Fiber Reinforced Composites

Abstract

Provided is a fiber-reinforced composite material including carbon fiber and a fluororesin, wherein the tensile elastic modulus measured under specific conditions is 40 GPa or more.

Description

[Technical field]

[0001] The present disclosure relates to fiber reinforced composite materials. [Background technology]

[0002] As a fiber-reinforced composite material containing a fluororesin as a matrix, Patent Document 1 describes a sheet that includes carbon fibers and a fluororesin layer located around single carbon fibers that constitute the carbon fibers, the fluororesin that constitutes the fluororesin layer being polyvinylidene fluoride, and having a tensile strength of 400 MPa or more.

[0003] Patent Document 2 describes a laminate comprising a fiber-reinforced resin layer containing a reinforcing fiber substrate and a resin component containing 50 volume % or more of the following fluororesin, in which the ratio of the volume of the reinforcing fiber substrate to the total volume of the reinforcing fiber substrate and the resin component is 0.30 to 0.70, and a substrate containing metal, paper, glass, or a resin component containing more than 50 volume % of the following non-fluororesin, in which at least one outermost layer is the fiber-reinforced resin layer, and the ratio of the total thickness of the fiber-reinforced resin layer to the total thickness of the substrate is 1 / 99 to 30 / 70. Fluorine resin: a fluororesin having at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxyl group, an epoxy group, an amide group, an amino group and an isocyanate group, having a melting point of 100 to 325°C, and being melt-moldable. Non-fluorine resin: A cured thermosetting resin or thermoplastic resin that does not contain fluorine atoms. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2018 / 207446 [Patent Document 2] International Publication No. 2019 / 203099 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present disclosure is to provide a fiber-reinforced composite material that has excellent mechanical strength and can be used in structural members that are subjected to loads. [Means for solving the problem]

[0006] According to the present disclosure, there is provided a fiber-reinforced composite material containing carbon fiber and a fluororesin, the fiber-reinforced composite material having a tensile modulus of elasticity of 40 GPa or more as measured under the following conditions. (Measurement conditions for tensile modulus) The measurements are made in accordance with ASTM D3039-17, except that the following conditions are used: Clip: INSTRON, model 2580-301, capacity ±100kN Strain gauge: Tokyo Measuring Instruments Laboratory, model: FLA-6-11-3LJCT Pulling speed: 2mm / min

[0007] In the fiber-reinforced composite material of the present disclosure, the fluororesin preferably contains chlorine atoms. In the fiber-reinforced composite material of the present disclosure, the chlorine atom content of the fluororesin is preferably 1.5 mass % or more. In the fiber-reinforced composite material of the present disclosure, the fluororesin is preferably at least one selected from the group consisting of polychlorotrifluoroethylene and chlorotrifluoroethylene copolymers. In the fiber-reinforced composite material of the present disclosure, it is preferable that the carbon fiber is composed of a single carbon fiber and a sizing agent adhered to the single carbon fiber, and the amount of the sizing agent adhered is 3% or less of the total mass of the single carbon fiber and the sizing agent. The fiber-reinforced composite material of the present disclosure preferably has a maximum point stress of 600 MPa or more. The fiber reinforced composite material of the present disclosure is preferably a tape. Effect of the Invention

[0008] According to the present disclosure, it is possible to provide a fiber-reinforced composite material that has excellent mechanical strength and can be used in structural members that are subjected to loads. [Brief description of the drawings]

[0009] [Figure 1] 1(a) to (c) are schematic diagrams each showing an example of the shape of a tape. [Diagram 2] FIG. 2 is a schematic diagram showing an example of a pipe configuration. [Diagram 3] FIG. 3 is a schematic diagram showing an example of a method for winding a tape. [Figure 4] 4(a) to (e) are schematic diagrams each showing an example of a tape winding state. [Diagram 5] FIG. 5 is a schematic diagram showing another example of the configuration of a pipe. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Specific embodiments of the present disclosure will be described in detail below, but the present disclosure is not limited to the following embodiments.

[0011] The fiber-reinforced composite material of the present disclosure contains carbon fiber and a fluororesin. Despite containing carbon fiber and a fluororesin, the fiber-reinforced composite material of the present disclosure has a tensile modulus of elasticity of 40 GPa or more.

[0012] The tensile modulus of conventional fiber-reinforced composite materials is about 11 GPa. In the fiber-reinforced composite material of the present disclosure, the constituent materials are appropriately selected, so that the tensile modulus is surprisingly improved compared to conventional fiber-reinforced composite materials, and the material can be used in structural members that have not been easily used in the past.

[0013] In the present disclosure, the tensile modulus is measured under the following conditions. (Measurement conditions for tensile modulus) The measurements are made in accordance with ASTM D3039-17, except that the following conditions are used: Clip: Instron, model 2580-301, capacity ±100kN Strain gauge: Tokyo Measuring Instruments Laboratory, model: FLA-6-11-3LJCT Pulling speed: 2mm / min

[0014] This measurement method differs from conventional methods for measuring tensile modulus, and can be an index of the degree to which a fiber-reinforced composite material satisfies the required mechanical strength when applied to a structural member. A higher tensile modulus measured by the above measurement method means that the fiber-reinforced composite material is less likely to break even when a large load is applied to the fiber-reinforced composite material when applied to a structural member.

[0015] The tensile modulus of the fiber reinforced composite material is 40 GPa or more, preferably 60 GPa or more, more preferably 80 GPa or more, and even more preferably 100 GPa or more. The upper limit of the tensile modulus of the fiber reinforced composite material is not particularly limited, and the higher the better, but from the viewpoint of obtaining a fiber reinforced composite material with an excellent balance of various properties, it is preferably 300 GPa or less, more preferably 200 GPa or less, even more preferably 150 GPa or less, and particularly preferably 130 GPa or less.

[0016] The maximum point stress of the fiber reinforced composite material of the present disclosure is preferably 600 MPa or more, more preferably 800 MPa or more, even more preferably 1000 MPa or more, and particularly preferably 1100 MPa or more. The upper limit may be 10000 MPa.

[0017] The maximum elongation of the fiber reinforced composite material of the present disclosure is preferably 0.5% or more, more preferably 0.7% or more, even more preferably 0.9% or more, and particularly preferably 1.1% or more. The upper limit may be 100%.

[0018] The maximum stress and maximum elongation of a fiber-reinforced composite material can be measured by the method described above for measuring the tensile modulus of a fiber-reinforced composite material.

[0019] The fiber reinforced composite material of the present disclosure contains carbon fibers. The carbon fibers are preferably included in the fiber reinforced composite material as a carbon fiber matrix.

[0020] The carbon fiber is preferably made of a single carbon fiber having an average fiber length of 5 mm or more, more preferably made of a single carbon fiber having an average fiber length of 50 mm or more, even more preferably made of a single carbon fiber having an average fiber length of 100 mm or more, even more preferably made of a single carbon fiber having an average fiber length of 250 mm or more, and is most preferably a continuous fiber.

[0021] The carbon fibers are preferably made of single carbon fibers having an average diameter of 3 to 15 μm, and more preferably made of single carbon fibers having an average diameter of 4 to 9 μm.

[0022] The carbon single fibers constituting the carbon fibers may be surface-treated, a treatment agent may be used, a sizing agent may be used, or the carbon single fibers may be plated with a metal or the like.

[0023] By the above surface treatment, for example, oxygen-containing functional groups, nitrogen-containing functional groups, etc. can be introduced onto the carbon fiber surface.

[0024] Examples of surface treatments for carbon fibers include chemical oxidation / electrolytic oxidation in liquid phase, and gas phase oxidation. Among these surface treatments, electrolytic oxidation in liquid phase is preferred from the viewpoints of productivity and uniformity of treatment. Examples of electrolytes used in electrolytic oxidation include inorganic acids such as sulfuric acid and nitric acid, inorganic hydroxides such as sodium hydroxide and potassium hydroxide, and inorganic salts such as ammonium sulfate and sodium hydrogen carbonate.

[0025] Examples of the sizing agent include surfactants such as nonionic surfactants, anionic surfactants, and amphoteric surfactants, mineral oils, and animal and vegetable oils. More specifically, ester compounds, alkylene glycol compounds, polyolefin compounds, phenyl ether compounds, polyether compounds, silicone compounds, polyethylene glycol compounds, amide compounds, sulfonate compounds, phosphate compounds, carboxylate compounds, fluorine compounds, urethane compounds, epoxy compounds, acrylic compounds, ionomer resins, silane coupling agents, polyvinyl alcohol compounds, polysulfone compounds, polyethersulfone compounds, polyetherimide compounds, polyimide compounds, tertiary amine compounds, mineral oils, emulsifiers, electrolyte compounds, and combinations of two or more of these can be used.

[0026] In order to improve the handling property, abrasion resistance, and fluff resistance of the carbon fiber, the sizing agent may contain known additives and auxiliary components, such as dispersants, surfactants, smoothing agents, and stabilizers.

[0027] The amount of sizing agent attached is preferably 3% or less, more preferably 2% or less, even more preferably 1% or less, particularly preferably 0.5% or less, and preferably 0.1% or more, based on the total mass of the carbon single fiber and the sizing agent, since a fiber-reinforced composite material having even greater mechanical strength can be obtained.

[0028] The amount of the sizing agent attached can be determined by washing the carbon fiber with a solvent, and calculating the mass of the carbon fiber before washing relative to the remaining amount after volatilizing the recovered solvent. A commonly used solvent can be used as the solvent, and acetone is preferably used.

[0029] As the treatment agent, epoxy resin, urethane resin, silane coupling agent, water-insoluble polyamide, water-soluble polyamide, fluororesin, silicone resin, and combinations of two or more of these can be used.

[0030] By using a treatment agent, functional groups can be introduced onto the surface of the carbon single fiber. The carbon single fiber preferably has, on its surface, an amide group, a carboxyl group, an acid anhydride group, an alkoxycarbonyl group, a cyano group, a carbonate group, a carboxylic acid halide group, a hydroxyl group, a glycidyl group, an imide group, a urethane group, a urea group, a sulfonyl group, a sulfo group, an epoxy group, an alkylene group, a hydrocarbon group, a halogen group, an N-oxide group, an N-hydroxy group, a nitro group, a nitroso group, azo group, a diazo group, an azide group, an oxo group, a phenyl group, a phosphino group, a thio group, an S-oxide group, a thioxy group, a peroxy group, a ketone group, an acyl group, an acetyl group, an enol group, an enamine group, a formyl group, a benzoyl group, an acetal group, a hemiacetal group, an oxime group, a thiol group, a urea group, an isonitrile group, an allene group, a thiol group, or a combination of two or more of these.

