WO2025178132A1 - Composition de résine, matériau composite, article moulé et procédé de production de composition de résine - Google Patents

Composition de résine, matériau composite, article moulé et procédé de production de composition de résine

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Publication number
WO2025178132A1
WO2025178132A1 PCT/JP2025/006129 JP2025006129W WO2025178132A1 WO 2025178132 A1 WO2025178132 A1 WO 2025178132A1 JP 2025006129 W JP2025006129 W JP 2025006129W WO 2025178132 A1 WO2025178132 A1 WO 2025178132A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
mass
aromatic polyether
parts
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/006129
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English (en)
Japanese (ja)
Inventor
健 須藤
雪乃 伊藤
創 渡辺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Idemitsu Kosan Co Ltd
Original Assignee
Idemitsu Kosan Co Ltd
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Publication date
Application filed by Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Publication of WO2025178132A1 publication Critical patent/WO2025178132A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols

Definitions

  • the present invention relates to a resin composition, a composite material, a molded article, and a method for producing a resin composition. Specifically, the present invention relates to a resin composition, a composite material, a molded article, and a method for producing a resin composition, which can produce a molded article having excellent mechanical properties and excellent thermal stability.
  • Aromatic polyethers have excellent heat resistance and mechanical strength, and are used as metal replacement materials. In recent years, their applications have expanded to include automobiles, aircraft, and the medical field.
  • Patent Document 1 describes a resin composition containing a thermoplastic resin having a melting point of 280°C or higher or a glass transition temperature of 220°C or higher, and nanodiamond particles, with the aim of suppressing crosslinking reactions caused by radicals in thermoplastic resins such as aromatic polyether ketone (improving thermal stability).
  • Patent Document 2 an attempt is made to improve thermal stability by incorporating 0.10 to 0.35% by mass of sodium dihydrogen orthophosphate and 0.08 to 0.25% by weight of disodium hydrogen phosphate into polyether ether ketone (PEEK).
  • One of the objects of the present invention is to provide a resin composition, composite material, and molded article that can be used to produce molded articles with excellent mechanical properties and excellent thermal stability, as well as a method for producing the resin composition.
  • a resin composition comprising: an aromatic polyether (A) having a radical amount of 6.5 ⁇ 10 15 to 9.0 ⁇ 10 17 spin/g at 25°C, measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance; and an inorganic metal phosphate (B) in an amount of 0.01 to 5.0 parts by mass per 100 parts by mass of the aromatic polyether (A).
  • an aromatic polyether (A) having a radical amount of 6.5 ⁇ 10 15 to 9.0 ⁇ 10 17 spin/g at 25°C, measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance
  • an inorganic metal phosphate (B) in an amount of 0.01 to 5.0 parts by mass per 100 parts by mass of the aromatic polyether (A).
  • R2 Loss tangent (tan ⁇ ) ⁇ complex viscosity ⁇ 7500 (R2) 12.
  • a composite material comprising the resin composition according to any one of 1 to 11 above and 0.01 to 500 parts by mass of reinforcing fibers (C) per 100 parts by mass of the resin composition.
  • the reinforcing fiber (C) comprises one or more fibers selected from the group consisting of carbon fiber, glass fiber, and aramid fiber. 14. 14.
  • 15. 12 A molded article made of the resin composition according to any one of 1 to 11 above. 16.
  • 15. A molded article made of the composite material according to any one of 12 to 14. 17.
  • a method for producing a resin composition comprising: 21.
  • a method for producing a resin composition comprising:
  • x to y represents a numerical range of "not less than x and not more than y.”
  • the upper and lower limits of the numerical ranges can be combined in any way.
  • a resin composition according to one embodiment of the present invention (hereinafter also referred to as "first resin composition”) comprises an aromatic polyether (A) having a radical amount of 6.5 ⁇ 10 15 to 9.0 ⁇ 10 17 spin/g at 25°C, measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance, and 0.01 to 5.0 parts by mass of an inorganic metal phosphate (B) relative to 100 parts by mass of the aromatic polyether (A).
  • the resin composition according to the present invention can exhibit excellent interfacial adhesive strength to reinforcing fibers such as inorganic fillers and also has excellent thermal stability. Furthermore, by using the resin composition in the production of composite materials or molded articles, composite materials or molded articles having excellent mechanical properties (e.g., tensile modulus and elongation) can be produced. The mechanical properties of the composite material and the molded article can be measured based on the method described in the Examples.
  • aromatic polyether (A) having a high radical concentration of 6.5 ⁇ 10 15 to 9.0 ⁇ 10 17 spin/g is thought to undergo partial structural changes depending on the kneading and molding conditions, etc., resulting in the formation of crosslinks, gels, etc., and to have limited strength improvement.
  • the inorganic metal phosphate (B) can reduce undesirable structural changes associated with crosslink formation by such radicals, suppressing destruction of the aromatic polyether (A) itself and contributing to improved strength and thermal stability. Furthermore, it is thought that the mechanical properties of composite materials and molded articles containing this resin composition can be significantly improved.
  • the complex viscosity of the resin composition is a value measured by the method described in the examples.
