CA2818247C/fr
Priority to EP10788206.0A priority patent/EP2648900A1/fr
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Priority to BR112013012716A priority patent/BR112013012716A2/pt
Priority to TW100144558A priority patent/TW201238865A/zh
Priority to ARP110104540A priority patent/AR084156A1/es
Publication of WO2012078129A1 publication Critical patent/WO2012078129A1/fr
Priority to ZA2013/03658A priority patent/ZA201303658B/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
    • B65D35/02—Body construction
    • B65D35/10—Body construction made by uniting or interconnecting two or more components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
    • B65D35/02—Body construction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
    • B65D35/02—Body construction
    • B65D35/04—Body construction made in one piece
    • B65D35/08—Body construction made in one piece from plastics material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/24—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1355—Elemental metal containing [e.g., substrate, foil, film, coating, etc.]
    • Y10T428/1359—Three or more layers [continuous layer]

Definitions

  • the present invention relates broadly to dispensers formed from laminates of polymers and foil, and more specifically to collapsible dispensers particularly suited to contain and dispense pastes, gels and creams.
  • Dispenser tubes formed of metallic and plastic materials have long been known in the packaging field. Metal dispenser tubes require a coating to prevent attack and corrosion of the metal by alkaline or acid contents of the tube and contamination of the contents by the reaction products.
  • Tubes formed of polyethylene and other plastic materials have enjoyed wide commercial success in the packaging of many products. These are both single-layer and multi-layer tubes.
  • U.S. Pat. App. Pub. No. 2007/0272711 Al discloses elastically deformable dispensers comprising thermoplastic elastomers, such as styrene-ethylene-butadiene-styrene block copolymers.
  • Plastics as exemplified by polyethylene are to a degree permeable to organics when employed in the relatively low wall thicknesses used in tubular containers. This results in the flavor oils embodied in most dentifrices being reduced in volume during storage, rendering the dentifrice less palatable.
  • JP2005306415A discloses that the properties of a laminate tube container can be improved through the "arbitrary" use of any of a large variety of different resins, such as LDPE, HDPE, acrylonitrile-styrene copolymers, acrylonitrile-butadiene-styrene copolymers, and many others.
  • laminates that overcome the aforementioned deficiencies of existing laminates. It is further desired to provide laminates of simplified construction, which have good impact tolerance and stiffness. It is still further desired to provide dispensers for pastes, gels and creams, which are durable and are perceived by consumers as feeling durable and being of good overall quality.
  • a first aspect of the invention comprises a dispenser for storing and dispensing a substance, the dispenser comprising:
  • an inner layer comprising an inner layer polymer
  • the outer layer comprises an outer layer polymer and a block copolymer effective to provide the outer layer with an impact resistance at least 5% greater than a reference structure.
  • the impact resistance of the outer layer is at least 20% greater than the impact resistance of the reference structure.
  • the impact resistance of the outer layer is greater than 180 g.
  • the inner layer polymer and the outer layer polymer are polyethylene.
  • the inner layer polymer comprises LDPE
  • the outer layer polymer comprises LDPE and HDPE
  • the block copolymer comprises an SBS block copolymer having thermoplastic elastomer properties.
  • the metal foil comprises aluminum.
  • the dispenser further comprises an inner adhesive layer between the inner layer and the barrier layer, and an outer adhesive layer between the barrier layer and the outer layer.
  • the inner adhesive layer and the outer adhesive layer preferably comprise ethylene acrylic acid.
  • the barrier layer is bonded directly to the inner layer and the outer layer without any adhesive therebetween.
  • the inner layer and the outer layer are radiation graft modified and/or plasma modified for direct adhesion to the barrier layer.
  • the dispenser is sufficiently collapsible such that the substance can be extruded from the opening.
  • the substance in the dispenser is a member selected from the group consisting of a paste, a gel and a cream.
  • the substance is preferably a dentifrice and more preferably a toothpaste.
