Composition

Abstract

To provide a composition that enables the efficient utilization of the reinforcing effects provided by inorganic fillers.SOLUTION: A composition contains: an aromatic polyether which contains a structural unit represented by formula (1) and a structural unit represented by formula (2), wherein the amount of bonded chlorine atoms is 10-10,000 mass ppm, and the amount of bonded fluorine atoms is 10-10,000 mass ppm; and an inorganic filler.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition. Specifically, the present invention relates to a composition that can efficiently exert the reinforcing effect of an inorganic filler. [Background technology]

[0002] Patent Document 1 discloses that a specific aromatic polyether produced by causing a component having a specific polymerization catalytic activity to be present in a reaction system is mixed with a reinforcing material or filler such as glass fiber, carbon fiber, aramid fiber, calcium carbonate, or calcium silicate and then used. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 64-065129 Summary of the Invention [Problem to be solved by the invention]

[0004] However, in the conventional techniques including Patent Document 1, there is room for further improvement in terms of efficiently exerting the reinforcing effect of the inorganic filler.

[0005] An object of the present invention is to provide a composition capable of efficiently exerting the reinforcing effect of an inorganic filler. [Means for solving the problem]

[0006] As a result of extensive investigations, the present inventors have found that when an inorganic filler is blended with a specific aromatic polyether, the reinforcing effect of the inorganic filler is efficiently exhibited, and have completed the present invention. According to the present invention, the following composition can be provided. 1. An aromatic polyether containing a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), in which the amount of bonded chlorine atoms is 10 to 10,000 ppm by mass and the amount of bonded fluorine atoms is 10 to 10,000 ppm by mass: and an inorganic filler. [ka] 2. The composition according to 1, wherein the aromatic polyether comprises an aromatic polyether (a-1) having a chlorine atom bonded thereto and an aromatic polyether (a-2) having a fluorine atom bonded thereto. 3. The composition according to 1 or 2, wherein the aromatic polyether comprises an aromatic polyether (a-1') formed using 4,4'-dichlorobenzophenone as a monomer component, and an aromatic polyether (a-2') formed using 4,4'-difluorobenzophenone as a monomer component. 4. The composition according to any one of 1 to 3, wherein the aromatic polyether contains a repeating unit represented by the following formula (3): [ka] 5. The composition according to any one of 1 to 4, wherein the inorganic filler has an average fiber length of 0.5 to 20 mm. 6. The composition according to any one of 1 to 5, wherein the content of the inorganic filler is 5 to 100 parts by mass based on 100 parts by mass of the aromatic polyether. 7. The composition according to any one of 1 to 6, having a tensile strength of more than 1.81 times the tensile strength of the aromatic polyether alone. 8. The composition according to any one of 1 to 6, which has a tensile strength of 1.65 to 5.00 times that of the aromatic polyether alone. 9. An aromatic polyether comprising a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), wherein the total chlorine content in the aromatic polyether is 10 to 10,000 ppm by mass and the total fluorine content in the aromatic polyether is 10 to 10,000 ppm by mass; and an inorganic filler. [ka] 10. An aromatic polyether comprising a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), in which the ratio of the total chlorine content in the aromatic polyether to the sum of the total chlorine content in the aromatic polyether and the total fluorine content in the aromatic polyether is 40 to 95 mass%, and an inorganic filler. [ka] 11. The composition according to 9 or 10, wherein the total chlorine content in the aromatic polyether is 100 to 10,000 ppm by mass, and the total fluorine content in the aromatic polyether is 100 to 10,000 ppm by mass. 12. The composition according to any one of 9 to 11, wherein the aromatic polyether contains a repeating unit represented by the following formula (3): [ka] 13. The composition according to any one of 9 to 12, wherein the inorganic filler has an average fiber length of 0.5 to 20 mm. 14. The composition according to any one of 9 to 13, wherein the content of the inorganic filler is 5 to 100 parts by mass based on 100 parts by mass of the aromatic polyether. 15. The composition according to any one of 9 to 14, having a tensile strength of more than 1.81 times the tensile strength of the aromatic polyether alone. 16. The composition according to any one of 9 to 14, having a tensile strength of 1.65 to 5.00 times that of the aromatic polyether alone. Effect of the Invention