  • the loss tangent (tan ⁇ ) after 60 minutes of measurement at a set temperature of 420°C using a viscoelasticity measuring device is 0.50 or greater, and may be 0.60 or greater, 0.70 or greater, 0.80 or greater, or 0.90 or greater. There is no particular upper limit, and it may be, for example, 15.0 or less, 10.0 or less, or 5.0 or less.
  • the resin When the loss tangent (tan ⁇ ) satisfies the above conditions, the resin is more likely to orient during molding of the resin composition, and the mechanical properties of the resulting molded body are expected to improve.
  • the loss tangent (tan ⁇ ) of the resin composition is a value measured by the method described in the examples.
  • the complex viscosity and loss tangent (tan ⁇ ) measured using a viscoelasticity measuring device at a set temperature of 420° C. satisfy the following formula (R2): Loss tangent (tan ⁇ ) ⁇ complex viscosity ⁇ 7500 (R2)
  • the product of the complex viscosity and the loss tangent (tan ⁇ ) measured using a viscoelasticity measuring device at a set temperature of 420°C is 7500 or less, and may be 7200 or less, 7000 or less, 6800 or less, 6500 or less, 6200 or less, or 6000 or less.
  • a first resin composition according to one aspect of the present invention includes an aromatic polyether (A) having a radical amount of 6.5 ⁇ 10 15 to 9.0 ⁇ 10 17 spin/g at 25° C., measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance.
  • Aromatic polyether (A) can exhibit excellent interfacial adhesive strength with reinforcing fibers such as inorganic fillers, and also has excellent toughness. Furthermore, by using it in the production of composite materials and molded articles, composite materials and molded articles with excellent mechanical properties can be produced.
  • the aromatic polyether has a large radical amount of 6.5 ⁇ 10 15 spin/g or more, which causes an interaction with the reinforcing fibers or forms chemical bonds.
  • the toughness of the aromatic polyether can be evaluated, for example, by the breaking strain (tensile elongation) measured by the method described in the Examples.
  • the radical amount of aromatic polyether is a value measured by the method described in the examples.
  • the "radical amount” of an aromatic polyether means the “radical amount per unit mass (unit: spin/g)" of the aromatic polyether.
  • “TEMPOL” means "4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl” unless otherwise specified.
  • the radical amount of the aromatic polyether (A) is 6.5 ⁇ 10 15 spin/g or more, 7.0 ⁇ 10 15 spin/g or more, 8.0 ⁇ 10 15 spin/g or more, 8.9 ⁇ 10 15 spin/g or more, 1.0 ⁇ 10 16 spin/g or more, 2.0 ⁇ 10 16 spin/g or more, 3.0 ⁇ 10 16 spin/g or more, 4.0 ⁇ 10 16 spin/g or more, or 5.0 ⁇ 10 16 spin/g or more, and 9.0 ⁇ 10 17 spin/g or less, 5.0 ⁇ 10 17 spin/g or less, 4.0 ⁇ 10 17 spin/g, 3.7 ⁇ 10 17 spin/g or less, or 1.0 ⁇ 10 It is 17 spin/g or less.
  • the radical amount of the aromatic polyether (A) is 6.5 ⁇ 10 15 spin/g or more, the above-mentioned composite effect and the like are easily obtained, and sufficient interfacial shear strength with the reinforcing fibers are easily obtained.
  • the radical amount of the aromatic polyether (A) is 9.0 ⁇ 10 17 spin/g or less, thermal stability is easily obtained, and sufficient mechanical properties are easily exhibited as a molded product.
  • the amount of radicals in aromatic polyethers can be increased to the above-mentioned range, for example, by using a monomer containing a chlorine atom as a reactive group (e.g., 4,4'-dichlorobenzophenone) as the monomer when synthesizing (polymerizing) the aromatic polyether.
  • a monomer containing a chlorine atom as a reactive group e.g., 4,4'-dichlorobenzophenone
  • the aromatic polyether (A) is a polyarylene ether ketone. In one embodiment, the aromatic polyether (A) comprises one or more selected from the group consisting of polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetherketone (PEK). In one embodiment, the aromatic polyether (A) comprises one or more selected from the group consisting of polyether ether ketone (PEEK) and polyether ketone (PEK). From the viewpoints of moldability, mechanical properties, and environmental resistance, the aromatic polyether (A) preferably comprises polyether ether ketone (PEEK).
  • 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, 99.5% by mass or more, or substantially 100% by mass of the aromatic polyether (A) is one or more selected from the group consisting of polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetherketone (PEK).
  • 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, 97% by weight or more, 99% by weight or more, 99.5% by weight or more, or substantially 100% by weight of the aromatic polyether (A) is polyether ether ketone (PEEK).
  • the aromatic polyether (A) contains a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).
  • the aromatic polyether (A) contains a structural unit represented by the following formula (3):
  • the structural unit represented by formula (3) is a linker between the structural unit represented by formula (1) and the structural unit represented by formula (2).
  • the aromatic polyether (A) does not contain any other structures other than the structural units represented by formula (1) and formula (2).