[0031] The form of the carbon fiber constituting the carbon fiber may be continuous fiber, long fiber, short fiber, etc. The form of the carbon fiber is not particularly limited, and includes all of the following: a unidirectional carbon fiber sheet in which carbon fiber is aligned in one direction, two or more unidirectional carbon fiber sheets stacked at different angles, carbon fiber randomly oriented in a two-dimensional direction, carbon fiber molded into a fabric such as a woven fabric, knitted fabric, or nonwoven fabric, and strand-shaped fabric such as braided fabric. These may be called, for example, filament, tow, staple yarn, woven fabric (cloth), braid, chopped yarn, milled, felt, mat, paper, etc. The woven fabric may be a bidirectional woven fabric, a multiaxial woven fabric, etc. Two or more of these may be used in combination. In addition, when stacking, it is preferable to stack multiple layers with the layers in different directions, stack alternately, or arrange symmetrically in the thickness direction. As the carbon fiber, a sheet-like carbon fiber is preferable because of its excellent tensile properties, a unidirectional carbon fiber sheet in which carbon fibers are aligned in one direction, a woven fabric or a nonwoven fabric is more preferable, and a unidirectional carbon fiber sheet is even more preferable.

[0032] When the carbon fiber is in a sheet form, the thickness of the sheet is preferably from 0.01 to 5 mm, more preferably from 0.05 to 2.5 mm, and even more preferably from 0.1 to 2 mm.

[0033] Examples of sheet-shaped carbon fibers include CO6142, CO6151B, CO6343, CO6343B, CO6347B, CO6644B, CO1302, CO1303, CO5642, CO7354, CO7359B, CK6244C, CK6273C, CK6261C, UT70-20G, UT70-30G, UT70-40G, UT70-45G, UT70-60G, UM46-30G, UM46-34G, UM46-40G, BT70-20, and BT70-30 manufactured by Toray Industries, Inc., and TR3110M, TR3523M, and TR61 10HM, TR6120HM, TRK101M, TRK510M, TR3160TMS, TR3163TMS, TRK979PQRW, TRK976PQRW, and W-1103, W-1104, W-3101, W-310A, W-3104, W-3108, W-310F, W-3112, W-3121, W-3161, W-3162, W-6101, W-6110, W-6E01, W-7101, W-7161, W-7U61, W-3801, W-3802, W-3302, W-3303, and W-3304 manufactured by Toho Tenax Co., Ltd.

[0034] Examples of carbon fibers include polyacrylonitrile-based, pitch-based, rayon-based, cellulose-based, lignin-based, phenol-based, vapor-grown, etc. Of these, polyacrylonitrile-based, pitch-based, or rayon-based carbon fibers are preferred, and polyacrylonitrile-based carbon fibers are more preferred because of their excellent tensile strength.

[0035] Examples of polyacrylonitrile carbon fibers include Toray Industries' T300, T300B, T400HB, T700SC, T800SC, T800HB, T830HB, T1000GB, T1100GC, M35JB, M40JB, M46JB, M50JB, M55J, M55JB, M60JB, and M30SC, and Mitsubishi Rayon's HT series products TR30S3L, TR50S6L, TR50S12L, TR50S15L, TR50D12L, TRH50 18M, TRH50 60M, and TRW40 50L, IM series products MR60H24P, and HM series products MS40 12M, HR40 12M, and HS40. Examples include 12P, HT series 34-700, 37-800, and Toho Tenax HTA40, HTS40, HTS45, STS40, UTS50, IMS40, IMS60, IMS65, HWA35, UMS40, UMS45, UMS55, and HTS40MC.

[0036] The tensile modulus of the carbon fiber (single fiber tensile modulus) is preferably 100 to 1000 GPa, more preferably 200 to 500 GPa, since the tensile strength of the fiber reinforced composite material is further increased. The tensile strength of the carbon fiber (single fiber tensile strength) is preferably 2000 to 10000 MPa, more preferably 3000 to 8000 MPa, since the tensile strength of the fiber reinforced composite material is further increased.

[0037] The tensile modulus of the polyacrylonitrile carbon fiber as the carbon fiber is preferably 100 to 1000 GPa, more preferably 200 to 500 GPa, since the tensile strength of the fiber reinforced composite material is further increased. The tensile strength of the polyacrylonitrile carbon fiber as the carbon fiber is preferably 2000 to 10000 MPa, more preferably 3000 to 8000 MPa, since the tensile strength of the fiber reinforced composite material is further increased.

[0038] The tensile modulus and the tensile strength of the carbon fiber are measured in accordance with JIS R7606 (2000).

[0039] The fiber-reinforced composite material of the present disclosure contains a fluororesin. The fluororesin is preferably contained in the fiber-reinforced composite material as a matrix resin.

[0040] The fluororesin used in the fiber-reinforced composite material of the present disclosure is a partially crystalline fluoropolymer, and is a fluoroplastic, not a fluororubber. The fluororesin has a melting point and has thermoplastic properties. The fluororesin may be melt-processable or non-melt-processable, but is preferably a melt-processable fluororesin.

[0041] In the present disclosure, melt-processable means that the polymer can be melted and processed using conventional processing equipment such as extruders, injection molding machines, etc. Thus, melt-processable fluororesins typically have a melt flow rate of 0.01 to 500 g / 10 min.

[0042] The melting point of the fluororesin is preferably 150°C or higher, more preferably 170°C or higher, even more preferably 180°C or higher, particularly preferably 190°C or higher, and most preferably 200°C or higher, and is preferably 320°C or lower, more preferably 300°C or lower, even more preferably 280°C or lower, particularly preferably 260°C or lower, and most preferably 253°C or lower.

[0043] The melt flow rate (MFR) of the fluororesin at any temperature (e.g., 230°C or 297°C) in the range of 230 to 350°C, which is a general molding temperature range, is preferably 0.5 g / 10 min or more, more preferably 1.0 g / 10 min or more, even more preferably 1.5 g / 10 min or more, particularly preferably 2.0 g / 10 min or more, most preferably 2.5 g / 10 min or more, preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, even more preferably 40 g / 10 min or less, and particularly preferably 35 g / 10 min or less. The melt flow rate can be determined, for example, by using a melt indexer to measure the mass (g) of the fluororesin flowing out from a nozzle with an inner diameter of 2 mm and a length of 8 mm per unit time (10 minutes) at any temperature (e.g., 230°C or 297°C) and any load (e.g., 2.16 kg or 5 kg).

[0044] The fluororesin is preferably one containing chlorine atoms, since it can provide a fiber-reinforced composite material with even greater mechanical strength. It has been found that the use of a fluororesin containing chlorine atoms as the fluororesin surprisingly improves the mechanical strength of the fiber-reinforced composite material, and can provide a fiber-reinforced composite material that can be used in structural members that are subjected to loads.

[0045] The chlorine atom content of the fluororesin is preferably 1.5 mass% or more, more preferably 3.0 mass% or more, even more preferably 4.0 mass% or more, particularly preferably 5.0 mass% or more, and most preferably 6.0 mass% or more, and is preferably 40 mass% or less, more preferably 35 mass% or less, and even more preferably 31 mass% or less, because a fiber-reinforced composite material having even better mechanical strength can be obtained.

[0046] The fluororesin preferably contains chlorotrifluoroethylene (CTFE) units. The content of the CTFE units in the fluororesin is preferably 15 mol% or more, more preferably 18 mol% or more, and the upper limit is preferably 100 mol% based on the total polymerized units constituting the fluororesin.

[0047] As the fluororesin, at least one selected from the group consisting of polychlorotrifluoroethylene (PCTFE) and chlorotrifluoroethylene (CTFE) copolymers is preferred, since a fiber-reinforced composite material having even greater mechanical strength can be obtained, at least one selected from the group consisting of PCTFE, CTFE / tetrafluoroethylene (TFE) copolymers, and ethylene / CTFE copolymers is more preferred, and PCTFE and CTFE / TFE copolymers are even more preferred.

[0048] PCTFE includes CTFE homopolymers and polymers containing CTFE units and small amounts of comonomer units.

[0049] The melting point of PCTFE is preferably 150 to 230° C., and more preferably 190 to 217° C. The melting point is the temperature corresponding to the maximum value on the heat of fusion curve when the temperature is increased at a rate of 10° C. / min using a differential scanning calorimeter [DSC].

[0050] The flow value of PCTFE is preferably 1×10 -4 ~5×10 -1 (cm 3 The flow value is the volume of resin extruded per second when PCTFE is melted at 230°C using a Koga type flow tester CFT-500D (manufactured by Shimadzu Corporation) and extruded from a nozzle with a diameter of 1 mm under a load of 100 kg.

[0051] The content of CTFE units in PCTFE is preferably from 95 to 100 mol %, more preferably from 98 to 100 mol %, and further preferably from 99 to 100 mol %.

[0052] The comonomer constituting the comonomer unit that can be contained in PCTFE is not particularly limited as long as it is a monomer copolymerizable with CTFE, and examples thereof include TFE, ethylene, vinylidene fluoride, perfluoroalkyl vinyl ether, and hexafluoropropylene.

[0053] CTFE copolymers include those that contain CTFE units and TFE, hexafluoropropylene (HFP), perfluoroalkyl vinyl ether (PAVE), vinylidene fluoride (VDF), vinyl fluoride, hexafluoroisobutene, formula: CH2=CX. 1 (CF2) n X 2 (In the formula, X 1 is H, F, or X 2 is H, F or Cl, and n is an integer of 1 to 10), and a unit derived from at least one monomer selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, vinyl chloride and vinylidene chloride.

[0054] The CTFE copolymer is more preferably at least one selected from the group consisting of ethylene / CTFE copolymers and copolymers containing CTFE units and units derived from at least one monomer selected from the group consisting of TFE, HFP and PAVE.

