Resin composition, composite material, and molded body

Abstract

This resin composition comprises: an aromatic polyether (A) having a radical amount at 25 °C of 6.5×1015-9.0×1017 spin / g, as measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance; and an amorphous resin (B) in an amount of 10-300 parts by mass with respect to 100 parts by mass of the aromatic polyether (A), wherein the glass transition temperature of the amorphous resin (B) is 180°C or higher.

Description

Resin composition, composite material and molded article

[0001] The present invention relates to a resin composition. More specifically, the present invention relates to a resin composition, a composite material, and a molded article containing an aromatic polyether and an amorphous resin.

[0002] Aromatic polyethers such as polyether ether ketone (PEEK) are classified as super engineering plastics and are thermoplastic resins with excellent heat resistance, chemical resistance, etc. Their applications as metal substitutes are expanding in fields requiring lightweight construction, such as automobiles, and methods for further improving their physical properties are being investigated.

[0003] For example, Patent Document 1 discloses a conductor coated with a polymer alloy of PEEK and polyetherimide (PEI) and a fiber-reinforced resin containing the polymer alloy. Patent Document 2 discloses the glass transition temperature of a polymer alloy of PEEK and PEI (FIG. 1), and discloses that the polymer alloy has improved toughness, reduced molding shrinkage, and improved dimensional stability.

[0004] JP-A-63-080411 JP-A-61-500023

[0005] Although the physical properties of aromatic polyethers have been improved through various studies, further improvements are required in heat resistance, etc. One object of the present invention is to provide an aromatic polyether composition having excellent heat resistance and moldability.

[0006] As a result of extensive research, the present inventors have found that a resin composition containing an aromatic polyether having a specific radical amount and a specified amorphous resin has better heat resistance and moldability than conventional polymer alloys containing aromatic polyethers, because the thermal properties can be well controlled by alloying, and have thus completed the present invention.

[0007] According to the present invention, the following resin composition can be 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 ~9.0 x 10 １７1. A resin composition comprising: an aromatic polyether (A) having a molecular weight of 1.0 ... １５ ~9.0 x 10 １７ 3. The resin composition according to 1 or 2, comprising 10 to 300 parts by mass of an amorphous resin (B) relative to 100 parts by mass of the aromatic polyether (A). 4. The resin composition according to 1 or 2, comprising an aromatic polyether (A) and 1 to 300 parts by mass of an amorphous resin (B) relative to 100 parts by mass of the aromatic polyether (A), wherein the radical amount at 25°C measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance is 10 x 10 １５ ~9.0 x 10 １７spin / g, and the glass transition temperature of the amorphous resin (B) is 180°C or higher. 5. The resin composition according to 4, comprising 10 to 300 parts by mass of the amorphous resin (B) per 100 parts by mass of the aromatic polyether (A). 6. The resin composition according to any one of 1 to 5, having a melting point (Tm) of 300 to 335°C and a difference (Tm - Tg) from the glass transition temperature (Tg) of less than 175°C. 7. The resin composition according to any one of 1 to 5, having a melting point (Tm) of 300 to 330°C and a difference (Tm - Tg) from the glass transition temperature (Tg) of less than 160°C. 8. The resin composition according to any one of 1 to 7, wherein the aromatic polyether (A) comprises one or more selected from the group consisting of polyetheretherketone (PEEK), polyetherketoneketone (PEKK), and polyetherketone (PEK). 9. The resin composition according to any one of 1 to 8, wherein the amorphous resin (B) comprises one or more selected from the group consisting of polyetherimide (PEI), polyethersulfone (PES), polyphenylene ether (PPE), polysulfone (PSU), and polyimide (PI). 10. A composite material comprising the resin composition according to any one of 1 to 9, and 10 to 500 parts by mass of reinforcing fibers (C) per 100 parts by mass of the resin composition. 11. The composite material according to 10, wherein the reinforcing fibers (C) comprise one or more selected from the group consisting of carbon fibers, glass fibers, and aramid fibers. 12. The composite material according to 10 or 11, wherein the reinforcing fibers (C) have an average fiber length of 5 mm or more. 13. A molded product comprising the resin composition according to any one of 1 to 9. 14. A molded product comprising the composite material according to any one of 10 to 12.

