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US20160185510A1 - Aerosol plastic container made from an isosorbide containing copolyester and aerosol dispenser comprising said aerosol plastic container - Google Patents

Aerosol plastic container made from an isosorbide containing copolyester and aerosol dispenser comprising said aerosol plastic container Download PDF

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Publication number
US20160185510A1
US20160185510A1 US14/911,540 US201414911540A US2016185510A1 US 20160185510 A1 US20160185510 A1 US 20160185510A1 US 201414911540 A US201414911540 A US 201414911540A US 2016185510 A1 US2016185510 A1 US 2016185510A1
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US
United States
Prior art keywords
container
aerosol
isosorbide
preform
copolyester
Prior art date
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Abandoned
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US14/911,540
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English (en)
Inventor
Laurent Degroote
Alain Dessaint
Cor Jansen
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.)
Plastipak BAWT SARL
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La Seda de Barcelona SA
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Filing date
Publication date
Application filed by La Seda de Barcelona SA filed Critical La Seda de Barcelona SA
Publication of US20160185510A1 publication Critical patent/US20160185510A1/en
Assigned to LA SEDA DE BARCELONA S.A. reassignment LA SEDA DE BARCELONA S.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DEGROOTE, LAURENT, Dessaint, Alain, JANSEN, COR
Assigned to PLASTIPAK BAWT, S.A.R.L. reassignment PLASTIPAK BAWT, S.A.R.L. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LA SEDA DE BARCELONA S.A.
Abandoned legal-status Critical Current

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    • 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 for dispensing liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising 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
    • B65D23/00—Details of bottles or jars not otherwise provided for
    • B65D23/10—Handles
    • B65D23/102—Gripping means formed in the walls, e.g. roughening, cavities, projections
    • 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 for dispensing liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant
    • B65D83/16—Actuating means
    • B65D83/20—Actuator caps
    • B65D83/206—Actuator caps comprising cantilevered actuating elements, e.g. levers pivoting about living hinges
    • 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 for dispensing liquid or semi-liquid contents by internal gaseous pressure, i.e. aerosol containers comprising propellant
    • B65D83/44—Valves specially adapted for the discharge of contents; Regulating devices
    • B65D83/48—Lift valves, e.g. operated by push action

Definitions

  • the present invention relates to a novel injection stretch blow molded aerosol container and to a novel plastic preform suitable to be stretch blow molded in order to form an aerosol container.
  • the invention also relates to a novel aerosol plastic dispenser for dispensing an aerosol or other comparably pressurized product.
  • Aerosol dispensers are well known in the art. More especially, aerosol dispensers comprise an aerosol container that contains an aerosol (or other comparably pressurized product), and that is fitted with a valve dispensing device for dispensing the aerosol. Aerosol dispensers comprising an aerosol container made of plastic are for example disclosed in US patent application US 2004/0149781 and in PCT application WO 2007/140407.
  • aerosol used herein encompasses both aerosol, literally, and also other liquids or flowable products that can be dispensed from pressurized containers in a manner comparable to aerolized products.
  • Such other liquids or flowable products include but are not limited to foam or gel preparations or to liquid products delivered from pressurized containers but not necessarily in a pulverized form.
  • Examples of typical aerosol compositions can be notably but not exhaustively insecticides, insect repellents, hairsprays, cosmetic sprays, air fresheners, cleaning preparation, shave preparations including foams and gels.
  • plastic aerosol dispensers have to fulfill the technical requirements of standard FEA 621 of March 2007 meeting the provisions of the Aerosol Dispensers Directive 75/324/EEC of May 1975 and related to the measurement of internal pressure resistance of empty containers without valves.
  • PET Polyethylene Terephthalate
  • ISBM Injection Stretched Blow Molded
  • polyesters like for example PET homo or copolymers, can advantageously exhibit strain-induced crystallization upon substantial orientation, in a region above the Natural Stretch Ratio (NSR) of the polymer.
