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WO2021106630A1 - 複合材料の製造方法 - Google Patents

複合材料の製造方法 Download PDF

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Publication number
WO2021106630A1
WO2021106630A1 PCT/JP2020/042425 JP2020042425W WO2021106630A1 WO 2021106630 A1 WO2021106630 A1 WO 2021106630A1 JP 2020042425 W JP2020042425 W JP 2020042425W WO 2021106630 A1 WO2021106630 A1 WO 2021106630A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluororesin
melt
composite material
prepreg
carbon fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/042425
Other languages
English (en)
French (fr)
Inventor
眞司 村上
宏和 湯川
圭祐 羽儀
尚哲 金森
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Fukuvi Chemical Industry Co Ltd
Original Assignee
Daikin Industries Ltd
Fukuvi Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries Ltd, Fukuvi Chemical Industry Co Ltd filed Critical Daikin Industries Ltd
Priority to EP20892651.9A priority Critical patent/EP4053192A4/en
Priority to CN202080081678.0A priority patent/CN114787247B/zh
Priority to KR1020227016342A priority patent/KR102788190B1/ko
Priority to JP2021561309A priority patent/JP7194845B2/ja
Publication of WO2021106630A1 publication Critical patent/WO2021106630A1/ja
Priority to US17/825,514 priority patent/US20220297394A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • 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
    • B29C70/28—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • 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
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/516—Oriented mono-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

Definitions

  • the present disclosure relates to a method for producing a composite material.
  • fiber-reinforced composite materials in which carbon fibers, glass fibers, aromatic polyamide fibers, etc. are mixed or sandwiched as reinforcing materials in a matrix such as synthetic resin have been developed and put on the market.
  • These fiber-reinforced composite materials can obtain excellent performance suitable for the purpose in various points such as strength, heat resistance, corrosion resistance, electrical properties, and light weight, depending on the selection of the matrix and the reinforcing material. It is used in a wide range of fields such as land transportation, ships, construction, civil engineering, industrial parts, and sports equipment, and has great social demand.
  • Examples of the usage form of the reinforcing fiber include those in which a plurality of filaments are arranged in a required width, those in which the filaments are cut to a predetermined size, those in which the filament is made into a cloth such as a woven fabric, and the like.
  • these reinforcing fibers are directly composited by a matrix, or a semi-finished product called a prepreg is manufactured by impregnating a sheet or woven fabric in which filaments are regularly arranged with a synthetic resin, and this prepreg is used. If necessary, an appropriate number of sheets are stacked, and a device such as an autoclave is used to complete the desired final product.
  • reinforcing fibers are provided in the form of multifilaments that are aligned and bonded with a sizing agent, and it is difficult to sufficiently impregnate the inside of the reinforcing fiber bundle with a thermoplastic resin having a high viscosity during processing. Therefore, a technique for opening reinforcing fibers to facilitate impregnation with a resin has been studied (see, for example, Patent Document 1).
  • Patent Documents 2 and 3 describe fiber-reinforced thermoplastic resin sheets using opened carbon fibers and non-fluorine-based matrix resins such as nylon and polypropylene.
  • An object of the present disclosure is to provide a method for producing a fluororesin / carbon fiber composite material in which a fluororesin film does not easily shrink in the width direction during preparation of a prepreg.
  • the present disclosure is a method for producing a composite material containing carbon fiber and a fluororesin that can be melt-processed.
  • a melt-processable fluororesin film having a back tension of 3.0 N / cm 2 or less is superposed on the opened carbon fiber, and then heated to a temperature equal to or higher than the melting point of the fluororesin and pressurized.
  • Step (1) to obtain prepreg by The present invention relates to a production method including a step (2) of obtaining the composite material by heating and pressurizing the prepreg to a temperature equal to or higher than the melting point of the fluororesin in a state where one or more prepregs are stacked in the thickness direction.
  • the fluororesins that can be melt-processed include tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer, polychlorotrifluoroethylene, and the like. , At least one selected from the group consisting of polyvinylidene fluoride.
  • the melt-processable fluororesin preferably has a melt flow rate of 0.1 to 100 g / 10 minutes and a melting point of 272 to 323 ° C.
  • the fluororesin that can be melt-processed is preferably a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer.
  • Fluororesin has many excellent properties such as heat resistance, chemical resistance, slidability, and low dielectric constant, and is used in many fields such as automobiles, aircraft, semiconductors, electricity, electrons, and chemistry. There are also problems such as lower strength and higher coefficient of linear expansion than the resin of.
  • One of the solutions is to combine with reinforcing fibers such as carbon fiber.
  • the fluororesin film will be formed in the width direction. The problem of shrinking occurs.
  • the fluororesin has a low elastic modulus, and when the fluororesin film is unwound with the same back tension as the non-fluororesin, the fluororesin film shrinks in the width direction due to the back tension and heat. I found that. Then, they found that the problem of contraction can be solved by controlling the back tension within a specific range.
  • the present disclosure will be specifically described.
  • the present disclosure is a method for producing a composite material containing carbon fiber and a fluororesin that can be melt-processed.
  • a prepreg is obtained by heating and pressurizing above the melting point of the fluororesin in a state where the opened carbon fiber and the fluororesin film having a back tension of 3.0 N / cm 2 or less and which can be melt-processed are superposed.
  • the melt-processable fluororesin film is unlikely to shrink in the width direction. As a result, quality stability during continuous production of the composite material can be improved.
  • the carbon fiber used in the step (1) is opened.
  • the carbon fibers are sufficiently impregnated with the fluororesin.
  • the method of opening the fibers is not particularly limited, and a method of passing uneven rolls alternately, a method of using a drum-shaped roll, a method of applying tension fluctuation to axial vibration, and a carbon fiber made of two friction bodies that reciprocate vertically. A method of varying the tension of the bundle, a method of blowing air on the carbon fiber bundle, or the like may be adopted. Further, the fiber opening method described in Japanese Patent No. 3064019 and Japanese Patent No. 3146200 can also be adopted.