  • a second aspect of the invention comprises a dispenser for storing and dispensing a substance, the dispenser comprising:
  • an inner layer comprising LDPE
  • outer layer comprises LDPE, HDPE and an SBS block copolymer having thermoplastic elastomer properties.
  • the outer layer has an impact resistance at least 5% greater than a reference structure.
  • the outer layer has an impact resistance at least 20% greater than a reference structure.
  • the dispenser further comprises an inner adhesive layer between the inner layer and the barrier layer, and an outer adhesive layer between the barrier layer and the outer layer, wherein the inner adhesive layer and the outer adhesive layer comprise ethylene acrylic acid.
  • the barrier layer is bonded directly to the inner layer and the outer layer without any adhesive therebetween.
  • the inner layer and the outer layer are radiation graft modified and/or plasma modified for direct adhesion to the barrier layer.
  • the outer layer has an impact resistance at least 20% greater than a reference structure; (b) when the outer layer has a thickness of 120 microns, the impact resistance of the outer layer is greater than 180 g; and (c) the substance is toothpaste.
  • FIG. 1 is a side elevational view of a dispenser of a first embodiment of the invention, wherein portions of the body walls are broken away to more fully illustrate the multilayered structure.
  • FIG. 2 is a side elevational view of a dispenser of a second embodiment of the invention, wherein portions of the body walls are broken away to more fully illustrate the multilayered structure.
  • the invention is largely based on the discovery that laminates comprising polyethylene and block copolymer possess qualities favorable to the production of collapsible dispensers.
  • laminates of the invention possess enhanced impact resistance as evidenced by improved performance in drop tests and puncture tests.
  • Block copolymers preferred for use in the invention are linear ABA block copolymers, including but not limited to styrenic block copolymers (SBC), such as styrene-butadiene-styrene (SBS) block copolymers and styrene-ethylene-butadiene-styrene block copolymers.
  • SBC styrenic block copolymers
  • SBS styrene-butadiene-styrene
  • SBS styrene-ethylene-butadiene-styrene block copolymers
  • SBS block copolymers having the properties of thermoplastic elastomers. Other properties preferably possessed by the copolymers include excellent thermostability, very high elongation at break and/or extreme elastic recovery.
  • STYROFLEXTM an SBS block copolymer available from BASF, is a particularly preferred example of a copolymer suitable for use in the invention. (See, e.g., Huber et al, "Impact modifier boosts toughness of films.” Plastics, Additives and Compounding. Volume 10, Issue 1, January-February 2008, Pages 30-33.)
  • the SBS block copolymer is STYROFLEXTM 2G 66.
  • the STYROFLEXTM 2G 66 has a styrene content of at least 65% and a rubber fraction of at least 70%.
  • Typical properties of STYROFLEXTM 2G 66 are:
  • Non-limiting examples of other suitable block copolymers include: KRATONTM D SBS series, such as D 1101, 1102, 1153, 1155, etc.; KRATONTM D styrene-isoprene-styrene (SIS) series, such as D 1111, 1113, 1117, 1119, etc.; KRATONTM G series, such as styrene-ethylene-butylene- styrene (SEBS): G 1633, 1650, 1651 etc. and styrene-ethylene-propylene-styrene (SEPS): G 1730, etc.
  • KRATONTM D SBS series such as D 1101, 1102, 1153, 1155, etc.
  • KRATONTM D styrene-isoprene-styrene (SIS) series such as D 1111, 1113, 1117, 1119, etc.
  • KRATONTM G series such as styrene-ethylene-butylene-
  • the block copolymer can be provided as discrete layer of the laminate and/or it can be blended with other materials, such as polyethylene, in layer of the laminate.
  • the laminate of dispenser 10 comprises a single outside layer 20, which comprises a blend of high-density polyethylene (HDPE), low-density polyethylene (LDPE) and STYROFLEXTM.
  • This embodiment is essentially a three-layer laminate of inner layer 12, barrier layer 16 and outside layer 20, with inner adhesive layer 14 of ethylene acrylic acid (EAA) bonding barrier layer 16 to inner layer 12 and outer adhesive layer 18 of EAA bonding barrier layer 16 to outside layer 20.
  • the laminate (and more specifically an inner surface of inner layer 12) defines a compartment for storing a substance to be dispensed. Selected amounts of the substance are dispensed through a resealable opening, such as a threaded nozzle and cap 22.
  • the layer preferably comprises a blend of 10 to 95 wt.% polyethylene and 0 to 50 wt.% of an SBS block copolymer, more preferably 70 to 90 wt.% polyethylene and 10 to 30 wt.% of an SBS block copolymer. More preferably, the outside layer comprises 0 to 10 wt.% LDPE, 70 to 85 wt.% HDPE and 10 to 20 wt.% of an SBS block copolymer, such as STYROFLEXTM.
