WO2019107991A1 - 연속섬유 보강 열가소성 수지 복합재료 및 그 제조방법 - Google Patents
연속섬유 보강 열가소성 수지 복합재료 및 그 제조방법 Download PDFInfo
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- WO2019107991A1 WO2019107991A1 PCT/KR2018/015006 KR2018015006W WO2019107991A1 WO 2019107991 A1 WO2019107991 A1 WO 2019107991A1 KR 2018015006 W KR2018015006 W KR 2018015006W WO 2019107991 A1 WO2019107991 A1 WO 2019107991A1
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- composite material
- thermoplastic resin
- reinforced thermoplastic
- continuous fiber
- nozzle
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- 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
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/047—Reinforcing macromolecular compounds with loose or coherent fibrous material with mixed fibrous material
- C08J5/048—Macromolecular compound to be reinforced also in fibrous form
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- 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
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/205—Means for applying layers
- B29C64/209—Heads; Nozzles
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- 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
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/30—Auxiliary operations or equipment
- B29C64/307—Handling of material to be used in additive manufacturing
- B29C64/321—Feeding
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- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/504—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands
- B29C70/506—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC] using rollers or pressure bands and impregnating by melting a solid material, e.g. sheet, powder, fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
- B29C70/52—Pultrusion, i.e. forming and compressing by continuously pulling through a die
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
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- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
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- 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
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2101/00—Use of unspecified macromolecular compounds as moulding material
- B29K2101/12—Thermoplastic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2307/00—Use of elements other than metals as reinforcement
- B29K2307/04—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2309/00—Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
- B29K2309/08—Glass
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- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
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- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- 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
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- 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
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2300/22—Thermoplastic resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
Definitions
- the present invention relates to a continuous fiber-reinforced thermoplastic resin composite material and a method of manufacturing the same. More particularly, the present invention relates to a continuous fiber-reinforced thermoplastic resin composite material which can be used as a reinforcing material of a thermoplastic resin injection product and a manufacturing method thereof.
- Polymer rods reinforced with continuous fibers have been used in various applications as structural reinforcements. It is used as a reinforcing rod to be inserted into concrete in place of reinforcing bars. Recently, it has been introduced into insert injection process and used as a reinforcing insert to be inserted into injection molded parts, thereby improving the mechanical properties of various injection parts while achieving light weight .
- thermoplastic resin only by introducing into 3D printing equipment, it is possible to produce a structure by laminating continuous rods or rod-shaped composite materials reinforced with continuous fibers by adding continuous fibers in the resin, An attempt has been made to produce a product that implements the product.
- the most conventional method of producing a continuous fiber-reinforced polymer in the form of a rod or a string is a drawing method in which a glass fiber or a carbon fiber is impregnated in a molten resin and then passed through a nozzle by applying a pulling force, To produce bars having various cross-sectional shapes.
- Drawing molding can produce high productivity and excellent quality, but it is a production method suitable for mass production. It requires large and expensive drawing and forming equipment, and mass production must be maintained to ensure economical production cost. Therefore, this process is not suitable for a product group requiring small quantity production of multiple types.
- Korean Patent Laid-Open Publication No. 2016-0054661 discloses a unidirectionally continuous fiber-reinforced thermoplastic composite material in which a reinforcing fiber having a continuous fiber form is impregnated with a thermoplastic resin and then cut into a circular shape and cut to a predetermined length,
- the process of molding a thin film-type thermoplastic composite material into a rod-forming machine by feeding it into a roll-forming machine is problematic in that the film is not curled and is crumbled or wrinkled, but fibers are broken during the process.
- a number of roll forming machines are required, and the inlet and outlet diameters of the roll forming machine must be maintained at a constant ratio, and the temperature of a plurality of roll forming machines must be separately controlled.
- Korean Patent No. 0766954 relates to a fiber reinforced polymer reinforcing bar having a self-impregnated protrusion and a method of manufacturing the fiber reinforced polymer reinforcing bar, and a typical drawing forming process is utilized as a method of manufacturing a fiber reinforced polymer reinforcing bar.
- a continuous round fiber is impregnated with a resin and then a pulling force is applied to the fiber to pass through a nozzle to produce a rod having a circular cross section.
- the second fiber and the third fiber are moved along the outer peripheral surface of the first fiber
- Drawing and molding equipment is large-scale equipment, and large-scale production must be maintained to ensure cost-effective product price. Additional equipment is also an expensive large-scale equipment, which requires a huge initial investment.
