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Plastics Pipe Plastikrohr Conduits En Plastique

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Plastics Pipe Plastikrohr Conduits En Plastique (19) TZZ_ZZ T (11) EP 1 708 880 B2 (12) NEW EUROPEAN PATENT SPECIFICATION After opposition procedure (45) Date of publication and mention (51) Int Cl.: of the opposition decision: B32B 27/32 (2006.01) C08L 23/04 (2006.01) 31.08.2016 Bulletin 2016/35 F16L 9/147 (2006.01) B32B 1/08 (2006.01) B29K 105/16 (2006.01) B29L 23/00 (2006.01) (2006.01) (2006.01) (45) Mention of the grant of the patent: B29C 47/00 B29C 47/02 (2006.01) (2006.01) 13.06.2012 Bulletin 2012/24 B29C 47/06 B29K 23/00 B29K 105/00 (2006.01) (21) Application number: 05702296.4 (86) International application number: PCT/IB2005/000134 (22) Date of filing: 20.01.2005 (87) International publication number: WO 2005/080077 (01.09.2005 Gazette 2005/35) (54) PLASTICS PIPE PLASTIKROHR CONDUITS EN PLASTIQUE (84) Designated Contracting States: (56) References cited: AT BE BG CH CY CZ DE DK EE ES FI FR GB GR EP-A- 0 174 611 EP-A- 1 216 823 HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR EP-A1- 1 004 618 EP-A2- 1 216 823 DE-A1- 2 622 973 DE-A1- 10 064 336 (30) Priority: 20.01.2004 GB 0401183 DE-A1- 19 509 613 DE-A1- 19 853 545 US-A- 6 068 026 (43) Date of publication of application: 11.10.2006 Bulletin 2006/41 • Produktdatenblatt "Exxelor(TM) VA1801" • Produktdatenblatt "Ciba(R) Irganox(R) 245" (73) Proprietor: Uponor Innovation AB • Produktdatenblatt "LOTADER(R) AX 8900" 73061 Virsbo (SE) • Y. P. SUN ET AL.: ’Functionalized Carbon Nanotubes: Properties and Applications’ ACC. (72) Inventor: JARVENKYLA, Jyri CHEM. RES. vol. 35, 2002, pages 1096 - 1104 FIN-15870 Hollala (FI) • K. OTHMER: ’Encyclpedia of Chemical Technology’, vol. 4, JOHN WILEY & SONS, INC. (74) Representative: Atkinson, Jonathan David Mark et pages 761 - 803 al • M. VOLL ET AL.: ’Ullmann’s Encyclopedia of HGF Limited IndustrialChemistry’, 2012, WILEY-VCH VERLAG 1 City Walk GMBH & CO. KGAA, WEINHEIM pages 1 - 22 Leeds LS11 9DX (GB) EP 1 708 880 B2 Printed by Jouve, 75001 PARIS (FR) EP 1 708 880 B2 Description [0001] This invention relates to plastics pipes, and more particularly to plastics pipes formed from extruded thermo- plastic polymers. 5 [0002] Extruded polyolefin pipes are well known for a variety of industrial applications. Typically they are used in the building industry for domestic water pipes, radiator pipes, floor-heating pipes and for similar applications in ship building etc. Polyolefin pipes can also be used as district heating pipes and as process pipes in the food industry etc. Other applications include the conveyance of gaseous fluids and slurries. [0003] Multilayer pipes wherein at least one of the layers comprises an extruded polyolefin are also well known and 10 a great many have been described in the literature. Multilayer pipes are used, for example, when improved long term strength at elevated temperatures is needed or, when barrier properties against oxygen permeation are necessary. Multilayer pipes can comprise dissimilar materials for particular applications. For example, multilayer pipes having dif- fusion barrier layers have been proposed. The diffusion barrier can be a polymeric layer such as EVOH, or a metallic layer which provides both a diffusion barrier and a strengthening layer. 15 [0004] EP 1216823 discloses a multilayer composite in which a polyamide layer and a polyolefin layer are joined to one another by a bonding agent which does not consist of a functionalised polyolefin alone. Thus EP 1216823 discloses a multilayer composite in which the adhesion between layers remains largely intact even on prolonged contact with alcohol-containing media or aqueous media at elevated temperatures. [0005] EP 0174611 discloses a laminated pipe comprising a layer of siloxane-crosslinked polyolefin, a layer of a 20 saponified product of ethylene-vinyl acetate copolymer, and a layer of siloxane-crosslinked polyolefin or polybutene. Thus EP 0174611 discloses a pipe suitable for hot water circulation. [0006] US 6,068,026 discloses a thermoplastic and elastomer composite product. In particular, US 6,068,026 discloses a pipe for conveying coolant fluid in a motor vehicle air conditioning circuit. The product disclosed comprises: an inside layer made of a mixture of a polyamide 6 and at least one modifying agent such as a grafted poly(1,2-vinylbutadiene), 25 a polyoctene, a brominated isobutylene-p-methylstyrene, a silane or an ethylene and acrylic acid copolymer; and a layer of an elastomer such as a brominated butyl rubber modified by a grafted poly(1,2-vinylbutadiene), a silane, an ethylene and acrylic acid copolymer or a copolymer of ethylene and of propylene grafted with maleic anhydride. [0007] DE 195 09 613 discloses a moulded product (e.g. a hollow section moulding) with an oxygen barrier layer. The product comprises a first layer made of organosilanegrafted polyolefin and an oxygen barrier. The oxygen barrier layer 30 can form covalent