WO2007070967A1 - Mélanges de polymères - Google Patents

Mélanges de polymères Download PDF

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Publication number
WO2007070967A1
WO2007070967A1 PCT/AU2006/001972 AU2006001972W WO2007070967A1 WO 2007070967 A1 WO2007070967 A1 WO 2007070967A1 AU 2006001972 W AU2006001972 W AU 2006001972W WO 2007070967 A1 WO2007070967 A1 WO 2007070967A1
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WO
WIPO (PCT)
Prior art keywords
container
blend
polymer blend
pet
weight
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Application number
PCT/AU2006/001972
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English (en)
Inventor
Robert Cecil Mcfadyen
Original Assignee
Vip Plastic Packaging Pty Ltd.
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 claimed from AU2005907246A external-priority patent/AU2005907246A0/en
Application filed by Vip Plastic Packaging Pty Ltd. filed Critical Vip Plastic Packaging Pty Ltd.
Priority to NZ569305A priority Critical patent/NZ569305A/en
Priority to AU2006326855A priority patent/AU2006326855B2/en
Publication of WO2007070967A1 publication Critical patent/WO2007070967A1/fr
Priority to AU2008201253A priority patent/AU2008201253A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
    • 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
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • C08L51/006—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 block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester 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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • 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
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to polymer blends for forming containers for the storage of liquid formulations such as paints, and containers for the storage of liquid formulations .
  • the present invention provides a polymer blend comprising two or more polymers, wherein the blend is capable of imparting a relatively high surface energy to a surface of an article formed from the blend, and is capable of imparting a barrier to permeation by water and oxygen to the article.
  • a surface of an article formed from the polymer blend of the present invention will have a relatively high surface energy, and anything that dries on the surface is more likely to remain adhered to the surface when compared to other surfaces having a lower surface energy (for example surfaces formed from HDPE or PP) .
  • An article formed from the polymer blend of the present invention also provides a barrier to permeation by oxygen and water, that is, oxygen and water cannot readily permeate through the article.
  • Polymer blends are advantageous because two or more polymers can be combined in order to produce a blend which can be used to form an article that has characteristics imparted by each of the polymers in the blend.
  • one of the polymers in the polymer blend might result in the relatively high surface energy of a surface of an article formed from the blend, and another polymer in the blend might result in the article providing a barrier to permeation by water and/or oxygen.
  • the polymer blend will usually further comprise a compatabiliser in order to increase the miscibility of the polymers in the polymer blend.
  • the article formed from the polymer blend is a container for the storage of a liquid formulation.
  • the liquid formulation is paint, resin or glue.
  • the paint may, for example, be an emulsion paint such as flat, semi-gloss or gloss acrylic paint.
  • a container In order for a container to be suitable for the storage of a liquid formulation containing water which sets when exposed to oxygen (for example, an emulsion paint) , it is necessary for the container to provide a barrier to permeation by water and oxygen to minimise any premature setting of the liquid formulation in the container. If sufficient water is able to permeate out of the container, the paint around the ullage areas of the container, as well as the surface layer of paint, may prematurely dry. If sufficient oxygen is able to permeate into the container, then oxidative cross-linking of the paint may occur, causing the paint to prematurely dry.
  • oxygen for example, an emulsion paint
  • the surface energy of the surface of the article formed from the polymer blend is, for an emulsion paint, equal to or greater than about 38 dyne/cm.
  • the surface energy of a surface is measured based on the specific liquid formulation that is wetting the surface. Thus, when quantifying a surface energy, it is necessary to take into account the specific liquid formulation wetting the surface.
  • the numerical values for surface energy referred to in this specification are with respect to an emulsion paint . As those skilled in the art would realise, however, the relatively high surface energies required to cause different liquid formulations to adhere to the surface typically only vary by small amounts (approximately 5 to 10%) .
  • a container having a surface energy of equal to or greater than about 38 dyne/cm, at which point an emulsion paint will wet and start to adhere to the surface will typically have less skinning than a container having a lower surface energy for any liquid formulation stored in the container. It is within the ability of those skilled in the art to determine the surface energy at which respective liquid formulations will adhere to a surface.
  • the polymer blend is processable to form the article using injection moulding, which is the method typically used to manufacture plastic containers for paint, etc.
