EP4544211A1 - Bendable multi-layer tube - Google Patents

Bendable multi-layer tube

Info

Publication number
EP4544211A1
EP4544211A1 EP23733972.6A EP23733972A EP4544211A1 EP 4544211 A1 EP4544211 A1 EP 4544211A1 EP 23733972 A EP23733972 A EP 23733972A EP 4544211 A1 EP4544211 A1 EP 4544211A1
Authority
EP
European Patent Office
Prior art keywords
layer
thin film
tube
winding
isolating
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP23733972.6A
Other languages
German (de)
French (fr)
Inventor
Jenny Zhaoxia Yu
Hua Chen
Vincent Yu
Shengyong SHI
Ying Zhang
John Anthony Brookes
Lihua JIA
Yonghao ZHANG
Wei Yan
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.)
Contitech Deutschland GmbH
Original Assignee
Contitech Deutschland GmbH
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 Contitech Deutschland GmbH filed Critical Contitech Deutschland GmbH
Publication of EP4544211A1 publication Critical patent/EP4544211A1/en
Pending legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
    • F16L11/081—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more layers of a helically wound cord or wire
    • F16L11/082—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall comprising one or more layers of a helically wound cord or wire two layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/16—Rigid pipes wound from sheets or strips, with or without reinforcement
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
    • B29C48/151—Coating hollow 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • 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
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/02—Layer formed of wires, e.g. mesh
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/12—Rigid pipes of plastics with or without reinforcement
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/12—Rigid pipes of plastics with or without reinforcement
    • F16L9/123—Rigid pipes of plastics with or without reinforcement with four layers
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • 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
    • B32B2274/00—Thermoplastic elastomer material
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/737—Dimensions, e.g. volume or area
    • B32B2307/7375—Linear, e.g. length, distance or width
    • B32B2307/7376—Thickness
    • 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
    • B32B2597/00—Tubular articles, e.g. hoses, pipes

Definitions

  • the present invention relates to a bendable multi-layer tube, in particular a plastic tube.
  • Multi-layer plastic tubes can be widely used for the delivery of a variety of liquids and gases.
  • a multi-layer tube currently on the market that is manufactured by extrusion mainly consists of three parts: an inner tube, reinforcing layers and an outer layer.
  • the reinforcing layers are generally formed by weaving or winding various metallic or non-metallic fibers.
  • An intermediate joining layer or isolating layer is generally also provided between the reinforcing layers, to connect the reinforcing layers or prevent friction therebetween.
  • an adhesive such as glue as an isolating layer
  • its addition between the reinforcing layers by a coating process are known in the prior art.
  • a process has the following shortcomings: the production process is quite complex; the amount of glue is difficult to control; the volatilization of some of the solvent during production is not environmentally friendly; and generally, the chief component of such an adhesive is a thermosetting resin which, when used in a plastic tube, makes recycling of the final product difficult.
  • the present invention needs to propose a new technical solution to solve at least one of the many technical problems mentioned above.
  • an objective of the present invention is to provide a bendable multi-layer tube which can be obtained by a simple and environmentally friendly process, and effectively prevents sliding and friction between reinforcing layers.
  • the present invention proposes a bendable multi-layer tube, comprising an inner tube, an outer layer, and at least two reinforcing layers located between the inner tube and the outer layer, with an isolating layer provided between each adjacent reinforcing layers, wherein the isolating layer is formed by winding a thin film, the thin film being of hardness 45 A - 85 A and thickness 0.1 mm - 2.0 mm.
  • the isolating layer can be formed by a simple process; little investment is needed for equipment, and there is flexibility in the choice of materials. Furthermore, no solvent is produced or volatilized during production, so the production workshop environment can be favorably improved.
  • the isolating layer thus formed can effectively prevent friction between the reinforcing layers, for example when the multi-layer tube is bent; over a long period of time, friction would damage the reinforcing layers and thus have an adverse effect on their reinforcing effect.
  • a thin film with suitable characteristics in order to reliably wind the thin film to form the isolating layer, a thin film with suitable characteristics must be chosen.
  • the thickness and hardness of the thin film are key indices.
  • the thin film has a hardness of 45 A - 85 A. This hardness is measured in accordance with standard ASTM D2240, under the condition of 15 s. When the hardness is less than 45 A, the thin film is too soft, easily slipping and falling off during winding, so production is not possible; when the hardness is greater than 85 A, the thin film is too hard and cannot wrap the reinforcing layer effectively, so production is not possible in this case either.
  • the thin film has a thickness of 0.1 mm - 2.0 mm. When the thickness of the thin film is less than 0.1 mm, the winding step cannot be performed; when the thickness exceeds 2.0 mm, the superposition of multiple layers in the tube will affect the outer diameter of the final finished tube.
  • the thin film has density of 0.7 - 1 .3 g/cm 3 determined in accordance with ASTM D792, and/or a tensile strength of 5.0 - 15.0 MPa determined in accordance with ASTM D412, and/or an elongation at break > 80% determined in accordance with ASTM D412.