  • the carbon fiber has a basis weight of 100 g / m 2 or less, more preferably 80 g / m 2 or less, further preferably 50 g / m 2 or less, and 10 g / m 2 or more. It is preferable to have. The lower the basis weight, the easier it is to impregnate the carbon fibers of the fluororesin. Further, the basis weight may be 30 g / m 2 or more.
  • Examples of the carbon fibers include polyacrylonitrile-based, pitch-based, rayon-based, cellulose-based, lignin-based, phenol-based, and vapor-phase growth-based fibers. Among them, polyacrylonitrile-based, pitch-based or rayon-based carbon fibers are preferable, and polyacrylonitrile-based carbon fibers are more preferable.
  • the carbon fiber may be surface-treated, a treatment agent may be used, or a sizing agent may be used.
  • the fluororesin used in the step (1) can be melt-processed.
  • the term "meltable” means that the polymer can be melted and processed by using conventional processing equipment such as an extruder and an injection molding machine.
  • the melt flow rate (MFR) of the fluororesin that can be melt-processed is preferably 0.1 to 100 g / 10 minutes, and more preferably 0.5 to 50 g / 10 minutes.
  • the MFR conforms to ASTM D1238, and the measurement temperature determined by the type of fluororesin using a melt indexer (for example, 372 ° C for PFA and FEP, 297 ° C for ETFE).
  • the fluororesin preferably has a melting point of 150 to 323 ° C, more preferably 200 to 323 ° C, further preferably 250 to 323 ° C, and even more preferably 272 ° C to 323 ° C. It is preferably 280 to 320 ° C., particularly preferably 280 to 320 ° C.
  • the melting point is a temperature corresponding to a maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter [DSC].
  • fluororesin examples include tetrafluoroethylene [TFE] / perfluoro (alkyl vinyl ether) [PAVE] copolymer [PFA], TFE / hexafluoropropylene [HFP] copolymer [FEP], and ethylene [Et] / TFE.
  • TFE tetrafluoroethylene
  • PFA perfluoro (alkyl vinyl ether)
  • HFP hexafluoropropylene
  • FEP hexafluoropropylene
  • Et ethylene
  • At least one selected from the group consisting of copolymer [ETFE], polychlorotrifluoroethylene [PCTFE], and polyvinylidene fluoride [PVDF] is preferable, and at least one selected from the group consisting of PFA, FEP, and ETFE.
  • PFA is even more preferred.
  • the PFA has a polymerization unit (TFE unit) based on tetrafluoroethylene (TFE) and a polymerization unit (PAVE unit) based on perfluoro (alkyl vinyl ether) (PAVE).
  • Rf 1 represents a perfluoroalkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.
  • Rf 1 represents a perfluoroalkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.
  • Perfluoro (ethyl vinyl ether) [PEVE] purple olo (propyl vinyl ether) [PPVE] are preferable.
  • the PFA is not particularly limited, but a copolymer in which the ratio of the TFE unit to the total of the TFE unit and the PAVE unit is 70 mol% or more and less than 99.5 mol% is preferable, and 70 mol% or more and 98.9 mol is preferable. A copolymer of% or less is more preferable, and a copolymer of 80 mol% or more and 98.7 mol% or less is further preferable.
  • the PFA may be a copolymer consisting of only TFE units and PAVE units, or the monomer units derived from the monomers copolymerizable with TFE and PAVE are 0.
  • Z 4 represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 2 to 10
  • CF 2 CF-OCH 2
  • alkyl perfluorovinyl ether derivative represented by ⁇ Rf 11 (in the formula, Rf 11 represents a perfluoroalkyl group having 1 to 5 carbon atoms).
  • each monomer unit constituting PFA can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis according to the type of monomer.
  • the melt-processable fluororesin film preferably has a thickness of 0.01 to 2 mm, more preferably 0.01 to 1 mm.
  • the back tension of the film is set to 3.0 N / cm 2 or less.
  • the back-tension is preferably at 2.5 N / cm 2 or less, more preferably 2.0 N / cm 2 or less, still more preferably 1.0 N / cm 2 or less, 0.8N / particularly preferably cm 2 or less, also is preferably 0.05 N / cm 2 or more, is 0.1 N / cm 2 or more Konomashikui.
  • the back tension is a tension applied to the film in the direction opposite to the transport direction of the film, and can be adjusted by the output of the control device. Examples of the control device include ZKB-0.6AM / YK manufactured by Mitsubishi Electric.
  • step (1) it is preferable that the carbon fiber and the fluororesin film are continuously conveyed.
  • the prepreg is obtained by heating and pressurizing the carbon fiber and the film having the back tension within the above range to a temperature equal to or higher than the melting point of the fluororesin.
  • the heating temperature may be equal to or higher than the melting point of the fluororesin, but is preferably 310 ° C. or higher, more preferably 340 ° C. or higher, and preferably 400 ° C. or lower.
  • the pressurizing pressure is preferably 0.01 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.
  • the heating and pressurization are preferably carried out by applying pressure with a roll heated to a temperature equal to or higher than the melting point of the fluororesin.
  • the prepreg may be one in which the carbon fiber and the fluororesin are heat-sealed. In the prepreg, it is preferable that the carbon fiber is impregnated with the fluororesin.
  • the amount of the carbon fibers is preferably 5 to 70% by volume based on the total amount of the carbon fibers and the fluororesin.
  • the carbon fiber is more preferably 10% by volume or more, further preferably 15% by volume or more, further preferably 60% by volume or less, and further preferably 50% by volume or less. ..
  • the manufacturing method of the present disclosure may further include a step of obtaining a chop material by cutting the prepreg obtained in the step (1).
  • the chop material may be used as a prepreg in the step (2). Since the chop material can be randomly oriented in the two-dimensional direction and laminated, the carbon fibers can be oriented in a pseudo-isotropic direction, and the difference in strength of the obtained composite material depending on the direction is reduced. Moreover, it can be easily molded into a complicated shape.
  • the manufacturing method of the present disclosure may further include a step of obtaining a chopped sheet by heating the two or more chopped materials in a state of being overlapped in the thickness direction.
  • the chopped sheet may be used as a prepreg in the step (2).
