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WO2006000770A1 - Produit et procede de rotomoulage - Google Patents

Produit et procede de rotomoulage Download PDF

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Publication number
WO2006000770A1
WO2006000770A1 PCT/GB2005/002466 GB2005002466W WO2006000770A1 WO 2006000770 A1 WO2006000770 A1 WO 2006000770A1 GB 2005002466 W GB2005002466 W GB 2005002466W WO 2006000770 A1 WO2006000770 A1 WO 2006000770A1
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WO
WIPO (PCT)
Prior art keywords
product
layer
polyolefin
plasma treated
pbt
Prior art date
Application number
PCT/GB2005/002466
Other languages
English (en)
Inventor
Brian Mccann
Original Assignee
Clarehill Plastics 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
Application filed by Clarehill Plastics Ltd filed Critical Clarehill Plastics Ltd
Publication of WO2006000770A1 publication Critical patent/WO2006000770A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/007—Treatment of sinter powders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/08—Conditioning or physical treatment of the material to be shaped by using wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/22—Making multilayered or multicoloured articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/006—PBT, i.e. polybutylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7172—Fuel tanks, jerry cans

Definitions

  • This invention concerns the use of plasma treated polyethylene during a rotational moulding process, in particular for bonding to Polybutylene Terephthalate (PBT) .
  • PBT Polybutylene Terephthalate
  • Rotational moulding is a process that is mainly used for making hollow plastic products. It can be used to produce a wide range of products with highly desirable characteristics, and is relatively inexpensive when compared to other thermoplastic moulding processes . The process was developed in the 1940s, and since then it has been shown that a wide range of thermoplastics can be moulded in this way. Nevertheless, polyethylene is by far the main polymer used in rotational moulding, accounting for about 90% of products made by the process. Polyethylene is used extensively in the rotational moulding industry due to its relatively low cost, good mechanical properties, and ability to withstand the prolonged oven cycles . While polyethylene can be used to make products which can successfully store liquids such as oil and diesel, it cannot be used for the storage of more volatile liquids such as petrol, as these liquids can simply permeate through the material and escape into the atmosphere.
  • PBT Polybutylene Terephthalate
  • Bonding these two materials together would enable a moulding to be produced that retains the excellent mechanical properties and low cost of polyethylene, while providing an excellent barrier to the permeation of fuel. With standard polyethylene however, this is not possible, as it is difficult to bond satisfactorily to other materials.
  • the one shot rotational moulding process has four main stages, which are: (1) Charging: a predetermined weight of cold powder is placed into a metal mould, and the mould is sealed. (2) Heating: the mould is indexed to an oven where it rotates biaxially. Initially all the polymer powder is free to tumble about inside the mould. Heat passes directly through the mould wall, causing the temperature of the polymer powder to rise at a constant rate. Eventually, the temperature of the mould surface and polymer are sufficiently hot to allow a first layer of polymer to adhere to the mould walls. Successive layers of polymer then build up on the mould wall until all the polymer is molten. The mould is removed from the oven once the melt has consolidated sufficiently. (3) Cooling: on removal from the oven the mould is indexed to a cooling chamber where it continues to rotate. Cooling can be by means of air, water or both. (4) Demoulding: once the mould is cooled sufficiently, the moulding is removed.
  • the above process will produce a single layer product, but in many cases multi-layer parts are desirable. Using multiple layers allows different materials to be incorporated into the part, for example to provide a barrier layer or to improve the structural integrity of the product.
  • an initial layer is produced as detailed above, but when the mould is removed from the oven, a second shot of material is added to the mould. This can be achieved by simply pouring the powder through a vent tube or other opening in the mould, or by use of a specially designed ⁇ drop-box' . The mould is then returned to the oven and the second shot is processed in the same way as the first. This can be repeated for as many layers as required.
  • a problem that is often encountered in multiple shot moulding is that there can be poor adhesion between different polymer layers. This is particularly true when trying to create multi-layer parts using polyethylene, as this material is extremely inert and can be difficult to bond to other materials. Whilst tie-layers such as maleic anhydride are known, they also interact with reactive materials and stop polymerisation from occurring.
  • VOC volatile organic compound
