WO2022009918A1 - Agent d'encollage, fibres encollées, préimprégné et dispersion - Google Patents

Agent d'encollage, fibres encollées, préimprégné et dispersion Download PDF

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Publication number
WO2022009918A1
WO2022009918A1 PCT/JP2021/025581 JP2021025581W WO2022009918A1 WO 2022009918 A1 WO2022009918 A1 WO 2022009918A1 JP 2021025581 W JP2021025581 W JP 2021025581W WO 2022009918 A1 WO2022009918 A1 WO 2022009918A1
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Prior art keywords
polymer
fiber
dispersion
surfactant
sizing agent
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PCT/JP2021/025581
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English (en)
Japanese (ja)
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朋也 細田
達也 寺田
舞 西
敦美 山邊
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Ａｇｃ株式会社
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Priority to JP2022535367A priority Critical patent/JPWO2022009918A1/ja
Priority to KR1020227037748A priority patent/KR20230036060A/ko
Priority to CN202180047429.4A priority patent/CN115803197A/zh
Publication of WO2022009918A1 publication Critical patent/WO2022009918A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
    • 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
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/095—Carboxylic acids containing halogens
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

  • the present invention relates to a dispersion containing a sizing agent containing a tetrafluoroethylene-based polymer, sized fibers, a prepreg, and a powder of the tetrafluoroethylene-based polymer.
  • Fiber reinforced plastic has excellent lightness and durability, and as reinforced fibers, inorganic fibers such as glass fiber, carbon fiber, boron fiber, and metal fiber, aramid fiber and zylon fiber with high impact resistance (poly (paraphenylene benzobisoxazole)) ), Organic fibers such as polyethylene fibers are used.
  • inorganic fibers such as glass fiber, carbon fiber, boron fiber, and metal fiber, aramid fiber and zylon fiber with high impact resistance (poly (paraphenylene benzobisoxazole))
  • Organic fibers such as polyethylene fibers are used.
  • carbon fiber reinforced composite materials in which matrix resin is reinforced with carbon fiber can be used as a composite material in place of metal, including aircraft members, spacecraft members, automobile members, and ship members. It is widely used in general industrial fields such as sports applications such as golf shafts and fishing rods, office equipment applications, and computer applications (IC trays, laptop housings, etc.).
  • Patent Document 1 discloses a prepreg obtained by impregnating a carbon fiber to which a sizing agent containing an aliphatic epoxy compound and an aromatic epoxy compound is attached with a specific epoxy resin composition as a matrix resin.
  • Patent Document 2 discloses a carbon fiber coated with a sizing agent containing a polymer having one of an ester bond, a urethane bond, and a carbonate bond in the main chain bond, and the carbon fiber has mechanical properties. It is disclosed that an excellent composite material can be obtained.
  • Patent Document 3 discloses an aqueous dispersion containing a powder of a tetrafluoroethylene polymer.
  • the dispersion liquid contains a surfactant for the purpose of enhancing the dispersion stability of the powder of the tetrafluoroethylene polymer.
  • the surfactant may remain on the surface of the base material, causing the surface of the base material to be rough and the appearance to be deteriorated. Further, the residual surfactant on the surface of the base material may reduce the electrical characteristics of the molded product and the adhesion to other base materials.
  • Japanese Unexamined Patent Publication No. 2014-40566 Japanese Unexamined Patent Publication No. 2020-23770 Japanese Unexamined Patent Publication No. 2019-52211
  • the molding temperature is also higher than before.
  • the sizing agent described in Patent Documents 1 and 2 thermally decomposes during heat molding to generate a volatile component and causes foaming in the molded product. There is a problem of affecting the peel strength and the like.
  • a sizing agent containing a heat-meltable tetrafluoroethylene polymer having a specific particle size has excellent interfacial adhesion with a super heat-resistant resin, and such a sizing agent is suitable.
  • a sizing agent containing a heat-meltable tetrafluoroethylene polymer having a specific particle size has excellent interfacial adhesion with a super heat-resistant resin, and such a sizing agent is suitable.
  • foaming during heat molding can be suppressed due to the heat resistance of the tetrafluoroethylene polymer, and a molded product with excellent appearance such as smoothness can be formed.
  • foaming during heat molding can be suppressed due to the heat resistance of the tetrafluoroethylene polymer, and a molded product with excellent appearance such as smoothness can be formed.
  • foaming during heat molding can be suppressed due to the heat resistance of the tetrafluoroethylene polymer, and a molded product with excellent appearance such
  • An object of the present invention is to provide a dispersion liquid containing a sizing agent that suppresses foaming during heating, sized fibers, a prepreg, a tetrafluoroethylene polymer powder having excellent dispersion stability, and a small amount of a surfactant. And.
  • the present invention has the following aspects.
  • the tetrafluoroethylene polymer has a unit based on perfluoro (alkyl vinyl ether) and a tetrafluoroethylene polymer having a polar functional group, or a unit based on perfluoro (alkyl vinyl ether) is 2.0 for all units.
  • the tetrafluoroethylene-based polymer having a polar functional group is a tetrafluoroethylene-based polymer having a carbonyl group-containing group, and the number of the carbonyl group-containing groups is 10 to 10 per 6 carbon atoms in the main chain.
  • the sizing agent of ⁇ 4> which is 5000 pieces.
  • ⁇ 7> The tetrafluoroethylene polymer powder having an average particle diameter of 10 to 100 ⁇ m, a surfactant, and a liquid dispersion medium are contained, and the content of the surfactant is 1 mass of the tetrafluoroethylene polymer powder.
  • the sizing agent of ⁇ 6> which is 0.01 part by mass or less with respect to the part.
  • ⁇ 8> A sizing-treated fiber to which a heat-meltable tetrafluoroethylene polymer is surface-adhered.
  • ⁇ 13> The dispersion liquid of ⁇ 11> or ⁇ 12>, wherein the surfactant is a silicone-based surfactant, a fluorine-based surfactant, a glycol-based surfactant, or an alkylamide ether-based surfactant.
  • the surfactant is a silicone-based surfactant, a fluorine-based surfactant, a glycol-based surfactant, or an alkylamide ether-based surfactant.
  • ⁇ 14> The dispersion liquid according to any one of ⁇ 11> to ⁇ 13>, wherein the content of the tetrafluoroethylene polymer is 25 to 60 parts by mass with respect to 100 parts by mass of the liquid dispersion medium.
  • a sizing agent consisting of the dispersion liquid according to any one of ⁇ 11> to ⁇ 14>.
  • the prepreg containing the fiber treated with the sizing agent of the present invention and the matrix resin has excellent adhesion between the fiber and the matrix resin. Further, the prepreg of the present invention has excellent adhesion between the fiber and the matrix resin during molding, foaming during heat molding is suppressed from the prepreg of the present invention, and molding has excellent appearance such as smoothness and water resistance. You get things. Further, according to the present invention, a dispersion liquid containing a tetrafluoroethylene polymer powder and a small amount of a surfactant and having excellent dispersion stability is provided. The coated substrate obtained from the dispersion liquid has an excellent appearance with less surface roughness and the like. Further, when the coated base material is bonded to another material, the adhesion is excellent.
  • the fiber as a base material, treating the fiber with a sizing agent composed of the dispersion liquid of the present invention, and impregnating the matrix resin with the sized fiber, a prepreg having excellent adhesion to the matrix resin can be obtained. ..
  • the "average particle size" of the powder is the volume-based cumulative 50% diameter of the object as defined by "D50” below.
  • D50 is a volume-based cumulative 50% diameter of the object obtained by the laser diffraction / scattering method. That is, the particle size distribution is measured by a laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the particle population as 100%, and the particle size is the point where the cumulative volume is 50% on the cumulative curve.
  • “D90” is the volume-based cumulative 90% diameter of the object, which is similarly measured.
  • the objects D50 and D90 are obtained by dispersing the particles in water and analyzing them by a laser diffraction / scattering method using a laser diffraction / scattering type particle size distribution measuring device (LA-920 measuring instrument manufactured by HORIBA, Ltd.). Be done.
  • the “polymer melting temperature (melting point)” is the temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
  • the “5% weight loss temperature of the polymer” is in accordance with JIS K7120, when the temperature is raised at a rate of 20 ° C./min over a temperature range of 23 to 900 ° C. in a nitrogen gas atmosphere using a TGA measuring device. The temperature at which a 5% weight loss is observed.
  • the "glass transition point (Tg) of the polymer” is a value measured by analyzing the polymer by the dynamic viscoelasticity measurement (DMA) method.
  • the "viscosity of the dispersion liquid” is a viscosity measured using a B-type viscometer under the condition of 25 ° C. and a rotation speed of 30 rpm. The measurement is repeated 3 times, and the average value of the measured values for 3 times is used.
  • the "thixotropic ratio" is a value calculated by dividing the viscosity ⁇ 1 measured under the condition of a rotation speed of 30 rpm by the viscosity ⁇ 2 measured under the condition of a rotation speed of 60 rpm of the liquid composition. .. The measurement of each viscosity is repeated 3 times, and the average value of the measured values for 3 times is used.
  • the "unit” in a polymer means an atomic group based on the one molecule of the monomer formed by the polymerization of the monomers.
  • the unit may be a unit directly formed by a polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by processing a polymer.
  • the unit based on the monomer A is also simply referred to as “monomer A unit”.
  • Tetrafluoroethylene-based polymer means a polymer containing a unit based on tetrafluoroethylene.
  • the sizing agent of the present invention (hereinafter, also referred to as “the sizing agent”) is also referred to as a heat-meltable tetrafluoroethylene polymer (hereinafter, also referred to as “F polymer”) having an average particle size of 0.1 to 200 ⁇ m. ) Powder (hereinafter, also referred to as "F powder”) is contained.
  • the sizing agent By arranging the sizing agent on the fiber and heat-treating it, it is possible to produce the sizing-treated fiber, preferably the sizing-treated carbon fiber.