  • FIG. 2 shows a non-limiting example of the embodiment of the invention wherein the copolymer is provided as a discrete layer of the laminate.
  • the laminate comprises first outer layer 24 of LDPE below second outer layer 26 of HDPE below third outer layer 28 of STYROFLEXTM.
  • the three layers are preferably coextruded together.
  • This embodiment is essentially a five-layer laminate of inner layer 12, barrier layer 16 and the three outer layers, with inner adhesive layer 14 of ethylene acrylic acid (EAA) bonding barrier layer 16 to inner layer 12 and outer adhesive layer 18 of EAA bonding barrier layer 16 to first outer layer 24.
  • EAA ethylene acrylic acid
  • the block copolymer will provide a soft touch and firm gripping surface.
  • Preferred laminates of the invention simplify construction of dispensers relative to current constructions, wherein six or more different resins are used to prepare at least three outer layers and at least three inner layers.
  • Preferred laminates of the invention comprise only 2 or (as shown above) only 3 different resins, in addition to the barrier layer and the adhesive layers. The simplification of construction is expected to result in reduced manufacturing costs.
  • inner layer 12 and outer layer 20 can be treated to adhere directly to barrier layer 16 so as to eliminate inner adhesive layer 14 and outer adhesive layer 18, which are present in the embodiment of FIG. 1.
  • Inner layer 12 and outer layer 20 can be made adherent by, e.g., radiation graft modification or plasma modification.
  • gamma radiation is used to graft a grafting agent to at least one of inner layer 12 and outer layer 20, such that the modified layer(s) adhere(s) directly to barrier layer 16.
  • Suitable grafting agents include but are not limited to acrylic acids, such as ethylene acrylic acid, and the like.
  • ethylene acrylic acid is radiation grafted to polyethylene layers to render the layers adherent to aluminum.
  • grafting techniques suitable for use in the present invention are disclosed in, e.g., U.S. Patent Nos. 3,115,418 and 3,270,090 and Guimon, "Radiation grafting of high density polyethylene and polypropylene.” Radiat. Phys. Chem. 14, pp. 841-846 (1979).
  • plasma modification is used to make at least one of inner layer 12 and outer layer 20 adhere directly to barrier layer 16.
  • plasma modification techniques suitable for use in the present invention are disclosed in, e.g., Statutory Invention Reg. No. HI 164, which discloses a method of treating the surface of polymer films, such as PE films, with a low temperature gas plasma so as to improve the subsequent bonding of aluminum to the polymer surface without the need for adhesives; Hall et al, "Activated gas plasma surface treatment of polymers for adhesive bonding" Journal of Applied Polymer Science, Volume 13 Issue 10, Pages 2085 - 2096 (2003); and Minford, "Handbook of aluminum bonding technology and data” (CRC Press, 1993) at e.g., p.l3.
  • the plasma is atmospheric plasma, such as that produced by an atmospheric plasma system available from Enercon Industries Corp. (Menomonee Falls, WI).
  • Preferred parameters for this treatment step are as follows:
  • the treatment is preferably conducted with a gaseous mixture of 80% HYDROSTA TM H-10 (which is a 90: 10 mixture of Ar:H 2 available from Praxair) and 20% Oxygen. It is further preferred to use a ceramic electrode having a width of 1500-1600 mm, more preferably 1524 mm for the treatment.
  • Plasma treatment increases the surface tension of polymeric substrates, as evidenced by increased dyne levels (e.g., above 50) and decreased contact angle values (e.g., below 60).
  • the resultant layers are preferably hot pressed to barrier layer 16 at an elevated pressure (preferably 172367 Pa - 689470 Pa (25-100 psi), more preferably 448156 Pa (65 psi)) and temperature (preferably 149-204°C (300-400°F), more preferably 177°C (350°F)) for a time (preferably 30-60 seconds, more preferably 40 seconds) sufficient to achieve satisfactory bonding without adhesives.
  • Inner layer 12 is preferably compatible with the contents of dispenser 10, as inner layer 12 contacts the contents. Inner layer 12 is ideally impenetrable and inert with respect to the contents under normal storage and usage conditions. When the contents of the container are intended for consumption and/or administration to living organisms, inner layer 12 preferably comprises only food and/or medical grade polymer(s). Inner layer 12 preferably comprises polyethylene, and particularly LDPE, such as LDPE 2420 F from BASF.