[0008] According to the present invention, an aromatic polyether composition having excellent heat resistance and moldability can be provided.

[0009] The resin composition, composite material, and molded article 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 arbitrarily. Furthermore, among the individual embodiments of the aspects of the present invention described below, two or more embodiments that are not mutually contradictory can be combined, and an embodiment combining two or more embodiments is also an embodiment of the aspects of the present invention.

[0010] 1-1. First Aspect of Resin Composition A resin composition according to a first aspect of the present invention is characterized by comprising the following resin components (A) and (B): (A) A radical amount 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 ~9.0 x 10 １７ spin / g: 100 parts by mass Amorphous resin (B): 1 to 300 parts by mass per 100 parts by mass of the component (A)

[0011] In this embodiment, the use of the component (A) results in a greater improvement in the glass transition temperature than when conventional aromatic polyethers are used. This improves the heat resistance of the resin composition. Furthermore, the use of component (A) having a predetermined radical content improves the compatibility between the amorphous resin (B) and the amorphous phase of component (A), thereby enabling control of the solidification rate. For example, reducing the crystallinity can control the crystallization behavior, which leads to improved dimensional stability, thereby improving moldability.

[0012] (Aromatic Polyether (A)) In one embodiment, the radical amount of the aromatic polyether (A) is 6.5 × 10 １５ spin / g or more, 7.0×10 １５ spin / g or more, 20×10 １５ spin / g or more, 30×10 １５ spin / g or more, 40×10 １５ spin / g or more or 50 x 10 １５ spin / g or more, and 9.0 × 10 １７ spin / g or less, 5.0×10１７ spin / g or less or 1.0 x 10 １７ The amount of radicals in the aromatic polyether (A) is 6.5×10 １５ On the other hand, when the radical amount of the aromatic polyether (A) is less than 9.0×10 １７ If the value exceeds spin / g, the thermal stability is insufficient and the molded article does not exhibit sufficient mechanical properties.

[0013] 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, 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 x 10 １５ spin / g or more 1.0×10 １７ spin / g or less.

[0014] The radical amount of the aromatic polyether (A) 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 (A). The radical amount of the aromatic polyether (A) is a value measured by the method described in the examples.

[0015] 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 viewpoints of moldability, thermal stability, and compatibility with the amorphous resin (B).

[0016] 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 (A) is one or more selected from the group consisting of PEEK, PEKK, and 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 (A) is PEEK.

[0017] In one embodiment, the aromatic polyether (A) contains a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

[0018] In one embodiment, the aromatic polyether (A) contains a structural unit represented by the following formula (3):

[0019] 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).

[0020] In one embodiment, the aromatic polyether (A) does not contain any other structure than the structural units represented by formula (1) and formula (2).

[0021] In one embodiment, the aromatic polyether (A) 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.

[0022] 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 (A) are structural units represented by formula (1) and structural units represented by formula (2), or structural units represented by formula (3).

[0023] In one embodiment, in the aromatic polyether (A), 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).

[0024] The terminal structure of the main chain of the aromatic polyether (A) 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 (A). 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 (A). 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 (A) 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.

[0025] The melt flow rate of the aromatic polyether (A) is not particularly limited. In one embodiment, the melt flow rate of the aromatic polyether (A) is 1500 g / 10 min or less, 1000 g / 10 min or less, 500 g / 10 min or less, 300 g / 10 min or less, 200 g / 10 min or less, 100 g / 10 min or less, 80 g / 10 min or less, or 60 g / 10 min or less, and is 0.0001 g / 10 min or more, 0.0005 g / 10 min or more, or 0.001 g / 10 min or more. The melt flow rate of the aromatic polyether (A) is, for example, 0.001 to 500 g / 10 min. From the viewpoint of mechanical properties, it is preferably 0.01 to 100 g / 10 min, and more preferably 0.1 to 50 g / 10 min. The melt flow rate of the aromatic polyether (A) is a value measured by the method described in the examples.

[0026] (Amorphous Resin (B)) The amorphous resin (B) 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 impart an excellent effect of high heat resistance. Specific examples include polyetherimide (PEI), polyethersulfone (PES), polyphenylene ether (PPE), polysulfone (PSU), polyimide (PI), and the like. Among these, PEI is preferred from the viewpoints of toughness, heat resistance, and moldability.

