Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • 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
  • B65D83/00—Containers or packages with special means for dispensing contents
  • B65D83/14—Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant
  • B65D83/38—Details of the container body
• • 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
  • B65D83/00—Containers or packages with special means for dispensing contents
  • B65D83/14—Containers or packages with special means for dispensing contents for delivery of liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant for a product delivered by a propellant
  • B65D83/60—Contents and propellant separated
  • B65D83/62—Contents and propellant separated by membrane, bag, or the like
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2207/00—Properties characterising the ingredient of the composition
  • C08L2207/06—Properties of polyethylene
  • C08L2207/064—VLDPE
• • 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.]
  • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
• • 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.]
  • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
  • Y10T428/1341—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
• • 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]
• • 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]
  • Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit

Definitions

• the present invention relates to a new container comprising a rigid external envelope and a flexible internal pocket. More particularly, the container according to the invention is intended to receive a butane gas under pressure.
• a container is well known. It consists of a rigid external envelope, for example made of metal (steel or aluminum) and an internal flexible pocket, said pocket being fixed to the external envelope and communicating with the exterior by means of a valve. . Gas, in particular butane gas, is introduced into the space between the internal pocket and the rigid envelope, and exerts pressure on the internal pocket. The user, by a mechanical action on the valve, can empty the contents of the bag under the action of gas.
• Such a container avoids contaminating the contents of the bag with the propellant gas and avoids spreading this gas in the atmosphere.
• These containers are commonly used today, for example for the manufacture of shaving foam bombs and the like.
• the internal pocket 0 In order to best fulfill its function, the internal pocket 0 must be flexible while remaining resistant, so as to be capable of being introduced into the rigid envelope immediately after the manufacture of said flexible pocket. Furthermore, this flexible pocket must have very low butane permeability, in order to avoid any contamination of the contents of the bag and / or any loss of pressure of the propellant. So we are looking for such pockets.
• US-A-3 873 667 describes such flexible bags made of a mixture of polyamide and polyolefin, optionally with an isomer resin. This mixture is then subjected to a heat treatment. Thus, according to this prior art, it is necessary to provide an additional treatment step before introduction of the flexible bag into the envelope, which increases the complexity of the process and its cost.
• Polyamides, in particular PA6, are already known which are very resistant and have good qualities of butane permeability.
• these polyamides are not flexible enough for the resulting bag to be able to be introduced into the rigid envelope immediately after its manufacture. It has therefore been proposed to incorporate plasticizers in the polyamide compositions; the quantities of plasticizer required to lower the flexural modulus to an acceptable value are however very high, more than 10% by weight.
• high amounts of additives, such as plasticizers, in polyamide compositions often cause the emission of harmful products, in particular fumes, at the high temperatures used for the transformation of polyamide compositions.
• Polyolefins would also not be suitable for the preparation of such flexible bags, since they do not have sufficient strength or low butane permeability. In order to remedy this problem, one could think of increasing the thickness of the flexible bag. However, a large thickness of the pocket raises problems during insertion into the rigid envelope and increases production costs
• compositions are therefore sought for such flexible bags, intended to be introduced into a rigid envelope of a container, said compositions having to: (a) have a low permeability for butane; (b) be convertible without emission problems;
• the subject of the present invention is a new container comprising a rigid external envelope and a flexible internal pocket, under butane gas pressure, in which the flexible internal pocket has a dry bending module of between 1000 and 2000 MPa, and is of a material comprising a mixture of (a) at least one matrix-forming polyamide;
• At least one functionalized ethylene polymer which is a homo- or copolymer of ethylene grafted with a carboxylic acid monomer, an anhydride of such an acid, a salt of such an acid, an unsaturated epoxide; and optionally (c) a non-functionalized polyethylene.
• the functionalized ethylene polymer (b) is a homo- or copolymer of ethylene grafted with maleic anhydride.
• functionalized (b) is a mixture of a polyethylene and an EPR, functionalized with an anhydride.
• the non-functionalized polyethylene when it is present, is an LDPE, an LLDPE, preferably a VLDPE, or a metallocene PE.
• the polyamide in the material of said pocket, is PA6.
• the material of said pocket further comprises (d) at least one plasticizer.
• An advantageous material for the flexible pouch according to the invention comprises, in% by weight relative to the weight of the material:
• Another advantageous material for the flexible pouch according to the invention comprises, in% by weight relative to the weight of the material:
• Another advantageous material for the flexible pouch according to the invention comprises, in% by weight relative to the weight of the material:
• the butane permeability of said pocket is less than 3 g / year, preferably less than 1 g / year.
• the container according to the invention is of conventional design, the pocket having for example a capacity of 0.1 to 1 liter.
• the external rigid envelope is made, from steel or aluminum for example, with the formation of a neck at the upper level of said envelope.
• the pocket is inserted into said envelope and it is sealed at the neck, the future content and the propellant being introduced in a conventional manner, before, during or after sealing.
