Resin composition, fiber-reinforced resin composition, and molded article

Abstract

The present invention provides a resin composition containing an aromatic polyether and a fluororesin, which exhibits excellent strength and rigidity. [Solution] The radical amount at 25°C was measured using TEMPOL as the standard substance and benzene as the solvent for the standard substance, and was 6.5 × 10 15 A resin composition comprising an aromatic polyether (A) with a spin / g or higher and a fluororesin (B).

Description

Technical Field

[0001] The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition containing an aromatic polyether and a fluororesin, a fiber reinforced resin composition, and a molded body.

Background Art

[0002] Aromatic polyethers such as polyetheretherketone (PEEK) are classified as super engineering plastics and are thermoplastic resins excellent in heat resistance, chemical resistance, etc. In recent years, the uses of aromatic polyethers as metal substitute materials have been expanding in fields where weight reduction is required, such as in automobiles and aircraft. Further, aromatic polyethers are also used for sliding parts such as gears and bearings, and means for further improving physical properties have been studied.

[0003] For example, Patent Document 1 discloses using a resin composition containing PEEK and a fluororesin to improve the slidability of PEEK.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in the resin composition of Patent Document 1, there was still room for further improvement in the strength and rigidity of the resin composition. One object of the present invention is to provide a resin composition containing an aromatic polyether and a fluororesin, which is excellent in strength and also excellent in rigidity.

Means for Solving the Problems

[0006] As a result of intensive studies, the inventors of the present invention have found that a resin composition containing an aromatic polyether having a specific radical amount and a predetermined fluororesin is superior in strength and rigidity to a resin composition containing a conventional aromatic polyether and a fluororesin, and have completed the present invention.

[0007] According to the present invention, the following resin compositions and the like can be provided. 1. A resin composition comprising an aromatic polyether (A) having a radical amount of 6.5×10 15 , 15 spin / g or more at 25°C, measured with TEMPOL as the standard substance and benzene as the solvent of the standard substance, and a fluororesin (B). 2. A resin composition comprising an aromatic polyether (A) and a fluororesin (B), having a radical amount of 6.5×10 15 spin / g or more at 25°C, measured with TEMPOL as the standard substance and benzene as the solvent of the standard substance. 3. The resin composition according to 1 or 2 above, wherein the mass ratio ((A) / (B)) of the aromatic polyether (A) to the fluororesin (B) is 99 / 1 to 50 / 50. 4. The resin composition according to any one of 1 to 3 above, wherein the aromatic polyether (A) contains one or more selected from the group consisting of polyether ether ketone (PEEK), polyether ketone ketone (PEKK), and polyether ketone (PEK). 5. The resin composition according to any one of 1 to 4 above, wherein the fluororesin (B) contains one or more selected from the group consisting of polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE), and polyvinylidene fluoride (PVDF). 6. A fiber-reinforced resin composition comprising the resin composition according to any one of 1 to 5 above and a reinforcing fiber (C). 7. The fiber-reinforced resin composition according to 6, wherein the reinforcing fiber (C) comprises one or more selected from the group consisting of glass fiber, carbon fiber, and aramid fiber. 8. A molded article obtained by molding one or more selected from the group consisting of the resin composition described in any of items 1 to 5 above and the fiber-reinforced resin composition described in item 6 or 7 above. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a resin composition comprising an aromatic polyether and a fluororesin, which has excellent strength and rigidity. [Modes for carrying out the invention]

[0009] The resin composition, fiber-reinforced resin composition, and molded article of the present invention will be described in detail below. In this specification, "x~y" represents a numerical range of "greater than or equal to x and less than or equal to y". The upper and lower limits specified for the numerical range can be combined in any way. Furthermore, it is possible to combine two or more non-conflicting embodiments of the embodiments of the present invention described below, and an embodiment that combines two or more embodiments is also an embodiment of the embodiments of the present invention.

[0010] 1.Resin composition A resin composition according to one aspect of the present invention is characterized by comprising the following resin components (A) and (B). • The radical amount at 25°C was measured using TEMPOL as the standard substance and benzene as the solvent for the standard substance, and was 6.5 × 10⁻⁶. 15 Aromatic polyether (A) (also called component (A)) with a spin / g or higher. Fluororesin (B) (also called component (B)).

