Aromatic polyether, resin composition, composite material, molded body, and methods for producing same

Abstract

Provided is an aromatic polyether in which the radical concentration measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance is 6.5×1015 spin / g or more at 25 °C, and the diameter of spherulites is 0.001-30 μm.

Description

Aromatic polyether, resin composition, composite material, molded article, and methods for producing the same

[0001] The present invention relates to an aromatic polyether, a resin composition, a composite material, a molded article, and methods for producing them. Specifically, the present invention relates to an aromatic polyether and resin composition that can exhibit excellent interfacial adhesive strength to reinforcing fibers such as inorganic fillers and also have excellent toughness, a composite material and molded article that have excellent mechanical properties, and methods for producing them.

[0002] Aromatic polyethers have excellent heat resistance and mechanical strength, and are used as metal replacement materials due to these characteristics. In recent years, their applications have expanded to include automobiles, aircraft, and the medical field. Among them, polyether ether ketone (abbreviated as "PEEK"), a type of aromatic polyether, is known as a representative resin for engineering plastics (Patent Document 1).

[0003] Japanese Unexamined Patent Publication No. 59-93724

[0004] Aromatic polyethers are sometimes used in combination with fillers such as carbon fibers to produce fiber-reinforced plastics (FRPs). The inventors have conducted studies and found that conventional aromatic polyethers have room for further improvement in terms of improving the interfacial adhesive strength to the filler and the toughness.

[0005] Therefore, the present inventors conducted extensive research and found that aromatic polyethers with controlled higher-order structures (specifically, with micronized spherulites) can exhibit excellent interfacial adhesive strength to reinforcing fibers such as inorganic fillers and also have excellent toughness, and thus completed the present invention.

[0006] One object of the present invention is to provide an aromatic polyether and resin composition that can exhibit excellent interfacial adhesive strength to reinforcing fibers such as inorganic fillers and also has excellent toughness, a composite material and molded article that have excellent mechanical properties, and methods for producing the same.

[0007] According to the present invention, the following aromatic polyethers and the like are provided: 1. The amount of radicals measured at 25°C using TEMPOL as a standard substance and benzene as a solvent for the standard substance is 6.5 x 10 １５ 1. An aromatic polyether having a weight average molecular weight of 80,000 or more, and a spherulite diameter of 0.001 to 30 μm. 2. The aromatic polyether according to 1, having a weight average molecular weight of 80,000 or more. 3. The aromatic polyether according to 1 or 2, having a melt flow rate of 2.0 g / 10 min or less. 4. The aromatic polyether comprises an aromatic polyether and a nucleating agent, and the aromatic polyether has a radical amount of 6.5 x 10 at 25°C, measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance. １５ 4. A resin composition according to claim 3, wherein the spherulite diameter of the resin composition is 0.001 to 30 μm. 5. A resin composition according to claim 4, wherein the spherulite diameter of the resin composition is 0.001 to 30 μm. 6. A resin composition comprising an aromatic polyether, wherein the radical amount at 25°C measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance is 6.5 x 10 １５spin / g or more, and the diameter of the spherulites is 0.001 to 30 μm. 7. The resin composition according to 6, further comprising 0.001 to 10 parts by mass of a nucleating agent relative to 100 parts by mass of the aromatic polyether. 8. The resin composition according to 4, 5, or 7, wherein the nucleating agent is one or more selected from the group consisting of organic nucleating agents and inorganic nucleating agents. 9. A method for producing the aromatic polyether according to any one of 1 to 3, comprising reacting 4,4'-dichlorobenzophenone and hydroquinone in diphenyl sulfone with stirring in the presence of potassium carbonate, and terminating the reaction when the solution viscosity reaches 242 cP or more at 300°C after adding a reaction terminator. 10. A method for producing the resin composition according to any one of claims 4 to 8, comprising kneading 0.001 to 10 parts by mass of a nucleating agent with 100 parts by mass of an aromatic polyether obtained by reacting 4,4'-dichlorobenzophenone and hydroquinone in diphenyl sulfone in the presence of potassium carbonate. 11. A composite material comprising reinforcing fibers and one or more selected from the group consisting of the aromatic polyether according to any one of claims 1 to 3, the resin composition according to any one of claims 4 to 8, the aromatic polyether obtained by the production method according to claim 9, and the resin composition obtained by the production method according to claim 10. 12. The composite material according to claim 11, wherein the reinforcing fibers comprise one or more selected from the group consisting of carbon fibers, glass fibers, and aramid fibers. 13. A method for producing a composite material, comprising compounding reinforcing fibers with one or more selected from the group consisting of the aromatic polyether according to any one of claims 1 to 3, the resin composition according to any one of claims 4 to 8, the aromatic polyether obtained by the production method according to claim 9, and the resin composition obtained by the production method according to claim 10. 14. 15. A method for producing a composite material according to claim 13, wherein the reinforcing fibers comprise at least one selected from the group consisting of carbon fibers, glass fibers, and aramid fibers. 16. A molded article obtained by molding at least one selected from the group consisting of the aromatic polyether according to any one of claims 1 to 3, the resin composition according to any one of claims 4 to 8, the aromatic polyether obtained by the production method according to claim 9, and the resin composition obtained by the production method according to claim 10.

[0008] According to the present invention, it is possible to provide an aromatic polyether and resin composition that can exhibit excellent interfacial adhesive strength to reinforcing fibers such as inorganic fillers and also has excellent toughness, a composite material and molded article that have excellent mechanical properties, and methods for producing the same.

[0009] Fig. 1 is a scattering image obtained in measuring the diameter of spherulites in Example 1. Fig. 2 is a scattering image obtained in measuring the diameter of spherulites in Comparative Example 1.

[0010] The aromatic polyether, resin composition, composite material, molded article, and methods for producing them of the present invention will be described in detail below. In this specification, "x to y" represents a numerical range of "x or more and y or less." The upper and lower limits of the numerical ranges can be combined in any combination.

[0011] 1. Aromatic Polyether The aromatic polyether according to one embodiment of the present invention has a radical amount of 6.5 × 10 at 25°C, measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance. １５ spin / g or more, and the diameter of the spherulites is 0.001 to 30 μm.

[0012] The aromatic polyether according to this embodiment can exhibit excellent interfacial adhesive strength to 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 reason for such effects is not entirely clear, but it is believed that the amount of radicals in the aromatic polyether is 6.5 × 10 １５It is speculated that the high spin / g or more may cause interactions with the reinforcing fibers or the formation of chemical bonds. Furthermore, it is speculated that the diameter of the spherulites, which are one of the crystalline forms present in crystalline polymers, is 0.001 to 30 μm, so that when an external force is applied to the aromatic polyether, stress is dispersed among multiple spherulites, preventing fracture and improving toughness. Furthermore, it is thought that these factors act synergistically to significantly improve the physical properties of the aromatic polyether, and significantly improve the physical properties of composite materials and molded articles containing the aromatic polyether and reinforcing fibers. The toughness of the aromatic polyether can be evaluated, for example, by the breaking strain measured by the method described in the Examples.

[0013] As a result of extensive research by the applicant, it was found that the amount of radicals in aromatic polyethers contributes to adhesion to reinforcing fibers (see, for example, Japanese Patent Application No. 2023-053516). The present invention further focuses on the diameter of the spherulites, and has discovered that aromatic polyethers can exhibit excellent interfacial adhesive strength to reinforcing fibers and also have excellent toughness. While the reason for this effect is not entirely clear, it is speculated that the fine spherulite diameters of aromatic polyethers, ranging from 0.001 μm to 30 μm, increase the adhesive surface area at the spherulite interface with the reinforcing fibers, resulting in a significant interaction with the reinforcing fibers.

[0014] The radical amount of the aromatic polyether is a value measured by the method described in the Examples. The spherulite diameter of the aromatic polyether is a value measured by the method described in the Examples.

[0015] In this specification, unless otherwise specified, the "radical amount" of an aromatic polyether means the "radical amount per unit mass (unit: spin / g)" of the aromatic polyether. In this specification, unless otherwise specified, "TEMPOL" means "4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl."

[0016] In one embodiment, the radical content of the aromatic polyether is 6.5×10 １５spin / 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, 5.0×10 １６ spin / g or more, or 6.0 x 10 １６ spin / g or more, and 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 x 10 １７ spin / g or less.

[0017] In one embodiment, the radical content of the aromatic polyether is 6.5×10 １５ spin / g or more 9.0×10 １７ spin / g or less, 7.0×10 １５ spin / g or more 9.0×10 １７ spin / g or less, 8.0×10 １５ spin / g or more 5.0×10 １７ spin / g or less, 8.9×10 １５ spin / g or more 5.0×10 １７ spin / g or less, 1.0×10 １６ spin / g or more 4.0×10 １７ spin / g, 2.0×10 １６ spin / g or more 4.0×10 １７ spin / g, 3.0×10 １６ spin / g or more 3.7×10 １７ spin / g or less, 4.0×10 １６ spin / g or more 3.7×10 １７ spin / g or less, or 5.0 x 10 １６ spin / g or more 1.0×10 １７ spin / g or less.

[0018] The amount of radicals in the aromatic polyether is 6.5 × 10 １５ If the amount of radicals in the aromatic polyether is less than 9.0×10, it may be difficult to obtain the above-mentioned composite effect, and the interfacial shear strength with the reinforcing fiber may not be sufficient. １７ If the value exceeds spin / g, the thermal stability tends to be insufficient, and the molded article may not exhibit sufficient mechanical properties.