  • the aromatic polyether (A) contains structures other than the structural units represented by formula (1) and formula (2), to the extent that the effects of the present invention are not impaired.
  • the aromatic polyether comprises a structural unit represented by the following formula (a) and one or more structural units selected from the group consisting of structures represented by the following formulas (b) and (c):
  • the structural unit represented by formula (a) corresponds to the structural unit represented by formula (3) described above, and is a linkage between the structural unit represented by formula (1) and the structural unit represented by formula (2).
  • the copolymer is a random copolymer, an alternating copolymer, or a block copolymer, preferably a random copolymer.
  • the substitution position (bonding position) of the phenyl group in the structural unit represented by formula (b) of the aromatic polyether can be any position on the benzene ring constituting the main chain shown on the far right in formula (b) (the phenyl group is introduced so as to replace one of the four hydrogen atoms on the benzene ring).
  • the aromatic polyether may contain one or more structures selected from the group consisting of a structure represented by the following (b1), a structure represented by the following (b2), and a structure represented by the following (b3):
  • 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, 97% by weight or more, 99% by weight or more, 99.5% by weight or more, or substantially 100% by weight of the aromatic polyether are structural units represented by formula (a) and structural units represented by formula (b).
  • substantially 100% by mass unavoidable impurities may be contained.
  • the molar ratio of the structural units represented by formula (b) to the total amount of the structural units represented by formula (a) and the structural units represented by formula (b) in the aromatic polyether is 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% or more, 6 mol% or more, 7 mol% or more, or 8 mol% or more, and is 99 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, or 40 mol% or less.
  • 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, 97% by weight or more, 99% by weight or more, 99.5% by weight or more, or substantially 100% by weight of the aromatic polyether are structural units represented by formula (a) and structural units represented by formula (c).
  • substantially 100% by mass unavoidable impurities may be contained.
  • the molar ratio of the structural units represented by formula (c) to the total amount of the structural units represented by formula (a) and the structural units represented by formula (c) in the aromatic polyether is 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% or more, 6 mol% or more, 7 mol% or more, or 8 mol% or more, and is 99 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, or 40 mol% or less.
  • the structural unit represented by formula (a) and one or more structural units selected from the group consisting of structures represented by formulas (b) and (c) can be copolymerized to the extent that the effects of the present invention are not impaired.
  • the aromatic polyether comprises a structural unit represented by the following formula (a) and a structural unit represented by the following formula (d), and has a radical amount of 6.5 ⁇ 10 15 to 9.0 ⁇ 10 17 (spin/g) at 25° C., measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance.
  • the copolymer is a random copolymer, an alternating copolymer, or a block copolymer, preferably a random copolymer.
  • the structural unit represented by formula (d) is a structural unit represented by formula (c).
  • the structural unit represented by formula (a) and the structural unit represented by formula (d) can be copolymerized to the extent that the effects of the present invention are not impaired.
  • 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, 97% by weight or more, 99% by weight or more, 99.5% by weight or more, or substantially 100% by weight of the aromatic polyether are structural units represented by formula (a) and structural units represented by formula (d).
  • substantially 100% by mass unavoidable impurities may be contained.
  • the molar ratio of the structural units represented by formula (d) to the total amount of the structural units represented by formula (a) and the structural units represented by formula (d) in the aromatic polyether is 1 mol% or more, 2 mol% or more, 3 mol% or more, 4 mol% or more, 5 mol% or more, 6 mol% or more, 7 mol% or more, or 8 mol% or more, and is 99 mol% or less, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, or 40 mol% or less.
  • 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, 99.5% by mass or more, or substantially 100% by mass of the aromatic polyether (A) are structural units represented by formula (1) and structural units represented by formula (2), or structural units represented by formula (3).
  • the content is "substantially 100% by mass", unavoidable impurities may be contained.
  • the molar ratio of the structural units represented by formula (1) to the structural units represented by formula (2) is 47.5:52.5 to 52.5:47.5, 48.0:52.0 to 52.0:48.0, 48.5:51.5 to 51.5:48.5, 49.0:51.0 to 51.0:49.0, or 49.5:50.5 to 50.5:49.5.
  • the number of moles of the structural unit represented by formula (1) may be larger than, smaller than, or the same as the number of moles of the structural unit represented by formula (2).
  • the terminal structure of the main chain of the aromatic polyether (A) is not particularly limited.
  • the structural unit represented by formula (1) is located at one or more ends of the main chain of the aromatic polyether (A).
  • the terminal structure bonded to the structural unit may be a halogen atom.
  • the halogen atom may be, for example, a chlorine atom (Cl) or a fluorine atom (F).
  • the structural unit represented by formula (2) is located at one or more ends of the main chain of the aromatic polyether (A).
  • the terminal structure bonded to the structural unit may be, for example, a hydrogen atom (H) or the like (when the terminal structure is a hydrogen atom (H), a hydroxyl group is formed together with the oxygen atom (O) in the structural unit).
  • the terminal structure of the aromatic polyether (A) may be, for example, a structure in which the above-mentioned halogen atom or hydroxyl group is replaced with a hydrogen atom (H), etc.
