WO2016060240A1 - 繊維強化樹脂中間材及びその製造方法 - Google Patents

繊維強化樹脂中間材及びその製造方法 Download PDF

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Publication number
WO2016060240A1
WO2016060240A1 PCT/JP2015/079297 JP2015079297W WO2016060240A1 WO 2016060240 A1 WO2016060240 A1 WO 2016060240A1 JP 2015079297 W JP2015079297 W JP 2015079297W WO 2016060240 A1 WO2016060240 A1 WO 2016060240A1
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Prior art keywords
resin
fiber
reinforcing fiber
reinforcing
intermediate material
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Ceased
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PCT/JP2015/079297
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English (en)
French (fr)
Inventor
秋夫 大野
安江　昭
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Japan Steel Works Ltd
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Japan Steel Works Ltd
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Publication date
Application filed by Japan Steel Works Ltd filed Critical Japan Steel Works Ltd
Priority to CA2964589A priority Critical patent/CA2964589C/en
Priority to CN202010894562.0A priority patent/CN112223789B/zh
Priority to EP15849984.8A priority patent/EP3208062B1/en
Priority to CN201580056265.6A priority patent/CN107073754B/zh
Priority to BR112017007894-5A priority patent/BR112017007894B1/pt
Priority to US15/519,237 priority patent/US10351994B2/en
Publication of WO2016060240A1 publication Critical patent/WO2016060240A1/ja
Anticipated expiration legal-status Critical
Priority to US16/430,532 priority patent/US10697114B2/en
Ceased legal-status Critical Current

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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
    • B29C70/30—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
    • 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
    • B29B15/105—Coating or impregnating independently of the moulding or shaping step of reinforcement of definite length with a matrix in solid form, e.g. powder, fibre or sheet form
    • 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]
    • 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
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D25/00—Woven fabrics not otherwise provided for
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0084—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments by electrical processes, e.g. potentials, corona discharge, electrophoresis, electrolytic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
    • D06N3/0093—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin by applying resin powders; by sintering
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/125—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
    • D06N7/0092—Non-continuous polymer coating on the fibrous substrate, e.g. plastic dots on fabrics
    • 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
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides 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
    • B29K2307/00—Use of elements other than metals as reinforcement
    • B29K2307/04—Carbon
    • 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
    • B29K2313/00—Use of textile products or fabrics as reinforcement
    • B29K2313/02—Use of textile products or fabrics as reinforcement coated
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0063—Density
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/08—Inorganic fibres
    • D06N2201/087—Carbon fibres
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00—Macromolecular materials of the coating layers
    • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/065—Polyamides

Definitions

  • the present invention relates to a fiber reinforced resin intermediate material used by being heated and pressurized in a laminated state and a method for producing the same.
  • fiber reinforced resin obtained by impregnating a resin with a reinforcing fiber base material such as carbon fiber and glass fiber has been widely used in various fields and applications. Application to parts and automobile parts is underway.
  • a fiber reinforced resin molded product has few defects such as voids in which the impregnation of the resin into the reinforcing fiber base is performed at a predetermined fiber volume content so that predetermined characteristics such as mechanical strength are exhibited. Things are required. And the shaping property which can be shape
  • various fiber reinforced resin intermediate materials have been proposed in which a reinforced fiber base material is impregnated with a resin and heated and pressed in a laminated state.
  • thermoplastic resin has a high melt viscosity and is difficult to impregnate into a reinforcing fiber bundle uniformly.
  • a thermoplastic resin nonwoven fabric is superimposed on a reinforcing fiber sheet in which a plurality of reinforcing fiber bundles are aligned in one direction.
  • a fiber-reinforced thermoplastic resin sheet in which a thermoplastic resin nonwoven fabric is melted by applying pressure while heating and a reinforcing fiber bundle is impregnated with a thermoplastic resin has been proposed.
  • This fiber-reinforced thermoplastic resin sheet is supposed to be in a semi-impregnated state in which there are voids that are not impregnated with the thermoplastic resin in the reinforcing fiber bundle.
  • Patent Document 2 includes a fiber base material formed in a layered manner, and a resin layer provided on at least one surface side of the fiber base material and formed of a resin composition, and in the fiber base material A prepreg in which a void layer not impregnated with the resin composition is formed on at least a part of is proposed.
  • the void layer of the prepreg may have a shape in which a part of the fiber substrate is exposed, and is preferably formed so as to communicate from one end to the other end of the prepreg.
  • gap layer which connects from one end to the other end should just exist in the intermediate part.
  • thermosetting resins such as a phenol novolak resin and a cresol novolak resin
  • thermoplastic resins such as a phenoxy resin and a polyimide resin
  • Patent Document 3 is a prepreg base material in which reinforcing fibers are aligned in one direction, and a plurality of rows of intermittent cuts are provided on the entire surface of the prepreg base material in a direction crossing the reinforcing fibers,
  • the projected length obtained by projecting the incision in the vertical direction of the reinforcing fiber is 30 ⁇ m to 10 mm, substantially all of the reinforcing fiber is divided by the incision, and the fiber length of the reinforcing fiber divided by the incision is 10 to 10
  • a notched prepreg base material with a fiber volume content of 45 to 65% has been proposed.
