WO2020166717A1 - Matériau de base fibreux rempli de résine, matériau composite renforcé par des fibres et procédé de production associé - Google Patents

Matériau de base fibreux rempli de résine, matériau composite renforcé par des fibres et procédé de production associé Download PDF

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Publication number
WO2020166717A1
WO2020166717A1 PCT/JP2020/005887 JP2020005887W WO2020166717A1 WO 2020166717 A1 WO2020166717 A1 WO 2020166717A1 JP 2020005887 W JP2020005887 W JP 2020005887W WO 2020166717 A1 WO2020166717 A1 WO 2020166717A1
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WIPO (PCT)
Prior art keywords
base material
fiber base
resin
fiber
mass
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PCT/JP2020/005887
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English (en)
Japanese (ja)
Inventor
成相 廣瀬
明子 平林
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第一工業製薬株式会社
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Application filed by 第一工業製薬株式会社 filed Critical 第一工業製薬株式会社
Priority to JP2020572351A priority Critical patent/JPWO2020166717A1/ja
Priority to CN202080013615.1A priority patent/CN113412189A/zh
Priority to KR1020217024490A priority patent/KR20210126574A/ko
Publication of WO2020166717A1 publication Critical patent/WO2020166717A1/fr

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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
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/18—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length in the form of a mat, e.g. sheet moulding compound [SMC]
    • 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
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10—Coating or impregnating independently of the moulding or shaping step
    • B29B15/12—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B29B15/122—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
    • B29B15/125—Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex by dipping
    • 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
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • 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
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • B29C70/22—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in at least two directions forming a two dimensional structure
    • 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
    • B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • 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
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete 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
    • 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
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/0854—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns in the form of a non-woven mat
    • B29K2105/0863—SMC, i.e. sheet moulding compound
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/0872—Prepregs

Definitions

  • the present disclosure relates to a resin-filled fiber base material, a fiber-reinforced composite material, and a manufacturing method thereof.
  • thermosetting resin such as an epoxy resin has been mainly used as the matrix resin of the fiber-reinforced composite material (see Patent Document 1).
  • thermosetting resin when used as the matrix resin, since a chemical reaction (curing reaction) of the thermosetting resin is involved during the molding of the fiber-reinforced composite material, it takes a long time to cure and the time required for molding becomes long, There was a problem that productivity was low. Further, there is a problem that it is not easy to reprocess the intermediate product of the fiber-reinforced composite material using the thermosetting resin as the matrix resin by changing the shape by pressing or the like.
  • thermoplastic resin does not involve a chemical reaction (curing reaction) at the time of molding a fiber-reinforced composite material, so that the time required for molding can be shortened. Since it can be processed into an arbitrary shape by laminating and heating under pressure, and it can be easily processed into a molded article of another shape by melting, thermoplastic resin has begun to be used as the matrix resin of the fiber-reinforced composite material. There is.
  • thermoplastic resin when used as a matrix resin, the affinity for fibers is low, and the strength of the fiber-reinforced composite material is low. Therefore, a sizing agent for improving the affinity between the thermoplastic resin and the fibers on the fiber surface.
  • a technique for treating a sizing agent has been proposed (Patent Documents 2 to 4).
  • the reinforcing fiber is cut into about 10 mm or less, mixed with thermoplastic resin pellets as short fibers, extruded using an extruder, and molded in a mold.
  • the method is generally used.
  • the reinforcing fibers are oriented shorter and randomly in the extruder, so that the strength and elastic modulus of the fibers cannot be efficiently utilized in the fiber-reinforced composite material.
  • the amount of voids inside the fiber-reinforced composite material is one of the factors that affect the performance of the fiber-reinforced composite material other than the affinity between the matrix resin and the fiber. Since the physical properties such as tensile strength can be enhanced as the amount of voids decreases, it is desirable to reduce the amount of voids.
  • the form of the reinforcing fiber used in the fiber-reinforced composite material is a yarn bundle formed by bundling thousands to tens of thousands of single yarns having a diameter of about 5 to 10 ⁇ m.
  • thermoplastic resin since the melt viscosity is higher than the viscosity of the thermosetting resin before curing, it is difficult to impregnate the resin into the gaps between single yarns or yarn bundles, especially as a reinforced fiber. It was difficult to produce a void-free fiber-reinforced composite material when using a woven fabric or a non-woven fabric-like base material of continuous fiber bundles.
  • Patent Document 1 is a urethane having a hydroxyl group obtained from an epoxy resin having a viscosity at 50° C. of more than 1,000 poise and not more than 20,000 poise, a polyol having an oxyalkylene unit and a polyisocyanate. It is an invention relating to forming a sizing agent from a compound and treating the carbon fiber with the sizing agent, and discloses a carbon fiber in which the amount of the sizing agent attached is 0.1 to 10% by weight in terms of solid content. ..
  • Patent Documents 2, 3 and 4 are techniques for improving the affinity between the thermoplastic resin as the matrix resin and the fiber by adding the modified polyolefin as the sizing agent to the continuous fiber bundle.
  • the amount of the sizing agent applied is 1 to 10% by mass with respect to the fiber, and the amount is not such that the gap between the single yarns can be completely filled and filled.