  • the terminal structure may have a structure other than those exemplified above.
  • the terminal structure may have a structure derived from a reaction terminator.
  • the aromatic polyether (A) has a melt flow rate (MFR) of 1500 g/10 min or less, 1000 g/10 min or less, 500 g/10 min or less, 300 g/10 min or less, 200 g/10 min or less, 100 g/10 min or less, 80 g/10 min or less, 60 g/10 min or less, or 50 g/10 min or less, and 0.0001 g/10 min or more, 0.0005 g/10 min or more, 0.001 g/10 min or more, 0.005 g/10 min or more, 0.01 g/10 min or more, 0.05 g/10 min or more, or 0.1 g/10 min or more.
  • MFR melt flow rate
  • the melt flow rate of the aromatic polyether (A) is, for example, 0.001 to 500 g/10 min, preferably 0.01 to 100 g/10 min from the viewpoint of mechanical properties, and more preferably 0.05 to 50 g/10 min from the viewpoint of moldability.
  • the melt flow rate of the aromatic polyether (A) can be measured by the method described in the Examples.
  • the aromatic polyether (A) has a potassium atom (K) content of 0 ppm or more and 200 ppm or less.
  • K potassium atom
  • the potassium atom content can be measured by the method described in the examples.
  • the inorganic metal phosphate (B) include LiPO4 , Na2HPO4 , NaH2PO4 , NaH2PO2, Na3PO4 , Na4P2O7 , Na2H2P2O7 , Na5P3O10 , Na6P4O13 , K2P2O7 , CaHPO4 , Ca ( H2PO4 ) 2 , CaHPO4 , Ca3 ( PO4 ) 2 , KH2PO4 , K2HPO4 , K3PO4 , K4P2O7 , K5P3O10 , Mg
  • the phosphate group include, but are not limited to, Mg2P2O7 , Mg ( H2PO4 ) , MgHPO4 , Mg3 ( PO4 ) 2 , Mg( PO3 ) 2 , Al( H2PO4 ), AlPO4 , Al( PO3 ) 3 , and hydrates thereof.
  • the content of sodium atoms (Na) in the second resin composition is 100 ppm or more, 150 ppm or more, 200 ppm or more, 400 ppm or more, 600 ppm or more, 800 ppm or more, or 1000 ppm or more.
  • the content of sodium atoms (Na) in the second resin composition is within the above range, the effect of excellent thermal stability is likely to be obtained.
  • the phosphorus atom (P) and sodium atom (Na) contents are values determined by inductively coupled plasma atomic emission spectroscopy as described in the examples.
  • reaction solvent for example, an aprotic polar solvent can be used.
  • aprotic polar solvents include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, and N-methyl-3-methyl-2-pyrrolidone.
  • the potassium carbonate preferably has a purity of 99% by mass or more and a water content of 0.01% by mass or less. Such potassium carbonate is commercially available. Potassium carbonate may be of general-purpose reagent grade, general industrial grade, or fine particle grade.
  • the average particle size ( D50 ) of potassium carbonate is preferably 1000 ⁇ m or less, 800 ⁇ m or less, 500 ⁇ m or less, 300 ⁇ m or less, 100 ⁇ m or less, or even 50 ⁇ m or less.
  • the lower limit of the average particle size ( D50 ) may be, for example, 0.1 ⁇ m or more, 0.5 ⁇ m or more, or 1 ⁇ m or more.
  • the reaction of the raw material mixture containing 4,4'-dichlorobenzophenone and hydroquinone can be carried out under heating.
  • the reaction temperature can typically be in the range of 150 to 380°C.
  • the reaction time can typically be 0.1 to 10 hours.
  • the point at which the reaction should be stopped can be determined based on the viscosity of the reaction solution (the raw material mixture in which the reaction has progressed). Stopping the reaction when the solution viscosity is 100 cP or higher makes it easier to obtain a high molecular weight product.
  • the solution viscosity is measured using a process viscometer (XL7-951-HT2-d28-E58, manufactured by Hydramotion Japan Co., Ltd.) or similar.
  • the reaction of the raw material mixture may be, for example, (i) raising the temperature to 180 to 220°C and maintaining the temperature for 0.5 to 2 hours; (ii) raising the temperature to 230 to 270°C and maintaining the temperature for 0.5 to 2 hours; and (iii)
  • the method may include a step of increasing the temperature to 280 to 320° C. and maintaining the increased temperature for 1 to 8 hours.
  • the temperature increase in (i) to (iii) can be carried out at a rate of, for example, 10° C./min or less, 5° C./min or less, or 3° C./min or less.
  • the temperature increase in (i) to (iii) is preferably, for example, 0.1 to 10°C/min or less, which allows the rate-determining step in the reaction of the raw material mixture to proceed smoothly, and makes it easier to obtain a high molecular weight aromatic polyether.
  • the washing step is a step of washing the aromatic polyether obtained in the reaction step with a washing solvent.
  • washing may be carried out once, washing may be carried out multiple times using one type of washing solvent, or washing may be carried out in combination with two or more types of washing solvents.
  • the washing solvent include water, an aqueous acid solution, and an organic solvent.