- Korean Patent Registration No. 1714772 relates to a 3D stereoscopic manufacturing robot for manufacturing a 3D stereoscopic material by using a material made of a plastic material which can be formed.
- the material used includes a strand, a yarn, a tow, a bundle a bundle, a band, or a tape.
- the present invention does not refer to a method of any molding process such as compaction of an input material, It can not be confirmed whether the quality can be used as a stiffener, such as strength and stiffness, cross-section and surface uniformity.
- R. Matsuzak et al., Scientific Reports (Nature), Vol. 6 (2016) 23058) is a method that can use a continuous fiber reinforced composite material in a 3D printer and increases the strength and rigidity of the product
- it uses a process of instantly impregnating the continuous fiber bundle and resin separately, and it is a method in which the thermoplastic resin supplied by applying heat from the nozzle portion of the 3D printer is melted and instantly impregnated into the continuous fiber supplied individually
- the 3D printer equipment is uneven and the production speed is difficult to increase because the impregnation process is added.
- thermoplastic resin determines the strength and rigidity of the composite material, it is necessary to maintain a high impregnation state by maintaining the high temperature and high pressure for a long time, and a device for making the high temperature and high pressure state inside the 3D printer equipment is mounted , It is difficult to maintain and utilize the 3D printer equipment, increase the unit price, and it is difficult to realize quick productivity and low quality problem.
- thermoplastic resin composite material which can be applied to the production of reinforcing materials of various thermoplastic injection products and to produce fiber-reinforced thermoplastic plastic parts utilizing 3D printing, And to propose a method for manufacturing the material having mechanical properties.
- the present invention provides a continuous fiber reinforced thermoplastic composite material in which a plurality of yarn or tape intermediate members are folded into a rod shape.
- the composite material has a porosity of 1 to 10% by volume.
- P and A are the cross-sectional area and cross-sectional area of the composite material, respectively.
- the tape has a thickness of 0.1 to 1.0 mm and a width of 3 to 30 mm.
- the continuous fiber reinforced thermoplastic resin composite material is characterized in that the yarn or the tape is poured into 2 to 10 yarns.
- the continuous fiber reinforced thermoplastic resin composite material is characterized in that the continuous fiber is glass fiber or carbon fiber.
- a method of manufacturing an image forming apparatus including the steps of: (a) continuously injecting an intermediate member in the form of a plurality of yarns or a tape into a heating unit; (b) heating at least the intermediate material to a temperature equal to or higher than a melting point of the thermoplastic resin included in the intermediate material to melt at least a part of the thermoplastic resin on the surface of the intermediate material; And (c) passing at least two of the molten intermediate materials through a nozzle to form a bar shape.
- the intermediate material has a continuous fiber content of 30 to 60 wt% and a thermoplastic resin content of 40 to 70 wt%.
- the heating in the step (b) is performed at a temperature 20 to 40 ° C higher than the melting point of the thermoplastic resin, thereby providing a method for manufacturing a continuous fiber-reinforced thermoplastic resin composite material.
- the present invention provides a method for manufacturing a continuous fiber-reinforced thermoplastic resin composite material, wherein the nozzle has no cross-sectional shape or at least one irregularity.
- the present invention also provides a method for manufacturing a continuous fiber-reinforced thermoplastic resin composite material, wherein the rod discharged through the nozzle is formed into a spiral shape by rotating the rod.
- the nozzle has a diameter ratio of the inlet end to the outlet end diameter of 1.5 to 5 and a ratio of the length to the outlet end diameter of 2 to 10.
- the present invention also provides a method of manufacturing a continuous fiber reinforced thermoplastic resin composite material.
- the present invention provides a method for manufacturing a continuous fiber-reinforced thermoplastic resin composite material, wherein the nozzle is formed in multiple stages and the diameter is reduced toward the outlet.
- continuous yarns are preliminarily impregnated with a thermoplastic resin, and yarn or tape-like intermediate members are used for yarn-folding, thereby providing a simple yarn without a drawing-forming apparatus or a thermoplastic resin-
- a continuous fiber-reinforced thermoplastic resin composite material capable of realizing high productivity and excellent quality only by a process, and a method of manufacturing the same.
