WO2017135491A1 - Matériau composite polymère - Google Patents

Matériau composite polymère Download PDF

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Publication number
WO2017135491A1
WO2017135491A1 PCT/KR2016/001522 KR2016001522W WO2017135491A1 WO 2017135491 A1 WO2017135491 A1 WO 2017135491A1 KR 2016001522 W KR2016001522 W KR 2016001522W WO 2017135491 A1 WO2017135491 A1 WO 2017135491A1
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WIPO (PCT)
Prior art keywords
polymer
fiber
filament
composite material
adhesive
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PCT/KR2016/001522
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English (en)
Korean (ko)
Inventor
누르 안나스 로즐란무함마드
조명현
Original Assignee
키스와이어 에스디엔 비에이치디
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Application filed by 키스와이어 에스디엔 비에이치디 filed Critical 키스와이어 에스디엔 비에이치디
Priority to US15/747,236 priority Critical patent/US20180371691A1/en
Priority to EP16813212.4A priority patent/EP3222775A4/fr
Publication of WO2017135491A1 publication Critical patent/WO2017135491A1/fr

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    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/0666—Reinforcing cords for rubber or plastic articles the wires being characterised by an anti-corrosive or adhesion promoting coating
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
    • D02G3/404—Yarns or threads coated with polymeric solutions
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/48—Tyre cords
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/005—Composite ropes, i.e. ropes built-up from fibrous or filamentary material and metal wires
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/02—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/02—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
    • D07B1/025—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics comprising high modulus, or high tenacity, polymer filaments or fibres, e.g. liquid-crystal polymers
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/02—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics
    • D07B1/04—Ropes built-up from fibrous or filamentary material, e.g. of vegetable origin, of animal origin, regenerated cellulose, plastics with a core of fibres or filaments arranged parallel to the centre line
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/06—Ropes or cables built-up from metal wires, e.g. of section wires around a hemp core
    • D07B1/0606—Reinforcing cords for rubber or plastic articles
    • D07B1/0613—Reinforcing cords for rubber or plastic articles the reinforcing cords being characterised by the rope configuration
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/12—Ropes or cables with a hollow core
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
    • D07B1/162—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber enveloping sheathing
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B1/00—Constructional features of ropes or cables
    • D07B1/16—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics
    • D07B1/165—Ropes or cables with an enveloping sheathing or inlays of rubber or plastics characterised by a plastic or rubber inlay
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B5/00—Making ropes or cables from special materials or of particular form
    • D07B5/06—Making ropes or cables from special materials or of particular form from natural or artificial staple fibres
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/10—Rope or cable structures
    • D07B2201/1012—Rope or cable structures characterised by their internal structure
    • D07B2201/102—Rope or cable structures characterised by their internal structure including a core
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2015—Strands
    • D07B2201/2046—Strands comprising fillers
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2047—Cores
    • D07B2201/2052—Cores characterised by their structure
    • D07B2201/2059—Cores characterised by their structure comprising wires
    • D07B2201/2061—Cores characterised by their structure comprising wires resulting in a twisted structure
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2047—Cores
    • D07B2201/2052—Cores characterised by their structure
    • D07B2201/2059—Cores characterised by their structure comprising wires
    • D07B2201/2062—Cores characterised by their structure comprising wires comprising fillers
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2201/00—Ropes or cables
    • D07B2201/20—Rope or cable components
    • D07B2201/2075—Fillers
    • D07B2201/2078—Fillers having a load bearing function
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2401/00—Aspects related to the problem to be solved or advantage
    • D07B2401/20—Aspects related to the problem to be solved or advantage related to ropes or cables
    • D07B2401/202—Environmental resistance
    • D07B2401/2025—Environmental resistance avoiding corrosion
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2401/00—Aspects related to the problem to be solved or advantage
    • D07B2401/20—Aspects related to the problem to be solved or advantage related to ropes or cables
    • D07B2401/2055—Improving load capacity
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2501/00—Application field
    • D07B2501/20—Application field related to ropes or cables
    • D07B2501/2015—Construction industries
    • D—TEXTILES; PAPER
    • D07—ROPES; CABLES OTHER THAN ELECTRIC
    • D07B—ROPES OR CABLES IN GENERAL
    • D07B2501/00—Application field
    • D07B2501/20—Application field related to ropes or cables
    • D07B2501/2061—Ship moorings

Definitions

  • the present invention relates to a polymer composite material, and more particularly, to a polymer composite material having light weight, high strength and high toughness, and excellent wear resistance by forming a multilayered structure by bonding one or more kinds of steel and fibers in a polymer to be bonded and bonded. will be.