[0055] The ethylene / CTFE copolymer (ECTFE) is preferably a copolymer containing ethylene units and CTFE units, and containing 46 to 52 mol% of ethylene units and 54 to 48 mol% of CTFE units relative to the total of the ethylene units and CTFE units. ECTFE may be a binary copolymer consisting of only ethylene units and CTFE units, or may contain, in addition to the ethylene units and CTFE units, polymerization units based on a monomer copolymerizable with ethylene and CTFE (e.g., PAVE). The content of the polymerization units based on a monomer copolymerizable with ethylene and CTFE is preferably 0.01 to 5 mol% relative to the total of the ethylene units, CTFE units, and polymerization units based on the above-mentioned copolymerizable monomers.

[0056] The MFR of ECTFE is preferably 0.01 to 100 g / 10 min. The MFR of ECTFE is measured at a temperature of 230° C. and a load of 2.16 kg.

[0057] The CTFE copolymer is preferably a copolymer containing CTFE units and TFE units (CTFE / TFE copolymer).

[0058] As the CTFE / TFE copolymer, one containing a CTFE unit, a TFE unit and a monomer (α) unit derived from a monomer (α) copolymerizable therewith is particularly preferred.

[0059] The monomer (α) is not particularly limited as long as it is a monomer copolymerizable with CTFE and TFE, and examples thereof include ethylene (Et), VDF, CF2=CF-ORf 1 (In the formula, Rf 1 Perfluoro(alkyl vinyl ether) (PAVE) represented by a perfluoroalkyl group having 1 to 8 carbon atoms, CX 3 X 4 =CX 5 (CF2) n X 6 (In the formula, X 3 , X 4 and X 5 are the same or different and are a hydrogen atom or a fluorine atom; X 6 is a hydrogen atom, a fluorine atom, or a chlorine atom; n is an integer of 1 to 10), 2 (In the formula, Rf 2 and alkyl perfluorovinyl ether derivatives represented by the formula (I) (a perfluoroalkyl group having 1 to 5 carbon atoms), among which at least one selected from the group consisting of PAVE, a vinyl monomer and an alkyl perfluorovinyl ether derivative is preferred, and at least one selected from the group consisting of PAVE and HFP is more preferred.

[0060] For PAVE, CF2=CF-ORf 3 (In the formula, Rf 3represents a perfluoroalkyl group having 1 to 5 carbon atoms.) is preferred, and examples thereof include perfluoro(methyl vinyl ether) [PMVE], perfluoro(ethyl vinyl ether) [PEVE], perfluoro(propyl vinyl ether) [PPVE], perfluoro(butyl vinyl ether), and the like. Among these, at least one selected from the group consisting of PMVE, PEVE, and PPVE is more preferred, and PPVE is even more preferred.

[0061] As the alkyl perfluorovinyl ether derivative, Rf 2 is preferably a perfluoroalkyl group having 1 to 3 carbon atoms, and CF2=CF-OCH2-CF2CF3 is more preferable.

[0062] The CTFE / TFE copolymer preferably contains 10 to 95 mol % CTFE units and 90 to 5 mol % TFE units, more preferably contains 15 to 90 mol % CTFE units and 85 to 10 mol % TFE units, even more preferably contains 15 to 50 mol % CTFE units and 85 to 50 mol % TFE units, and particularly preferably contains 15 to 25 mol % CTFE units and 85 to 75 mol % TFE units.

[0063] It is also preferable that the CTFE / TFE copolymer contains 90 to 99.9 mol % in total of CTFE units and TFE units, and 0.1 to 10 mol % of monomer (α) units.

[0064] As the CTFE / TFE copolymer, the CTFE / TFE / PAVE copolymer is particularly preferred. In the CTFE / TFE / PAVE copolymer, the PAVE may be perfluoro(methyl vinyl ether) [PMVE], perfluoro(ethyl vinyl ether) [PEVE], perfluoro(propyl vinyl ether) [PPVE], perfluoro(butyl vinyl ether), etc., and among them, at least one selected from the group consisting of PMVE, PEVE and PPVE is preferred, and PPVE is more preferred. In the CTFE / TFE / PAVE copolymer, the content of the PAVE unit is preferably 0.5 mol% or more, more preferably 2.0 mol% or more, preferably 5 mol% or less, more preferably 4 mol% or less, based on the total polymerized units.

[0065] The content of each monomer in the fluororesin can be calculated by appropriately combining NMR and elemental analysis depending on the type of monomer.

[0066] The melting point of the CTFE / TFE copolymer is preferably 150°C or higher, more preferably 170°C or higher, even more preferably 190°C or higher, particularly preferably 210°C or higher, and most preferably 230°C or higher, and is preferably less than 324°C, more preferably 320°C or lower, and even more preferably 270°C or lower.

[0067] The MFR (297°C) of the CTFE / TFE copolymer is preferably 0.5 g / 10 min or more, more preferably 2.0 g / 10 min or more, even more preferably 3.0 g / 10 min or more, particularly preferably 4.0 g / 10 min or more, most preferably 5.0 g / 10 min or more, preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, even more preferably 40 g / 10 min or less, particularly preferably 35 g / 10 min or less. The MFR of the CTFE / TFE copolymer is measured at a temperature of 297°C and a load of 5 kg.

[0068] The fluororesin preferably has a reactive functional group, since this allows for the production of a fiber-reinforced composite material having even greater mechanical strength. The reactive functional group is preferably at least one selected from the group consisting of a carbonyl group, a hydroxyl group, a heterocyclic group, and an amino group.

[0069] As the reactive functional group, an amide group, a carbamoyl group, a hydroxyl group, a carboxyl group, a carbonate group, a carboxylic acid halide group, or an acid anhydride bond is preferred, from the viewpoints of ease of introduction and of the fluororesin having appropriate heat resistance and good adhesive properties at relatively low temperatures, and an amide group, a carbamoyl group, a hydroxyl group, a carbonate group, a carboxylic acid halide group, or an acid anhydride bond is more preferred.

[0070] As the reactive functional group, at least one selected from the group consisting of a carbonate group and a carboxylic acid halide group is preferable. The carbonate group and the carboxylic acid halide group may be the groups described in WO 99 / 45044.

[0071] The fluororesin may be a polymer having a reactive functional group at either the main chain end or the side chain of the polymer, or may be a polymer having a reactive functional group at both the main chain end and the side chain. When the reactive functional group is at the main chain end, it may be at both ends of the main chain, or only at one end. When the reactive functional group also has an ether bond, the reactive functional group may further be present in the main chain.

[0072] As the fluororesin, one made of a polymer having a reactive functional group at the end of the main chain is preferred because it does not significantly deteriorate the mechanical properties and chemical resistance, and is advantageous in terms of productivity and cost.

[0073] Regarding the number of reactive functional groups, a main chain carbon number of 10 is preferred because it provides a fiber-reinforced composite material with superior mechanical strength. 6The number of carbon atoms in the main chain is preferably 3 to 800, more preferably 15 or more, even more preferably 30 or more, particularly preferably 50 or more, and preferably 400 or less, more preferably 300 or less. In addition, when the fluororesin has at least one selected from the group consisting of a carbonate group and a carboxylic acid halide group, the total number of carbonate groups and carboxylic acid halide groups is preferably 10 or less than the number of carbon atoms in the main chain. 6 The number per molecule is preferably 3 to 800, more preferably 15 or more, further preferably 30 or more, particularly preferably 50 or more, and is preferably 400 or less, more preferably 300 or less.

[0074] The number of reactive functional groups is determined by analyzing the infrared absorption spectrum of a film sheet having a thickness of 50 to 200 μm obtained by compression molding a fluororesin at a molding temperature 50° C. higher than its melting point and at a molding pressure of 5 MPa using an infrared spectrophotometer, comparing the infrared absorption spectrum with that of a known film to determine the type of characteristic absorption of the reactive functional groups, and calculating the number from each difference spectrum using the following formula.

[0075] Number of reactive functional groups (main chain carbon number 10 6 (per piece) = (l × K) / t l: Absorbance K: Correction coefficient t: film thickness (mm) The correction factors for the target terminal reactive functional groups are shown in Table 1.

[0076] [Table 1]

[0077] The correction coefficients in Table 1 are for main chain carbon number 10 6 This value was determined from the infrared absorption spectrum of a model compound in order to calculate the number of reactive functional groups per molecule.

[0078] The fiber-reinforced composite material of the present disclosure is preferably obtained by combining a fluororesin film or powder with carbon fiber, more preferably obtained by combining a fluororesin film or powder with a sheet-like carbon fiber, even more preferably obtained by combining a fluororesin film or powder with a unidirectional carbon fiber sheet, and even more preferably obtained by combining a fluororesin film with a unidirectional carbon fiber sheet.

[0079] In the fiber-reinforced composite material of the present disclosure, it is also preferable that at least a part of the carbon single fibers constituting the carbon fibers is impregnated with a fluororesin. It is also preferable that at least a part of the carbon single fibers is embedded in a fluororesin film. It is also preferable that at least a part of the carbon single fibers penetrates into the fluororesin film.

[0080] The composite can be formed, for example, by forming a film from a fluororesin, and then hot pressing the film and carbon fiber. The carbon fiber is preferably in the form of a sheet, and more preferably in the form of a unidirectional carbon fiber sheet. When using a sheet-like carbon fiber or a unidirectional carbon fiber sheet, the carbon fiber may be opened. When using a sheet-like carbon fiber or a unidirectional carbon fiber sheet, a fluororesin film may be placed on both sides of the carbon fiber, and then the composite may be formed by hot pressing, or the composite may be formed after stacking multiple layers.

[0081] The film used for the composite can be obtained by molding the fluororesin using a method such as extrusion molding or press molding.

[0082] The maximum point stress of the fluororesin film is preferably 5 to 500 MPa, and more preferably 10 to 100 MPa.

[0083] The maximum elongation of the fluororesin film is preferably 50 to 2000%, and more preferably 100 to 1000%.

[0084] The tensile modulus of the fluororesin film is preferably 0.1 to 30 GPa, and more preferably 0.2 to 2 GPa.

[0085] The maximum stress, maximum elongation and tensile modulus of the fluororesin film are measured according to ASTM D638.

[0086] In the fiber reinforced composite material, the mass ratio of the fluororesin to the carbon fiber (fluororesin:carbon fiber) is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, even more preferably 30:70 to 70:30, and most preferably 40:60 to 60:40, because the tensile strength, tensile modulus and tensile elongation of the fiber reinforced composite material will be further increased.