  • the F polymer is attached to the surface of the obtained sizing-treated fiber.
  • the fibers sized with this sizing agent are less likely to generate decomposition products even when molding prepregs containing super heat-resistant resin as a matrix resin or fiber-reinforced composite materials, and foaming during heat molding is suppressed. To. Therefore, it is possible to form a molded product having particularly excellent appearance such as smoothness, adhesiveness and water resistance.
  • the mechanism of action is not clear, but it is estimated as follows.
  • the present sizing agent contains an F polymer, and it is considered that the F polymer is likely to be more densely and uniformly distributed on the surface of the sizing-treated fiber obtained by treating with the present sizing agent.
  • the F polymer tends to form microspherulites, and the adhesion to the sizing-treated fiber and the matrix resin tends to increase. Further, since the F polymer itself has excellent heat resistance and water resistance, it is difficult to decompose even if it is molded at a high temperature, and it is considered that it contributes to the improvement of the characteristics of the obtained molded product.
  • the average particle size (D50) of the F powder in this sizing agent is 0.1 to 200 ⁇ m.
  • the D50 of the F powder is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less.
  • the D50 of the F powder is preferably 0.03 ⁇ m or more, more preferably 0.1 ⁇ m or more.
  • the D90 of the F powder is preferably 10 ⁇ m or less. In D50 and D90 in this range, the fluidity of the F powder becomes good, and the F powder tends to be uniformly distributed on the fiber surface. In addition, the heat resistance and electrical characteristics (low dielectric constant, etc.) of the F polymer are most likely to be exhibited.
  • the bulk density of the F powder is preferably 0.15 g / m 2 or more from the viewpoint of uniformly distributing the F powder on the fiber surface.
  • the bulk density of the F powder is preferably 0.50 g / m 2 or less.
  • the F powder in the present sizing agent may contain a resin or an inorganic compound other than the F polymer, but it is preferable that the F polymer is the main component.
  • the content of the F polymer in the F powder is preferably 80% by mass or more, more preferably 100% by mass.
  • the resin include heat-resistant resins such as aromatic polyester, polyamide-imide, thermoplastic polyimide, polyphenylene ether, and polyphenylene oxide.
  • the inorganic compound include silica and boron nitride.
  • the F powder may form a core-shell structure having an F polymer as a core and a resin or an inorganic compound other than the F polymer as a shell, and the F polymer as a shell and a resin or an inorganic compound other than the F polymer as a core. It may form a core-shell structure.
  • the F polymer in the present invention is a heat-meltable polymer containing a unit based on tetrafluoroethylene (hereinafter, also referred to as TFE unit) (hereinafter, also referred to as TFE unit).
  • TFE unit tetrafluoroethylene
  • the fluorine content of the F polymer is preferably 70 to 76% by mass.
  • the melting temperature of the F polymer is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, further preferably 260 ° C. or higher, and particularly preferably 280 ° C. or higher.
  • the melting temperature of the F polymer is preferably 325 ° C or lower, more preferably 320 ° C or lower.
  • the melting temperature of the F polymer is preferably 180 to 325 ° C, more preferably 260 to 325 ° C, and even more preferably 280 to 325 ° C. In such a case, the heat resistance of the molded product formed from the present composition tends to be excellent.
  • the glass transition point of the F polymer is preferably 50 ° C. or higher, more preferably 75 ° C. or higher, more preferably 150 ° C. or lower, and even more preferably 125 ° C. or lower.
  • the glass transition point of the F polymer is preferably 75 to 125 ° C, more preferably 80 to 100 ° C.
  • F polymer examples include a polymer (PFA) containing TFE units and units based on perfluoro (alkyl vinyl ether) (PAVE) (PAVE units), a polymer containing TFE units and units based on hexafluoropropene (HFP), and TFE.
  • PFA polymer
  • PAVE perfluoro (alkyl vinyl ether)
  • HFP hexafluoropropene
  • TFE TFE
  • EFEs ethylene, heat-meltable polytetrafluoroethylene (PTFE), and the like, preferably PFA and FEP, more preferably PFA.
  • the polymer may further contain units based on other comonomeres.
  • CF 2 CFOCF 3
  • CF 2 CFOCF 2 CF 3
  • CF 2 CFOCF 2 CF 2 CF 3
  • PPVE CFOCF 2 CF 2 CF 3
  • the F polymer preferably has a polar functional group, and more preferably has an atomic group containing an oxygen atom.
  • the polar functional group may be contained in a unit in the F polymer, or may be contained in the terminal group of the main chain of the polymer.
  • an F polymer having a polar functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like, or an F polymer having a polar functional group obtained by subjecting the F polymer to plasma treatment or ionization line treatment can be used. Can be mentioned.
  • the polar functional group having an atomic group containing an oxygen atom a hydroxyl group-containing group, a carbonyl group-containing group and a phosphono group-containing group are preferable, and the dispersion stability when this sizing agent is used as a dispersion liquid in the sizing treatment of the fiber is preferable.
  • a hydroxyl group-containing group and a carbonyl group-containing group are more preferable, and a carbonyl group-containing group is further preferable.
  • the number of carbonyl group-containing groups in the F polymer is preferably 10 to 5000, more preferably 100 to 3000, per 1 ⁇ 10 6 carbon atoms in the main chain.
  • the number of carbonyl group-containing groups in the F polymer can be quantified by the composition of the polymer or the method described in International Publication No. 2020/145133.
  • a carbonyl group-containing group is a group containing a carbonyl group (> C (O)).
  • the carbonyl group-containing group include a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, a carbamate group (-OC (O) NH2), an acid anhydride residue (-C (O) OC (O)-), and an imide. Residues (-C (O) NHC (O) -etc.) and carbonate groups (-OC (O) O-) are preferred, and acid anhydride residues are more preferred.
  • the F polymer contains a polymer having a polar functional group (1) including TFE units and PAVE units, and 2.0 to 5.0 mol% of PAVE units with respect to all units including TFE units and PAVE units.
  • the polymer (2) having no polar functional group is preferable.
  • These F polymers not only have excellent dispersion stability when the powder is a dispersion liquid of the present sizing agent, but also are more dense and homogeneous on the surface of the sizing-treated fiber obtained by treating with the present sizing agent. Easy to distribute.
  • microspherulites are likely to be formed in the molded product, and the adhesion to the sizing-treated fiber and the matrix resin is likely to be improved. Further, since it is excellent in heat resistance, it is easier to obtain a molded product having an excellent appearance (surface smoothness).
  • the polymer (1) is preferably a polymer containing TFE units, PAVE units and units based on a monomer having a polar functional group, and 90 to 99 mol% of these units are added to all units in this order, 0 to 99 mol%. More preferably, the polymer contains 5.5 to 9.97 mol% and 0.01 to 3 mol%. Further, as the monomer having a polar functional group, itaconic anhydride, citraconic anhydride and 5-norbornen-2,3-dicarboxylic acid anhydride (hereinafter, also referred to as “NAH”) are preferable. Specific examples of the polymer (1) include the polymers described in International Publication No. 2018/16644.
  • the polymer (2) is composed of only TFE units and PAVE units, and preferably contains 95.0 to 98.0 mol% of TFE units and 2.0 to 5.0 mol% of PAVE units with respect to all the units. ..
  • the content of PAVE units in the polymer (2) is preferably 2.1 mol% or more, more preferably 2.2 mol% or more, based on all the units.
  • Such a polymer has a higher degree of freedom in molecular conformation, and the above-mentioned mechanism of action is likely to be enhanced.
  • the polymer (2) does not have polar functional groups when the number of polar functional groups of the polymer is less than 500 with respect to 1 ⁇ 10 6 carbon atoms constituting the polymer main chain. It means that there is.
  • the number of the polar functional groups is preferably 100 or less, more preferably less than 50.
  • the lower limit of the number of polar functional groups is usually 0.
  • the polymer (2) may be produced by using a polymerization initiator, a chain transfer agent, or the like that does not generate a polar functional group as the terminal group of the polymer chain, and is derived from an F polymer having a polar functional group (derived from the polymerization initiator).
  • An F polymer or the like having a polar functional group at the terminal group of the main chain of the polymer may be fluorinated to produce the polymer. Examples of the fluorination treatment method include a method using fluorine gas (see JP-A-2019-194314).
  • the 5% weight loss temperature of the F polymer is preferably 360 ° C. or higher, more preferably 400 ° C. or higher.
  • the 5% weight loss temperature of the F polymer is preferably 600 ° C. or lower.
  • This sizing agent is a glass fiber such as E glass, D glass, L glass, S glass, T glass, Q glass, UN glass, NE glass used as a reinforcing fiber in the technical field of fiber reinforced plastic; aramid fiber, polyolefin.
  • Organic fibers such as fibers, modified polyphenylene ether fibers, vinylon fibers, rayon fibers, polyester fibers, and natural fibers; can be used as sizing agents for boron fibers, carbon fibers, metal fibers, and the like.
  • the shape of the fiber may be any of chopped strands, surfing, roving or mats, woven fabrics, non-woven fabrics and the like thereof. Further, the fiber length and the cross-sectional shape of the fiber are not particularly limited. Above all, it is preferable to use this sizing agent as a sizing agent for carbon fibers.
  • the carbon fibers pitch-based, rayon-based, polyacrylonitrile (PAN) -based, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanofibers and the like can be used.
  • PAN polyacrylonitrile
  • properties such as fineness and strength of carbon fibers.
  • an acrylonitrile (PAN) system is preferable from the viewpoints of operability, process passability, and mechanical properties.
  • PAN-based carbon fiber for example, a carbon fiber precursor fiber made of a PAN-based polymer is subjected to flame resistance treatment at 200 to 300 ° C. in an oxidizing atmosphere, and then precarbonized at 500 to 1200 ° C. in an inert atmosphere. It is obtained by performing a treatment and then carbonizing at 1200 to 2000 ° C. in an inert atmosphere.