[0011] In this embodiment, by using component (A) in the resin composition, superior strength and rigidity are achieved compared to when conventional aromatic polyethers are used. Although the reason for obtaining such an improvement effect in mechanical properties is not necessarily clear, it is presumed that by using the aromatic polyether having a specific radical amount, the chemical bond and interaction at the interface with the fluororesin are strengthened.

[0012] In this specification, the strength of the resin composition (sometimes referred to as "mechanical strength") is evaluated by the tensile strength. The tensile strength of the resin composition can be measured by the method described in the examples.

[0013] In one embodiment, the tensile strength of the resin composition is 80 MPa or more, 85 MPa or more, or 90 MPa or more.

[0014] In this specification, the rigidity of the resin composition is evaluated by the tensile modulus of elasticity. The tensile modulus of elasticity of the resin composition can be measured by the method described in the examples.

[0015] In one embodiment, the tensile modulus of elasticity of the resin composition is 4.0 GPa or more, 4.3 GPa or more, or 4.5 GPa or more.

[0016] [Aromatic polyether (A)] In one embodiment, the radical amount of the aromatic polyether (A) is 6.5×10 15 spin / g or more.

[0017] The lower limit of the radical amount of the aromatic polyether (A) is 7.0×10 15 spin / g or more, 20×10 15 (2.0×10 16 )spin / g or more, 30×10 15 (3.0×10 16 )spin / g or more, 40×10 15 (4.0×10 16 )spin / g or more, or 50×10 15 (5.0×10 16 )spin / g or more may be used. The upper limit of the radical amount of the aromatic polyether (A) is 9.0×10 17 spin / g or less, 5.0×1017 spin / g or less, or 1.0 × 10 17 It may be less than spin / g.

[0018] In one embodiment, the amount of radicals in aromatic polyether (A) is 6.5 × 10⁻⁶. 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, 20×10 15 spin / g or more 5.0×10 17 spin / g or less, 30×10 15 spin / g or more 5.0×10 17 spin / g or less, 40×10 15 spin / g or more 1.0×10 17 spin / g or less, or 50 × 10 15 spin / g or more 1.0×10 17 It is less than spin / g.

[0019] The amount of radicals in aromatic polyether (A) is 6.5 × 10 15 When the spin / g value is greater than or equal to a certain level, the aforementioned improvements in mechanical properties (strength, stiffness, etc.) are more likely to be achieved. On the other hand, the amount of radicals in aromatic polyether (A) is 9.0 × 10 17 When the spin / g value is below a certain level, sufficient thermal stability can be obtained, and the molded product is likely to exhibit sufficient mechanical properties.

[0020] The amount of radicals in aromatic polyether (A) can be increased to the range described above, for example, by using a monomer containing a chlorine atom as a reactive group (e.g., 4,4'-dichlorobenzophenone) as the monomer when synthesizing (polymerizing) aromatic polyether (A). The amount of radicals in aromatic polyether (A) is the value measured by the method described in the examples.

[0021] In one embodiment, the aromatic polyether (A) is a polyarylene ether ketone. For example, the aromatic polyether (A) includes one or more selected from the group consisting of polyether ether ketone (PEEK), polyether ketone ketone (PEKK), and polyether ketone (PEK). Among these, PEEK is preferred from the viewpoint of moldability and thermal stability.

[0022] In one embodiment, 50% or more by mass of aromatic polyether (A) is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass is one or more selected from the group consisting of PEEK, PEKK, and PEK. In one embodiment, 50% or more by mass of the aromatic polyether (A), 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass is PEEK.

[0023] In one embodiment, the aromatic polyether (A) comprises a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). [ka]

[0024] In one embodiment, the aromatic polyether (A) includes a structural unit represented by the following formula (3). [ka]

[0025] The structural unit represented by equation (3) is a combination of the structural unit represented by equation (1) and the structural unit represented by equation (2).

[0026] In one embodiment, the aromatic polyether (A) does not contain any structures other than the structural units represented by formulas (1) and (2). However, as is obvious from the definition, it may also contain the structural unit represented by formula (3).