- the method of manufacturing continuous fiber-reinforced thermoplastic resin composite material according to the present invention can have various sizes and cross-sectional shapes by only the amount of the intermediate material to be wound and the shape distortion of the nozzle.
- FIGS. 1 and 2 are a flowchart and a schematic view showing a process for producing a continuous fiber-reinforced thermoplastic composite material according to the present invention
- FIG. 3 is a photograph showing a state in which the intermediate member used in the present invention is put into a heating apparatus according to each mode
- FIG. 4 is a photograph exemplarily showing nozzles having various internal diameters, lengths and cross-sectional shapes in the present invention
- FIG. 5 is a photograph showing various shapes of the continuous fiber-reinforced thermoplastic resin composite material produced according to the present invention.
- FIG. 6 is a schematic view of an inner cross-section of a nozzle according to an embodiment of the present invention.
- FIG. 7 is a view illustrating a shape of a nozzle according to an embodiment of the present invention.
- FIG 9 and 10 are cross-sectional photographs of the intermediate material according to Example 10 of the present invention and cross-sectional photographs of rod-shaped composite materials, respectively.
- the present inventors have repeatedly studied a method of making a continuous fiber-reinforced thermoplastic resin composite material capable of being applied to the production of reinforcing materials of various thermoplastic injection products and making fiber-reinforced thermoplastic plastic parts utilizing 3D printing by a simple method and having excellent mechanical properties
- a yarn or yarn-intermediate material in which continuous fibers are pre-impregnated with a thermoplastic resin it is possible to produce a continuous yarn without any draw-forming equipment or thermoplastic resin impregnation equipment, High productivity and excellent quality can be achieved, leading to the present invention.
- the present invention discloses a continuous fiber reinforced thermoplastic composite material in which a plurality of yarn or tape intermediate members are folded together to form a rod.
- the continuous fiber-reinforced thermoplastic composite material comprises (a) continuously injecting a plurality of yarn or tape-like intermediate members into a heating unit; (b) heating at least the intermediate material to a temperature equal to or higher than a melting point of the thermoplastic resin included in the intermediate material to melt at least a part of the thermoplastic resin on the surface of the intermediate material; And (c) shaping the molten intermediate material into a rod shape by passing at least two of the molten intermediate materials through a nozzle and winding the same.
- FIG. 1 and FIG. 2 are a sequence diagram and a schematic view showing a manufacturing process of the continuous fiber-reinforced thermoplastic composite material according to the present invention, respectively.
- a method for manufacturing a continuous fiber-reinforced thermoplastic composite material includes the steps of: (a) injecting an intermediate member into a heating unit of a heating apparatus (S100) using a heater equipped with a nozzle; (b) melting the intermediate material (S200); And (c) passing the molten intermediate material through the nozzle (S300).
- the intermediate member 200 to be charged into the heating apparatus 100 is a thermoplastic composite resin reinforced with continuous fibers.
- the thermoplastic resin is not particularly limited to a thermoplastic resin, but may be a polypropylene resin, a polyethylene terephthalate resin, a polycarbonate resin, Amide resin and the like can be used, and preferably a polypropylene resin is included. Accordingly, the intermediate member may be advantageous in improving both the cost strength and the shock absorbing performance.
- the polypropylene resin may include polypropylene alone or a resin obtained by copolymerizing polypropylene and other types of monomers, and examples thereof include a polypropylene homopolymer resin, a propylene-ethylene copolymer resin, a propylene-butene copolymer resin, an ethylene- A copolymer resin, and a combination thereof.
- the continuous fiber may be a material commonly used in the art in the production of a fiber reinforced composite material for improving the strength and rigidity of the resin, but may preferably be glass fiber or carbon fiber.
- the continuous fibers constituting the continuous fiber-reinforced thermoplastic resin composite intermediate material 200 are present in a continuous form without being interrupted inside.
- the continuous fibers may be made by a continuous process. Therefore, the intermediate material may be a continuous fiber-reinforced thermoplastic composite intermediate material in which continuous fibers are continuously supplied to the continuous process.
- FIG. 3 is a photograph showing a state in which the intermediate member used in the present invention is put into a heating apparatus according to each mode.
- the intermediate member is in the form of a yarn (Fig. 2 (a)) or a tape (Fig. 2 (b)).
- the yarn means a thermoplastic composite material in the form of a noodle in which continuous fibers are reinforced in the field of the composite material, and a composite material which is generally drawn and sold can be used.