  • the sizing agent may be in the form of powder or may be in the form of liquid.
  • the liquid sizing agent comprises a dispersion liquid containing an F polymer powder having an average particle size of 0.1 to 200 ⁇ m and a liquid dispersion medium (hereinafter, also referred to as “the main dispersion liquid (1)”).
  • the main dispersion liquid (1) a liquid dispersion medium
  • a method for arranging the sizing agent on the fiber a method in which the dispersion liquid (1) is prepared, attached to the fiber, and heat-treated to attach the F polymer to the surface of the fiber is preferable.
  • the liquid dispersion medium for dispersing the F powder in the present dispersion (1) is preferably an aprotonic compound that is liquid at 25 ° C., which is classified as polar under atmospheric pressure, and is selected from amides, ketones and esters. It is more preferable that it is a polar compound to be used. When such a liquid dispersion medium is used, the dispersion stability of the F powder in the present dispersion is excellent.
  • the boiling point of the liquid dispersion medium is preferably in the range of 50 to 240 ° C. Two or more kinds of liquid dispersion media may be used in combination.
  • the liquid dispersion medium water, N, N-dimethylformamide, N, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, N-methyl- Examples thereof include 2-pyrrolidone, ⁇ -butyrolactone, cyclohexanone, cyclopentanone, butyl acetate, methyl isopropyl ketone and methyl ethyl ketone.
  • the content of the liquid dispersion medium in the dispersion liquid (1) is preferably 30 to 90% by mass, more preferably 50 to 80% by mass.
  • the content of the F powder in the dispersion liquid (1) is preferably 1% by mass or more, more preferably 5 to 50% by mass, based on the total mass of the dispersion liquid (1). preferable.
  • the present dispersion (1) may further contain various surfactants added from the viewpoint of imparting dispersibility.
  • the content thereof is preferably 1 to 15% by mass with respect to the total mass of the present dispersion (1).
  • the present dispersion liquid (1) having excellent dispersion stability and handleability can be produced without necessarily using a surfactant. Therefore, when the present dispersion liquid (1) is adhered to the fiber, the sizing agent is likely to be uniformly dispersed on the fiber surface, and the F polymer is likely to be densely and uniformly arranged on the fiber surface after the heat treatment.
  • the surfactant anionic, cationic, nonionic surfactants and the like can be used, and among them, nonionic surfactants are preferable.
  • the hydrophilic moiety of the surfactant is preferably a polyoxyethylene group or an alcoholic hydroxyl group.
  • the hydrophobic moiety of the surfactant is preferably an acetylene group, a polysiloxane group, a fluorine-containing organic group (perfluoroalkyl group or the like), or a polyoxyalkylene group composed of an oxyalkylene having 3 or more carbon atoms.
  • an acetylene-based surfactant a silicone-based surfactant, a fluorine-based surfactant, an alkylamide ether-based surfactant, and a glycol-based surfactant are preferable. Two or more kinds of these surfactants may be used. When two kinds of surfactants are used, the surfactants are preferably a silicone-based surfactant and a glycol-based surfactant. As the silicone-based surfactant, the same one as the silicone-based surfactant in the present dispersion (2) described later is preferable.
  • surfactants include “Futergent” series (manufactured by Neos), “Surflon” series (manufactured by AGC Seimi Chemical), “Megafuck” series (manufactured by DIC), and “Unidyne” series (Daikin). (Made by Kogyo Co., Ltd.).
  • the present dispersion (1) is a thixotropic agent, a viscosity modifier, an antifoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, and a weather resistant agent as long as the effects of the present invention are not impaired.
  • Antioxidants Heat Stabilizers, Lubricants, Antistatic Agents, Whitening Agents, Coloring Agents, Conductive Agents, Release Agents, Surface Treatment Agents, Flame Retardants, Various Inorganic Fillers, Various Organic Fillers, etc. It may be included.
  • Specific examples of the inorganic filler include the same as the inorganic filler that may be contained in the present dispersion (2) described later.
  • the present dispersion liquid (1) may further contain a resin material other than the F polymer from the viewpoint of improving the adhesiveness between the sizing agent and the matrix resin.
  • a resin material may be thermosetting or thermoplastic, may be modified, may be dissolved in the present dispersion (1), or may be dispersed without being dissolved.
  • resin materials include tetrafluoroethylene polymers other than F polymer, polyimide resin, polyamic acid which is a polyimide precursor, polyamideimide resin, maleimide resin, acrylic resin, phenol resin, liquid crystal polyester resin, and liquid crystal polyesteramide resin.
  • Polyimide resin modified polyphenylene ether resin, polyfunctional cyanate ester resin, polyfunctional maleimide-cyanic acid ester resin, polyfunctional maleimide resin, vinyl ester resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, melamine- Urea cocondensation resin, styrene resin, aromatic elastomer, polycarbonate resin, polyarylate resin, polysulfone, polyallylsulfone, aromatic polyamide resin, aromatic polyetheramide, polyphenylensulfide, polyallyl ether ketone, polyamideimide, polyphenylene ether , Epoxy resin and the like.
  • non-heat-meltable polytetrafluoroethylene is preferable from the viewpoint of improving the electrical properties of the sizing-treated fiber.
  • the dispersion liquid (1) contains a resin material, the content thereof is preferably 40% by mass or less with respect to the entire dispersion liquid (1).
  • the non-heat-meltable polytetrafluoroethylene is preferably contained in the dispersion liquid (1) as a powder of the non-heat-meltable polytetrafluoroethylene.
  • the ratio of the content of the powder in the dispersion liquid (1) is preferably 1 or more, more preferably 2 or more, with the content of the F powder being 1.
  • the above ratio is preferably 10 or less, more preferably 5 or less.
  • the D50 of such powder is preferably 0.1 to 1 ⁇ m.
  • the viscosity of the dispersion liquid (1) is preferably 75 to 10000 mPa ⁇ s. In this case, in addition to being excellent in dispersion stability, the handling property and the homogeneity of the sizing process on the fiber are likely to be improved. In addition, the dispersion liquid (1) is more compatible with varnishes of different resin materials.
  • the thixotropic ratio of the dispersion liquid (1) is preferably 1.0 to 2.2, more preferably 1.5 to 2.0. In this case, the dispersion stability is excellent and the handleability is also good, and the homogeneity of the sizing treatment on the fiber is likely to be improved. In addition, the dispersion liquid (1) is more compatible with varnishes of different resin materials.
  • a part of the roll is immersed in the dispersion liquid (1) to adhere the dispersion liquid (1) to the roller surface, and then the said.
  • a roller sizing method in which the fibers are brought into contact with the roll to adhere the dispersion liquid (1), the fibers are directly immersed in the dispersion liquid (1), and then passed through a nip roll as necessary to form the dispersion liquid (1). Examples thereof include a roller dipping method for controlling the amount of adhesion, a spray method in which the dispersion liquid (1) is atomized and sprayed onto a fiber bundle.
  • a roller dipping method is preferable in which the dispersion liquid (1) can be easily uniformly applied even to a fiber bundle having a large number of single fibers per bundle. Further, the amount of the sizing agent adhered can also be adjusted by adjusting the amount of the excess main dispersion (1) to be squeezed out after the present dispersion (1) is applied.
  • the amount of the sizing agent (1) attached to the fiber is in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the fiber as the amount of the F polymer attached to the sizing-treated fiber after the heat treatment described later. It is preferably in the range of 0.2 to 5 parts by mass, and more preferably in the range of 0.2 to 5 parts by mass.
  • the means for arranging the sizing agent on the fiber may be either a batch type or a continuous type, but the continuous type is preferable from the viewpoint of easily suppressing uneven placement of the sizing agent on the fiber and improving productivity.
  • the fibers may be vibrated by ultrasonic waves when the sizing agent is applied.
  • the fiber on which the present dispersion liquid (1) is arranged and evaporate the dispersion medium to obtain a sizing-treated fiber to which the F polymer is surface-adhered.
  • the F polymer that adheres to the surface of the fiber is more preferably a fired product of the F polymer.
  • the sizing-treated fiber to which the fired product of the F polymer is adhered to the surface is obtained by evaporating the dispersion medium from the fiber on which the present dispersion liquid (1) is arranged and further heat-treating the F polymer to be fired.
  • the heat treatment for evaporation of the dispersion medium is performed by holding the fiber on which the present dispersion liquid (1) is placed at the volatilization temperature of the dispersion medium and drying the liquid film arranged on the fiber.
  • the heat treatment for firing the F polymer is carried out by holding the dry film at a temperature higher than the melting temperature of the F polymer. In this way, the fired product of the F polymer is formed on the fiber surface.
  • the temperature at the time of drying usually means the temperature of the dry atmosphere.
  • the dispersion medium does not necessarily have to be completely evaporated.
  • the amount of the dispersion medium to be evaporated is preferably 50% by mass or more of the liquid dispersion medium contained in the present dispersion liquid (1).
  • Drying may be carried out in one step at a constant temperature, or may be carried out in two or more steps at different temperatures.
  • the drying method include a method using an oven, a method using a ventilation drying furnace, and a method of irradiating heat rays such as infrared rays, and any of a contact method and a non-contact method may be adopted. Drying may be carried out under either normal pressure or reduced pressure.
  • the dry atmosphere may be any of an oxidizing gas atmosphere (oxygen gas, etc.), a reducing gas atmosphere (hydrogen gas, etc.), and an inert gas atmosphere (helium gas, neon gas, argon gas, nitrogen gas, etc.). ..
  • the drying temperature is preferably 50 to 280 ° C.
  • the drying time is preferably 0.1 to 30 minutes.
  • Examples of the method for firing the F polymer include a method using an oven, a method using a ventilation drying oven, and a method of irradiating heat rays such as infrared rays, and a method in which infrared heating and hot air heating are combined may be used.