  • the thin film is preferably insulating.
  • the winding of the thin film according the present invention may be achieved in different ways.
  • the isolating layer is formed by winding the thin film longitudinally in the length direction of the multi-layer tube.
  • the thin film is provided in the form of strip material for example; when the thin film is applied, the longitudinal direction i.e. the length direction of the strip material is kept in line with the length direction of the multi-layer tube, and the thin film is wound widthwise around the entirety of the periphery of the tube to be wound, thereby surrounding the periphery of the tube.
  • the thin film surrounds the periphery of the reinforcing layer.
  • This winding method does not require additional winding equipment, and can achieve relatively uniform wrapping with the thin film.
  • the width of the thin film corresponds to the outer circumference of the tube wound by the thin film.
  • the isolating layer is formed in a helical shape by winding the thin film longitudinally in a diameter direction of the multi-layer tube.
  • the thin film is also provided in the form of strip material for example; when the thin film is applied, the longitudinal direction i.e.
  • the length direction of the strip material forms a certain angle with the circumferential direction of the multi-layer tube, and the strip material is wound helically, ring by ring, thereby surrounding the periphery of the tube.
  • the strip material surrounds the periphery of the reinforcing layer.
  • a helical isolating layer is thus formed.
  • the width of the thin film and the helical winding angle may both be adjusted as required.
  • the two thin film winding methods described above may be flexibly used for the isolating layers in a single multi-layer tube.
  • the isolating layers in a single multi-layer tube may employ the same thin film winding method or different thin film winding methods.
  • the winding of the thin film according to the present invention does not require additional joining; firstly, the thin film itself has a certain degree of adhesiveness; secondly, the reinforcing layer outside the isolating layer has the effect of fixing the isolating layer thin film; and furthermore, when the outer layer is formed by extrusion at the outermost part, applied heat causes further fusion of the thin film.
  • a material of the inner tube is a thermosoft plastic or a thermoplastic elastomer
  • a material of the outer layer is a thermosoft plastic or a thermoplastic elastomer.
  • the thermosoft plastic or thermoplastic elastomer the following may for example be used: polypropylene (PP), polyethylene (PE), polymethylpentene (PMP), thermoplastic elastomers (TPE), polyamide (e.g.
  • PA6, PA66, PA11 , PA12, PA46, PA610, PA9T, PA6T polyvinyl chloride (PVC), polystyrene (PS), fluoropolymers, silicone polymers, polyether ether ketone (PEEK), polyketone (POK), etc.
  • PVC polyvinyl chloride
  • PS polystyrene
  • fluoropolymers silicone polymers
  • PEEK polyether ether ketone
  • POK polyketone
  • the thin film is formed of a thermoplastic elastomer.
  • the thermoplastic elastomer has good compatibility with the thermoplastic material used in the inner tube and outer layer, and is easy to recycle.
  • TPE thermoplastic elastomer
  • the following may preferably be used: thermoplastic vulcanizate (TPV), styrene thermoplastic elastomer (TPS), polyurethane thermoplastic elastomer (TPU) or polyolefin thermoplastic elastomer (TPO).
  • thermoplastic elastomer such as polyamide thermoplastic elastomer (TPAE), polyester thermoplastic elastomer (TPEE) or polyvinyl chloride thermoplastic elastomer (PVC-TPE) to form the thin film, and thereby form the isolating layer of the present invention.
  • TPAE polyamide thermoplastic elastomer
  • TPEE polyester thermoplastic elastomer
  • PVC-TPE polyvinyl chloride thermoplastic elastomer
  • the thin film wraps the entire length of the multi-layer tube, thereby effectively preventing slippage and friction between the reinforcing layers.
  • the reinforcing layer may use fibers, yam or cord as a reinforcing element, applied by weaving or helical winding.
  • materials suitable for use as reinforcing elements are: metal wire, aromatic polyamide (also called aramid, e.g. para-aramid or meta-aramid), polyamide, polyester (e.g. polyethylene terephthalate (PET)), polyvinyl alcohol (PVOH), or a combination of the abovementioned materials in the form of a mixed system.
  • the reinforcing layer is formed by weaving or winding steel wire, or polyester or aramid fibers.
  • the number of reinforcing layers between the inner tube and outer layer may vary according to the application conditions. For example, for high-pressure tube (10 - 100 MPa) applications, 3 - 4 reinforcing layers are generally applied. For low-pressure tube (0.1 - 1 .6 MPa) applications, 1 - 2 reinforcing layers are generally applied.
  • the isolating layer is provided between the inner tube and the innermost reinforcing layer, thereby preventing relative slippage between the reinforcing layer and the inner tube.
  • the multi-layer tube is a high-pressure delivery tube.
  • the multi-layer tube according to the present invention may be used as a hose or a hard tube, both of which can bend.
  • the present invention also proposes a method for manufacturing a multi-layer tube, comprising the following steps:
  • the isolating layer is formed of a thin film by a winding process.
  • the inner tube and/or outer layer is/are formed of a thermoplastic elastomer
  • the elastomer is finally vulcanized to obtain the finished tube.