  • steel wires are used in mooring steel ropes for offshore oil and gas production facilities, steel ropes for offshore cranes, mining ropes, cables for structures and bridges, and the like. Steel is also used as a reinforcement for sports, industrial materials, automobiles and tires.
  • Steel ropes for mooring or steel cranes for offshore cranes should be made of steel with high corrosion resistance because steel is easily corroded, and steel with excellent corrosion resistance should be used while reducing the weight as the depth applied to the rope increases.
  • the present invention is to solve the above-mentioned problems, and more specifically, by polymerizing one or more kinds of steel and fiber in the polymer adhesive bonding to form a multi-layer structure, a lightweight, high strength and high toughness, excellent wear resistance polymer composite material It is about.
  • the polymer composite material of the present invention for achieving the above object comprises a polymer, a filament planted inside the polymer and adhesively bonded to the polymer, a fiber planted inside the polymer and adhesively bonded to the polymer, Any one of the filament or the fiber is embedded in the polymer and bonded to the polymer, or the filament and the fiber are simultaneously planted inside the polymer and bonded to the polymer, so that it has light strength and high toughness. It is characterized by.
  • the filament of the polymer composite material of the present invention for achieving the above object is preferably made of at least one steel or fiber, the polymer is adhesively treated with an adhesive is preferably adhesively bonded to the filament or the fiber.
  • the filaments or the fibers are plasma surface modified to be adhesively bonded to the polymer.
  • an adhesive force ratio of the polymer and the filament or the polymer and the fiber of the polymer composite material of the present invention is 5% or more, and is formed between the polymer and the filament or the polymer and the fiber. It is preferable that the contact interface void ratio of the contact interface used becomes 90% or less.
  • the filament of the polymer composite material of the present invention for achieving the above object is located in the center of the polymer, the fiber is preferably located around the filament, the fiber is made of a plurality, the fiber around the filament It is preferable to form a layer, and the fiber layer is composed of at least one layer.
  • the polymer composite material of the present invention for achieving the above object further comprises a filler which is embedded in the polymer and bonded to the polymer, the filler is preferably made of steel or fiber, the filament and the fiber is It is preferred that the polymer is planted in any one or more of straight, twisted, and woven fabrics.
  • the polymer of the polymer composite material of the present invention for achieving the above object is made of any one or more of TPU (Thermoplastic Polyurethane), HDPE (high Density Polyethylene), PE (Polyethylene), PP (polypropylene), polyester, It is preferable that a fiber consists of any one or more of aramid, polyester, nylon, and polyethylene.
  • TPU Thermoplastic Polyurethane
  • HDPE high Density Polyethylene
  • PE Polyethylene
  • PP polypropylene
  • polyester It is preferable that a fiber consists of any one or more of aramid, polyester, nylon, and polyethylene.
  • the cross section of the polymer composite material of the present invention for achieving the above object is preferably formed in any one shape of a circle, a square, a plate, a sheet, the polymer is a high pressure and rapid cooling treatment, the inside of the polymer It is preferable that the void area ratio is formed to be 2% or less.
  • the HDPE polymer is preferably made of HDPE and HDPE-g-MAH additive, when the polymer is HDPE, 5% silane and 95% of ions
  • the fibers or filaments are adhesively bonded to the polymer by treatment with water or a solution consisting of 5% silane and 95% ethanol.
  • one or more kinds of steel and fiber are adhesively bonded by planting in the polymer.
  • excellent tensile strength and cutting load can be obtained.
  • the adhesive treatment of the polymer and the filament or fiber, and the adhesive bonding of the filament and the fiber to the polymer by the plasma surface modification treatment has the advantage of increasing the adhesive strength of the filament and the polymer or fiber and the polymer.
  • 1 to 3 is a view showing a composite material according to an embodiment of the present invention.
  • FIG. 4 is a view showing a cross section of FIG.
  • 5 to 7 is a view showing a composite material according to an embodiment of the present invention.
  • FIG. 10 is a view showing the tensile strength of the composite material according to an embodiment of the present invention.