[0027] The amorphous resin (B) may be used alone or in combination of two or more. In one embodiment, the amorphous resin (B) substantially contains one or more selected from the group consisting of PEI, PES, PPE, PSU, and PI. Alternatively, the amorphous resin (B) may consist of only one type.

[0028] The content of the amorphous resin (B) in the resin composition is 1 to 300 parts by mass relative to 100 parts by mass of the aromatic polyether (A). In one embodiment, the content of the amorphous resin (B) in the resin composition is 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 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 relative to 100 parts by mass of the aromatic polyether (A), and is 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. From the viewpoint of dimensional stability of the molded article, 5 parts by mass or more is preferred, and from the viewpoint of crystallization rate (presence of crystals in the molded article), 100 parts by mass or less is preferred. Furthermore, from the viewpoint of controlling the degree of crystallization, the content of the amorphous resin (B) is preferably 15 parts by mass or more.

[0029] The resin composition may contain other components in addition to the aromatic polyether (A) and the amorphous resin (B) as long as the effects of the present invention are not impaired. Examples of the other components include resins other than the aromatic polyether (A). Examples of the other resins include fluororesins such as polytetrafluoroethylene. One type of the other component may be used alone, or two or more types may be used in combination. The resin composition may also contain known resin additives such as antioxidants and nucleating agents.

[0030] In one embodiment, the aromatic polyether (A) and the amorphous resin (B) account for 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 resin composition. Note that "substantially 100% by mass" may include inevitable impurities.

[0031] The content of each component in the resin composition described above can also be applied to the amount of each component blended during preparation of the resin composition. The radical amount of the aromatic polyether (A) described above can also be applied to the radical amount of the aromatic polyether (A) during preparation of the resin composition (immediately before mixing with the amorphous resin (B)). The radical amount of the aromatic polyether (A) described above can also be applied to the radical amount per unit mass of the resin composition.

[0032] In one embodiment, the amount of radicals per unit mass of the resin composition at 25°C measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance is 7.0 x 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 more, or 40 x 10 １５ spin / g or more, and １７ spin / g or less, 6.0×10 １７ spin / g or less or 3.0 x 10 １７ spin / g or less.

[0033] In one embodiment, the resin composition has a melting point (Tm) of 300 to 335°C or 300 to 330°C, and the difference (Tm - Tg) from the glass transition temperature (Tg) is less than 175°C or less than 160°C. This can reduce deformation and residual stress during molding. The melting point (Tm) of the resin composition may be 310°C or higher, 320°C or higher, or 325°C or higher. In one embodiment, the melting point (Tm) of the resin composition is 310 to 330°C, 320 to 330°C, 325 to 330°C, 310 to 335°C, 320 to 335°C, or 325 to 335°C. The difference (Tm - Tg) may be 159°C or lower, 158°C or lower, or 157°C or lower. The lower limit of the difference (Tm - Tg) is not particularly limited, but is, for example, 140°C or higher.

[0034] In one embodiment, the crystallinity of the resin composition is 25% or less, 22% or less, or 20% or less, and 5% or more, hi one embodiment, the crystallinity of the resin composition is 5% to 25%, 5% to 22%, or 5% to 20%.

[0035] The melting point (Tm) is the endothermic peak temperature observed when the sample is cooled from a molten state to 50°C at a rate of 20°C / min and then heated at a rate of 20°C / min in a differential scanning calorimeter measurement. The glass transition temperature (Tg) is the specific heat capacity inflection temperature observed when the sample is cooled from a molten state to 50°C at a rate of 20°C / min and then heated at a rate of 20°C / min in a differential scanning calorimeter measurement. The crystallinity (%) is calculated by dividing the heat of fusion (ΔH) by 130 J / g. Details of the methods for measuring the melting point, glass transition temperature, and crystallinity are shown in the examples.

[0036] The method for producing the resin composition of this embodiment is not particularly limited, and known means can be used. For example, the resin composition can be produced by mixing the aromatic polyether (A) and the amorphous resin (B) and, if necessary, optional components in a predetermined ratio, followed by melt-kneading. A known device such as an extruder can be used for melt-kneading.