  • the contents of dispenser 10 are preferably in the form of a paste, a gel, or a cream, and find application in, e.g., the cosmetic, pharmaceutical, veterinary, construction, maintenance and/or mechanical arts.
  • Examples of the contents (or substance) suitable for storage in and extrusion from dispenser 10 include but are not limited to dentifrices, toothpastes, tooth gels, tooth creams, skin creams, sun blocks, adhesives, paints, lubricants, and cleaning materials.
  • Inner layer 12 is preferably inert with respect to the contents. Practically speaking, however, it is also within the scope of the invention for inner layer 12 to absorb some amount of flavorant and/or other ingredients from the contents of dispenser 10. It is also within the scope of the invention for inner layer 12 to be somewhat permeable with respect to the contents of dispenser 10, or select ingredients therein.
  • Inner adhesive layer 14 bonds inner layer 12 to barrier layer 16.
  • Suitable adhesives include but are not limited to a copolymer of ethylene and acrylic acid or methacrylic acid, or sodium or zinc salts thereof in a diluent system.
  • Non-limiting examples of preferred adhesives include the ethylene acrylic acids PRIMACORTM 3340 from Dow Chemical Co. and NUCRELTM 30707 from DuPont.
  • inner layer 12 bonds directly to barrier layer 16 without inner adhesive layer 14.
  • Barrier layer 16 is provided to prevent the transfer of materials across the multilayered laminate structure of dispenser 10.
  • barrier layer 16 comprises a metal foil, such as aluminum foil.
  • a non- limiting example of a preferred aluminum foil is 8011 alloy from North China Aluminum Co. Ltd.
  • Outer adhesive layer 18 bonds the outermost side of barrier layer 16 to outer layer 20 (in the embodiment of FIG. 1) or first outer layer 24 (in the embodiment of FIG. 2).
  • the materials of outer adhesive layer 18 are preferably and independently selected from the same materials as inner adhesive layer 14.
  • outer layer 20 or first outer layer 24 bonds directly to barrier layer 16 without outer adhesive layer 18.
  • inner layer 12 also bonds directly to barrier layer 16 without inner adhesive layer 14.
  • the thicknesses of the laminate and the layers thereof are largely dictated by desired functionality and costs.
  • the preferred thickness range of each of the layers is as follows:
  • the figures show preferred embodiments of the inventive dispenser 10, wherein the dispenser is provided in the form of a collapsible tube. Suitable techniques for forming such tubes are disclosed in U.S. Pat. No. 3,295,725. Other types of dispensers are also within the scope of the invention.
  • the dispensers can be flexible or rigid.
  • the shape of dispensers is not particularly limited, but is preferably tubular.
  • laminates of the invention can be used for the components of a pump dispenser inclusive of the barrel, piston, diaphragm, nozzle, spout and the like. However, a preferred use is in dentifrice tubes.
  • a three-layer film with a total thickness of 120 microns was blown according to the outer film structure (24/26/28) shown in Table 2.
  • a control film was prepared, which had the same 120 ⁇ thickness as the film of Example 1, but comprised the following laminate structure:
  • LLDPE-LDPE 80-20
  • HDPE-LLDPE 60-40
  • LLDPE-LDPE 80-20
  • each layer was respectively 18 ⁇ , 84 ⁇ and 18 ⁇ .
  • a one-layer film with a total thickness of 120 microns was blown according to the outer film structure (20) shown in Table 1.
  • the film had an impact resistance of 182 g, 20% greater than the film of Comparative Example 1.
  • a laminate (or film) of the invention having a thickness of 120 microns has an impact resistance greater than 152 g or greater than 160 g or greater than 180 g or greater than 200 g or greater than 300 g or greater than 375 g.
  • the 120 ⁇ laminate (or film) of the invention has an impact resistance less than 1000 g or less than 750 g or less than 500 g, and preferably has an impact resistance of 180-400 g.
  • a laminate (or film) of the invention has an impact resistance at least 5% or at least 10% or at least 20% or at least 50% greater than a reference structure.
  • the term "reference structure” means a laminate (or film) of the same thickness as the inventive laminate (or film), which comprises at least one of the same polymer(s) as the inventive laminate (or film) but is free of the block copolymer. More preferably, the reference structure is identical in composition to the inventive laminate (or film) but for the absence of the block copolymer.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Tubes (AREA)
  • Wrappers (AREA)
  • Cosmetics (AREA)