  • FIG. 11 is a view showing a cutting load of the composite material according to an embodiment of the present invention.
  • 12A is a view showing an adhesive interface between an adhesive polymer and a filament or fiber according to an embodiment of the present invention.
  • FIG. 12B is a diagram illustrating components analyzed by EDX at an adhesive interface between an adhesive polymer and a filament or fiber.
  • 13A is a view showing an adhesive interface between an untreated polymer and a filament or fiber according to an embodiment of the present invention.
  • FIG. 13B is a diagram illustrating an analysis of components by EDX on an adhesive interface between an untreated polymer and a filament or fiber.
  • FIG 14 is a view showing the adhesive force between the polymer and the filament or fiber before and after the adhesive treatment according to an embodiment of the present invention.
  • 15 is a view showing the adhesion of the polymer to which the adhesion promoter according to an embodiment of the present invention.
  • 16 is a view showing an adhesive interface before and after plasma surface modification according to an embodiment of the present invention.
  • 17 is a view showing the adhesive force before and after the plasma surface modification process according to an embodiment of the present invention.
  • FIG. 18 is a diagram illustrating an adhesive interface according to an embodiment of the present invention.
  • 19A and 19B are views illustrating changes in the area of pores of a polymer before and after high pressure and rapid cooling according to an embodiment of the present invention.
  • 20A and 20B are graphs showing a polymer internal void ratio (%) before and after high pressure and rapid cooling according to an embodiment of the present invention.
  • the present invention relates to a polymer composite material, and more particularly, to a polymer composite material having light weight, high strength and high toughness, and excellent wear resistance by forming a multilayered structure by bonding one or more kinds of steel and fibers in a polymer to be bonded and bonded. will be.
  • Tensile strength (N / mm2) increases in proportion to tensile load (N), and cutting strength (N / mm2) increases in proportion to breaking load (N). Therefore, when the tensile load (N) and the cutting load (N) increases, the tensile strength (N / mm2) and cutting strength (N / mm2) increases. Therefore, in the following description, the increase in tensile load (N) or cutting load (N) refers to the increase in tensile strength (N / mm2) and cutting strength (N / mm2).
  • the polymer composite material 100 of the present invention comprises a polymer 110, filament 120, fiber 130. Only one of the filament 120 or the fiber 130 may be planted inside the polymer 110 to be adhesively bonded to the polymer 110 in the polymer 110, and the filament 120 and the fiber ( 130 may be simultaneously planted inside the polymer 110 to be adhesively bonded to the polymer 110.
  • the filament 120 is planted inside the polymer 110 and adhesively bonded to the polymer 110.
  • the filament 120 may be made of at least one steel or fiber. That is, the filament 120 may be made of steel or may be made of fiber.
  • the filament 120 may be made of one, it may be made of two or more.
  • the polymer composite material 100 of the present invention may further include the fiber 130.
  • the fiber 130 is positioned around the filament 120, and may be formed of a plurality of fibers to form a fiber layer 131 around the filament 120. That is, the polymer composite material 100 may be formed in a form in which the filament 120 is positioned at the center thereof and the fiber 130 is surrounded by the fiber layer 131.
  • the filament 120 and the fiber 130 are planted inside the polymer 110 and adhesively bonded to the polymer 110.
  • the polymer 110 may be formed of a first polymer 111 and a second polymer 112.
  • the first polymer 111 surrounds the filament 120.
  • the second polymer 112 surrounds the fiber 130.
  • the filament 120 is planted and bonded to the first polymer 111, and the fiber 130 is planted and bonded to the second polymer 112.
  • the first polymer 111 and the second polymer 112 may be the same type of polymer, and different types of polymers may be used.
  • the fiber layer 131 formed of a plurality of fibers 130 may be formed of one layer, and the fiber layer 131 may be formed of two or more layers.
  • the filler 140 may be planted in the polymer 110 to be adhesively bonded to the polymer 110, and the filler 140 may be made of steel or fiber.
  • the filler 140 may be planted in an empty space between the fiber 130 or an empty space between the fiber 130 and the filament 120. As the filler 140 is planted in the empty space, a decrease in strength of the empty space may be prevented. Therefore, the strength of the composite material 100 is increased by planting the filler 140 having high strength in the empty space. Since the filler 140 is made of steel or fiber having high toughness, there is an effect of increasing the toughness of the composite material 100.