  • This incision prepreg base material has a good fluidity, a molding followability, an excellent formability, and a prepreg base material that is an intermediate base material of fiber reinforced plastic that is suitably used for automobile parts, sports equipment, etc. It is said that materials can be provided.
  • the fiber reinforced thermoplastic resin intermediate material is required to have formability.
  • the fiber reinforced thermoplastic resin sheet is impregnated in a prepreg which is in a semi-impregnated state.
  • the fiber reinforced thermoplastic resin sheet described in Patent Document 1 and the prepreg described in Patent Document 2 are preferable to the cut prepreg base material described in Patent Document 3 in that an additional step is not required.
  • the fiber-reinforced thermoplastic resin sheet described in Patent Document 1 has a problem that voids are easily formed. That is, the fiber-reinforced thermoplastic resin sheet is molded by heating and pressing a fabric made of thermoplastic resin fibers stacked on the fiber-reinforced sheet. For this reason, in this fiber reinforced thermoplastic resin sheet, the molten thermoplastic resin layer is pressed and compacted so that the surface of the reinforced fiber sheet is covered with a film, so that it is difficult to be impregnated with the thermoplastic resin. There is a problem in that air in the reinforcing fiber sheet is difficult to escape and voids are easily formed.
  • the prepreg described in Patent Document 2 is a prepreg in which a fiber base material is impregnated with a resin composition based on a thermosetting resin, and a resin composition consisting only of a thermoplastic resin having a higher viscosity than the thermosetting resin. It is unclear whether it can be applied in the same way even if it is a product. Moreover, this prepreg has a resin layer formed on the entire upper surface of the fiber base material, and has a void layer formed so as to communicate from one end to the other end under the resin layer.
  • the resin layer is a resin layer formed by a roll-to-roll method or a liquid resin composition such as a varnish of the resin composition, which is cured on a fiber substrate. For this reason, the prepreg described in Patent Document 2 has a problem that air in the prepreg cannot be sufficiently discharged because the air travel distance becomes long and it is difficult for air to escape.
  • the cut prepreg base material described in Patent Document 3 is produced as follows. That is, the epoxy resin composition was applied onto a 100 ⁇ m-thick release paper that had been silicone-coated using a reverse roll coater to produce a resin film, and then applied to both sides of carbon fibers arranged in one direction. It is described that a prepreg base material was produced by impregnating a resin by overlapping and heating and pressurizing each resin film, and it is easy to form voids as in the fiber reinforced thermoplastic resin sheet described in Patent Document 1. There is a problem.
  • the present invention provides a fiber reinforced resin intermediate material having a good formability, including defects such as voids, including a thermoplastic resin as well as a thermosetting resin, and a method for producing the same.
  • the purpose is to provide.
  • the fiber reinforced resin intermediate material according to the present invention has a resin attached to an outer surface portion of a reinforcing fiber base formed of opened reinforcing fibers, and is heated to a temperature equal to or higher than the melting point of the resin to cause the resin to become the reinforcing fiber base.
  • the resin to be adhered to the reinforcing fiber base material is preferably a powder.
  • the reinforcing fiber substrate is preferably carbon fiber, and its basis weight is preferably 40 to 250 g / m 2 .
  • the fiber reinforced resin intermediate material according to the present invention preferably has an apparent density ⁇ that is 1/2 to 1/50 of the following target apparent density ⁇ c.
  • the fiber reinforced resin intermediate material in which the reinforcing fiber base as described above is impregnated with the resin in a semi-impregnated state and has voids opened on the outer surface can be produced by the following method. That is, the fiber reinforced resin intermediate material of the present invention has a predetermined fiber volume content of the reinforcing fiber base based on the outer diameter of the reinforcing fiber forming the reinforcing fiber base and the bulk density of the reinforcing fiber base.
  • the resin powder having a predetermined average particle diameter can be suitably produced by electrostatically adhering to the reinforcing fiber base so as to have a value.
  • the fiber reinforced resin intermediate material according to the present invention is rich in formability and impregnation. For this reason, by laminating this fiber reinforced resin intermediate material, heating and pressurizing, even if it is a complicated shape, it has a desired fiber volume content and is sufficiently impregnated and has few defects such as voids A reinforced resin molded product (molded product) can be produced.
  • FIG. 1 (a) is a drawing schematically showing a reinforcing fiber substrate in which resin powder is adhered to a reinforcing fiber substrate
  • FIG. 1 (b) is a reinforcing fiber substrate impregnated with resin powder. It is drawing which shows typically the microstructure of a part of.
  • FIG. 2 is a drawing showing a molded shape of the fiber-reinforced resin molded product of the example.
  • FIG. 3 is an optical micrograph of the surface of a reinforcing fiber substrate to which the resin powder of Example is electrostatically attached.
  • FIG. 4 is an SEM photograph of the surface of the fiber reinforced resin intermediate material of the example.
  • FIG. 5 is an optical micrograph of a cross section of the fiber-reinforced resin molded product of the example.
  • the fiber reinforced resin intermediate material according to the present invention has a resin attached to an outer surface portion of a reinforcing fiber base formed of opened reinforcing fibers, and is heated to a temperature equal to or higher than the melting point of the resin to cause the resin to become the reinforcing fiber base.