- yang is an intermediate material produced during the production of long fiber composite material (LFT), which is commonly sold in the thermoplastic composite material market, and preferably has a diameter of 1 to 3 mm in the present invention.
- the tape shape is, for example, a sheet-shaped composite material that is slitted.
- a material having a thickness of 0.1 to 1.0 mm and a width of 3 to 30 mm more preferably 0.2 to 0.8 mm and a width of 5 to 25 mm may be used, more preferably a thickness of 0.3 to 0.7 mm and a width of 5 to 20 mm may be used, and most preferably 0.4 to 0.6 mm And a width of 5 to 15 mm may be used. If the width of the tape-like intermediate member is too large, the composite material may be wrinkled during the application to the heating apparatus, or fibers may be broken during the process.
- the drawing-forming equipment and the thermoplastic resin impregnation equipment are not provided separately.
- the yarn or tape may be applied to the heating apparatus at a rate of 2 to 10, preferably 3 to 8, more preferably 3 to 6 at the same time in the diameter of the yarn or the thickness and width of the tape Can be injected.
- the flexural strength tends to decrease and the yarn efficiency may decrease as the amount of yarn (yarn or tape) is increased.
- the reinforced polypropylene rod exhibited a high bending strength of 300 MPa or more at all times in the range of the above amount
- the intermediate material 200 may have a content ratio of 30 to 60% by weight of the continuous fibers and 40 to 70% by weight of the thermoplastic resin. If the content of the continuous fibers is less than a certain range, it may be difficult to achieve the required stiffening effect. If the content is excessive, the viscosity of the resin may increase during molding and nozzle discharging.
- the intermediate member 200 in the form of a yarn or a tape is continuously unwound from a plurality of bobbin creel 300 so that the intermediate member 200 can be fed into the heating unit of the heating apparatus 100 without being tangled with each other, 100).
- the intermediate member 200 charged into the heating unit of the heating apparatus 100 is heated and melted in the heating unit. That is, the intermediate member 200 is heated to a temperature equal to or higher than the melting point of the thermoplastic resin included in the intermediate member 200, thereby melting at least a portion of the thermoplastic resin on the surface of the intermediate member 200.
- the temperature of the heating unit 100 should be set to be higher than the melting point of the thermoplastic resin constituting the intermediate member 200, but it may preferably be 20 to 40 ° C higher than the melting point of the thermoplastic resin.
- the temperature of the heating part 100 can be set at 180 to 220 ° C.
- the thermoplastic resin on the composite material surface may be injected into the nozzle in a state in which the thermoplastic resin is not completely melted to reduce the collapsing performance and deteriorate the mechanical properties, (100) temperature is set too high, the effect of increasing the mechanical properties may not be large compared with the increase of the process cost.
- the heat source of the heating unit 100 is not particularly limited, but a halogen lamp, a hot air fan, a laser heater, or the like can be used as a heat source.
- the intermediate material melted and preliminarily mixed in the heating part 100 passes through the nozzle 400 and is finally re-mixed and molded into a rod shape. That is, an intermediate member, which is passed through the heating unit 100 and at least the thermoplastic resin on the surface is melted, is injected into the nozzle 400 so that the sectional area inside the nozzle becomes smaller than the sectional area of the heating unit.
- the material of the nozzle 400 is not particularly limited.
- the nozzle 400 is made of phosphor bronze material containing 0.05 to 0.5% by weight of phosphorus (P) and has excellent heat resistance and corrosion resistance and excellent abrasion resistance ) May be used.
- the internal composite material a nozzle 400 that is a surface of the nozzle 400 is polished through the average surface roughness (R a) that can be used to precisely finish with less than 1 ⁇ m level, in which case the nozzle 400 It is possible to minimize the damage of the material due to friction in the sliding process between the composite material and the nozzle face.
- the nozzle 400 can be mounted and demounted to the heating apparatus 100, and various diameters, lengths, and cross-sectional shapes can be used, and various outlet diameters can be applied to the intermediate member 200 can be changed in accordance with the amount of the continuous fiber-reinforced thermoplastic resin composite material 500 in the rod shape.
- 4 (d) and 4 (i) show a shape in which the inner end surface of the nozzle gradually narrows from the inlet end toward the outlet end.
- the composite material finally produced according to various shapes of the nozzle 400 may satisfy the following Equation 1 on a sectional basis.