  • containers may also be manufactured from the polymer blend using other techniques, such as injection blow moulding, extrusion blow moulding or injection stretch blow moulding.
  • the polymer blend may, for example, comprise polyethylene terephthalate (PET) and one or more p ⁇ lyolefins .
  • PET polyethylene terephthalate
  • the one or more polyolefins may be selected from the group consisting of: polyethylene (PE), polypropylene (PP), high density polyethylene (HDPE) and low density polyethylene (LDPE) .
  • the PET may be provided as recycled PET flake.
  • the polymer blend may further comprise a compatabiliser to increase the miscibility of the polymers.
  • a suitable compatabiliser for a polymer blend comprising PP and PET is maleic anhydride modified styrene ethylene butylene styrene (MAH modified SEBS) .
  • the present invention provides a polymer blend comprising two or more polymers, the blend being processable to form a container for storing a liquid formulation, wherein the blend is capable of imparting a relatively high surface energy to a surface of the container, and capable of imparting a barrier to permeation by water and oxygen to the container.
  • the present invention provides a polymer blend comprising 10-65% by weight PP, PE, HDPE or LDPE, or a mixture of PP and HDPE, or a mixture of two or more of PP, PE, HDPE and LDPE; 5-15% by weight of a compatabiliser; and 25-80% by weight PET.
  • the polymer blend of the third aspect comprises 10-25% by weight PP, PE, HDPE or LDPE, or a mixture of PP and HDPE, or a mixture of two or more of PP, PE, HDPE and LDPE; 5-10% by weight of a compatabiliser; and 65-80% by weight PET.
  • the present invention provides a container for a liquid formulation, the container being formed from a polymer blend according to the first, second or third aspect of the present invention. - S -
  • the present invention provides a container for a liquid formulation, wherein at least part of the inner surface of the container has a relatively- high surface energy such that any of the formulation that dries on the surface adheres to the surface, and wherein the container provides a barrier to permeation by water and oxygen.
  • all of the inner surface of the container has a relatively high surface energy.
  • the liquid formulation is preferably an emulsion paint.
  • the surface energy of the inner surface of the container is equal to or greater than about 38 dyne/cm for an emulsion paint.
  • the surface having a high surface energy may be formed from a polymer blend according to the first, second or third aspect of the present invention.
  • the present invention provides a method for forming a container for the storage of a liquid formulation, the method comprising the steps of: preparing a polymer blend comprising two or more polymers, wherein the blend is capable of imparting to a container formed from the blend (1) a barrier to permeation by water and oxygen through the container, and (2) a relatively high surface energy to the surfaces of the container such that any of the formulation that dries on the surface adheres to the surface; and - forming the container from the polymer blend.
  • the container is formed using injection moulding .
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • UHMWHDPE ultra high molecular weight high density polyethylene
  • PET polyethylene terephthalate
  • PEN polyethylene napthalate
  • APET amorphous polyethylene terephthalate
  • PETG polyethylene terephthalate glycol
  • HIPS high impact polystyrene SEBS - styrene ethylene butylene styrene
  • the polymer blend of the present invention may be used to form an article that has a surface having a relatively high surface energy and which provides a barrier to permeation by water and oxygen.
  • the blend may be used to form a container for the storage of a liquid formulation such as paint, or part of a container for the storage of a liquid formulation such as paint.
  • a container for the long term storage of a liquid formulation preferably has a number of further properties in addition to providing a barrier to permeation by water and oxygen.
  • the container is preferably strong enough to withstand the rigours of normal use (eg it is not brittle) , resistant to degrading when exposed to UV light, and resistant to chemical degradation.
  • a container for the long term storage of a liquid formulation also preferably provides a barrier to any volatile organic compounds that may be in the liquid formulation.
  • gloss paint typically contains aliphatic petroleum solvent and, for a container to be suitable for the storage of gloss paint, that solvent must not be able to escape from the container otherwise the paint stored in the container will prematurely dry.
  • Such properties are typically imparted to a container formed from a polymer blend of the present invention by the polymers in the polymer blend that impart the high surface energy and the barrier to permeation by water and oxygen.
  • additional polymer (s) may be added to the blend which impart these further properties to the container.
  • the surface of a container formed from the polymer blend of the present invention has a relatively high surface energy compared to conventional plastic containers (e.g. containers made from HDPE or PP) .
  • conventional plastic containers e.g. containers made from HDPE or PP
  • any skin of dried liquid formulation which forms on the inner surface of the container e.g. the lid and ullage areas of the container
  • any formulation that forms a skin on a surface of the container remains adhered to the surface and does not therefore contaminate the bulk liquid formulation.
