Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
  • C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
  • C08J2363/02—Polyglycidyl ethers of bis-phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
  • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• Japanese Patent Application Laid-Open No. 2016-166347 discloses a woven fabric and/or non-woven fabric, a woven fabric and/or non-woven fabric filled with the woven fabric and/or a non-woven fabric, and a surface of the woven fabric and/or non-woven fabric.
• a prepreg having a semi-cured resin composition containing an epoxy resin, a curing agent, and a fluororesin filler has been proposed.
• the tensile strength is within the range of 0.5 GPa or more and 2.5 GPa, and the tensile modulus is within the range of 25 GPa or more and 120 GPa or less.
• the prepreg according to the second aspect of the present invention is used to manufacture the above-mentioned fiber-reinforced resin molded article.
• This prepreg includes polyimide fibers and a resin or a resin precursor.
• the "resin precursor” herein refers to a monomer composition (which may contain a crosslinking agent, etc.) before curing, a polymer precursor, and the like.
• the fiber-reinforced resin molded article according to the embodiment of the present invention is mainly made of polyimide fibers and resin.
• polyimide fibers may be used in combination with glass fibers, aramid fibers, (liquid crystal) polyester fibers, polyacrylic fibers, carbon fibers, etc., as long as the gist of the present invention is not impaired.
• aramid fibers liquid crystal polyester fibers
• polyacrylic fibers polyacrylic fibers
• carbon fibers etc.
• the above-mentioned polyimide fiber preferably has a tensile modulus of elasticity in the range of 100 GPa or more and 170 GPa or less, more preferably 110 GPa or more and 150 GPa or less.
• Examples of the above-mentioned epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, cresol novolac epoxy resin, and diaminodiphenylmethane epoxy.
• Examples include resins and epoxy resins made flame retardant by halogenating some of the hydrogen atoms in these epoxy resin structures.
• examples of the curing agent for this epoxy resin include amide curing agents such as dicyandiamide and aliphatic polyamide, amine curing agents such as diaminodiphenylmethane and triethylenediamine, and phenolic curing agents such as phenol novolak resin and bisphenol A type novolac resin. Examples include curing agents, acid anhydride compounds, mercaptan compounds, phenol resins, and amino resins.
• aromatic diamines examples include 4,4'-diaminodiphenyl ether, paraphenylenediamine (PPD), metaphenylenediamine (MPDA), 2,5-diaminotoluene, 2,6-diaminotoluene, and 4,4'-diaminotoluene.
• the fiber-reinforced resin molded article according to the embodiment of the present invention has a dielectric constant of 4.0 or less and a dielectric loss tangent of 0.02 or less in a frequency band of 5 GHz or more and 80 GHz or less.
• the dielectric constant is preferably in the range of 1.0 or more and 4.0 or less, and the dielectric loss tangent is preferably in the range of 0 or more and 0.02 or less.
• the dielectric constant is more preferably in the range of 1.0 or more and 3.5 or less, and the dielectric loss tangent is more preferably in the range of 0 or more and 0.015 or less. This is because the transmission speed can be increased thereby.
• the fiber-reinforced resin molded article according to the embodiment of the present invention has no frequency dependence in dielectric constant or dielectric loss tangent even in a wide frequency band of 5 GHz or more and 80 GHz or less, so it can be used for satellite mobile phones and next-generation mobile phones ( 1.0 GHz to 2.5 GHz) casings or parts, network compatible terminals (computers, mobile phones, mobile games, tablets, portable music players) casings or parts, wireless LAN (5 GHz to 60 GHz) casings or parts , wireless communication: There is no need to adjust the dielectric constant etc. in the field of AWA (22 GHz to 45 GHz) housings or components, and it can be suitably used.
• AWA 22 GHz to 45 GHz
• the tensile strength of the fiber-reinforced resin molded body in the fiber direction is within the range of 0.5 GPa or more and 2.5 GPa or less. It is preferably in the range of 0.75 GPa or more and 2.5 GPa or less, and even more preferably in the range of 1.0 GPa or more and 2.5 GPa or less.
• the tensile modulus of the fiber reinforced resin molded product is preferably within the range of 25 GPa or more and 120 GPa or less, more preferably within the range of 30 GPa or more and 120 GPa or less, and within the range of 35 GPa or more and 120 GPa or less. It is even more preferable that there be.