[0087] The fiber-reinforced composite material may further contain other components in addition to the fluororesin and carbon fiber, such as fillers, plasticizers, processing aids, release agents, pigments, flame retardants, lubricants, light stabilizers, weather stabilizers, conductive agents, antistatic agents, UV absorbers, antioxidants, foaming agents, fragrances, oils, softeners, dehydrofluorination agents, nucleating agents, softeners, surfactants, impregnation aids, etc.

[0088] Examples of the filler include polytetrafluoroethylene, mica, silica, talc, celite, clay, titanium oxide, barium sulfate, etc. Examples of the conductive agent include carbon black, etc. Examples of the plasticizer include dioctyl phthalate, pentaerythritol, etc. Examples of the processing aid include carnauba wax, sulfone compounds, low molecular weight polyethylene, fluorine-based aids, etc. Examples of the dehydrofluorination agent include organic oniums, amidines, etc.

[0089] In the fiber-reinforced composite material, multiple fluororesins may be blended, other resins other than fluororesins may be blended, or other rubbers may be blended. Among them, a blend with at least one selected from the group consisting of polyetheretherketone (PEEK) and polytetrafluoroethylene (PTFE) is preferred.

[0090] The fiber-reinforced composite material of the present disclosure is preferably a tape. The tape is preferably a strip-shaped body having flexibility that can be wound (or wrapped).

[0091] The shape of the tape of the present disclosure is not particularly limited as long as it is substantially strip-shaped, but the following are examples.

[0092] (1) Those with a rectangular cross-sectional shape The tape of embodiment (1) has a simple shape and is easy to manufacture. Figure 1(a) shows a cross section of one example of the tape of embodiment (1).

[0093] (2) Those with thin sections on both widthwise ends The tape of aspect (2) can be wrapped around an object without gaps by overlapping the adjacent thin portions of the tape during winding, so that even when the tape is applied to a tape layer constituting a flexible pipe through which a high-temperature fluid flows, the permeation of the high-temperature fluid to the outside can be easily suppressed. Moreover, by overlapping the thin portions, the thickness of the obtained tape layer can be easily made uniform.

[0094] The thin portions at both ends in the width direction are preferably provided at opposite ends in the thickness direction, i.e., one thin portion is preferably provided at the upper end side in the thickness direction and the other thin portion is preferably provided at the lower end side.

[0095] Fig. 1(b) shows a cross section of an example of a tape of embodiment (2). At both ends in the width direction of the tape 1b, there are provided thin portions 3 which are thinner than the central portion 2. One thin portion 3 is provided at the upper end side in the thickness direction of the tape 1b, and the other thin portion 3 is provided at the lower end side. Note that embodiment (2) does not include embodiment (3), which will be described later.

[0096] (3) A shape that allows the widthwise ends of the tape to be locked together with the widthwise ends of adjacent tapes when wrapped. Examples of the tape of aspect (3) include, but are not limited to, those having a cross-sectional shape of a substantially Z-shape, a substantially U-shape, a substantially S-shape, a substantially T-shape, a substantially I-shape, etc. The tape of aspect (3) can be wound so that the ends of adjacent tapes in the width direction are interlocked with each other to obtain a tape layer in which the tapes are locked together. Therefore, when the tape is applied to a tape layer constituting a flexible tube through which a high-temperature fluid flows, it is possible to prevent the tape from slipping when the flexible tube is bent or twisted. As a result, it is possible to more reliably prevent the outflow of the fluid flowing inside the flexible tube.

[0097] Among the tapes of the embodiment (3), those having a substantially Z-shaped cross section are preferred. More specifically, it is preferred that the tape has thin portions at both ends in the width direction and protrusions protruding in opposite directions (opposing directions) in the thickness direction from the thin portions at both ends in the width direction. Since this tape has hook-shaped structured portions (hook portions) at both ends in the width direction, when the tape is wound, the hook portions of adjacent tapes are engaged with each other, that is, the tape is wound so that the protrusions of one tape are fitted into the recesses formed by the protrusions and thin portions of the other tape, thereby obtaining a tape layer in which the tapes are locked together.

[0098] Fig. 1(c) shows a cross section of an example of the tape of embodiment (3). The cross section of the tape 1c is substantially Z-shaped. Thin portions 5 are provided at both ends in the width direction of the tape 1c, and protrusions 4 are provided protruding in opposite directions (opposing directions) from the two thin portions 5 in the thickness direction.

[0099] The tape of the present disclosure is particularly preferably the tape of embodiment (3).

[0100] The tape of the present disclosure can be produced by molding the fluororesin and the carbon fiber, if necessary together with the other components, by a method such as extrusion molding, pultrusion molding, press molding, melt impregnation molding, extrusion lamination molding, dry powder coating molding, or the like. These molding methods may also be combined. The carbon fiber used is preferably wired. The fluororesin, if necessary together with the other components, may be processed into a thread-like shape, which may then be woven into a desired shape to form a woven tape, which may then be combined with the carbon fiber.

[0101] As the above-mentioned pultrusion molding, dry powder coating molding and extrusion lamination molding, the methods described in the following documents can be adopted. Goichi Ben, "Molding Method and Characteristics of Continuous Fiber FRTP", Nikkan Kogyo Shimbun, March 30, 2015, pp. 75, 85, 143

[0102] The width, thickness, and length of the tape of the present disclosure can be appropriately set depending on the application. When the tape of the present disclosure is applied to flexible pipes such as riser pipes through which high-temperature fluids flow, the width can be, for example, 1 mm to 10 m, and the thickness can be 10 μm to 5 cm. The length can be determined depending on the amount of tape used, etc., but when applied to flexible pipes through which high-temperature fluids flow, it can be about 1 m to 1000 km. These may be cut and used in lengths of 1 cm to 1 m.

[0103] The present disclosure is also a laminate comprising a first layer and a second layer formed on the first layer, the second layer being made of a fiber-reinforced composite material.

[0104] Each layer in the laminate may be surface-treated on one or both sides by a method such as plasma discharge treatment or corona discharge treatment. An adhesive may also be applied. The first layer and the second layer may or may not be bonded to each other.

[0105] The first layer preferably comprises a polymer, such as a fluoropolymer, polyetheretherketone (PEEK), polyimide, polyetherketone, polyetherketoneketone, polyetherketoneetherketoneketone, polyamide, polyethylene, and the like, and mixtures thereof.

[0106] The laminate may include layers other than the first layer and the second layer. For example, depending on the application, another layer may be provided on the surface of the first layer opposite to the second layer and / or on the surface of the second layer opposite to the first layer.

[0107] The laminate is preferably a pipe or a sheet. When the laminate is a pipe or a sheet, the fiber reinforced composite material is preferably a tape. When the laminate is a pipe, the first layer may be a flexible tube.

[0108] The present disclosure also relates to a pipe including a first layer and a second layer formed on the first layer and made of a fiber-reinforced composite material, the first layer and the second layer being laminated in this order from the inside of the pipe, and the second layer being formed by wrapping a tape of the fiber-reinforced composite material around the outer periphery of the first layer. The first layer and the second layer may or may not be bonded to each other.

[0109] The first layer is preferably a flexible tube. The flexible tube may have a single-layer structure or a multi-layer structure. The method for producing the multi-layer structure is not particularly limited, but known sequential extrusion molding, co-extrusion molding, etc. are preferred.

[0110] The material for forming the tube is not particularly limited as long as it can impart flexibility to the tube, and for example, a known material used for various flexible tubes can be selected according to the application. The material includes polymers, and more specifically, fluoropolymers, polyetheretherketone (PEEK), polyimide, polyetherketone, polyetherketoneketone, polyetherketoneetherketoneketone, polyamide, polyethylene, and mixtures thereof.

[0111] In the second layer, the tapes of the fiber-reinforced composite material are preferably arranged so as to be adjacent to each other in the width direction. Furthermore, it is preferable that the ends of adjacent tapes in the width direction are locked to each other. This embodiment is realized, for example, by using the tape of embodiment (3). In the second layer, the tapes may be laminated in multiple layers.

[0112] In the pipe of the present disclosure, the first layer and the second layer each constitute a tubular body, and the second layer is formed on the first layer. Figure 2 shows a schematic diagram of an example of the configuration of the pipe of the present disclosure.

[0113] In the pipe of the present disclosure, the second layer is formed by wrapping the tape around the outer periphery of the first layer. In this way, when the second layer is a tape-wrapped layer in which the tape is wrapped around the outer periphery of the first layer, there is play between the tapes, so that the tape does not stretch when the pipe is bent, and therefore, there is an effect that the physical properties of the tape layer do not deteriorate or deformation does not occur when the pipe returns to its original state.

[0114] The method of winding the tape is not particularly limited, but for example, a method of spirally winding the tape around the outer periphery of the first layer is preferred. An example of a method of winding the tape is shown in FIG. 3. Tape 14 (the tape of the present disclosure) is spirally wound around the outer periphery of the tubular inner layer 11 (first layer) in the direction of the arrow in the figure.

[0115] When winding, the tape may be wound around the outer periphery of the first layer so that the widthwise ends of adjacent tapes do not overlap each other (see, for example, FIG. 4(a)). When winding multiple layers of the tape, the angle at which the tape is wound may be changed for each layer. Furthermore, the tape may be wound in a similar manner around the outer periphery of the obtained tape-wound layer, shifting the winding position so as to cover the boundary of the tape already wound (see, for example, FIG. 4(b)). In this way, the permeation of high-temperature fluids can be more reliably suppressed. In this case, the tape may be wound in the same direction for the lower layer (inner layer) and the upper layer (outer layer), but it is preferable to wind them in opposite directions because this balances the tension applied to the pipe during winding and makes winding easier.

[0116] The tape may also be wrapped so that the widthwise ends of adjacent tapes overlap each other (see, for example, FIG. 4(c)). In this way, the permeation of high-temperature fluids can be more reliably suppressed. In this embodiment, the tape may also be wrapped in multiple layers in the same or opposite directions.

[0117] Furthermore, when the tape has thin portions at both ends in the width direction, it is preferable to wrap the tape so that the thin portions of adjacent tapes overlap each other (see, for example, FIG. 4(d)). In this way, it is possible to more reliably suppress the permeation of high-temperature fluids. Also, it is possible to easily make the thickness of the resulting tape-wrapped layer uniform. In this embodiment, the tape may be wrapped in multiple layers in the same or opposite directions.