  • suitable organic solvents include nitrogen-containing compounds such as nitriles, nitromethane, and N-methyl-2-pyrrolidone; esters such as methyl formate, methyl acetate, butyl acetate, methyl propionate, ethyl propionate, and phosphate triesters; glymes such as diglyme, triglyme, and tetraglyme; ketones such as acetone, diethyl ketone, methyl ethyl ketone, and methyl isobutyl ketone; sulfones such as sulfolane; oxazolidinones such as 3-methyl-2-oxazolidinone; and sultones such as 1,3-propane sultone, 4-butane sultone, and naphtha sultone. Among these, acetone is preferred as the organic solvent. These organic solvents may be used alone or in combination.
  • Drying can be carried out at a temperature depending on the type of solvent remaining in the aromatic polyether, for example, at a temperature equal to or higher than the boiling point of the remaining solvent.
  • the drying temperature can be selected from, for example, 50 to 250° C., 80 to 200° C., or 100 to 180° C.
  • the drying can be carried out by drying under reduced pressure (vacuum drying) using a vacuum pump or the like.
  • the drying time is not particularly limited, but can be, for example, 1 minute or more, 10 minutes or more, 30 minutes or more, 1 hour or more, etc.
  • the upper limit of the drying time is not particularly limited, but can be, for example, 24 hours or less, 12 hours or less, 6 hours or less, 3 hours or less, etc.
  • the kneading step is a step in which 100 parts by mass of the aromatic polyether obtained in the aromatic polyether drying step is melt-kneaded with 0.01 to 5.0 parts by mass of the inorganic metal phosphate (B) to obtain a kneaded product.
  • the mode of melt-kneading is not particularly limited, but for example, the inorganic metal phosphate (B) is kneaded with a molten aromatic polyether.
  • the method for kneading the inorganic metal phosphate (B) is not particularly limited, and examples thereof include melt kneading using an extruder, etc.
  • the inorganic metal phosphate (B) may be side-fed into the aromatic polyether using a twin-screw kneader.
  • the second manufacturing method according to one aspect of the present invention produces a resin composition according to one aspect of the present invention.
  • the details described in the first manufacturing method according to one embodiment of the present invention can be applied to the reaction step and washing step.
  • the mixing step is a step in which 100 parts by mass of the aromatic polyether obtained in the washing step is mixed with 0.01 to 5.0 parts by mass of the inorganic metal phosphate (B) in the presence of a solvent to obtain a mixture.
  • the aromatic polyether obtained in the washing step may contain a solvent and may be in the form of, for example, a cake or slurry of resin (aromatic polyether)/solvent.
  • 100 parts by mass of aromatic polyether means 100 parts by mass of the aromatic polyether remaining after excluding the solvent from the entire cake or slurry.
  • Solvents that can be used in the mixing step include, for example, water, acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone.
  • the above solvents may be used alone or in combination of two or more. From the perspective of the solubility of inorganic phosphate, it is preferable to use water alone or a water/acetone mixed solution.
  • mixing is carried out in the presence of 50 to 1,000 parts by weight, 100 to 800 parts by weight, or 300 to 700 parts by weight of a solvent per 100 parts by weight of aromatic polyether.
  • the mixture drying step is a step of removing the solvent from the mixture obtained in the mixing step.
  • the solvent to be removed is not limited to the solvent used in the mixing step, but also includes, for example, the remaining reaction solvent and washing solvent. It is not necessary to completely remove the solvent from the mixture, but at least a portion of the solvent may be removed, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more of the solvent in the mixture may be removed.
  • drying means a known dryer, a thermo-hygrostat, etc. can be used.
  • the drying method is not particularly limited, but a vibration dryer, hot air dryer, vacuum dryer, flash dryer, etc. can be used.
  • Drying can be carried out at a temperature depending on the type of solvent remaining in the mixture, for example, at a temperature equal to or higher than the boiling point of the remaining solvent.
  • the drying temperature can be selected from, for example, 50 to 250° C., 80 to 200° C., or 100 to 180° C.
  • the drying can be carried out by drying under reduced pressure (vacuum drying) using a vacuum pump or the like.
  • the drying time is not particularly limited, but can be, for example, 1 minute or more, 10 minutes or more, 30 minutes or more, 1 hour or more, etc.
  • the upper limit of the drying time is not particularly limited, but can be, for example, 24 hours or less, 12 hours or less, 6 hours or less, 3 hours or less, etc.
  • a filtration step may be added before drying to remove the solvent.
  • the amount of solvent to be removed can be reduced, and the process time, drying time, and dryer capacity can be reduced, thereby reducing the environmental load and enabling the resin composition to be obtained efficiently.
  • the method for producing a resin composition according to one embodiment of the present invention may employ steps, methods, conditions, etc. that are commonly used in the field of resin compositions, as long as the effects of the present invention are not impaired.
  • Composite Material A composite material according to one aspect of the present invention comprises the resin composition according to one aspect of the present invention (the first resin composition and/or the second resin composition) and 0.01 to 500 parts by mass of reinforcing fibers (C) per 100 parts by mass of the resin composition.