  • the composite material 100 may have a cross section of various shapes.
  • the cross section of the composite material 100 may be generally circular, but is not limited thereto, and may have a shape of a rectangle, a plate, a sheet, or the like.
  • the cross section of the composite material 100 may be formed in another release form (trapezoid, H cross-sectional shape, Z cross-sectional shape, etc.).
  • the filament 120 and the fiber 130 may be planted in various shapes inside the polymer 110 to be adhesively bonded.
  • the filament 120 and the fiber 130 may be planted in the polymer 110 in a straight line. Referring to FIG. 3, the filament 120 and the fiber 130 may be twisted in the form of the polymer. It can be planted in (110). In addition, the filament 120 and the fiber 130 may be planted in the polymer 110 in the form of a fabric (mesh or braded).
  • the filament 120 and the fiber 130 may be planted extending in one direction in the polymer 110, and may be planted in the form of a fabric extending simultaneously in the horizontal and vertical directions.
  • the filament 120 and the fiber 130 are planted in the polymer 110 is not limited thereto, but may be planted in various forms.
  • the shape of the composite material 100 is not limited to the above-described shape, but may be formed in various shapes. Referring to FIG. 7, two filaments 120 are planted in the center of the polymer 110, four fibers 130 are bundled, and four fibers 130 form the fiber layer 131. Can be formed. In addition to the one that can increase the strength of the composite material 100, it can be made in a variety of shapes.
  • the polymer 110 may be TPU (Thermoplastic Polyurethane), HDPE (High Density Polyethylene), PE (Polyethylene), PP (polypropylene), Polyester, etc., and the type of the fiber 130 may be aramid, polyester , Nylon, polyethylene and the like can be used.
  • the type of the polymer 110 and the fiber 130 is not limited thereto, and various kinds may be used as long as the strength of the composite material 100 may be increased.
  • TPU Thermoplastic Polyurethane
  • HDPE High Density Polyethylene
  • PE Polyethylene
  • PP polypropylene
  • Polyester etc., which are types of the polymer 110
  • aramid polyester, nylon, polyethylene, etc., which are types of the fiber 130 Is a well-known technology, detailed description thereof will be omitted.
  • metal plated steel may be used, and steel without metal plating may be used.
  • the plated steel may be zinc plated, brass plated, or the like, and various other metals may be plated on the steel.
  • An important quality characteristic of the composite material 100 is a spinning factor (%), and the annual efficiency (%) is between the filament 120 and the fiber 130 and the polymer 110 planted in a polymer. Determined by adhesion force ratio (%).
  • Adhesive Force Ratio (%) (Adhesive Strength (N / mm2) / Polymer Tensile Strength (N / mm2)) * 100
  • Adhesive strength is a value obtained by dividing the adhesion force (N) of the polymer 110 and the filament 120 or the polymer 110 and the fiber 130 by the area of the adhesive interface.
  • FIGS. 8 and 9 are views showing the relationship between the adhesive force ratio (%) and the annual efficiency (%)
  • Figure 9 is a view showing the relationship between the annual efficiency (%) and the tensile load (N).
  • the adhesive force (%) of the polymer 110 and the filament 120 or the polymer 110 and the fiber 130 is preferably 5% or more.
  • the adhesive force ratio (%) is 5% or less, since the tensile load and the cutting load of the composite material 100 become small, it becomes difficult to obtain the desired strength of the composite material 100. Therefore, the adhesive force (%) of the polymer 110 and the filament 120 or the polymer 110 and the fiber 130 is preferably 5% or more.
  • 10 and 11 are views showing tensile strength and cutting load according to elongation of the composite material 100.
  • the composite material 100 can be seen that the tensile strength and the cutting load increases compared to the polyester, the elongation is reduced. That is, the elongation when the composite material 100 reaches the tensile strength and the cutting load is reduced compared to the elongation when the polyester reaches the tensile strength and the cutting load.
  • the elongation decreases as a property of a steel material, and the composite material 100 is similar to that of steel as the filament 120 and the fiber 130 are planted in the polymer 110. There is.
  • the composite material 100 can be seen that the tensile load and the cutting load increases as the adhesive strength ratio (%) as described above, in order to increase the adhesive strength ratio (%) the polymer 110 and the filament 120 Or increase the adhesion between the polymer 110 and the fiber 130.
  • the polymer 110 may be adhesively bonded to the filament 120 or the fiber 130 after the adhesive treatment through the adhesive.