[0118] Furthermore, when the above tapes have a shape that allows them to be locked together, it is preferable to wrap the tapes so that the widthwise ends of adjacent tapes interlock with each other (see, for example, FIG. 4(e)). In this way, a tape-wrapped layer in which the tapes are locked together can be obtained, which can prevent the tapes from shifting when the pipe is bent or twisted. As a result, permeation of high-temperature fluids can be more reliably suppressed. Also, the thickness of the tape-wrapped layer obtained can be easily made uniform. In this embodiment, the above tape may be wrapped in multiple layers in the same or opposite directions.

[0119] The tape may be wound using a known tape winding device.

[0120] In the second layer, the widthwise ends of adjacent tapes are preferably locked to each other. This embodiment is realized, for example, by winding the tape of embodiment (3) around the outer periphery of the first layer so that the widthwise ends of adjacent tapes are interlocked.

[0121] The pipe of the present disclosure preferably further includes a third layer formed on the second layer. Materials that can be used for the third layer include metal, resin, rubber, and the like. Among them, metal is preferable. The third layer can be formed by, for example, covering the outer periphery of the second layer with a necessary material by a known method. FIG. 5 shows a schematic example of a configuration of a pipe according to this embodiment. The pipe 20 is formed by laminating a first layer 21, a second layer 22, and a third layer 23 (reinforcement layer) in this order from the inner layer side.

[0122] In the pipe of the present disclosure, depending on the application, a further layer may be provided on the outer periphery of the third layer, or a further layer may be provided on the inner periphery of the first layer.

[0123] The tape and pipe of the present disclosure can be suitably used as a riser pipe and a flow line. The riser pipe and the flow line can be suitably used as a riser pipe and a flow line for transporting materials from the seabed to the sea surface in an undersea oil or gas field. The materials include fluids such as crude oil, petroleum gas, and natural gas.

[0124] The fiber-reinforced composite material or tape of the present disclosure can be used in applications other than riser pipes and flow lines, and can be suitably used, for example, as a fiber-reinforced composite material or tape for forming a friction-resistant layer of a fluid-transporting metal pipe for crude oil or natural gas, whether underground, on land, or on the seabed. Crude oil and natural gas contain carbon dioxide and hydrogen sulfide, which cause corrosion of metal pipes, and the fiber-reinforced composite material or tape can be used as a barrier to suppress corrosion of metal pipes and reduce fluid friction of highly viscous crude oil. In addition, an adhesive may be used to bond to metal, or a treatment may be applied to roughen the metal surface. In addition, the fiber reinforced composite material or tape of the present disclosure has suitable properties for use as seals, bellows, diaphragms, hoses, tubes, electric wires, and the like, such as gaskets and non-contact and contact type packings (self-sealing packings, piston rings, split ring type packings, mechanical seals, oil seals, etc.) that require heat resistance, oil resistance, fuel oil resistance, LLC resistance, and steam resistance in high-temperature parts around automobile engines or parts where chemical resistance is required, such as the engine body, main motion system, valve train, lubrication / cooling system, fuel system, intake / exhaust system, etc., transmission system, etc. of drive systems, steering system, brake system, etc. of chassis, basic electrical components of electrical equipment, electrical components of control systems, electrical components for equipment, etc. In addition to automobiles, the material is also suitable for applications such as oil-resistant, chemical-resistant, heat-resistant, steam-resistant, or weather-resistant packing, O-rings, hoses, other sealing materials, diaphragms, and valves in transportation means such as ships and aircraft, similar packing, O-rings, sealing materials, diaphragms, valves, hoses, rolls, tubes, chemical-resistant coatings, and linings in chemical plants, similar packing, O-rings, hoses, sealing materials, belts, diaphragms, valves, rolls, and tubes in food plant equipment and food equipment (including household products), similar packing, O-rings, hoses, sealing materials, diaphragms, valves, and tubes in nuclear plant equipment, and similar packing, O-rings, hoses, sealing materials, diaphragms, valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber sheets, weather strips, and roll blades in PPC copiers in general industrial parts.In addition, since the fiber-reinforced composite material or tape disclosed herein has chemical resistance, low elution, and low odor, it can be used in the medical and chemical fields for oil-resistant, chemical-resistant, heat-resistant, steam-resistant, or weather-resistant sealing materials, covering materials, belts, rolls, hoses, tubes, films, coatings, linings, joints, containers, and the like.

[0125] The laminate of the present disclosure can also be applied to piping. In this case, the piping made of the laminate can be produced by a normal method without any particular limitation. The piping also includes a corrugated tube.

[0126] The fiber-reinforced composite material or tape of the present disclosure has excellent mechanical properties, heat resistance, oil resistance, amine resistance, chemical resistance, and the like, and can be used as various parts in various fields such as the automotive industry, the aircraft industry, and the semiconductor industry.

[0127] Examples of fields in which it is used include semiconductor-related fields, automobiles, aircraft, space and rockets, ships, chemicals such as chemical plants, pharmaceuticals such as medicines, photography such as developing machines, printing such as printing machines, painting such as painting equipment, analytical and physicochemical machinery such as analytical instruments and meters, food equipment including food plant equipment and household goods, food beverage manufacturing equipment, pharmaceutical manufacturing equipment, medical parts, chemical transport equipment, nuclear power plant equipment, steel such as steel plate processing equipment, general industry, electricity, fuel cells, electronic parts, optical equipment parts, space equipment parts, petrochemical plant equipment, energy resource exploration and mining equipment parts for oil and gas, oil refining, and oil transportation equipment parts.

[0128] Examples of the use forms of the fiber reinforced composite material or tape of the present disclosure include various sealing materials and packings such as rings, packings, gaskets, diaphragms, oil seals, bearing seals, lip seals, plunger seals, door seals, lip and face seals, gas delivery plate seals, wafer support seals, barrel seals, etc. As sealing materials, they can be used in applications requiring heat resistance, solvent resistance, chemical resistance, and non-stickiness.

[0129] In addition, the rubber can be used as a tube, a hose, a roll, various rubber rolls, a flexible joint, a rubber plate, a coating, a belt, a damper, a valve, a valve seat, a valve body of a valve, a chemical-resistant coating material, a laminating material, a lining material, a material for a pump impeller or a casing, etc.

[0130] The cross-sectional shape of the ring, packing, and seal may be of various shapes, specifically, for example, a square, O-shaped, ferrule shape, or an irregular shape such as a D-shape, L-shape, T-shape, V-shape, X-shape, Y-shape, etc.

[0131] In the above-mentioned semiconductor-related fields, the present invention can be used, for example, in semiconductor manufacturing equipment, liquid crystal panel manufacturing equipment, plasma panel manufacturing equipment, plasma display panel manufacturing equipment, plasma addressed liquid crystal panel manufacturing equipment, organic EL panel manufacturing equipment, field emission display panel manufacturing equipment, solar cell substrate manufacturing equipment, semiconductor conveying equipment, etc. Examples of such equipment include CVD equipment, gas control equipment such as semiconductor gas control equipment, dry etching equipment, wet etching equipment, plasma etching equipment, reactive ion etching equipment, reactive ion beam etching equipment, sputter etching equipment, ion beam etching equipment, oxidation diffusion equipment, sputtering equipment, ashing equipment, plasma ashing equipment, cleaning equipment, ion implantation equipment, plasma CVD equipment, exhaust equipment, exposure equipment, polishing equipment, film formation equipment, dry etching cleaning equipment, UV / O3 cleaning equipment, ion beam cleaning equipment, laser beam cleaning equipment, plasma cleaning equipment, gas etching cleaning equipment, etc. Examples of such equipment include equipment for performing plasma treatments such as NF3 plasma treatment, O2 plasma treatment, and fluorine plasma treatment, extraction and cleaning equipment, Soxhlet extraction and cleaning equipment, high temperature and high pressure extraction and cleaning equipment, microwave extraction and cleaning equipment, supercritical extraction and cleaning equipment, cleaning equipment that uses hydrofluoric acid, hydrochloric acid, sulfuric acid, ozone water, etc., steppers, coater / developers, CMP equipment, excimer laser exposure machines, chemical liquid piping, gas piping, equipment for performing plasma treatments such as NF3 plasma treatment, O2 plasma treatment, and fluorine plasma treatment, heat treatment and film formation equipment, wafer transport equipment, wafer cleaning equipment, silicon wafer cleaning equipment, silicon wafer processing equipment, equipment used in LP-CVD processes, equipment used in lamp annealing processes, and equipment used in reflow processes.

[0132] Specific examples of uses in the semiconductor-related field include various sealing materials such as O-rings and gaskets for gate valves, quartz windows, chambers, chamber lits, gates, bell jars, couplings, and pumps; various sealing materials such as O-rings for resist developer and stripper solutions, hoses and tubes; linings and coatings for resist developer tanks, stripper tanks, wafer cleaning solution tanks, turntables, chuck pins, and wet etching tanks; diaphragms for pumps; rolls for transporting wafers; hoses and tubes for wafer cleaning solutions; sealing materials for clean facilities such as sealants for clean rooms and other clean facilities; sealing materials for semiconductor manufacturing equipment and storage facilities for storing devices such as wafers; and diaphragms for transporting chemical solutions used in the semiconductor manufacturing process.

[0133] In the above-mentioned automotive field, the material can be used in the engine body, main motion system, valve train system, lubrication / cooling system, fuel system, intake / exhaust system, transmission system of the drive system, steering system of the chassis, brake system, basic electrical components, control system electrical components, equipment electrical components, etc. The above-mentioned automotive field also includes motorcycles.

[0134] In the engine body and its peripheral devices as described above, the tapes of the present disclosure can be used for various sealing materials that require heat resistance, oil resistance, fuel oil resistance, engine cooling antifreeze resistance, and steam resistance. Examples of such sealing materials include gaskets, shaft seals, valve stem seals, and other seals; self-sealing packings, piston rings, split ring packings, mechanical seals, oil seals, and other non-contact or contact type packings; bellows, diaphragms, hoses, tubes, as well as electric wires, cushioning materials, vibration-proofing materials, and various sealing materials used in belt AT devices.