  • NSR Natural Stretch Ratio
  • the NSR of a polymer can be knowingly determined in a free-blowing experiment.
  • Free-blowing of thermoplastics, in particular PET and PET copolymers is a well known technique used to obtain empirical data on the stretching behavior of a particular resin formulation.
  • the method of free blowing PET preforms is described in “Blow Molding Handbook”, edited by Donald V. Rosato, Dominick V. Rosato, Kunststoff 1989.
  • the term“free-blowing” means that a preform is blow-molded without using a mold. Free-blowing a bottle from a preform involves heating the preform to a temperature above its glass transition temperature and then expanding the preform outside of a mold so that it is free to expand without restriction until the onset of strain hardening.
  • Strain hardening can be detected in a stress-strain curve as an upswing in stress following the flow plateau. To a large extent the strain hardening is associated with molecular ordering processes in the resin. If the blow pressure and heating of the preform is properly set for a given preform, it will continue to expand until all of the PET is oriented to the point that stretching will stop at about the natural stretch ratio, or slightly beyond.
  • Standard ISBM grade PET even in the strain-hardening region, is however generally not suitable for making pressure-resistant ISBM aerosol containers that withstand high internal pressure, and more generally for making pressure-resistant ISBM aerosol containers that would fulfill the technical requirements of standard FEA 621 of March 2007.
  • the diol 1,4:3,6-dianhydro-D-sorbitol referred to hereinafter as isosorbide, the structure of which is illustrated below, is readily made from renewable resources, such as sugars and starches, in particular natural starch extracted from maize, wheat, potatoes and peas.
  • isosorbide can be made from D-glucose by hydrogenation followed by acid-catalyzed dehydration.
  • Isosorbide has been already used as a monomer for incorporation into polyesters such as PET at low levels.
  • the incorporation of isosorbide as comonomer in a copolyester knowingly reduces the intrinsic viscosity of the copolyester.
  • Isosorbide containing copolyesters and in particular Polyethylene Terephthalate containing Isosorbide (PEIT) polymers, as well as their process of manufacturing by melt polymerization or by solvent polymerization are thus well-known in the art.
  • PEIT Polyethylene Terephthalate containing Isosorbide
  • Isosorbide containing copolyesters and in particular Polyethylene Terephthalate containing Isosorbide (PEIT) polymers, are used to date in many applications, and for example for making films or containers.
  • PEIT Polyethylene Terephthalate containing Isosorbide
  • PEIT can be used for making hot-fillable containers that withstand high temperatures.
  • the incorporation of isosorbide as comonomer in a copolyester increases the glass transition temperature (Tg) of the copolyester (see FIG. 2 —Variation of Tg versus mol % of Isosorbide), and has also an impact on the strain hardening characteristics of the polymer: “Properties and Strain Hardening Character of Polyethylene Terephthalate Containing Isosorbide ”, Ramesh M. Gohil, Polymers Engineering and Science—2009 pages 544-553.
  • Isosorbide containing copolyesters and in particular Polyethylene Terephthalate containing Isosorbide (PEIT) polymers can be used to date in many applications, one cannot find on the market ISBM aerosol containers made form a isosorbide containing copolyesters and in particular made from a PEIT polymer.
  • PEIT Polyethylene Terephthalate containing Isosorbide
  • ISBM pressure-resistant aerosol containers made from an isosorbide containing copolyester and in particular made from a PEIT polymer.
  • a main objective of the invention is thus to propose a novel pressure-resistant aerosol plastic container made from an isosorbide containing copolyester, and in particular (but not only) made from a PEIT polymer.
  • a first object of the invention is a plastic preform adapted to be stretch blow molded in order to form an aerosol container or an injection stretch blow molded aerosol container, said preform or aerosol container being made from a polymeric material that comprises a copolyester including at least 1 mole % of isosorbide as comonomer and having an intrinsic viscosity of at least 0.7 dL/g.