- P and A are the cross-sectional area and cross-sectional area of the composite material, respectively.
- the inner end surface of the nozzle 400 may be gradually narrowed from the inlet end toward the outlet end.
- the outlet end diameter The ratio of the inlet end diameter L2 to the outlet end diameter L1 is 1.5 to 5 and the ratio of the length L3 to the outlet end diameter L1 is 2 to 10 (see FIG. 6).
- a nozzle system capable of improving the productivity due to the load due to the compaction of the composite material when passing through the nozzle 400 and the deterioration of the mechanical properties due to the increase in porosity due to insufficient consolidation Can be considered. That is, in the present invention, the nozzles 400 are formed in multiple stages and the diameters of the nozzles 400 are decreased toward the outlet, so that the compaction time of the composite material can be controlled, thereby improving the mechanical properties 7).
- the continuous fiber-reinforced thermoplastic composite material 500 produced according to the present invention may have a certain level of porosity, that is, a level of 1 to 10% by volume, and preferably a porosity of 1 to 5% by volume. If it is desired to have a porosity of less than 1% by volume, it is necessary to heat to a temperature higher than necessary, which may lead to a decrease in the productivity of the rod-shaped composite material 500 without further strength improvement. If it is intended to have a porosity of more than 10% by volume, the productivity may be improved, but it may be difficult to satisfy the required mechanical properties.
- the continuous fiber-reinforced thermoplastic composite material produced according to the present invention can be produced by using a process in which a yarn or a tape-shaped intermediate material is used to make a yarn using nozzles without using a plurality of roll forming machines having a high defect ratio, And a thermoplastic resin impregnation device, a high productivity and excellent quality can be realized by a simple flashing process.
- the composite material according to the present invention is produced by the process of continuous yarns that are pre-impregnated with a thermoplastic resin in the form of a yarn or a tape in the form of an intermediate material, the productivity of a product requiring a small- And a low-cost bar-type composite material product suitable for various purposes such as a material for reinforcing bars and a material for 3D printers.
- Reinforced thermoplastic resin composite material in the form of a bar was prepared in the same manner as in Example 1, except that the intermediate material was prepared in the form of a tape (thickness: 0.5 mm, width: 12 mm) .
- thermoplastic resin composite material was prepared in the same manner as in Example 2, except that four intermediate materials were put in Example 2.
- thermoplastic resin composite material was prepared in the same manner as in Example 2, except that five intermediate materials were put in Example 2.
- thermoplastic resin composite material in the form of a rod was produced in the same manner as in Example 2, except that 6 intermediate materials were charged in Example 2 (see Fig. 3 (b)).
- a rod-shaped continuous fiber-reinforced thermoplastic resin composite material was prepared in the same manner as in Example 3, except that the heating portion temperature was set at 170 ⁇ in Example 3.
- a rod-like continuous fiber-reinforced thermoplastic resin composite material was prepared in the same manner as in Example 3, except that the heating portion temperature was set to 190 ⁇ in Example 3.
- a rod-shaped continuous fiber-reinforced thermoplastic resin composite material was prepared in the same manner as in Example 3 except that the heating portion temperature was set to 200 ° C in Example 3.
- a rod-shaped continuous fiber-reinforced thermoplastic resin composite material was prepared in the same manner as in Example 3, except that the heating portion temperature was set at 210 ⁇ in Example 3.
- a rod-shaped continuous fiber-reinforced thermoplastic resin composite material was prepared in the same manner as in Example 3, except that the heating portion temperature was set to 220 ⁇ in Example 3.
- the bending strength (see FIG. 8) and the porosity of the rod-shaped continuous fiber-reinforced thermoplastic resin composite material prepared according to Examples 1 to 10 were measured according to the following methods. The results are shown in Table 1 below. Cross-sectional photographs of the intermediate material according to Example 5 and cross-sectional photographs of the rod-shaped composite material are shown in FIGS. 9 and 10, respectively.
- the bending strength was measured in accordance with ASTM D4474.
- the maximum load point was measured by applying a three-point bending load to the rod-shaped continuous fiber-reinforced thermoplastic resin composite material as shown in FIG.
- the porosity was measured in accordance with ASTM D2734 test standard and measured and calculated according to the following equation (2). And is calculated by the following equation (2) by comparing the theoretical abnormal density of the composite material with the experimental density measured experimentally. The porosity was calculated from the average value after three or more measurements using different samples.