[0007] According to the present invention, it is possible to provide a composition that can efficiently exert the reinforcing effect of the inorganic filler. This provides an effect of reducing the amount of inorganic filler to be blended compared to conventional techniques when imparting a certain level of strength to the composition, for example. By reducing the amount of inorganic filler to be blended, an increase in the viscosity of the composition is suppressed, improving kneadability, and also providing an effect of reducing the weight of the composition. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] The composition of the present invention will be described in detail below. In this specification, "x to y" represents a numerical range of "not less than x and not more than y." The upper and lower limit values ​​described in relation to the numerical ranges can be combined in any combination.

[0009] The composition according to one aspect of the present invention (also referred to as the first aspect) comprises: An aromatic polyether comprising a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), the amount of bonded chlorine atoms being 10 to 10,000 ppm by mass, and the amount of bonded fluorine atoms being 10 to 10,000 ppm by mass: and an inorganic filler. [ka]

[0010] According to the composition of this embodiment, the reinforcing effect of the inorganic filler can be efficiently exerted. This provides an effect of reducing the amount of inorganic filler to be blended compared to conventional techniques when imparting a certain level of strength to the composition, for example. By reducing the amount of inorganic filler to be blended, an increase in the viscosity of the composition is suppressed, improving kneadability, and also providing an effect of reducing the weight of the composition.

[0011] (Aromatic polyether) The following describes the method for measuring the amount of chlorine atoms bonded to the aromatic polyether (Cl-1), the amount of chlorine atoms contained as free components in the aromatic polyether (Cl-2, also referred to as the "content of inorganic chlorine"), and the total amount of these chlorine atoms (Cl-3, also referred to as the "content of total chlorine in the aromatic polyether"). The following also describes the method for measuring the amount of fluorine atoms bonded to the aromatic polyether (F-1), the amount of fluorine atoms contained as free components in the aromatic polyether (F-2, also referred to as the "content of inorganic fluorine"), and the total amount of these fluorine atoms (F-3, also referred to as the "content of total fluorine in the aromatic polyether"). The following also describes the method for measuring the amount of potassium atoms and the amount of sodium atoms contained as free components in the aromatic polyether.

[0012] <Calculation of the amount of chlorine atoms (Cl-1) bonded to aromatic polyether> a. Calculate the total chlorine content (mass ppm) (Cl-3) from the results of measuring the total chlorine content (*1: described below) of aromatic polyether. b. For aromatic polyether, calculate the potassium content (ppm by mass) from the measured potassium amount (*2: described below), and calculate the inorganic chlorine content (ppm by mass) (Cl-2) assuming that it contains an equal mole number of inorganic chlorine (chlorine atoms that are not bonded to aromatic polyether) to the potassium. c. Calculate the amount of chlorine atoms (ppm by mass) (Cl-1) bonded to the aromatic polyether by subtracting the inorganic chlorine content (ppm by mass) (Cl-2) from the total chlorine content (ppm by mass) (Cl-3).

[0013] <Calculation of the amount of fluorine atoms (F-1) bonded to aromatic polyether> a. Calculate the total fluorine content (ppm by mass) (F-3) from the results of measuring the total fluorine content (*1: described later) of the aromatic polyether. b. For aromatic polyether, calculate the sodium content (ppm by mass) from the measured sodium amount (*2: described below), and calculate the inorganic fluorine content (ppm by mass) (F-2) assuming that it contains an equal mole number of inorganic fluorine (fluorine atoms that are not bonded to aromatic polyether) to sodium. c. The amount of fluorine atoms (ppm by mass) (F-1) bonded to the aromatic polyether is calculated by subtracting the inorganic fluorine content (ppm by mass) (F-2) from the total fluorine content (ppm by mass) (F-3).