• the fiber-reinforced resin molded article according to the embodiment of the present invention can be molded by either a method using prepreg or a method not using prepreg.
• the polyimide fibers may be long fibers or short fibers cut to any length.
• Examples of the method using prepreg include a method in which a fiber base material made of the above-mentioned fibers is laminated with a plurality of prepregs impregnated with a resin, and then the laminate is heated and pressurized to cure it.
• a so-called UD sheet in which fibers are arranged in one direction, or a material obtained by weaving or knitting long fiber filament yarn can be preferably used.
• the woven fabric include multi-axial woven fabrics such as bidirectional woven fabrics and triaxial woven fabrics.
• knitted fabrics include those knitted with a weft knitting machine such as a circular knitting machine, a warp knitting machine such as a tricot knitting machine, a Russell knitting machine, a Milanese knitting machine, etc.
• a method that does not go through prepreg for example, a method of preparing a varnish containing the above-mentioned resin, impregnating the varnish into a fiber base material, and curing it by heating and pressurizing, specifically, a hand lay-up method. , filament winding method, pultrusion method, etc.
• a UD prepreg was produced by heating at 120°C for 30 minutes. Next, the obtained UD prepreg was sandwiched between plate-shaped molds and bagged, and then the UD prepreg was heated and pressurized at 130° C. for 90 minutes at 6 atm in an autoclave to obtain a fiber-reinforced resin molded body. At this time, the temperature increase/decrease rate of the autoclave was 2° C./min. The thickness of the obtained fiber-reinforced resin molded article was 65 ⁇ m, and the volume content of polyimide fibers was 56%.
• the dielectric constant, dielectric loss tangent, and tensile properties of the obtained fiber-reinforced resin molded article were measured using the following methods.
• a fiber-reinforced resin molded body was obtained in the same manner as described in Example 1, except that the fiber-reinforced resin molded body was manufactured so that the volume content of polyimide fibers was 60%.
• the thickness of the obtained fiber-reinforced resin molded article was 62 ⁇ m.
• the dielectric constant and dielectric loss tangent of the fiber-reinforced resin molded product and the tensile properties of the fiber-reinforced resin molded product in the frequency band of 5 GHz to 80 GHz were measured using the same method as described in Example 1, it was found that The dielectric constant at a frequency of 10 GHz is 3.48, the dielectric constant at a frequency of 20 GHz is 3.46, the dielectric constant at a frequency of 28 GHz is 3.47, and the dielectric constant at a frequency of 40 GHz is 3.48.
• the dielectric loss tangent at a frequency of 5 GHz is 0.0120
• the dielectric loss tangent at a frequency of 10 GHz is 0.0127
• the dielectric loss tangent at a frequency of 20 GHz is 0.0129
• the dielectric loss tangent at a frequency of 28 GHz is 0.0120. 0125
• the dielectric loss tangent at a frequency of 80 GHz was 0.0114.
• the tensile strength of the fiber-reinforced resin molded article was 1.55 GPa
• the tensile modulus was 44.8 GPa.
• the thickness of the obtained fiber-reinforced resin molded article was 93 ⁇ m.
• the dielectric constant and dielectric loss tangent of the fiber-reinforced resin molded product in the frequency band of 5 GHz to 80 GHz and the tensile properties of the fiber-reinforced resin molded product were measured using the same method as described in Example 1, it was found that the 5 GHz dielectric constant is 3.32, the dielectric constant at a frequency of 10 GHz is 3.34, the dielectric constant at a frequency of 20 GHz is 3.31, the dielectric constant at a frequency of 28 GHz is 3.18, and the dielectric constant at a frequency of 40 GHz is The dielectric constant was 3.22, the dielectric constant at a frequency of 60 GHz was 3.20, and the dielectric constant at a frequency of 80 GHz was 3.12.
• the dielectric loss tangent at a frequency of 5 GHz is 0.0198
• the dielectric loss tangent at a frequency of 10 GHz is 0.0189
• the dielectric loss tangent at a frequency of 20 GHz is 0.0197
• the dielectric loss tangent at a frequency of 28 GHz is 0. 0194
• the dielectric loss tangent at a frequency of 40 GHz was 0.0174
• the dielectric loss tangent at a frequency of 60 GHz was 0.0165
• the dielectric loss tangent at a frequency of 80 GHz was 0.0194.