  • the modified polyolefin is thermally cured by the drying treatment, it cannot be applied to a fiber base material for a continuous fiber reinforced composite material using a thermoplastic resin as a matrix.
  • thermoplastic resins such as ease of molding over thermosetting resins
  • fiber-reinforced composite materials using thermoplastic resins as matrix resins as a means for reducing the weight of automobiles and the like. ing.
  • the present disclosure aims to prevent the occurrence of voids and enhance mechanical properties such as strength and elastic modulus in a fiber-reinforced composite material in which a thermoplastic resin is used as a matrix resin and molded using reinforcing fibers.
  • the purpose is to improve the fixing force between the reinforcing fiber and the matrix resin of the thermoplastic resin and increase the strength of the fiber-reinforced composite material without using a sizing agent or a sizing agent.
  • the present disclosure as a means for solving the above problems is constituted by filling a space between fibers of a fiber base material with a thermoplastic polyurethane, and an application amount of the thermoplastic polyurethane to the fiber base material is a solid.
  • the resin-filled fiber base material may be 25 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the fiber base material in terms of minutes.
  • the amount of the thermoplastic polyurethane applied to the fiber base material is 25 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the fiber base material in terms of solid content. It may be a characteristic resin-filled fiber base material.
  • a cross-linking agent may be added to the thermoplastic polyurethane, which may be a resin-filled fiber base material.
  • the amount of the crosslinking agent added is 0.5 parts by mass or more and 10 parts by mass or less in terms of solid content based on 100 parts by mass of the fiber base material. It may be a fiber base material.
  • the cross-linking agent may be at least one of an oxazoline group-containing compound and a carbodiimide group-containing compound, and may be a resin-filled fiber base material.
  • the fiber base material has a sheet shape or a yarn bundle shape, and the resin-filled fiber base material has a sheet shape or a string shape. Good.
  • the diameter of the thermoplastic polyurethane particles may be 0.01 ⁇ m or more and 0.2 ⁇ m or less, and the resin-filled fiber base material may be used.
  • a fiber-reinforced composite material may be formed by laminating the above resin-filled fiber base material.
  • a fiber-reinforced composite material molded article characterized by being molded from the above fiber-reinforced composite material may be used.
  • thermoplastic polyurethane particles are dispersed in an aqueous medium
  • thermoplastic polyurethane particles are dispersed in an aqueous medium
  • the aqueous medium is removed by a drying treatment to form a space between the fibers of the fiber substrate.
  • a method for producing a resin-filled fiber base material comprising: filling a thermoplastic polyurethane, and imparting the thermoplastic polyurethane to 25 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the fiber base material and molding. May be.
  • a method for producing a resin-filled fiber base material may be characterized in that a crosslinking agent is added to the thermoplastic polyurethane.
  • the addition amount of the crosslinking agent is 0.5 parts by mass or more and 10 parts by mass or less in terms of solid content based on 100 parts by mass of the fiber base material.
  • a method for producing a resin-filled fiber base material may be used.
  • the fiber base material is a sheet shape or a yarn bundle shape
  • the resin-filled fiber base material is a sheet shape or a string shape.
  • a method of manufacturing the base material may be used.
  • the resin-filled fiber base material formed by the method for producing a resin-filled fiber base material described above is laminated, pressed and heated, and integrally formed. Good.
  • the fiber-reinforced composite material formed by the above-described method for producing a fiber-reinforced composite material is singly laminated or aligned, heated under pressure and simultaneously formed into a predetermined shape, It may be a method of manufacturing a molded product.
  • the space between the fibers of the fiber base material is configured to be filled with the thermoplastic polyurethane, it becomes possible to fill the synthetic resin between the fibers without a gap, and Prevents the occurrence of voids in the fiber-reinforced composite material that uses the thermoplastic resin as a matrix resin for molding, and strengthens the fixation between the matrix resin and the fiber base material, and improves the mechanical properties such as strength and rigidity of the fiber-reinforced composite material. It has become possible to raise it.
  • thermoplastic polyurethane since a cross-linking agent is added to the thermoplastic polyurethane, it is possible to firmly hold the synthetic resin filled between the fibers, so that the thermoplastic resin molded using the reinforcing fibers is used as the matrix resin and is reinforced with fibers. Voids can be further prevented in the composite material, the matrix resin and the fiber base material are more firmly fixed, and the mechanical properties such as strength and rigidity of the fiber reinforced composite material can be further enhanced.
  • thermoplastic polyurethane filled in the spaces between the fibers of the fiber base material and the thermoplastic polyurethane of the matrix resin laminated on the outer surface of the fiber base material firmly adhere to each other, a sizing agent or a sizing agent is used. Even without it, the fixing force between the reinforcing fiber and the matrix resin of the thermoplastic resin can be improved, and the strength of the fiber-reinforced composite material can be increased.
  • this fiber-reinforced composite material uses a thermoplastic resin as a matrix resin, it becomes easy to reheat and re-mold it into a fiber-reinforced composite material having a desired shape.
  • thermoplastic resin does not involve a chemical reaction
  • the resin can be impregnated between the fibers in a short time, so that the molding cycle of the fiber-reinforced composite material can be shortened and the productivity can be reduced to reduce the cost. ..