  • step (2) a composite material containing carbon fibers and a fluororesin that can be melt-processed is produced by heating and pressurizing one or more of the prepregs in the thickness direction to a temperature equal to or higher than the melting point of the fluororesin. obtain.
  • the step (2) it is preferable to stack two or more of the prepregs in the thickness direction.
  • the orientation of the carbon fibers constituting each prepreg may be the same or different.
  • the prepreg to be overlapped is the above-mentioned chop material, it is preferable to orient the prepreg in two dimensions at random.
  • the heating temperature in the step (2) may be equal to or higher than the melting point of the fluororesin, but is preferably 310 ° C. or higher, more preferably 340 ° C. or higher, and 400 ° C. or lower. preferable.
  • the pressurizing pressure in the step (2) is preferably 0.05 to 10 MPa, more preferably 2 to 5 MPa.
  • molding may be performed at the same time to obtain a composite molded product containing the carbon fiber and the fluororesin.
  • the above heating and pressurization may be performed using a compression molding machine.
  • the composite material obtained by the production method of the present disclosure is obtained from two or more prepregs, it is preferable that two or more prepregs are integrated.
  • integration means that the prepregs are heat-sealed to form one material.
  • the interface between the heat-sealed prepregs does not necessarily have to be clear.
  • the carbon fiber is preferably 5 to 70% by volume based on the total amount of the carbon fiber and the fluororesin.
  • the carbon fiber is more preferably 10% by volume or more, further preferably 15% by volume or more, further preferably 60% by volume or less, and further preferably 50% by volume or less. ..
  • the composite material can be molded by a known molding method such as compression molding to obtain a molded product. Further, as described above, molding can also be performed in the step (2).
  • the composite material can be used in a wide range of fields such as aerospace, land transportation, ships, construction, civil engineering, industrial parts, and sports equipment. Among them, it can be suitably used as a member for a semiconductor cleaning device.
  • MFR According to ASTM D3307, the mass of the polymer flowing out from the nozzle per 10 minutes was measured at a measurement temperature of 372 ° C. and a load of 5 kg.
  • Example 1 ⁇ Making a UD sheet (prepreg)> A UD sheet was prepared using the following materials. Carbon fiber bundle (T700SC-12000-60E manufactured by Toray Industries, Inc.) PFA film (MFR 14 g / 10 minutes, melting point 306 ° C, thickness 0.05 mm) Using a known fiber-spreading method, each of the five carbon fiber bundles was spread to a width of 42 mm and arranged in the width direction to form a sheet-shaped spread-fiber carbon fiber sheet (with a basis weight of 38.1 g / m 2 ). Made.
  • Carbon fiber bundle T700SC-12000-60E manufactured by Toray Industries, Inc.
  • PFA film MFR 14 g / 10 minutes, melting point 306 ° C, thickness 0.05 mm
  • the back tension of the PFA film is 0.6 N / cm.
  • the film was laminated as No. 2 and run between heating and pressurizing rolls set to a heating temperature of 360 ° C. (linear speed: 10 m / min) to prepare a UD sheet.
  • a UD sheet having a Vf (carbon fiber volume content) of 29.7% and a thickness of 0.072 mm could be obtained without the PFA film shrinking in the width direction.
  • Example 2 A UD sheet was produced in the same manner as in Example 1 except that the thickness of the PFA film was 0.025 mm and the back tension was 0.25 N / cm 2. A UD sheet having a Vf of 45.8% and a thickness of 0.046 mm could be obtained without the PFA film shrinking in the width direction.
  • Example 3 A UD sheet was produced in the same manner as in Example 1 except that the thickness of the PFA film was 0.050 mm and the back tension was 2.5 N / cm 2. Although the PFA film shrank by about 2 to 3 mm in the width direction, a UD sheet having a Vf of 29.7% and a thickness of 0.072 mm could be obtained.
  • Example 4 The same as in Example 1 except that the three carbon fiber bundles were opened to a width of 75 mm and arranged in the width direction to prepare a 225 mm spread carbon fiber sheet (with a grain of 26.7 g / m 2) in the form of a sheet.
  • UD sheet was prepared. Although the PFA film shrank by about 2 to 3 mm in the width direction, a UD sheet having a Vf of 22.7% and a thickness of 0.064 mm could be obtained.
  • a chop material was produced by cutting with a known supply mechanism and cutting mechanism to a width of 5 mm along the fiber direction and a length of 20 mm along the direction orthogonal to the fiber direction.
  • a chopped sheet was prepared by the method described in JP-A-2016-27956.
  • a UD sheet cutting mechanism a chop material conveying mechanism, a sheet integrating mechanism, and a sheet winding mechanism were used.
  • the UD sheet was cut to a width of 5 mm along the fiber direction by a UD sheet cutting mechanism, and cut to a length of 20 mm along the direction orthogonal to the fiber direction to prepare a chop material.
  • the obtained chop material having a width of 5 mm and a length of 20 mm was naturally dropped onto a transport belt and dispersed. Two or more chop materials stacked on the belt are stacked in the thickness direction.
  • the chopped material was melted and integrated with a heating roller set to a heating temperature of 360 ° C. (linear speed: 0.6 m / min) to prepare a chopped sheet.
  • the obtained chopped sheet had a basis weight of 500 g / m 2 and a thickness of 0.6 mm.
  • a composite material was produced from each of the above UD sheet, chopped material, and chopped sheet using a known press molding machine.
  • UD sheets are combined so that the width is 298 mm and the length is 298 mm, 940 sheets are laminated so that the thickness of the molded product is 40 mm, the mold is set to a heating temperature of 360 ° C., and 5 MPa. It was heated and pressurized at the pressure of 5 minutes. Then, the mold was set to a temperature of 30 ° C. and pressurized at a pressure of 7 MPa for 20 minutes.
  • Comparative Example 1 An attempt was made to prepare a UD sheet in the same manner as in Example 2 except that the spread carbon fiber sheet and the PFA film were laminated with the back tension of the PFA film set to 5.0 N / cm 2, but heating was performed. When the PFA film was run between the pressure rolls, the PFA film stretched in the length direction, shrunk by 20 mm or more in the width direction, and the thickness also changed, so that it was not possible to obtain a UD sheet with the set specifications.