Abstract

L'invention concerne un distributeur pour stocker et distribuer une substance, qui comprend : (a) une couche interne incluant un polymère à couche interne ; (b) une couche externe ; (c) une couche barrière en feuil métallique entre la couche interne et la couche externe ; (d) un compartiment pour stocker la substance ; et (e) une ouverture refermable. La couche externe comporte un polymère de couche externe et un copolymère bloc servant à conférer à la couche externe une résistance aux impacts supérieure d'au moins 5 % à une structure de référence. Le polymère de la couche interne est de préférence du LDPE, le polymère de la couche externe est de préférence un mélange de LDPE, de HDPE et d'un copolymère bloc ou, en variante, la couche externe est subdivisée en couches de LDPE, HDPE et de copolymère bloc, dans cet ordre. Le copolymère bloc est de préférence un copolymère bloc SBS ayant des propriétés élastomères thermoplastiques. Le distributeur est particulièrement bien adapté pour distribuer du dentifrice.
PCT/US2010/059071 2010-12-06 2010-12-06 Tube stratifié ayant une résilience améliorée par un copolymère bloc Ceased WO2012078129A1 (fr)

Priority Applications (16)

Application Number Priority Date Filing Date Title
US13/991,938 US20130260069A1 (en) 2010-12-06 2010-12-06 Laminate Tube Having a Resilent Copolymer Coating
RU2013131000/12A RU2013131000A (ru) 2010-12-06 2010-12-06 Многослойная туба, имеющая улучшенную упругость благодаря блок-сополимеру
MX2013006312A MX2013006312A (es) 2010-12-06 2010-12-06 Tubo laminado que tiene resiliencia aumentada por un copolimero de bloque.
PCT/US2010/059071 WO2012078129A1 (fr) 2010-12-06 2010-12-06 Tube stratifié ayant une résilience améliorée par un copolymère bloc
JP2013539810A JP2014504237A (ja) 2010-12-06 2010-12-06 ブロックコポリマーによって強化された弾力性を有するラミネートチューブ
SG2013031406A SG189521A1 (en) 2010-12-06 2010-12-06 Laminate tube having enhanced resiliency by a block copolymer
AU2010365033A AU2010365033B2 (en) 2010-12-06 2010-12-06 Laminate tube having enhanced resiliency by a block copolymer
MYPI2013001866A MY160320A (en) 2010-12-06 2010-12-06 Laminate tube having enhanced resiliency by a block copolymer
PH1/2013/501149A PH12013501149A1 (en) 2010-12-06 2010-12-06 Laminate tube having enhanced resiliency by a block copolymer
CN2010800705464A CN103249550A (zh) 2010-12-06 2010-12-06 具有嵌段共聚物的增强的弹性的层压材料管
EP10788206.0A EP2648900A1 (fr) 2010-12-06 2010-12-06 Tube stratifié ayant une résilience améliorée par un copolymère bloc
CA2818247A CA2818247C (fr) 2010-12-06 2010-12-06 Tube stratifie ayant une resilience amelioree par un copolymere bloc
BR112013012716A BR112013012716A2 (pt) 2010-12-06 2010-12-06 tubo laminado tendo uma resiliência intensificada por um copolímero em blocos
TW100144558A TW201238865A (en) 2010-12-06 2011-12-05 Laminate tube having a resilient copolymer coating
ARP110104540A AR084156A1 (es) 2010-12-06 2011-12-05 Tubos laminados que tienen un recubrimiento de copolimero flexible
ZA2013/03658A ZA201303658B (en) 2010-12-06 2013-05-20 Laminate tube having enhanced resiliency by a block copolymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2010/059071 WO2012078129A1 (fr) 2010-12-06 2010-12-06 Tube stratifié ayant une résilience améliorée par un copolymère bloc