[0037] 1-2. Second Aspect of Resin Composition The resin composition according to the second aspect of the present invention comprises an aromatic polyether (A) and 1 to 300 parts by mass of an amorphous resin (B) relative to 100 parts by mass of the aromatic polyether (A). The amount of radicals measured at 25°C using TEMPOL as a standard substance and benzene as a solvent for the standard substance is 10 x 10 １５ ~9.0 x 10 １７ spin / g, and the glass transition temperature of the amorphous resin (B) is 180° C. or higher.

[0038] In this embodiment, the resin composition of the present invention is defined by the radical amount, and the effects are the same as those of the first embodiment of the resin composition described above. The components such as the aromatic polyether (A), the amorphous resin (B), and other components are also the same as those of the first embodiment of the resin composition described above.

[0039] In one embodiment, the amount of radicals per unit mass of the resin composition at 25°C measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance is 10 x 10 １５ spin / g or more, 20×10 １５ spin / g or more, 30×10 １５ spin / g or more, or 40 x 10 １５spin / g or more, and １７ spin / g or less, 6.0×10 １７ spin / g or less or 3.0 x 10 １７ spin / g or less.

[0040] In one embodiment, the amount of radicals per unit mass of the resin composition is 10.0 × 10 １５ spin / g or more 9.0×10 １７ spin / g or less, 20×10 １５ spin / g or more 9.0×10 １７ spin / g or less, 30×10 １５ spin / g or more 6.0×10 １７ spin / g or less, or 40 x 10 １５ spin / g or more 3.0×10 １７ spin / g or less.

[0041] In one embodiment, the resin composition has a melting point (Tm) of 300 to 335°C or 300 to 330°C, and the difference (Tm - Tg) from the glass transition temperature (Tg) is less than 175°C or less than 160°C. This can reduce deformation and residual stress during molding. The melting point (Tm) of the resin composition may be 310°C or higher, 320°C or higher, or 325°C or higher. In one embodiment, the melting point (Tm) of the resin composition is 310 to 330°C, 320 to 330°C, 325 to 330°C, 310 to 335°C, 320 to 335°C, or 325 to 335°C. The difference (Tm - Tg) may be 159°C or lower, 158°C or lower, or 157°C or lower. The lower limit of the difference (Tm - Tg) is not particularly limited, but is, for example, 140°C or higher. In one embodiment, the crystallinity of the resin composition is 25% or less, 22% or less, or 20% or less, and is 5% or more. In one embodiment, the crystallinity of the resin composition is 5% to 25%, 5% to 22%, or 5% to 20%. The methods for measuring the melting point, glass transition temperature, and crystallinity, and the method for producing the resin composition of this aspect are the same as those for the resin composition of the first aspect.

[0042] 2. Composite Material A composite material according to one aspect of the present invention comprises the resin composition according to one aspect of the present invention described above and 10 to 500 parts by mass of reinforcing fibers (C) per 100 parts by mass of the resin composition. The composite material according to this aspect exhibits excellent interfacial shear strength between the resin composition and the reinforcing fibers, resulting in excellent mechanical strength (e.g., tensile strength) as a composite material. While the reason for this effect is not entirely clear, it is presumed that a new structure that has adhesive properties to the reinforcing fibers is formed due to the effect of the high concentration of radicals in the aromatic polyether (A).

[0043] In one embodiment, the content of the reinforcing fiber (C) in the composite material is 20 parts by mass or more, 30 parts by mass or more, or 40 parts by mass or more, and 400 parts by mass or less, 300 parts by mass or less, or 200 parts by mass or less, relative to 100 parts by mass of the resin composition. In one embodiment, the content of the reinforcing fiber (C) in the composite material is 20 parts by mass or more and 400 parts by mass or less, 30 parts by mass or more and 300 parts by mass or less, or 40 parts by mass or more and 200 parts by mass or less, relative to 100 parts by mass of the resin composition.

[0044] In one embodiment, the reinforcing fibers (C) comprise one or more selected from the group consisting of carbon fibers, glass fibers, and aramid fibers. In one embodiment, 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, 99 mass% or more, 99.5 mass% or more, or substantially 100 mass% of the reinforcing fibers (C) are one or more selected from the group consisting of carbon fibers, glass fibers, and aramid fibers.

[0045] 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, phenolic carbon fiber, vapor-grown carbon fiber, and recycled carbon fiber (RCF). In one embodiment, 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, 99 mass% or more, 99.5 mass% or more, or substantially 100 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, phenolic carbon fiber, vapor-grown carbon fiber, and recycled carbon fiber (RCF).