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Abstract

プリプレグ作製時にフッ素樹脂フィルムが幅方向に収縮しにくい、フッ素樹脂／炭素繊維複合材料の製造方法を提供する。炭素繊維と溶融加工可能なフッ素樹脂とを含む複合材料の製造方法であって、開繊された炭素繊維と、バックテンションを３．０Ｎ／ｃｍ２以下とした溶融加工可能なフッ素樹脂のフィルムとを重ね合わせた状態で、前記フッ素樹脂の融点以上の温度に加熱し加圧することによりプリプレグを得る工程（１）、及び、前記プリプレグを厚み方向に１枚以上重ね合わせた状態で、前記フッ素樹脂の融点以上に加熱し加圧することにより前記複合材料を得る工程（２）を含む製造方法である。

Description

複合材料の製造方法
本開示は、複合材料の製造方法に関する。
近年、合成樹脂等のマトリックスに強化材として炭素繊維やガラス繊維、芳香族ポリアミド繊維等を混入するか又は挟み混んだ繊維強化の複合材料が数多く開発され市販されている。これらの繊維強化複合材料は、マトリックスと強化材の選択に応じて、強度、耐熱性、耐食性、電気特性、軽量性等の諸点で目的に合致した優れた性能を得ることができることから、航空宇宙、陸上輸送、船舶、建築、土木、工業用部品、スポーツ用品等の広い分野に利用されており、大きな社会的需要を有している。
強化繊維の使用形態としては、必要な幅に複数本のフィラメントを配列したもの、フィラメントを所定寸法にカットしたもの、織物等の布状にしたもの等がある。複合材料としては、これらの強化繊維をマトリックスによって直接的に複合化するもの、あるいはフィラメントを規則的に配列したシートや織物等に合成樹脂を含浸させプリプレグと呼ばれる半製品を製造し、このプリプレグを必要に応じて適当な枚数重ね合わせ、オートクレーブ等の装置で目的とする最終製品に完成させるもの等が挙げられる。
これらの強化繊維は引き揃えられサイジング剤で結合されたマルチフィラメントの形態で提供されており、加工時の粘度が高い熱可塑性樹脂では強化繊維束の中まで樹脂を充分に含浸することが困難であるため、強化繊維を開繊し樹脂を含浸しやすくする技術が検討されている（例えば、特許文献１参照）。
また、特許文献２及び３には、開繊された炭素繊維と、ナイロン、ポリプロピレン等の非フッ素系マトリックス樹脂とを用いた繊維強化熱可塑性樹脂シートが記載されている。
国際公開第９７／４１２８５号 特開２００３－１６５８５１号公報 特開２０１２－１４８５６８号公報
本開示は、プリプレグ作製時にフッ素樹脂フィルムが幅方向に収縮しにくい、フッ素樹脂／炭素繊維複合材料の製造方法を提供することを目的とする。
本開示は、炭素繊維と溶融加工可能なフッ素樹脂とを含む複合材料の製造方法であって、
開繊された炭素繊維と、バックテンションを３．０Ｎ／ｃｍ２以下とした溶融加工可能なフッ素樹脂のフィルムとを重ね合わせた状態で、上記フッ素樹脂の融点以上の温度に加熱し加圧することによりプリプレグを得る工程（１）、及び、
上記プリプレグを厚み方向に１枚以上重ね合わせた状態で、上記フッ素樹脂の融点以上に加熱し加圧することにより上記複合材料を得る工程（２）を含む製造方法に関する。
上記溶融加工可能なフッ素樹脂は、テトラフルオロエチレン／パーフルオロ（アルキルビニルエーテル）共重合体、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体、エチレン／テトラフルオロエチレン共重合体、ポリクロロトリフルオロエチレン、及び、ポリフッ化ビニリデンからなる群より選択される少なくとも１種であることが好ましい。
上記溶融加工可能なフッ素樹脂は、メルトフローレートが０．１～１００ｇ／１０分であり、融点が２７２～３２３℃であることが好ましい。
上記溶融加工可能なフッ素樹脂は、テトラフルオロエチレン／パーフルオロ（アルキルビニルエーテル）共重合体であることが好ましい。
本開示によれば、プリプレグ作製時にフッ素樹脂フィルムが幅方向に収縮しにくい、フッ素樹脂／炭素繊維複合材料の製造方法を提供することができる。
フッ素樹脂は耐熱性、耐薬品性、摺動性、低誘電率等の多くの優れた特性を持ち、自動車、航空機、半導体、電気、電子、化学等の多くの分野に利用されているが他の樹脂に比べ強度が低い、線膨張係数が大きい等の課題もある。その解決策の１つとして、炭素繊維等の強化繊維との複合化が挙げられるが、ナイロン等の非フッ素系マトリックス樹脂を使用する場合と同じ条件でプリプレグを作製すると、フッ素樹脂フィルムが幅方向に収縮するという問題が発生する。鋭意検討の結果、本発明者らは、フッ素樹脂は弾性率が低く、非フッ素系樹脂と同じバックテンションでフッ素樹脂フィルムを繰り出すと、バックテンションと熱により、フッ素樹脂フィルムが幅方向に収縮することを見出した。そして、バックテンションを特定の範囲内に制御することで、上記収縮の問題が解決することを見出した。
以下、本開示を具体的に説明する。
本開示は、炭素繊維と溶融加工可能なフッ素樹脂とを含む複合材料の製造方法であって、
開繊された炭素繊維と、バックテンションを３．０Ｎ／ｃｍ２以下とした溶融加工可能なフッ素樹脂のフィルムとを重ね合わせた状態で、上記フッ素樹脂の融点以上に加熱し加圧することによりプリプレグを得る工程（１）、及び、上記プリプレグを厚み方向に１枚以上重ね合わせた状態で、上記フッ素樹脂の融点以上の温度に加熱し加圧することにより上記複合材料を得る工程（２）を含む製造方法に関する。
本開示の製造方法では、プリプレグを作製する工程（１）において、上記溶融加工可能なフッ素樹脂のフィルムが幅方向に収縮しにくい。その結果、上記複合材料を連続生産する際の品質の安定性を向上させることができる。