  • the fiber-reinforced resin intermediate material of the present invention comprises an impregnated portion impregnated with molten resin on the outer surface portion of the reinforcing fiber base, and an unimpregnated portion where no molten resin is present, and has voids due to the unimpregnated portion. Impregnating properties can be provided at the same time as shaping.
  • “the resin is in a semi-impregnated state” means that the outer surface portion of the reinforcing fiber base material is mixed with an impregnated portion impregnated with the molten resin and an unimpregnated portion where the molten resin is not present. It is distinguished from the state where the outer surface portion of the reinforcing fiber base is covered with the molten resin.
  • the fiber reinforced resin intermediate material composed of the reinforcing fiber base material in which the resin is semi-impregnated is preferably prepared by electrostatically attaching the resin powder to the reinforcing fiber base material and heating and impregnating the resin powder. . That is, first, the resin powder 20 is electrostatically attached to the reinforcing fiber base 10. When observed macroscopically, the resin powder 20 adheres to the surface of the reinforcing fiber base 10 with a uniform thickness and a uniform distribution. However, when observed microscopically, as shown in FIG. 1A, the surface of the reinforcing fiber base 10 formed from a large number of reinforcing fibers 11 in a bundle has one or more layers of resin powder 20.
  • the fiber volume content of the reinforcing fiber substrate 10 becomes a predetermined value based on the outer diameter of the reinforcing fiber 11 forming the reinforcing fiber substrate 10 and the bulk density of the reinforcing fiber substrate 10.
  • the resin powder 20 having a predetermined average particle diameter can be generated by electrostatic adhesion to the reinforcing fiber substrate 10.
  • the reinforcing fiber substrate 10 to which the resin powder 20 is adhered is heated to the melting point of the resin powder 20 or higher.
  • the reinforcing fiber base material 10 to which the resin powder 20 is adhered is not pressurized.
  • the resin powder 20 adhering to the reinforcing fiber base 10 melts on the surface of the reinforcing fiber base 10 in the heating operation.
  • a film-like molten layer that maintains the distribution according to the situation and covers the entire surface of the reinforcing fiber base 10 is not formed.
  • the melted resin reduces its surface area due to its surface tension, and forms an unimpregnated portion where no molten resin exists on the surface of the reinforcing fiber base 10.
  • the molten resin is impregnated in the voids in the reinforcing fiber base 10 through the reinforcing fibers 11.
  • the temperature and time for melting and impregnating the resin are appropriately selected according to the reinforcing fiber base material 10 and the resin powder 20.
  • the term “opening” means that when the reinforcing fiber is made of a bundle of fibers, it is flattened. This fiber opening makes it easy to form the semi-impregnated state in which the reinforcing fiber base material is impregnated with the resin in a semi-impregnated state and has voids opened on the outer surface of the reinforcing fiber base material.
  • the outer surface of the reinforcing fiber base means the outer side of the reinforcing fiber 11 that forms the surface of the reinforcing fiber base 10.
  • the outer surface portion of the reinforcing fiber base means to include the surface of the reinforcing fiber base 10 and a portion under the surface.
  • the term “opening” means that a bundle of dense fibers to be impregnated is flattened to have a certain thickness (for example, 100 ⁇ m) or less, and is made of short fibers such as chopped. Even if it is a thing.
  • the reinforcing fibers 11 are preferably carbon fibers, and the basis weight of the reinforcing fiber substrate 10 made of carbon fibers is preferably 40 to 250 g / m 2 .
  • the basis weight of the reinforcing fiber substrate 10 made of carbon fibers is preferably 40 to 250 g / m 2 .
  • the reinforcing fiber 11 may be a glass fiber or a natural fiber, and an appropriate basis weight range is determined for each of the reinforcing fiber bases 10 made of these fibers.
  • Resin powder 20 is polycarbonate (PC), polysulfone (PSU), polyethersulfone (PES), polyamideimide (PAI), polyetherimide (PEI), polyamide resin (PA6, PA11, PA66), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyether ether ketone (PEEK), polyether ketone ketone (PEKK) and the like can be used.
  • PC polycarbonate
  • PSU polysulfone
  • PES polyamideimide
  • PEI polyetherimide
  • PA6 PA11, PA66 polyamide resin
  • PBT polyethylene terephthalate
  • PPS polyphenylene sulfide
  • PEEK polyether ether ketone
  • PEKK polyether ketone ketone
  • the resin powder 20 may be a powder having an average particle diameter that is 1/2 to 30 times the outer diameter of the reinforcing fiber 11. This average particle diameter is appropriately selected according to the density, viscosity, fiber shape, and final fiber volume content of the resin used.
  • a resin powder 20 having an average particle diameter has an advantage that it can be easily electrostatically attached to the reinforcing fiber substrate 10. Further, by using the resin powder 20 having an average particle diameter in the above range, the fiber volume content of the reinforcing fiber base 10 can be set to a predetermined value, specifically 15 to 70%.
  • the resin powder 20 is used to adhere the resin to the reinforcing fiber substrate, and the resin powder 20 is attached to the reinforcing fiber substrate 10 by electrostatic adhesion.
  • the adhesion of the resin powder 20 to the reinforcing fiber substrate 10 can be prepared microscopically.