[0014] (*1) Measurement method for total chlorine (Cl-3) and total fluorine (F-3) content in aromatic polyethers The sample (aromatic polyether) is introduced into a combustion furnace and burned in combustion gas containing oxygen. The generated gas is collected in an absorption liquid, which is then separated and quantified using an ion chromatograph. The quantitative value is determined based on a calibration curve created from references of known concentrations. The measurement conditions are as follows: <Sample Combustion> Combustion equipment: AQF-2100H manufactured by Nitto Seiko Analytech Co., Ltd. Combustion furnace temperature setting: front stage 800℃, rear stage 1100℃ Argon flow rate: 400ml / min Oxygen flow rate: 200ml / min Absorbing liquid: Hydrogen peroxide <Ion chromatograph> Analytical equipment: Thermo Fisher Scientific Integrion Column: A guard column (Dionex IonPac AG12A) and a separation column (Dionex IonPac AS12A) were used in conjunction (both columns were manufactured by Thermo Fisher Scientific). Eluent: Na 2 CO 3 (2.7 mmol / l)+NaHCO 3 (0.3mmol / l) Flow rate: 1.5ml / min Column temperature: 30℃ Measurement mode: Suppressor method Detector: Electrical conductivity detector

[0015] (*2) Method for measuring the amount of potassium and sodium in aromatic polyether (the amount of potassium atoms and the amount of sodium atoms contained as free components in aromatic polyether) The contents of potassium atoms (K) and sodium atoms (Na) in the aromatic polyether are measured by ICP emission spectrometry in the following manner: the aromatic polyether is pretreated, and Na is measured at 589.592 nm and K is measured at 766.481 nm. 1 g of the sample is weighed onto a platinum dish, concentrated sulfuric acid is added to it, and then the dish is heated to perform a carbonization treatment. The platinum dish is then placed into an electric furnace and ashed at 550°C for 12 hours. After ashing, hydrochloric acid is added and then heat treatment is performed. After cooling, the volume is adjusted to a constant level with ultrapure water. If the sample contains an inorganic filler, after ashing, hydrofluoric acid is added and then heat treatment is performed to dryness, after cooling, hydrochloric acid is added and then heat treatment is performed. After cooling, the volume is adjusted to a constant level with ultrapure water. The quantitative value is calculated based on a calibration curve prepared from references of known concentrations. The calibration curve solution has the same hydrochloric acid concentration as the sample solution.

[0016] Regarding the calculation of the amount of chlorine atoms (ppm by mass) bound to the aromatic polyether (Cl-1) and the amount of fluorine atoms (ppm by mass) bound to the aromatic polyether (F-1), if 4,4'-difluorobenzophenone or 4,4'-dichlorobenzophenone, which is a monomer (reactant) used in the synthesis of the aromatic polyether, remains in the aromatic polyether, the amount of fluorine atoms contained as 4,4'-difluorobenzophenone and the amount of chlorine atoms contained as 4,4'-dichlorobenzophenone in the aromatic polyether are quantified by the following method, and their influence is eliminated. First, the solid sample (aromatic polyether) is pulverized in a blender, washed with acetone and water in that order, and dried in an explosion-proof dryer at 180°C. When the reaction mixture (product) immediately after the reaction to produce aromatic polyether is used as the sample, the product is cooled and solidified after the reaction is completed to obtain the solid sample. The blender used is not particularly limited, and for example, a Waring 7010HS can be used. Next, weigh out about 1 g of the dried sample into a recovery flask, add 100 ml of cyclohexanone and boiling stones, heat under reflux with a mantle heater for 1 hour, leave to cool to room temperature, and then remove the solids by filtration. The resulting solution is then measured by gas chromatography to calculate the amount of 4,4'-difluorobenzophenone (ppm by mass) and the amount of 4,4'-dichlorobenzophenone (ppm by mass) in the sample. Here, the amount of 4,4'-difluorobenzophenone (ppm by mass) and the amount of 4,4'-dichlorobenzophenone (ppm by mass) in the sample are determined based on a calibration curve created from a reference of known concentration. The measurement conditions for the gas chromatograph are shown below.