bonds with the grafted organosilane groups in the first layer and is coextruded directly onto the first layer under pressure. [0008] In recent years multilayer pipes having aluminium based barrier layers have become very popular. When installing domestic heating systems the metal barrier provides a specific and important benefit, which is that when the pipe is bent it retains its new configuration, in contrast to plastics pipes without a metal barrier layer, which tend to recov er 35 their original shape. [0009] However, multilayer plastics pipes comprising two or more layers of polyolefin homopolymers or copolymers having an intermediate metallic barrier or str engthening layer disposed between them tend to have poorer performance over the long-term than, for example, PEX pipes, comprising a single layer of cross-linked polyethylene. In addition, the difference between the coefficients of thermal expansion of a metallic barrier layer and the plastics layers can lead to 40 delamination. Nevertheless, the presence of a metal barrier layer is often very desirable in certain applications of plastics pipes, for example, in domestic and district heating and in the oil,petroleum and gas industries. Multilayer plastics pipes with metal barrier layers also find use in cold water applications where potable water needs to be protected from aromatic substances found in the soil. [0010] A further benefit of plastics pipes with metallic barrier layers is that the metal layer prevents UV light from 45 reaching the inner plastics layer (s) beneath it, thereby protecting these layer (s) from UV degradation. This protection obviates the need for the addition of UV stabilisers to the inner layer (s) and enables the stabiliser packages of the inner and outer plastics layers to be optimised, with the inner layer (s) requiring only thermal and chemical stabilisation. Examples of plastics pipes having metal barrier and strengthening layers and methods for their manufacture are disclosed in the following patents: CH 655986 JP 93-293870 EP 0644031 EP 0353977 EP 0581208 The entire disclosures of 50 which are incorporated herein by reference for all purposes. [0011] Typical multilayer pipe constructions consist of five layers where the innermost layer comprises, for example, PE-RT (polyethylene for higher temperatures), which is overlaid with-a first adhesive layer, an overlapped or butt welded aluminium strengthening and barrier layer, a second adhesive layer and an outer layer of PE-RT or silane cross- linked PEX (cross-linked polyethylene). The adhesive layers are necessary because many polymers, including polyolefins, 55 have very poor adhesion to aluminium. [0012] This construction has several drawbacks. Firstly the inner plastics layer and the first adhesive layer are together rather thin and in some manufacturing processes the thickness of the first adhesive layer is difficult to control. [0013] Secondly the first adhesive layer is usually made of a thermoplastic polymer that is mechanically weaker than 2 EP 1 708 880 B2 the inner plastics layer and hence does not improve the long- term hydrostatic strength of the pipe. This means in practice that omitting the first adhesive layer would provide advantages in the form of improved long term strength, easier quality control and easier extrusion tool design. [0014] Thirdly, in manufacturing processes wherein the inner plastics layer is directly extruded into a freshly formed 5 and welded aluminium tube comprising the barrier layer, the thermal shrinkage of the hot extruded inner plastics layer tends to cause delamination, requiring the use of a high strength adhesive as the first adhesive layer. [0015] It has been proposed to limit the thermal shrinkage of a thermoplastic polymer by compounding relatively large particle size fillers into the polymeric matrix. However, the loading level needs to be rather high in order to reach the desired effect and this reduces the flexibility of the pipe. The use of high levels of filler also introduces further problems, 10 including the difficulty of obtaining good wetting of the filler by the polymeric matrix, which is necessary in order to obtain good mechanical properties. [0016] Polyolefins, for example, are non-polar and incompatible with hydrophilic fillers. Thus, poor adhesion between the filler surface and the matrix is a frequent outcome. [0017] Some improvement in the wetting of the filler surface by the polymeric matrix may be obtained by the use of 15 coating agents, for example, fatty acids such as stearic acid, and salts of fatty acids, which can react with,-for example, hydroxyl groups on the filler surface, but further improvements would be highly desirable. [0018] Stabilisation of thermoplastic polymers is usually accomplished by melt blending with one or more stabilisers. [0019] In this way a heterophase polymer/stabiliser system is formed, which may be best described as a physical dispersion of a low molecular weight stabiliser in a polymer matrix.
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