  • the polymer blend imparts to the container a barrier to water and oxygen which can delay the drying of a liquid formulation stored in the container.
  • the containers formed from the polymer blend of the present invention are therefore even less susceptible to contamination of the liquid formulation due to skinning than conventional plastic containers.
  • At least one of the polymers in the polymer blend of the present invention must be capable of imparting a relatively high surface energy to a surface of an article
  • the surface energy of a surface required to reduce the problem of contamination associated with skinning will depend on the liquid formulation in contact with the surface.
  • the present inventor has found that when the liquid formulation is a typical emulsion paint, and the surface energy of the surface inside the container is equal to or greater than about 38 dyne/cm, any emulsion paint skin which forms adheres to the inner surface of the container, thereby preventing or reducing contamination of the bulk paint due to skinning.
  • the surface energy of the surface inside the container is therefore preferably greater than about 38 dyne/cm, more preferably greater than about 40 dyne/cm and, more preferably still, greater than 45 dyne/cm. In some embodiments, however, the surface energy may be between 38 and 42 dyne/cm. In other embodiments, the surface energy is between 40 and 42 dyne/cm.
  • thermoplastics used to form containers for paint are HDPE and PP. Articles formed from such thermoplastics alone have relatively low surface energies of 33 and 29-30 dyne/cm respectively. As such, there is a noted lack of adhesion of emulsion paints to surfaces made from such thermoplastics compared to containers formed from the polymer blends of the present invention.
  • PET is polar and the surfaces of articles formed from PET alone have a surface energy of 41-42 dyne/cm. However, whilst the oxygen barrier of articles formed from PET alone is high, the barrier to water is relatively low. Accordingly, PET may not be a suitable material for use on its own for forming containers for storing liquid formulations such as paint because the paint may prematurely set as water permeates out of the container.
  • PET is hygroscopic and must usually be thoroughly dried before processing, otherwise the material can degrade during processing.
  • This polymer can also be quite difficult to process using an injection moulding process (the preferred process for the manufacture of paint containers) and articles formed from PET may be brittle and easily damaged. Accordingly, whilst PET has a number of properties that make it desirable for use in forming containers for storing liquid formulations, it is typically not suitable for use in this respect on its own.
  • PET being a polar polymer, also provides a barrier to permeation by organic molecules to articles formed from PET.
  • PC polycarbonate
  • nylons polyamides
  • nylons polyamides
  • polyether etherketone 41 dyne/cm
  • PVC polyvinyl vapor deposition
  • PVdC 40 dyne/cm
  • polyamides Whilst some polyamides can also provide an effective barrier to water and oxygen, articles formed only from polyamides tend to be brittle and are therefore unsuitable for use as containers for storing liquid formulations. Polyamides are also quite expensive.
  • PET Eastar 9221
  • liquid formulations start to set upon exposure to the oxygen in the atmosphere due to oxidative cross-linking of the components in the formulation. Furthermore, if water is allowed to escape from a container containing a water based liquid formulation, such as an emulsion paint, the formulation inside the container may start to dry out, potentially exacerbating skinning problems and/or resulting in the formation of a skin on the surface of the paint . It is therefore necessary that containers used to store such liquid formulations provide a barrier to permeation by water and oxygen.
  • a water based liquid formulation such as an emulsion paint
  • polymer in the polymer blend of the present invention may impart to the article formed from the blend the barrier to permeation by both water and oxygen.
  • one polymer in the polymer blend may provide the barrier to permeation by water whilst another polymer provides the barrier to permeation by oxygen.
  • Polymers that can be used to form a container having a barrier to permeation by water include many of the common polyolefins such as PE, PP, HDPE, LDPE or UHMWHDPE.
  • Cross-linked PE or cross-linked PP may also be used, as may TPX (polymethyl pentene) , but this is relatively expensive.
  • the polymer blend of the present invention will comprise one or more polyolefins because these polymers are relatively cheap and will impart a number of desirable properties to articles formed from the blend.
  • many polyolefins will impart a barrier to permeation by water.
  • they are also thermoplastic polymers which are well suited to use in injection moulding systems.
  • articles formed from blends comprising appropriate quantities of one or more polyolefins tend to be strong and robust and not easily broken or shattered.
  • the one or more polyolefins is/are selected from the group consisting of polyethylene (PE) , polypropylene (PP) , high density polyethylene (HDPE) and low density polyethylene (LDPE) .
  • the one or more polyolefins is/are selected from the group consisting of polyethylene (PE) , polypropylene (PP) and high density polyethylene (HDPE) .
  • Polymers that can be used to form a container having a barrier to permeation by oxygen include PA, APET, PVC or PEN.