  • the interfacial shear strength between the resin composition and the reinforcing fibers is excellent, and therefore the effect of the composite material being excellent in mechanical properties (for example, tensile modulus and elongation) can be obtained.
  • the content of the reinforcing fiber (C) in the composite material is 0.01 parts by mass or more, 0.1 parts by mass or more, 1 part by mass or more, or 10 parts by mass or more, and 500 parts by mass or less, 300 parts by mass or less, 200 parts by mass or less, or 100 parts by mass or less, relative to 100 parts by mass of the resin composition.
  • the content of the reinforcing fibers relative to 100 parts by mass of the resin composition is 0.01 parts by mass or more, the reinforcing effect of the reinforcing fibers is more easily obtained, and when the content is 500 parts by mass or less, the suitability for kneading and molding the composite material is more easily improved.
  • the reinforcing fibers (C) include one or more selected from the group consisting of carbon fibers, glass fibers, and aramid fibers.
  • 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, 99.5% by mass or more, or substantially 100% by mass of the reinforcing fibers (C) are one or more types selected from the group consisting of carbon fibers, glass fibers, and aramid fibers.
  • the carbon fiber comprises one or more selected from the group consisting of PAN-based carbon fiber, pitch-based carbon fiber, thermoset-based carbon fiber, phenolic-based carbon fiber, vapor-grown carbon fiber, and recycled carbon fiber (RCF).
  • 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, 99.5% by mass or more, or substantially 100% by mass of the carbon fibers are one or more types selected from the group consisting of PAN-based carbon fibers, pitch-based carbon fibers, thermosetting-based carbon fibers, phenol-based carbon fibers, vapor-grown carbon fibers, and recycled carbon fibers (RCF).
  • the carbon fiber may be treated with a sizing agent.
  • the sizing agent can bind the reinforcing fibers into bundles. Reinforcing fibers treated with a sizing agent have the sizing agent adhered to their surface.
  • the sizing agent There are no particular limitations on the sizing agent, and examples include epoxy-based sizing agents, urethane-based sizing agents, and polyamide-based sizing agents.
  • Aromatic polyethers can also be used as sizing agents. These sizing agents may be used alone or in combination of two or more. Reinforcing fibers may not be treated with a sizing agent.
  • the sizing agents may be used in combination with silane coupling agents such as aminosilane, isocyanate silane, and acrylic silane.
  • Glass fibers of various compositions such as E-glass, low-dielectric glass, and silica glass, can be selected and used depending on the purpose and application.
  • Glass fibers may also be treated with a sizing agent.
  • the sizing agent allows the glass fibers to be bound into bundles.
  • Glass fibers treated with a sizing agent have the sizing agent adhered to their surface.
  • the sizing agent There are no particular limitations on the sizing agent, and examples include epoxy-based sizing agents, urethane-based sizing agents, and vinyl acetate-based sizing agents.
  • Aromatic polyethers can also be used as sizing agents. These sizing agents may be used alone or in combination of two or more. Glass fibers that have not been treated with a sizing agent may also be used.
  • the above sizing agents may be used in combination with a silane coupling agent such as aminosilane, isocyanate silane, or acrylic silane.
  • the average fiber length of the reinforcing fibers (C) in the composite material is preferably 5 mm or more.
  • the average fiber length of the reinforcing fibers (C) is 5 mm or more, they are also called “continuous fibers.”
  • the average fiber length is determined by the arithmetic mean of the values measured with a vernier caliper.
  • the composite material may contain other components that do not fall under the category of the resin composition and the reinforcing fiber (C).
  • C reinforcing fiber
  • One type of other component may be used alone, or two or more types may be used in combination.
  • At least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 97%, at least 99%, at least 99.5%, or substantially 100% by weight of the composite material is A resin composition and a reinforcing fiber (C),
  • the components are a resin composition, reinforcing fibers (C), and the other components described above.
  • the composite material may be a fiber composite material containing a resin composition as a matrix and reinforcing fibers (C).
  • the fiber composite material may be a so-called fiber-reinforced thermoplastic (FRTP).
  • the method for producing the composite material is not particularly limited.
  • a method of melt-kneading the resin composition and the reinforcing fibers (C), or a method of melting and impregnating an aggregate of the reinforcing fibers (C) with one or more forms of the resin composition selected from the group consisting of powder, film, and pellets can be used.
  • the reinforcing fibers (C) may be side-fed into the resin composition using a twin-screw kneader.
  • the aggregate of reinforcing fibers (C) may be in one or more forms selected from the group consisting of woven fabric, nonwoven fabric, and unidirectional material (also called "UD material"). In these forms, the average fiber length of the reinforcing fibers (C) may be 5 mm or more. That is, the reinforcing fibers (C) may be continuous fibers. This further improves the strength of the composite material.
  • Pellets of the composite material may be produced, and the pellets can be used as a raw material for producing a molded article, which will be described later.
  • the method for producing pellets includes cutting reinforcing fibers (C) into chopped strands and then adding a resin composition to the reinforcing fibers (C). The short fibers and the resin composition are mixed and granulated to produce pellets (also referred to as "short fiber pellets").