[0027] In one embodiment, the aromatic polyether (A) includes other structures other than the structural units represented by formulas (1) and (2), to the extent that the effects of the present invention are not impaired.

[0028] In one embodiment, 50% or more by mass of aromatic polyether (A) is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass is a structural unit represented by formula (1) and / or formula (2), or a structural unit represented by formula (3).

[0029] In one embodiment, in aromatic polyether (A), the molar ratio of structural units represented by formula (1) to structural units represented by formula (2) (structural units represented by formula (1):structural units represented by formula (2)) is 47.5:52.5~52.5:47.5, 48.0:52.0~52.0:48.0, 48.5:51.5~51.5:48.5, 49.0:51.0~51.0:49.0, or 49.5:50.5~50.5:49.5. The number of moles of the structural unit represented by equation (1) may be greater than, less than, or the same as the number of moles of the structural unit represented by equation (2).

[0030] 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). [ka]

[0031] In one embodiment, an aromatic polyether can also be defined as 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).

[0032] In one embodiment, the copolymer is a random copolymer, an alternating copolymer, or a block copolymer, and is preferably a random copolymer.

[0033] In aromatic polyethers, 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, as shown on the far right of formula (b) (the phenyl group is introduced to substitute for any of the four hydrogen atoms on the benzene ring).

[0034] In aromatic polyethers, the substitution position (bonding position) of the cyano group in the structural unit represented by formula (c) can be any position on the benzene ring constituting the main chain, as shown on the leftmost side of formula (c). One of the five carbon atoms that can be bonded on the benzene ring forms a single bond with an adjacent structural unit, and one of the remaining four carbon atoms is bonded to the cyano group.

[0035] In an aromatic polyether, if there are two or more adjacent structural units represented by formula (b), the aromatic polyether may contain one or more structures selected from the group consisting of the structure represented by (b1), the structure represented by (b2), and the structure represented by (b3). [ka]

[0036] Each of the structures represented by formulas (b1) to (b3) above has different substitution positions of the phenyl group in the two structural units represented by formula (b) that form the structure. The effects of the present invention are well exhibited regardless of which of these structures is included.

[0037] Here, we have described the case where two or more structural units represented by formula (b) are adjacent to each other. However, 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.

[0038] In one embodiment, 50% or more by mass of the aromatic polyether is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass is the structural unit represented by formula (a) and the structural unit represented by formula (b). Furthermore, in the case of "substantially 100% by mass," it is acceptable for unavoidable impurities to be present.

[0039] In one embodiment, 50% or more by mass of the aromatic polyether is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass is the structural unit represented by formula (a) and the structural unit represented by formula (c). Furthermore, in the case of "substantially 100% by mass," it is acceptable for unavoidable impurities to be present.

[0040] The ratio of the structural unit represented by formula (a) to one or more structural units selected from the group consisting of formulas (b) and (c) is not particularly limited and can be appropriately selected within a range that does not impair the effects of the present invention.

[0041] The terminal structure of the main chain of aromatic polyether (A) is not particularly limited. In one embodiment, a structural unit represented by formula (1) is arranged at one or more ends of the main chain of an aromatic polyether (A). In this case, the end 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 arranged at one or more ends of the main chain of an aromatic polyether (A). In this case, the terminal structure bonded to the structural unit may be, for example, a hydrogen atom (H) (when the terminal structure is a hydrogen atom (H), a hydroxyl group is formed together with the oxygen atom (O) in the structural unit). The terminal structure of the aromatic polyether (A) may be, for example, a structure in which the halogen atoms or hydroxyl groups mentioned above are replaced by hydrogen atoms (H), etc. Furthermore, the terminal structure may have structures other than those exemplified above.

[0042] The weight-average molecular weight (Mw) of aromatic polyether (A) is not particularly limited. In one embodiment, the weight-average molecular weight (Mw) of aromatic polyether (A) is 40,000 or more, 50,000 or more, or 55,000 or more, and also 150,000 or less, 140,000 or less, or 135,000 or less. Furthermore, the weight-average molecular weight (Mw) of the aromatic polyether (A) is, for example, 40,000 to 150,000. From the viewpoint of moldability, it is preferably 50,000 to 140,000, and from the viewpoint of mechanical properties, it is more preferably 55,000 to 135,000. The weight-average molecular weight (Mw) of aromatic polyether (A) is the value measured by the method described in the examples.