  • the ISBM aerosol container of the invention exhibit very good mechanical properties, and in particular can advantageously withstand high internal pressure.
  • Aerosol containers are generally containers of small volumes, typically not more than 750 ml. Consequently, when aerosol containers are made by using ISBM technology, only low stretch ratios can be practiced.
  • isosorbide as comonomer in a copolyester has a strong impact on the onset of the strain-hardening region of the copolyester, and more particularly increases the NSR of the copolyester. Otherwise stated, isosorbide containing copolyesters, and in particular Polyethylene Terephthalate containing Isosorbide (PEIT) polymers, require a much higher elongation for reaching the strain-hardening region than a standard PET homopolymer.
  • PEIT Polyethylene Terephthalate containing Isosorbide
  • the invention removed this prejudice by increasing the intrinsic viscosity of the isosorbide containing copolyester, for example by carrying out a Solid State Polymerization (SSP) of the copolyester for a period sufficient to achieve an IV of at least 0.7 dL/g.
  • SSP Solid State Polymerization
  • This increase of IV advantageously decreases the NSR of the copolyester and enables to obtain a copolyester combining a high level of isosorbide and a lower NSR and suitable for making pressure-resistant ISBM aerosol containers.
  • the preform or ISBM aerosol container of the invention can have any one of the following optional characteristics:
  • the invention also relates to an aerosol dispenser comprising the aforesaid injection stretch blow molded aerosol container and a valve dispensing device suitable for dispensing an aerosol contained in the aerosol container.
  • FIG. 1 is a longitudinal cross-section view of preform suitable to be stretch blow molded in order to form a pressure-resistant aerosol plastic container.
  • FIG. 2 is a longitudinal cross-section view of an aerosol dispenser comprising an ISBM aerosol container that has been obtained by biaxially stretch blow molding the preform of FIG. 1 , and that is fitted with a valve dispensing device suitable for dispensing an aerosol contained in the aerosol container.
  • the aerosol dispenser 2 comprises a pressure resistant aerosol container 20 which is knowingly hermetically closed by a valve dispensing device 21 .
  • Said valve dispensing device 21 comprises a closure 210 that is covering the top opening 200 of the aerosol container 20 , and that is sealingly attached to the neck 201 of the aerosol container 20 .
  • Said closure 210 includes a valve member 211 having an axially extending valve stem 212 which can be either depressed or tilted to release the aerosol contained within the container 20 .
  • the structure and functioning of the valve dispensing device 21 are well known in the art and will not be described in details. One skilled in the art can besides refer to the disclosure of US 2004/0149781.
  • the pressure resistant plastic aerosol container 20 is an injection stretch blow molded container.
  • FIG. 1 shows a plastic preform 1 suitable to be stretch blow molded in order to form a pressure-resistant aerosol plastic container
  • This preform 1 is made of a substantially tubular body of axial length L 1 , which is closed at its bottom end and has a pouring opening at its upper end. More especially, said preform 1 comprises a neck portion 10 terminated by a pouring opening 100 , a so-called gate portion 12 forming a closed bottom end, and a body portion 11 that is extending between said gate portion 12 and said neck portion 10 .
  • the neck portion 10 comprises a protruding neck support ring 101 of bigger diameter.
  • the body portion 11 comprises a main cylindrical portion 110 of substantially constant wall thickness WT and an upper transition portion 111 .
  • the inner face of the main portion 110 can be also conical.
  • the gate portion 12 is made of a convex portion having substantially a hemi-spherical shape, and terminated by a small central protruding injection point 20 .
  • the size of this injection point 20 corresponds to the size of the output orifice of the hot runner nozzle that is being used for injecting the plastic material in the mould.
  • the shape of the gate portion 12 is not necessarily hemi-spherical, but the gate portion 12 can have any other shape, and in particular can be for example conical.
  • this preform 1 is biaxially stretch blow molded in a mould
  • the neck portion 10 is used for maintaining the preform in the blowing mould, and is thus not stretched.