  • the electrostatic adhesion of the resin powder 20 can be performed by charging the resin powder 20 in a mixed state with air and applying a higher voltage immediately before the resin powder 20 is adhered to the reinforcing fiber base 10. .
  • the resin powder 20 preferably has a small average particle size from the viewpoint of impregnation, but is disadvantageous in that the unit price is high.
  • the resin powder 20 in order to control the electrostatic adhesion state of the resin powder 20 and form a reinforced fiber base material having voids opened on the outer surface, the resin powder 20 preferably has a larger average particle diameter.
  • the apparent density ⁇ is preferably set within a predetermined range. That is, the apparent density ⁇ of the reinforcing fiber substrate is set to the density (target apparent density ⁇ c) when the fiber reinforced resin intermediate material made of the reinforcing fiber substrate is composed of reinforcing fibers and resin and there is no void at all. 1/2 to 1/50 is recommended.
  • ⁇ c Vr ⁇ ⁇ r + Vf ⁇ ⁇ f, where Vf is the fiber volume content of the carbon fiber and ⁇ f is the density, and Vr is the resin volume content of the resin and ⁇ r is the density.
  • the apparent density ⁇ is about 1/2 of the target apparent density ⁇ c
  • the reinforcing fiber base material composed of the woven fabric obtained by folding the opened warp and weft
  • the apparent density ⁇ is 1/50 of the target apparent density ⁇ c.
  • a mat-like reinforcing fiber substrate made of opened chopped.
  • the apparent density ⁇ is obtained by dividing the mass of the reinforcing fiber base by the apparent volume.
  • the fiber reinforced resin intermediate material according to the present invention has been described above.
  • the fiber reinforced resin intermediate material is laminated in a predetermined mold, heated and pressurized, and formed into a fiber reinforced resin molded product having a predetermined shape.
  • a fiber reinforced resin molded product having a fiber volume content of 15 to 70%, a void ratio of 1.5% or less, and a void ratio of 0.5% or less can be formed.
  • a fiber-reinforced resin intermediate material in which a polyamide (PA6) resin is impregnated into a reinforcing fiber substrate made of carbon fiber is prepared, laminated, heated and pressed to form a rectangular fiber-reinforced resin shown in FIG.
  • the test which produces the goods 30 was done.
  • the reinforcing fiber base material used was a carbon fiber bundle having a basis weight of 63 g / m 2 produced by opening a 7 ⁇ m diameter carbon fiber bundle (1,000 pieces) to a width of 2 mm and cut out from this. .
  • PA6 resin powder having an average particle diameter of 20 ⁇ m was used as the impregnating resin.
  • FIG. 3 shows an optical micrograph of the surface state in which PA6 resin powder is electrostatically attached to the reinforcing fiber substrate. The surface of the reinforcing fiber substrate is still mottled, but it is observed as if it was thinly laid in powder snow.
  • FIG. 4 shows a scanning electron microscope (SEM) photograph of the surface of the produced fiber-reinforced resin intermediate material.
  • the surface of the fiber reinforced resin intermediate material has a portion where the carbon fiber bundle is covered with a thick coat like water candy, there is a portion covered with a thin film, and there is almost an exposed portion of the carbon fiber bundle as it is. Observe as.
  • the thick coating portion is dotted with elongated and various groove-like portions along the direction of the carbon fiber that could not be filled. That is, it is observed that the reinforcing fiber base has voids opened on the outer surface in a semi-impregnated state with PA6 resin.
  • FIG. 5 shows an optical micrograph of 400 times magnification of the cross section of the molded fiber reinforced resin molded product.
  • This fiber-reinforced resin molded product had a void ratio of 0.5% or less. Further, the formability of the fiber reinforced resin molded product 30 was good, and the end portion 31 of the groove shown in FIG.