[0135] Specific uses in the above fuel systems include O-rings used in fuel injectors, cold start injectors, fuel line quick connectors, sender flange quick connectors, fuel pumps, fuel tank quick connectors, gasoline mixing pumps, gasoline pumps, fuel tube bodies, fuel tube connectors, injectors, etc.; seals used in intake manifolds, fuel filters, pressure regulators, canisters, fuel tank caps, fuel pumps, fuel tanks, fuel tank sender units, fuel injection systems, high pressure fuel pumps, fuel line connector systems, pump timing control valves, suction control valves, solenoid sub-assemblies, fuel cut valves, etc.; canister purge solenoid valve seals, on-board refueling vapor recovery (ORVR) valve seals, oil seals for fuel pumps, fuel sender seals, fuel tank rollover valve seals, filler seals, injector seals, filler cap seals, filler cap valve seals; fuel hoses, Fuel supply hoses, fuel return hoses, vapor (evaporation) hoses, vent (breather) hoses, filler hoses, filler neck hoses, hoses inside fuel tanks (in-tank hoses), carburetor control hoses, fuel inlet hoses, fuel breather hoses, and other hoses; gaskets used in fuel filters, fuel line connector systems, and flange gaskets used in carburetors; line materials such as vapor recovery lines, fuel feed lines, and vapor / ORVR lines; diaphragms used in canisters, ORVRs, fuel pumps, fuel tank pressure sensors, gasoline pumps, carburetor sensors, composite air control devices (CACs), pulsation dampers, canisters, autococks, and pressure regulator diaphragms for fuel injection devices; valves for fuel pumps, carburetor needle valves, rollover check valves, check valves, and other types of valves; vents (breathers), tubes used inside fuel tanks; tank packings for fuel tanks, and packings for carburetor acceleration pump pistons; fuel sender vibration isolation parts for fuel tanks;O-rings and diaphragms for controlling fuel pressure; accelerator pump cups; in-tank fuel pump mounts; injector cushion rings for fuel injection systems; injector seal rings; carburetor needle valve cores; carburetor accelerator pump pistons; valve seats for compound air control systems (CAC); fuel tank bodies; and sealing parts for solenoid valves.

[0136] Specific uses in the above brake systems include diaphragms used in master bags, hydraulic brake hoses, air brakes, and air brake brake chambers; hoses used in brake hoses, brake oil hoses, vacuum brake hoses, etc.; various sealing materials such as oil seals, O-rings, packing, and brake piston seals; atmospheric valves and vacuum valves for master bags, and check valves for brake valves; piston cups (rubber cups) and brake cups for master cylinders; boots for hydraulic brake master cylinders and vacuum boosters, and wheel cylinders of hydraulic brakes, as well as O-rings and grommets for anti-lock braking systems (ABS).

[0137] Specific examples of uses of the basic electrical components include insulators and sheaths for electrical wires (harnesses), tubes for harness exterior parts, and grommets for connectors. Specific examples of applications in electrical control system components include coating materials for various sensor wires.

[0138] Specific examples of the use of the above-mentioned electrical equipment parts include O-rings and packings for car air conditioners, cooler hoses, high-pressure air conditioner hoses, air conditioner hoses, gaskets for electronic throttle units, plug boots for direct ignition, diaphragms for distributors, etc. The material can also be used to bond electrical equipment parts.

[0139] Specific examples of applications in the above intake and exhaust systems include packings used in intake manifolds, exhaust manifolds, etc., and throttle body packings for throttles; diaphragms used in EGR (exhaust gas recirculation), pressure control (BPT), wastegates, turbo wastegates, actuators, variable turbine geometry (VTG) turbo actuators, exhaust purification valves, etc.; hoses such as EGR (exhaust gas recirculation) control hoses, emission control hoses, turbocharger turbo oil hoses (supply), turbo oil hoses (return), turbo air hoses, intercooler hoses, turbocharger hoses, hoses connected to the compressors of turbo engines equipped with intercoolers, exhaust gas hoses, air intake hoses, turbo hoses, DPF (diesel particulate filter) sensor hoses, etc.; air ducts and turbo air ducts; intake manifold gaskets; EGR sealing materials, afterburn prevention valve seats for AB valves, turbine shaft seals (for turbochargers, etc.), and sealing materials used in grooved parts such as rocker covers and air intake manifolds used in automobile engines.

[0140] Other applications include seals for vapor recovery canisters, catalytic converters, exhaust gas sensors, oxygen sensors, etc. in emission control components; seals for vapor recovery and vapor canister solenoid armatures; and intake manifold gaskets.

[0141] In addition, in diesel engine parts, it can be used as an O-ring seal for direct injectors, a rotary pump seal, a control diaphragm, a fuel hose, an EGR, a priming pump, a diaphragm for a boost compensator, etc. It can also be used for O-rings, seal materials, hoses, tubes, and diaphragms used in urea SCR systems, the urea water tank body of the urea SCR system, and a seal material for the urea water tank, etc.

[0142] Specific examples of applications in the above-mentioned transmission system include transmission-related bearing seals, oil seals, O-rings, packing, torque converter hoses, etc.

[0143] Examples include transmission oil seals, AT transmission oil hoses, ATF hoses, O-rings, and packings.

[0144] Transmissions include AT (automatic transmission), MT (manual transmission), CVT (continuously variable transmission), DCT (dual clutch transmission), etc.

[0145] Other examples include oil seals, gaskets, O-rings, and packings for manual or automatic transmissions, oil seals, gaskets, O-rings, and packings for continuously variable transmissions (belt type or toroidal type), as well as packings for ATF linear solenoids, oil hoses for manual transmissions, ATF hoses for automatic transmissions, CVTF hoses for continuously variable transmissions (belt type or toroidal type), and the like.

[0146] Specific examples of uses in steering systems include power steering oil hoses and high-pressure power steering hoses.

[0147] Examples of forms used in the engine body of an automobile engine include gaskets such as cylinder head gaskets, cylinder head cover gaskets, oil pan packings, and general gaskets; seals such as O-rings, packings, and timing belt cover gaskets; hoses such as control hoses; anti-vibration rubber for engine mounts, control valve diaphragms, and camshaft oil seals. In the main drive system of an automobile engine, it can be used as a shaft seal such as a crankshaft seal or a camshaft seal.

[0148] In the valve train of an automobile engine, it can be used for valve stem oil seals of engine valves, valve seats of butterfly valves, etc.

[0149] In the lubrication and cooling systems of automobile engines, it can be used in engine oil cooler hoses, oil return hoses, seal gaskets for engine oil coolers, water hoses around radiators, radiator seals, radiator gaskets, radiator O-rings, vacuum pump oil hoses for vacuum pumps, as well as radiator hoses, radiator tanks, oil pressure diaphragms, fan coupling seals, etc.

[0150] Thus, specific examples of uses in the automotive field include, but are not limited to, engine head gaskets, oil pan gaskets, manifold packings, oxygen sensor seals, oxygen sensor bushings, nitric oxide (NOx) sensor seals, nitric oxide (NOx) sensor bushings, sulfur oxide sensor seals, temperature sensor seals, temperature sensor bushings, diesel particle filter sensor seals, diesel particle filter sensor bushings, injector O-rings, injector packings, fuel pump O-rings and diaphragms, gearbox seals, power piston packings, cylinder liner seals, valve stem seals, static valve stem seals, dynamic valve stem seals, automatic transmission front pump seals, rear axle pinion seals, universal joint gaskets, speedometer pinion seals, and foot brake pistons. Cups, O-rings and oil seals for torque transmission devices, seals and bearing seals for exhaust gas re-burning devices, hoses for re-burning devices, diaphragms for carburetor sensors, anti-vibration rubber (engine mounts, exhaust parts, muffler hangers, suspension bushes, center bearings, strut bumper rubber, etc.), anti-vibration rubber for suspensions (strut mounts, bushes, etc.), anti-vibration rubber for drive systems (dampers, etc.), fuel hoses, EGR tubes and hoses, twin carburetor tubes, carburetor needle valve core valves, carburetor flange gaskets, oil hoses, oil cooler hoses, ATF hoses, cylinder head gaskets, water pump seals, gearbox seals, needle valve tips, reed valve leads for motorcycles, oil seals for automobile engines, seals for gasoline hose guns, seals for car air conditioners, rubber hoses for engine intercoolers, fuel line connector devices (fuel line connectorsSeals for automotive systems, CAC valves, needle tips, engine wiring, filler hoses, car air conditioner O-rings, intake gaskets, fuel tank materials, distributor diaphragms, water hoses, clutch hoses, PS hoses, AT hoses, master back hoses, heater hoses, air conditioner hoses, ventilation hoses, oil filler caps, PS rack seals, rack and pinion boots, CVJ boots, ball joint dust covers, strut dust covers, weather strips, glass runs, center unit packing, body site welts, bumper rubber, door latches, dash insulators, high tension cords, flat belts, poly V belts, timing belts, toothed belts, V-ribbed belts, tires, wiper blades, diaphragms and plungers for LPG vehicle regulators, diaphragms and valves for CNG vehicle regulators rubber parts for DME, diaphragms and boots for auto tensioners, diaphragms and valves for idle speed controls, actuators for auto speed controls, diaphragms, check valves and plungers for vacuum pumps, diaphragms and O-rings for OPS, gasoline pressure relief valves, O-rings and gaskets for engine cylinder sleeves, O-rings and gaskets for wet cylinder sleeves, seals and gaskets for differential gears (gear oil seals and gaskets), seals and gaskets for power steering units (PSF seals and gaskets), seals and gaskets for shock absorbers (SAF seals and gaskets), seals and gaskets for constant velocity joints, seals and gaskets for wheel bearings, coating agents for metal gaskets, caliper seals, boots, wheel bearing seals, and bladders used in the vulcanization molding of tires.

[0151] In the above-mentioned aircraft, space / rocket and ship fields, the composition can be used particularly in fuel systems and lubricating oil systems.

[0152] In the above-mentioned aircraft field, the composition can be used, for example, as various sealing parts for aircraft, various aircraft parts for aircraft engine oil applications, jet engine valve stem seals, gaskets and O-rings, rotating shaft seals, gaskets for hydraulic equipment, firewall seals, fuel supply hoses, gaskets and O-rings, aircraft cables, oil seals and shaft seals, etc.

[0153] In the space and rocket fields, they can be used, for example, as lip seals, diaphragms, and O-rings for spacecraft, jet engines, missiles, etc., O-rings for oil-resistant gas turbine engines, and vibration isolation pads for missile ground control.