[0046] The types of glass fibers and aramid fibers are not particularly limited, and glass fibers of various compositions, such as E-glass, low dielectric glass, and silica glass, can be selected and used depending on the purpose and application.

[0047] In one embodiment, the average fiber length of the reinforcing fibers (C) is 5 mm or more from the viewpoint of mechanical properties such as strength, elastic modulus, and impact resistance of the molded article. The average fiber length is determined as the arithmetic mean of values ​​measured with a vernier caliper.

[0048] In one embodiment, 50% by weight or more, 60% by weight or more, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, 97% by weight or more, 99% by weight or more, 99.5% by weight or more, or substantially 100% by weight of the composite material is the resin composition and the reinforcing fiber (C).

[0049] The method for producing the composite material (composite method) is not particularly limited. For example, a method of melt-kneading a resin composition with reinforcing fibers, or a method of melting and impregnating an aggregate of reinforcing fibers with a powder, film, or pellet-like resin composition can be used. Composite materials containing continuous reinforcing fibers with an average fiber length of 5 mm or more can be in one or more forms selected from the group consisting of woven fabrics, nonwoven fabrics, and unidirectional materials (also called "UD materials").

[0050] 3. Molded Article The molded article according to one aspect of the present invention is made of the resin composition according to one aspect of the present invention. The molded article according to this aspect has excellent heat resistance.

[0051] A molded article according to another aspect of the present invention is made of the composite material according to one aspect of the present invention. The molded article according to this aspect exhibits excellent interfacial shear strength between the resin composition and the reinforcing fibers in the composite material, thereby achieving excellent mechanical strength (e.g., tensile strength).

[0052] 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.

[0053] The uses of the resin composition, composite material, and molded article described above are not particularly limited and can be widely applied to various applications requiring strength, for example. The resin composition and composite material are suitable, for example, as a metal replacement material, particularly for applications requiring heat resistance, solvent resistance, and durability. More specifically, they can be suitably used for aerospace components, automotive components, sliding components such as gears and bearings, filaments for 3D printers, semiconductor manufacturing equipment components, etc.

[0054] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0055] [Resin Composition] Example 1 (1) Production of Aromatic Polyether Into a 2000 mL four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet pipe, and a water collection container connected to a cooling pipe, 285.63 g (1.138 mol) of 4,4′-dichlorobenzophenone (manufactured by Sino-high Corporation), 123.40 g (1.121 mol) of hydroquinone (manufactured by Tokyo Chemical Industry Co., Ltd.), 159.53 g (1.154 mol) of potassium carbonate (FG-F20 manufactured by AGC Corporation), and 970.30 g of diphenyl sulfone (manufactured by Sino-high Corporation) were placed, and nitrogen gas was passed through.

[0056] After raising the temperature inside the reactor to 150 ° C, the raw materials were dissolved at 150 ° C and a stirring speed of 110 rpm. Subsequently, the stirring speed was increased to 250 rpm, the temperature was raised to 200 ° C over 30 minutes, held at 200 ° C for 1 hour, and the temperature was raised from 200 ° C to 250 ° C over 70 minutes. After holding at 250 ° C for 1 hour, the temperature was raised from 250 ° C to 300 ° C over 110 minutes, and the reaction was carried out for 90 minutes at 300 ° C. Thereafter, 22.51 g (0.090 mol) of 4,4'-dichlorobenzophenone was added as a reaction terminator, and the mixture was held at a stirring speed of 250 rpm for 60 minutes. The contents were then removed to a stainless steel tray and cooled to room temperature to solidify.

[0057] After the reaction was completed, the product was pulverized in a blender (7010HS manufactured by Waring), washed successively with acetone, an aqueous oxalic acid solution, and water, and then dried in a dryer at 180°C to obtain a powdery aromatic polyether (A-1) (PEEK). The melt flow rate of the obtained aromatic polyether (A-1) was measured under the following conditions, and the melt flow rate was 15 g / 10 min.