  • Macrocyclic polyester oligomers mixed with a suitable polymerization catalyst system, have a number of processing advantages that make them attractive to the rotational moulding industry.
  • the cyclic rings When heated during processing, the cyclic rings, with the aid of a catalyst, open and quickly connect or polymerise to form the high molecular weight polymer material.
  • What is interesting about this transformation process, and this material, is that it starts as a solid, and when heated to temperatures above 300 a F (149 a C) , becomes fully molten with a viscosity range of 150 mPa.s. This step is then followed by a reduction in viscosity (polymerisation) to ranges below 20 mPa.s.
  • One object of the present invention is to provide multilayer products with these materials.
  • ptPE plasma treated polyethylene
  • ptPE has been found to act as a tie-layer between otherwise incompatable layers, because it cannot adhere to other materials. It is believed that it increases the surface tension of the polyolefin, to provide the integral bonding between the layers.
  • ptPE can be used as a tie-layer between polyolefins, such as polyethylene (PE) and polypropylene, etc, and Polybutylene Terephthalate (PBT) .
  • tie-layer extends to the inclusion of ptPE within one or both of the other material layers, which may or may not form a physical distinctive layer in the moulding process or moulded products. That is, ptPE could be admixed with one or more of the main layer materials, such as the polyolefin or PBT or PBT-precursor, prior to the moulding process.
  • Plasma treated polyethylene can be provided by placing standard polyethylene in a reaction chamber and treating it with oxygen plasma. The chemical structure of the powder surface changes from a non- polar to a polar structure, increasing its surface tension. Carrying out plasma treating in this manner allows the material to be used in applications requiring adhesion to foams, paint, coating or other adhesive fixtures. It is not subject to the variations in product quality or shape which can result from manually controlled hot flame methods used to prepare parts for painting. The material provides far better long-term adhesion properties and higher quality adhesion.
  • Standard PE cannot be painted due to its highly non-polar molecular structure, which results in very low surface tension.
  • the plasma treatment changes the structure to a more polar one, and thus increases the surface tension, paint will adhere to the resulting material. Whilst bonding between layers can be achieved at a ptPE/PE mixture ratio as low as 3/97, to paint the moulded article, a minimum ratio of about 25/75 is needed.
  • plasma treated PE is more than double the price of normal PE, such that it should still be used in a cost-effective manner.
  • One possible PBT-precursor is a cyclic (poly)butylene terephthalate resin, derived from a blend of macrocyclics polybutylene terephthalate oligomers and a suitable catalyst system, such as the Cyclics PBT resin system.
  • This range of resins is known in the art as "CBT® Resins". These are available from Cyclics Corporation, USA.
  • CBT ® Resins are a line of Polybutylene Terephthalate (PBT) resin systems that polymerise reactively like thermosets but have the material properties of thermoplastics .
  • Particularly suitable category of CBT® Resins include 'XB3-CA5' materials.
  • CBT ® Resins start as a solid at room temperature, melt to low viscosity at elevated temperature, and then polymerise in the presence of a catalyst to form high molecular weight PBT thermoplastic.
  • a distinct feature of CBT Resins is their initial low "water-like" viscosity, which promotes easy processing in a variety of applications.
  • CBT Resins are solid (powder, pellet, flake) at room temperature and when heated are fully molten above 160 0 C (320 0 F), with a viscosity in the range of 150 mPa.s (15OcP), and drops in viscosity to below 20 mPa.s (2OcP) at 180 0 C (355°F) .
  • normal thermoplastic PBT melts to the consistency of chewing gum, making it difficult to combine with fibre and fillers, or make thin wall parts, for example.
  • CBT Resins require a catalyst to polymerise and process into the engineering thermoplastic, PBT.
  • PBT engineering thermoplastic
  • the fabrication process employed determines the type of catalyst and how the catalyst is introduced. Importantly, the cyclic resin and catalyst combination allow polymerisation in the time frame of a rotational moulding process .
  • Liquid catalysts can be used in meter/mix equipment, for example, in various reaction injection moulding (RIM) applications (including RTM, SRIM, RRIM and so on) .
  • Some catalysts can be pre-combined with Cyclic Resin, making a "one-part” system that does not require metering or mixing of the catalyst.
  • These "one-part” systems come as a solid (e.g., powder, pellet or flake) , and begin to polymerize when the material is melted.
  • Such "one-part” systems are applicable, for example, to making prepreg or sheet moulding compound (SMC) .
  • CBT® Resins process reactively like a thermoset, but produce a thermoplastic, a variety of both traditional thermoset and thermoplastic processing technologies can be used.