[0154] In addition, in the marine field, the material can be used, for example, as a stern seal for a screw propeller shaft, a valve stem seal for the intake and exhaust of a diesel engine, a valve seal for a butterfly valve, a valve seat or shaft seal for a butterfly valve, a shaft seal for a butterfly valve, a stern tube seal, a fuel hose, a gasket, an O-ring for an engine, a cable for a ship, an oil seal for a ship, a shaft seal for a ship, etc.

[0155] In the chemical field such as the above-mentioned chemical plants and the chemical field such as pharmaceuticals, the material can be used in processes that require a high level of chemical resistance, for example, processes for producing chemical products such as pharmaceuticals, agricultural chemicals, paints, and resins.

[0156] Specific uses in the above-mentioned chemical and pharmaceutical fields include chemical equipment, chemical pumps and flow meters, chemical piping, heat exchangers, agricultural chemical sprayers, agricultural chemical transfer pumps, gas piping, fuel cells, analytical equipment and physicochemical equipment (for example, column fittings for analytical equipment and instruments), shrink joints for flue gas desulfurization equipment, nitric acid plants, seals used in power plant turbines, etc., seals used in medical sterilization processes, seals for plating solutions, roller seals for papermaking belts, joint seals for wind tunnels; O-rings used in chemical equipment such as reactors and mixers, analytical equipment and instruments, chemical pumps, pump housings, valves, tachometers, etc., O-rings for mechanical seals, O-rings for compressor sealing; packing used in high-temperature vacuum dryers, tube connections for gas chromatography and pH meters, etc.; glass cooling for sulfuric acid manufacturing equipment. Examples of suitable applications include cooler packings; diaphragms used in diaphragm pumps, analytical equipment, and physicochemical equipment; gaskets used in analytical equipment and instruments; ferrules used in analytical equipment and instruments; valve seats; U-cups; linings used in chemical equipment, gasoline tanks, wind tunnels, etc., and corrosion-resistant linings for anodized tanks; coatings for masking jigs for plating; valve parts for analytical equipment and physicochemical equipment; expansion joints in flue gas desulfurization plants; acid-resistant hoses for concentrated sulfuric acid, chlorine gas transfer hoses, oil-resistant hoses, and rainwater drain hoses for benzene and toluene storage tanks; chemical-resistant tubes and medical tubes used in analytical equipment and physicochemical equipment; trichlene-resistant rolls and dyeing rolls for textile dyeing; pharmaceutical stoppers; medical rubber stoppers; chemical solution bottles, chemical solution tanks, bags, chemical containers; and protective equipment such as strong acid- and solvent-resistant gloves and boots.

[0157] In the photographic field such as the developing machines, the printing field such as printing machines, and the coating field such as coating equipment, the composition can be used as rolls, belts, seals, valve parts, etc. of dry copying machines.

[0158] Specific examples of use in the above-mentioned photographic, printing and coating fields include the surface layer of a transfer roll in a copier, a cleaning blade in a copier, and a belt in a copier; rolls (for example, fixing rolls, pressure rolls, etc.) and belts for office automation equipment such as copiers, printers and facsimiles; rolls, roll blades and belts in PPC copiers; rolls in film developing machines and X-ray film developing machines; printing rolls, scrapers, tubes, valve parts and belts in printing machines; ink tubes, rolls and belts in printers; coating rolls, scrapers, tubes and valve parts in coating and painting equipment; developing rolls, gravure rolls, guide rolls, guide rolls in magnetic tape production coating lines, gravure rolls and coating rolls in magnetic tape production coating lines, etc.

[0159] In the food equipment field, including the food plant equipment and household goods, the present invention can be used in food manufacturing processes, food transport devices, or food storage devices.

[0160] Specific examples of use in the food equipment field include seals for plate-type heat exchangers, solenoid valve seals for vending machines, packing for jar pots, sanitary pipe packing, packing for pressure cookers, seals for water heaters, gaskets for heat exchangers, diaphragms and packing for food processing equipment, rubber materials for food processing equipment (for example, heat exchanger gaskets, various seals such as diaphragms and O-rings, piping, hoses, sanitary packing, valve packing, packing for filling used as a joint between the mouth of a bottle or the like and the filler during filling), etc. Other examples include packing, gaskets, tubes, diaphragms, hoses, joint sleeves, etc. used in products such as alcoholic beverages and soft drinks, filling equipment, food sterilization equipment, brewing equipment, water heaters, various automatic food vending machines, etc.

[0161] In the field of nuclear power plant equipment, the material can be used for check valves and pressure reducing valves around nuclear reactors, seals for uranium hexafluoride enrichment equipment, and the like.

[0162] Specific examples of use in the above general industrial fields include sealing materials for hydraulic equipment such as machine tools, construction machinery, and hydraulic machinery; seals and bearing seals for hydraulic and lubricating machines; sealing materials used for mandrels, etc.; seals used for windows of dry cleaning equipment, etc.; cyclotron seals and (vacuum) valve seals, proton accelerator seals, automatic packaging machine seals, pump diaphragms for airborne sulfur dioxide and chlorine gas analyzers (pollution measuring devices), snake pump linings, rolls and belts for printing machines, transport belts (conveyor belts), squeeze rolls for pickling iron plates, etc., robot cables, solvent squeeze rolls for aluminum rolling lines, O-rings for couplers, acid-resistant cushioning materials, dust seals and lip rubbers for the sliding parts of cutting machines, gaskets for food waste incineration machines, friction materials, metal or rubber surface modifiers, coating materials, etc. It can also be used as a gasket or sealing material for equipment used in papermaking processes, a sealant for clean room filter units, a construction sealant, a protective coating for concrete and cement, a glass cloth impregnation material, a processing aid for polyolefins, a moldability improving additive for polyethylene, a fuel container for small generators and lawnmowers, a precoated metal obtained by subjecting metal plates to a primer treatment, etc. In addition, it can be used as a sheet or belt by impregnating woven fabric and baking it.

[0163] Specific examples of the use in the steel industry include iron plate processing rolls in iron plate processing equipment.

[0164] Specific examples of use in the electrical field include insulating oil caps for bullet trains, venting seals for liquid-sealed transformers, transformer seals, jackets for oil well cables, seals for ovens such as electric furnaces, window frame seals for microwave ovens, seals used to bond the wedge and neck of a CRT, seals for halogen lamps, fixing agents for electrical components, seals for the end treatment of sheathed heaters, and seals used for insulating and moisture-proofing treatment of lead wire terminals for electrical equipment. In addition, it can be used as a coating material for oil-resistant and heat-resistant electric wires, high heat-resistant electric wires, chemical-resistant electric wires, high insulation electric wires, high-voltage power transmission lines, cables, electric wires used in geothermal power generation equipment, and electric wires used around automobile engines. It can also be used as an oil seal or shaft seal for vehicle cables. Furthermore, it can be used as an electrical insulating material (for example, insulating spacers for various electrical devices, insulating tapes for cable joints and ends, materials used for heat-shrinkable tubes, etc.), and materials for electrical and electronic devices used in high-temperature atmospheres (for example, materials for motor lead wires and materials for electric wires around high-temperature furnaces). It can also be used as a sealing layer or protective film (back sheet) for solar cells.

[0165] In the field of fuel cells, the material can be used as a sealing material between electrodes and between electrodes and separators in polymer electrolyte fuel cells, phosphate fuel cells, etc., as a seal or packing for piping for hydrogen, oxygen, generated water, etc., or as a separator, etc.

[0166] In the above electronic component field, it can be used as a heat dissipation material raw material, an electromagnetic wave shielding material raw material, a gasket for a computer hard disk drive (magnetic recording device), etc. It can also be used as a shock absorbing rubber (crash stopper) for a hard disk drive, a binder for an electrode active material of a nickel-hydrogen secondary battery, a binder for an active material of a lithium ion battery, a polymer electrolyte for a lithium secondary battery, a binder for a positive electrode of an alkaline storage battery, a binder for an EL element (electroluminescence element), a binder for an electrode active material of a capacitor, a sealant, a sealing agent, a quartz coating material for an optical fiber, a film or sheet such as an optical fiber coating material, potting, coating or adhesive seal for electronic components and circuit boards, a fixing agent for electronic components, a modifying agent for a sealant such as epoxy, a coating agent for a printed circuit board, a modifying agent for a printed wiring board prepreg resin such as epoxy, a shatterproofing material for a light bulb, a gasket for a computer, a cooling hose for a large computer, a packing such as a gasket or an O-ring for a secondary battery, particularly a lithium secondary battery, a sealing layer covering one or both sides of the outer surface of an organic EL structure, a connector, a damper, etc.

[0167] In the field of chemical transport equipment, the valves can be used in safety valves, shipping valves, etc. for trucks, trailers, tank trucks, ships, etc.

[0168] In the field of oil, gas and other energy resource exploration and mining equipment parts, they are used as various sealing materials used in mining oil, natural gas and the like, and as boots for electrical connectors used in oil wells.

[0169] Specific uses in the above-mentioned energy resource exploration and mining equipment parts field include drill bit seals, pressure adjustment diaphragms, seals for horizontal drilling motors (stators), stator bearing (shaft) seals, sealing materials used in blowout preventers (BOP), sealing materials used in rotary blowout preventers (pipe wipers), sealing materials and gas-liquid connectors used in MWDs (real-time drilling information detection systems), logging tool seals (e.g., O-rings, seals, packing, gas-liquid connectors, boots, etc.) used in logging equipment, expansion packers, completion packers and packer seals used therein, seals and packings used in cementing equipment, perforators, etc. Examples of seals used in drilling equipment, seals, packings and motor linings used in mud pumps, underground hearing tester covers, U-cups, composition seating cups, rotary seals, laminated elastomeric bearings, flow control seals, sand control seals, safety valve seals, seals for hydraulic fracturing equipment, seals and packings for linear packers and linear hangers, wellhead seals and packings, seals and packings for chokes and valves, LWD (logging while drilling) sealing materials, diaphragms used in oil exploration and drilling applications (for example, diaphragms for supplying lubricating oil to oil drilling pits), gate valves, electronic boots, and sealing elements for drilling guns.

[0170] Other uses include sealing joints in kitchens, bathrooms, washrooms, etc.; covering cloths for outdoor tents; seals for printing materials; rubber hoses for gas heat pumps, fluorocarbon-resistant rubber hoses; agricultural films, linings, and weather-resistant covers; and tanks such as laminated steel plates used in the construction and home appliance fields.