• the tensile strength of the fiber-reinforced resin molded article was 0.60 GPa
• the tensile modulus was 29.8 GPa.
• a fiber-reinforced resin molded body was obtained in the same manner as described in Example 1, except that the fiber-reinforced resin molded body was manufactured so that the volume content of polyimide fibers was 58%.
• the dielectric loss tangent at a frequency of 5 GHz is 0.0137
• the dielectric loss tangent at a frequency of 10 GHz is 0.0138
• the dielectric loss tangent at a frequency of 20 GHz is 0.0138
• the dielectric loss tangent at a frequency of 28 GHz is 0. 0134
• the dielectric loss tangent at a frequency of 80 GHz was 0.0133.
• the tensile strength of the fiber-reinforced resin molded article was 1.50 GPa
• the tensile modulus was 43.1 GPa.
• the thickness of the obtained fiber-reinforced resin molded article was 83 ⁇ m.
• the dielectric constant and dielectric loss tangent of the fiber-reinforced resin molded product and the tensile properties of the fiber-reinforced resin molded product in the frequency band of 5 GHz to 80 GHz were measured using the same method as described in Example 1, it was found that The dielectric constant at a frequency of 10 GHz is 3.33, the dielectric constant at a frequency of 20 GHz is 3.35, the dielectric constant at a frequency of 28 GHz is 3.25, and the dielectric constant at a frequency of 40 GHz is 3.34.
• the thickness of the obtained fiber-reinforced resin molded article was 62 ⁇ m, and the volume content of aramid fibers was 56.3%.
• the dielectric constant and dielectric loss tangent of the fiber-reinforced resin molded product and the tensile properties of the fiber-reinforced resin molded product in the frequency band of 5 GHz to 80 GHz were measured using the same method as described in Example 1, it was found that The dielectric constant at a frequency of 10 GHz was 3.63, the dielectric constant at a frequency of 20 GHz was 3.58, and the dielectric constant at a frequency of 28 GHz was 3.56.
• the dielectric loss tangent at a frequency of 5 GHz is 0.0201
• the dielectric loss tangent at a frequency of 10 GHz is 0.0210
• the dielectric loss tangent at a frequency of 20 GHz is 0.0226
• the dielectric loss tangent at a frequency of 28 GHz is 0. It was 0223.
• the dielectric constant and dielectric loss tangent in a frequency band of 40 GHz or higher could not be measured due to large losses.
• the tensile strength of the fiber-reinforced resin molded article was 1.53 GPa
• the tensile modulus was 54.1 GPa.
• Example 2 A fiber-reinforced resin molded body was obtained in the same manner as described in Example 1, except that the polyimide fiber was replaced with glass fiber (ECG150 1/0 manufactured by Nittobo Co., Ltd.).
• the thickness of the obtained fiber-reinforced resin molded body was 70 ⁇ m, and the volume content of glass fiber was 55.7%.
• the dielectric constant and dielectric loss tangent of the fiber-reinforced resin molded product and the tensile properties of the fiber-reinforced resin molded product in the frequency band of 5 GHz to 80 GHz were measured using the same method as described in Example 1, it was found that The dielectric constant at a frequency of 10 GHz is 5.03, the dielectric constant at a frequency of 20 GHz is 4.77, the dielectric constant at a frequency of 28 GHz is 4.78, and the dielectric constant at a frequency of 40 GHz is 4.85.
• the dielectric constant at the frequency was 4.74.

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• Organic Chemistry (AREA)
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• Manufacturing & Machinery (AREA)
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• General Chemical & Material Sciences (AREA)
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• 2023
  • 2023-06-08 JP JP2024516653A patent/JP7601476B2/ja active Active
  • 2023-06-08 US US18/873,658 patent/US20250361370A1/en active Pending
  • 2023-06-08 CN CN202380046369.3A patent/CN119384450A/zh active Pending
  • 2023-06-08 EP EP23823823.2A patent/EP4538317A4/en active Pending
  • 2023-06-08 WO PCT/JP2023/021355 patent/WO2023243532A1/ja not_active Ceased
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