  • the present invention has the following advantages: the isolating layer can be formed on the reinforcing layer by a simple process, thus effectively avoiding friction between reinforcing layers; little investment is needed for equipment to accomplish this, and there is flexibility in the choice of materials for the isolating layer; furthermore, no solvent is produced or volatilized during production, which is environmentally friendly.
  • Fig. 1 shows an embodiment of a multi-layer tube according to the present invention in a 3D drawing.
  • Fig. 2 shows a thin film winding method for forming an isolating layer according to the present invention.
  • Fig. 3 shows another thin film winding method for forming an isolating layer according to the present invention.
  • Fig. 1 shows an embodiment of a multi-layer tube according to the present invention.
  • Radially innermost and outermost parts of the multi-layer tube are an inner tube 1.1 and an outer layer 1.3 respectively.
  • Four reinforcing layers 1 .2 are provided between the inner tube 1.1 and the outer layer 1 .3.
  • Isolating layers 1.4 are provided between the reinforcing layers 1.2.
  • an isolating layer 1.4 may also be provided between the inner tube 1.1 and the innermost reinforcing layer 1.2, but this is not necessary.
  • the multi-layer tube can be prepared by the following process.
  • thermosoft plastic is applied to a core rod by extrusion to form the inner tube 1 .1 ; a thermoplastic elastomer thin film is then optionally wound on the inner tube 1 .1 to form an inner isolating layer; steel wire is woven or wound on the inner tube 1 .1 or optional inner isolating layer to form an innermost first reinforcing layer 1 .2; a thermoplastic elastomer thin film is then wound on the innermost reinforcing layer to form a first isolating layer 1 .4; a second reinforcing layer, a second isolating layer, a third reinforcing layer, a third isolating layer and an outermost fourth reinforcing layer are then sequentially applied to the first isolating layer; and a thermosoft plastic is then applied by extrusion to the outermost fourth reinforcing layer to form the outer layer 1 .3. All of the isolating layers wrap the entire length of the tube. Finally, the multi-layer plastic
  • thermoplastic elastomer may also be used as the material of the inner tube 1.1 and/or the outer layer 1 .3.
  • the multi-layer tube is taken off the core rod after vulcanizing the elastomer.
  • the reinforcing layers 1.2 may be formed by weaving or winding non-metallic polyester or aramid fibers.
  • the multi-layer tube shown in Fig. 1 is suitable for use as a high- pressure delivery tube.
  • a smaller number of reinforcing layers may be provided between the inner tube and the outer layer.
  • precisely 2 reinforcing layers may be provided between the inner tube and the outer layer, and the multi-layer tube thus obtained is suitable for use as a low-pressure delivery tube.
  • the longitudinal direction i.e. the length direction of the thin film strip is laid on the tube in the length direction of the tube.
  • the width of the thin film strip corresponds to the outer circumference of the tube to be wound.
  • the thin film is wound widthwise around the entirety of the periphery of the tube to be wound, such that the thin film precisely surrounds the periphery of the tube, thereby forming a sleeve-shaped isolating layer.
  • the longitudinal direction i.e. the length direction of the thin film strip forms a certain angle with the circumferential direction of the tube, and winding is performed helically, ring by ring, with the aid of winding equipment, thereby surrounding the periphery of the tube to be wound and thus forming a helical isolating layer.
  • thermoplastic vulcanizate TPV
  • the hardness of the thin film is 45 A (ASTM D2240, 15 s)
  • the thickness of the thin film is 0.1 mm
  • the density of the thin film is 0.7 g/cm 3
  • the tensile strength is 5.0 Mpa
  • the elongation at break is 85%.
  • the thin film is wound longitudinally in the length direction of the tube.
  • a thin film formed of a styrenic thermoplastic elastomer is used; the hardness of the thin film is 60 A (ASTM D2240, 15 s), the thickness of the thin film is 0.8 mm, the density of the thin film (ASTM D792) is 0.9 g/cm 3 , the tensile strength (ASTM D412) is 15.0 Mpa, and the elongation at break (ASTM D412) is 85%.
  • the thin film is wound longitudinally in the length direction of the tube.
  • a thin film formed of polyurethane thermoplastic elastomer (TPU) is used; the hardness of the thin film is 70 A (ASTM D2240, 15 s), the thickness of the thin film is 1 .5 mm, the density of the thin film (ASTM D792) is 1 .1 g/cm 3 , the tensile strength (ASTM D412) is 20.0 Mpa, and the elongation at break (ASTM D412) is 90%.
  • the thin film is wound longitudinally in a helical shape in a diameter direction of the tube.
  • a thin film formed of a polyolefin thermoplastic elastomer (TPO) is used; the hardness of the thin film is 85 A (ASTM D2240, 15 s), the thickness of the thin film is 2.0 mm, the density of the thin film (ASTM D792) is 1 .3 g/cm 3 , the tensile strength (ASTM D412) is 25.0 Mpa, and the elongation at break (ASTM D412) is 90%.