[0043] [Fluororesin (B)] The fluororesin (B) is not particularly limited as long as it is a thermoplastic resin containing fluorine. For example, specific examples include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene tetrafluoroethylene copolymer (ETFE), and polyvinylidene fluoride (PVDF). Among these, PFA and PTFE are preferred from the viewpoint of mechanical properties, heat resistance, and moldability.

[0044] Fluororesin (B) may be used alone or in combination of two or more types. In one embodiment, fluororesin (B) includes one or more selected from the group consisting of PTFE, PFA, FEP, ETFE, and PVDF. Alternatively, fluororesin (B) may consist of only one type.

[0045] In one embodiment, the content of fluororesin (B) in the resin composition is 0.1 to 300 parts by mass per 100 parts by mass of aromatic polyether (A). In one embodiment, the content of fluororesin (B) in the resin composition is 0.5 parts by mass or more, 1 part by mass or more, 5 parts by mass or more, 10 parts by mass or more, 25 parts by mass or more, 40 parts by mass or more, 60 parts by mass or more, or 80 parts by mass or more, and also 200 parts by mass or less, 150 parts by mass or less, 130 parts by mass or less, or 100 parts by mass or less, based on 100 parts by mass of aromatic polyether (A).

[0046] In one embodiment, the content of fluororesin (B) in the resin composition is 1 to 200 parts by mass, more preferably 5 to 150 parts by mass from the viewpoint of moldability, and most preferably 10 to 100 parts by mass from the viewpoint of mechanical properties.

[0047] In one embodiment, the mass ratio ((A) / (B)) of aromatic polyether (A) to fluororesin (B) is 99 / 1 to 50 / 50, 95 / 5 to 50 / 50, 90 / 10 to 50 / 50, or 85 / 15 to 50 / 50. Within the above range, it is easy to obtain the effect of excellent formability and mechanical properties.

[0048] The resin composition may also contain other components besides the aromatic polyether (A) and fluororesin (B), as long as they do not impair the effects of the present invention. Other components include known resin additives such as antioxidants.

[0049] In one embodiment, 50% or more by mass of the resin composition is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass is aromatic polyether (A) and fluororesin (B). Furthermore, in the case of "substantially 100% by mass," it is acceptable for unavoidable impurities to be present.

[0050] The content of each component in the resin composition described above can also be applied to the amount of each component to be blended during the preparation of the resin composition.

[0051] In one embodiment, the amount of radicals per unit mass of the resin composition at 25°C, measured using TEMPOL as the standard substance and benzene as the solvent for the standard substance, was 6.5 × 10⁻⁶. 15 spin / g or more, 7.0×10 15 spin / g or more, 10×10 15 spin / g or more, 20×10 15 spin / g or more, 30×10 15 spin / g or higher, or 40 × 10 15 spin / g or higher, and 9.0 × 10 17 spin / g or less, 6.0×10 17 spin / g or less or 3.0 × 10 17 It is less than spin / g.

[0052] In one embodiment, the amount of radicals in the resin composition 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, 20×10 15 spin / g or more 5.0×10 17 spin / g or less, 30×10 15 spin / g or more 5.0×10 17 spin / g or less, 40×10 15 spin / g or more 1.0×10 17 spin / g or less, or 50 × 10 15spin / g or more 1.0×10 17 It is less than spin / g.

[0053] The radical amount of the resin composition is 6.5 × 10 15 When the spin / g value is greater than or equal to a certain level, the aforementioned improvements in mechanical properties (strength, stiffness, etc.) are more likely to be achieved. On the other hand, the radical amount of the resin composition is 9.0 × 10 17 When the spin / g value is below a certain level, sufficient thermal stability can be obtained, and the molded product is likely to exhibit sufficient mechanical properties.

[0054] The amount of radicals in the resin composition can be increased to the range described above by using an aromatic polyether (A) with a high radical content. The amount of radicals in the resin composition is the value measured by the method described in the examples.