  • the type of adhesive may vary depending on the type of the polymer 110.
  • the polymer 110 is high density polyethylene (HDPE)
  • HDPE high density polyethylene
  • the filament 120 or the fiber 130 may be adhesively bonded.
  • an adhesion treatment chemical treatment
  • the adhesion between the polymer 110 and the filament 120 or the polymer 110 and the filament 120 is improved, and thus the tensile load of the composite material 100. And cutting load is also increased.
  • FIG. 12A and 12B illustrate that the high density polyethylene (HDPE) in the polymer 110 is bonded with 5% silane and 95% deionized water to bond the galvanized steel. It is a figure which shows the adhesion interface of a sample. Referring to FIG. 12A, it can be seen that pores or pores of the adhesive interface are very small, which means that the polymer 110 is well bonded to the steel.
  • HDPE high density polyethylene
  • 12B is a graph of the components of the adhesive sample described above with EDX. 12B, it can be seen that carbon (C), which is a chemical component of the polymer 110, and a zinc component of zinc-plated steel are uniformly distributed. This means that the polymer 110 and the steel are well chemically bonded.
  • Figures 13a and 13b show the sample without adhesion of 5% silane and 95% deionized water to high density polyethylene (HDPE) and galvanized steel in the sample described above. It is a figure which shows an adhesive interface. Referring to 13a, large gaps or pores exist in the adhesive interface. This indicates that the adhesion between the polymer 110 and the steel is not properly made.
  • HDPE high density polyethylene
  • 13b is a graph in which the above-described sample is analyzed by EDX, and it can be seen that carbon (C), which is a chemical component of the polymer 110, is not uniformly distributed. This means that the chemical adhesion between the polymer 110 and the steel is not good.
  • the filament 120 or the fiber 130 is treated with 5% silane and 95% deionized water. It can be seen that when the adhesive bond to the adhesive strength increases.
  • the polymer 110 is a high density polyethylene (HDPE)
  • HDPE high density polyethylene
  • 5% silane and 95% ethanol May be used.
  • the type of adhesive may be a different type of adhesive according to the type of the polymer 110, and when the polymer 110 is a TPU or a polyester, a Chemlok adhesive may be used. Chemlok adhesive is a commercially available adhesive and its detailed description is omitted. By using such an adhesive it is possible to increase the adhesive strength of the polymer 110 and the filament 120 or the polymer 110 and the fiber 130. 14 is a view comparing the adhesive force before and after the adhesive treatment to the TPU through the adhesive. Referring to Figure 14, it can be seen that the adhesive force increases when the adhesive treatment to the TPU through the adhesive.
  • the type of the adhesive is not limited thereto, and various adhesives capable of increasing the adhesive force of the polymer 110 may be used according to the type of the polymer 110.
  • the polymer 110 may be made by adding an adhesion promoter.
  • the polymer 110 is dissolved and mixed with the adhesion promoter.
  • the adhesion promoter may improve adhesion between the polymer 110 and the filament 120 or the polymer 110 and the fiber 130.
  • the adhesion promoter may be used in various kinds according to the type of the polymer 110, and when the polymer 110 is made of high density polyethylene (HDPE), the adhesion promoter may be HDPE-g-MAH.
  • HDPE high density polyethylene
  • FIG. 15 illustrates that the polymer 110 is 90% made of high density polyethylene (HDPE) and has improved adhesion by using 10% HDPE-g-MAH adhesion promoter.
  • the adhesion promoter may be carbon black in addition to HDPE-g-MAH.
  • the filament 120 or the fiber 130 may be subjected to an Atmospheric pressure plasma surface modification treatment Plasma surface modification treatment ").
  • the plasma surface modification treatment of the filament 120 or the fiber 130 improves adhesion to the polymer 110.
  • FIG. 16 is a view showing adhesion sites with the polymer 110 before and after the filament 120 or the fiber 130 is subjected to plasma surface modification.
  • Plasma surface modification can reduce gaps occurring at the adhesive interface.
  • the gap Gap is a void of the adhesive interface, and the plasma surface modification process reduces the void of the adhesive interface, and thus the polymer 110, the filament 120, or the polymer 110 and the fiber ( 130) can improve the adhesion.