  • the resin-filled fiber substrate of the present disclosure is configured by filling the spaces between the fibers of the fiber substrate with thermoplastic polyurethane, and the amount of the thermoplastic polyurethane applied to the fiber substrate is 100 parts by mass of the fiber substrate. It is a resin-filled fiber base material of 25 parts by mass or more and 100 parts by mass or less.
  • between the fibers means between the single yarns and between the yarn bundles in which the single yarns are bundled.
  • the fiber-reinforced composite material of the present disclosure is a fiber-reinforced composite material formed by laminating the resin-filled fiber base material of the present disclosure.
  • the fiber-reinforced composite material molded product of the present disclosure is a molded product molded from one or more fiber-reinforced composite materials of the present disclosure into a predetermined shape.
  • the fiber base material is a skeleton portion of a fiber reinforced composite material formed by using fibers for reinforcing synthetic resin, and the fibers and the fiber base material are for reinforcing a matrix resin composed of a thermoplastic resin. ..
  • the shape of the fiber base material is not particularly limited, but may be a sheet shape or a yarn bundle shape.
  • the form of the sheet-shaped fibrous base material is not limited to this, but may be a knitted product obtained by knitting a single yarn or a bundle of plural single yarns in a bundle, a single yarn or a woven fabric of the yarn bundle, and a single yarn. Examples thereof include non-woven bonded or entangled non-woven fabrics, single yarns or yarn bundles aligned in one direction, interdigital products, paper-like products, and the like.
  • the form of the fiber base material in the form of a yarn bundle is not limited to this, but a plurality of single yarns are knitted, or a yarn bundle formed into a bundle without knitting, a plurality of yarn bundles are knitted, or knitted. For example, a bundled product may be used.
  • the fiber base material In the case of a knitted fabric, a woven fabric, a fiber bundle in a state of being aligned in one direction, or a fiber base material in one direction, it is preferable to use continuous fibers from one end to the other end of the fiber base material. It is preferable to use a fiber having a continuous length or more from one end to the other end. That is, it is preferable to use continuous long fibers in the portion for reinforcing the fiber-reinforced composite material. With such a structure, the strength of the fiber-reinforced composite material can be increased. Further, the thickness of the fiber base material is not particularly limited as long as it is equal to or less than the fiber reinforced composite material.
  • the fiber as the reinforcing material of the thermoplastic resin is not particularly limited, but carbon fiber, aramid fiber, glass fiber, vinylon fiber, PBO fiber, etc. can be used. These fibers may be used alone or in combination of two or more.
  • the diameter of the fiber is not particularly limited, a fiber having a diameter of 5 to 10 ⁇ m can be used.
  • the yarn bundle in which the single yarns are bundled is not particularly limited, but a bundle of about 1,000 to 50,000 single yarns can be used.
  • thermoplastic polyurethane The space between the fibers of the fiber base material is filled with thermoplastic polyurethane, and the outer surface of the fiber base material is laminated with thermoplastic polyurethane to form a resin-filled fiber base material.
  • thermoplastic polyurethane is for filling the spaces between the fibers of the fiber base material to prevent generation of voids in the fiber reinforced composite material, and for increasing the stress against displacement of the fiber reinforced composite material. Is.
  • the reason why the thermoplastic polyurethane is used as the thermoplastic resin that fills the spaces between the fibers of the fiber base material is that it has good film-forming properties that can connect the single yarns in a dry state.
  • the thermoplastic resin with which the space between the fibers is filled is preferably as high in heat resistance as possible. Furthermore, since the fiber-reinforced composite material is laminated in one layer or a plurality of layers to be reformed into another shape, it is preferable that it has thermoplasticity even after the thermoplastic resin is dried or cured.
  • thermoplastic polyurethane is used as the thermoplastic resin. Is preferable since it is easy to remold a flat fiber-shaped fiber-reinforced composite material into a product having a curved surface or the like, which has sufficient thermoplasticity even after being dried or cured.
  • the form of filling the space between the fibers of the fiber base material with the thermoplastic polyurethane is not particularly limited, but in order to surely and uniformly fill the space between the fibers, the particles of the thermoplastic polyurethane are mixed with an aqueous medium. It is preferably in the form of an aqueous resin dispersion dispersed therein.
  • the average particle size of the thermoplastic polyurethane particles is not particularly limited, but may be set to about 0.01 to 1 ⁇ m in order to uniformly fill the spaces between the fibers, but the space between the fibers of the fiber base material may be shortened in a short time. In order to fill and evenly fill, 1/10 or less of the fiber diameter is preferable. Specifically, since the diameter of the fiber is usually 5 to 10 ⁇ m, it is preferably 0.5 ⁇ m or less, more preferably 0.1 ⁇ m or less, still more preferably 0.03 ⁇ m or less.
  • the average particle diameter of the thermoplastic polyurethane particles is preferably 0.01 ⁇ m or more and 0.2 ⁇ m or less.
  • the average particle diameter of the thermoplastic polyurethane particles means the 50% particle diameter (D50) measured by the laser diffraction light scattering method.
  • the concentration of non-volatile components in the water-based resin dispersion in which thermoplastic polyurethane particles are dispersed in water is not particularly limited, but the thermoplastic resin easily spreads into the space between single yarns and completely fills the space between single yarns. Therefore, the viscosity is preferably low, while the concentration is preferably high. Therefore, the mass ratio of the particles of the thermoplastic resin in the aqueous resin dispersion is preferably 20 to 40% by mass, more preferably 25 to 36% by mass. % Is preferred.