  • the thin film is wound longitudinally in a helical shape in a diameter direction of the tube.
  • Examples 1 - 4 above all successfully form the isolating layer by winding, and preserve the physical properties of the multi-layer plastic tube.
  • thermoplastic vulcanizate TPV
  • the hardness of the thin film is 40 A (ASTM D2240, 15 s)
  • the thickness of the thin film is 0.1 mm
  • the density of the thin film is 0.7 g/cm 3
  • the tensile strength is 5.0 Mpa
  • the elongation at break is 85%.
  • the thin film is wound longitudinally in the length direction of the tube.
  • thermoplastic vulcanizate TPV
  • the hardness of the thin film is 90 A (ASTM D2240, 15 s)
  • the thickness of the thin film is 0.1 mm
  • the density of the thin film is 0.7 g/cm 3
  • the tensile strength is 5.0 Mpa
  • the elongation at break is 85%.
  • the thin film is wound longitudinally in the length direction of the tube.
  • a thin film formed of polyurethane thermoplastic elastomer (TPU) is used; the hardness of the thin film is 70 A (ASTM D2240, 15 s), the thickness of the thin film is 0.05 mm, the density of the thin film (ASTM D792) is 1 .1 g/cm 3 , the tensile strength (ASTM D412) is 20.0 Mpa, and the elongation at break (ASTM D412) is 90%.
  • the thin film is wound longitudinally in a helical shape in a diameter direction of the tube.
  • a thin film formed of polyurethane thermoplastic elastomer (TPU) is used; the hardness of the thin film is 70 A (ASTM D2240, 15 s), the thickness of the thin film is 2.5 mm, the density of the thin film (ASTM D792) is 1 .1 g/cm 3 , the tensile strength (ASTM D412) is 20.0 Mpa, and the elongation at break (ASTM D412) is 90%.
  • the thin film is wound longitudinally in a helical shape in a diameter direction of the tube.
  • the hardness of the thin film in Comparative example 1 is too low, so the thin film is too soft, sliding and falling off in the winding process, and thus unable to form the isolating layer.
  • the hardness of the thin film in Comparative example 2 is too high, so the thin film is too hard and cannot effectively wrap the tube, so is unable to form the isolating layer.
  • the thickness of the thin film in Comparative example 3 is too small, so the thin film cannot be effectively wound and is unable to form the isolating layer.
  • the thickness of the thin film in Comparative example 4 is too large, so after applying multiple isolating layers and reinforcing layers according to Fig. 1 , the outer diameter of the final finished tube is too large.

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Abstract

The present invention relates to a bendable multi-layer tube, comprising an inner tube (1.1), an outer layer (1.3), and at least two reinforcing layers (1.2) located between the inner tube (1.1) and the outer layer (1.3), with an isolating layer (1.4) provided between each adjacent reinforcing layers (1.2), wherein the isolating layer (1.4) is formed by winding a thin film, the thin film being of hardness 45 A - 85 A and thickness 0.1 mm - 2.0 mm. The technical problem solved by the present invention is to form an isolating layer by a simple and environmentally friendly process, to effectively prevent sliding and friction between reinforcing layers.

Description

Description
Title of the Invention
Bendable multi-layer tube
Technical Field
The present invention relates to a bendable multi-layer tube, in particular a plastic tube.
Background Art
Multi-layer plastic tubes can be widely used for the delivery of a variety of liquids and gases. A multi-layer tube currently on the market that is manufactured by extrusion mainly consists of three parts: an inner tube, reinforcing layers and an outer layer. The reinforcing layers are generally formed by weaving or winding various metallic or non-metallic fibers. An intermediate joining layer or isolating layer is generally also provided between the reinforcing layers, to connect the reinforcing layers or prevent friction therebetween.
The use of an adhesive such as glue as an isolating layer, and its addition between the reinforcing layers by a coating process, are known in the prior art. However, such a process has the following shortcomings: the production process is quite complex; the amount of glue is difficult to control; the volatilization of some of the solvent during production is not environmentally friendly; and generally, the chief component of such an adhesive is a thermosetting resin which, when used in a plastic tube, makes recycling of the final product difficult.
The application of an intermediate layer between the reinforcing layers by an extrusion process is also known in the prior art. However, such a process has the following shortcomings: co-extrusion equipment is needed, which requires a large investment and involves a complex process; and when this process is used, the processing process parameters of the intermediate layer material need to be close to those of the inner tube material to enable extrusion in the co-extrusion equipment, and consequently the choice of materials is limited.
For these reasons, the present invention needs to propose a new technical solution to solve at least one of the many technical problems mentioned above.
Summary of the Invention
Based on the prior art described above, an objective of the present invention is to provide a bendable multi-layer tube which can be obtained by a simple and environmentally friendly process, and effectively prevents sliding and friction between reinforcing layers.
To achieve the abovementioned technical objective, the present invention proposes a bendable multi-layer tube, comprising an inner tube, an outer layer, and at least two reinforcing layers located between the inner tube and the outer layer, with an isolating layer provided between each adjacent reinforcing layers, wherein the isolating layer is formed by winding a thin film, the thin film being of hardness 45 A - 85 A and thickness 0.1 mm - 2.0 mm.