  • the body portion 11 is biaxially stretched (in a longitudinal direction X and in a radial direction Y) in order to form a container body of higher volume.
  • the gate portion 12 is also biaxially stretched in order to form typically the bottom base of the injection stretch blow molded container.
  • a “one stage process” or a “two stages process” can be used.
  • the stretch-blow moulding step of the preform is performed in line immediately after the first injection step (preform injection).
  • the stretch-blow moulding step of the preform is postponed, and a reheating of the preform is performed prior to this stretch-blow molding step.
  • the final shape and size of the container will depend of the blow mold that is being used and of the stretch ratios that are practiced.
  • the preform 1 can thus be stretch blow molded in order to make the pressure-resistant aerosol container 20 of FIG. 2 .
  • the invention is however not limited to the particular shape or dimensions of the aerosol container 20 of FIG. 2 .
  • the base 202 ( FIG. 2 ) of the aerosol container 20 is not necessarily spherical like the container depicted on FIG. 2 , but can be of any shape. More especially, the base 202 of the aerosol container 20 can also be a base including an inwardly-oriented central dome, also commonly called “champagne” base, or can be a “petaloid” base like for example the base of the container of FIG. 8D of WO 2007/140407.
  • the sidewall of the container comprises a main central portion 203 which is concave and forms a kind of hyperboloid configuration, which provides a very ergonomic structure that can be easily handled by a user.
  • the sidewall of the container 2 can have any other shape, including straight wall portion, convex wall portions, etc. . . .
  • the polymeric material used for making the preform 1 or container 2 is a copolyester including at least 1 mole % of isosorbide as comonomer and having an intrinsic viscosity of at least 0.7 dL/g, more preferably of at least 0.8 dL/g, and even more preferably of at least 0.9 dL/g.
  • the intrinsic viscosity of the Isosorbide containing copolyester has generally to be increased for example by carrying out a Solid State Polymerization (SSP) of the copolyester for a period sufficient to achieve the required minimum IV.
  • SSP Solid State Polymerization
  • This increase of IV enables advantageously to lower the NSR of the isosorbide containing polyester and to at least partially compensate the increase of the NSR caused by the incorporation of isosorbide in the copolyester.
  • the required IV level can however also be obtained directly, i.e. without a SSP post-treatment, by carrying out a suitable polymerization process.
  • the isosorbide containing polyester comprises a copolyester that includes at least 5 mole % of isosorbide as comonomer.
  • the isosorbide containing polyester comprises a copolyester that includes not more than 15 mole % of isosorbide as comonomer, and even more preferably not more than 8 mole % of isosorbide as comonomer.
  • the isosorbide containing copolyester may be formed by any method known in the art.
  • the polyester is formed by solvent or melt polymerization.
  • the isosorbide containing copolyester is Polyethylene Terephtalate containing Isosorbide (PEIT), although other polyesters are also suitable for practicing the invention.
  • PEIT Polyethylene Terephtalate containing Isosorbide
  • the isosorbide containing copolyester comprises terephthaloyl moieties; optionally, one or more other aromatic diacid moieties; ethylene glycol moieties; isosorbide moieties; and, optionally one or more other diol moieties.
  • terephthaloyl moieties can be derived from terephthalic acid or dimethyl terephthalate.
  • isosorbide containing copolyester can further comprise diethylene glycol moieties
  • Aforesaid one or more other diol moieties can be derived from aliphatic alkylene glycols or branched aliphatic glycols having from 3-12 carbon atoms and having the empirical formula HO-CnH2n-OH, where n is an integer from 3-12; including branched diols such as 2,2-dimethyl-1,3-propanediol; cis or trans-1,4-cyclohexanedimethanol and mixtures of the cis and trans isomers; triethylene glycol; 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane; 1,1-bis[4(2-hydroxyethoxy)phenyl]cyclohexane; 9,9-bis[4-(2hydroxyethoxy)phenyl]fluorene; 1,4:1,4:3,6-dianhydromannitol; 1,4:1,4:3,6-dianhydroiditol; and 1,4-anhydroerythrito
  • the number of terephthaloyl moieties in the polymer is in the range of about 25% to about 75 mole % (mole % of the total polymer).