  • the F polymer may be fired under either normal pressure or reduced pressure.
  • the firing atmosphere may be any of an oxidizing gas atmosphere, a reducing gas atmosphere and an inert gas atmosphere.
  • the firing temperature is preferably equal to or higher than the melting temperature of the F polymer and not more than the temperature of 5% weight loss of the F polymer, and is usually 300 to 380 ° C.
  • the firing time is preferably 30 seconds to 30 minutes, more preferably 1 to 15 minutes. If the F polymer is fired under such conditions, it is easy to increase the productivity and suppress the generation of hydrofluoric acid due to the decomposition of the F polymer.
  • the carbon fibers may be brought into contact with a heated roller to evaporate the dispersion medium by a contact-type drying means, and the F polymer may be further fired.
  • the fibers introduced into the heated roller are pressed against the heated roller by tension and dried rapidly, so that the flat morphology of the fibers widened by the heated roller is easily fixed by the sizing agent. Since the contact area between single fibers of a fiber having a flat morphology is small, the fiber opening property tends to be high.
  • the sized fiber of the present invention is a fiber to which the F polymer is surface-adhered.
  • the definition and scope of the F polymer is similar to that of the F polymer in the sizing agent described above, including its preferred embodiments.
  • the amount of the F polymer adhered to the sized fiber is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the fiber.
  • the sized fiber of the present invention is preferably obtained from the sizing agent by the same method as described above.
  • the sizing-treated fiber of the present invention has excellent adhesion to the matrix resin and high impregnation property of the matrix resin into the fiber bundle, the prepreg having excellent mechanical properties and the fiber-reinforced composite material can be obtained from the fiber. Easy to get.
  • a prepreg containing the sized fiber of the present invention hereinafter, also referred to as “sizing treated fiber” (hereinafter, also referred to as “the present prepreg”) will be described.
  • the present prepreg contains the above-mentioned sizing-treated fiber and the matrix resin, and typically the sizing-treated fiber is impregnated with the matrix resin.
  • the prepreg can be produced, for example, by impregnating the sizing-treated fiber with a matrix resin or a matrix resin composition, and then drying and semi-curing the prepreg. Specifically, it can be produced by a wet method in which a matrix resin or a matrix resin composition is dissolved in a solvent such as methyl ethyl ketone or methanol to reduce the viscosity and impregnate it, or a hot melt method in which the matrix resin or the matrix resin composition is impregnated by reducing the viscosity by heating.
  • the prepreg can be produced by immersing the sizing-treated fiber in a liquid containing a matrix resin, pulling it up, and evaporating the solvent using an oven or the like.
  • the hot melt method a method of directly impregnating a sizing-treated fiber with a matrix resin or a matrix resin composition whose viscosity has been reduced by heating, or a film in which a matrix resin or a matrix resin composition is once coated on a release paper or the like is first applied.
  • a prepreg can be produced by producing, then stacking the film from both sides or one side of the sizing treated fiber and heating and pressurizing to impregnate the sized fiber with the matrix resin.
  • the hot melt method can be said to be a preferable means from the viewpoint that there is no solvent remaining in the prepreg.
  • the sizing-treated fiber may be used as a fiber bundle or as a sheet-shaped reinforcing fiber material.
  • the sheet-like material include a material in which fibers are arranged in a sheet shape in one direction, a material obtained by molding a fiber material into a woven or knitted fabric, a non-woven fabric, or the like, and a multi-axis fabric.
  • the sizing-treated fiber may be used as a continuous fiber or may be a discontinuous fiber. When a discontinuous fiber is used, it may be a mixture of a fiber which has been completely opened to form a single yarn and a reinforcing fiber which has been incompletely opened to form a fiber bundle.
  • the orientation of the fibers may be aligned in the same direction, and a random mat oriented in a random direction is also preferably used.
  • the thickness when the fiber is in the form of a sheet is not particularly limited, but is preferably in the range of 0.01 to 0.2 mm for laminated board applications, and the woven fabric subjected to super-spreading treatment or filling treatment has dimensions. It is suitable from the viewpoint of stability.
  • thermosetting resin As the matrix resin, a thermosetting resin or a thermoplastic resin is used.
  • thermosetting resin prepolymerization of epoxy resin, unsaturated polyester resin, phenol resin, vinyl ester resin, cyanate ester resin, urethane acrylate resin, phenoxy resin, alkyd resin, urethane resin, maleimide resin and cyanate ester resin. Examples thereof include resins, bismaleimide resins, polyimide resins having acetylene terminals and polyisoimide resins, and polyimide resins having nadic acid ends. These thermosetting resins may be used alone or in combination of two or more. Further, the thermosetting resin may be a thermosetting resin composition containing various additives in addition to a curing agent and a curing accelerator.
  • thermoplastic resin examples include polysulfone, polyphenylsulfone, polyethersulfone, aromatic polyetherketone (polyetherketone, polyetheretherketone, polyetherketoneketone, polyetheretherketoneketone, etc.), polyamide, aromatic polyester, and the like.
  • aromatic polycarbonate examples include aromatic polycarbonate, polyetherimide, polyarylene oxide, thermoplastic polyimide, polyamideimide, polyacetal, polyphenylene oxide, polyphenylene sulfide, liquid crystal polyester, polyarylate, polyacrylonitrile, polybenzimidazole and the like.
  • thermoplastic resin may be used alone, or two or more thereof may be used in combination.
  • the thermoplastic resin may be a thermoplastic resin composition containing various additives.
  • thermosetting resin or the thermoplastic resin is a resin composition
  • various additives include a plasticizer, a weather resistant agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, and a colorant.
  • the matrix resin is a heat-resistant resin selected from the group consisting of polysulfone, polyphenylsulfone, polyethersulfone, aromatic polyetherketone, polyetherimide, polyphenylene sulfide, and liquid crystal polyester. These are classified into so-called super heat-resistant resins, so-called super engineering plastics, and the effects of the sizing-treated fibers are more likely to be exhibited.
  • the matrix resin has a polar functional group such as a carbonyl group, a sulfone group, or an ester group in its structure and the F polymer of the present invention also has a polar functional group, the polar functional group in the matrix resin and the polar functionality of the F polymer have. It is presumed that the group interacts with each other and high adhesiveness is developed, which is preferable.
  • the fiber mass fraction in the prepreg is preferably 40 to 90% by mass, more preferably 50 to 80% by mass. Within the above range, the mass of the obtained fiber-reinforced composite material does not become excessive, and the advantages of the fiber-reinforced composite material having excellent specific strength and specific elastic modulus can be utilized.
  • the prepreg containing the fiber sized with this sizing agent can be easily impregnated with the matrix resin to be compounded, and is a high-quality material with less unevenness in mechanical properties.
  • the prepreg containing such reinforcing fibers may contain various additives as long as the original purpose is not impaired.
  • the prepreg containing the sized fiber and the matrix resin of the present invention has excellent adhesion to the matrix resin and high impregnation property of the matrix resin into the fiber. Therefore, when molded, the fiber is reinforced with excellent mechanical properties. A composite material is obtained.
  • a method can be applied in which the prepreg is laminated and then the matrix resin is heated while applying pressure to the laminate to form a laminate.
  • the method of applying heat and pressure include a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method and an internal pressure molding method, and particularly for sports equipment, the wrapping tape method and the internal pressure molding method are preferable.
  • the autoclave molding method is preferred for aircraft applications where higher quality and higher performance laminated composites are required.
  • the press molding method is preferable for the exterior of various vehicles.
  • resin transfer molding, filament winding molding, sheet winding molding and the like can also be applied.
  • a metal-clad laminate can be obtained by stacking the above-mentioned prepregs and arranging a metal base material on one side or both sides thereof for laminating molding.
  • a metal-clad laminated board can be produced by stacking one or a plurality of the above-mentioned prepregs, arranging a metal base material on one side or both sides thereof, and laminating and molding.
  • the metal constituting the metal base material include iron, stainless steel, aluminum, copper, brass, nickel, zinc, titanium, alloys of these metals, and the like.
  • the usual method of a laminated board for a printed wiring board and a multi-layer board can be applied.
  • a multi-stage press machine a multi-stage vacuum press machine, a continuous forming machine, an autoclave forming machine, etc.
  • laminating molding is performed at a temperature of 180 to 350 ° C., a heating time of 100 to 300 minutes, and a surface pressure of 20 to 100 kg / cm 2.
  • a surface pressure of 20 to 100 kg / cm 2.
  • the fiber composite material may be further laminated with another substrate.
  • the other substrate include a heat-resistant resin film and a prepreg which is a precursor of a fiber-reinforced resin plate, and examples of such a fiber composite material include a fiber-reinforced composite material having a heat-resistant resin film layer and a fiber reinforced material having a prepreg layer.
  • Composite materials can be mentioned.
  • the heat-resistant resin film is a film containing one or more heat-resistant resins, and examples of the heat-resistant resin include the above-mentioned resins.
  • Examples of the laminating method include a method of hot-pressing a laminated body obtained by laminating and heating a prepreg with another substrate.
  • the hot press conditions are preferably such that the temperature is 120 to 400 ° C., the atmospheric pressure is a vacuum of 20 kPa or less, and the press pressure is 0.2 to 10 MPa.
  • the fiber-reinforced composite material of the present invention is suitably used for applications in which strength, abrasion resistance, chemical resistance, and flame retardancy are required.
  • exteriors and interiors of transportation equipment such as automobiles, motorcycles, and aircraft, sliding parts such as gears and bearings, insulating parts, sports equipment such as rackets and bats, industrial machinery, robots, parts for medical equipment, and oil drilling equipment.
  • Oil transport hoses hydrogen tanks, hydrogen tank pressure vessels, blades of wind power generators, etc.
  • the fiber-reinforced composite material of the present invention and the above-mentioned laminate can also be used as a low vibration member.