[0019] The amount of radicals in the aromatic polyether 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 a monomer when synthesizing (polymerizing) the aromatic polyether.

[0020] In this specification, the "diameter of a spherulite" of an aromatic polyether means twice the length of the spherulite radius of a spherulite contained in the aromatic polyether. A spherulite in this specification refers to a semi-crystal of an aromatic polyether solidified into a spherical shape.

[0021] In one embodiment, the diameter of the spherulites of the aromatic polyether is 0.001 μm or more, 0.005 μm or more, 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, 1 μm or more, or 5 μm or more, and 30 μm or less, 25 μm or less, 20 μm or less, or 15 μm or less. In one embodiment, the diameter of the spherulites of the aromatic polyether is 0.001 μm or more and 30 μm or less, 0.005 μm or more and 30 μm or less, 0.01 μm or more and 25 μm or less, 0.05 μm or more and 25 μm or less, 0.1 μm or more and 20 μm or less, 1 μm or more and 20 μm or less, or 5 μm or more and 15 μm or less. When the diameter of the spherulites of the aromatic polyether is within the above range, the effect of excellent toughness is likely to be obtained.

[0022] In one embodiment, the weight average molecular weight (Mw) of the aromatic polyether is 45,000 or more, 50,000 or more, 55,000 or more, 60,000 or more, 65,000 or more, 70,000 or more, 75,000 or more, 80,000 or more, 85,000 or more, 90,000 or more, 95,000 or more, or 100,000 or more, and 180,000 or less, 170,000 or less, or 150,000 or less.

[0023] From the viewpoint of mechanical properties, the weight average molecular weight (Mw) of the aromatic polyether is preferably 80,000 or more.

[0024] In one embodiment, the melt flow rate (MFR) of the aromatic polyether is 100 g / 10 min or less, 50 g / 10 min or less, 25 g / 10 min or less, 10 g / 10 min or less, 5.0 g / 10 min or less, 2.0 g / 10 min or less, 1.0 g / 10 min or less, 0.5 g / 10 min or less, or 0.1 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, 0.01 g / 10 min or more, or 0.1 g / 10 min or more. From the viewpoint of mechanical properties, the melt flow rate (MFR) of the aromatic polyether is preferably 0.001 g / 10 min or more and 2.0 g / 10 min or less, and more preferably 0.1 g / 10 min or more and 2.0 g / 10 min or less. The melt flow rate (MFR) of the aromatic polyether is a value measured by the method described in the examples.

[0025] In one embodiment, the aromatic polyether is a polyarylene ether ketone. In one embodiment, the aromatic polyether comprises one or more selected from the group consisting of polyether ether ketone (PEEK), polyether ketone ketone (PEKK), and polyether ketone (PEK). In one embodiment, the aromatic polyether comprises polyether ether ketone (PEEK).

[0026] In one embodiment, 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 is one or more selected from the group consisting of polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetherketone (PEK). In one embodiment, 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 is polyetheretherketone (PEEK). Note that "substantially 100% by mass" may contain inevitable impurities.

[0027] In one embodiment, the aromatic polyether contains a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

[0028] In one embodiment, the aromatic polyether comprises a structural unit represented by the following formula (3):

[0029] The structural unit represented by formula (3) is a bond between the structural unit represented by formula (1) and the structural unit represented by formula (2).

[0030] In one embodiment, the aromatic polyether does not contain any other structure other than the structural units represented by formula (1) and formula (2).

[0031] In one embodiment, the aromatic polyether contains a structure other than the structural units represented by formula (1) and formula (2) within a range that does not impair the effects of the present invention.

[0032] In one embodiment, 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 is a structural unit represented by formula (1) and a structural unit represented by formula (2), or a repeating unit represented by formula (3). Note that when it is "substantially 100% by mass", it may contain inevitable impurities.

[0033] In one embodiment, in the aromatic polyether, the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) (structural unit represented by formula (1) : structural unit 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 greater than, smaller than, or the same as the number of moles of the structural unit represented by formula (2).

[0034] The structural unit represented by formula (1) and the structural unit represented by formula (2) can be copolymerized within a range that does not impair the effects of the present invention.

[0035] In one embodiment, 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):

[0036] In one embodiment, the aromatic polyether can also be said to be a copolymer of a structural unit represented by formula (a) and one or more structural units selected from the group consisting of formulas (b) and (c).

[0037] In one embodiment, the copolymer is a random copolymer, an alternating copolymer, or a block copolymer, preferably a random copolymer.

[0038] In one embodiment, in the aromatic polyether, the substitution position (bonding position) of the phenyl group in the structural unit represented by formula (b) 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 substitute any of the four hydrogen atoms on the benzene ring).

[0039] When two or more structural units represented by formula (b) are adjacent in an aromatic polyether, 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):

[0040] In each of the structures represented by the formulas (b1) to (b3), the substitution positions of the phenyl groups in the two structural units represented by the formula (b) that form the structure are different from each other. The effects of the present invention are well exhibited in any of the structures.

[0041] Here, the case where two or more structural units represented by formula (b) are adjacent to each other has been described, but even when two or more structural units represented by formula (b) are arranged via other structural units (for example, structural units represented by formula (a)), the substitution positions of the phenyl groups in these structural units represented by formula (b) may be the same or different. In either case, the effects of the present invention are well exhibited.

[0042] In one embodiment, the aromatic polyether comprises 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 structural unit represented by formula (a) and the structural unit represented by formula (b). Note that "substantially 100% by mass" may contain inevitable impurities.

[0043] In one embodiment, the aromatic polyether has a molar ratio of the structural unit represented by formula (b) to the total amount of the structural unit represented by formula (a) and the structural unit represented by formula (b) of 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.

[0044] In one embodiment, the aromatic polyether comprises 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 structural unit represented by formula (a) and the structural unit represented by formula (c). Note that "substantially 100% by mass" may contain inevitable impurities.

[0045] In one embodiment, the aromatic polyether has a molar ratio of the structural unit represented by formula (c) to the total amount of the structural unit represented by formula (a) and the structural unit represented by formula (c) of 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 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.

[0046] 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 within a range that does not impair the effects of the present invention.

[0047] In one embodiment, the aromatic polyether includes 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 at 25 ° C., measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance. １５ ~9.0 x 10 １７ (spin / g).

[0048]

[0049] In one embodiment, the copolymer is a random copolymer, an alternating copolymer, or a block copolymer, preferably a random copolymer.

[0050] In one embodiment, the structural unit represented by formula (d) is a structural unit represented by formula (c).

[0051] 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.

[0052] In one embodiment, the aromatic polyether comprises 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. Note that "substantially 100% by mass" may contain inevitable impurities.

[0053] In one embodiment, the aromatic polyether has a molar ratio of the structural unit represented by formula (d) to the total amount of the structural unit represented by formula (a) and the structural unit represented by formula (d) of 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 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.

[0054] The terminal structure of the main chain of the aromatic polyether is not particularly limited. In one embodiment, a structural unit represented by formula (1) is disposed at one or more ends of the main chain of the aromatic polyether. In this case, 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). In one embodiment, a structural unit represented by formula (2) is disposed at one or more ends of the main chain of the aromatic polyether. In this case, 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 may be, for example, a structure in which the above-mentioned halogen atom or hydroxyl group is replaced with a hydrogen atom (H). The terminal structure may have a structure other than those exemplified above. For example, the terminal structure may have a structure derived from a reaction terminator.

[0055] 2. Method for Producing Aromatic Polyether A method for producing an aromatic polyether according to one aspect of the present invention will now be described. This method comprises reacting 4,4'-dichlorobenzophenone with hydroquinone in the presence of potassium carbonate in diphenyl sulfone, with the molar ratio of 4,4'-dichlorobenzophenone to hydroquinone being 0.990 to 1.025. This results in a radical amount of 6.5 x 10 １５ It is possible to obtain aromatic polyethers having a molecular weight of at least 10 ...

[0056] [4,4'-Dichlorobenzophenone] 4,4'-Dichlorobenzophenone is a monomer for polymerizing aromatic polyethers and corresponds to the structural unit represented by the above formula (1). 4,4'-Dichlorobenzophenone can be easily synthesized and is also commercially available.

[0057] [Hydroquinone] Hydroquinone is a monomer for polymerizing aromatic polyethers and corresponds to the structural unit represented by the above formula (2). Hydroquinone can be easily synthesized and is also commercially available.

[0058] [Potassium Carbonate] 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 also commercially available. Potassium carbonate may be of general-purpose reagent grade, general industrial grade, or fine particle grade. The average particle size (D ５０ The average particle size (D) is preferably 1000 μm or less, 800 μm or less, 500 μm or less, 300 μm or less, 100 μm or less, or even 50 μm or less. ５０ The lower limit of the average particle size (D ５０ ) is a value measured by the following method. ５０ Measurement method for particle size distribution] Using a CAMSIZER manufactured by Microtrac Bell Co., Ltd., particle size distribution is measured by a dry method. A sample (potassium carbonate) is dropped into the measurement section using a vibrating feeder, and the particles are photographed with a camera to measure the particle diameter. When processing the observed image, the average particle diameter (D ５０ ) is calculated.