  • the polyol is not particularly limited, and a polyether type, a polyester type, a polycarbonate type, or the like is used.
  • the polyether type is used. preferable.
  • the amount of the thermoplastic polyurethane applied to the fiber base material is preferably an amount capable of filling the spaces between the fibers of the fiber base material more, and more preferably, the amount more than completely filling the spaces between the fibers of the fiber base material. preferable.
  • thermoplastic polyurethane can completely fill the space between the fibers of the fiber base material by giving a volume of 10.2% to the volume of the fiber base material, that is, the fiber base material. Therefore, the amount of the thermoplastic polyurethane filled in the space between the fibers applied to the fiber base material is 10% or more in volume conversion with respect to the volume of the fiber base material, depending on the material of the fiber base material. You can
  • the amount of thermoplastic polyurethane applied to the fiber base material is a synthetic resin having a volume not less than that required to fill the space between the single yarns. Is preferably applied to the fiber base material.
  • the applied amount of the thermoplastic polyurethane to the fiber base material is more preferably 11% to 30%, and even more preferably 11% to 20%, based on the volume of the fiber base material.
  • the method of filling the space between the fibers of the thermoplastic polyurethane is not particularly limited, using a water-based resin dispersion prepared by dispersing particles of the thermoplastic polyurethane in an aqueous medium, a known spray method, It is possible to use a method such as a dipping method or a roller impregnation method that can uniformly apply a required amount.
  • a drying treatment is performed to remove components other than the aqueous medium and the thermoplastic polyurethane in the aqueous resin dispersion.
  • a drying method a method of contacting with hot air or a drying roller, a commonly used drying method such as infrared heating, sunlight, or other heating can be adopted.
  • thermoplastic polyurethane By impregnating the fiber base material with the water-based resin dispersion in which the particles of the thermoplastic polyurethane are dispersed in the water-based medium, the thermoplastic polyurethane easily spreads between the single yarns and between the yarn bundles, and between the fibers.
  • the space can be completely filled with the thermoplastic polyurethane, the generation of voids can be prevented, and a fiber-reinforced composite material with higher mechanical properties can be realized.
  • thermoplastic polyurethane is a base material of the fiber reinforced composite material
  • thermoplastic resin used as the matrix resin is the same thermoplastic polyurethane as the thermoplastic resin filled in the spaces between the fibers.
  • the thermoplastic polyurethane as the matrix resin is laminated on the entire outer surface of the fiber base material, but may be laminated on only a part of the outer surface of the fiber base material.
  • thermoplastic polyurethane laminated on the outer surface of the fiber base material is, for example, when the fiber base material is in the form of a sheet, both the upper and lower surfaces of the sheet-like fiber base material and the entire surface or a part of one of the upper and lower surfaces. It is also possible to have a structure in which only one layer is laminated. Then, the matrix resin has a three-layer structure in which it is arranged on both upper and lower surfaces of one resin-filled fiber base material, and a two-layer structure in which one of the upper surface and the lower surface of one resin-filled fiber base material is arranged. And so on. When the fiber base material is in the form of a yarn bundle, the fiber base material in the form of a yarn bundle may be laminated on the entire side surface or only a part thereof.
  • thermoplastic polyurethane is used as the matrix resin because it has good film-forming properties that can connect yarn bundles or fiber substrates in a dry state. Further, the higher the heat resistance of the matrix resin is, the more preferable, and the thermoplastic polyurethane having excellent heat resistance is preferable. Furthermore, since the fiber reinforced composite material is laminated in one layer or a plurality of layers to be reformed into another shape, it is preferable that it has thermoplasticity, and has sufficient thermoplasticity even after being dried or cured to have a flat plate shape or the like. This is because it is easy to remold the fiber-reinforced composite material of (1) into a product having a curved surface, which is preferable.
  • an aqueous resin in which particles of the thermoplastic polyurethane are dispersed in an aqueous medium is used. It is preferably in the form of a dispersion.
  • the diameter of the particles of thermoplastic polyurethane as the matrix resin, the concentration of non-volatile components of the water-based resin dispersion prepared by dispersing the particles of thermoplastic polyurethane in water, and the polyol are not particularly limited, but the spaces between the fibers are filled. It can be the same as the thermoplastic polyurethane.
  • the method for laminating thermoplastic polyurethane on the fiber base material as a matrix resin is not particularly limited, and filling of spaces between fibers of thermoplastic polyurethane and It is preferable to carry out at the same time. By carrying out at the same time, the production of the fiber-reinforced composite material can be facilitated. When it is carried out simultaneously, it can be carried out by a method of filling the space between the fibers of the fiber base material with the above-mentioned thermoplastic polyurethane.
  • the step of laminating the thermoplastic polyurethane as a matrix resin on the fiber base material is performed separately from the step of filling the space between the fibers of the fiber base material of the thermoplastic polyurethane, and the thermoplastic polyurethane is laminated on the fiber base material independently.