  • polymers that impart a barrier to permeation by both water and oxygen are relatively rare because polymers tend to be either polar (and thus provide a good barrier to oxygen) or non-polar (and thus provide a good barrier to water) .
  • An example of a polymer that does impart a barrier to permeation by both water and oxygen is PEN, however, this polymer is relatively expensive.
  • the rate of permeation of oxygen and water through an article formed from a polymer blend can readily be measured using standard techniques known in the art.
  • the permeation of water through an article formed from a polymer blend of the present invention is less than about 20, more preferably less than about 10 cc.25 microns/m 2 .24 hours.90% humidity.
  • the permeation of oxygen through an article formed from a polymer blend of the present invention is less than about 400, more preferably less than about 300 and most preferably less than about 150 cc.25 microns/m 2 .24 hours . atmosphere .
  • exemplary polymers that can be used to impart a barrier to permeation by water to an article are Basell EP243R (PP) and Quenos GC7260 (HDPE) .
  • An exemplary polymer that can be used to impart a barrier to permeation by oxygen to an article is Eastar 9221 (PET) .
  • polymer blends comprising two or more polymers will usually further comprise a compatabiliser .
  • the compatabiliser facilitates the mixing of the polymers in the blend, for example, by increasing the miscibility of two immiscible polymers .
  • compatabiliser used will depend on the polymers present in the polymer blend. A range of compatabilisers are known to those skilled in the art and can be selected based on the polymers that require compatabilisation.
  • Compatabilisers suitable for use in the present invention include (but are not restricted to) the following: SEBS, MAH modified SEBS (Kraton) , MAH modified PP (Equistar) , and MAH. Two or more compatabilisers may be used to increase the miscibility of the polymers in the polymer blend.
  • SEBS is a rubber
  • SEBS or MAH modified SEBS is used as a compatabiliser, impact resistance is also imparted to the resultant article. Additional components in the polymer blend
  • the polymer blend may also include additional components.
  • an initiator may be included in the polymer blend in order to aid in the processability of the blend.
  • a small amount of talc may be added to the blend to aid in processing.
  • the polymer blend may also include a colouring agent in order to provide the article with a colour.
  • Compounds providing a colour to the polymer blend may be dyes or pigments .
  • Blending the polymer blend and forming an article from the blend may be prepared by mixing the two or more polymers (and any additional components) using techniques known in the art.
  • each of the components of the polymer blend can be added to a mixing system such as a screw extruder.
  • the components are then thoroughly mixed and heated in the screw such that they melt and become homogeneous.
  • the resultant homogeneous mixture may be injected into a mould by using the screw as a plunger. Once the polymer blend has set, the mould can be opened and the moulded article removed .
  • a master-batch comprising one or more polymers and one or more compatabilisers can be prepared and added as a concentrate to an appropriate quantity of one of the base resins (eg. PET) to form the polymer blend.
  • a master-batch may be pre- compounded and added to the base resin along with an additional amount of a compatabiliser in order to form the final blend in-situ in the moulding machine. The inventor has found that this method often provides the best miscible mix of the polymer blend and articles which have consistent properties.
  • the present invention provides a container for a liquid formulation, wherein at least part of the inner surface of the container has a relatively high surface energy such that any of the formulation that dries on the surface adheres to the surface, and wherein the container provides a barrier to permeation by water and oxygen.
  • a container may be prepared by using a polymer blend to prepare a coating for a standard container for storing liquid formulations (e.g. a metal paint container) , where the surface of the coating has a relatively high surface energy.
  • This coating may be applied to the inner surfaces of the container, thus providing the relatively high surface energy to the inner surface of the container.
  • the barrier to permeation by water and oxygen may be provided by the container itself, so it is not necessary to provide a polymer in the polymer blend that is capable of imparting a barrier to permeation by water and oxygen.
  • the container may be prepared by co-injection, two colour moulding, insert moulding or in-mould labelling.
  • two colour moulding a first article is moulded and another article is then moulded over the first article.
  • a blend of one or more polymers may be used to form the central portion of a lid (i.e. the portion of the lid which will be exposed to the liquid formulation) and the outside rim that holds the lid on the container is subsequently over-moulded from another material onto the central portion.
  • a container is formed from a polymer blend comprising PP and/or HDPE and PET.
  • PE may be used in place of or in addition to PP.
  • a compatabiliser which the inventor has found to be suitable is MA modified SEBS.
  • the MA modified SEBS may, for example, be added at about 5-10% by weight of the total weight of the polymer blend.