[0058] [Melt flow rate measurement conditions] Measurements were performed in accordance with JIS K 7210-1:2014 (ISO 1133-1:2011). Apparatus: Melt indexer (Tateyama Scientific Industrial Co., Ltd. L-220) Measurement temperature: 380 ° C. Measurement load (including piston mass): 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 mass: 110.0 g) Procedure: The sample was dried at 190 ° C. for 2 hours or more in advance. The sample was placed in the cylinder, the piston was inserted, and preheated for 6 minutes. A load was applied, the piston guide was removed, and the molten sample was extruded from the die. A sample was cut out at a predetermined range of piston movement and a predetermined time (t [s]), and the mass was measured (m [g]). The melt flow rate (MFR) was calculated using the following formula: MFR [g / 10 min] = 600 / t x m

[0059] (2) Production of Resin Composition 100 parts by mass of the obtained aromatic polyether (A-1), 43 parts by mass of the amorphous resin (B) polyetherimide (SABIC, Ultem 1000, glass transition temperature 217 ° C.: 337 ° C., MFR at 6.6 kg = 9 g / 10 min), and 0.25 parts by mass of a phosphoric acid compound (Ultranox 626) were dry-blended to obtain a dry blend raw material. The dry blend raw material was melt-kneaded using a twin-screw extruder (Thermo Fisher Scientific "Process-11", cylinder volume 20 cc) having a cylinder diameter of 11 mm, at a screw rotation speed of 200 rpm and a set temperature of 370 ° C. Here, the dry blend raw material was supplied from the root (upstream side of the screw) of the twin-screw extruder at 7 g / min. The residence time in the twin-screw extruder was 3 minutes. The strands discharged from the twin-screw extruder were cooled in water and then pelletized using a pelletizer to obtain a resin composition.

[0060] Examples 2 and 3 As shown in Table 1, resin compositions (pellets) were obtained in the same manner as in Example 1, except that the compounding ratio of the aromatic polyether (A-1) and the amorphous resin (B) was changed.

[0061] Example 4 (1) Production of Aromatic Polyether Nitrogen gas was circulated through a 240 L reactor equipped with a stirrer, thermometer, 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, the temperature was raised to 160°C, and after confirming that it had melted, 39.00 kg (155 mol) of 4,4'-dichlorobenzophenone (manufactured by Sino-High Corporation), 16.85 kg (153 mol) of hydroquinone, and 24.32 kg (176 mol) of potassium carbonate (AGC Corporation, fine powder) were added in that order. The reaction mixture was reacted under the following temperature control, followed by the addition of 6.15 kg (25 mol) of 4,4'-dichlorobenzophenone as a reaction terminator.

[0062] <Temperature control> (1) At a stirring speed of 100 rpm, the temperature is raised from 160°C to 200°C over 90 minutes. (2) The temperature is maintained at 200°C for 60 minutes. (3) The temperature is raised from 200°C to 250°C over 80 minutes. (4) The temperature is maintained at 250°C for 60 minutes. (5) The temperature is raised from 250°C to 300°C over 150 minutes. (6) The temperature is maintained at 300°C for 13 minutes. (7) The reaction is stopped by adding a reaction stopper and the temperature is maintained at 300°C. The reaction is terminated when the solution viscosity reaches 330 cP.

[0063] After the reaction was completed, the contents were transferred to a SUS tray and cooled to room temperature to solidify. The product was coarsely pulverized and pulverized using 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. A powdery aromatic polyether (A-3) (PEEK) was obtained. The MFR of the obtained aromatic polyether (A-3) was 4 g / 10 min.

[0064] (2) Production of Resin Composition 100 parts by mass of the obtained aromatic polyether (A-3) was mixed with 100 parts by mass of water. ２ HPO ４ " and Fujifilm Wako Pure Chemical Industries, Ltd. "NaH ２ P.O. ４ " mass ratio (Na ２ HPO ４ : NaH ２ P.O. ４) 3:2) 0.25 parts by mass was added and mixed at 25 ° C. for 30 minutes. After mixing, the mixture was dried at 140 ° C. for 24 hours. Thereafter, 5 parts by mass of polyetherimide (manufactured by SABIC Corporation, Ultem 1000, glass transition temperature 217 ° C.: 337 ° C., MFR = 9 g / 10 min at 6.6 kg) as amorphous resin (B) and 0.25 parts by mass of nucleating agent (manufactured by ADEKA Corporation "NA-21") were dry-blended to obtain a dry-blended raw material. The dry-blended raw material was melt-kneaded at a screw rotation speed of 250 rpm and a set temperature of 380 ° C. using a twin-screw extruder (manufactured by Thermo Fisher Scientific Corporation "Process-11", cylinder volume 20 cc) having an 11 mm cylinder diameter. The dry-blended raw material was supplied from the base of the twin-screw extruder (upstream side of the screw) at 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.