  • a film-shaped thermoplastic polyurethane serving as a matrix resin is laminated on a fiber substrate filled with thermoplastic polyurethane, and the matrix resin is heated under pressure to melt the matrix resin, It can be manufactured by bonding a fiber base material and a matrix resin.
  • the fiber-reinforced composite material is formed by laminating a plurality of fiber base materials in which spaces between the fibers are filled with thermoplastic polyurethane and a matrix resin, in other words, by laminating a resin-filled fiber base material to form a fiber base material. Is sandwiched between or covered with a matrix resin.
  • the form of lamination is not particularly limited, and when the resin-filled fiber base material is in the form of a sheet, a resin-filled fiber base material having a three-layer structure in which a matrix resin is arranged on both upper and lower surfaces of one fiber base material is laminated. It is possible to adopt a structured structure, a structure in which a plurality of fiber base materials and a matrix resin are alternately laminated, or the like.
  • a matrix resin is arranged on the outer surface of one fiber base material, and a two-layer structure in which the fiber base material and the matrix resin are laminated, and one fiber base material
  • One or more resin-filled fiber base materials may be arranged on the outer side surface of the material on the outer side of the matrix resin, and the matrix resin may be arranged on the outer side surface of the resin-filled fiber base material to form a laminated structure.
  • laminating the fiber base material and the matrix resin also includes covering the fiber base material with the matrix resin, and laminating the string-shaped resin-filled fiber base material includes two or more string-shaped resins. Bundling the filled fiber substrates is also included.
  • the amount of thermoplastic polyurethane applied to the fiber base material is preferably 25 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the fiber base material in terms of solid content.
  • the amount of the thermoplastic polyurethane applied to the fiber base material is preferably 25 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the fiber base material in terms of solid content.
  • the amount of the thermoplastic polyurethane applied to the fiber base material is more preferably 40 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the fiber base material in terms of solid content.
  • the content of the fiber in the fiber-reinforced composite material and the content of the thermoplastic polyurethane are not particularly limited, and may be selected depending on the type of fiber, the form of the fiber base material, etc. in order to produce a predetermined fiber-reinforced composite material. I can.
  • a crosslinking agent may be added to the thermoplastic polyurethane.
  • the cross-linking agent cross-links the thermoplastic polyurethane molecules filled in the spaces between the fibers, the thermoplastic polyurethane molecules as the matrix, and the thermoplastic polyurethane molecules filled in the spaces between the fibers and the thermoplastic polyurethane molecules as the matrix.
  • the purpose of this is to prevent the thermoplastic polyurethane from flowing out from the space between the fibers and to securely fix the matrix resin to the fiber base material. Therefore, the cross-linking agent is for increasing the stress against the displacement of the fiber-reinforced composite material.
  • a cross-linking agent having a self-crosslinking property and a compound having a plurality of functional groups that react with a carboxy group in the molecule can be used.
  • Specific examples include an oxazoline group-containing compound, a carbodiimide group-containing compound, an isocyanate group-containing compound, an epoxy group-containing compound, a melamine compound, a urea compound, a zirconium salt compound, a silane coupling agent, and the like. You may mix and use thing.
  • oxazoline group-containing compounds, carbodiimide group-containing compounds, isocyanate group-containing compounds and epoxy group-containing compounds are preferable, and oxazoline group-containing compounds and carbodiimide group-containing compounds are more preferable. That is, it is preferable that the crosslinking agent contains at least one of an oxazoline group-containing compound and a carbodiimide group-containing compound.
  • the oxazoline group-containing compound is not particularly limited as long as it has at least two or more oxazoline groups in the molecule.
  • 2,2'-bis(2-oxazoline), 2,2'-ethylene-bis(4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline) examples thereof include compounds having an oxazoline group such as bis(2-oxazolinylcyclohexane)sulfide, and polymers containing an oxazoline group. These compounds may be used alone or in combination of two or more. Among these, a compound having an oxazoline group is preferable from the viewpoint of easy handling.
  • the carbodiimide group-containing compound is not particularly limited as long as it has at least two carbodiimide groups in the molecule.
  • Compounds having a carbodiimide group such as p-phenylene-bis(2,6-xylylcarbodiimide), tetramethylene-bis(t-butylcarbodiimide), cyclohexane-1,4-bis(methylene-t-butylcarbodiimide)
  • polycarbodiimide which is a polymer having a carbodiimide group. These may be used alone or in combination of two or more. Among these, polycarbodiimide is preferable because it is easy to handle.
  • Examples of commercially available products of polycarbodiimide include carbodilite series manufactured by Nisshinbo. Specific products include, for example, water-soluble type “SV-02”, “V-02”, “V-02-L2", “V-04”, emulsion type “E-01”, “E”. -02”, organic solution type “V-01”, “V-03”, “V-07”, “V09”, solventless type “V-05” and the like.
  • the isocyanate group-containing compound is not particularly limited as long as it has at least two isocyanate groups in the molecule.
  • the modified product is obtained by modifying the diisocyanate of the polyfunctional isocyanate compound by a known method, for example, allophanate group, buret group, carbodiimide group, uretonimine group, uretdione group, Examples thereof include polyfunctional isocyanate compounds having an isocyanurate group and the like, and further adduct type polyfunctional isocyanate compounds modified with a polyfunctional alcohol such as trimethylolpropane.