[0055] The method for producing the resin composition of this embodiment is not particularly limited, and known means can be applied. For example, it can be produced by mixing the aromatic polyether (A) and fluororesin (B) with optional components as needed in a predetermined ratio, and then melt-kneading them. Known equipment such as an extruder can be used for melt-kneading.

[0056] 2. Fiber-reinforced resin composition A fiber-reinforced resin composition according to one aspect of the present invention comprises the resin composition according to one aspect of the present invention described above, and 1 to 300 parts by mass of reinforcing fibers (C) per 100 parts by mass of the resin composition. According to the fiber-reinforced resin composition according to this aspect, excellent interfacial shear strength between the resin composition and the reinforcing fibers is obtained, resulting in excellent mechanical strength (e.g., tensile strength) as a fiber-reinforced resin composition. The reason for obtaining such an effect is not entirely clear, but it is presumed that a new structure having an adhesive effect on the reinforcing fibers is formed due to the effect of the high concentration of radicals of aromatic polyether (A).

[0057] In one embodiment, the content of reinforcing fibers (C) in the fiber-reinforced resin composition is 2 parts by mass or more, 5 parts by mass or more, or 10 parts by mass or more, and also 250 parts by mass or less, 200 parts by mass or less, 150 parts by mass or less, or 100 parts by mass or less, per 100 parts by mass of the resin composition.

[0058] In one embodiment, the content of reinforcing fibers (C) in the fiber-reinforced resin composition is 2 parts by mass or more and 250 parts by mass or less, 2 parts by mass or more and 200 parts by mass or less, 5 parts by mass or more and 150 parts by mass or less, or 10 parts by mass or more and 100 parts by mass or less, per 100 parts by mass of the resin composition.

[0059] In one embodiment, the reinforcing fiber (C) includes one or more selected from the group consisting of glass fiber, carbon fiber, and aramid fiber. In one embodiment, 50% or more by mass of the reinforcing fiber (C) is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass is one or more selected from the group consisting of glass fiber, carbon fiber, and aramid fiber.

[0060] In one embodiment, the carbon fiber includes 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% or more by mass of the carbon fiber is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass 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).

[0061] The types of glass fibers and aramid fibers are not particularly limited. As glass fibers, for example, glass fibers of various compositions such as E-glass, low-dielectric glass, and silica glass can be selected and used according to the purpose and application.

[0062] In one embodiment, from the viewpoint of mechanical properties such as strength, elastic modulus, and impact resistance of the molded product, the average fiber length of the reinforcing fiber (C) is 5 mm or more. The average fiber length is calculated by the arithmetic mean of the values ​​measured with calipers.

[0063] In one embodiment, 50% or more by mass of the fiber-reinforced resin composition is 60% or more by mass, 70% or more by mass, 80% or more by mass, 90% or more by mass, 95% or more by mass, 97% or more by mass, 99% or more by mass, 99.5% or more by mass, or substantially 100% by mass is the resin composition and reinforcing fibers (C).

[0064] The method for producing (compounding) the fiber-reinforced resin composition is not particularly limited. For example, a method of melt-kneading the resin composition and reinforcing fibers, or a method of melting and impregnating a reinforcing fiber aggregate with a resin composition in powder, film, or pellet form can be used. The fiber-reinforced resin composition containing continuous fibers with an average fiber length of 5 mm or more may be in one or more forms selected from the group consisting of, for example, woven fabrics, nonwoven fabrics, and unidirectional materials (also referred to as "UD materials").

[0065] Pellet forms of the composite material may be manufactured. These pellets can be used as raw materials for manufacturing molded articles, as described later.

[0066] In one embodiment, the method for producing pellets includes cutting reinforcing fibers into 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 with the aromatic polyether or resin composition and granulating them.

[0067] In one embodiment, the pellet manufacturing method involves immersing reinforcing fiber rovings in molten aromatic polyether or resin composition, drawing them, and then cutting them to the desired pellet length to produce pellets (also referred to as "long fiber pellets"). When long fiber pellets are manufactured in this manner, breakage of the reinforcing fibers can be suppressed.

[0068] 3. Molded body A molded article according to one aspect of the present invention is made of a resin composition according to one aspect of the present invention. The molded article according to this aspect has excellent heat resistance.