[0059] In one embodiment, a method for producing an aromatic polyether includes reacting 4,4'-dichlorobenzophenone and hydroquinone in diphenyl sulfone in the presence of potassium carbonate by stirring, and terminating the reaction when the solution viscosity reaches 242 cP or more at 300°C after adding a reaction terminator. "Terminating the reaction" specifically refers to stopping the stirring and removing the resulting reaction product. The solution viscosity is measured using a process viscometer (XL7-951-HT2-d28-E58, manufactured by Hydramotion Japan Co., Ltd.). This allows the diameter of the spherulites contained in the aromatic polyether to be 0.001 to 30 μm.

[0060] The solution viscosity at the end of the reaction can be, for example, the value measured in real time with a process viscometer when 4,4'-dichlorobenzophenone and hydroquinone are reacted in diphenyl sulfone in the presence of potassium carbonate, a reaction terminator is added, and the solution viscosity reaches 242 cP or more. Note that the solution viscosity during the reaction may be less than 242 cP.

[0061] In one embodiment, the solution viscosity at the end of the reaction is 242 cP or more. A solution viscosity of 242 cP or more at the end of the reaction is preferred from the viewpoint of mechanical properties. In one embodiment, the solution viscosity at the end of the reaction is 450 cP or less. A solution viscosity of 450 cP or less at the end of the reaction is preferred from the viewpoint of moldability.

[0062] In one embodiment, after the addition of the reaction quenching agent, the mixture is stirred while maintaining the temperature before the addition of the reaction quenching agent. In one embodiment, after the addition of the reaction quenching agent, the mixture is stirred while decreasing the temperature from the temperature before the addition of the reaction quenching agent.

[0063] The solution viscosity at the end of the reaction can be adjusted by the temperature conditions of the raw material mixture (maximum temperature, temperature holding time, etc.) and the "reaction concentration" (defined below) of the raw material mixture. In this specification, the maximum temperature during the reaction is the maximum temperature that the reaction mixture reaches from the start of the reaction of the raw material mixture to the completion of the reaction. The "reaction concentration" is defined by the following formula based on the number of moles of OH groups [mol] calculated from the total amount (blended amount) of phenolic monomers (e.g., hydroquinone) to be reacted (blended into the reaction mixture): Reaction concentration [mol / kg] = number of moles of OH groups [mol] / mass of solvent [kg]

[0064] 3. Resin Composition A resin composition according to one aspect of the present invention (also referred to as a first resin composition) includes an aromatic polyether and a nucleating agent, and the aromatic polyether has a radical amount of 6.5 × 10 at 25°C, measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance. １５The spherulite diameter is 0.001 to 30 μm, and the content of the nucleating agent is 0.001 to 10 parts by mass relative to 100 parts by mass of the aromatic polyether.

[0065] The resin composition according to this embodiment can exhibit excellent interfacial adhesive strength to reinforcing fibers such as inorganic fillers, and also has excellent toughness. Furthermore, by using the composition in the production of composite materials and molded articles, composite materials and molded articles with excellent mechanical properties can be produced. The reason for such effects is not entirely clear, but it is believed that the amount of aromatic polyether radicals in the resin composition is 6.5 × 10 １５ It is speculated that the high nucleating agent content (spin / g or more) interacts with the reinforcing fibers or forms chemical bonds. It is also speculated that the inclusion of a nucleating agent reduces the diameter of the aromatic polyether spherulites in the resin composition (e.g., 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less), improving toughness. Furthermore, it is thought that these factors act synergistically to significantly improve the physical properties of composite materials and molded articles containing the resin composition and reinforcing fibers. The toughness of the resin composition can be evaluated, for example, by the breaking strain measured by the method described in the Examples.

[0066] In one embodiment, the diameter of the spherulites of the first resin composition is 0.001 to 30 μm. When the diameter of the spherulites of the resin composition is in this range, it is easy to exhibit excellent interfacial adhesive strength with the reinforcing fibers and to obtain the effect of excellent toughness. Although the reason for such effects is not necessarily clear, it is presumed that the spherulite diameter in the resin composition is as fine as 0.001 μm to 30 μm, which increases the adhesive area of ​​the spherulite interface with the reinforcing fibers and exerts a large interaction with the reinforcing fibers.

[0067] A resin composition according to another embodiment of the present invention (also referred to as a second resin composition) contains an aromatic polyether, and the resin composition has a radical amount of 6.5 × 10 at 25°C, measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance. １５The resin composition has a spherulite diameter of 0.001 to 30 μm.

[0068] The resin composition according to this embodiment can exhibit excellent interfacial adhesive strength to reinforcing fibers such as inorganic fillers, and also has excellent toughness. Furthermore, by using the composition in the production of composite materials and molded articles, composite materials and molded articles with excellent mechanical properties can be produced. The reason for such effects is not entirely clear, but the radical content of the resin composition is 6.5 × 10 １５ It is presumed that the high spherulite diameter of 0.001 to 30 μm increases the adhesive surface area of ​​the spherulite interface with the reinforcing fibers, resulting in a significant interaction with the reinforcing fibers. Furthermore, it is presumed that these factors act synergistically to significantly improve the physical properties of composite materials and molded articles containing the resin composition and reinforcing fibers.

[0069] In one embodiment, the radical amount of the second resin composition 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, or 4.0 x 10 １６ spin / g or more, 5.0×10 １６ spin / g or more, or 6.0 x 10 １６ spin / g or more, and 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 x 10 １７ spin / g or less.

[0070] In one embodiment, the radical amount of the second resin composition is 6.5×10１５ spin / g or more 9.0×10 １７ spin / g or less, 7.0×10 １５ spin / g or more 9.0×10 １７ spin / g or less, 8.0×10 １５ spin / g or more 5.0×10 １７ spin / g or less, 8.9×10 １５ spin / g or more 5.0×10 １７ spin / g or less, 1.0×10 １６ spin / g or more 4.0×10 １７ spin / g, 2.0×10 １６ spin / g or more 4.0×10 １７ spin / g, 3.0×10 １６ spin / g or more 3.7×10 １７ spin / g or less, 4.0×10 １６ spin / g or more 3.7×10 １７ spin / g or less, 5.0×10 １６ spin / g or more 1.0×10 １７ spin / g or less, or 6.0 x 10 １６ spin / g or more 1.0×10 １７ spin / g or less.

[0071] The radical amount of the resin composition is a value measured by the method described in the examples.

[0072] The resin composition according to an embodiment of the present invention (including the first resin composition and the second resin composition) contains an aromatic polyether. The aromatic polyether in the resin composition can be applied to the aromatic polyether according to an embodiment of the present invention.

[0073] From the viewpoint of mechanical properties, the weight average molecular weight (Mw) of the aromatic polyether in the resin composition is preferably 45,000 or more, and more preferably 80,000 or more. The weight average molecular weight (Mw) of the aromatic polyether in the first resin composition is preferably 45,000 or more. The weight average molecular weight (Mw) of the aromatic polyether in the second resin composition is preferably 80,000 or more.

[0074] From the viewpoint of mechanical properties, the melt flow rate (MFR) of the aromatic polyether in the resin composition is preferably 0.001 g / 10 min or more and 50 g / 10 min or less, or 0.4 g / 10 min or more and 100 g / 10 min or less.

[0075] [Nucleating Agent] The first resin composition according to one aspect of the present invention includes a nucleating agent. In one embodiment, the second resin composition according to one aspect of the present invention includes a nucleating agent.

[0076] The nucleating agent may include one or more selected from the group consisting of organic nucleating agents and inorganic nucleating agents.

[0077] Examples of organic nucleating agents include aliphatic monocarboxylic acids, metal salts of aliphatic monocarboxylic acids, and metal phosphate salts. Examples of aliphatic monocarboxylic acids include tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid, tricosylic acid, and lignoceric acid. Examples of metals in metal salts of aliphatic monocarboxylic acids include lithium, sodium, magnesium, aluminum, calcium, gallium, strondium, and indium. Examples of metals in phosphate metal salts include lithium, sodium, magnesium, aluminum, calcium, gallium, strondium, and indium. Examples of phosphate acids include phosphorus-containing oxo acids. Examples of phosphate metal salts include phosphate ester metal salts. Examples of the phosphate metal salt include 2,4,8,10-Tetra(tert-butyl)-6-hydroxy-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxide, sodium salt (available as "ADK STAB NA-11" manufactured by ADEKA Corporation), (Hydroxy aluminum bis(2,4,8,10-tetra-trans-butyl-6-hydroxy-12H-dibenzo[d,g][1.3.2]dioxaphosphocin-6-oxide)) (available as "ADK STAB NA-21" manufactured by ADEKA Corporation), and the like. These organic nucleating agents may be used alone or in combination of two or more.

[0078] Examples of inorganic nucleating agents include talc, clay, mica, silica, dolomite powder, quartz powder, diatomaceous earth, etc. These inorganic nucleating agents may be used alone or in combination of two or more.

[0079] The content of the nucleating agent is 0.001 to 10 parts by mass relative to 100 parts by mass of the aromatic polyether.

[0080] In one embodiment, the content of the nucleating agent is 0.002 parts by mass or more, 0.005 parts by mass or more, 0.01 parts by mass or more, 0.02 parts by mass or more, 0.05 parts by mass or more, 0.1 parts by mass or more, 0.2 parts by mass or more, 0.5 parts by mass or more, or 1.0 part by mass or more, relative to 100 parts by mass of the aromatic polyether. When the content of the nucleating agent is 0.002 parts by mass or more, relative to 100 parts by mass of the aromatic polyether, the amount of nuclei present in the resin composition increases, and the number of crystal growth starting points increases, which is desirable.