[0065] Comparative Examples 1 to 3 As shown in Table 1, resin compositions (pellets) were obtained in the same manner as in Examples 1 to 3, except that aromatic polyether (A-2) (commercially available PEEK (Victrex, 151G), MFR at 380°C and 2.16 kg: 36 g / 10 min) was used as the aromatic polyether.

[0066] Comparative Example 4 As shown in Table 2, a resin composition (pellet) was obtained in the same manner as in Example 4, except that aromatic polyether (A-4) (commercially available PEEK (Victrex, 150G), MFR at 380°C and 2.16 kg: 3 g / 10 min) was used as the aromatic polyether.

[0067] [Measurement and Evaluation Methods] (1) Radical Amount The radical amount of the aromatic polyether and the radical amount per unit mass of the resin composition were measured by ESR (Electron Spin Resonance) under the following conditions and procedures. [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

[0068] [Procedure] TEMPOL was dissolved in benzene at a concentration of 5 μM, and 400 μL was added to an ESR sample tube, and ESR was measured under the above measurement conditions. The obtained integral value of the peak derived from TEMPOL was divided by the integral value of the peak of Mn for normalization (integral value A). The measurement sample was then weighed (weighed value B), filled into an ESR sample tube, and ESR was measured under the above measurement conditions. The obtained integral value of the peak derived from the sample was divided by the integral value of the peak of Mn for normalization (integral value C). Using the obtained values ​​of A, B, and C, the amount of radicals per unit mass of the sample was calculated according to the following formula: Amount of radicals per unit mass of sample = (5 x 10 －６ x400 x 10 －６ x 6.02 x 10 ２３ × C) / (A × B)

[0069] The radical amount of aromatic polyether (A-1) is 64×10 １５ The radical amount of the aromatic polyether (A-2) was 6.2 × 10 １５ The radical amount of the aromatic polyether (A-3) was 72×10 １５ The amount of radicals in the aromatic polyether (A-4) was 6.4 × 10 １５ The radical amount of the resin composition is shown in Table 1.

[0070] (2) Glass Transition Temperature (Tg), Melting Point (Tm), and Crystallinity A differential scanning calorimeter (DSC) (PerkinElmar DSC No. 9) was used. 5 mg of the resin composition was placed in an aluminum pan, and 1) the temperature was increased to 420°C at a rate of 20°C / min and held for 1 minute. 2) The temperature was then decreased to 50°C at a rate of 20°C / min and held for 1 minute. 3) The temperature was then increased to 420°C at a rate of 20°C / min. The glass transition temperature (Tg) (°C) was measured from the change in specific heat capacity observed in step 3), and the melting point (Tm) (°C) was measured from the temperature of the endothermic peak. The crystallinity (%) was calculated by dividing the heat of fusion (ΔH) by 130 J / g. The results are shown in Tables 1 and 2. The radical amount and thermal properties of the resins used are also shown in Table 3.

[0071]

[0072]

[0073]

[0074] As can be seen from Table 1, the resin composition of Example 1 has a significantly larger amount of radicals than the resin composition of Comparative Example 1, and as a result, the glass transition temperature (Tg) of Example 1 is higher than that of Comparative Example 1. On the other hand, there is no significant change in the melting point (Tm) between the Examples, and therefore it is clear that the difference (Tm - Tg) can be controlled by the blending amount of amorphous resin (B), and the Examples can make the difference (Tm - Tg) smaller than the Comparative Examples.

[0075] [Composite Material and Molded Article] Example 5 A dry blend raw material (100 parts by mass of aromatic polyether (A-1), 67 parts by mass of amorphous resin (B), and 0.25 parts by mass of a phosphoric acid compound) prepared in the same manner as in Example 2 was fed at a rate of 7 g / min from the base (upstream side of the screws) of the twin-screw extruder used in Example 2. The screw rotation speed was set to 200 rpm, and the cylinder temperature was set to 370°C.