  • FIG. 17 is a view showing the adhesive force before and after the plasma surface modification treatment to the filament 120 or the fiber 130, the brass plate when the polymer 110 is TPU and the fiber 130 is aramid ( It is a test result showing the adhesive strength with the brass plate and the adhesive force with the brass plate when the polymer 110 is a polyester and the fiber 130 is aramid.
  • the adhesive strength is improved by about 2 times through plasma surface modification, and when the polymer 110 is a polyester, about 5 times through the plasma surface modification. It can be seen that the adhesive force is improved.
  • the polymer 110 and the filament 120 or the polymer 110 and the fiber 130 are bonded to the polymer 110 and the filament 120 or the polymer 110 and the fiber 130 Voids occur in the adhesive interface generated between them, and the void ratio at adhesion interface (%) is preferably 90% or less.
  • the adhesive interfacial void ratio (%) is when the composite material 100 is cut
  • % Of adhesive interface pore (sum of all pore lengths at adhesive interface / total length of adhesive interface) * 100.
  • the adhesive interface void percentage (%) is greater than 90%, as the voids become larger, the adhesion between the polymer 110 and the filament 120 or the polymer 110 and the fiber 130 decreases, thus The tensile load and the cutting load of the composite material 100 are reduced. Therefore, it is preferable to keep the adhesive interface void ratio (%) at 90% or less.
  • the polymer 110 occupies 15-40% of the total cross-sectional area of the composite material 100. Therefore, when the strength of the polymer 110, which occupies a large area of the composite material 100, is increased, the strength of the composite material 100 may be increased.
  • the polymer 110 is melted and used to produce the composite material 100.
  • 19A and 19B are diagrams showing voids inside the polymer 110 before and after the polymer 110 is rapidly cooled at a high pressure.
  • 19A is a view before rapid cooling of the polymer 110 at high pressure
  • FIG. 19B is a view after rapid cooling of the polymer 110 at high pressure.
  • 19A and 19B when the polymer 110 is rapidly cooled at a high pressure, the pore area is reduced from 2698.57 ⁇ m to 173.78 ⁇ m, and the pore area is reduced to 1/15 compared with the initial pore area. This reduction in porosity increases the tensile strength of the polymer 110.
  • the polymer internal void area ratio (%) is preferably 2% or less.
  • Polymer internal void area ratio (%) is measured by cutting the composite material 100, the polymer internal void area ratio (%) is defined as follows.
  • the measurement method of the polymer void area percentage (%) is as follows.
  • the composite material 100 is cut and photographed at x 5000 magnification using an electron microscope. By adding the area of the pores shown in the picture and dividing by the area of the picture, the ratio of the pore area inside the polymer is obtained.
  • the polymer internal pore area ratio (%) can be measured by cutting the area having only the polymer 110 instead of the contact interface formed therein and observing it under a microscope.
  • 20A and 20B are diagrams showing a polymer internal void area ratio (%) before and after rapid cooling of the polymer 110 at high pressure.
  • 20A is a view before rapid cooling of the polymer 110 at high pressure
  • FIG. 20B is a view after rapid cooling of the polymer 110 at high pressure.
  • the sum of the area of the pores is reduced, thereby reducing the polymer pore area ratio (%).
  • 20A and 20B measure two samples, and by rapidly cooling the polymer 110 at high pressure, the polymer void area percentage decreases from 2.71% to 0.11% and from 4.14% to 0.18%. Able to know.
  • [Table 1] shows the adhesion of the polymer 110, the filament 120, the fiber type 130 and the adhesion according to specific embodiments of the present invention.
  • the polymer 110, the filament 120, and the fiber 130 were prepared in an in-line facility by using a polymer adhesive sample.
  • the process of in-line equipment consists of adhesive coating, drying and polymer bonding in the extruder.
  • the adhesion force (N) of the sample was measured by the tensile load when the polymer 110 and the filament 120 or the fiber 130 is separated from each other through a tensile tester.
  • the polymer 110 is a high density polyethylene (HDPE) and the filament 120 is galvanized, 5% silane and 95% deionized water or 5% silane It can be seen that the adhesion is improved when the adhesive treatment with (silane) and 95% ethanol. In addition, it can be seen that the polymer 110 is 90% made of high density polyethylene (HDPE) and 10% is improved adhesion when using the HDPE-g-MAH adhesion promoter.