[0069] A molded article according to another aspect of the present invention is made of a fiber-reinforced resin composition according to one aspect of the present invention. According to the molded article of this aspect, the interfacial shear strength between the resin composition and the reinforcing fibers in the fiber-reinforced resin composition is excellent, and therefore excellent mechanical strength (e.g., tensile strength) is obtained.

[0070] The form of the molded article according to one aspect of the present invention and other aspects is not particularly limited. In one embodiment, the molded body is an injection-molded body, an extruded body, or a compression-molded body.

[0071] The applications of the resin compositions, fiber-reinforced resin compositions, and molded articles described above are not particularly limited and can be broadly applied to various applications where strength is required. The resin compositions and fiber-reinforced resin compositions are particularly suitable as metal substitutes for applications requiring heat resistance, solvent resistance, and durability. More specifically, they can be suitably used in aerospace components, automotive components, sliding components such as gears and bearings, 3D printer filaments, semiconductor manufacturing equipment components, and the like. [Examples]

[0072] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments.

[0073] Manufacturing Example 1 1. Production of aromatic polyethers Nitrogen gas was circulated through a 240L reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube, and water recovery container connected to a cooling tube. 132.47 kg of diphenyl sulfone (manufactured by Sino-High) was added in stages, and the temperature was raised to 160°C. After confirming melting, 39.00 kg (155 mol) of 4,4'-dichlorobenzophenone (manufactured by Sino-High), 16.85 kg (153 mol) of hydroquinone, and 22.20 kg (161 mol) of potassium carbonate (AGC Inc., fine powder) were added in order. The reaction concentration was 2.31 mol / kg. Here, the "reaction concentration" is defined by the following formula, based on the number of moles [mol] of OH groups calculated from the total amount (amount added) of phenolic monomers (e.g., hydroquinone) used in the reaction (added to the reaction mixture). Reaction concentration [mol / kg] = number of moles of OH groups [mol] / mass of solvent [kg]

[0074] The reaction mixture was carried out under the following temperature control, and then 6.15 kg (25 mol) of 4,4'-dichlorobenzophenone was added as a reaction stopper.

[0075] <Temperature control> (1) Heat from 160°C to 200°C over 90 minutes at a stirring speed of 100 rpm. (2) Hold at 200°C for 60 minutes (3) Increase the temperature from 200°C to 250°C over 80 minutes. (4) Hold at 250°C for 60 minutes (5) Increase the temperature from 250°C to 300°C over 150 minutes. (6) Hold at 300°C for 263 minutes (7) Add the reaction stopper and maintain the temperature at 300°C. Terminate the reaction when the solution viscosity reaches 295 cP.

[0076] After the reaction was complete, the contents were removed into a SUS tray and cooled to room temperature to solidify. The product was coarsely ground, then ground again with a pin mill (Hosokawa Micron Corporation 160UPZ), washed in the order of acetone, oxalic acid aqueous solution, and water, and vacuum dried to obtain a powdered aromatic polyether.

[0077] 2. Evaluation of aromatic polyethers (1) Measurement of weight-average molecular weight (Mw) The weight-average molecular weight (Mw) of the obtained aromatic polyethers was measured by GPC (gel permeation chromatography) under the following conditions and procedure. The results are shown in Table 1.

[0078] [GPC measurement conditions] • GPC device: HLC-8420GPC (manufactured by Tosoh Corporation) GPC column: Use TSK gel guardcolumn HH (4.6mm I.D. x 35mm) and two TSK gel Super HM-M (6mm I.D. x 150mm) in this order in series. • Solvent: PFP / CHCl3 mixed solvent ·Temperature: 40℃ ·Flow rate: 0.6mL / min ·Injection amount: 20μL • Calibration curve: Calibration according to PS standard

[0079] [procedure] Aromatic polyethers were dissolved in pentafluorophenol (PFP), and the GPC distribution was measured under the above measurement conditions. The weight-average molecular weight (Mw) was calculated from the obtained GPC distribution using a calibration curve with a polystyrene (PS) standard.

[0080] (2) Measurement of radical quantity The obtained powdered aromatic polyether was used to measure the radical concentration (radical concentration at 25°C, measured with the standard substance as TEMPOL and the solvent as benzene) by ESR (electron spin resonance) under the following conditions and procedure. The results are shown in Table 1.