- Example 1 yarn 6 180 415 ⁇ 17 2.5 ⁇ 0.1
- Example 2 tape 3 180 376 ⁇ 39 3.1 ⁇ 0.7
- Example 3 tape 4 180 362 ⁇ 19 4.9 ⁇ 0.3
- Example 4 tape 5 180 337 ⁇ 38 4.6 ⁇ 0.6
- Example 5 tape 6 180 312 ⁇ 39 4.3 ⁇ 0.5
- Example 7 tape 4 190 358 ⁇ 34 4.5 ⁇ 0.7
- Example 8 tape 4 200 373 ⁇ 40 3.1 ⁇ 0.1
- Example 9 tape 4 210 365 ⁇ 42 4.8 ⁇ 0.7
- Example 10 4 220 386 ⁇ 24 3.3 ⁇ 0.1
- FIG. 9 and FIG. 10 in the case of a composite material made of a yarn-shaped intermediate material having a diameter of 1.2 mm or 3 to 6 intermediate materials having a thickness of 0.5 mm and a width of 12 mm, %, And exhibits excellent mechanical properties with a flexural strength of at least 300 MPa.
- the temperature of the heating part is close to the melting point of the thermoplastic resin (see example 6)
- the bending strength is relatively lowered
- the temperature of the heating part is higher than a certain level, It can be confirmed that a preferable heating temperature range exists in the piling process according to the invention.
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Abstract
Description
구분 | 중간재형태 | 개수(개) | 가열부 온도(℃) | 굴곡강도(MPa) | 기공률(부피%) |
실시예 1 | 얀 | 6 | 180 | 415±17 | 2.5±0.1 |
실시예 2 | 테이프 | 3 | 180 | 376±39 | 3.1±0.7 |
실시예 3 | 테이프 | 4 | 180 | 362±19 | 4.9±0.3 |
실시예 4 | 테이프 | 5 | 180 | 337±38 | 4.6±0.6 |
실시예 5 | 테이프 | 6 | 180 | 312±39 | 4.3±0.5 |
실시예 6 | 테이프 | 4 | 170 | 278±23 | 5.4±0.9 |
실시예 7 | 테이프 | 4 | 190 | 358±34 | 4.5±0.7 |
실시예 8 | 테이프 | 4 | 200 | 373±40 | 3.1±0.1 |
실시예 9 | 테이프 | 4 | 210 | 365±42 | 4.8±0.7 |
실시예 10 | 테이프 | 4 | 220 | 386±24 | 3.3±0.1 |
Claims (13)
- 복수의 얀(yarn) 또는 테이프(tape) 중간재가 합사되어 봉 형태로 형성된 연속섬유 보강 열가소성 복합재료.
- 제1항에 있어서,상기 복합재료는 기공률이 1~10부피%인 것을 특징으로 하는 연속섬유 보강 열가소성 수지 복합재료.
- 제1항에 있어서,상기 복합재료는 상기 복합재료의 단면 기준으로 하기 수학식 1을 만족시키는 것을 특징으로 하는 연속섬유 보강 열가소성 수지 복합재료:[수학식 1]0.2mm-1 ≤ P/A ≤ 5mm-1수학식 1에서, P 및 A는 각각 상기 복합재료의 단면 둘레 길이 및 단면 면적이다.
- 제1항에 있어서,상기 테이프는 0.1~1.0mm의 두께 및 3~30mm의 폭을 가진 것을 특징으로 하는 연속섬유 보강 열가소성 수지 복합재료.
- 제1항에 있어서,상기 합사는 상기 얀 또는 테이프 2~10개가 투입되어 합사된 것을 특징으로 하는 연속섬유 보강 열가소성 수지 복합재료.
- 제1항에 있어서,상기 연속섬유는 유리섬유 또는 탄소섬유인 것을 특징으로 하는 연속섬유 보강 열가소성 수지 복합재료.
- (a) 복수의 얀(yarn) 또는 테이프(tape) 형태의 중간재를 가열부에 연속적으로 투입하는 단계;(b) 상기 중간재를 상기 중간재에 포함된 열가소성 수지의 녹는점 이상의 온도로 가열하여 적어도 상기 중간재 표면의 열가소성 수지 일부를 용융시키는 단계; 및(c) 상기 용융된 중간재 2개 이상을 노즐에 통과시켜 합사시켜 봉 형태로 성형하는 단계;를 포함하는 연속섬유 보강 열가소성 수지 복합재료 제조방법.