[0081] In one embodiment, the content of the nucleating agent is 10 parts by mass or less, 9.0 parts by mass or less, 8.0 parts by mass or less, 7.0 parts by mass or less, 6.0 parts by mass or less, 5.0 parts by mass or less, 4.0 parts by mass or less, 3.0 parts by mass or less, or 2.0 parts by mass or less, relative to 100 parts by mass of the aromatic polyether. If the content of the nucleating agent is 2.0 parts by mass or less, relative to 100 parts by mass of the aromatic polyether, it is desirable because it is less likely to become saturated. Here, saturated state means a state in which the nucleating agent is saturated and crystal growth does not begin within the resin composition.

[0082] In one embodiment, the content of the nucleating agent is, relative to 100 parts by weight of the aromatic polyether, 0.002 parts by weight to 10 parts by weight, 0.005 parts by weight to 9.0 parts by weight, 0.01 parts by weight to 8.0 parts by weight, 0.02 parts by weight to 7.0 parts by weight, 0.05 parts by weight to 6.0 parts by weight, 0.1 parts by weight to 5.0 parts by weight, 0.2 parts by weight to 4.0 parts by weight, 0.2 parts by weight to 3.0 parts by weight, 0.2 parts by weight to 2.0 parts by weight, 0.5 parts by weight to 3.0 parts by weight, 0.5 parts by weight to 2.0 parts by weight, or 1.0 parts by weight to 2.0 parts by weight.

[0083] The resin composition may contain other components that do not fall under the category of aromatic polyether and nucleating agent. The other components are not particularly limited, and examples include other resins that are not aromatic polyethers, antioxidants, etc. Examples of the other resins include fluororesins such as polytetrafluoroethylene. Other examples of the other resins include amorphous resins. The amorphous resin is an amorphous thermoplastic resin having a glass transition temperature of 180°C or higher. A glass transition temperature of 180°C or higher can provide excellent heat resistance. Specific examples include polyetherimide (PEI), polyethersulfone (PES), polyphenylene ether (PPE), polysulfone (PSU), polyimide (PI), etc. Among these, PEI is preferred from the viewpoints of toughness, heat resistance, and moldability. Examples of antioxidants include phosphate compounds, phenolic compounds, amine compounds, and sulfur-based compounds. As the other components, one type may be used alone, or two or more types may be used in combination.

[0084] Examples of the phosphoric acid compound include triphenyl phosphite (available as "JP-360" manufactured by Johoku Chemical Industry Co., Ltd.), trisnonylphenyl phosphite (available as "JP-351" manufactured by Johoku Chemical Industry Co., Ltd.), tricresyl phosphite (available as "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd.), tris(2-ethylhexyl) phosphite (available as "JP-308E" or "JPE-308E" manufactured by Johoku Chemical Industry Co., Ltd.), tridecyl phosphite (available as "JP-310" manufactured by Johoku Chemical Industry Co., Ltd.), trilauryl phosphite (available as "JP-312L" manufactured by Johoku Chemical Industry Co., Ltd.), and tris(tridecyl) phosphite (available as "JP-3" manufactured by Johoku Chemical Industry Co., Ltd.). 33E"), diphenyl mono(2-ethylhexyl) phosphite (available from Johoku Chemical Industry Co., Ltd. as "JPM-308"), diphenyl monodecyl phosphite (available from Johoku Chemical Industry Co., Ltd. as "JPM-311"), diphenyl mono(tridecyl) phosphite (available from Johoku Chemical Industry Co., Ltd. as "JPM-313"), tetraphenyl dipropylene glycol diphosphite (available from Johoku Chemical Industry Co., Ltd. as "JPP-100"), tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite (available from Johoku Chemical Industry Co., Ltd. as "JA-805"), 4,4'-butylidenebis(3-methyl-6-t-butylphenyl ditridecyl phosphite) (available as "JPH-1200" manufactured by Johoku Chemical Industry Co., Ltd.), a mixture of bis(tridecyl)pentaerythritol diphosphite and bis(nonylphenyl)pentaerythritol diphosphite (available as "JPP-88" manufactured by Johoku Chemical Industry Co., Ltd.), bis(decyl)pentaerythritol diphosphite (available as "JPE-10" manufactured by Johoku Chemical Industry Co., Ltd.), bis(tridecyl)pentaerythritol diphosphite (available as "JPE-13R" manufactured by Johoku Chemical Industry Co., Ltd.), tristearyl phosphite (available as "JPE-318E" manufactured by Johoku Chemical Industry Co., Ltd.), distearyl pentaerythritol diphosphite (available as "JPP-2000PT" manufactured by Johoku Chemical Industry Co., Ltd.), tris(2,4-di-tert-butylphenyl) phosphite (available from Johoku Chemical Industry Co., Ltd. as "JP-650"), hydrogenated bisphenol A pentaerythritol phosphite polymer (available from Johoku Chemical Industry Co., Ltd. as "JPH-3800"), diethyl (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate (available from Johoku Chemical Industry Co., Ltd. as "JC-356"), 3,9-Bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-dip phosphaspiro[5.5]undecane (available as "ADK STAB PEP-8" manufactured by ADEKA Corporation), 3,9-Bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphospiro[5.5]undecane (available as "ADK STAB PEP-36" manufactured by ADEKA Corporation), 2,2'-Methylenebis(4,6-di-tert-butylphenyl) 2-ethylhexyl phosphate (available as "ADK STAB HP-10" manufactured by ADEKA Corporation), Tris(2,4-ditert-butylphenyl) phosphate (available as "ADK STAB 2112" / "ADK STAB 2112RG" manufactured by ADEKA Corporation), Tris(nonylphenyl) phosphate (available as "ADK STAB 1178" manufactured by ADEKA Corporation), Tetra-C12-15-alkyl(propane-2,2-diylbis(4,1-phenylene)) Bis(phosphate) (available as "ADK STAB 1500" manufactured by ADEKA Corporation), 2-Ethylhexyl diphenyl phosphate (available as "ADK STAB 135A" manufactured by ADEKA Corporation), Triisodecyl phosphate (available as "ADK STAB 3010" manufactured by ADEKA Corporation), Triphenyl phosphate (available as "ADK STAB TPP" manufactured by ADEKA Corporation), 2-Ethylhexyl diphenyl phosphate (available as "ADK STAB C" manufactured by ADEKA Corporation), Bis-(2,4-di-tert-butyl-phenyl)-phosphiterythritol diphosphate (available as "Ultranox 626" manufactured by SI Corporation) and the like.

[0085] Examples of phenol compounds include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (available as "ADEKA STAB AO-20" manufactured by ADEKA Corporation), 4,4',4''-(1-methylpropanol), l-3-ylidene)tris(6-tert-butyl-m-cresol) (available as "ADK STAB AO-30" manufactured by ADEKA Corporation), 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol (available as "ADK STAB AO-40" manufactured by ADEKA Corporation), Octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (available as "ADK STAB AO-50" manufactured by ADEKA Corporation), Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (available from ADEKA Corporation as "ADK STAB AO-60"), 3,9-Bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane (available from ADEKA Corporation as "ADK STAB AO-80"), 1,3,5-tris(3,5-di-tert-butyl)propionate, tyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene (available as "ADK STAB AO-330" manufactured by ADEKA Corporation), styrenated phenol (available as "NOCRAC SP, SP-N" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol) (available as "NOCRAC NS-5" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) (available as "NOCRAC NS-6" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), 4,Examples of such an ester include 4'-butylidenebis(6-tert-butyl-m-cresol) (available as "Nocrac NS-30" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), 4,4'-thiobis(3-methyl-6-tert-butylphenol) (available as "Nocrac 300" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), a butylated reaction product of p-cresol and dicyclopentadiene (available as "Nocrac PBK" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), 2,5-di-tert-butylhydroquinone (available as "Nocrac NS-7" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), and 2,6-di-tert-butyl-4-methylphenol (available as "Nocrac 200 Crystal" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.).

[0086] Examples of the amine compound include a reaction product of diphenylamine and acetone (available as "Nocrac B, B-N" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), N-phenyl-1-naphthylamine (available as "Nocrac PA" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), alkylated diphenylamine (available as "Nocrac ODA, ODA-N" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), octylated diphenylamine (available as "Nocrac AD-F" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (available as "Nocrac CD" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), p-(p-toluenesulfonylamido)diphenylamine (available as "Nocrac TD" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), and N,N'-di-2-naphthyl-p-phenylenediamine (available as "Nocrac White" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.). available as "Nocrac 810-NA" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), N-isopropyl-N'-p-phenylenediamine (available as "Nocrac 810-NA" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (available as "Nocrac 6C" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), N-(3-methacryloyloxy-2-hydroxypropyl)-N'-phenyl-p-phenylenediamine (available as "Nocrac 6C" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), Nocrac G-1), 2,2,4-trimethyl-1,2-dihydroquinoline polymer (available as Nocrac 224 (224-S) manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline (available as Nocrac AW, AW-N manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate (available as "ADK STAB LA-57" manufactured by ADEKA Corporation), Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate (available as "ADK STAB LA-52" manufactured by ADEKA Corporation), 1,2,3,4-Butanetetracarboxylic acid,tetramethyl ester, reaction products with 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β', β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-dieth anol (available as “ADEKA STAB LA-63P” manufactured by ADEKA Co., Ltd.), 1,2,3,4-Butanetetracarboxylic acid, tetramethyl ester, reaction products with 2,2,6,6-tetramethyl-4-piperidinol and β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol (available as "ADK STAB LA-68" manufactured by ADEKA Corporation), Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (available as "ADK STAB LA-72" manufactured by ADEKA Corporation), Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (available as "ADK STAB LA-72" manufactured by ADEKA Corporation), (ethyl-4-piperidyl) sebacate (available from ADEKA Corporation as "ADK STAB LA-77Y" / "ADK STAB LA-77G"), Bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (available from ADEKA Corporation as "ADK STAB LA-81"), 1,2,2,6,6-Pentamethyl-4-piperidyl Examples of such methacrylate include 2,2,6,6-tetramethyl-4-piperidyl methacrylate (available as "ADK STAB LA-82" manufactured by ADEKA Corporation), 2,2,6,6-tetramethyl-4-piperidyl methacrylate (available as "ADK STAB LA-87" manufactured by ADEKA Corporation), 2,2,6,6-tetramethylpiperidin-4-yl hexadecanoate, and 2,2,6,6-tetramethylpiperidin-4-yl octadecanoate (available as "ADK STAB LA-40MP" or "ADK STAB LA-40Si" manufactured by ADEKA Corporation).