  • Examples of members that require low vibration include rotating parts of motors, rotating parts of compressors, rotating parts of machine tools (lathes, milling cutters, etc.), interiors and exteriors of transportation equipment such as automobiles, two-wheeled vehicles, and aircraft. .. Further, since the fiber-reinforced composite material of the present invention has excellent mechanical properties at low temperatures, it can be used for members used at extremely low temperatures such as liquid hydrogen tanks.
  • the average particle size of the F powder in this sizing agent is 10 to 100 ⁇ m.
  • a dispersion liquid containing an F powder having an average particle size, a surfactant and a liquid dispersion medium, and having a surfactant content of 0.01 parts by mass or less with respect to 1 part by mass of the F powder having an average particle size (
  • the average particle size (D50) of the F powder in the dispersion liquid (2) is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less.
  • the average particle size of the F powder in the dispersion liquid (2) is preferably 20 ⁇ m or more.
  • the D90 of the F powder in the present dispersion (2) is preferably 40 ⁇ m or more, more preferably 60 ⁇ m or more, from the viewpoint of the dispersibility of the present dispersion (2).
  • the D90 of the F powder in the dispersion liquid (2) is preferably 100 ⁇ m or less, more preferably 90 ⁇ m or less.
  • this dispersion liquid (2) contains a surfactant.
  • the content of the surfactant is 0.01 or less with respect to 1 part by mass of the content of F powder. Since the F powder in the dispersion liquid (2) has a relatively large average particle size and a small surface area, it is highly stabilized by a small amount of surfactant and dispersed in the dispersion medium. Therefore, the dispersion liquid (2) Has excellent dispersion stability.
  • this dispersion liquid (2) is smaller than the content of the F powder, when it is used for the production of the coated base material described later, the surface of the obtained coated base material is less roughened. Excellent appearance. Further, when the obtained coated base material is adhered to another material, the adhesion is excellent.
  • the fiber as a base material, treating the fiber with a sizing agent composed of the present dispersion (2), and impregnating the matrix resin with the sized fiber, a prepreg having excellent adhesion can be obtained.
  • the content of the surfactant in the present dispersion (2) is preferably 0.008 or less, more preferably 0.005 or less, based on 1 part by mass of the F powder.
  • the content of the surfactant is preferably 0.0001 or more with respect to the content of 1 part by mass of the F powder.
  • the above-mentioned silicone-based surfactant, fluorine-based surfactant, glycol-based surfactant, and alkylamide ether-based surfactant are preferable. Two or more kinds of these surfactants may be used. When two or more kinds are used, the total content thereof may be within the range of the content. When two kinds of surfactants are used, the surfactants are preferably a silicone-based surfactant and a glycol-based surfactant.
  • the surface tension of the surfactant is preferably 28 mN / m or less, more preferably 26 mN / m or less.
  • the surface tension of the surfactant is preferably 20 mN / m or more.
  • the surfactant is preferably nonionic.
  • a silicone-based surfactant is a surfactant in which a hydrophilic substituent is introduced into a part of silicone having a siloxane bond in which silicon and oxygen are alternately linked by a chemical bond in the main skeleton.
  • examples thereof include organopolysiloxanes, polyether-modified polysiloxanes, polyester-modified polysiloxanes, aralkyl-modified polysiloxanes, and acrylic-modified polysiloxanes.
  • the fluorine-based surfactant is a surfactant having a hydroxyl group, a carboxyl group, a sulfo group, a hydrophilic moiety having a group derived from these groups, and a hydrophobic moiety having a fluorine-containing organic group.
  • the "Futergent” series (Futtergent manufactured by Neos Co., Ltd. is a registered trademark)
  • the "Surflon” series (Surflon manufactured by AGC Seimi Chemical Co., Ltd. is a registered trademark)
  • the "Megafuck” series Megafuck manufactured by DIC Corporation is registered).
  • Trademark "Unidyne” series (Unidyne manufactured by Daikin Industries, Ltd. is a registered trademark).
  • a glycol-based surfactant is a surfactant composed of a glycol derivative in which a hydrophilic moiety such as a hydroxyl group or an ester group and a hydrophobic moiety such as a hydrocarbon group are bonded.
  • a hydrophilic moiety such as a hydroxyl group or an ester group
  • a hydrophobic moiety such as a hydrocarbon group
  • glycol monoalkyl ether, glycol monoaryl ether, glycol monoalkyl ether acetate, glycol monoaryl ether acetate can be mentioned.
  • the alkylamide ether-based surfactant is a nonionic surfactant in which a carboxylic acid and a polyoxyalkylamine are amide-bonded. Examples thereof include polyoxyethylene alkyl amides and polyoxyethylene oleic acid amides.
  • silicone-based surfactants are more preferable from the viewpoint of dispersion stability of the present dispersion.
  • organopolysiloxane is preferable, and polyether-modified polysiloxane, polyester-modified polysiloxane, aralkyl-modified polysiloxane, or acrylic-modified polysiloxane is preferable.
  • the organopolysiloxane may have an organopolysiloxane structure in the main chain or an organopolysiloxane structure in the side chain, and has an organopolysiloxane structure in both the main chain and the side chain. You may have.
  • the organopolysiloxane is preferably a linear polymer.
  • the organopolysiloxane is more preferably polydiorganosiloxane.
  • an organopolysiloxane containing a dimethylsiloxane unit ((CH 3 ) 2 SiO 2/2 ) is preferable, and an organopolysiloxane having a dimethylsiloxane unit in the main chain and a polyoxyalkylene at the end of the main chain ( 1), or an organopolysiloxane (2) containing a dimethylsiloxane unit and a diorganosiloxane unit represented by the formula (R 1 ) (R 2 ) SiO 2/2 is more preferable.
  • R 1 in the formula indicates an alkyl group, and a methyl group is preferable.
  • the R 2 in the formula represents a group having a polyoxyalkylene, group (wherein the formula -X 2 -O-Y 2 -Z 2 , X 2 is an alkylene group, Y 2 is polyoxy
  • the alkylene group, Z 2 indicates any of a hydrogen atom, an alkyl group or an acyl group) is preferable.
  • the polyoxyalkylene contained in the organopolysiloxane (1) or (2) may be composed of only one kind of oxyalkylene group or may be composed of two or more kinds of oxyalkylene groups. In the latter case, the different oxyalkylene groups may be linked in a random manner or may be linked in a block shape.
  • the oxyalkylene group in the polyoxyalkylene is preferably an oxyethylene group or an oxypropylene group.
  • the number of oxyalkylene group units (degree of polymerization) in the polyoxyalkylene is preferably 2 or more.
  • the number of oxyalkylene group units is preferably 100 or less, more preferably 50 or less, still more preferably 20 or less.
  • the degree of polymerization of the organopolysiloxane is preferably 2 or more.
  • the degree of polymerization of the organopolysiloxane is preferably 1000 or less, more preferably 100 or less, still more preferably 50 or less.
  • the ratio of the number of dimethylsiloxane units to the number of diorganosiloxane units (degree of polymerization) in the organopolysiloxane (2) is preferably more than 1. The ratio is preferably 20 or less.
  • the weight average molecular weight of the organopolysiloxane is preferably 300 to 100,000, more preferably 500 to 10,000, still more preferably 500 to 2000.
  • the HLB of the organopolysiloxane is preferably 8 to 18.
  • the HLB value is a value calculated by the Griffin formula, and is a value obtained by multiplying the total of the formula weights of the hydrophilic portions by the molecular weight by 20.
  • the polyoxyalkylene in the organopolysiloxane is used as the hydrophilic portion, and the value obtained by dividing the molecular weight of the polyoxyalkylene by the molecular weight of the organopolysiloxane is multiplied by 20.
  • organopolysiloxane examples include “BYK-347”, “BYK-349”, “BYK-378”, “BYK-3450”, “BYK-3451”, “BYK-3455”, and “BYK-3456”. (Manufactured by Big Chemie Japan), “KF-6011”, “KF-6043” (manufactured by Shin-Etsu Chemical Co., Ltd.) can be mentioned.
  • the boiling point of the liquid dispersion medium in the present dispersion (2) is preferably 75 ° C. or higher, more preferably 100 ° C. or higher.
  • the boiling point of the dispersion medium is preferably 300 ° C. or lower, more preferably 250 ° C. or lower.
  • the liquid dispersion medium may be water or a non-aqueous liquid dispersion medium, and a liquid dispersion medium selected from the group consisting of water, alcohols, amides, ketones, esters, and hydrocarbons is preferable.
  • the non-aqueous liquid dispersion medium may or may not be fluorinated.
  • As the alcohol methanol, ethanol, isopropanol, butanol and hexanol are preferable.
  • the liquid dispersion medium may be a mixture of two or more kinds.
  • the liquid dispersion medium is preferably degassed from the viewpoint of reducing the uniformity of the component distribution of the molded product obtained by using the present dispersion liquid (2) and suppressing voids. Of these liquid dispersion media, water is more preferable.
  • the amount of F powder in the present dispersion liquid (2) is 100 parts by mass of the liquid dispersion medium. 25 to 100 parts by mass is preferable. Normally, the surface energy of F powder is low and the powders tend to aggregate with each other, so that the amount of F powder in the dispersion can be kept low, but this dispersion (2) is stable in dispersion even if the amount of F powder is increased. Excellent in sex.
  • the amount of F powder in the present dispersion (2) is more preferably 40 parts by mass or more with respect to 100 parts by mass of the liquid dispersion medium.
  • the dispersion liquid (2) is obtained by mixing F powder, a predetermined amount of a surfactant and a dispersion medium.
  • the mixing method include a method of mixing the F powder with a predetermined amount of the surfactant and a dispersion medium together, or a method of mixing a predetermined amount of the surfactant and the dispersion medium in advance and adding the F powder to the mixture. Be done.
  • the addition may be batch, continuous or intermittent.