  • ethylene glycol monomer units are present in amounts of about 5 mole % to about 49.75 mole %.
  • the polymer may also contain diethylene glycol moieties. Depending on the method of manufacture, the amount of diethylene glycol moieties is for example in the range of about 0.0 mole % to about 25 mole %.
  • the mold blowing step was performed with an axial stretch ratio S a around 2.4 mm.
  • This axial stretch ratio (S a ) is knowingly defined in a standard way by formula:
  • L is the container developed length ( FIG. 2 ) and l is the preform neutral fibre developed length ( FIG. 1 ).
  • the radial stretch ratio (S r ) was around 2.55 mm. This radial stretch ratio (S r ) is knowingly defined in a standard way by formula:
  • the first batch (Ref. A) of ISBM aerosol containers was made from Polyethylene Terephthalate containing Isosorbide (PEIT) [i.e. Poly(etyhylene-co-isosorbide)terephthalate]. More particularly, said PEIT was containing 5.8 mole % of Isosorbide (5.8 mole % PEIT). This 5.8 mole % PEIT was obtained in a known way by melt polymerization. This 5.8 mole % PEIT issued from the melt polymerization was subjected to a SSP during a period of time sufficient to raise the IV of the Isosorbide containing copolyester up to about 0.95 dL/g.
  • PEIT Polyethylene Terephthalate containing Isosorbide
  • the second batch (Ref B) of ISBM aerosol containers was made from a PET resin of standard grade having an intrinsic viscosity of about 0.86 dL/g.
  • the third batch (Ref;C) of ISBM aerosol containers was made from a PET resin having an intrinsic viscosity of about 0.95 dL/g.
  • Said PET resin was a copolymer PET commercialized by Artenius Tech Polymers under commercial reference “Artenius HOT”.
  • the intrinsic viscosity (IV) of the resin before injection was measured pursuant to following method based on the ISO 1628 standard:
  • the intrinsic viscosity (IV) of the preforms of the three batches was also measured by carrying out the aforesaid method with m-cresol as solvent. The results showed an IV drop due to a degradation of the polymer during the injection process.
  • the IV of the preforms of the first batch (Ref. A) was around 0.8 dL/g.
  • the IV of the preforms of the second batch (Ref. B) was around 0.73 dL/g.
  • the IV of the preforms of the third batch (Ref. C) was around 0.78 dL/g.
  • the glass transition temperature (Tg) of the resins was knowingly measured by Differential Scanning calorimetry (DSC) with an equipment DSC 821e from Mettler Toledo.
  • the Tg of the 5.8 mole % PEIT (Ref. A) was around 89.6° C.
  • the Tg of the PET resin of the second batch (Ref. B) was around 79.6C.
  • the Tg of the PET resin of the third batch (Ref. C) was around t 79.5° C.
  • Test pressure needs to be 50% higher than the internal pressure in the container at 50° C.
  • the goal of this test is to evaluate the container when it is dropped from a height of 1.8 m to a concrete floor and this at different temperatures. Ensure that the orientation, of the test container at drop is statistically random, but that direct impact on the valve or valve closure is avoided. Aerosol containers must be designed that it shall not break or leak.
  • the goal of this test is to evaluate the ability of an aerosol container to withstand to a certain internal pressure. Pressure at which the container is bursting needs to be minimum 20% higher than the test pressure.
  • the goal of this test is to indicate the temperature where the deformation of the container is induced. Temperature for this test is 7° C. lower than Tg with a max. test temperature of 75° C. and min temperature of 65° C. It is allowed that the containers deform, but without breakage or leakage creating a hazardous environment.