  • HDPE high density polyethylene
  • the filament 120 is galvanized, 5% silane and 95% deionized water or 5% silane
  • the brass plate and the fiber were subjected to plasma surface modification treatment at room temperature, the molten polymer was infiltrated therebetween, and applied under a constant pressure.
  • the polymer dissolution temperature was 195 to 205 degrees and the plasma surface modification rate was 5 m / min.
  • Table 2 Adhesion results with and without plasma surface modification treatment depending on the type of polymer are listed in Table 2. Referring to [Table 2], after the plasma surface modification treatment, the adhesive strength was increased in both the polymer TPU and the polymer Polyseter. When the polymer was polyester, the adhesive strength was remarkably increased.
  • Table 3 shows the measured values of tensile strength and cutting load according to the adhesive interface void ratio (%) and the adhesive force ratio (%) as specific examples of the present invention.
  • Five samples were prepared by using a composite material composed of brass plated steel cord (filament), aramid (fiber), and TPU (polymer). The manufacturing method was plasma surface modified or chemlock adhesive on the surface of brass plated steel cord and adhesively bonded to the TPU polymer. After a 9-stranded aramid and plasma surface modification treatment, the TPU polymer was adhesively bonded (manufacture of the composite material of FIG. 7). At this time, five kinds of samples having different adhesive strength ratios (%) were changed under different plasma surface modification treatment conditions. Was produced. The bonding temperature of the TPU polymer was 195 to 205 degrees.
  • the results of calculating the adhesive interfacial porosity (%) of the sample through the above-described method for measuring the interfacial porosity (%) are described in Table 3 below. Looking at the following [Table 3], it can be seen that as the adhesive force ratio (%) increases the annual efficiency and cutting load increases. In particular, when the adhesive force ratio (%) is 3%, a very low cutting load is obtained, so that the adhesive force ratio (%) is preferably 5% or more in order to obtain a desired cutting load. In addition, the adhesive force percentage (%) was found to be related to the adhesive interface void percentage (%). Referring to the following [Table 3], it can be seen that as the adhesive interface void ratio (%) is smaller, the adhesive force ratio (%) increases.
  • the adhesive interface void ratio (%) 90% or less.
  • the adhesive interface void ratio (%) can be made small through the above-described plasma surface modification treatment and the adhesive treatment using the adhesive described above. That is, through the above-described plasma surface modification treatment and the above-described adhesion treatment, the adhesive interface void ratio (%) may be formed to 90% or less, thereby increasing the tensile strength and cutting load of the composite material 100. Will be.
  • the following examples are provided to aid the understanding of the present invention, and do not limit the present invention.
  • Table 4 is a table showing the characteristics before and after the rapid cooling of the polymer 110 to a specific embodiment of the present invention.
  • four types of samples were prepared by increasing the pressure of the polymer bond and increasing the cooling rate when the polymer was TPU.
  • Working conditions of the four types of samples are as described in Table 4 below.
  • the composite material 100 of the present invention is the adhesive to the polymer 110 and the filament 120 or the polymer 110 to improve the adhesion between the polymer 110 and the fiber 130 through an adhesive
  • the adhesion may be improved through an adhesion promoter (eg, HDPE-g-MAH additive when the polymer 110 is a high density polyethylene (HDPE)).
  • the filament 120 and the fiber 130 may be subjected to plasma surface modification to improve adhesion.
  • the adhesion force percentage (%) is 5% or more
  • the adhesion interface void percentage (%) is preferably 90% or less.
  • the adhesive force ratio (%) should be 5% or more and the adhesive interface void ratio (%) should be 90% or less to obtain the desired tensile strength and cutting load of the composite material 100.
  • the polymer 110 may be rapidly cooled to a high pressure so that the polymer internal void ratio (%) is 2% or less. Reducing the polymer internal void ratio (%) of the polymer 110 to 2% can improve the tensile strength of the polymer 110, since the polymer 110 occupies a large volume in the composite material 100 It is possible to increase the strength of the composite material (100).
  • the composite material 100 which is rapidly treated at high pressure by an adhesive treatment through an adhesive, using an adhesion promoter, a plasma surface modification treatment, and high pressure may have the following effects.
  • the composite material 100 of the present invention can obtain excellent tensile strength and cutting load by bonding the filament 120 and the fiber 130 to the polymer 110.