  • Examples of the mixer used for mixing include a mixer with a stirring blade, a Henshell mixer, a ribbon blender, a swing type mixer, and a vibration type mixer.
  • the mixing method may be either a batch method or a continuous method.
  • a Henschel mixer, a pressurized kneader, a Banbury mixer and a planetary mixer are preferable.
  • the temperature of mixing with the F powder, a predetermined amount of the surfactant, and the dispersion medium is not particularly limited as long as the F powder is uniformly dispersed, but is usually carried out at 20 ° C. or higher. Further, the mixing is carried out at a temperature lower than the boiling point of the dispersion medium, and it is preferable to carry out the mixing at 100 ° C. or lower.
  • the dispersion liquid (2) may further contain at least one selected from the group consisting of an inorganic filler and an aromatic polymer (hereinafter, also referred to as a third component).
  • an inorganic filler When the inorganic filler is contained, the molded product obtained by applying the present dispersion liquid (2) to the base material tends to be excellent in electrical characteristics and low linear expansion.
  • the aromatic polymer When the aromatic polymer is contained, the molded product obtained by applying the present dispersion liquid (2) to the base material tends to have excellent adhesiveness and UV processability.
  • the inorganic filler a nitride filler and an inorganic oxide filler are preferable, and a boron nitride filler, an aluminum nitride filler, a verilia filler (a filler of an oxide of berylium), a silica filler, a wollastonite filler, and a talc are preferable.
  • a silicate filler such as a filler and a metal oxide filler such as cerium oxide, aluminum oxide, magnesium oxide, zinc oxide and titanium oxide are more preferable, and a silica filler is further preferable.
  • the inorganic filler is preferably surface-treated with a silane coupling agent.
  • the D50 of the inorganic filler is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the D50 is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more.
  • the shape of the inorganic filler may be granular, needle-shaped (fibrous), or plate-shaped. Specific shapes of the inorganic filler include spherical, scaly, layered, leafy, apricot kernel, columnar, chicken crown, equiaxed, leafy, mica, block, flat plate, wedge, rosette, and mesh. The shape and the prismatic shape can be mentioned.
  • Suitable specific examples of the inorganic filler include silica filler (“Admafine (registered trademark)” series manufactured by Admatex Co., Ltd.), zinc oxide surface-treated with an ester such as propylene glycol dicaprate (Sakai Chemical Industry Co., Ltd.). "FINEX (registered trademark)” series, etc.), spherical fused silica (“SFP (registered trademark)” series, etc.
  • aromatic polymer aromatic elastomers such as aromatic polyimides, aromatic polyamides, aromatic polyamideimides, aromatic maleimides and styrene elastomers and aromatic polyamic acids are preferable, and aromatic polyimides, aromatic polyamideimides and aromatics are preferable.
  • Aromatic elastomers such as maleimide, polyphenylene ether and styrene elastomers are more preferred, and aromatic polyimides, aromatic polyamideimides and aromatic polyamic acids are even more preferred.
  • the aromatic polyimide may be thermoplastic or thermosetting.
  • the thermoplastic polyimide means a polyimide that has been imidized and does not undergo a further imidization reaction.
  • aromatic polyimides include “Neoprim (registered trademark)” series (manufactured by Mitsubishi Gas Chemical Company), “Spixeria (registered trademark)” series (manufactured by Somar), and “Q-PILON (registered trademark)” series ( PI Technology Research Institute), “WINGO” series (Wingo Technology), “Toamide (registered trademark)” series (T & K TOKA), “KPI-MX” series (Kawamura Sangyo), “Yupia (“ Registered trademark) -AT “series (manufactured by Ube Kosan Co., Ltd.) can be mentioned.
  • aromatic polyamide-imide include HPC-1000 and HPC-2100D (both manufactured by Showa Denko Materials Co., Ltd.).
  • styrene elastomer examples include styrene-butadiene copolymer, hydrogenated-styrene-butadiene copolymer, hydrogenated-styrene-isoprene copolymer, styrene-butadiene-styrene block copolymer, and styrene-isoprene-styrene block copolymer.
  • examples thereof include a hydrogenated product of a styrene-butadiene-styrene block copolymer, a hydrogenated product of a styrene-isoprene-styrene block copolymer, and the like.
  • the dispersion liquid (2) may further contain a non-heat-meltable polytetrafluoroethylene powder as a third component.
  • the molded product formed from the present dispersion liquid (2) tends to have excellent electrical characteristics.
  • the mass ratio of the content of the powder in the dispersion liquid (2) is preferably 0.5 or more, more preferably 1 or more, with the content of the F powder being 1.
  • the above ratio is preferably 10 or less, more preferably 5 or less.
  • the D50 of such powder is preferably 0.1 to 1 ⁇ m.
  • the mixing method may be the same as the above-mentioned mixing method.
  • the third component may be added at any stage of producing the dispersion liquid.
  • the third component may be previously mixed with the F powder and / or a predetermined amount of the surfactant, or when the F powder is mixed with the predetermined amount of the surfactant and the dispersion medium, the third component may be mixed. May be added.
  • a mixture of F powder, a predetermined amount of the surfactant and the dispersion medium, and a mixture of the third component and the dispersion medium may be mixed in advance, or the third component is added to the dispersion liquid after obtaining the dispersion liquid. You may.
  • the addition may be performed in a batch or in a divided manner, or may be added continuously or intermittently.
  • the component sedimentation rate of the present dispersion (2) obtained as described above is preferably 60% or more, more preferably 70% or more.
  • the upper limit of the erythrocyte sedimentation rate is 100%.
  • the dispersion liquid (2) tends to have excellent dispersion stability due to the above-mentioned mechanism of action.
  • the dispersion liquid (2) obtained as described above preferably has a viscosity of 10 mPa ⁇ s or more, preferably 20 mPa ⁇ s or more, from the viewpoint of coatability or impregnation property on the base material when producing a coated base material described later. More preferred.
  • the viscosity of the dispersion liquid (2) is preferably 100,000 mPa ⁇ s or less, more preferably 10,000 mPa ⁇ s or less, and even more preferably 2000 mPa ⁇ s or less.
  • the viscosity of the dispersion liquid (2) can be set in a desired range by controlling the amount of F powder, the type and amount of the dispersion medium.
  • the thixotropic ratio of the dispersion liquid (2) is preferably 1.0 to 2.2.
  • the dispersion liquid (2) having such a thixotropic ratio is excellent in coatability, impregnation property, and homogeneity.
  • the thixotropic ratio is calculated by dividing the viscosity of the dispersion liquid (2) measured under the condition of a rotation speed of 30 rpm by the viscosity of the main dispersion liquid (2) measured under the condition of a rotation speed of 60 rpm.
  • the foam volume ratio in the present dispersion (2) is preferably less than 10%, preferably less than 5%. More preferred.
  • the foam volume ratio is preferably 0% or more.
  • the foam volume ratio measured volume of the dispersion in the standard atmospheric pressure and 20 °C (2) (V N ), it was combined foam when the pressure was reduced to 0.003MPa volume and (V V) However, it is a value obtained by the following formula.
  • the solid content of the dispersion liquid (2) contains the third component, these third components are also included in the solid content.
  • the solid content of the present dispersion liquid (2) also includes other insoluble components in the main dispersion liquid (2) other than the F powder.
  • the concentration of the solid content is preferably 25% by mass or more, more preferably 50% by mass or more, with the total mass of the dispersion liquid being 100% by mass. Further, from the viewpoint of dispersibility of the present dispersion liquid (2), the solid content concentration is preferably 80% by mass or less, more preferably 60% by mass or less.
  • the amount of F powder in the solid content is preferably 50% by mass or more, more preferably 70% by mass or more, with the total mass of the solid content being 100% by mass.
  • the amount of F powder in the solid content is preferably 99% by mass or less.
  • the dispersion liquid (2) contains thixotropic agents, viscosity modifiers, defoamers, silane coupling agents, dehydrating agents, plasticizers, weather resistant agents, antioxidants, heat stabilizers, and lubricants. , Antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, flame retardants, various organic fillers and the like.
  • the coated base material coated with the base material by the F layer can be obtained.
  • the contact method is, for example, a method of applying the present dispersion liquid (2) to the surface of the base material, a method of immersing the base material in the main dispersion liquid (2), and a method of impregnating the base material with the main dispersion liquid (2). Examples thereof include a method of spraying the present dispersion liquid (2) on the material.
  • the base material examples include metal foil, resin film, woven fabric, non-woven fabric, fiber and the like.
  • the coated substrate include a metal-clad laminate having a metal foil and an F layer formed on at least one surface thereof, and a multilayer having a resin film and an F layer formed on at least one surface thereof.
  • examples thereof include a coated woven fabric obtained by impregnating a film, a woven fabric or a nonwoven fabric with the present dispersion liquid (2) and coating the fibers in the woven fabric or the nonwoven fabric with an F layer.
  • the dispersion liquid (2) may be brought into direct contact with the fiber and fired to coat the fiber with the F polymer.
  • the F layer may cover the entire surface of the base material or a part of the base material, and the F polymer may be attached to the surface of the base material.
  • the F layer may have holes.
  • metal foil examples include metal substrates such as copper, nickel, aluminum, titanium, and metal foils such as alloys thereof.
  • Resin films include polyimide, polyarylate, polysulfone, polyallylsulfone, polyamide, polyetheramide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, liquid crystal polyester, liquid crystal polyesteramide, F polymer, and non-heat meltable tetra.
  • a resin film such as a fluoroethylene polymer and a prepreg which is a precursor of a fiber-reinforced resin substrate.
  • the F polymer and the non-heat-meltable tetrafluoroethylene polymer in the resin film are preferable.
  • the shape of these metal foils or resin films may be flat, curved, uneven, and may be foil, plate, film, or fibrous.