  • the isocyanate group-containing compound may contain monoisocyanate in the range of 20% by mass or less. In addition, these compounds may be used alone or in combination of two or more.
  • the isocyanate group-containing compound can be usually obtained by reacting a polyfunctional isocyanate compound with a monovalent or polyvalent nonionic polyalkylene ether alcohol.
  • a polyfunctional isocyanate compound examples include Bayhydur 3100, Bayhydur VPLS2150/1, SBU isocyanate L801, Desmodur N3400, Desmodur VPLS2102, and Desmodur VPLS2025 manufactured by Sumitomo Bayer Urethane Co., Ltd.
  • the epoxy group-containing compound is not particularly limited as long as it has at least two epoxy groups in the molecule.
  • bisphenol A diglycidyl ether bisphenol A ⁇ -dimethylglycidyl ether, bisphenol F diglycidyl ether, tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, brominated bisphenol A diglycidyl ether, chlorinated bisphenol A diglycidyl ether, Hydrogenated bisphenol A diglycidyl ether, bisphenol A alkylene oxide adduct diglycidyl ether, novolac glycidyl ether, polyalkylene glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol diglycidyl ether, glycidyl ether type such as epoxy urethane resin, Glycidyl ether/ester types such as p
  • Examples of commercially available epoxy compounds include water-based ones suitable for the present disclosure, for example, Denacol series (EM-150, EM-101, etc.) manufactured by Nagase Chemtex, and Adeka Resin series manufactured by Adeka. ..
  • the cross-linking agent When the cross-linking agent is added to the thermoplastic polyurethane filled in the spaces between the fibers of the fiber base material and/or the thermoplastic polyurethane as the matrix resin, the form of the spaces between the fibers and the thermoplastic polyurethane molecules are In order to reliably and uniformly fill the space, it is preferable that the resin is dispersed in an aqueous solution or an organic solution.
  • the composition containing the thermoplastic polyurethane and the cross-linking agent may be filled in the space between the fibers of the fiber base material and laminated on the outer surface of the fiber base material.
  • thermoplastic polyurethane when the thermoplastic polyurethane is in the form of an aqueous resin dispersion, a fiber base material as a composition in which a crosslinking agent is dispersed in the aqueous medium by the method as described above. It is also possible to fill the space between the fibers with the thermoplastic polyurethane and the crosslinking agent, and laminate the thermoplastic polyurethane and the crosslinking agent on the outer surface of the fiber base material.
  • the addition amount of the cross-linking agent is not limited to this, because the processability and recyclability of the resin laminated base material and mechanical properties such as strength and elastic modulus are compatible with each other, but the solid content relative to 100 parts by mass of the fiber base material. It is preferably 0.5 to 10 parts by mass in terms of conversion.
  • the addition amount of the crosslinking agent is more preferably 1 part by mass or more and 8 parts by mass or less, and further preferably 1.5 parts by mass or more and 5 parts by mass or less, in terms of solid content, based on 100 parts by mass of the fiber base material.
  • the addition amount of the crosslinking agent is not limited to this, but is preferably 1 part by mass to 15 parts by mass in terms of solid content with respect to 100 parts by mass of the thermoplastic polyurethane.
  • the addition amount of the cross-linking agent is more preferably 2 parts by mass or more and 12 parts by mass or less, and further preferably 3 parts by mass or more and 8 parts by mass or less in terms of solid content with respect to 100 parts by mass of the thermoplastic polyurethane.
  • the fiber-reinforced composite material molded product is a molded product molded into a predetermined shape by using one or more fiber-reinforced composite materials of the present disclosure, and a product manufactured using the fiber-reinforced composite material or a part thereof. It will be.
  • the resin-filled fiber base material and the fiber-reinforced composite material will be described.
  • the case where a crosslinking agent is added will be described, but when the crosslinking agent is not added, the step of adding the crosslinking agent in the following method may be omitted.
  • a water-based resin dispersion as a composition in which particles of a thermoplastic polyurethane and a cross-linking agent are dispersed in an aqueous medium
  • the fiber base material and the water-based resin dispersion are contacted by a known spray method or roller impregnation method.
  • the spaces between the fibers of the fiber base material are filled with particles of the thermoplastic polyurethane, and the particles of the thermoplastic polyurethane are adhered to the outer surface of the fiber base material to be laminated, and at the same time, a cross-linking agent is applied between the fibers of the fiber base material. And is added between the thermoplastic polyurethane molecules attached to the outer space of the fiber and the outer surface of the fiber.
  • a drying treatment such as heat drying is performed to form a resin-filled fiber base material.
  • aqueous resin dispersion prepared by dispersing thermoplastic polyurethane particles in an aqueous medium the spaces between the fibers of the fiber base material are filled with the thermoplastic polyurethane particles, and heat is applied to the outer surface of the fiber base material.
  • a cross-linking agent dispersed in an aqueous solution or an organic solution is used to contact the particles of the thermoplastic polyurethane adhered to the fiber substrate by a known spray method or roller impregnation method.
  • the cross-linking agent may be attached in the spaces between the fibers of the fiber base material and between the thermoplastic polyurethane molecules attached to the outer surfaces of the fibers.