• a valve then covers the neck.
• the bag is produced in a conventional manner, for example by extrusion blow molding or injection blow molding of granules of polymer material.
• the gas used is butane gas, this term designating in particular n-butane, 1 iso-butane and their mixtures. However, any other suitable gas could be used.
• the invention mainly resides in the material used for the manufacture of internal flexible bags, based on polyamide, functionalized ethylene polymers and optionally non-functionalized polyethylene and plasticizer.
• polyamide conventionally designates the condensation products:
• alpha-omega-amino acids such as those containing for example from 6 to 12 carbon atoms
• examples of such ammo acids are ammocaproic, ammo-7-heptano ⁇ que, ammo-11-undécéno ⁇ que and ammo-12-dodécano ⁇ que acids; or
• lactams corresponding to the above amino acids; examples of such lactams are caprolactam, oenanlactam and lauryllactam; or
• the polyamide is PA6, PA6, 6, PA6.10, PAU, PA12, PA6.12 and PA12.12.
• the preferred polyamide is PA6.
• the molecular weight of polyamides can vary widely, which one skilled in the art will appreciate.
• This polyamide forms the matrix of the polymer material, the ethylene polymers being dispersed in this phase in the form of nodules, the diameter of which can be from 0.1 to 5 ⁇ m.
• the polyamide / ethylene polymers ratio (components (b) and (c)) in the material according to the invention can vary over a wide range, which will be appreciated by those skilled in the art.
• the polyamide is present in an amount sufficient to constitute the matrix phase; for example, the polyamide represents from 30 to 80%, advantageously from 50 to 70% by weight, relative to the weight of the material.
• component (b) designates the polymer products of which ethylene constitutes a substantial part and which additionally carry reaction or functional groups on or along the chain.
• the invention provides homo- or copolymers of ethylene grafted with a carboxylic acid monomer, an anhydride of such an acid, a salt of such an acid (such as a metal salt, for example with Zn), an unsaturated epoxide (such as glycidyl (meth) acrylate).
• ethylene homopolymers or copolymers of ethylene copolymerized with butene, hexene, octene, optionally mixed with ethylene-propylene copolymers said ethylene / alpha-olefin copolymers containing, for example, 35 to 80% by weight of ethylene; these polymers are grafted, for example, with an anhydride, for example maleic, the degree of grafting with the anhydride can be between 0.01 and 1% by weight, for example between 0.05 and 0.5%, relative to the total weight of polymer.
• maleic anhydride which is the preferred anhydride
• another di carboxylic acid anhydride such as citraconic acid anhydride, itaconic anhydride, tetrahydrophthalic anhydride, anhydride methyl-2-maleic, dimethyl-2,3-maleic anhydride.
• a functionalized polyethylene which is a polyethylene (ethylene / alpha-olefin homopolymer or copolymer) in mixture with an ethylene-propylene copolymer (EPR), then functionalized for example by grafting, is a functionalized elastomeric polyethylene.
• EPR ethylene-propylene copolymer
• the proportion of EPR is generally less than 20%, preferably between 5 and 15% by weight.
• This elastomeric polyethylene is a preferred functionalized polyethylene.
• nonfunctionalized polyethylene denotes homopolymers or copolymers of ethylene which are not functionalized.
• polyethylene polyethylene, copolymers of ethylene with alpha-olefins, ethylene representing for example 35 to 80% by weight, metallocene and Ziegler PE;
• esters of carboxylic acids (i) esters of carboxylic acids; (ii) vinyl esters of saturated carboxylic acids such as vinyl acetate; and (m) esters of unsaturated carboxylic acids, such as alkyl (meth) acrylate, ethylene representing for example from 35 to 80% by weight;
• copolymers mentioned above can be copolymerized in a statistical or sequenced fashion and have a linear or branched structure.
• polyethylene HDPE, LDPE, LLDPE or VLDPE
• metallocene PE or Ziegler ethylene / vinyl acetate (EVA) copolymers
• EVA ethylene / vinyl acetate copolymers
• ethylene / methyl or butyl acrylate copolymers ethylene / methyl or butyl acrylate copolymers.
• the molecular weight of polyethylenes can vary widely, which one skilled in the art will appreciate.
• the preferred non-functionalized polyethylene is polyethylene VLDPE.
• a polyamide can be a mixture of two or more polyamides
• a polyethylene can be a mixture of two or more polyethylenes, - "a functionalized polyethylene” may be a mixture of two or more functionalized polyethylenes, etc.
• plasticizer has the meaning commonly accepted in art.
• BBSA butylbenzene sulfonamide
• EHPB ethyl hexyl-para-hydroxy-benzoate
• DHPB decyl hexyl-para-hydroxy-benzoate
• the bag according to the invention has a conventional thickness, for example between 50 and 500 ⁇ m, preferably between 150 and 250 ⁇ m.
• Example 1 illustrates the invention without limiting it. Unless otherwise indicated, the proportions are expressed in parts by weight. In the example, the MFI represents the melt flow index. Example 1.
• the following material is prepared: 65 parts of PA6, having an MFI of 17-20 (235 ° C., 2.16 kg);
• the material components are introduced into the hopper of a Werner twin screw extruder with a diameter of 40mm.
• the total throughput of the extruder is 50 kg / h and the rotation speed is 150 rpm.
• the material temperatures at the barrel and at the head are 260 ° C, 230 ° C, 235 ° C and 255 ° C respectively.
• the granules obtained are injection molded to obtain bars of 80x10x4 mm on which the dry bending module and the bending module are measured in the conditioned state. These granules are also transformed by extrusion blow molding into bags having an average thickness of 200 ⁇ m, on which the butane permeability is measured.
• the dry flexural modulus is measured in accordance with ISO standard 178, and is expressed in MPa.
• the flexural modulus in the conditioned state (14 days at 23 ° C. and 50% relative humidity) is measured in accordance with ISO standard 178, and is expressed in MPa.
• the butane permeability is measured by gravimetry under the following conditions: surface: 210cm2; thickness: 200 ⁇ m; temperature: 35 ° C; butane permeation is expressed in g / year.
• the material of the example above is tested to determine the dry flexural modulus, the butane permeability, as well as the flexural modulus in the conditioned state.