  • a method for producing pellets involves immersing a roving of the reinforcing fiber (C) in a molten resin composition, pultrusion molding the roving, and then cutting the roving into a desired pellet length to produce pellets (also referred to as "long fiber pellets"). When producing long fiber pellets as described above, breakage of the reinforcing fiber (C) can be suppressed.
  • Molded Article A molded article according to an aspect of the present invention is made from the resin composition according to an aspect of the present invention.
  • the breakage of the aromatic polyether (A) in the resin composition is suppressed by the inorganic metal phosphate (B) or by the phosphorus atom and the sodium atom, and therefore, excellent mechanical properties (e.g., tensile modulus, elongation) can be obtained.
  • excellent mechanical properties e.g., tensile modulus, elongation
  • C reinforcing fibers
  • a molded article according to another aspect of the present invention is made of the composite material according to one aspect of the present invention.
  • the interfacial shear strength between the resin composition and the reinforcing fibers (C) in the composite material is excellent, and therefore the effect of excellent mechanical properties (for example, tensile modulus and elongation) can be obtained.
  • the reinforcing fibers (C) the matters described in the composite material according to one embodiment of the present invention can be applied.
  • 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 99% by mass or more, 99.5% by mass or more, and 100% by mass or less, 99.9% by mass or less, or substantially 100% by mass of the molded body is Is it a resin composition?
  • a resin composition and a reinforcing fiber (C) The components are a resin composition, reinforcing fibers (C), and the other components described above.
  • unavoidable impurities may be contained.
  • the shape of the molded article according to one embodiment and another embodiment of the present invention is not particularly limited.
  • the molded body is an injection molded body, an extrusion molded body, or a compression molded body (also called a "press molded body").
  • the method for producing a molded article according to one embodiment of the present invention is not particularly limited, and for example, a molded article can be produced by molding a resin composition or composite material according to one embodiment of the present invention (which may be in the form of pellets as described above).
  • a resin composition or composite material according to one embodiment of the present invention (which may be in the form of pellets as described above).
  • Known methods such as injection molding, extrusion molding, and blow molding can be used for molding.
  • the composite material can also be press-molded, and known methods such as cold pressing and hot pressing can be used.
  • the composite material can be used as a resin composite material for a 3D printer and molded using a 3D printer.
  • Example 1 Kneading of aromatic polyether 100 parts by mass of the aromatic polyether obtained in Production Example 1, 0.6 parts by mass of inorganic metal phosphate salt NaH 2 PO 4 , and 0.4 parts by mass of inorganic metal phosphate salt Na 2 HPO 4 were dry blended to obtain a dry blend raw material.
  • the dry blend raw material was melt-kneaded using a twin-screw extruder having a cylinder diameter of 11 mm (ThermoFisher Scientific "Process-11", cylinder volume 20 cc) at a screw rotation speed of 200 rpm and a set temperature of 380 ° C.
  • the dry blend raw material was fed from the base of the twin-screw extruder (upstream side of the screw) at a rate of 6 g per minute.
  • the residence time in the twin-screw extruder was 3.5 minutes.
  • the strands discharged from the twin-screw extruder were cooled in water and then pelletized using a pelletizer to obtain a resin composition.
  • Viscoelasticity measuring device MCR302 (manufactured by Anton Paar) ⁇ Jig: SHAFT FOR DISPOSABLE MEASUREMENT SYSTEM D-CP/PP25 Disposable dish: ⁇ 41mm Disposable parallel plate: ⁇ 25mm Temperature: 380°C, 400°C, or 420°C Preheating time: 3 min Gap: 0.8 mm ⁇ Time: 300min Shear strain: 1% ⁇ Angular frequency: 2.76 rad/s
  • a disk-shaped resin composition was placed on a disposable dish and measured under the above conditions. Before the measurement, the disk was sandwiched between the disposable dish and a disposable plate with a gap of 0.8 mm, preheated, and then trimmed to a diameter of 25 mm.
  • the “discs” were obtained in the following manner.
  • the resin composition was filled into a mold and pressed at a temperature of 380° C. using a vacuum press (IMC-6215 manufactured by Imoto Machinery Co., Ltd.) After pressing, it was rapidly cooled to 25° C. and molded into a disk having a diameter of 25 mm and a thickness of 1.0 mm.
  • a vacuum press IMC-6215 manufactured by Imoto Machinery Co., Ltd.
  • the detection limit (lower detection limit) for the above elemental analysis measurements is 1 ppm.
  • “N.D.” (Not Detected) means below the detection limit (i.e., less than 1 ppm).
  • test pieces were subjected to a tensile test under the following conditions to measure the maximum tensile strength, tensile modulus, and breaking strain (tensile elongation).
  • the results are shown in Table 1.
  • Example 2 A resin composition was obtained in the same manner as in Example 1, except that the inorganic metal phosphate salt NaH 2 PO 4 was changed to 0.3 parts by mass and the inorganic metal phosphate salt Na 2 HPO 4 was changed to 0.2 parts by mass.