[0171] Furthermore, it can also be used as an article combined with a metal such as aluminum, etc. Examples of such uses include door seals, gate valves, pendulum valves, solenoid tips, as well as piston seals and diaphragms combined with metals, metal-rubber parts combined with metals such as metal gaskets, etc. It can also be used for rubber parts, brake shoes, brake pads, etc. in bicycles.

[0172] In addition, one of the forms of the fiber-reinforced composite material or tape of the present disclosure is a belt. Examples of the above-mentioned belt include the following. Power transmission belts (including flat belts, V-belts, V-ribbed belts, toothed belts, etc.), conveyor belts (conveyor belts), flat belts used in various high-temperature areas such as around the engines of agricultural machinery, machine tools, industrial machinery, etc.; conveyor belts for conveying loose materials and granular materials such as coal, crushed stone, soil, ore, wood chips, etc. in high-temperature environments; conveyor belts used in steelworks such as blast furnaces; conveyor belts for applications exposed to high-temperature environments in precision equipment assembly factories, food factories, etc.; V-belts and V-ribbed belts for agricultural machinery, general equipment (for example, office automation equipment, printing machines, commercial dryers, etc.), automobiles, etc.; transmission belts for conveying robots; toothed belts such as transmission belts for food machinery and machine tools; toothed belts for automobiles, office automation equipment, medical use, printing machines, etc. In particular, a timing belt is a typical example of a toothed belt for an automobile.

[0173] The belt may have a single layer structure or a multi-layer structure. If multi-layered, the belt may be comprised of layers of fiber reinforced composite materials or tapes of the present disclosure and other materials. In the multi-layer belt, the layers made of other materials include layers made of other rubbers, layers made of thermoplastic resins, various fiber reinforcement layers, canvas, metal foil layers, and the like.

[0174] The fiber reinforced composite material or tape of the present disclosure can also be used for industrial anti-vibration pads, anti-vibration mats, railway slab mats, pads, automotive anti-vibration rubber, etc. Automotive anti-vibration rubber includes anti-vibration rubber for engine mounts, motor mounts, member mounts, strut mounts, bushes, dampers, muffler hangers, center bearings, etc.

[0175] Other examples of applications include joint members such as flexible joints and expansion joints, boots, grommets, etc. In the marine field, examples of applications include marine pumps, etc.

[0176] Joint materials are connectors used in piping and piping equipment, and are used for purposes such as preventing vibrations and noise generated by piping systems, absorbing expansion and contraction and displacement caused by temperature and pressure changes, absorbing dimensional fluctuations, and mitigating or preventing the effects of earthquakes and land subsidence. The flexible joints and expansion joints can be preferably used as complex shaped molded articles for, for example, shipbuilding piping, mechanical piping such as pumps and compressors, chemical plant piping, electrical piping, civil engineering / water piping, automobiles, etc.

[0177] The boots can be preferably used as complex shaped molded articles such as automobile boots such as constant velocity joint boots, dust covers, rack and pinion steering boots, pin boots, piston boots, etc., agricultural machinery boots, industrial vehicle boots, construction machinery boots, hydraulic machinery boots, pneumatic machinery boots, centralized lubricator boots, liquid transfer boots, firefighting boots, various liquefied gas transfer boots, and other various industrial boots.

[0178] They can also be used as diaphragms for filter presses, blowers, water supply diaphragms, liquid storage tanks, pressure switches, accumulators, and air spring diaphragms for suspensions, etc.

[0179] It can also be used as a cushioning material for hot press molding when producing decorative plywood, printed circuit boards, electrical insulating boards, hard polyvinyl chloride laminates, etc., made of melamine resin, phenol resin, epoxy resin, etc.

[0180] They can also contribute to impermeability of various substrates, such as sealing gaskets for weapons-related applications and protective clothing against contact with aggressive chemical agents.

[0181] In addition, it can be used for O-rings, V-rings, X-rings, packings, gaskets, diaphragms, oil seals, bearing seals, lip seals, plunger seals, door seals, lip and face seals, gas delivery plate seals, wafer support seals, barrel seals and other various sealing materials used to seal lubricating oils (engine oils, transmission oils, gear oils, etc.) containing amine-based additives (particularly amine-based additives used as antioxidants and detergent dispersants) used in transportation such as automobiles and ships, and can also be used as tubes, hoses, various rubber rolls, coatings, belts, valve bodies of valves, etc. It can also be used as a laminating material and a lining material.

[0182] The material can be used as a coating material for heat- and oil-resistant electric wires used in lead wires of sensors that come into contact with transmission oil and / or engine oil in internal combustion engines of automobiles, etc. and detect the oil temperature and / or oil pressure, and can also be used in high-temperature oil environments such as in automatic transmissions and engine oil pans.

[0183] Other applications include non-adhesive oil-resistant rolls for copying machines, weather-resistant anti-icing weather strips, rubber stoppers for infusions, rubber vial stoppers, release agents, non-adhesive light-duty conveying belts, anti-adhesive coatings for plate gaskets in automobile engine mounts, coating processing of synthetic fibers, bolt members or joints with a thin packing coating layer, etc.

[0184] The applications of the fiber-reinforced composite material or tape of the present disclosure to automobile-related parts also include applications to motorcycle parts having a similar structure. Furthermore, examples of the fuels used in automobiles include diesel oil, gasoline, and fuels for diesel engines (including biodiesel fuels).

[0185] The use of fiber reinforced composites, tapes, laminates, pipes, risers or flowlines in high temperature environments is also an aspect of the present disclosure.

[0186] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims. EXAMPLES

[0187] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to these examples.

[0188] The values ​​in the examples were measured by the following methods.

[0189] <Fluororesin composition> A nuclear magnetic resonance spectrometer AC300 (manufactured by Bruker-Biospin) was used, and the measurement temperature was set to (polymer melting point + 20)°C. 19 F-NMR measurements were performed, and the integral values ​​of each peak were calculated. Depending on the type of monomer, the results of elemental analysis were appropriately combined to determine the value.

[0190] <Chlorine atom content of fluororesin> This was calculated from the composition of the fluororesin.

[0191] <Melting point of fluororesin (℃)> Heat measurements were carried out using a differential scanning calorimeter RDC220 (Seiko Instruments) in accordance with ASTM D-4591 at a temperature rise rate of 10° C. / min, and the melting point was determined from the peak of the obtained endothermic curve.

[0192] <Flow value of fluororesin> Using a Takashita flow tester CFT-500D (Shimadzu Corporation), the resin was extruded through an orifice with a diameter of 1 mm and a length of 1 mm at a temperature of 230°C and a load of 100 kgf, and the volume of resin flowing per second (cm 3 / sec) was used as the flow value.

[0193] <Melt flow rate (MFR) of fluororesin> In accordance with ASTM D3307-01, a melt indexer (manufactured by Toyo Seiki Seisakusho) was used, and the mass of polymer flowing out per 10 minutes from a nozzle with an inner diameter of 2 mm and a length of 8 mm under a load of 5 kg at 297°C or 230°C (g / 10 min) was defined as the MFR.

[0194] Examples 1-2 and Comparative Examples 1-2 A fluororesin film as shown in Table 2 was prepared. [Table 2]

[0195] Fluorine resin (4) Polyvinylidene fluoride (Solvay, Solef 60512)

[0196] The sheets were arranged in the order of fluororesin film / carbon fiber sheet / fluororesin film, with the mixing ratio (mass ratio) of fluororesin to carbon fiber being 40:60 to 45:55. Heat pressing was carried out under the following conditions to obtain a sheet-shaped fiber reinforced composite material. The thickness of the obtained sheet-shaped fiber reinforced composite material was 0.24 mm.

[0197] Carbon Fiber Toray Industries, Inc. T700SC-12000-60E (tensile strength: 4900 MPa, tensile modulus: 230 GPa, sizing agent adhesion amount: 0.2%)

[0198] Heat press conditions Press temperature: 300℃ Keep warm time: 5 minutes Press time: 10 minutes Pressure: 15kN

[0199] Tensile tests were conducted in accordance with ASTM D638 to measure the maximum stress, maximum elongation and tensile modulus of the fluororesin film. The results are shown in Table 3.

[0200] Tensile tests were carried out according to ASTM D3039-17 under the following conditions to measure the maximum stress, maximum elongation and tensile modulus of the obtained fiber-reinforced composite material. The results are shown in Table 3. Sample shape: Thickness: 0.24mm, Width: 20mm, Length: 250mm Clip: Instron, model 2580-301, capacity ±100kN Strain gauge: Tokyo Measuring Instruments Laboratory, model: FLA-6-11-3LJCT Pulling speed: 2mm / min. Distance between gauge lines: 130mm

[0201] [Table 3] [Explanation of symbols]

[0202] 1a, 1b, 1c: Tape 2: Central part 3: Thin section 4: Convex part 5: Thin section 10: Pipe 11: 1st layer 12:Second layer 14, 15, 16: Tape 20: Pipe 21: 1st layer 22:Second layer 23:Third layer

Claims

1. A fiber-reinforced composite material containing carbon fiber and a fluororesin, The tensile modulus measured under the following conditions is 40 GPa or more, the fluororesin is at least one selected from the group consisting of polychlorotrifluoroethylene and chlorotrifluoroethylene copolymers, The chlorine atom content of the fluororesin is 4.0% by mass or more, The carbon fiber is a sheet-like carbon fiber, A fiber-reinforced composite material in which a mass ratio of the fluororesin to the carbon fibers (fluororesin:carbon fibers) is 10:90 to 90:

10. (Measurement conditions for tensile modulus) The measurements are made in accordance with ASTM D3039-17, except for the following conditions: Clip: Instron, model 2580-301, capacity ±100kN Strain gauge: Tokyo Measuring Instruments Laboratory, model: FLA-6-11-3LJCT Tensile speed: 2 mm / min

2. 2. The fiber-reinforced composite material according to claim 1, wherein the carbon fiber is composed of a carbon single fiber and a sizing agent adhered to the carbon single fiber, and the amount of the sizing agent adhered is 3% or less with respect to the total mass of the carbon single fiber and the sizing agent.

3. 3. The fiber-reinforced composite material according to claim 1, having a maximum point stress of 600 MPa or more.

4. The fiber-reinforced composite material according to any one of claims 1 to 3, which is a tape.

Images