  • the advantages of CBT® Resins include:
  • CBT® Resins are converted into PBT thermoplastic polyester resin.
  • Commercially available PBT grades exhibit a wide range of mechanical, electrical and thermal properties when combined with typical polymer additives and fillers, making PBT thermoplastic a very versatile material.
  • the plasma treated PE material does not adversely affect the polymerisation reaction of materials such as CBTs.
  • the multilayer products of the present invention are useable in a number of different areas such as chemical or hazardous liquid storage tanks, vessels, receptacles, conduits, etc, including horticultural spray tanks, solvent tanks.
  • areas such as chemical or hazardous liquid storage tanks, vessels, receptacles, conduits, etc, including horticultural spray tanks, solvent tanks.
  • One particular area is fuel tanks,
  • One particular benefit of the products formed by the present invention is low permeability.
  • the permeability of a polymer is driven by three main properties - the crystallinity level, the molecular weight, and its inherent incompatibility with the liquid (eg solvent) being contained.
  • a rotomoulded CBT product from the present invention can have the same level of crystallinity as injection moulded PBT, and hence its permeability performance is equal in this respect.
  • Injection moulded PBT generally has a molecular weight of approx. 60,000 g/mol
  • a rotomoulded CBT product from the present invention can have a molecular weight in the range 120,000 to 150,000 g/mol.
  • rotomoulded CBT products have a lower permeability performance than injection moulded PBT products.
  • rotational moulding is a relatively slower process, compared to e.g. injection moulding, which gives the material more time and correct conditions to polymerise, hence building up greater molecular weight. The higher the molecular weight, the greater the expected impermeability.
  • polyolefin is well known in the art, and includes polyethylene, polypropylene (PP) ,polybutylene, etc.
  • PP can be painted without any additional use of ptPE, and has better ESCR (environmental stress cracking resistance) properties than PE, with approximately the same flexural properties.
  • a process for forming by rotational moulding a polyolefin and Polybutylene Terephthalate (PBT) multi-layer product comprising the steps of:
  • obtaining a polyolefin and PBT precursor adding the polyolefin and PBT precursor separately or jointly into the mould; adding plasma treated Polyethylene (ptPE) either separately or jointly with the polyolefin and/or the PBT precursor into the mould; rotationally moulding each material, either simultaneously or separately; and cooling the mould and removing the moulded product from the mould.
  • the process may be a one shot or multiple shot process depending upon the possible premixing of one or more of the precursor materials and the ptPE.
  • the process can provide a product having at least two different layers.
  • the process allows the multi- layering to be any number of layers as desired or necessary.
  • each layer depends upon the desired properties of the final product.
  • 'Standard' PE is an inexpensive raw material, such that the PE would generally form the majority of the thickness of rotomoulded products. It is known that the stiffness of a layer is proportional to the thickness of material cubed, so doubling the wall thickness increases the stiffness by a factor of 8. Thus the present invention provides the easy ability to increase the mechanical properties of the product by using any thickness of PE, whilst keeping the cost low.
  • the present invention allows increased strength due to using a thicker PE layer, as there is a very good bond between the layers.
  • a polyolefin and Polybutylene Terephthalate (PBT) bonded multi-layer rotationally moulded product which includes plasma treated Polyethylene (ptPE) .
  • the ptPE is generally in the form of a tie-layer which bonds the PE and PBT layers together.
  • the PBT precursor is a CBT® resin, particularly a XB3-CA5 material.
  • the present invention extends to such bonded multi- layer moulded products being provided by a process as hereinbefore described, and/or through use of ptPE as hereinbefore described.
  • the materials were prepared.
  • the CBT material was dried in an oven at 95 a C for at least seven hours in order to remove any moisture. If a mixture of plasma treated PE and standard PE is to be used, then this was well mixed using the desired proportions.
  • the properties of the CBT material, and in particular its impact properties, are heavily dependent on the level of crystallisation and crystal type. This phenomenon has been well understood for many years, and it is also well understood that the crystal type achieved in PBT is a function of the rate of cooling. With injection moulding very high cooling rates can be achieved, but rotomoulding cooling rates are many orders of magnitude slower. This means that rotomoulded CBT parts have a different crystal structure and type to injection moulded parts when they are cooled below the optimum cooling rate. Thus rapid cooling of the part is desirable in order to obtain the best morphology. Rapid cooling is also desirable to achieve a product with low void content, by minimising the effect of different crystallisation temperatures.