  • the complex viscosity, loss tangent (tan ⁇ ), radical amount, sodium atom (Na) content, and phosphorus atom (P) content of the obtained resin composition were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 A resin composition was obtained in the same manner as in Example 1, except that the inorganic metal phosphate salt NaH 2 PO 4 was changed to 0.06 parts by mass, and the inorganic metal phosphate salt Na 2 HPO 4 was changed to 0.04 parts by mass.
  • the complex viscosity, loss tangent (tan ⁇ ), radical amount, sodium atom (Na) content, and phosphorus atom (P) content of the obtained resin composition were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 is superior to the molded body produced in Comparative Example 1 in mechanical properties (tensile modulus, elongation). It is also apparent that the resin compositions used in Examples 1 to 3 have superior thermal stability compared to the resin composition not containing an inorganic metal phosphate (the aromatic polyether used in Comparative Example 1). Furthermore, the aromatic polyether of Production Example 1 used in Examples 1 to 3 has a significantly larger amount of radicals than the aromatic polyether of Production Example 2 used in Comparative Example 2, and when composited, it is expected to have excellent interfacial shear strength between the aromatic polyether and the reinforcing fiber.
  • Example 4 Water was added to the resin/water cake of Production Example 3 so that the total amount of water was 65 parts by mass per 12 parts by mass of resin, followed by addition of 0.057 parts by mass of inorganic metal phosphate NaH2PO4 and 0.039 parts by mass of inorganic metal phosphate Na2HPO4 , and mixing was continued at 50 to 60°C for 20 minutes. After mixing, the mixture was filtered, and the amount of water recovered was 35 parts by mass. The recovered cake was dried at 150° C. for 5 hours.
  • the contents of NaH2PO4 and Na2HPO4 per 100 parts by mass of resin were evaluated based on the following calculation formula:
  • the phosphate contents per 100 parts by mass of resin were NaH2PO4 : 0.2 parts by mass and Na2HPO4 : 0.1 parts by mass.
  • Amount of phosphate in resin ((total amount of water - amount of water recovered by filtration)/total amount of water) x 100/12
  • Example 5 The same procedure as in Example 4 was carried out except that the total amount of water was 72 parts by mass, the inorganic metal phosphate NaH 2 PO 4 was 0.112 parts by mass, and the inorganic metal phosphate Na 2 HPO 4 was 0.075 parts by mass. After mixing, the mixture was filtered and the amount of water recovered was 42 parts by mass. The contents of the phosphates relative to 100 parts by mass of the resin were NaH 2 PO 4 : 0.4 part by mass and Na 2 HPO 4 : 0.3 part by mass.
  • Example 6 The same procedure as in Example 4 was carried out except that the total amount of water was 87 parts by mass, the inorganic metal phosphate NaH 2 PO 4 was 0.227 parts by mass, and the inorganic metal phosphate Na 2 HPO 4 was 0.153 parts by mass. After mixing, the mixture was filtered and the amount of water recovered was 57 parts by mass. The contents of the phosphates relative to 100 parts by mass of the resin were NaH 2 PO 4 : 0.7 parts by mass and Na 2 HPO 4 : 0.4 parts by mass.
  • Table 2 shows that the resin compositions obtained in Examples 4 to 6 have superior thermal stability compared to those containing no inorganic metal phosphate (resin produced in Comparative Example 3).

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette composition de résine contient : un polyéther aromatique (A) ayant une quantité radicalaire à 25°C de 6,5 × 10 15 -9,0 × 10 17 spin/g telle que mesurée avec une substance standard de TEMPOL et un solvant pour la substance standard du benzène; et un sel métallique de phosphate inorganique (B) en une quantité de 0,01 à 5,0 parties en masse par rapport à 100 parties en masse du polyéther aromatique (A).
PCT/JP2025/006129 2024-02-22 2025-02-21 Composition de résine, matériau composite, article moulé et procédé de production de composition de résine Pending WO2025178132A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018520257A (ja) * 2015-07-22 2018-07-26 アルケマ フランス ポリ（アリーレン−エーテル−ケトン）（ｐａｅｋ）から製造された組成物を安定化させる方法
WO2023008365A1 (fr) * 2021-07-30 2023-02-02 ポリプラスチックス株式会社 Composition de résine de poly éther cétone entièrement aromatique, procédé pour la production de celle-ci, article moulé et procédé pour l'amélioration de la stabilité de séjour de la viscosité à l'état fondu de ladite composition de résine
JP2023163884A (ja) * 2022-04-28 2023-11-10 出光興産株式会社 樹脂組成物及び樹脂組成物の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018520257A (ja) * 2015-07-22 2018-07-26 アルケマ フランス ポリ（アリーレン−エーテル−ケトン）（ｐａｅｋ）から製造された組成物を安定化させる方法
WO2023008365A1 (fr) * 2021-07-30 2023-02-02 ポリプラスチックス株式会社 Composition de résine de poly éther cétone entièrement aromatique, procédé pour la production de celle-ci, article moulé et procédé pour l'amélioration de la stabilité de séjour de la viscosité à l'état fondu de ladite composition de résine
JP2023163884A (ja) * 2022-04-28 2023-11-10 出光興産株式会社 樹脂組成物及び樹脂組成物の製造方法

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