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Abstract

　本発明は、熱可塑性樹脂のみならず熱硬化性樹脂を含め、ボイドなどの欠陥が生じ難く賦形性に富んだ繊維強化樹脂中間材及びその製造方法を提供する。本発明に係る繊維強化樹脂中間材は、開繊された強化繊維で形成される強化繊維基材の外面部に樹脂を付着させ、その樹脂の融点以上に加熱して樹脂を強化繊維基材に含浸させた繊維強化樹脂中間材であって、強化繊維基材は、外面に開口した空隙を有し、樹脂が半含浸状態にあるものである。

Description

繊維強化樹脂中間材及びその製造方法
　本発明は、積層状態で加熱及び加圧されて使用される繊維強化樹脂中間材及びその製造方法に関する。
　近年、軽量化や機械強度の向上を目的として、炭素繊維、ガラス繊維などの強化繊維基材に樹脂を含浸させて複合化した繊維強化樹脂が種々の分野・用途に広く利用されており、航空機部品や自動車部品への適用が進められている。このような繊維強化樹脂成形品は、機械的強度など所定の特性が発揮されるように、強化繊維基材への樹脂の含浸が所定の繊維体積含有率で行われたボイドなどの欠陥の少ないものが求められる。そして、複雑な形状であっても成形できるような賦形性が求められる。このような要求に対し、強化繊維基材に樹脂が含浸されてなり、積層状態で加熱及び加圧されて使用される繊維強化樹脂中間材が種々提案されている。
　特許文献１に、熱可塑性樹脂は溶融粘度が高く強化繊維束中に均一に含浸させ難いところ、複数本の強化繊維束を一方向に引き揃えた強化繊維シートに熱可塑性樹脂不織布を重ね合わせて加熱しつつ加圧することにより、熱可塑性樹脂不織布を溶融させ強化繊維束中に熱可塑性樹脂を含浸させた繊維強化熱可塑性樹脂シートが提案されている。この繊維強化熱可塑性樹脂シートは、強化繊維束中に熱可塑性樹脂が含浸しない空隙部が存在する半含浸の状態とすることができるとされる。このため、繊維強化熱可塑性樹脂シートの製造にかかる時間を短縮でき、柔軟性を有する繊維強化熱可塑性樹脂シートが得られ、強化繊維シートを薄くできることから、未含浸部分を少なくすることができ、最終成形品に加工する際の加熱しつつ加圧するときに十分な含浸ができるとされる。
　特許文献２に、層状に形成された繊維基材と、前記繊維基材の少なくとも一方の面側に設けられており、樹脂組成物で構成された樹脂層と、を備え、前記繊維基材中の少なくとも一部に、前記樹脂組成物の含浸されていない空隙層が形成されたプリプレグが提案されている。このプリプレグの空隙層は、繊維基材の一部が露出した形状であってもよく、プリプレグの一端から他端まで連通するように形成されていることが好ましいとされる。また、繊維基材の両面に樹脂層を有するものであっても、その中間部に一端から他端まで連通するような空隙層が存在すればよいとされる。このようなプリプレグを積層する場合は、樹脂が繊維基材によって支持されているため繊維基材が波打つことを防ぐことができ、プリプレグの積層時に空気が抜けやすく気泡が発生しにくいとされる。そして、上記樹脂組成物として、フェノールノボラック樹脂、クレゾールノボラック樹脂等の熱硬化性樹脂が列挙され、フェノキシ樹脂、ポリイミド樹脂等の熱可塑性樹脂を併用してもよいとされる。
　特許文献３に、強化繊維が一方向に引き揃えられたプリプレグ基材であって、該プリプレグ基材の全面に強化繊維を横切る方向へ断続的な切り込みからなる列が複数列設けられており、前記切り込みを強化繊維の垂直方向に投影した投影長さが30μm～10mmであり、実質的に強化繊維のすべてが前記切り込みにより分断され、前記切り込みにより分断された強化繊維の繊維長さが10～100mmであり、繊維体積含有率が45～65%の範囲内である切込プリプレグ基材が提案されている。この切込プリプレグ基材は、良好な流動性を有し成形追従性を有して賦形性に優れ、自動車部品やスポーツ用具等に好適に用いられる繊維強化プラスチックの中間基材であるプリプレグ基材を提供することができるとされる。
日本国特開２００３－１６５８５１号公報 日本国特開２０１３－１８０４０６号公報 日本国特開２００８－２０７５４４号公報
　上記のように、繊維強化熱可塑性樹脂中間材には賦形性が要求されるが、特許文献１～３においては、繊維強化熱可塑性樹脂シートを半含浸の状態にする、プリプレグに含浸されていない空隙層を設ける、あるいは切込プリプレグ基材に切り込みを設けることにより、それらの繊維強化樹脂中間材の賦形性の向上を図っている。追加工程を要しないという点で、特許文献１に記載の繊維強化熱可塑性樹脂シート及び特許文献２に記載のプリプレグは、特許文献３に記載の切込プリプレグ基材より好ましい。
　一方、ボイド等の欠陥を生じ難いか否かという点において、特許文献１に記載の繊維強化熱可塑性樹脂シートは、ボイドを形成しやすいという問題がある。すなわち、繊維強化熱可塑性樹脂シートは、繊維強化シートに重ねた熱可塑性樹脂繊維からなる布帛を加熱しつつ加圧して成形される。このため、この繊維強化熱可塑性樹脂シートにおいては、溶融した熱可塑性樹脂層が加圧されて圧密化した強化繊維シートの表面をフィルム状に被った状態になるので、熱可塑性樹脂が含浸され難く強化繊維シート内の空気が抜け難くなり、ボイドを形成しやすいという問題がある。