  • the polymer blend may contain (by weight) :
  • the 10-25% PP in the polymer blend may be replaced with 10-25% PE, 10-25% HDPE, or a mixture of PP and HDPE which amounts to 10-25% of the final blend (PP and HDPE have similar specific gravities and can therefore be readily substituted for one another) .
  • the resultant blend has excellent processability, easily filling a mould over very long flow paths, and containers formed from this blend have excellent toughness and stiffness.
  • a further beneficial outcome of using the above blend to form a container is that, as it is not necessary to dry the PET, it is possible to use recycled PET flake. The steps of re-pelletising and crystallising the PET, which usually need to be performed, are not necessary.
  • the presence of moisture in the undried PET lowers the intrinsic viscosity of the PET (by degrading the polymer and reducing its molecular weight) thereby making it more flowable .
  • the compatabiliser subsequently links the degraded PET fractions to the PP and/or HDPE 7 thereby- avoiding the typical brittleness of materials formed from PET alone.
  • a preferred method for preparing one of the polymer blends described above involves pre-preparing a blend containing specific proportions of the PP, PET and MA modified SEBS, and adding this pre-blend to specific quantities of PET or a mixture of PP and HDPE in the moulding machine such that the resultant polymer blend in the moulding machine has the appropriate quantities of each of the components.
  • This method provides optimal mixing conditions and also provides the opportunity to adjust the level of the MA modified SEBS in the final blend in order to control the miscibility and rheology of the final melt.
  • the inventor has found that this method provides a good miscible mix of the polymer blend and that articles prepared using the method tend to be less brittle and have consistent properties.
  • PET also provides a good barrier for some organic solvents. Accordingly, a container formed from a polymer blend including PET would also have application in storing liquid formulations which contain organic solvents, for example, gloss paint, resin, glue, printing inks, oils, or agricultural chemicals, even though such liquid formulations do not necessarily suffer from skinning problems .
  • organic solvents for example, gloss paint, resin, glue, printing inks, oils, or agricultural chemicals
  • the degradation by-products are low molecular weight resins (most likely degraded PET fractions) .
  • the presence of such containments on the surface may lower the surface energy of the surface .
  • the inventor has found that, in some cases, adding an additional 0.5% MAH to the polymer blend before the blend is moulded reduces the surface contamination.
  • the degradation by-products can be removed from the surface in order to provide higher surface energy levels using a number of techniques known in the art.
  • the contaminated surface can be flamed, or treated using Corona treatment or plasma treatment, etc.
  • Corona treatment may provide the article formed from the polymer blend of the present invention with a surface energy of approximately 50 dyne/cm. It is believed that the flame/Corona/plasma treatment physically cleans the surface .
  • all paint contact surfaces are typically treated using Corona or Plasma treatment in order to decontaminate the surfaces (i.e. by burning off the contaminant) .
  • the Corona or Plasma treatment will also remove other potential contaminants such as mould, grease etc.
  • Another way to remove the surface contaminant is to physically abrade the surface by scrubbing. Again, levels of around 50 dyne/cm can be obtained by dry rubbing the surface with a scouring pad.
  • a pre-blend was formed from 44% by weight PET, 28% by weight PP and 28% by weight MAH modified SEBS in a twin screw extruder. The pre-blend was then mixed in a ratio of 34% by weight pre-blend to 3% by weight of MAH modified SEBS and 65% by weight undried PET PCR in the barrel of an injection moulding machine. The resultant composition of the polymer blend in the final mixture was about 80% by weight PET, 10% by weight PP and 10% by weight MA modified SEBS.
  • Two litre pails and lids were made by injecting the molten polymer blend into the cavity of a mould.
  • One of these containers was filled with acrylic emulsion paint and placed in a sealed test chamber containing approximately 30mm of water, and the test chamber was stored at 4O 0 C in an oven for 4 weeks.
  • a control container having a similar pail and lid, but which was moulded from only PP was also placed in the test chamber alongside the container made from the PP/PET blend.
  • both containers were removed from the oven and allowed to cool.
  • the lids were removed and the contents examined for traces of skin formation.
  • the container made of PP had a noticeable skin formed on the lid and in the headspace above the emulsion paint . This skin was loosely adhered to the container and parts of it had fallen from the wall and lid into the paint as a result of removal of the lid.
  • the container made from the PP/PET blend had a significantly smaller amount of skin formation. Further, the adhering paint was still mostly wet and the wet paint could be easily incorporated into the bulk of the liquid paint. The light skin that had formed on the surface of the container was also more difficult to remove; it could be wiped with a brush without dislodging it, and could only be removed by use of a hard scraper.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Wrappers (AREA)