[0081] [ESR measurement conditions] • ESR device: JESFA200 model manufactured by JEOL Ltd. ·ESR sample tube diameter: 5mm • Microwave output: 0.5mW Modulated magnetic field: 0.3mT ·Time constant: 0.03 seconds • Magnetic field range: 328~344mT • Measurement time: 60 seconds ·Mn strength: 650 ·Measurement temperature: 25℃

[0082] [procedure] TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl) was dissolved in benzene at a concentration of 5 μM, and 400 μL was added to an ESR sample tube. The ESR was measured under the above measurement conditions. The integral value of the peak derived from TEMPOL was divided by the integral value of the peak derived from Mn to normalize it (integral value A). Then, the sample to be measured (in this case, a resin composition) was weighed (weighed value B), filled into an ESR sample tube, and the ESR was measured under the above measurement conditions. The integral value of the peak derived from the sample was divided by the integral value of the peak derived from Mn to normalize it (integral value C). Using the obtained values ​​A, B, and C, the amount of radicals per unit mass of the sample (radical concentration) was calculated using the following formula. Radical concentration [spin / g] = (5 × 10 -6 ×400×10 -6 ×6.02×10 23 ×C) / (A×B)

[0083] Manufacturing Example 2 For a commercially available aromatic polyether (PEEK, Solvay, KT-820), the weight-average molecular weight (Mw) and radical content were evaluated in the same manner as in Production Example 1. The results are shown in Table 1.

[0084] [Table 1]

[0085] Example 1 1. Manufacturing of resin compositions To 100 parts by mass of aromatic polyether obtained in Production Example 1, 100 parts by mass of water were mixed. Then, 0.25 parts by mass of inorganic metal phosphate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., with a mass ratio of "Na2HPO4" to "NaH2PO4" of 2:3) was added and mixed at 25°C for 30 minutes. After mixing, the resulting mixture was dried at 140°C for 24 hours. Then, 100 parts by mass of the dried mixture, 0.25 parts by mass of a nucleating agent (manufactured by ADEKA Corporation, "NA-21"), and 25 parts by mass of PTFE (a fluororesin manufactured by Daikin Industries, Ltd., L-5) were dry-blended to obtain a blended raw material. This blended raw material was melt-kneaded using a Thermo Fisher Scientific "Process-11" with a cylinder diameter of 11 mm, at a screw rotation speed of 250 rpm and a set temperature of 380°C. Here, the dry-blended raw material was supplied at a rate of 6 g / min from the base of the twin-screw extruder (upstream side of the screw). The residence time in the twin-screw extruder was 3.5 minutes. After cooling the strands extruded from the twin-screw extruder in water, they were pelletized using a pelletizer to obtain the resin composition.

[0086] 2. Preparation of tensile test specimens The resulting resin composition pellets were injection molded using an injection molding machine (Thermo Fisher Scientific "Mini Jet Pro") under the following conditions to obtain ISO 527-2-1BA tensile test specimens.

[0087] <Injection conditions> (1) Cylinder temperature: 400℃ (2) Mold temperature: 210℃ (3) Preheating time: 3 min (4) Holding time: 10s

[0088] 3. Evaluation The amount of radicals was evaluated using the resin composition pellets obtained in "1. Manufacturing of Resin Composition" above, by the following method. In addition, the tensile modulus and tensile strength were measured for the test specimens obtained in "2. Preparation of Tensile Test Specimens" above, by the following method. The results are shown in Table 2.

[0089] (1) Measurement of radical quantity The radical concentration of the resin composition (measured at 25°C using TEMPOL as the standard substance and benzene as the solvent) was measured by ESR (electron spin resonance) under the following conditions and procedure.