　特許文献２に記載のプリプレグは、繊維基材に熱硬化性樹脂を基本とする樹脂組成物を含浸させたプリプレグであり、熱硬化性樹脂と比べて粘度の高い熱可塑性樹脂のみからなる樹脂組成物であっても同様に適用できるか不明である。また、このプリプレグは、繊維基材の上面全体に樹脂層が形成され、その樹脂層の下部に、一端から他端に連通するように形成された空隙層を有している。そして、この樹脂層は、ロール・ツゥ・ロール方式により形成した樹脂層、あるいは樹脂組成物のワニスなど液状の樹脂組成物を供給し繊維基材上で硬化させて形成した樹脂層である。このため、特許文献２に記載のプリプレグは、空気の移動距離が長くなって空気が抜け難くなるため、プリプレグ内の空気が必ずしも充分に排出できないという問題がある。
　特許文献３に記載の切込プリプレグ基材は、実施例によると以下のように作製される。すなわち、エポキシ樹脂組成物を、リバースロールコーターを用いてシリコーンコーティング処理された厚さ100μmの離型紙上に塗布して樹脂フィルムを作製し、次に、一方向に配列させた炭素繊維の両面に樹脂フィルムをそれぞれ重ね、加熱及び加圧することによって樹脂を含浸させてプリプレグ基材を作製したことが記載されており、特許文献１に記載の繊維強化熱可塑性樹脂シートと同様にボイドを形成しやすいという問題がある。
　本発明は、このような従来の問題点に鑑み、熱可塑性樹脂のみならず熱硬化性樹脂を含め、ボイドなどの欠陥が生じ難く賦形性に富んだ繊維強化樹脂中間材及びその製造方法を提供することを目的とする。
　本発明に係る繊維強化樹脂中間材は、開繊された強化繊維で形成される強化繊維基材の外面部に樹脂を付着させ、その樹脂の融点以上に加熱して前記樹脂を前記強化繊維基材に含浸させた繊維強化樹脂中間材であって、前記強化繊維基材は、外面に開口した空隙を有し、前記樹脂が半含浸状態にあるものである。
　上記発明において、強化繊維基材に付着させる樹脂は粉体であるのがよい。また強化繊維基材は、炭素繊維であるのが好ましく、その目付が40～250g/m2であるのがよい。
　また、本発明に係る繊維強化樹脂中間材は、見かけ密度ρが以下の目標見かけ密度ρcの1/2～1/50であることが好ましい。ここで、目標見かけ密度ρcは、炭素繊維の繊維体積含有率をVf及び密度をρf、樹脂の樹脂体積含有率をVr及び密度をρrとするとき、ρc＝Vr×ρr＋Vf×ρfである。
　上記の繊維強化樹脂中間材を積層し、加熱及び加圧して成形することにより、複雑な形状で欠陥の少ない繊維強化樹脂成形体（成形品）を成形することができる。
　また、上記のような強化繊維基材が、樹脂を半含浸状態で含浸し外面に開口した空隙を有している繊維強化樹脂中間材は、以下の方法により製造することができる。すなわち、本発明の繊維強化樹脂中間材は、強化繊維基材を形成する強化繊維の外径とその強化繊維基材の嵩密度に基づいて、前記強化繊維基材の繊維体積含有率が所定の値になるように、所定の平均粒径の樹脂粉体を前記強化繊維基材に静電付着させることにより好適に製造することができる。
　本発明に係る繊維強化樹脂中間材は、賦形性と同時に含浸性に富む。このため、本繊維強化樹脂中間材を積層し、加熱及び加圧することにより、複雑な形状であっても所望の繊維体積含有率を有し、含浸が充分に行われボイドなどの欠陥の少ない繊維強化樹脂成形体（成形品）を製造することができる。
図１（ａ）は、樹脂粉体を強化繊維基材に付着させた強化繊維基材を模式的に示す図面であり、図１（ｂ）は、樹脂粉体を含浸させた強化繊維基材の一部分のミクロ組織を模式的に示す図面である。 図２は、実施例の繊維強化樹脂成形品の成形形状を示す図面である。 図３は、実施例の樹脂粉体を静電付着させた強化繊維基材表面の光学顕微鏡写真である。 図４は、実施例の繊維強化樹脂中間材表面のSEM写真である。 図５は、実施例の繊維強化樹脂成形品断面の光学顕微鏡写真である。
　以下、本発明を実施するための形態について図面を基に説明する。本発明に係る繊維強化樹脂中間材は、開繊された強化繊維で形成される強化繊維基材の外面部に樹脂を付着させ、その樹脂の融点以上に加熱して前記樹脂を前記強化繊維基材に含浸させた繊維強化樹脂中間材であって、前記強化繊維基材は、外面に開口した空隙を有し、前記樹脂が半含浸状態にあるものである。本発明の繊維強化樹脂中間材は、強化繊維基材の外面部に溶融樹脂が含浸した含浸部と、溶融樹脂の存在しない未含浸部を備え、未含浸部による空隙を有しているため、賦形性と同時に含浸性を備えることができる。なお、本明細書において、「樹脂が半含浸状態にある」とは、強化繊維基材の外面部に溶融樹脂が含浸した含浸部と溶融樹脂の存在しない未含浸部が混在している状態をいい、強化繊維基材の外面部が溶融樹脂により覆われた状態と区別するものである。