According to the present invention, by using a thin film instead of an adhesive (e.g. glue) and a thin film winding process instead of an adhesive coating process, the shortcomings of the adhesive coating process can be avoided. Firstly, by winding the thin film directly onto the reinforcing layer of the plastic tube, the isolating layer can be formed by a simple process; little investment is needed for equipment, and there is flexibility in the choice of materials. Furthermore, no solvent is produced or volatilized during production, so the production workshop environment can be favorably improved. The isolating layer thus formed can effectively prevent friction between the reinforcing layers, for example when the multi-layer tube is bent; over a long period of time, friction would damage the reinforcing layers and thus have an adverse effect on their reinforcing effect.
According to the present invention, in order to reliably wind the thin film to form the isolating layer, a thin film with suitable characteristics must be chosen. The thickness and hardness of the thin film are key indices. The thin film has a hardness of 45 A - 85 A. This hardness is measured in accordance with standard ASTM D2240, under the condition of 15 s. When the hardness is less than 45 A, the thin film is too soft, easily slipping and falling off during winding, so production is not possible; when the hardness is greater than 85 A, the thin film is too hard and cannot wrap the reinforcing layer effectively, so production is not possible in this case either. At the same time, the thin film has a thickness of 0.1 mm - 2.0 mm. When the thickness of the thin film is less than 0.1 mm, the winding step cannot be performed; when the thickness exceeds 2.0 mm, the superposition of multiple layers in the tube will affect the outer diameter of the final finished tube.
In addition, in order to ensure the physical properties of the multi-layer tube, preferably, the thin film has density of 0.7 - 1 .3 g/cm3 determined in accordance with ASTM D792, and/or a tensile strength of 5.0 - 15.0 MPa determined in accordance with ASTM D412, and/or an elongation at break > 80% determined in accordance with ASTM D412. Furthermore, the thin film is preferably insulating.
The winding of the thin film according the present invention may be achieved in different ways.
Preferably, the isolating layer is formed by winding the thin film longitudinally in the length direction of the multi-layer tube. For this purpose, the thin film is provided in the form of strip material for example; when the thin film is applied, the longitudinal direction i.e. the length direction of the strip material is kept in line with the length direction of the multi-layer tube, and the thin film is wound widthwise around the entirety of the periphery of the tube to be wound, thereby surrounding the periphery of the tube. When wound on the reinforcing layer, the thin film surrounds the periphery of the reinforcing layer. A sleeve-shaped isolating layer is thus formed. This winding method does not require additional winding equipment, and can achieve relatively uniform wrapping with the thin film.
When the isolating layer is formed by winding the thin film longitudinally in the length direction of the multi-layer tube, preferably, the width of the thin film corresponds to the outer circumference of the tube wound by the thin film. Thus, when the thin film is wound widthwise around the entirety of the periphery of the tube to be wound, it precisely surrounds the periphery of the tube. Also preferably, the isolating layer is formed in a helical shape by winding the thin film longitudinally in a diameter direction of the multi-layer tube. For this purpose, the thin film is also provided in the form of strip material for example; when the thin film is applied, the longitudinal direction i.e. the length direction of the strip material forms a certain angle with the circumferential direction of the multi-layer tube, and the strip material is wound helically, ring by ring, thereby surrounding the periphery of the tube. When wound on the reinforcing layer, the strip material surrounds the periphery of the reinforcing layer. A helical isolating layer is thus formed. With this winding method, the helical winding needs to be performed with the aid of winding equipment.
When the isolating layer is formed in a helical shape by winding the thin film longitudinally in a diameter direction of the multi-layer tube, the width of the thin film and the helical winding angle may both be adjusted as required.
The two thin film winding methods described above may be flexibly used for the isolating layers in a single multi-layer tube. The isolating layers in a single multi-layer tube may employ the same thin film winding method or different thin film winding methods.
Moreover, the winding of the thin film according to the present invention does not require additional joining; firstly, the thin film itself has a certain degree of adhesiveness; secondly, the reinforcing layer outside the isolating layer has the effect of fixing the isolating layer thin film; and furthermore, when the outer layer is formed by extrusion at the outermost part, applied heat causes further fusion of the thin film.
Preferably, a material of the inner tube is a thermosoft plastic or a thermoplastic elastomer, and/or a material of the outer layer is a thermosoft plastic or a thermoplastic elastomer. As the thermosoft plastic or thermoplastic elastomer, the following may for example be used: polypropylene (PP), polyethylene (PE), polymethylpentene (PMP), thermoplastic elastomers (TPE), polyamide (e.g. PA6, PA66, PA11 , PA12, PA46, PA610, PA9T, PA6T), polyvinyl chloride (PVC), polystyrene (PS), fluoropolymers, silicone polymers, polyether ether ketone (PEEK), polyketone (POK), etc. When the inner tube and outer layer are formed of a thermosoft plastic or thermoplastic elastomer, they are easy to form and process, and can be recycled repeatedly.