- 제7항에 있어서,상기 중간재는 상기 연속섬유 함량이 30~60중량% 및 상기 열가소성 수지 함량이 40~70중량%인 것을 특징으로 하는 연속섬유 보강 열가소성 수지 복합재료 제조방법.
- 제7항에 있어서,상기 (b) 단계에서의 가열은 상기 열가소성 수지의 녹는점보다 20~40℃ 높은 온도로 수행되는 것을 특징으로 하는 연속섬유 보강 열가소성 수지 복합재료 제조방법.
- 제7항에 있어서,상기 노즐은 단면 형상이 굴곡이 없거나 1 이상의 요철이 형성된 것을 특징으로 하는 연속섬유 보강 열가소성 수지 복합재료 제조방법.
- 제4항에 있어서,상기 노즐을 통해 토출되는 상기 봉을 회전시켜 나선 형상으로 형성시키는 것을 특징으로 하는 연속섬유 보강 열가소성 수지 복합재료 제조방법.
- 제4항에 있어서,상기 노즐은 출구 단부 직경에 대한 입구 단부의 직경비가 1.5~5 및 출구 단부 직경에 대한 길이의 비가 2~10인 것을 특징으로 하는 연속섬유 보강 열가소성 수지 복합재료 제조방법.
- 제4항에 있어서,상기 노즐은 다단 형성되고 출구 쪽으로 직경이 감소하는 것을 특징으로 하는 연속섬유 보강 열가소성 수지 복합재료 제조방법.
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CN201880076639.4A CN111417675A (zh) | 2017-11-29 | 2018-11-29 | 连续纤维增强热塑性树脂复合材料及其制造方法 |
US16/768,139 US20210362406A1 (en) | 2017-11-29 | 2018-11-29 | Continuous Fiber Reinforced Thermoplastic Resin Composite Material and Method for Producing Same |
JP2020527101A JP7340521B2 (ja) | 2017-11-29 | 2018-11-29 | 連続繊維補強熱可塑性樹脂複合材料及びその製造方法 |
US18/133,663 US20230241837A1 (en) | 2017-11-29 | 2023-04-12 | Continuous Fiber Reinforced Thermoplastic Resin Composite Material and Method for Producing Same |
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KR1020170161580A KR102334459B1 (ko) | 2017-11-29 | 2017-11-29 | 연속섬유 보강 열가소성 수지 복합재료 및 그 제조방법 |
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US18/133,663 Division US20230241837A1 (en) | 2017-11-29 | 2023-04-12 | Continuous Fiber Reinforced Thermoplastic Resin Composite Material and Method for Producing Same |
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WO2021127329A1 (en) * | 2019-12-20 | 2021-06-24 | Universal Fibers, Inc. | Multifilament feedstocks for fused deposition modeling |
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US11981069B2 (en) * | 2013-03-22 | 2024-05-14 | Markforged, Inc. | Three dimensional printing of composite reinforced structures |
US9579851B2 (en) | 2013-03-22 | 2017-02-28 | Markforged, Inc. | Apparatus for fiber reinforced additive manufacturing |
EP3725497A1 (en) | 2013-03-22 | 2020-10-21 | Mark, Gregory Thomas | Three-dimensional printer |
US9694544B2 (en) | 2013-03-22 | 2017-07-04 | Markforged, Inc. | Methods for fiber reinforced additive manufacturing |
US9126365B1 (en) | 2013-03-22 | 2015-09-08 | Markforged, Inc. | Methods for composite filament fabrication in three dimensional printing |
WO2023186656A1 (en) | 2022-03-28 | 2023-10-05 | Signify Holding B.V. | A method for printing a 3d object using fiber bundles |
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- 2017-11-29 KR KR1020170161580A patent/KR102334459B1/ko active IP Right Grant
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- 2018-11-29 CN CN201880076639.4A patent/CN111417675A/zh active Pending
- 2018-11-29 US US16/768,139 patent/US20210362406A1/en not_active Abandoned
- 2018-11-29 JP JP2020527101A patent/JP7340521B2/ja active Active
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US20210362406A1 (en) | 2021-11-25 |
JP7340521B2 (ja) | 2023-09-07 |
US20230241837A1 (en) | 2023-08-03 |
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