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• Chemical & Material Sciences (AREA)
• Medicinal Chemistry (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Mechanical Engineering (AREA)
• Engineering & Computer Science (AREA)
• Dispersion Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Packages (AREA)
• Laminated Bodies (AREA)
• Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
• Bag Frames (AREA)
• Medical Preparation Storing Or Oral Administration Devices (AREA)

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• 1997
  • 1997-04-18 EP EP97400878A patent/EP0803539A1/de not_active Withdrawn
  • 1997-04-21 CN CN97109775A patent/CN1069330C/zh not_active Expired - Fee Related
  • 1997-04-21 CA CA002203287A patent/CA2203287A1/fr not_active Abandoned
  • 1997-04-21 NO NO971831A patent/NO971831L/no unknown
  • 1997-04-22 JP JP9537787A patent/JP2000508707A/ja active Pending
  • 1997-04-22 JP JP9118740A patent/JP2992246B2/ja not_active Expired - Lifetime
  • 1997-04-22 US US08/837,834 patent/US5935666A/en not_active Expired - Fee Related
  • 1997-04-22 EP EP97920801A patent/EP0895527A1/de not_active Withdrawn
  • 1997-04-22 KR KR1019970014956A patent/KR100279860B1/ko not_active IP Right Cessation
  • 1997-04-22 WO PCT/FR1997/000719 patent/WO1997040101A1/fr not_active Application Discontinuation
  • 1997-05-20 TW TW086106850A patent/TW334410B/zh active

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