  • thermoplastic polyurethane are applied to the spaces between the fibers of the fiber base material and the outer surface, and the cross-linking agent is added to the fiber base material. It may be added in the spaces between the fibers and between the thermoplastic polyurethane molecules attached to the outer surfaces of the fibers.
  • a space between the fibers is filled with thermoplastic polyurethane and a crosslinking agent, and a matrix resin is laminated on both upper and lower surfaces, that is, one resin-filled fiber.
  • a plurality of sheet-shaped resin-filled fiber base materials having a structure in which the matrix resin is arranged on the upper and lower surfaces of the base material are laminated, and the matrix resin is heated under pressure to melt the matrix resin. Then, the matrix resins of the resin-filled fiber base material are adhered to each other to produce a sheet-shaped fiber-reinforced composite material.
  • the resin-filled fiber base material is made into a plurality of layers with the surface on which the matrix resin is laminated and the surface not laminated facing each other. Layering, heating the matrix resin under pressure, melting the matrix resin, and adhering the fiber base material of one resin-filled fiber base material and the matrix resin of the other resin-filled fiber base material facing each other To manufacture.
  • a resin-filled fiber base material is formed by using a yarn bundle-shaped fiber bundle as the fiber base material.
  • a fiber bundle-like fiber base material in which a space between fibers is filled with thermoplastic polyurethane and a cross-linking agent and a matrix resin is laminated on the surface of the fiber base material, that is, a matrix is provided on the outer surface of one resin-filled fiber base material.
  • a two-layer structure string-shaped resin-filled fiber base material in which a resin is arranged is manufactured, and a plurality of the two-layer structure resin-filled fiber base materials are bundled and laminated, and the matrix resin is heated under pressure. , Melt the matrix resin. Then, the matrix resins of the resin-filled fiber base material are adhered to each other to manufacture a string-shaped fiber-reinforced composite material.
  • laminating the fiber base material and the matrix resin also includes covering the fiber base material with the matrix resin.
  • a plurality of thread-bundle-shaped resin-filled fiber base materials may be bundled, heated under pressure to melt the matrix resin, and the matrix resins are adhered to each other to produce the fiber-reinforced composite material.
  • the matrix resin may be attached to the fiber base material in a separate step, instead of being attached to the fiber base material at the same time as the thermoplastic polyurethane filling the space between the fibers.
  • a film-like thermoplastic polyurethane is used, a fiber base material in which spaces between fibers are filled with the thermoplastic polyurethane and a film-like matrix resin are laminated, and heated under pressure to melt the matrix resin,
  • the resin-filled fiber base material or the fiber-reinforced composite material may be manufactured by adhering the fiber base material filled with the thermoplastic polyurethane with each other.
  • the cross-linking agent can be added to both the thermoplastic polyurethane filled in the spaces between the fibers and the thermoplastic polyurethane as the matrix resin, but can be added to only one of them. ..
  • the matrix resin may be installed on the entire surface of the fiber substrate filled with thermoplastic polyurethane, but it may be installed on only one of the upper and lower surfaces of the sheet-shaped fiber substrate, or
  • the yarn bundle may be manufactured without being installed on both end surfaces in the length direction and the matrix resin may be installed only on a part of the surface of the resin-filled fiber base material.
  • the resin-filled fiber base material is obtained by injecting molten matrix resin into a mold or the like, and applying the matrix resin to the fiber base material filled with thermoplastic polyurethane in the space between the fibers, which is placed in the mold.
  • the fiber base material and the matrix resin may be adhered and solidified and laminated to manufacture.
  • a plurality of fiber-reinforced composite materials molded as described above may be laminated and heated under pressure to melt and bond the matrix resins to each other. ..
  • the fiber-reinforced composite material alone is put into a mold, heated under pressure, and simultaneously molded into a predetermined shape to manufacture a fiber-reinforced composite material molded product. Further, a plurality of fiber-reinforced composite materials are laminated, bundled or aligned, put in a mold, heated under pressure, and simultaneously molded into a predetermined shape to manufacture a fiber-reinforced composite material molded product.
  • a unidirectional non-crimp fabric (made by Sakai Sangyo Co., Ltd.) having a width of 250 mm and using 84 carbon roving T300-12K manufactured by Toray Industries, Inc. was used.
  • Each of these 250 mm ⁇ 125 mm fibrous base materials has a water-based polyurethane resin manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • thermoplastic polyurethane (Superflex 130 (SF-130), non-yellowing, ether-based, average particle size 0.03 ⁇ m , Solid content 35 wt%) in an amount of 25 parts by mass or more and 70 parts by mass or less in terms of solid content based on 100 parts by mass of the fiber base material, and after drying in the sun, dried in a vacuum dryer at 100° C. for 1 hour.
  • the dry film of Superflex 130 has a glass transition temperature of 101°C, a softening temperature of 174°C, and a heat melting temperature of 216°C.
  • a unidirectional non-crimp fabric made by Sakai Sangyo Co., Ltd. having a width of 250 mm and using 84 carbon roving T300-12K manufactured by Toray Industries, Inc. was used.
  • Each of these 250 mm ⁇ 125 mm fibrous base materials has a water-based polyurethane resin manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as a thermoplastic polyurethane (Superflex 130 (SF-130), non-yellowing, ether-based, average particle size 0.03 ⁇ m).