　このように樹脂が半含浸状態の強化繊維基材からなる繊維強化樹脂中間材の作製は、強化繊維基材に樹脂粉体を静電付着させ、これを加熱し含浸させて作製するのがよい。すなわち、先ず、樹脂粉体20を強化繊維基材10に静電付着させる。この樹脂粉体20は、マクロ的に観察すれば強化繊維基材10の表面に均一の厚さ、均一の分布で付着している。しかしながら、ミクロ的に観察すれば、図１（ａ）に示すように、束になった多数の強化繊維11から形成される強化繊維基材10の表面は、樹脂粉体20が一層又は複層に付着した部分があり、あるいは樹脂粉体20が付着していない部分がある。このような状態は、強化繊維基材10を形成する強化繊維11の外径とその強化繊維基材10の嵩密度に基づいて、強化繊維基材10の繊維体積含有率が所定の値になるように、所定の平均粒径の樹脂粉体20を、強化繊維基材10に静電付着させることによって生じさせることができる。
　次に、樹脂粉体20が付着した強化繊維基材10を樹脂粉体20の融点以上に加熱する。本発明においては、この樹脂粉体20が付着した強化繊維基材10の加圧は行わない。このため、図１（ｂ）に示すように強化繊維基材10に付着している樹脂粉体20は、加熱操作において、強化繊維基材10の表面で溶融するが、前述のミクロ的な付着状況に応じた分布を保ち、強化繊維基材10の表面全体を被うようなフィルム状の溶融層は形成されない。そして、溶融した樹脂は、その表面張力によりその表面積を縮小し、強化繊維基材10の表面に溶融樹脂の存在しない未含浸部を形成する。また、溶融した樹脂は、強化繊維11の間をぬって強化繊維基材10中の空隙部に含浸されていく。この樹脂の溶融・含浸のための温度と時間は、強化繊維基材10及び樹脂粉体20に合わせて適宜最適な条件が選ばれる。
　本発明において、開繊とは、強化繊維が繊維の束からなるときは、これが扁平になるようにすることを意味する。この開繊により、本繊維強化樹脂中間材は、強化繊維基材に樹脂が半含浸状態で含浸され、その強化繊維基材の外面に開口した空隙を有する半含浸状態を形成し易くなる。強化繊維基材の外面とは、強化繊維基材10の表面を形成する強化繊維11の外方の意味である。強化繊維基材の外面部とは、強化繊維基材10の表面及びその表面下の部分を含む意味である。なお、本発明において開繊とは、含浸すべき密集してなる繊維の束を扁平にして一定の厚み（例えば、100μm）以下になるようにすることであり、チョップドのような短繊維からなるものであっても適用される。
　本発明において、強化繊維11は、炭素繊維が好ましく、炭素繊維からなる強化繊維基材10の目付は、40～250g/m2であるのがよい。40g/m2以上の目付にすることにより、得られる繊維強化樹脂中間材一枚当たりの強化繊維の総量が少なくなるのを防ぐことができ、繊維強化樹脂成形品を成形する際に必要な繊維強化樹脂中間材の枚数が無用に多くならず実用的である。250g/m2以下の目付とすることにより、加熱時に、溶融した樹脂が、強化繊維11の間をぬって強化繊維基材10中の空隙部に含浸される工程に長時間を要するのを防ぐことができるため実用的である。なお、強化繊維11は、ガラス繊維、天然繊維であってもよく、これらの繊維からなる強化繊維基材10においても、それぞれに適切な目付範囲が決められる。
　樹脂粉体20は、ポリカーボネート（PC）、ポリスルホン（PSU）、ポリエーテルスルホン（PES）、ポリアミドイミド（PAI）、ポリエーテルイミド（PEI）、ポリアミド系樹脂（PA６，PA11，PA66）、ポリブチレンテレフタレート（PBT）、ポリエチレンテレフタレート（PET）、ポリフェニレンスルフィド（PPS）、ポリエーテルエーテルケトン（PEEK）、ポリエーテルケトンケトン（PEKK）等を使用することができる。また、上記のような熱可塑性樹脂の粉体に限らずフェノール樹脂、エポキシ樹脂等の熱硬化性樹脂の粉体であってもよい。
　本発明において樹脂粉体20は、強化繊維11の外径の1/2～30倍の平均粒径を有する粉体を使用することができる。この平均粒径は、使用する樹脂の密度、粘度、繊維の外形、および最終の繊維体積含有率に合せて適宜選定される。このような、平均粒径の樹脂粉体20は、強化繊維基材10に静電付着させ易いという利点がある。また、前記範囲の平均粒径を有する樹脂粉体20を用いることで、強化繊維基材10の繊維体積含有率を所定の値、具体的には15～70％とすることができる。
　上述のように、本発明においては、樹脂を強化繊維基材に付着させるのに樹脂粉体20を用いており、樹脂粉体20を静電付着により強化繊維基材10に付着させている。このため、本発明においては、樹脂粉体20の強化繊維基材10への付着をミクロ的に調製することができる。樹脂粉体20の静電付着は、樹脂粉体20を空気に混合した状態で帯電させ、樹脂粉体20の強化繊維基材10への付着直前にさらに高電圧をかけることにより行うことができる。なお、樹脂粉体20は、含浸という観点からは平均粒径が小さいものが好ましいが、単価が高くなるという点では不利になる。一方、樹脂粉体20の静電付着状態を制御し外面に開口した空隙を有する強化繊維基材を成形するには、樹脂粉体20の平均粒径が大きい方が好ましい。