工程（１）で使用する炭素繊維は、開繊されている。これにより、上記炭素繊維に上記フッ素樹脂が充分に含浸する。
開繊の方法は特に限定されず、凹凸ロールを交互に通過させる方法、太鼓型ロールを使用する方法、軸方向振動に張力変動を加える方法、垂直に往復運動する２個の摩擦体による炭素繊維束の張力を変動させる方法、炭素繊維束にエアを吹き付ける方法等を採用してよい。また、特許第３０６４０１９号公報及び特許第３１４６２００号公報に記載される開繊方法を採用することもできる。
上記炭素繊維は、目付が１００ｇ／ｍ２以下であることが好ましく、８０ｇ／ｍ２以下であることがより好ましく、５０ｇ／ｍ２以下であることが更に好ましく、また、１０ｇ／ｍ２以上であることが好ましい。目付が低いほどフッ素樹脂の炭素繊維への含浸が容易になる。また、上記目付は３０ｇ／ｍ２以上であってもよい。
上記炭素繊維としては、ポリアクリロニトリル系、ピッチ系、レーヨン系、セルロース系、リグニン系、フェノール系、気相成長系等が挙げられる。なかでも、ポリアクリロニトリル系、ピッチ系又はレーヨン系の炭素繊維が好ましく、ポリアクリロニトリル系の炭素繊維がより好ましい。
上記炭素繊維は、表面処理されていてもよく、処理剤が使用されていてもよく、サイジング剤が使用されていてもよい。
工程（１）で使用するフッ素樹脂は、溶融加工可能である。本明細書において、溶融加工可能であるとは、押出機及び射出成形機等の従来の加工機器を用いて、ポリマーを溶融して加工することが可能であることを意味する。
上記溶融加工可能なフッ素樹脂は、メルトフローレート（ＭＦＲ）が０．１～１００ｇ／１０分であることが好ましく、０．５～５０ｇ／１０分であることがより好ましい。
本明細書において、ＭＦＲは、ＡＳＴＭ　Ｄ１２３８に準拠し、メルトインデクサーを用いて、フッ素樹脂の種類によって定められた測定温度（例えば、ＰＦＡやＦＥＰの場合は３７２℃、ＥＴＦＥの場合は２９７℃）、荷重（例えば、ＰＦＡ、ＦＥＰ及びＥＴＦＥの場合は５ｋｇ）において内径２ｍｍ、長さ８ｍｍのノズルから１０分間あたりに流出するポリマーの質量（ｇ／１０分）として得られる値である。
上記フッ素樹脂は、融点が１５０～３２３℃であることが好ましく、２００～３２３℃であることがより好ましく、２５０～３２３℃であることが更に好ましく、２７２℃～３２３℃であることが更により好ましく、２８０～３２０℃であることが特に好ましい。
上記融点は、示差走査熱量計〔ＤＳＣ〕を用いて１０℃／分の速度で昇温したときの融解熱曲線における極大値に対応する温度である。
上記フッ素樹脂としては、テトラフルオロエチレン［ＴＦＥ］／パーフルオロ（アルキルビニルエーテル）［ＰＡＶＥ］共重合体［ＰＦＡ］、ＴＦＥ／ヘキサフルオロプロピレン［ＨＦＰ］共重合体［ＦＥＰ］、エチレン［Ｅｔ］／ＴＦＥ共重合体［ＥＴＦＥ］、ポリクロロトリフルオロエチレン［ＰＣＴＦＥ］、及び、ポリフッ化ビニリデン［ＰＶＤＦ］からなる群より選択される少なくとも１種が好ましく、ＰＦＡ、ＦＥＰ及びＥＴＦＥからなる群より選択される少なくとも１種がより好ましく、ＰＦＡが更に好ましい。
上記ＰＦＡは、テトラフルオロエチレン（ＴＦＥ）に基づく重合単位（ＴＦＥ単位）、及び、パーフルオロ（アルキルビニルエーテル）（ＰＡＶＥ）に基づく重合単位（ＰＡＶＥ単位）を有する。
上記ＰＡＶＥとしては、特に限定されず、例えば、下記一般式（１）
ＣＦ２＝ＣＦ－ＯＲｆ１　　　（１）
（式中、Ｒｆ１は、炭素数１～１０、好ましくは炭素数１～５のパーフルオロアルキル基を表す。）で表されるものが挙げられ、なかでもパーフルオロ（メチルビニルエーテル）〔ＰＭＶＥ〕、パーフルオロ（エチルビニルエーテル）〔ＰＥＶＥ〕、パープルオロ（プロピルビニルエーテル）〔ＰＰＶＥ〕が好ましい。
上記ＰＦＡとしては、特に限定されないが、ＴＦＥ単位とＰＡＶＥ単位との合計に対するＴＦＥ単位の割合が７０モル％以上９９．５モル％未満である共重合体が好ましく、７０モル％以上９８．９モル％以下である共重合体がより好ましく、８０モル％以上９８．７モル％以下である共重合体が更に好ましい。上記ＰＦＡは、ＴＦＥ単位及びＰＡＶＥ単位のみからなる共重合体であってもよいし、全単量体単位に対しＴＦＥ及びＰＡＶＥと共重合可能な単量体に由来する単量体単位が０．１～１０モル％であり、ＴＦＥ単位及びＰＡＶＥ単位が合計で９０～９９．９モル％である共重合体であることも好ましい。ＴＦＥ及びＰＡＶＥと共重合可能な単量体としては、ＨＦＰ、ＣＺ１Ｚ２＝ＣＺ３（ＣＦ２）ｎＺ４（式中、Ｚ１、Ｚ２及びＺ３は、同一若しくは異なって、水素原子又はフッ素原子を表し、Ｚ４は、水素原子、フッ素原子又は塩素原子を表し、ｎは２～１０の整数を表す。）で表されるビニル単量体、及び、ＣＦ２＝ＣＦ－ＯＣＨ２－Ｒｆ１１（式中、Ｒｆ１１は炭素数１～５のパーフルオロアルキル基を表す。）で表されるアルキルパーフルオロビニルエーテル誘導体等が挙げられる。
本明細書において、ＰＦＡを構成する各単量体単位の含有量は、ＮＭＲ、ＦＴ－ＩＲ、元素分析、蛍光Ｘ線分析を単量体の種類によって適宜組み合わせることで算出できる。
上記溶融加工可能なフッ素樹脂のフィルムは、厚みが０．０１～２ｍｍであることが好ましく、０．０１～１ｍｍであることがより好ましい。
工程（１）では、上記炭素繊維と上記フッ素樹脂のフィルムとを重ね合わせる際に、上記フィルムのバックテンションを３．０Ｎ／ｃｍ２以下とする。バックテンションを上記範囲内にすることで、プリプレグ作製時の上記フィルムの幅方向の収縮を抑制することができる。
上記バックテンションは、２．５Ｎ／ｃｍ２以下であることが好ましく、２．０Ｎ／ｃｍ２以下であることがより好ましく、１．０Ｎ／ｃｍ２以下であることが更に好ましく、０．８Ｎ／ｃｍ２以下であることが特に好ましく、また、０．０５Ｎ／ｃｍ２以上であることが好ましく、０．１Ｎ／ｃｍ２以上であることがより好ましくい。