[0087] Examples of sulfur-based compounds include 2-mercaptobenzimidazole (available as "Nocrac MB" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), 2-mercaptomethylbenzimidazole (available as "Nocrac MMB" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), zinc salt of 2-mercaptobenzimidazole (available as "Nocrac MBZ" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), nickel dibutyldithiocarbamate (available as "Nocrac NBC-P (NBC)" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), dilauryl thiodipropionate (available as "Nocrac 400" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), 2,2-Bis{"3-(dodecylthio)-1-oxopropoxy"methyl}propane-1,3-diyl Examples of the sulfur-based compound include bis(3-(dodecylthio)propionate) (available as "ADK STAB AO-412S" manufactured by ADEKA Corporation) and di(tridecyl) 3,3'-thiodipropionate (available as "ADK STAB AO-503" manufactured by ADEKA Corporation). In one embodiment, the sulfur-based compound used is a compound that is not a diphenyl sulfone or a diaryl sulfone.

[0088] In one embodiment, the resin composition comprises 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 and the nucleating agent. Note that "substantially 100% by mass" may contain inevitable impurities.

[0089] The contents of each component in the resin composition explained above can also be applied to the blending amounts of each component when preparing the aromatic polyether.

[0090] The radical amount of the aromatic polyether explained above can also be applied to the radical amount of the aromatic polyether during preparation of the resin composition (immediately before kneading with the nucleating agent, etc.).

[0091] Furthermore, the radical amount of the aromatic polyether described above can also be applied to the radical amount per unit mass of the resin composition. In other words, in one embodiment, the first resin composition has a radical amount of 6.5 × 10 at 25°C, measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance. １５ ~9.0 x 10 １７ spin / g.

[0092] 4. Method for Producing Resin Composition A method for producing the resin composition according to one aspect of the present invention described above will be described. This method comprises kneading 0.001 to 10 parts by mass of the nucleating agent with 100 parts by mass of an aromatic polyether obtained by reacting 4,4'-dichlorobenzophenone and hydroquinone in diphenyl sulfone in the presence of potassium carbonate. This results in a resin composition containing the aromatic polyether and the nucleating agent, with a radical content of the aromatic polyether of 6.5 x 10 １５ spin / g or more, the diameter of the spherulites is 0.001 to 30 μm, and the content of the nucleating agent is 0.001 to 10 parts by mass per 100 parts by mass of the aromatic polyether; or a resin composition containing an aromatic polyether, the amount of radicals at 25°C measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance is 6.5 × 10 １５ It is possible to obtain a resin composition having a spherulite diameter of 0.001 to 30 μm.

[0093] The aromatic polyether in the method for producing a resin composition can be prepared according to the same method described above for the aromatic polyether according to an embodiment of the present invention. The 4,4'-dichlorobenzophenone, hydroquinone, potassium carbonate, and various reaction conditions can be prepared according to the same method described above for the aromatic polyether according to an embodiment of the present invention. The nucleating agent can be prepared according to the same method described above for the resin composition according to an embodiment of the present invention.

[0094] In one embodiment, the amount of the nucleating agent to be kneaded is 0.002 parts by mass or more, 0.005 parts by mass or more, 0.01 parts by mass or more, 0.02 parts by mass or more, 0.05 parts by mass or more, 0.1 parts by mass or more, 0.2 parts by mass or more, 0.5 parts by mass or more, or 1.0 parts by mass or more, relative to 100 parts by mass of the aromatic polyether. Also, in one embodiment, the amount of the nucleating agent to be kneaded is 10 parts by mass or less, 9.0 parts by mass or less, 8.0 parts by mass or less, 7.0 parts by mass or less, 6.0 parts by mass or less, 5.0 parts by mass or less, 4.0 parts by mass or less, 3.0 parts by mass or less, or 2.0 parts by mass or less, relative to 100 parts by mass of the aromatic polyether.

[0095] In one embodiment, the amount of the nucleating agent to be kneaded is, relative to 100 parts by weight of the aromatic polyether, 0.002 parts by weight to 10 parts by weight, 0.005 parts by weight to 9.0 parts by weight, 0.01 parts by weight to 8.0 parts by weight, 0.02 parts by weight to 7.0 parts by weight, 0.05 parts by weight to 6.0 parts by weight, 0.1 parts by weight to 5.0 parts by weight, 0.2 parts by weight to 4.0 parts by weight, 0.2 parts by weight to 3.0 parts by weight, 0.2 parts by weight to 2.0 parts by weight, 0.5 parts by weight to 3.0 parts by weight, 0.5 parts by weight to 2.0 parts by weight, or 1.0 parts by weight to 2.0 parts by weight.

[0096] The method for kneading the nucleating agent is not particularly limited, and examples thereof include melt kneading using an extruder or the like. The nucleating agent may be side-fed into the aromatic polyether using a twin-screw kneader. In one embodiment, the nucleating agent is kneaded into the molten aromatic polyether.

[0097] 5. Composite Material A composite material according to one aspect of the present invention comprises one or more selected from the group consisting of (i) the aromatic polyether according to one aspect of the present invention, (ii) the resin composition according to one aspect of the present invention, (iii) the aromatic polyether obtained by the method for producing an aromatic polyether according to one aspect of the present invention, and (iv) the resin composition obtained by the method for producing a resin composition according to one aspect of the present invention, and reinforcing fibers.

[0098] According to the composite material of this embodiment, a composite material having excellent mechanical properties can be obtained. The reason why such an effect is obtained is not entirely clear, but it is believed that the amount of radicals in the aromatic polyether (or the aromatic polyether in the resin composition) is 6.5 × 10 １５ It is speculated that the high spin / g or more interacts with the reinforcing fibers and forms chemical bonds. It is speculated that the small diameter of the aromatic polyether spherulites (e.g., 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less, or 0.001 to 30 μm) improves toughness. Furthermore, it is thought that these factors act synergistically to significantly improve the physical properties of the composite material. The mechanical properties of the composite material can be evaluated, for example, by the maximum tensile strength measured by the method described in the Examples.

[0099] The aromatic polyether, resin composition, method for producing an aromatic polyether, and method for producing a resin composition according to one aspect of the present invention can be applied to the matters described in each aspect.

[0100] [Reinforcing Fiber] The composite material according to one aspect of the present invention contains reinforcing fiber.

[0101] Examples of reinforcing fibers include carbon fibers, glass fibers, and aramid fibers. These reinforcing fibers may be used alone or in combination of two or more.

[0102] The content of the reinforcing fibers in the composite material is not particularly limited. In one embodiment, the content of the reinforcing fibers is 0.01 parts by mass or more, 0.1 parts by mass or more, 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, or 30 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 aromatic polyether or resin composition. When the content of the reinforcing fibers is 0.01 parts by mass or more, the reinforcing effect of the reinforcing fibers is more easily obtained, and when it is 500 parts by mass or less, the suitability for kneading and molding the composite material is more easily improved.

[0103] In one embodiment, the average fiber length of the reinforcing fibers in the composite material is 5 mm or more. When the average fiber length of the reinforcing fibers is 5 mm or more, the fibers are also called "continuous fibers." The average fiber length is determined by the arithmetic mean of values ​​measured with a vernier caliper.

[0104] In one embodiment, the average fiber diameter of the reinforcing fibers is 1 to 30 μm. From the viewpoints of dispersibility of the reinforcing fibers in the aromatic polyether resin composition and the surface smoothness and mechanical properties of the molded body described below, the average fiber diameter of the reinforcing fibers is preferably 3 to 25 μm, 6 to 20 μm, or even 6 to 13 μm. The average fiber diameter of the reinforcing fibers is determined as the arithmetic mean of values ​​measured in accordance with JIS R 7607:2000.

[0105] In one embodiment, 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 is one or more types selected from the group consisting of carbon fiber, glass fiber, and aramid fiber. Note that when it is "substantially 100% by mass", it may contain inevitable impurities.

[0106] In one embodiment, the carbon fiber comprises one or more selected from the group consisting of PAN-based carbon fiber, pitch-based carbon fiber, thermosetting carbon fiber, phenol-based carbon fiber, vapor-grown carbon fiber, and recycled carbon fiber (RCF). In one embodiment, 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 fiber is one or more selected from the group consisting of PAN-based carbon fiber, pitch-based carbon fiber, thermosetting carbon fiber, phenol-based carbon fiber, vapor-grown carbon fiber, and recycled carbon fiber (RCF). Note that "substantially 100% by mass" may contain inevitable impurities.