  • the fiber base material a unidirectional non-crimp fabric of width 250 mm using 84 carbon roving T300-12K manufactured by Toray Industries, Inc. (manufactured by Sakai Sangyo Co., Ltd.) was used, and each of these fiber base materials of 250 mm ⁇ 125 mm was used.
  • a thermoplastic polyurethane a water-based polyurethane resin manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (Superflex 210 (SF-210), non-yellowing, ester-based, average particle size 0.04 ⁇ m, solid content 35 wt%) was used as a fiber base material.
  • the fiber base material used in Examples 1 and 2 was used, a frame mold was placed in a flat plate mold at room temperature, and a silicone mold release agent was applied to the inside of the frame mold.
  • a polypropylene (PP) film having a basis weight of 136 g/m 2 is placed on the upper and lower surfaces, melted at 200° C. for 5 minutes, and pressed at a pressure of about 7 MPa while maintaining 200° C. to integrate to obtain a fiber-reinforced composite material. (Comparative example 1).
  • the fiber base material a unidirectional non-crimp fabric of width 250 mm using 84 carbon roving T300-12K manufactured by Toray Industries, Inc. (manufactured by Sakai Sangyo Co., Ltd.) was used, and each of these fiber base materials of 250 mm ⁇ 125 mm was used.
  • a thermoplastic polyurethane a water-based polyurethane resin manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (Superflex 130 (SF-130), non-yellowing, ether-based, average particle diameter 0.03 ⁇ m, solid content 35 wt%) was used as a fiber base material.
  • the fiber base material a unidirectional non-crimp fabric of width 250 mm using 84 carbon roving T300-12K manufactured by Toray Industries, Inc. (manufactured by Sakai Sangyo Co., Ltd.) was used, and each of these fiber base materials of 250 mm ⁇ 125 mm was used.
  • a thermoplastic polyurethane a water-based polyurethane resin (Superflex 130 (SF-130), non-yellowing, ether-based, average particle size 0.03 ⁇ m, solid content 35 wt%) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was used as a fiber base material.
  • Example 1 The results of Examples 1 to 4 and Comparative Example 1 are shown in Table 1.
  • the numerical values of water-based polyurethane resin SF-130 (Superflex 130), water-based polyurethane resin SF-210 (Superflex 210), and PP (polypropylene) in Table 1 are parts by mass with respect to 100 parts by mass of the fiber base material. ..
  • the physical adhesion amount and the solid content conversion adhesion amount are described.
  • Table 2 shows the results of Examples 5 to 10.
  • the numerical values of the water-based polyurethane resin SF-130 (Superflex 130), the carbodiimide-based cross-linking agent and the oxazolidine-based cross-linking agent in Table 2 are parts by mass based on 100 parts by mass of the fiber base material.
  • the water-based polyurethane resin SF-130, the carbodiimide-based cross-linking agent, and the oxazolidine-based cross-linking agent are described in terms of the physical adhesion amount and the solid content conversion adhesion amount, respectively.
  • thermoplastic polyurethane is applied to 25 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the fiber base material, and the space between the fibers of the fiber base material is filled with the thermoplastic polyurethane.
  • the bending strength is increased by laminating the thermoplastic polyurethane as the matrix resin on the outer surface of the fiber base material.
  • the bending strength is further increased by adding the crosslinking agent to the thermoplastic polyurethane in the range of 0.5 parts by mass or more and 10 parts by mass or less in terms of solid content with respect to 100 parts by mass of the fiber base material. ..
  • a fiber-based material is impregnated with an aqueous resin dispersion in which thermoplastic polyurethane particles are dispersed in an aqueous medium to fill the spaces between the fibers of the fiber-based material with the thermoplastic polyurethane, and at the same time, the thermoplastic polyurethane matrix resin is used.

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Abstract

La présente invention vise à empêcher l'apparition de cavités et améliorer la force de fixation entre les fibres de renforcement et une résine de matrice qui est composée d'une résine thermoplastique, ce qui permet ainsi d'améliorer les caractéristiques mécaniques telles que la résistance mécanique et le module d'élasticité par rapport à un matériau composite renforcé par des fibres qui est moulé par utilisation d'un matériau de base fibreux, tout en utilisant une résine thermoplastique en tant que résine de matrice. L'invention concerne à cet effet un matériau de base fibreux rempli de résine, qui est obtenu par remplissage des espaces entre les fibres d'un matériau de base fibreux avec un polyuréthanne thermoplastique, et qui est conçu de façon que la quantité du polyuréthanne thermoplastique appliqué au matériau de base fibreux soit de 25 parties en masse à 100 parties en masse (limites comprises) pour 100 parties en masse du matériau de base fibreux, les parties étant exprimées en extrait sec.
PCT/JP2020/005887 2019-02-15 2020-02-14 Matériau de base fibreux rempli de résine, matériau composite renforcé par des fibres et procédé de production associé WO2020166717A1 (fr)

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CN202080013615.1A CN113412189A (zh) 2019-02-15 2020-02-14 树脂填充纤维基材、纤维强化复合材料及其制备方法
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WO2016067711A1 (fr) * 2014-10-29 2016-05-06 風間均 Matériau composite renforcé de fibres et son procédé de fabrication

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