上記バックテンションは、上記フィルムの搬送方向とは逆向きに上記フィルムに対して付加される張力であり、制御機器の出力により調整することができる。制御機器としては、例えば、三菱電機製　ＺＫＢ－０．６ＡＭ／ＹＫ等が挙げられる。
工程（１）では、上記炭素繊維及び上記フッ素樹脂のフィルムが連続的に搬送されることが好ましい。
工程（１）では、上記炭素繊維と、バックテンションを上記範囲内とした上記フィルムとを重ね合わせた状態で、上記フッ素樹脂の融点以上の温度に加熱し加圧することによりプリプレグを得る。加熱・加圧することで、上記フッ素樹脂が上記炭素繊維に含浸する。
上記加熱の温度は、上記フッ素樹脂の融点以上であればよいが、３１０℃以上であることが好ましく、３４０℃以上であることがより好ましく、また、４００℃以下であることが好ましい。
上記加圧の圧力は、０．０１～５．０ＭＰａであることが好ましく、０．１～１．０ＭＰａであることがより好ましい。
上記加熱及び加圧は、上記フッ素樹脂の融点以上の温度まで加熱したロールで圧力を掛けることにより実施することが好ましい。
上記プリプレグは、上記炭素繊維と上記フッ素樹脂とが熱融着したものであってよい。上記プリプレグにおいては、上記フッ素樹脂が上記炭素繊維に含浸していることが好ましい。
上記プリプレグにおいては、上記炭素繊維が、上記炭素繊維と上記フッ素樹脂との合計量に対し、５～７０体積％であることが好ましい。上記炭素繊維は、１０体積％以上であることがより好ましく、１５体積％以上であることが更に好ましく、また、６０体積％以下であることがより好ましく、５０体積％以下であることが更に好ましい。
本開示の製造方法は、工程（１）で得られたプリプレグを切断することによりチョップ材を得る工程を更に含んでもよい。上記チョップ材を、工程（２）におけるプリプレグとして用いてもよい。
上記チョップ材は二次元方向にランダムに配向させて積層することができるので、炭素繊維を疑似等方に配向させることができ、得られる複合材料の、方向による強度差が少なくなる。また、複雑な形状にも容易に成形することができる。
本開示の製造方法は、２枚以上の上記チョップ材を厚み方向に重ね合わせた状態で加熱することにより、チョップドシートを得る工程を更に含んでもよい。上記チョップドシートを、工程（２）におけるプリプレグとして用いてもよい。
工程（２）では、上記プリプレグを厚み方向に１枚以上重ね合わせた状態で、上記フッ素樹脂の融点以上に加熱し加圧することにより、炭素繊維と溶融加工可能なフッ素樹脂とを含む複合材料を得る。
工程（２）では、上記プリプレグを厚み方向に２枚以上重ね合わせることが好ましい。この場合、各プリプレグを構成する炭素繊維の配向は、同じであってもよく、異なってもよい。重ね合わせるプリプレグが上記チョップ材である場合は、二次元方向にランダムに配向させることが好ましい。
工程（２）における加熱の温度は、上記フッ素樹脂の融点以上であればよいが、３１０℃以上であることが好ましく、３４０℃以上であることがより好ましく、また、４００℃以下であることが好ましい。
工程（２）における加圧の圧力は、０．０５～１０ＭＰａであることが好ましく、２～５ＭＰａであることがより好ましい。
工程（２）では、成形を同時に行って、上記炭素繊維及び上記フッ素樹脂を含む複合成形品を得てもよい。この場合は、例えば、上記の加熱及び加圧を、圧縮成形機を用いて行えばよい。
本開示の製造方法により得られる複合材料は、２枚以上の上記プリプレグから得られる場合、２枚以上の上記プリプレグが一体化されていることが好ましい。ここで、一体化とは、上記プリプレグ同士が熱融着し、１の材料を構成することを意味する。熱融着した上記プリプレグ同士の界面は、必ずしも明確でなくてよい。
上記複合材料においては、上記炭素繊維が、上記炭素繊維と上記フッ素樹脂との合計量に対し、５～７０体積％であることが好ましい。上記炭素繊維は、１０体積％以上であることがより好ましく、１５体積％以上であることが更に好ましく、また、６０体積％以下であることがより好ましく、５０体積％以下であることが更に好ましい。
上記複合材料は、圧縮成形等の公知の成形方法により成形し、成形品とすることができる。また、上述のように、工程（２）において成形を行うこともできる。
上記複合材料は、航空宇宙、陸上輸送、船舶、建築、土木、工業用部品、スポーツ用品等の広い分野に利用することができる。なかでも、半導体洗浄装置用の部材に好適に利用することができる。
次に実施例を挙げて本開示を更に詳しく説明するが、本開示はこれらの実施例のみに限定されるものではない。
実施例の各数値は以下の方法により測定した。
（１）ＭＦＲ
ＡＳＴＭ　Ｄ３３０７に準拠し、測定温度３７２℃、荷重５ｋｇにおいてノズルから１０分間あたりに流出するポリマーの質量を測定した。
実施例１
＜ＵＤシート（プリプレグ）の作製＞
以下の材料を用いて、ＵＤシートを作製した。
炭素繊維束（東レ社製Ｔ７００ＳＣ－１２０００－６０Ｅ）
ＰＦＡフィルム（ＭＦＲ１４ｇ／１０分、融点３０６℃、厚み０．０５ｍｍ）
公知の開繊方法を用い、上記炭素繊維束５本をそれぞれ幅４２ｍｍに開繊して幅方向に並べ、シート状にした幅２１０ｍｍの開繊炭素繊維シート（目付３８．１ｇ／ｍ２）を作製した。この開繊炭素繊維シートと上記ＰＦＡフィルムとを、上記ＰＦＡフィルムのバックテンションを制御機器（三菱電機製　ＺＫＢ－０．６ＡＭ／ＹＫ）の出力を５％以下とすることで、０．６Ｎ／ｃｍ２として積層し、３６０℃の加熱温度に設定された加熱加圧ロール間を走行させ（線速：１０ｍ／ｍｉｎ）、ＵＤシートを作製した。上記ＰＦＡフィルムが幅方向に収縮することなく、Ｖｆ（炭素繊維体積含有率）２９．７％、厚み０．０７２ｍｍのＵＤシートを得ることができた。
実施例２