  • the polymer 110 and the fiber 130 has a lower self-weight than steel and can produce a light composite material 100 having excellent tensile strength and cutting load, and have low elongation at tensile strength and cutting load. It has the advantage of having similar characteristics. That is, the composite material 100 of the present invention can be light, yet have high strength and high toughness.
  • the polymer 110 is bonded to the filament 120 and the fiber 130 by adhesive treatment with a solution composed of 5% silane and 95% of ions removed, or 5% silane and 95% ethanol.
  • Adhesive bonding, and the polymer 110 and the filament 120 or the polymer 110 and the fiber by adhesively bonding the filament 120 and the fiber 130 to the polymer 110 by the plasma surface modification treatment There is an advantage that can improve the adhesion of the 130.
  • the polymer 110 has an advantage of increasing the tensile strength of the polymer 110 by reducing the polymer internal voids by high pressure and rapid cooling treatment.
  • the composite material 100 of the present invention described above is a process of bonding the adhesive through an adhesive, using an adhesion promoter, plasma surface modifying the filament 120 or the fiber 130, and rapidly cooling the polymer 110 at a high pressure. All of them can be rough.
  • the composite material 100 is not limited thereto, and some processes may be omitted.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

La présente invention concerne un matériau composite polymère qui est léger, mais présente une résistance élevée, une ténacité élevée, et une excellente résistance à l'usure. Le matériau composite polymère présente une structure multicouche dans laquelle un ou plusieurs types d'aciers et de fibres sont implantés dans un polymère et liés à celui-ci. Le matériau composite polymère comprend : le polymère; un filament implanté dans le polymère et lié au polymère; et une fibre implantée dans le polymère et liée au polymère. Un seul parmi le filament et la fibre est implanté dans le polymère et lié au polymère, ou à la fois le filament et la fibre sont simultanément implantés dans le polymère et liés au polymère.
PCT/KR2016/001522 2016-02-05 2016-02-16 Matériau composite polymère WO2017135491A1 (fr)

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EP16813212.4A EP3222775A4 (fr) 2016-02-05 2016-02-16 Matériau composite polymère

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KR1020160014999A KR101680284B1 (ko) 2016-02-05 2016-02-05 폴리머 복합소재

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US4670349A (en) * 1984-12-20 1987-06-02 Mitsui Petrochemical Industries, Ltd. Adhesive resin composition
KR20050026689A (ko) * 2001-10-03 2005-03-15 엔.브이. 베카에르트 에스.에이. 중간 필라멘트가 폴리머로 코팅된 다층 스틸 코드
KR20090009723A (ko) * 2007-07-20 2009-01-23 넥쌍 전기 제어 케이블
KR20110107797A (ko) * 2008-12-16 2011-10-04 엔브이 베카에르트 에스에이 개선된 접착 촉진 코팅부를 가진 코드
KR20120007469A (ko) * 2010-07-14 2012-01-20 마누엘 호드리게스 돌리베이라 에씨아 필류스 에씨아 하이브리드 코드 제조 방법

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JP4064668B2 (ja) * 2001-12-26 2008-03-19 東京製綱株式会社 複合型ワイヤロープ
EP1942224A1 (fr) 2007-01-08 2008-07-09 NV Bekaert SA Câble à bas allongement structurel
DE102011011112A1 (de) * 2011-02-12 2012-08-16 Casar Drahtseilwerk Saar Gmbh Verfahren zur Herstellung einer Litze oder eines Seils

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US4670349A (en) * 1984-12-20 1987-06-02 Mitsui Petrochemical Industries, Ltd. Adhesive resin composition
KR20050026689A (ko) * 2001-10-03 2005-03-15 엔.브이. 베카에르트 에스.에이. 중간 필라멘트가 폴리머로 코팅된 다층 스틸 코드
KR20090009723A (ko) * 2007-07-20 2009-01-23 넥쌍 전기 제어 케이블
KR20110107797A (ko) * 2008-12-16 2011-10-04 엔브이 베카에르트 에스에이 개선된 접착 촉진 코팅부를 가진 코드
KR20120007469A (ko) * 2010-07-14 2012-01-20 마누엘 호드리게스 돌리베이라 에씨아 필류스 에씨아 하이브리드 코드 제조 방법

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KR101680284B1 (ko) 2016-11-29
US20180371691A1 (en) 2018-12-27
EP3222775A1 (fr) 2017-09-27
EP3222775A4 (fr) 2018-08-22

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