[0107] The carbon fibers may be treated with a sizing agent. The sizing agent can bind the reinforcing fibers into a bundle. Reinforcing fibers treated with a sizing agent have the sizing agent adhered to their surfaces. The sizing agent is not particularly limited, and examples include epoxy-based sizing agents, urethane-based sizing agents, and polyamide-based sizing agents. Aromatic polyethers can also be used as the sizing agent. These sizing agents may be used alone or in combination of two or more. Reinforcing fibers that have not been treated with a sizing agent may also be used. The sizing agent may be used in combination with a silane coupling agent such as aminosilane, isocyanate silane, or acrylic silane.

[0108] The type of glass fiber is not particularly limited, and glass fibers of various compositions such as E-glass, low dielectric glass, silica glass, etc. can be selected and used depending on the purpose and application. The average fiber diameter of the glass fiber is preferably 5 to 20 μm, more preferably 7 to 17 μm, and the glass fiber is preferably a single fiber.

[0109] The glass fibers may also be treated with a sizing agent. The sizing agent can bind the glass fibers into bundles. The glass fibers treated with a sizing agent have the sizing agent adhered to their surfaces. The sizing agent is not particularly limited, and examples thereof 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 sizing agent may be used in combination with a silane coupling agent such as aminosilane, isocyanate silane, or acrylic silane.

[0110] The composite material may contain other components that do not fall under the category of aromatic polyether or resin composition and reinforcing fibers. The other components are not particularly limited, and examples thereof include other resins that are not aromatic polyethers. Examples of other resins include fluororesins such as polytetrafluoroethylene. One type of other component may be used alone, or two or more types may be used in combination.

[0111] In one embodiment, 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, 100% by mass or less, 99.9% by mass or less, or substantially 100% by mass of the composite material is an aromatic polyether or resin composition and reinforcing fibers, or an aromatic polyether or resin composition, reinforcing fibers, and the other components described above. Note that when it is "substantially 100% by mass", it may contain inevitable impurities.

[0112] In one embodiment, the reinforcing fibers are in the form of one or more selected from the group consisting of chopped strands, woven fabrics, nonwoven fabrics, and unidirectional materials (also referred to as "UD materials"), which further improves the strength of the composite material.

[0113] In one embodiment, the composite material may be a fiber composite material comprising an aromatic polyether or resin composition as a matrix and reinforcing fibers, which may be a so-called fiber reinforced thermoplastic (FRTP).

[0114] 6. Method for Producing Composite Material A method for producing the composite material according to one aspect of the present invention will now be described. This method includes compounding one or more selected from the group consisting of (i) the aromatic polyether according to one aspect of the present invention, (ii) the resin composition according to one aspect of the present invention, (iii) the aromatic polyether obtained by the method for producing an aromatic polyether according to one aspect of the present invention, and (iv) the resin composition obtained by the method for producing a resin composition according to one aspect of the present invention with reinforcing fibers. This allows for the production of a composite material containing reinforcing fibers and one or more selected from the group consisting of (i) the aromatic polyether according to one aspect of the present invention, (ii) the resin composition according to one aspect of the present invention, (iii) the aromatic polyether obtained by the method for producing an aromatic polyether according to one aspect of the present invention, and (iv) the resin composition obtained by the method for producing a resin composition according to one aspect of the present invention.

[0115] The aromatic polyether, resin composition, method for producing the aromatic polyether, and method for producing the resin composition according to an embodiment of the present invention can be applied to the aromatic polyether, resin composition, method for producing the aromatic polyether, and method for producing the resin composition according to an embodiment of the present invention. The reinforcing fibers can be applied to the composite material according to an embodiment of the present invention.

[0116] The method for producing the composite material (composite method) is not particularly limited. For example, a method of melt-kneading an aromatic polyether or resin composition with reinforcing fibers, or a method of melting and impregnating an aggregate of reinforcing fibers with one or more forms of an aromatic polyether or resin composition selected from the group consisting of powder, film, and pellets, can be used. A twin-screw kneader may be used to side-feed the reinforcing fibers into the aromatic polyether or resin composition. The aggregate of reinforcing fibers may be in one or more forms selected from the group consisting of, for example, a woven fabric, a nonwoven fabric, and a unidirectional material (also called a "UD material"). In these forms, the average fiber length of the reinforcing fibers may be 5 mm or more. That is, the reinforcing fibers may be continuous fibers.

[0117] Pellets of the composite material may be produced. The pellets can be used as a raw material for producing a molded article, which will be described later. In one embodiment, the method for producing pellets includes cutting reinforcing fibers short to form chopped strands, and then adding an aromatic polyether or resin composition to the reinforcing fibers. Pellets (also referred to as "short fiber pellets") can be produced by mixing the short fibers and the aromatic polyether or resin composition and granulating them. In one embodiment, the method for producing pellets involves immersing a roving of reinforcing fibers in a molten aromatic polyether or resin composition, pultrusion molding the mixture, and then cutting the roving into a desired pellet length to produce pellets (also referred to as "long fiber pellets"). When long fiber pellets are produced as described above, breakage of the reinforcing fibers can be suppressed.

[0118] 7. Molded Article and Manufacturing Method Thereof A molded article according to an aspect of the present invention is manufactured using one or more selected from the group consisting of (i) the aromatic polyether according to an aspect of the present invention, (ii) the resin composition according to an aspect of the present invention, (iii) the aromatic polyether obtained by the method for manufacturing an aromatic polyether according to an aspect of the present invention, and (iv) the resin composition obtained by the method for manufacturing a resin composition according to an aspect of the present invention.

[0119] The molded article according to this embodiment has the effect of providing excellent mechanical properties. The reason for this effect is not entirely clear, but it is believed that the amount of radicals in the aromatic polyether (or the aromatic polyether in the resin composition) is 6.5 × 10 １５ It is speculated that the high spin / g or more interacts with the reinforcing fibers and forms chemical bonds. It is speculated that the small diameter of the aromatic polyether spherulites (e.g., 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less, or 0.001 to 30 μm) improves toughness. Furthermore, it is thought that these factors act synergistically to significantly improve the physical properties of the molded body.

[0120] The aromatic polyether, resin composition, method for producing an aromatic polyether, and method for producing a resin composition according to one aspect of the present invention can be applied to the matters described in each aspect.

[0121] The molded article according to one aspect of the present invention may contain reinforcing fibers. The reinforcing fibers are applicable to the matters described in the composite material according to one aspect of the present invention.

[0122] In one embodiment, 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, 100% by mass or less, 99.9% by mass or less, or substantially 100% by mass of the molded article is an aromatic polyether or resin composition, an aromatic polyether or resin composition and reinforcing fibers, or an aromatic polyether or resin composition, reinforcing fibers, and the other components described above. Note that when it is "substantially 100% by mass", it may contain inevitable impurities.

[0123] The shape of the molded article according to one aspect and another aspect of the present invention is not particularly limited. In one embodiment, the molded article is an injection molded article, an extrusion molded article, or a compression molded article.

[0124] The method for producing the molded article according to one embodiment of the present invention is not particularly limited. For example, a molded article can be produced by molding the 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, using known methods such as cold pressing and hot pressing. Furthermore, the composite material can be used as a resin composite material for a 3D printer and molded using a 3D printer.

[0125] The applications of the aromatic polyether, resin composition, composite material, and molded article of the present invention are not particularly limited, and can be widely applied to various applications requiring toughness, for example. The composition of the present invention is suitable, for example, as a metal replacement material, particularly for applications requiring heat resistance, solvent resistance, and durability. More specifically, it is suitable for, for example, bearings, gaskets, gears, structural materials, automotive parts, battery-related parts, semiconductor manufacturing parts, aircraft structural members, medical instruments, etc.

[0126] The present invention will be explained in more detail below by showing examples, but the scope of the present invention is not limited to the descriptions of these examples in any way.

[0127] (Production Example 1) 1. Synthesis of Aromatic Polyether Nitrogen gas was circulated through a 240 L reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a water collection container connected to a cooling tube. 132.47 kg of diphenyl sulfone (manufactured by Sino-High Corporation) was added stepwise, and the temperature was raised to 160°C. Once melting was confirmed, 39.00 kg (155 mol) of 4,4'-dichlorobenzophenone (manufactured by Sino-High Corporation), 16.85 kg (153 mol) of hydroquinone, and 21.78 kg (158 mol) of potassium carbonate (AGC Corporation, fine powder) were added in that order. The reaction concentration at this time was 2.31 mol / kg.

[0128] The reaction mixture was reacted under the following temperature control, and then 6.15 kg (25 moles) of 4,4'-dichlorobenzophenone was added as a reaction terminator. <Temperature control> (1) At a stirring speed of 100 rpm, the temperature was raised from 160°C to 200°C over 90 minutes. (2) The temperature was maintained at 200°C for 60 minutes. (3) The temperature was raised from 200°C to 250°C over 80 minutes. (4) The temperature was maintained at 250°C for 60 minutes. (5) The temperature was raised from 250°C to 300°C over 150 minutes. (6) The temperature was maintained at 300°C for 300 minutes. (7) The reaction terminator was added, and the temperature was maintained at 300°C. The reaction was terminated when the solution viscosity reached 177 cP.

[0129] After the reaction was completed, the contents were transferred to a SUS tray, cooled to room temperature, and solidified. The product was coarsely pulverized and pulverized in a pin mill (160UPZ, manufactured by Hosokawa Micron Corporation), washed with acetone, an aqueous oxalic acid solution, and water in that order, and then vacuum dried to obtain a powdery aromatic polyether.