  • Specific examples of the covering base material include a metal foil, a metal-clad laminate having an F layer on at least one surface of the metal foil, a polyimide film, and a multilayer film having an F layer on both surfaces of the polyimide film.
  • These laminated bodies are excellent in various physical properties such as electrical characteristics, and are suitable as a printed circuit board material or the like. Specifically, the laminated body can be used for manufacturing a flexible printed circuit board or a rigid printed circuit board.
  • the metal foil is preferably a copper foil.
  • a metal-clad laminate in which the base material is a copper foil is particularly useful as a printed circuit board material.
  • the ten-point average roughness of the surface of the metal foil is preferably 0.01 to 0.05 ⁇ m.
  • the resin film is preferably a polyimide film or an F polymer film.
  • a multilayer film, which is a film on which a base material is applied, is useful as an electric wire coating material and a printed circuit board material.
  • the F layer is formed on at least one side of the surface of the base material, and even if the F layer is formed on only one side of the base material. Often, the F layer may be formed on both sides of the base material.
  • the surface of the base material may be surface-treated with a silane coupling agent or the like.
  • the woven fabric When the woven fabric is impregnated with the present dispersion liquid (2) and dried by heating, the woven fabric is coated with the F layer, and a sized coated woven fabric is obtained.
  • a glass fiber woven fabric, a carbon fiber woven fabric, an aramid fiber woven fabric and a metal fiber woven fabric are preferable, and a glass fiber woven fabric and a carbon fiber woven fabric are more preferable.
  • Examples of the method of impregnating the woven fabric with the present dispersion (2) include a method of immersing the woven fabric in the present dispersion (2) and a method of applying the present dispersion to the woven fabric.
  • a coated fiber in which the fiber is coated with the F layer can be obtained.
  • the fiber include the same as the reinforcing fiber to which the above-mentioned sizing agent can be used.
  • the present dispersion (2) By coating the above fibers with the F layer, a sizing effect that suppresses yarn breakage and fluffing of the fibers can be obtained.
  • a necessary additive may be appropriately added to the present dispersion (2) depending on the fibers used.
  • the fiber sized by the dispersion liquid (2) has excellent heat resistance and adhesiveness to other polymers.
  • the surface tension of the base material is larger than the surface tension of the surfactant.
  • the base material is easily wetted by the dispersion liquid (2), and the surface of the coated base material is not easily roughened.
  • the surface tension of the substrate is preferably 5 mN / m or more higher than the surface tension of the surfactant, and more preferably 10 mN / m or more.
  • the surface tension of the base material is particularly preferably 35 mN / m or more.
  • the F layer is preferably formed by further firing the F polymer after removing the dispersion medium by heating.
  • the temperature for removing the dispersion medium is preferably a temperature equal to or lower than the boiling point of the dispersion medium, and more preferably a temperature 50 to 150 ° C. lower than the boiling point.
  • N-methyl-2-pyrrolidone having a boiling point of about 200 ° C. it is preferable to heat it at 150 ° C. or lower, preferably 100 to 120 ° C.
  • water having a boiling point of about 100 ° C. it is preferable to heat it at 90 ° C. or lower, preferably 70 to 80 ° C. It is preferable to blow air in the step of removing the dispersion medium.
  • the base material After removing the dispersion medium, it is preferable to heat the base material to a temperature range in which the F polymer is fired to form the F layer, and it is preferable to fire the polymer in the range of, for example, 300 to 400 ° C.
  • the F layer preferably contains a fired product of the F polymer.
  • the F layer is formed through a step of contacting the dispersion liquid (2) with the substrate, a step of removing the dispersion medium, and a step of firing the F polymer. These steps may be performed once or twice or more.
  • the present dispersion liquid (2) is applied to a base material, and the dispersion medium is removed by heating to form a film.
  • the present dispersion liquid (2) may be further applied on the formed film to remove the dispersion medium by heating, and the F polymer may be further fired by heating to form the dispersion medium. From the viewpoint of easily obtaining a thick film having an excellent appearance, the steps of applying, drying and firing the present dispersion (2) may be performed twice.
  • the thickness of the F layer is preferably 0.1 ⁇ m or more, and more preferably 1 ⁇ m or more.
  • the upper limit of the thickness is 200 ⁇ m. In this range, the F layer having excellent crack resistance can be easily formed.
  • the peel strength between the F layer and the substrate is preferably 10 mN / m or more, more preferably 15 mN / m or more. The peel strength is preferably 100 mN / m or less.
  • the void ratio of the F layer is preferably 20% or less, more preferably 10% or less. The void ratio is preferably 0.1% or more.
  • the void ratio is determined by image processing to determine the void portion of the F layer from the SEM photograph of the cross section of the molded product observed using a scanning electron microscope (SEM), and the area occupied by the void portion is the area occupied by the F layer. It is the ratio (%) divided by the area.
  • the area occupied by the void portion is obtained by approximating the void portion to a circle.
  • Examples of the structure of the metal-clad laminate or the multilayer film include a base material / F layer / base material / F layer / base material, a base material / base material / F layer / base material / base material, and the like. Each base material may be the same or different, and the base material or the F layer may further contain a glass cloth or a filler.
  • Such metal-clad laminates are useful as antenna parts, printed films, aircraft parts, automobile parts, sports equipment, food industry supplies, heat dissipation parts, paints, cosmetics, etc., and specifically, aircraft electric wires and the like.
  • Sliding members such as bearings, gears, cams, belt conveyors, food transport belts, tools such as shovels, shavings, cuttings, saws, boilers, hoppers, pipes, ovens, baking molds, dies, dies, toilet bowls, container covering materials.
  • Power devices transistors, thyristors, rectifiers, transformers, power MOS FETs, CPUs, heat dissipation fins and metal heat dissipation plates. More specifically, sealing materials for processing machines, vacuum ovens, plasma processing equipment, etc. that heat-treat under low oxygen, such as housings for personal computers and displays, electronic device materials, interior and exterior of automobiles, spattering and various dry etching. It is useful as a heat dissipation component in a processing unit such as a device.
  • the dispersion liquid (2) is impregnated into an insulating layer of a printed wiring board, a thermal interface material, a substrate for a power module, a coil used in a power device such as a motor, dried, and a heat conductive heat-resistant coating layer. It can also be used for forming a heat exchanger, for adhering ceramic parts and metal parts to each other in an in-vehicle engine, and for imparting corrosion resistance to a heat exchanger and fins or pipes constituting the heat exchanger.
  • the present dispersion liquid (2) is suitable as the present sizing agent, and when the present dispersion liquid (2) is used as the sizing agent, the appearance of the fiber coated with the F layer is excellent, so that the reinforcing fiber and the matrix resin are used. In the fiber reinforced plastic contained, the adhesion between the reinforced fiber and the matrix resin is improved. Therefore, the prepreg containing the fiber and the matrix resin that have been sized by contacting the dispersion liquid (2) with the fiber has excellent mechanical properties. Further, since the F layer has excellent heat resistance, the prepreg tends to have excellent surface smoothness even when processed at a high temperature.
  • Examples of the reinforcing fiber include the same fibers as described above, and among them, carbon fiber, glass fiber, aramid fiber and boron fiber are preferable.
  • Examples of the matrix resin include the same as the matrix resin in the present prepreg. Since the F layer has excellent heat resistance, it is difficult to decompose even if it is heated when molding a prepreg using such a heat-resistant resin as a matrix resin or when further processing the prepreg, and the prepreg and its processed product have a smooth surface. Easy to excel in sex.
  • Examples of the manufacturing method for obtaining the prepreg from the present dispersion liquid (2) include the same manufacturing method as the above-mentioned manufacturing method for obtaining the present prepreg from the present dispersion liquid (1).
  • the prepreg obtained from the dispersion liquid (2) can be further molded into the fiber-reinforced composite material by the same method as the above-mentioned method for molding the prepreg into the fiber-reinforced composite material.
  • the present dispersion liquid (2) has excellent dispersion stability, and the coated base material coated with the base material by the F layer using the present dispersion liquid (2) has an excellent surface appearance and is different from other base materials. Has excellent adhesiveness.
  • the present dispersion (2) is suitably used as a sizing agent.
  • this dispersion liquid (2) is used as a sizing agent, the appearance of the fiber coated with the F layer is excellent, and the adhesiveness between the reinforcing fiber and the matrix resin is improved in the fiber reinforced plastic containing the reinforcing fiber and the matrix resin. .. Therefore, the prepreg containing the fiber and the matrix resin that have been sized by contacting the dispersion liquid (2) with the fiber has excellent mechanical properties.
  • the present invention is not limited to the configuration of the above-described embodiment.
  • the sizing agent, the dispersion liquid (1), the sizing-treated fiber, and the dispersion liquid (2) may have any other configuration added to the configuration of the embodiment, or may have the same function. It may be replaced with any configuration that exerts.
  • F powder 11 Contains 97.9 mol%, 0.1 mol%, 2.0 mol% of TFE units, NAH units, and PPVE units in this order, and contains 1 x 10 6 acid anhydride residues in the main chain.
  • Powder consisting of 1000 polymers per polymer (melting temperature 300 ° C, 5% weight loss temperature: 400 ° C or higher) (average particle diameter 2 ⁇ m, bulk density 0.18 g / m 2 )
  • F powder-12 A polymer having no polar functional group containing 97.5 mol% and 2.5 mol% of TFE units and NAH units in this order (melting temperature 305 ° C., 5% weight loss temperature: 400 ° C. or higher).
  • Epoxy resin 1 (Average particle size 2 ⁇ m, bulk density 0.19 g / m 2 )
  • Epoxy resin 1 "Epicoat 828" manufactured by Japan Epoxy Resin
  • the polymer of F powder 11 has 1000 carbonyl groups per 1 ⁇ 10 6 main chain carbon atoms.
  • Surfactant A Polyoxyethylene / Polyoxypropylene / Polyoxyethylene triblock copolymer ("Pluronic F88" manufactured by Asahi Denka Co., Ltd.)