Publications (1)

Publication Number Publication Date
WO2012078129A1 true WO2012078129A1 (fr) 2012-06-14

Family

ID=44318179

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/059071 Ceased WO2012078129A1 (fr) 2010-12-06 2010-12-06 Tube stratifié ayant une résilience améliorée par un copolymère bloc

Country Status (16)

Country Link
US (1) US20130260069A1 (fr)
EP (1) EP2648900A1 (fr)
JP (1) JP2014504237A (fr)
CN (1) CN103249550A (fr)
AR (1) AR084156A1 (fr)
AU (1) AU2010365033B2 (fr)
BR (1) BR112013012716A2 (fr)
CA (1) CA2818247C (fr)
MX (1) MX2013006312A (fr)
MY (1) MY160320A (fr)
PH (1) PH12013501149A1 (fr)
RU (1) RU2013131000A (fr)
SG (1) SG189521A1 (fr)
TW (1) TW201238865A (fr)
WO (1) WO2012078129A1 (fr)
ZA (1) ZA201303658B (fr)

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WO2016109963A1 (fr) 2015-01-08 2016-07-14 Colgate-Palmolive Company Stratifié holographique et tube fabriqué à partir de ce dernier
WO2018063775A1 (fr) * 2016-09-29 2018-04-05 Dow Global Technologies Llc Film coextrudé multicouche pour réguler la migration de graisse

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FR2987985B1 (fr) * 2012-03-15 2014-06-06 Albea Services Tube flexible avec bouchon applicateur
CN108274850A (zh) * 2013-10-30 2018-07-13 高露洁-棕榄公司 包装和用于制作包装的材料
US10654635B2 (en) * 2014-08-08 2020-05-19 Bemis Company, Inc. Transparent retail bag-in-box package

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016109963A1 (fr) 2015-01-08 2016-07-14 Colgate-Palmolive Company Stratifié holographique et tube fabriqué à partir de ce dernier
EP3233507A4 (fr) * 2015-01-08 2018-07-04 Colgate-Palmolive Company Stratifié holographique et tube fabriqué à partir de ce dernier
WO2018063775A1 (fr) * 2016-09-29 2018-04-05 Dow Global Technologies Llc Film coextrudé multicouche pour réguler la migration de graisse

Also Published As

Publication number Publication date
CN103249550A (zh) 2013-08-14
PH12013501149A1 (en) 2013-07-22
SG189521A1 (en) 2013-05-31
EP2648900A1 (fr) 2013-10-16
CA2818247C (fr) 2014-10-28
RU2013131000A (ru) 2015-01-20
BR112013012716A2 (pt) 2016-09-06
AR084156A1 (es) 2013-04-24
CA2818247A1 (fr) 2012-06-14
MY160320A (en) 2017-02-28
MX2013006312A (es) 2013-07-29
TW201238865A (en) 2012-10-01
AU2010365033B2 (en) 2014-12-04
JP2014504237A (ja) 2014-02-20
US20130260069A1 (en) 2013-10-03
AU2010365033A1 (en) 2013-05-02
ZA201303658B (en) 2016-01-27

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