[0076] Reinforcing fiber (C) ("TR06U" manufactured by Mitsubishi Engineering Plastics Corporation, chopped carbon fiber, average fiber length 6 mm, filament diameter 7 μm) was fed (side feed) from the middle of the twin-screw extruder at 3 g / min. The strand discharged from the twin-screw extruder was cooled in water and then pelletized using a pelletizer to obtain a composite material (pellet) containing 30 mass% of reinforcing fiber (C) (43 mass parts of reinforcing fiber (C) per 100 mass parts of resin composition).

[0077] Comparative Example 5 A composite material (pellets) was obtained in the same manner as in Example 5, except that the aromatic polyether (A-1) obtained in Example 1 was replaced with the aromatic polyether (A-2).

[0078] Tensile test specimens were molded from the pellets obtained in Example 5 and Comparative Example 5 and evaluated. Specifically, the pellets were injection molded using an injection molding machine ("Mini Jet Pro" manufactured by Thermo Fisher Scientific) under conditions of a cylinder temperature of 400°C, a mold temperature of 200°C, and a dwell time of 10 seconds to prepare ISO527-2-5A tensile test specimens. The tensile modulus [GPa] and tensile strength [MPa] of these tensile test specimens were measured under conditions of a temperature of 23°C and a tensile speed of 2 mm / min. The results are shown in Table 4. The higher the tensile modulus and tensile strength, the better the mechanical strength.

[0079]

[0080] From Table 4, it can be seen that the composite material of Example 5 is superior to the composite material of Comparative Example 5 in tensile modulus and tensile strength.

[0081] 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 ~9.0 x 10 １７ and 1 to 300 parts by mass of an amorphous resin (B) relative to 100 parts by mass of the aromatic polyether (A), wherein the glass transition temperature of the amorphous resin (B) is 180° C. or higher.

2. The standard substance was TEMPOL and the solvent for the standard substance was benzene. The amount of radicals at 25°C was 7.0 x 10 １５ ~9.0 x 10 １７ The resin composition according to claim 1, wherein the viscosity is 1000 s / g.

3. The resin composition according to claim 1 or 2, which contains 10 to 300 parts by mass of an amorphous resin (B) per 100 parts by mass of the aromatic polyether (A).

4. A compound containing an aromatic polyether (A) and 1 to 300 parts by mass of an amorphous resin (B) per 100 parts by mass of the aromatic polyether (A), the amount of radicals at 25°C measured using TEMPOL as a standard substance and benzene as a solvent for the standard substance is 10 x 10 １５ ~9.0 x 10 １７ spin / g, and the glass transition temperature of the amorphous resin (B) is 180° C. or higher.

5. The resin composition according to claim 4, which contains 10 to 300 parts by mass of an amorphous resin (B) per 100 parts by mass of the aromatic polyether (A).

6. A resin composition according to any one of claims 1 to 5, having a melting point (Tm) of 300 to 335°C and a difference (Tm - Tg) between the melting point (Tm) and the glass transition temperature (Tg) of less than 175°C.

7. A resin composition according to any one of claims 1 to 5, having a melting point (Tm) of 300 to 330°C and a difference (Tm - Tg) between the melting point (Tm) and the glass transition temperature (Tg) of less than 160°C.

8. The resin composition according to any one of claims 1 to 7, wherein the aromatic polyether (A) comprises one or more members selected from the group consisting of polyetheretherketone (PEEK), polyetherketoneketone (PEKK) and polyetherketone (PEK).

9. The resin composition according to any one of claims 1 to 8, wherein the amorphous resin (B) comprises at least one selected from the group consisting of polyetherimide (PEI), polyethersulfone (PES), polyphenylene ether (PPE), polysulfone (PSU) and polyimide (PI).

10. A composite material comprising the resin composition according to any one of claims 1 to 9 and 10 to 500 parts by mass of reinforcing fibers (C) per 100 parts by mass of the resin composition.

11. The composite material according to claim 10, wherein the reinforcing fibers (C) comprise at least one type selected from the group consisting of carbon fibers, glass fibers, and aramid fibers.

12. The composite material according to claim 10 or 11, wherein the average fiber length of the reinforcing fibers (C) is 5 mm or more.

13. A molded article made of the resin composition according to any one of claims 1 to 9.

14. A molded article made of the composite material according to any one of claims 10 to 12.

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