[0130] 2. Evaluation The weight average molecular weight (Mw) and melt flow rate (MFR) of the aromatic polyether were evaluated by the following methods. The results are shown in Table 1.

[0131] (1) Weight-Average Molecular Weight (Mw) The weight-average molecular weight (Mw) of the aromatic polyether was measured by GPC (gel permeation chromatography) under the following conditions and procedures.

[0132] [GPC measurement conditions] GPC apparatus: HLC-8420GPC (manufactured by Tosoh Corporation) GPC column: TSK gel guard column H-H (4.6 mm I.D. x 35 mm) and two TSK gel Super HM-M (6 mm I.D. x 150 mm) in series in this order Solvent: PFP / CHCl ３ Mixed solvent Temperature: 40°C Flow rate: 0.6 mL / min Injection flow rate: 20 μL Calibration curve: Calibration using PS standard

[0133] [Procedure] Aromatic polyether was dissolved in pentafluorophenol (PFP), and the GPC distribution was measured under the above measurement conditions. In the obtained GPC distribution, the object to be analyzed was selected from the group consisting of polyethers with a horizontal axis of LogM of 10 ６ The weight average molecular weight (Mw) was calculated from a calibration curve using a polystyrene (PS) standard, assuming that the main peak appeared in the following range:

[0134] (2) Melt Flow Rate (MFR) The melt flow rate (MFR: g / 10 min) of the aromatic polyether was measured using a melt indexer (L-220, manufactured by Tateyama Scientific High-Technologies Co., Ltd.) in accordance with JIS K 7210-1:2014 (ISO 1133-1:2011) under the following measurement conditions. [Measurement Conditions] Measurement temperature (resin temperature): 380 ° C. Measurement load: 2.16 kg Cylinder inner diameter: 9.550 mm Die inner diameter: 2.095 mm Die length: 8.000 mm Piston head length: 6.35 mm Piston head diameter: 9.474 mm Piston weight: 110.0 g (the above measurement load includes the piston weight) Procedure: The sample is dried in advance at 150 ° C. for at least 2 hours. The sample is placed in the cylinder, the piston is inserted, and the mixture is preheated for 6 minutes. A load is applied, the piston guide is removed, and the molten sample is extruded from the die. A sample is cut out at a predetermined range of piston movement and a predetermined time (t [s]) and its weight is measured (m [g]). The MFR [g / 10 min] is calculated using the following formula: MFR [g / 10 min] = 600 / t × m

[0135] (Production Example 2) 1. Synthesis of aromatic polyether Powdery aromatic polyether was obtained in the same manner as in Production Example 1, except that the reaction was carried out under the following temperature control. <Temperature control> (1) to (5) were the same as in Production Example 1. (6) The temperature was maintained at 300°C for 263 minutes. (7) A reaction terminator was added, the temperature was maintained at 300°C, and the reaction was terminated when the solution viscosity reached 295 cP.

[0136] 2. Evaluation The weight average molecular weight (Mw) and melt flow rate (MFR) were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0137] (Production Example 3) A powdery aromatic polyether was obtained and evaluated in the same manner as in Production Example 2, except that the amount of potassium carbonate used in Production Example 2 was changed to 22.20 kg (161 mol) and the reaction was carried out under the following temperature control. The evaluation results are shown in Table 1. <Temperature control> (1) to (5) were the same as in Production Example 1. (6) Maintained at 300°C for 60 minutes. (7) A reaction terminator was added and the temperature was maintained at 300°C, and the reaction was terminated when the solution viscosity reached 406 cP.

[0138] Production Example 4 A commercially available aromatic polyether (PEEK, manufactured by Victrex, 151G) was evaluated for weight average molecular weight (Mw) and melt flow rate (MFR) in the same manner as in Example 1. The results are shown in Table 1.

[0139] (Production Example 5) A commercially available aromatic polyether (PEEK, manufactured by Victrex, 450G) was evaluated for weight average molecular weight (Mw) and melt flow rate (MFR) in the same manner as in Example 1. The results are shown in Table 1.

[0140]

[0141] (Example 1) 1. Kneading of Resin Composition 100 parts by mass of the aromatic polyether obtained in Production Example 1, 1 part by mass of a nucleating agent ("NA-21" manufactured by ADEKA Corporation), and 0.25 parts by mass of an antioxidant ("Ultranox 626" manufactured by ADEKA Corporation, (2,4-di-tert-butyl-phenyl)-phosphiterythritol diphosphate) were dry-blended to obtain a dry blend raw material. The dry blend raw material was melt-kneaded at a screw rotation speed of 200 rpm and a set temperature of 370 ° C. using a twin-screw extruder ("Process-11" manufactured by Thermo Fisher Scientific, cylinder volume 20 cc) having a cylinder diameter of 11 mm. Here, the dry blend raw material was supplied from the base (upstream side of the screw) of the twin-screw extruder 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.

[0142] 2. Evaluation The amount of radicals and the diameter of spherulites of the obtained resin composition pellets and the aromatic polyether pellets described below were evaluated by the following methods. The results are shown in Table 2. The diameter of spherulites evaluated for the resin composition means the diameter of spherulites of the resin composition, and the diameter of spherulites evaluated for the aromatic polyether means the diameter of spherulites of the aromatic polyether.

[0143] (1) Measurement of Radical Amount The radical concentrations of the aromatic polyether and the resin composition (radical concentrations at 25°C measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance) were measured by an ESR (electron spin resonance) method under the following conditions and procedures.

[0144] [ESR measurement conditions] ESR device: JESFA200 model manufactured by JEOL Ltd. ESR sample tube diameter: 5 mm Microwave output: 0.5 mW Modulation magnetic field: 0.3 mT Time constant: 0.03 seconds Magnetic field range: 328 to 344 mT Measurement time: 60 seconds Mn intensity: 650 Measurement temperature: 25°C

[0145] [Procedure] TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl) was dissolved in benzene to a concentration of 5 μM, and 400 μL of this solution was added to an ESR sample tube. ESR was measured under the above-mentioned measurement conditions. The integral of the peak derived from TEMPOL obtained was divided by the integral of the peak of Mn for normalization (integral value A). The measurement sample was then weighed (weighed value B), loaded into an ESR sample tube, and ESR was measured under the above-mentioned measurement conditions. The integral of the peak derived from the sample obtained was divided by the integral of the peak of Mn for normalization (integral value C). The obtained values ​​of A, B, and C were used to calculate the amount of radicals per unit mass of the sample (radical concentration) according to the following formula: Radical concentration [spin / g] = (5 x 10 －６ x400 x 10 －６ x 6.02 x 10 ２３ × C) / (A × B)

[0146] (2) Measurement of spherulite diameter The spherulite radius was calculated from the scattering vector qmax of the maximum intensity of the scattering profile obtained by small-angle light scattering using the theoretical formula spherulite radius = 4.09 / qmax, and twice this value was used as the spherulite diameter. The scattering vector qmax was measured using a polymer phase structure analysis system (PP-1000) manufactured by Otsuka Electronics Co., Ltd., with the measurement sample set on a standard sample stage under the following measurement conditions. The obtained scattering image is shown in Figure 1.

[0147] The "measurement sample" was prepared by sandwiching 0.1 g of pelletized resin composition or pelletized aromatic polyether between iron plates and using a vacuum press (IMC-6215, manufactured by Imoto Machinery Co., Ltd.) under the following conditions: [Pressing conditions] Mold temperature: 400°C Load: 20 kN Preheating time: 1 minute Pressure holding time: 1 minute After pressure holding, the vacuum was broken and the mold temperature was allowed to return to room temperature over 12 hours while the load was still applied.

[0148] <<Measurement conditions>> Measurement mode: 1 shot Polarization state: Hv HDR function: ON Exposure time 1: 50 msec Exposure time 2: 5 msec Exposure time 3: 100 μsec Camera gain: None Sample-stage distance: 150.3 mm (299.6 mm for Comparative Example 1 only) ND filter: 100% Maximum scattering vector: 2.47 μm －１

[0149] Example 2 1. Kneading of aromatic polyether 100 parts by mass of the powdered aromatic polyether obtained in Production Example 2 and 0.25 parts by mass of an antioxidant were dry-blended to obtain a dry-blend raw material, which was melt-kneaded using a twin-screw extruder having a cylinder diameter of 11 mm at a screw rotation speed of 200 rpm and a set temperature of 370°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 strand discharged from the twin-screw extruder was cooled in water and then pelletized using a pelletizer to obtain pelletized aromatic polyether.

[0150] 2. Evaluation The amount of radicals and the diameter of spherulites of the obtained aromatic polyether pellets were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0151] Example 3 Aromatic polyether pellets were obtained in the same manner as in Example 2, except that the powdered aromatic polyether obtained in Production Example 3 was used instead of the powdered aromatic polyether obtained in Production Example 2. The amount of radicals and the diameter of spherulites of the obtained aromatic polyether pellets were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0152] Example 4 A resin composition was obtained in the same manner as in Example 1, except that the amount of nucleating agent ("NA-21" manufactured by ADEKA Corporation) to be dry-blended was changed from 1 part by mass to 0.5 parts by mass. The amount of radicals and the diameter of spherulites of the obtained pellet-shaped resin composition were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0153] Example 5 A resin composition was obtained in the same manner as in Example 1, except that 1 part by mass of nucleating agent B-2 ("NA-B99P" manufactured by ADEKA Corporation) was used instead of 1 part by mass of nucleating agent ("NA-21" manufactured by ADEKA Corporation). The amount of radicals and the diameter of spherulites of the obtained pellet-shaped resin composition were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0154] Comparative Example 1 Aromatic polyether pellets were obtained in the same manner as in Example 1, except that the dry blending of NA-21 was omitted. The obtained aromatic polyether pellets were evaluated for the radical amount and the spherulite diameter in the same manner as in Example 1. The results are shown in Table 2.