ＰＦＡフィルムの厚みを０．０２５ｍｍにし、バックテンションを０．２５Ｎ／ｃｍ２にした以外実施例１と同様にしてＵＤシートを作製した。上記ＰＦＡフィルムが幅方向に収縮することなく、Ｖｆ４５．８％、厚み０．０４６ｍｍのＵＤシートを得ることができた。
実施例３
ＰＦＡフィルムの厚みを０．０５０ｍｍにし、バックテンションを２．５Ｎ／ｃｍ２にした以外実施例１と同様にしてＵＤシートを作製した。上記ＰＦＡフィルムが幅方向に２～３ｍｍ程度収縮したが、Ｖｆ２９．７％、厚み０．０７２ｍｍのＵＤシートを得ることができた。
実施例４
上記炭素繊維束３本をそれぞれ幅７５ｍｍに開繊して幅方向に並べ、シート状にした２２５ｍｍの開繊炭素繊維シート（目付２６．７ｇ／ｍ２）を作製した以外実施例１と同様にしてＵＤシートを作製した。上記ＰＦＡフィルムが幅方向に２～３ｍｍ程度収縮したが、Ｖｆ２２．７％、厚み０．０６４ｍｍのＵＤシートを得ることができた。
＜チョップ材の作製＞
上記のＵＤシートを用いて、公知の供給機構及び切断機構により、繊維方向に沿って幅５ｍｍ、繊維方向に直交する方向に沿って長さ２０ｍｍに切断して、チョップ材を作製した。
＜チョップドシートの作製＞
上記のＵＤシートを用いて、特開２０１６－２７９５６号公報記載の方法によりチョップドシートを作製した。この方法では、ＵＤシート切断機構、チョップ材搬送機構、シート一体化機構、シート巻取機構を用いた。
先ず、ＵＤシート切断機構にてＵＤシートを繊維方向に沿って幅５ｍｍに切断し、繊維方向に直交する方向に沿って長さ２０ｍｍに切断してチョップ材を作製した。
次に得られた幅５ｍｍ×長さ２０ｍｍのチョップ材を搬送ベルト上に自然落下させて分散させた。ベルト上に重ねられたチョップ材は厚さ方向に２枚以上重ねられたものである。
次に３６０℃の加熱温度に設定された加熱ローラでチョップ材を溶融一体化させ（線速：０．６ｍ／ｍｉｎ）、チョップドシートを作製した。得られたチョップドシートは、目付量５００ｇ／ｍ２、厚み０．６ｍｍであった。
＜複合材料の作製＞
上記のＵＤシート、チョップ材、チョップドシートのそれぞれから、公知のプレス成形機を用いて複合材料を作製した。
ＵＤシートからの作製は、幅２９８ｍｍ×長さ２９８ｍｍとなるようにＵＤシートを組み合わせ、成形品厚みが４０ｍｍになるように、９４０枚積層し、金型を３６０℃の加熱温度に設定し、５ＭＰａの圧力で５分間加熱加圧した。その後、金型を３０℃の温度に設定し、７ＭＰａの圧力で２０分間加圧した。
比較例１
上記開繊炭素繊維シートと上記ＰＦＡフィルムとを、上記ＰＦＡフィルムのバックテンションを５．０Ｎ／ｃｍ２として積層したこと以外は実施例２と同様にして、ＵＤシートを作製しようとしたが、加熱加圧ロール間を走行させる際に上記ＰＦＡフィルムが長さ方向に伸び、幅方向に２０ｍｍ以上収縮し、厚みも変化したため、設定した仕様でのＵＤシートを得ることができなかった。

Claims (4)

  1. 炭素繊維と溶融加工可能なフッ素樹脂とを含む複合材料の製造方法であって、
    開繊された炭素繊維と、バックテンションを３．０Ｎ／ｃｍ２以下とした溶融加工可能なフッ素樹脂のフィルムとを重ね合わせた状態で、前記フッ素樹脂の融点以上の温度に加熱し加圧することによりプリプレグを得る工程（１）、及び、
    前記プリプレグを厚み方向に１枚以上重ね合わせた状態で、前記フッ素樹脂の融点以上に加熱し加圧することにより前記複合材料を得る工程（２）を含む製造方法。
  2. 前記溶融加工可能なフッ素樹脂は、テトラフルオロエチレン／パーフルオロ（アルキルビニルエーテル）共重合体、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体、エチレン／テトラフルオロエチレン共重合体、ポリクロロトリフルオロエチレン、及び、ポリフッ化ビニリデンからなる群より選択される少なくとも１種である請求項１記載の製造方法。
  3. 前記溶融加工可能なフッ素樹脂は、メルトフローレートが０．１～１００ｇ／１０分であり、融点が２７２～３２３℃である請求項１又は２記載の製造方法。
  4. 前記溶融加工可能なフッ素樹脂は、テトラフルオロエチレン／パーフルオロ（アルキルビニルエーテル）共重合体である請求項１～３のいずれかに記載の製造方法。
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0258545A (ja) * 1988-06-20 1990-02-27 E I Du Pont De Nemours & Co 連続フイラメント繊維で強化されたフルオロポリマーの構造用複合体
WO1997041285A1 (en) 1996-05-01 1997-11-06 Fukui Prefecture Multi-filament split-yarn sheet, and method and device for the manufacture thereof
JP2003165851A (ja) 2001-11-28 2003-06-10 Fukui Prefecture 繊維強化熱可塑性樹脂シート及びそれを用いた構造材並びに繊維強化熱可塑性樹脂シートの製造方法
JP2003181832A (ja) * 2001-12-21 2003-07-02 Fukui Prefecture 熱可塑性樹脂プリプレグシート材の製造装置及びその製造方法
JP2010084372A (ja) * 2008-09-30 2010-04-15 Nippon Steel Composite Co Ltd 織成繊維強化シート及びその製造方法
JP2012148568A (ja) 2006-11-22 2012-08-09 Fukui Prefecture 熱可塑性樹脂補強シート材、熱可塑性樹脂多層補強シート材及びその製造方法、並びに熱可塑性樹脂多層補強成型品