　上述のように、強化繊維基材が外面に開口した空隙を有する程度に樹脂を強化繊維基材に半含浸状態に含浸させてなる繊維強化樹脂中間材を作製するには、強化繊維基材の見かけ密度ρを所定の範囲にするのがよい。すなわち、その強化繊維基材からなる繊維強化樹脂中間材が強化繊維と樹脂からなり、まったく空隙がないとしたときの密度（目標見かけ密度ρc）に対して、強化繊維基材の見かけ密度ρを1/2～1/50にするのがよい。ここで、炭素繊維の繊維体積含有率をVf及び密度をρf、樹脂の樹脂体積含有率をVr及び密度をρrとしてとき、ρc＝Vr×ρr＋Vf×ρfである。見かけ密度ρが目標見かけ密度ρcの1/2付近である場合は、開繊された経糸と緯糸を折り込んだ織物からなる強化繊維基材において好ましく、見かけ密度ρが目標見かけ密度ρcの1/50付近である場合は、開繊したチョップドからなるマット状の強化繊維基材において好ましい。なお、見かけ密度ρは、強化繊維基材の質量を見かけの体積で除したものである。
　以上、本発明に係る繊維強化樹脂中間材について説明した。本繊維強化樹脂中間材は、所定の型内に積層して、加熱及び加圧されて所定の形状の繊維強化樹脂成形品に形成される。本繊維強化樹脂中間材を使用することにより、繊維体積含有率が15～70%、ボイド率が1.5%以下、さらにはボイド率が0.5%以下の繊維強化樹脂成形品を成形することができる。
　炭素繊維からなる強化繊維基材にポリアミド（PA6）樹脂を含浸させた繊維強化樹脂中間材を作製し、これを積層し、加熱及び加圧することにより、図２に示す矩形形状の繊維強化樹脂成形品30を作製する試験を行った。強化繊維基材は、直径7μｍの炭素繊維束（１千本）を幅2mmとなる様に開繊して目付が63g/m2の平織の炭素繊維織物を作製し、これから切り出したものを用いた。含浸樹脂は、平均粒径20μmのPA6樹脂粉体を用いた。
　上記炭素繊維基材に、PA6樹脂粉体を繊維体積含有率が60％となるように静電付着させ、付着後速やかにIRヒータを用いてPA6樹脂粉体を溶融させた。作製された繊維強化樹脂中間材の厚みは180μmであった。図３に、強化繊維基材にPA6樹脂粉体を静電付着させた表面状態の光学顕微鏡写真を示す。強化繊維基材の表面は、いまなおまだらであるが、薄く粉雪に敷き詰められた様に観察される。
　図４は、作製した繊維強化樹脂中間材の表面の走査電子顕微鏡（SEM）写真を示す。繊維強化樹脂中間材の表面は、炭素繊維束が水あめ様の厚目の被膜に被われた部分があり、薄い皮膜に被われた部分があり、また、ほとんど炭素繊維束そのままむき出しの部分があるように観察される。厚目の被膜部分には、あたかも埋めきれなかったような炭素繊維の方向に沿った細長く、様々の長さの溝様の部分が点在する。すなわち、強化繊維基材は、PA6樹脂による半含浸状態で外面に開口した空隙を有していることが観察される。
　上記繊維強化樹脂中間材を金型内に16枚積層し、260℃まで昇温した後にその温度を維持し、5MPaで加圧した。加圧時間は70秒であった。図５に、成形された繊維強化樹脂成形品断面の倍率400倍の光学顕微鏡写真を示す。この繊維強化樹脂成形品は、ボイド率が0.5％以下であった。また、繊維強化樹脂成形品30の賦形性は良好で、図２に示す溝の端部31も繊維のズレが無く良好に成形できた。
　本発明を詳細にまた特定の実施形態を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は、２０１４年１０月１７日出願の日本特許出願（特願２０１４－２１３１１４）に基づくものであり、その内容はここに参照として取り込まれる。
　10　　強化繊維基材
　11　　強化繊維
　20　　樹脂粉体
　30　　繊維強化樹脂成形品
　31　　溝の端部

Claims (6)

  1. 　開繊された強化繊維で形成される強化繊維基材の外面部に樹脂を付着させ、その樹脂の融点以上に加熱して前記樹脂を前記強化繊維基材に含浸させた繊維強化樹脂中間材であって、
    　前記強化繊維基材は、外面に開口した空隙を有し、前記樹脂が半含浸状態にある繊維強化樹脂中間材。
  2. 　強化繊維基材に付着させる樹脂が粉体である請求項１に記載の繊維強化樹脂中間材。
  3. 　前記強化繊維は炭素繊維であり、前記強化繊維基材の目付が40～250g/m2である請求項１又は２に記載の繊維強化樹脂中間材。
  4. 　見かけ密度ρが以下の目標見かけ密度ρcの1/2～1/50である請求項１～３のいずれか１項に記載の繊維強化樹脂中間材。
    　目標見かけ密度ρcは、炭素繊維の繊維体積含有率をVf及び密度をρf、樹脂の樹脂体積含有率をVr及び密度をρrとするとき、ρc＝Vr×ρr＋Vf×ρfである。
  5. 　請求項１～４に記載の繊維強化樹脂中間材を積層し、加熱及び加圧して成形される繊維強化樹脂成形体。
  6. 　強化繊維基材が、樹脂を半含浸状態で含浸し外面に開口した空隙を有している繊維強化樹脂中間材の製造方法であって、
    　前記強化繊維基材を形成する強化繊維の外径とその強化繊維基材の嵩密度に基づいて、前記強化繊維基材の繊維体積含有率が所定の値になるように、所定の平均粒径の樹脂粉体を前記強化繊維基材に静電付着させる繊維強化樹脂中間材の製造方法。
PCT/JP2015/079297 2014-10-17 2015-10-16 繊維強化樹脂中間材及びその製造方法 Ceased WO2016060240A1 (ja)

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