Abstract

La présente invention concerne un mélange polymère comprenant deux polymères ou plus, le mélange étant capable de conférer une énergie de surface relativement élevée à la surface d'un article formé à partir du mélange, ainsi que de former une barrière à la perméation de l'eau et de l'oxygène vers l'article. La présente invention concerne également des récipients formés à partir du mélange polymère, par exemple des récipients de stockage de peintures.
PCT/AU2006/001972 2005-12-22 2006-12-22 Mélanges de polymères WO2007070967A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
NZ569305A NZ569305A (en) 2005-12-22 2006-12-22 Polymer blends
AU2006326855A AU2006326855B2 (en) 2005-12-22 2006-12-22 Polymer blends
AU2008201253A AU2008201253A1 (en) 2005-12-22 2008-03-17 Container or Lid Composition and Manufacturing Method

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2005907246 2005-12-22
AU2005907246A AU2005907246A0 (en) 2005-12-22 Polymer blends

Publications (1)

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WO2007070967A1 true WO2007070967A1 (fr) 2007-06-28

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PCT/AU2006/001972 WO2007070967A1 (fr) 2005-12-22 2006-12-22 Mélanges de polymères

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AU (1) AU2006326855B2 (fr)
NZ (1) NZ569305A (fr)
WO (1) WO2007070967A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012095285A1 (fr) * 2011-01-11 2012-07-19 Alpla Werke Alwin Lehner Gmbh & Co. Kg Contenant en matière plastique produit selon un procédé de soufflage-étirage en deux étapes et préforme pour sa fabrication
CN104530664A (zh) * 2015-01-27 2015-04-22 上海吉虞实业有限公司 一种以改性pet为基料的板材、加工方法及其加工设备
CN104592613A (zh) * 2014-12-31 2015-05-06 东莞市技塑塑胶科技有限公司 挤出级发泡pp/pe材料及其制备方法
CN105385085A (zh) * 2015-11-06 2016-03-09 安徽雄亚塑胶科技有限公司 高抗菌高耐磨tpe吸震护膝及其制备方法
EP3275652A1 (fr) * 2016-07-27 2018-01-31 Greif International Holding BV. Composition de mélange de polymères haute barrière
US10975228B2 (en) 2015-06-15 2021-04-13 Imertech Sas Compositions for injection moulding
CN115386167A (zh) * 2022-09-27 2022-11-25 上海金发科技发展有限公司 一种聚丙烯组合物及其制备方法和应用

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0105244A1 (fr) * 1982-09-27 1984-04-11 General Electric Company Masses à mouler modifiées à base de polyesters thermoplastiques et articles formés à partir de ces masses
EP0104130B1 (fr) * 1982-08-18 1986-10-08 The Goodyear Tire & Rubber Company Articles en polyester partiellement cristallins
EP0274248A2 (fr) * 1986-12-16 1988-07-13 Mitsui Petrochemical Industries, Ltd. Composition de poly(4-méthyl-1-pentène) et produits fabriqués de cette composition
JPH021756A (ja) * 1988-06-10 1990-01-08 Mitsubishi Rayon Co Ltd 耐熱性中空容器
EP0372995A2 (fr) * 1988-12-09 1990-06-13 Hoechst Celanese Corporation Résine de polytéréphtalate d'éthylène moulable par injection, à résistance au choc modifiée
EP0533304A1 (fr) * 1991-09-18 1993-03-24 Johnson Service Company Compositions de polyester et de polyoléfine contenant un élastomère fonctionnalisé
WO1993008233A1 (fr) * 1991-10-15 1993-04-29 E.I. Du Pont De Nemours And Company Composition de resine polyester
JPH08239561A (ja) * 1995-03-07 1996-09-17 Shokuhin Sangyo Ecological Packing Gijutsu Kenkyu Kumiai 熱可塑性樹脂組成物
JPH08302170A (ja) * 1995-05-09 1996-11-19 Mitsubishi Plastics Ind Ltd 再生ポリエステル系樹脂組成物および熱成形用シートの製造方法
JPH1180369A (ja) * 1997-09-08 1999-03-26 Nippon Eco Support:Kk Ｐｅｔ樹脂成形材料
EP0666285B1 (fr) * 1994-02-02 2000-05-17 European Economic Community E.E.C. Matériau d'emballage de PET
JP2002138172A (ja) * 2000-11-02 2002-05-14 Apex:Kk ポリエチレンテレフタレート樹脂成形品およびその製造方法