WO2015174545A1 (ja) * 2014-05-16 2015-11-19 株式会社トッパン・コスモ 不燃シートおよびその製造方法
JP2016027956A (ja) 2014-07-08 2016-02-25 福井県 擬似等方補強シート材及びその製造方法
WO2017191735A1 (ja) * 2016-05-02 2017-11-09 ダイキン工業株式会社 繊維強化複合材料、積層体、パイプ、ライザー管及びフローライン
JP2017537824A (ja) * 2014-10-07 2017-12-21 サン−ゴバン パフォーマンス プラスティックス コーポレイション 強度保持布帛

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62193824A (ja) * 1986-02-20 1987-08-26 セントラル硝子株式会社 柔軟性のあるガラス繊維強化フツ素樹脂複合材料
US5069959A (en) * 1988-06-20 1991-12-03 E. I. Du Pont De Nemours And Company Structural composites of fluoropolymers reinforced with continuous filament fibers
JP3108644B2 (ja) * 1996-12-25 2000-11-13 株式会社巴川製紙所 フッ素樹脂繊維シートの製造方法
JP4497711B2 (ja) * 2000-12-18 2010-07-07 三井・デュポンフロロケミカル株式会社 熱溶融性フッ素樹脂混合繊維及びその製造方法
JP2002283517A (ja) * 2001-03-27 2002-10-03 Daikin Ind Ltd フッ素樹脂積層シート
US7211210B2 (en) * 2003-01-16 2007-05-01 Textiles Coated International Dry fibrillated PTFE film and its method of manufacture
JP4720202B2 (ja) * 2004-02-10 2011-07-13 ダイキン工業株式会社 フッ素樹脂層積層体製造方法及びフッ素樹脂層積層体
JP2010106219A (ja) * 2008-10-31 2010-05-13 Nippon Zeon Co Ltd プリプレグ、繊維強化樹脂成形体、及び積層体
CN104411752B (zh) * 2012-07-05 2017-06-23 大金工业株式会社 改性含氟共聚物、氟树脂成型品以及氟树脂成型品的制造方法
JP2016088039A (ja) * 2014-11-11 2016-05-23 スターライト工業株式会社 フッ素樹脂複合シート及びフッ素樹脂フィルムの接合方法
JP6766827B2 (ja) * 2016-01-13 2020-10-14 Ａｇｃ株式会社 プリプレグ、その製造方法および繊維強化成形品
JP7234921B2 (ja) * 2017-05-18 2023-03-08 Ａｇｃ株式会社 熱プレス積層体、および、熱プレス積層体の製造方法

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0258545A (ja) * 1988-06-20 1990-02-27 E I Du Pont De Nemours & Co 連続フイラメント繊維で強化されたフルオロポリマーの構造用複合体
WO1997041285A1 (en) 1996-05-01 1997-11-06 Fukui Prefecture Multi-filament split-yarn sheet, and method and device for the manufacture thereof
JP2003165851A (ja) 2001-11-28 2003-06-10 Fukui Prefecture 繊維強化熱可塑性樹脂シート及びそれを用いた構造材並びに繊維強化熱可塑性樹脂シートの製造方法
JP2003181832A (ja) * 2001-12-21 2003-07-02 Fukui Prefecture 熱可塑性樹脂プリプレグシート材の製造装置及びその製造方法
JP2012148568A (ja) 2006-11-22 2012-08-09 Fukui Prefecture 熱可塑性樹脂補強シート材、熱可塑性樹脂多層補強シート材及びその製造方法、並びに熱可塑性樹脂多層補強成型品
JP2010084372A (ja) * 2008-09-30 2010-04-15 Nippon Steel Composite Co Ltd 織成繊維強化シート及びその製造方法
WO2015174545A1 (ja) * 2014-05-16 2015-11-19 株式会社トッパン・コスモ 不燃シートおよびその製造方法
JP2016027956A (ja) 2014-07-08 2016-02-25 福井県 擬似等方補強シート材及びその製造方法
JP2017537824A (ja) * 2014-10-07 2017-12-21 サン−ゴバン パフォーマンス プラスティックス コーポレイション 強度保持布帛
WO2017191735A1 (ja) * 2016-05-02 2017-11-09 ダイキン工業株式会社 繊維強化複合材料、積層体、パイプ、ライザー管及びフローライン

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4053192A4

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