[0155] Comparative Example 2 The aromatic polyether (PEEK, manufactured by Victrex, 151G) of Production Example 4 was evaluated for the radical amount and the diameter of the spherulites in the same manner as in Example 1. The results are shown in Table 2.

[0156] Comparative Example 3 The aromatic polyether (PEEK, manufactured by Victrex, 450G) of Production Example 5 was evaluated for the radical amount and the diameter of spherulites in the same manner as in Example 1. The results are shown in Table 2.

[0157]

[0158] (Example 6) 1. Preparation of Tensile Test Pieces The pellets of the resin composition obtained in Example 1 were injection molded using an injection molding machine ("Mini Jet Pro" manufactured by Thermo Fisher Scientific) under the following conditions to obtain ISO527-2-1BA tensile test pieces. <Injection conditions> (1) Cylinder temperature: 400°C (2) Mold temperature: 210°C (3) Preheating time: 3 min (4) Pressure holding time: 10 s

[0159] 2. Evaluation The obtained test pieces were subjected to a tensile test under the following conditions to measure the maximum tensile strength and breaking strain (tensile elongation). <Tensile conditions> Temperature: 23°C Speed: 20 mm / min Chuck distance: 50 mm The larger the value, the better the mechanical properties. The results are shown in Table 3.

[0160] Example 7 A tensile test piece was prepared and evaluated in the same manner as in Example 6, except that the aromatic polyether pellets obtained in Example 2 were used.

[0161] Example 8 A tensile test piece was prepared and evaluated in the same manner as in Example 6, except that the aromatic polyether pellets obtained in Example 3 were used.

[0162] Example 9 A tensile test piece was prepared and evaluated in the same manner as in Example 6, except that the pellet-shaped resin composition obtained in Example 4 was used.

[0163] Example 10 A tensile test piece was prepared and evaluated in the same manner as in Example 6, except that the pellet-shaped resin composition obtained in Example 5 was used.

[0164] Comparative Example 4 A tensile test piece was prepared and evaluated in the same manner as in Example 6, except that the aromatic polyether pellets obtained in Comparative Example 1 were used.

[0165]

[0166] From the results of Examples 6 and 9 to 10, it was found that the amount of radicals at 25°C was 6.9 × 10 when measured using an aromatic polyether and a nucleating agent, the content of the nucleating agent was 1.0 part by mass (0.001 to 10 parts by mass) relative to 100 parts by mass of the aromatic polyether, TEMPOL as a standard substance, and benzene as a solvent for the standard substance. １６ spin / g (6.5×10 １５ It was confirmed that the resin compositions having a tensile strength of 1000 MPa or more (spin / g or more) had excellent maximum tensile strength and breaking strain (tensile elongation). The diameters of the spherulites in these resin compositions were in the range of 0.001 to 30 μm (see Table 1).

[0167] From the results of Examples 7 and 8, the amount of radicals measured at 25°C using TEMPOL as the standard substance and benzene as the solvent was 6.5 x 10 １５ It was confirmed that aromatic polyethers having a spherulite diameter in the range of 0.001 to 30 μm have excellent maximum tensile strength and breaking strain (tensile elongation) when used to produce molded articles.

[0168] The aromatic polyether of Comparative Example 4 had a radical amount of 6.5 x 10 at 25°C, measured using TEMPOL as the standard substance and benzene as the solvent for the standard substance. １５ The aromatic polyether of Comparative Example 4, which had a large spherulite diameter (31 μm), was inferior in ultimate tensile strength and breaking strain (tensile elongation) when used to produce a molded article, compared with the aromatic polyethers of Examples 8 and 9, which had spherulite diameters in the range of 0.001 to 30 μm.

[0169] (Example 11) 1. Production of Composite Material A composite material (pellets) containing a resin composition and 43 parts by mass of reinforcing fibers per 100 parts by mass of the resin composition was obtained in the same manner as in the production of the resin composition in Example 1, except that in the production of the resin composition in Example 1, reinforcing fibers ("TR06U" manufactured by Mitsubishi Engineering-Plastics Corporation, chopped carbon fiber, average fiber length 6 mm, filament diameter 7 μm) were fed (side fed) from the middle of the twin-screw extruder at 3 g per minute.

[0170] 2. Evaluation of Composite Material Using the obtained composite material, 4 mm thick test pieces according to ISO527-2-1BA were prepared, and the obtained test pieces were subjected to a tensile test at 20 mm / min with a chuck distance of 50 mm to measure the maximum tensile strength. The results are shown in Table 4.

[0171] Comparative Example 5 A composite material was produced and evaluated in the same manner as in Example 11, except that the aromatic polyether of Comparative Example 3 was used instead of the resin composition obtained in Example 1. The results are shown in Table 4.

[0172]

[0173] From the results of Example 11, it was found that the amount of radicals measured at 25°C using TEMPOL as a standard substance and benzene as a solvent was 6.9 × 10 １６ spin / g (6.5×10 １５ It was confirmed that the composite material using the resin composition having a tensile strength of 1.5g / g or more had excellent ultimate tensile strength. The diameter of the spherulites of this resin composition was 13 μm (within the range of 0.001 to 30 μm) (see Table 1).

[0174] The aromatic polyether used in the composite material of Comparative Example 5 had a small spherulite diameter (4.4 μm), but the amount of radicals at 25° C. measured using TEMPOL as a standard substance and benzene as the solvent was 6.0×10 １５ The composite material of Comparative Example 5 was inferior to the composite material of Example 11 in ultimate tensile strength.

[0175] Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will readily be able to make numerous modifications to these exemplary embodiments and / or examples without substantially departing from the novel teachings and advantages of the present invention. Accordingly, these numerous modifications are within the scope of the present invention. The contents of all documents cited in this specification and of the applications from which this application claims priority under the Paris Convention are incorporated by reference in their entirety.

Claims

1. The standard substance was TEMPOL, and the solvent for the standard substance was benzene. The amount of radicals at 25°C was 6.5 x 10 １５ spin / g or more, and the diameter of the spherulites is 0.001 to 30 μm.

2. The aromatic polyether according to claim 1, having a weight average molecular weight of 80,000 or more.

3. The aromatic polyether according to claim 1 or 2, having a melt flow rate of 2.0 g / 10 min or less.

4. A compound comprising an aromatic polyether and a nucleating agent, wherein the aromatic polyether has a radical amount of 6.5 x 10 at 25°C, measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance. １５ spin / g or more, the diameter of the spherulites is 0.001 to 30 μm, and the content of the nucleating agent is 0.001 to 10 parts by mass per 100 parts by mass of the aromatic polyether.

5. The resin composition according to claim 4, wherein the diameter of the spherulites of said resin composition is 0.001 to 30 μm.

6. Contains aromatic polyethers. The radical amount at 25°C is 6.5 x 10, measured using TEMPOL as the standard substance and benzene as the solvent. １５ spin / g or more, and the diameter of the spherulites is 0.001 to 30 μm.

7. The resin composition according to claim 6, further comprising 0.001 to 10 parts by mass of a nucleating agent per 100 parts by mass of the aromatic polyether.

8. The resin composition according to claim 4, 5, or 7, wherein the nucleating agent is one or more selected from the group consisting of organic nucleating agents and inorganic nucleating agents.

9. A method for producing the aromatic polyether according to any one of claims 1 to 3, comprising reacting 4,4'-dichlorobenzophenone and hydroquinone in diphenyl sulfone with stirring in the presence of potassium carbonate, and terminating the reaction when the solution viscosity reaches 242 cP or more at 300°C after adding a reaction terminator.

10. A method for producing the resin composition according to any one of claims 4 to 8, comprising kneading 0.001 to 10 parts by mass of a nucleating agent with 100 parts by mass of an aromatic polyether obtained by reacting 4,4'-dichlorobenzophenone and hydroquinone in diphenyl sulfone in the presence of potassium carbonate.

11. A composite material comprising at least one selected from the group consisting of the aromatic polyether according to any one of claims 1 to 3, the resin composition according to any one of claims 4 to 8, the aromatic polyether obtained by the production method according to claim 9, and the resin composition obtained by the production method according to claim 10, and reinforcing fibers.

12. The composite material of claim 11, wherein the reinforcing fibers comprise one or more selected from the group consisting of carbon fibers, glass fibers, and aramid fibers.

13. A method for producing a composite material, comprising compounding one or more selected from the group consisting of the aromatic polyether according to any one of claims 1 to 3, the resin composition according to any one of claims 4 to 8, the aromatic polyether obtained by the production method according to claim 9, and the resin composition obtained by the production method according to claim 10, with reinforcing fibers.

14. The method for producing a composite material according to claim 13, wherein the reinforcing fibers include at least one selected from the group consisting of carbon fibers, glass fibers, and aramid fibers.

15. A molded article obtained by molding one or more selected from the group consisting of the aromatic polyether described in any one of claims 1 to 3, the resin composition described in any one of claims 4 to 8, the aromatic polyether obtained by the manufacturing method described in claim 9, and the resin composition obtained by the manufacturing method described in claim 10.

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