Preferably, the thin film is formed of a thermoplastic elastomer. The thermoplastic elastomer has good compatibility with the thermoplastic material used in the inner tube and outer layer, and is easy to recycle. As the thermoplastic elastomer (TPE) forming the thin film, the following may preferably be used: thermoplastic vulcanizate (TPV), styrene thermoplastic elastomer (TPS), polyurethane thermoplastic elastomer (TPU) or polyolefin thermoplastic elastomer (TPO). However, the choice of materials is not limited to this, and it is also possible to use a thermoplastic elastomer such as polyamide thermoplastic elastomer (TPAE), polyester thermoplastic elastomer (TPEE) or polyvinyl chloride thermoplastic elastomer (PVC-TPE) to form the thin film, and thereby form the isolating layer of the present invention.
Preferably, the thin film wraps the entire length of the multi-layer tube, thereby effectively preventing slippage and friction between the reinforcing layers.
The reinforcing layer may use fibers, yam or cord as a reinforcing element, applied by weaving or helical winding. Examples of materials suitable for use as reinforcing elements are: metal wire, aromatic polyamide (also called aramid, e.g. para-aramid or meta-aramid), polyamide, polyester (e.g. polyethylene terephthalate (PET)), polyvinyl alcohol (PVOH), or a combination of the abovementioned materials in the form of a mixed system. Preferably, the reinforcing layer is formed by weaving or winding steel wire, or polyester or aramid fibers.
The number of reinforcing layers between the inner tube and outer layer may vary according to the application conditions. For example, for high- pressure tube (10 - 100 MPa) applications, 3 - 4 reinforcing layers are generally applied. For low-pressure tube (0.1 - 1 .6 MPa) applications, 1 - 2 reinforcing layers are generally applied.
Also preferably, the isolating layer is provided between the inner tube and the innermost reinforcing layer, thereby preventing relative slippage between the reinforcing layer and the inner tube.
Preferably, the multi-layer tube is a high-pressure delivery tube. The multi-layer tube according to the present invention may be used as a hose or a hard tube, both of which can bend.
Correspondingly, the present invention also proposes a method for manufacturing a multi-layer tube, comprising the following steps:
- forming an inner tube, for example by extrusion;
- optionally, applying an inner isolating layer on the inner tube;
- applying a reinforcing layer on the inner tube or inner isolating layer by weaving or winding;
- applying an outer layer on the outermost reinforcing layer, for example by extrusion, wherein at least two reinforcing layers are provided between the inner tube and outer layer, with an isolating layer applied between each adjacent reinforcing layers; for this purpose, the isolating layer is formed of a thin film by a winding process.
In the case where the inner tube and/or outer layer is/are formed of a thermoplastic elastomer, the elastomer is finally vulcanized to obtain the finished tube.
The abovementioned features applying to the multi-layer tube of the present invention likewise apply to the manufacturing method of the present invention, so to avoid redundancy are not repeated here.
The present invention has the following advantages: the isolating layer can be formed on the reinforcing layer by a simple process, thus effectively avoiding friction between reinforcing layers; little investment is needed for equipment to accomplish this, and there is flexibility in the choice of materials for the isolating layer; furthermore, no solvent is produced or volatilized during production, which is environmentally friendly.
Brief Description of the Drawings
The present invention is explained further below with reference to the drawings. All of the drawings use a simplified schematic form and imprecise proportions.
Fig. 1 shows an embodiment of a multi-layer tube according to the present invention in a 3D drawing. Fig. 2 shows a thin film winding method for forming an isolating layer according to the present invention.
Fig. 3 shows another thin film winding method for forming an isolating layer according to the present invention.
Detailed Description of the Invention
To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention is described clearly and completely below in conjunction with embodiments and comparative examples. Obviously, the embodiments described are some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort shall fall within the scope of protection of the present invention.
Fig. 1 shows an embodiment of a multi-layer tube according to the present invention. Radially innermost and outermost parts of the multi-layer tube are an inner tube 1.1 and an outer layer 1.3 respectively. Four reinforcing layers 1 .2 are provided between the inner tube 1.1 and the outer layer 1 .3. Isolating layers 1.4 are provided between the reinforcing layers 1.2. In addition, as shown in the figure, an isolating layer 1.4 may also be provided between the inner tube 1.1 and the innermost reinforcing layer 1.2, but this is not necessary.
The multi-layer tube can be prepared by the following process.
Firstly, a thermosoft plastic is applied to a core rod by extrusion to form the inner tube 1 .1 ; a thermoplastic elastomer thin film is then optionally wound on the inner tube 1 .1 to form an inner isolating layer; steel wire is woven or wound on the inner tube 1 .1 or optional inner isolating layer to form an innermost first reinforcing layer 1 .2; a thermoplastic elastomer thin film is then wound on the innermost reinforcing layer to form a first isolating layer 1 .4; a second reinforcing layer, a second isolating layer, a third reinforcing layer, a third isolating layer and an outermost fourth reinforcing layer are then sequentially applied to the first isolating layer; and a thermosoft plastic is then applied by extrusion to the outermost fourth reinforcing layer to form the outer layer 1 .3. All of the isolating layers wrap the entire length of the tube. Finally, the multi-layer plastic tube is taken off the core rod.