  • Carbon fiber Carbon fiber 1: "MR50R” manufactured by Mitsubishi Chemical Corporation
  • NMP N-methyl-2-pyrrolidone
  • Film 1 Polyetherketone A film obtained by melt-extruding a ketone (“Kepstan 7003” manufactured by Arkema France) (thickness: 15 ⁇ m).
  • Example 1-1 Preparation of dispersion of sizing agent, placement on carbon fiber [Example 1-1]
  • F powder 11 (10 parts by mass) and NMP (90 parts by mass) were put into a pot, and zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to obtain a dispersion liquid 11 (viscosity: 400 mPa ⁇ s).
  • the dispersion liquid 11 obtained in (1) above was placed on carbon fibers by a roller dipping method, passed through a drying oven at 120 ° C. for 5 minutes, heated and dried. Then, it is heated in a far-infrared furnace at 340 ° C.
  • a film 1 is layered on both sides of a sheet-shaped carbon fiber base material having a carbon fiber grain of 75 g / m 2 in which the carbon fiber T1 is oriented in one direction, and the two films 1 are heated and melted to form a carbon fiber base material.
  • the prepreg 1 was produced by impregnation. After cutting the prepreg 1 to a predetermined size, the prepregs were laminated in a steel mold so that the fiber axial directions of the prepregs were aligned in one direction.
  • the mold on which the laminate is placed is compressed with a heating and cooling two-stage press (manufactured by Kondo Metal Industry Co., Ltd., 50 ton press) at 380 ° C. and 5 MPa for 30 minutes, and the temperature is lowered to 200 ° C. in a few minutes to increase the thickness.
  • a laminate 1 having a thickness of about 2 mm was obtained.
  • the laminated body 1 and a copper foil having a thickness of 18 ⁇ m were laminated and compressed under the same conditions to obtain a molded body 1.
  • Example 1-2 A molded product 2 was obtained in the same manner as in Example 1-1 except that F powder 12 was used instead of F powder 11.
  • Example 1-3 Epoxy resin 1 (80 parts by mass) and surfactant A (20 parts by mass) were mixed, and phase inversion emulsification was performed to obtain a dispersion liquid 12.
  • a molded product 3 was obtained in the same manner as in Example 1-1 except that the dispersion liquid 12 was used instead of the dispersion liquid 11. 1-3. Evaluation The appearance, peel strength and water resistance of the molded products 1 to 3 were evaluated according to the following criteria.
  • ⁇ Appearance of molded product> The surface of the molded product was visually observed and evaluated as follows. ⁇ : No foaming is seen on the surface of the molded body and it is smooth. ⁇ : Foaming is seen on the surface of the molded body and it is not smooth. ⁇ Peeling strength of molded product> A sample was prepared by cutting the molded product into a rectangular shape (length: 100 mm, width: 10 mm). Next, when the position of 50 mm from one end in the length direction of the sample was fixed, the tensile speed was 50 mm / min, and the copper foil and the laminate were peeled off from one end in the length direction at 90 ° to the sample. The maximum load (N / cm) applied to the surface was measured.
  • the peel strength was evaluated according to the following criteria. ⁇ : 10 N / cm or more ⁇ : Less than 10 N / cm ⁇ Water resistance of the molded product> After holding the molded body in an atmosphere of 85 ° C. and a relative humidity of 85% for 72 hours, the peeling strength of the molded body after water absorption was determined in the same manner as the above ⁇ peeling strength of the molded body> except that a sample was prepared. It was measured. For each molded body, the ratio of the peeling strength of the molded body after water absorption to the peeling strength of the molded body measured in the above ⁇ peeling strength of the molded body> was obtained and evaluated according to the following criteria. ⁇ : 90% or more ⁇ : less than 90% Table 1 shows the evaluation results of the molded products 1 to 3.
  • F powder 21 A polymer containing 97.9 mol%, 0.1 mol%, and 2.0 mol% of TFE units, NAH units, and PPVE units in this order and having a polar functional group (melting temperature 300 ° C., 5% weight).
  • F powder 22 Powder (D50: 28 ⁇ m) composed of a polymer containing 97.5 mol% and 2.5 mol% of TFE units and PPVE units in this order (melting temperature 305 ° C., 5% weight loss temperature: 400 ° C. or higher).
  • F powder 23 Powder (D50: 2 ⁇ m) composed of a polymer containing 97.5 mol% and 2.5 mol% of TFE units and PPVE units in this order (melting temperature 305 ° C., 5% weight loss temperature: 400 ° C. or higher).
  • the polymer of F powder 21 has 1000 carbonyl group-containing groups per 1 ⁇ 10 6 main chain carbon atoms, and the polymers of F powder 22 and F powder 23 do not have polar functional groups.
  • Surfactant 1 Polyoxyalkylene-modified polydimethylsiloxane (surface tension: 26 mN / m)
  • Surfactant 2 Polyoxyalkylene-modified polyorganosiloxane (surface tension: 30 mN / m) [Liquid dispersion medium] Water (surface tension: 72 mN / m) [Base material]
  • Base material 1 Carbon fiber (surface tension: 38 mN / m)
  • Base material 2 Hydrophilic treated resin fiber (surface tension: 25 mN / m)
  • Example 2-1 Dispersion Liquid Production Example [Example 2-1] First, the powder 21, the surfactant 1, and water as a liquid dispersion medium were put into the pot, and the zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour, and the dispersion liquid 21 (viscosity: 30 mPa.) Containing powder 21 (50 parts by mass), surfactant 1 (0.2 parts by mass), and water (49.8 parts by mass). s) was obtained.
  • dispersion liquid 21 viscosity: 30 mPa.
  • Dispersions 22 to 26 were prepared in the same manner as the dispersion 21 except that the types of the F powder, the surfactant, the liquid dispersion medium and the amount of the surfactant were changed as shown in Table 2.
  • the components of the dispersions 21 to 26 obtained above are summarized in Table 2. Further, a coated base material was prepared by the following method using the dispersion liquids 21 to 26, and evaluated according to the evaluation criteria. Table 2 also summarizes the results of evaluation of the coated substrate obtained from each dispersion according to the following evaluation criteria.
  • coated base material The dispersion liquid 21 was applied to the surface of a long copper foil (thickness 18 ⁇ m) using a bar coater to form a wet film. Next, the metal foil on which the wet film was formed was passed through a drying oven at 120 ° C. for 5 minutes and dried by heating to obtain a dry film. Then, the dry membrane was heated at 380 ° C. for 3 minutes in a nitrogen oven. As a result, a coated base material 1 having a metal foil and a polymer layer (thickness 5 ⁇ m) as a molded product containing a melt-fired product of powder 21 on the surface thereof was manufactured. The coated base materials 2 to 6 were manufactured in the same manner as the coated base material 1 except that the dispersion liquid 21 was changed to each of the dispersion liquids 22 to 26.
  • Component sedimentation rate (%) (height of sedimentation layer) / (height of the entire dispersion) x 100 [Evaluation criteria]
  • ⁇ The component sedimentation rate measured by the above method is 70% or more.
  • ⁇ The component sedimentation rate measured by the above method is less than 70% and 60% or more.
  • X The component sedimentation rate measured by the above method is less than 60%.
  • ⁇ The entire surface of the polymer layer is smooth.
  • ⁇ Unevenness due to lack of agglomerates or powder is visible on the edge of the surface of the polymer layer.
  • X Unevenness due to lack of agglomerates or powder is visible on the entire surface of the polymer layer.
  • the sizing agent of the present invention, the sizing-treated fiber, and the prepreg formed from the fiber can suppress foaming during heat molding, have excellent appearance such as smoothness, and have adhesiveness and water resistance when formed into a laminate. It is possible to form a particularly excellent molded product.
  • the obtained molded products include printed substrates, aircraft parts, spacecraft parts, automobile parts, ship parts, civil engineering and building materials, petroleum drilling parts, hydrogen tanks, hydrogen tank pressure vessels, wind power generator blades and sporting goods. Can be suitably used in the field.
  • the present dispersion liquid (2) is excellent in dispersibility and dispersion stability. Further, the surface of the coated base material formed from the present dispersion liquid (2) is excellent in uniformity and excellent appearance.
  • the coated base material obtained by coating the base material with the present dispersion liquid (2) highly expresses the properties of the F polymer. Further, when the present dispersion (2) is used as a sizing agent, it is considered that a sizing effect can be obtained. It is considered that the prepreg containing the fiber and the matrix resin sized by the dispersion liquid (2) has excellent mechanical properties.

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Abstract

L'invention concerne un agent d'encollage spécifique, des fibres encollées et un préimprégné qui permettent de supprimer le moussage pendant la formation à chaud et de former un objet moulé qui a un excellent aspect, y compris le lissé, et, dans un stratifié, une excellente adhérence et une excellente résistance à l'eau. L'invention concerne également une dispersion qui contient une poudre de polymère de tétrafluoroéthylène et présente une excellente stabilité de dispersion, même lorsque la quantité de tensioactif est réduite.　L'invention concerne également un agent d'encollage qui contient une poudre de polymère de tétrafluoroéthylène thermofusible qui a une dimension moyenne des particules de 0,1 à 200 µm. L'invention concerne également des fibres encollées et un préimprégné qui comprend les fibres et une résine de matrice. Une dispersion qui comprend une poudre de polymère de tétrafluoroéthylène thermofusible qui a une dimension moyenne des particules de 10 à 100 µm, un tensioactif et un milieu de dispersion liquide, la dispersion ne contenant pas plus de 0,01 partie en masse du tensioactif pour 1 partie en masse de la poudre de polymère de tétrafluoroéthylène thermofusible.
PCT/JP2021/025581 2020-07-09 2021-07-07 Agent d'encollage, fibres encollées, préimprégné et dispersion WO2022009918A1 (fr)

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