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0104130B1 (fr) * 1982-08-18 1986-10-08 The Goodyear Tire & Rubber Company Articles en polyester partiellement cristallins
EP0105244A1 (fr) * 1982-09-27 1984-04-11 General Electric Company Masses à mouler modifiées à base de polyesters thermoplastiques et articles formés à partir de ces masses
EP0274248A2 (fr) * 1986-12-16 1988-07-13 Mitsui Petrochemical Industries, Ltd. Composition de poly(4-méthyl-1-pentène) et produits fabriqués de cette composition
JPH021756A (ja) * 1988-06-10 1990-01-08 Mitsubishi Rayon Co Ltd 耐熱性中空容器
EP0372995A2 (fr) * 1988-12-09 1990-06-13 Hoechst Celanese Corporation Résine de polytéréphtalate d'éthylène moulable par injection, à résistance au choc modifiée
EP0533304A1 (fr) * 1991-09-18 1993-03-24 Johnson Service Company Compositions de polyester et de polyoléfine contenant un élastomère fonctionnalisé
WO1993008233A1 (fr) * 1991-10-15 1993-04-29 E.I. Du Pont De Nemours And Company Composition de resine polyester
EP0666285B1 (fr) * 1994-02-02 2000-05-17 European Economic Community E.E.C. Matériau d'emballage de PET
JPH08239561A (ja) * 1995-03-07 1996-09-17 Shokuhin Sangyo Ecological Packing Gijutsu Kenkyu Kumiai 熱可塑性樹脂組成物
JPH08302170A (ja) * 1995-05-09 1996-11-19 Mitsubishi Plastics Ind Ltd 再生ポリエステル系樹脂組成物および熱成形用シートの製造方法
JPH1180369A (ja) * 1997-09-08 1999-03-26 Nippon Eco Support:Kk Ｐｅｔ樹脂成形材料
JP2002138172A (ja) * 2000-11-02 2002-05-14 Apex:Kk ポリエチレンテレフタレート樹脂成形品およびその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012095285A1 (fr) * 2011-01-11 2012-07-19 Alpla Werke Alwin Lehner Gmbh & Co. Kg Contenant en matière plastique produit selon un procédé de soufflage-étirage en deux étapes et préforme pour sa fabrication
CN104592613A (zh) * 2014-12-31 2015-05-06 东莞市技塑塑胶科技有限公司 挤出级发泡pp/pe材料及其制备方法
CN104530664A (zh) * 2015-01-27 2015-04-22 上海吉虞实业有限公司 一种以改性pet为基料的板材、加工方法及其加工设备
US10975228B2 (en) 2015-06-15 2021-04-13 Imertech Sas Compositions for injection moulding
CN105385085A (zh) * 2015-11-06 2016-03-09 安徽雄亚塑胶科技有限公司 高抗菌高耐磨tpe吸震护膝及其制备方法
EP3275652A1 (fr) * 2016-07-27 2018-01-31 Greif International Holding BV. Composition de mélange de polymères haute barrière
EP3797990A1 (fr) * 2016-07-27 2021-03-31 Greif International Holding B.V. Récipient monocouche
CN115386167A (zh) * 2022-09-27 2022-11-25 上海金发科技发展有限公司 一种聚丙烯组合物及其制备方法和应用
CN115386167B (zh) * 2022-09-27 2023-08-22 上海金发科技发展有限公司 一种聚丙烯组合物及其制备方法和应用

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AU2006326855A8 (en) 2008-07-24
AU2006326855A1 (en) 2007-06-28
NZ569305A (en) 2011-11-25
AU2006326855B2 (en) 2013-03-28

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