In some embodiments, a thermoplastic elastomer may also be used as the material of the inner tube 1.1 and/or the outer layer 1 .3. In this case, the multi-layer tube is taken off the core rod after vulcanizing the elastomer.
In some embodiments, the reinforcing layers 1.2 may be formed by weaving or winding non-metallic polyester or aramid fibers.
The multi-layer tube shown in Fig. 1 is suitable for use as a high- pressure delivery tube. In some embodiments, a smaller number of reinforcing layers may be provided between the inner tube and the outer layer. For example, precisely 2 reinforcing layers may be provided between the inner tube and the outer layer, and the multi-layer tube thus obtained is suitable for use as a low-pressure delivery tube.
To form the isolating layer 1 .4, see the two methods of winding the thermoplastic elastomer thin film shown in Figs. 2 and 3.
According to the thin film winding method shown in Fig. 2, when the thin film is applied, the longitudinal direction i.e. the length direction of the thin film strip is laid on the tube in the length direction of the tube. The width of the thin film strip corresponds to the outer circumference of the tube to be wound. The thin film is wound widthwise around the entirety of the periphery of the tube to be wound, such that the thin film precisely surrounds the periphery of the tube, thereby forming a sleeve-shaped isolating layer.
According to the thin film winding method shown in Fig. 3, when the thin film is applied, the longitudinal direction i.e. the length direction of the thin film strip forms a certain angle with the circumferential direction of the tube, and winding is performed helically, ring by ring, with the aid of winding equipment, thereby surrounding the periphery of the tube to be wound and thus forming a helical isolating layer.
In accordance with the two thin film winding methods described above, Examples 1 - 4 and Comparative examples 1 - 4 below are specifically implemented.
Example 1 :
A thin film formed of thermoplastic vulcanizate (TPV) is used; the hardness of the thin film is 45 A (ASTM D2240, 15 s), the thickness of the thin film is 0.1 mm, the density of the thin film (ASTM D792) is 0.7 g/cm3, the tensile strength (ASTM D412) is 5.0 Mpa, and the elongation at break (ASTM D412) is 85%. The thin film is wound longitudinally in the length direction of the tube.
Example 2:
A thin film formed of a styrenic thermoplastic elastomer (TPS) is used; the hardness of the thin film is 60 A (ASTM D2240, 15 s), the thickness of the thin film is 0.8 mm, the density of the thin film (ASTM D792) is 0.9 g/cm3, the tensile strength (ASTM D412) is 15.0 Mpa, and the elongation at break (ASTM D412) is 85%. The thin film is wound longitudinally in the length direction of the tube.
Example 3:
A thin film formed of polyurethane thermoplastic elastomer (TPU) is used; the hardness of the thin film is 70 A (ASTM D2240, 15 s), the thickness of the thin film is 1 .5 mm, the density of the thin film (ASTM D792) is 1 .1 g/cm3, the tensile strength (ASTM D412) is 20.0 Mpa, and the elongation at break (ASTM D412) is 90%. The thin film is wound longitudinally in a helical shape in a diameter direction of the tube.
Example 4:
A thin film formed of a polyolefin thermoplastic elastomer (TPO) is used; the hardness of the thin film is 85 A (ASTM D2240, 15 s), the thickness of the thin film is 2.0 mm, the density of the thin film (ASTM D792) is 1 .3 g/cm3, the tensile strength (ASTM D412) is 25.0 Mpa, and the elongation at break (ASTM D412) is 90%. The thin film is wound longitudinally in a helical shape in a diameter direction of the tube.
Examples 1 - 4 above all successfully form the isolating layer by winding, and preserve the physical properties of the multi-layer plastic tube.
Comparative example 1 :
A thin film formed of thermoplastic vulcanizate (TPV) is used; the hardness of the thin film is 40 A (ASTM D2240, 15 s), the thickness of the thin film is 0.1 mm, the density of the thin film (ASTM D792) is 0.7 g/cm3, the tensile strength (ASTM D412) is 5.0 Mpa, and the elongation at break (ASTM D412) is 85%. The thin film is wound longitudinally in the length direction of the tube.
Comparative example 2:
A thin film formed of thermoplastic vulcanizate (TPV) is used; the hardness of the thin film is 90 A (ASTM D2240, 15 s), the thickness of the thin film is 0.1 mm, the density of the thin film (ASTM D792) is 0.7 g/cm3, the tensile strength (ASTM D412) is 5.0 Mpa, and the elongation at break (ASTM D412) is 85%. The thin film is wound longitudinally in the length direction of the tube.