[0090] [ESR measurement conditions] • ESR device: JESFA200 model manufactured by JEOL Ltd. ·ESR sample tube diameter: 5mm • Microwave output: 0.5mW Modulated magnetic field: 0.3mT ·Time constant: 0.03 seconds • Magnetic field range: 328~344mT • Measurement time: 60 seconds ·Mn strength: 650 ·Measurement temperature: 25℃

[0091] [procedure] TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl) was dissolved in benzene at a concentration of 5 μM, and 400 μL was added to an ESR sample tube. The ESR was measured under the above measurement conditions. The integral value of the peak derived from TEMPOL was divided by the integral value of the peak derived from Mn to normalize it (integral value A). Then, the sample to be measured (in this case, a resin composition) was weighed (weighed value B), filled into an ESR sample tube, and the ESR was measured under the above measurement conditions. The integral value of the peak derived from the sample was divided by the integral value of the peak derived from Mn to normalize it (integral value C). Using the obtained values ​​A, B, and C, the amount of radicals per unit mass of the sample (radical concentration) was calculated using the following formula. Radical concentration [spin / g] = (5 × 10 -6 ×400×10 -6 ×6.02×10 23 ×C) / (A×B)

[0092] (2) Measurement of tensile modulus and tensile strength The tensile modulus and tensile strength of test specimens, which are molded articles of the resin composition, were measured under the following conditions. [Tensile test conditions] ·Temperature: 23℃ ·Speed: 20mm / min • Chuck spacing: 50mm A higher numerical value indicates superior mechanical properties (strength, rigidity). The results are shown in Table 3.

[0093] Comparative Example 1 The blended raw material obtained by dry blending 100 parts by mass of aromatic polyether from Production Example 2 with 25 parts by mass of PTFE (L-5, manufactured by Daikin Industries, Ltd.), a fluororesin, was melt-kneaded at a screw rotation speed of 250 rpm and a set temperature of 380°C using a cylinder with a cylinder diameter of 11 mm (Thermo Fisher Scientific "Process-11", cylinder capacity 20 cc). Here, the dry-blended raw material was supplied at a rate of 6 g / min from the base of the twin-screw extruder (upstream side of the screw). The residence time in the twin-screw extruder was 3.5 minutes. After cooling the strand discharged from the twin-screw extruder in water, it was pelletized using a pelletizer to obtain the resin composition. Tensile test specimens were prepared and evaluated using the obtained resin composition in the same manner as in Example 1. The results are shown in Table 2.

[0094] [Table 2]

[0095] Table 2 shows that, among resin compositions of aromatic polyethers having similar weight-average molecular weights, the resin composition of Example 1 using the aromatic polyether of Production Example 1 has a higher radical content and superior tensile modulus and tensile strength compared to the resin composition of Comparative Example 1 using the aromatic polyether of Production Example 2. It can be seen that by using aromatic polyethers with a high radical content, it is possible to provide a resin composition containing aromatic polyethers and fluororesins that has excellent strength and rigidity.

Claims

1. The radical amount at 25°C was measured using TEMPOL as the standard substance and benzene as the solvent for the standard substance, and was 6.5 × 10⁻⁶. １５ A resin composition comprising an aromatic polyether (A) having a spin / g or higher concentration and a fluororesin (B).

2. It comprises an aromatic polyether (A) and a fluororesin (B), The radical amount at 25°C was measured using TEMPOL as the standard substance and benzene as the solvent for the standard substance, and was 6.5 × 10⁻⁶. １５ A resin composition having a spin / g or higher.

3. The resin composition according to claim 1 or 2, wherein the mass ratio ((A) / (B)) of the aromatic polyether (A) to the fluororesin (B) is 99 / 1 to 50 / 50.

4. The resin composition according to any one of claims 1 to 3, wherein the aromatic polyether (A) comprises one or more selected from the group consisting of polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetherketone (PEK).

5. The resin composition according to any one of claims 1 to 4, wherein the fluororesin (B) comprises one or more selected from the group consisting of polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylenepropene copolymer (FEP), ethylenetetrafluoroethylene copolymer (ETFE), and polyvinylidene fluoride (PVDF).

6. A fiber-reinforced resin composition comprising the resin composition according to any one of claims 1 to 5 and reinforcing fibers (C).

7. The fiber-reinforced resin composition according to claim 6, wherein the reinforcing fiber (C) comprises one or more selected from the group consisting of glass fiber, carbon fiber, and aramid fiber.

8. A molded article obtained by molding one or more selected from the group consisting of the resin composition according to any one of claims 1 to 5 and the fiber-reinforced resin composition according to claim 6 or 7.

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