  • the goal of this test is to evaluate the aerosol containers resistance to a vertical load before its first deformation.
  • Equipment used for this test is the INSTRON 3366 Top load tester with a load cell of 5000N. The result is the maximum compressive load (in kgf) a container can withstand before it loses 1% of the compressive load applied. Test is done with a speed of 50 mm/min.
  • the objective of the accelerated stress cracking is to simulate stress experienced by containers during pressure filling, shipping and storage.
  • the test is performed as follows:
  • the goal of this test is to measure the Oxygen transmission rate of the aerosol container.
  • Equipment used to determine the permeation is the MOCON Oxtran 2/20 that uses a Coulometric Sensor (Coulox) to determine the O2 concentration.
  • Test method used is derived from the ASTM D 3985 and the ASTM F 1307.
  • the Aerosol container is mounted on a metal fixture and flushed with N2 to purge the air out of the bottle. As the outside of the bottle is in contact with ambient air (20.9% O 2 ), O 2 permeates trough the bottle wall and is transported with the N 2 flow to the Coulox Sensor.
  • the test is performed as follows:
  • the invention is not limited to an injection stretch blow molded aerosol container made from a copolyester including at least 1 mole % of isosorbide as comonomer and having an intrinsic viscosity of at least about 0.7 dL/g.
  • the invention can be also practiced with a polymer blend comprising said copolyester including at least 1 mole % of isosorbide as comonomer and having an intrinsic viscosity of at least about 0.7 dL/g and another polymer, in particular another polyester.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
US14/911,540 2013-08-14 2014-08-07 Aerosol plastic container made from an isosorbide containing copolyester and aerosol dispenser comprising said aerosol plastic container Abandoned US20160185510A1 (en)

Applications Claiming Priority (3)

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EP13180376.9 2013-08-14
EP20130180376 EP2837581A1 (en) 2013-08-14 2013-08-14 Aerosol plastic container made from an isosorbide containing copolyester and aerosol dispenser comprising said aerosol plastic container
PCT/EP2014/066958 WO2015022254A1 (en) 2013-08-14 2014-08-07 Aerosol plastic container made from an isosorbide containing copolyester and aerosol dispenser comprising said aerosol plastic container

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US (1) US20160185510A1 (pt)
EP (1) EP2837581A1 (pt)
JP (1) JP2016529171A (pt)
CN (1) CN105658539A (pt)
AU (1) AU2014307974A1 (pt)
BR (1) BR112016002884A2 (pt)
CA (1) CA2919889A1 (pt)
MX (1) MX2016001991A (pt)
RU (1) RU2016108984A (pt)
WO (1) WO2015022254A1 (pt)
ZA (1) ZA201600794B (pt)

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US20190169367A1 (en) * 2016-08-02 2019-06-06 Roquette Freres Semi-crystalline thermoplastic polyester for producing an aerosol container
US20190169366A1 (en) * 2016-08-02 2019-06-06 Roquette Freres Semi-crystalline thermoplastic polyester for producing biaxially stretched hollow bodies
US11396579B2 (en) 2017-06-26 2022-07-26 Sk Chemicals Co., Ltd. Polyester film and manufacturing method thereof
US11447603B2 (en) 2017-05-31 2022-09-20 Sk Chemicals Co., Ltd. Polyester resin, method for preparing same, and resin molded product formed therefrom
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FR3019803B1 (fr) * 2014-04-10 2016-12-23 Fareva Generateur aerosol en matiere plastique
KR102571703B1 (ko) * 2015-12-24 2023-08-29 에스케이케미칼 주식회사 폴리에스테르 수지, 이의 제조 방법 및 이로부터 형성된 수지 성형품
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JP2016529171A (ja) 2016-09-23
CA2919889A1 (en) 2015-02-19
AU2014307974A1 (en) 2016-02-18
EP2837581A1 (en) 2015-02-18
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RU2016108984A (ru) 2017-09-19
MX2016001991A (es) 2016-05-18

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