  • PE & ptPE / CBT In this variation standard PE alone is the first shot, and the second shot is a mixture of ptPE and CBT.
  • the ratio of ptPE to PE can be in the range 3% upwards, and the second shot can be added manually through the breather or via a drop box.
  • the utility of this process is that it uses the minimal amount of ptPE to achieve a good bond between the layers. Since the ptPE has a much higher viscosity than the ultra low viscosity CBT, the two materials separate completely leaving the CBT to polymerise as the inside layer in a container, where its impermeability properties can be exploited. The ptPE material locates itself at the PE / CBT interface where it is most required.
  • ptPE & PE / CBT In this case ptPE is used in the first shot, with a mixture of PE and CBT in the second shot.
  • the amount of ptPE used depends on the mould surface area as the aim is to produce a relatively thin layer over the entire surface of the mould.
  • the amounts of PE and CBT used depend on the necessary mechanical properties and the required permeability performance respectively.
  • a drop box can be used for the second shot or it can be added manually through the breather. As in the above process the PE and CBT will separate into two distinct layers due to their widely different melting points, viscosities, and specific gravities before the polymerisation of the CBT occurs.
  • This process is to produce an outer surface which is 100% ptPE, and thus has a very good surface energy. This means that it is easier to paint the part. Thus this process is used where a high quality painted finish is desired.
  • ptPE / PE & CBT Here a mixture of ptPE and PE are added in the first shot, with CBT alone in the second shot.
  • the CBT can be added via a drop box or manually.
  • the ratio of ptPE to PE would depend on the required surface energy of the part, ie whether or not it had to be painted.
  • the utility of this variation is to produce a part with a 100% CBT inner layer, having no contamination from either form of PE. This produces a part with maximum permeability performance, for applications where this is the key requirement.
  • CBT & ptPE / PE In this case CBT is added as the first shot, and a mixture of ptPE and PE as the second shot. A ratio of 3% ptPE would be used in this case to achieve an adequate bond between the layers. No more is necessary since it would be on the inner layer, which has no need to be painted. The amount of CBT used would depend on the requirements of the specific part.
  • the utility of this process is to place the CBT on the outside of the part, where its low viscosity allows it to form very complex surface features such as small sized text.
  • the CBT outer layer would also provide better scratch resistance and more toughness than PE, which may be desirable in certain applications.
  • the second shot of' the PE mixture should be added by a drop box. This is because the CBT has a melting point of about 230 a C, and were the mould to be removed from the oven the CBT layer would solidify and would be very difficult to re- melt.
  • PE / ptPE / CBT In this case PE is added first, followed by the tie layer of ptPE, and finally the CBT layer.
  • the amount of ptPE is a factor of the part geometry as all that is required is a thin coating over the entire surface of the PE.
  • the second and third shots can be added either by drop box or manually through the breather.
  • the first advantage of this process is that it uses the minimal amount of ptPE to gain a good bond, as the ptPE is 100% concentrated where it is needed at the interface, and not ⁇ wasted' in the PE or CBT layers.
  • this process produces a part with a 100% pure CBT layer, with the associated advantages of better permeability performance due to the absence of contamination.
  • CBT / ptPE / PE In this case the CBT is used as the first shot, followed by the ptPE tie layer and finally a PE layer. Again the amount of ptPE used is just enough to coat the CBT layer, while the amount of PE is dependant on the required mechanical properties . The amount of CBT used depends on the specific application.
  • the utility of this process is to place the CBT on the outside of the part, where it can be used to form complex surface features such as small text due to its low viscosity. It also provides a more scratch resistant, tougher surface than PE, which might be desirable in certain applications.
  • New standards will require an 85% reduction in plastics fuel tank permeation and a 95% reduction in fuel system hose permeation from new motorcycles beginning in 2008.
  • the present invention provides a simple but effective process for bonding PBT and polyolefins like PE.
  • the low viscosity prior to polymersiation allows separation of the layers, and subsequent bonding even when intimately mixed.
  • the polymerization is not adversely affected by the bonding, which is the case when chemical coupling agents are used.