Comparative example 3:
A thin film formed of polyurethane thermoplastic elastomer (TPU) is used; the hardness of the thin film is 70 A (ASTM D2240, 15 s), the thickness of the thin film is 0.05 mm, the density of the thin film (ASTM D792) is 1 .1 g/cm3, the tensile strength (ASTM D412) is 20.0 Mpa, and the elongation at break (ASTM D412) is 90%. The thin film is wound longitudinally in a helical shape in a diameter direction of the tube.
Comparative example 4:
A thin film formed of polyurethane thermoplastic elastomer (TPU) is used; the hardness of the thin film is 70 A (ASTM D2240, 15 s), the thickness of the thin film is 2.5 mm, the density of the thin film (ASTM D792) is 1 .1 g/cm3, the tensile strength (ASTM D412) is 20.0 Mpa, and the elongation at break (ASTM D412) is 90%. The thin film is wound longitudinally in a helical shape in a diameter direction of the tube.
The hardness of the thin film in Comparative example 1 is too low, so the thin film is too soft, sliding and falling off in the winding process, and thus unable to form the isolating layer. The hardness of the thin film in Comparative example 2 is too high, so the thin film is too hard and cannot effectively wrap the tube, so is unable to form the isolating layer. The thickness of the thin film in Comparative example 3 is too small, so the thin film cannot be effectively wound and is unable to form the isolating layer. The thickness of the thin film in Comparative example 4 is too large, so after applying multiple isolating layers and reinforcing layers according to Fig. 1 , the outer diameter of the final finished tube is too large. It will be understood that the above embodiments are merely exemplary embodiments used to illustrate the principles of the present invention, and the present invention is not limited thereto. Various modifications and improvements can be made by a person skilled in the art without departing from the spirit and essence of the present invention, and these modifications and improvements are also considered as falling within the protection scope of the present invention.

Claims

Claims
1 . A bendable multi-layer tube, comprising an inner tube (1.1 ), an outer layer (1.3), and at least two reinforcing layers (1.2) located between the inner tube (1.1 ) and the outer layer (1.3), with an isolating layer (1.4) provided between each adjacent reinforcing layers (1.2), wherein the isolating layer (1 .4) is formed by winding a thin film, the thin film being of hardness 45 A - 85 A and thickness 0.1 mm - 2.0 mm.
2. The bendable multi-layer tube as claimed in claim 1 , wherein the isolating layer (1.4) is formed by winding the thin film longitudinally in the length direction of the multi-layer tube.
3. The bendable multi-layer tube as claimed in claim 2, wherein the width of the thin film corresponds to the outer circumference of the tube wound by the thin film.
4. The bendable multi-layer tube as claimed in claim 1 , wherein the isolating layer (1 .4) is formed in a helical shape by winding the thin film longitudinally in a diameter direction of the multi-layer tube.
5. The bendable multi-layer tube as claimed in any one of claims 1 - 4, wherein a material of the inner tube (1.1 ) is a thermosoft plastic or a thermoplastic elastomer, and/or a material of the outer layer (1 .3) is a thermosoft plastic or a thermoplastic elastomer.
6. The bendable multi-layer tube as claimed in any one of claims 1 - 4, wherein the thin film is formed of a thermoplastic elastomer.
7. The bendable multi-layer tube as claimed in any one of claims 1 - 4, wherein the thin film wraps the entire length of the multi-layer tube.
8. The bendable multi-layer tube as claimed in any one of claims 1 - 4, wherein the reinforcing layer (1 .2) is formed by weaving or winding steel wire, or polyester or aramid fibers.
9. The bendable multi-layer tube as claimed in any one of claims 1 - 4, wherein the isolating layer (1 .4) is provided between the inner tube (1.1 ) and the innermost reinforcing layer (1.2).
10. The bendable multi-layer tube as claimed in any one of claims 1 - 4, wherein the multi-layer tube is a high-pressure delivery tube.
EP23733972.6A 2022-06-24 2023-06-20 Bendable multi-layer tube Pending EP4544211A1 (en)

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CN202210726404.3A CN117307832A (en) 2022-06-24 2022-06-24 A multilayer tube that can be bent
PCT/EP2023/066709 WO2023247583A1 (en) 2022-06-24 2023-06-20 Bendable multi-layer tube

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US5052444A (en) * 1987-04-30 1991-10-01 The Fluorocarbon Company Reinforced fluid hose having on-bonded tape
EP0969236A3 (en) * 1998-06-29 2002-01-02 Parker Hannifin GmbH Kink resistant high pressure hose
CN203743647U (en) * 2014-02-27 2014-07-30 广州励进管道科技有限公司 Flexible reinforced thermoplastic composite tube bonded in grouped mode
CN204254065U (en) * 2014-10-31 2015-04-08 中国石油天然气集团公司 A kind of fiber reinforcement corrosion resistant alloy composite pipe
ITUA20164375A1 (en) * 2016-06-15 2017-12-15 Deregibus Tubigomma MULTILAYER CONTAINMENT AND PROTECTION TUBE FOR TANKS, CABLES AND THE LIKE
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CN110701399A (en) * 2019-09-27 2020-01-17 五行科技股份有限公司 Large-diameter industrial filament reinforced hose and preparation method thereof

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