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Abstract

La présente invention a trait à un procédé ou système de rotomoulage à polymérisation multicouche dans lequel du polyéthylène traité au plasma est utilisé. On a découvert que le polyéthylène traité au plasma agit comme une couche de liaison entre des couches autrement incompatibles, car il ne peut pas adhérer à d'autres matériaux. On présume que cela accroît la tension de surface de la polyoléfine pour assurer une liaison intégrale entre les couches. En particulier, le polyéthylène traité au plasma peut être utilisé en tant que couche de liaison entre des polyoléfines, telles que le polyéthylène et le polypropylène, et le polybutylène téréphtalate.
PCT/GB2005/002466 2004-06-26 2005-06-23 Produit et procede de rotomoulage WO2006000770A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0414372A GB0414372D0 (en) 2004-06-26 2004-06-26 Rotational moulding product and process
GB0414372.3 2004-06-26

Publications (1)

Publication Number Publication Date
WO2006000770A1 true WO2006000770A1 (fr) 2006-01-05

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WO2014020482A1 (fr) 2012-08-02 2014-02-06 Gary Wayne Ferguson Articles en matière plastique moulée présentant un contact entre deux matières plastiques dissemblables
US9220860B2 (en) 2003-12-31 2015-12-29 Resmed Limited Compact oronasal patient interface
WO2017160243A1 (fr) 2016-03-18 2017-09-21 Scg Chemicals Company Limited Composition de polyoléfine pour moulage rotatif
US10441738B2 (en) 2010-09-30 2019-10-15 ResMed Pty Ltd Mask system
US10449317B2 (en) 2010-09-30 2019-10-22 ResMed Pty Ltd Patient interface systems
US10561812B2 (en) 2005-06-06 2020-02-18 ResMed Pty Ltd Mask system
US10974009B2 (en) 2009-06-02 2021-04-13 ResMed Pty Ltd Unobtrusive nasal mask
WO2022018292A1 (fr) 2020-07-24 2022-01-27 Basf Se Structure multicouche et son procédé de préparation

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CN117734193A (zh) * 2018-11-28 2024-03-22 浙江酷尔智能科技有限公司 保温箱的箱体制造系统

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WO1996030180A1 (fr) * 1995-03-31 1996-10-03 Exxon Chemical Patents Inc. Articles expanses moules par rotation
JP2000117757A (ja) * 1998-10-14 2000-04-25 Nippon Zeon Co Ltd 反応性重合回転成形方法および金型装置
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Title
BOERSCH, D. ERICH ET AL: "Plasma modified polyolefin powders for rotational molding", ANNUAL TECHNICAL CONFERENCE - SOCIETY OF PLASTICS ENGINEERS , 61ST(VOL. 1), 1278-1281 CODEN: ACPED4; ISSN: 0272-5223, 2003, XP009056315 *
DATABASE WPI Section Ch Week 198227, Derwent World Patents Index; Class A17, AN 1982-56198E, XP002351695 *
DATABASE WPI Section Ch Week 200031, Derwent World Patents Index; Class A32, AN 2000-358501, XP002351781 *

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CN104684703A (zh) * 2012-08-02 2015-06-03 加里·韦恩·弗格森 在两种不同塑料之间具有接触部的模制塑料制品
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