[0017] <Gas chromatograph measurement conditions> Analyzer: Agilent Technologies 8890 GC column: Agilent Technologies DB-HeavyWAX (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) Inlet temperature: 250℃ Oven temperature: 250℃ (constant) Flow rate: 1ml / min Injection volume: 1μl Split ratio: 40:1 Detector: FID Detector temperature: 250℃

[0018] The amount of fluorine atoms (ppm by mass) contained in the aromatic polyether as 4,4'-difluorobenzophenone and the amount of chlorine atoms (ppm by mass) contained in the aromatic polyether as 4,4'-dichlorobenzophenone are calculated using the following formula. Amount of fluorine atoms contained in aromatic polyether as 4,4'-difluorobenzophenone (ppm by mass) = amount of 4,4'-difluorobenzophenone in sample (ppm by mass) ÷ 218.20 (molecular weight of 4,4'-difluorobenzophenone) × 19.00 (atomic weight of fluorine) × 2 Amount of chlorine atoms contained in aromatic polyether as 4,4'-dichlorobenzophenone (ppm by mass) = amount of 4,4'-dichlorobenzophenone in sample (ppm by mass) ÷ 251.11 (molecular weight of 4,4'-dichlorobenzophenone) × 35.45 (atomic weight of chlorine) × 2

[0019] When the amount (ppm by mass) of fluorine atoms contained in the aromatic polyether as 4,4'-difluorobenzophenone and the amount (ppm by mass) of chlorine atoms contained in the aromatic polyether as 4,4'-dichlorobenzophenone are both less than 100 ppm by mass, which is the lower limit of quantification, there is no effect on the calculation results of the amount (F-1) of fluorine atoms bonded to the aromatic polyether and the amount (Cl-1) of chlorine atoms bonded to the aromatic polyether described above (the effect is deemed to be negligible). When the amount (ppm by mass) of fluorine atoms contained in the aromatic polyether as 4,4'-difluorobenzophenone (F-4) is 100 ppm by mass or more, the amount (ppm by mass) of fluorine atoms bonded to the aromatic polyether (F-1) can be calculated by subtracting the inorganic fluorine content (ppm by mass) (F-2) from the total fluorine content (ppm by mass) (F-3) and then subtracting the amount (ppm by mass) of fluorine atoms contained as 4,4'-difluorobenzophenone (F-4). When the amount (ppm by mass) of chlorine atoms contained in the aromatic polyether as 4,4'-dichlorobenzophenone (Cl-4) is 100 ppm by mass or more, the amount (ppm by mass) of chlorine atoms bonded to the aromatic polyether (F-1) can be calculated by subtracting the content (ppm by mass) of inorganic chlorine (Cl-2) from the content (ppm by mass) of total chlorine (Cl-3) and then subtracting the amount (ppm by mass) of chlorine atoms contained as 4,4'-dichlorobenzophenone (Cl-4).

[0020] In one embodiment, the amount of chlorine atoms bonded to the aromatic polyether (Cl-1) is 10 mass ppm or more, 50 mass ppm or more, 100 mass ppm or more, 500 mass ppm or more, 1000 mass ppm or more, or 2000 mass ppm or more, and 10000 mass ppm or less, 6000 mass ppm or less, 5000 mass ppm or less, or 4000 mass ppm or less. In one embodiment, the amount of chlorine atoms bonded to the aromatic polyether (Cl-1) is 10 to 10000 mass ppm, 500 to 6000 mass ppm, 1000 to 5000 mass ppm, or 2000 to 4000 mass ppm. In one embodiment, the content of inorganic chlorine (Cl-2) in the aromatic polyether is 0 ppm by mass, 0 ppm by mass or more, 10 ppm by mass or more, 20 ppm by mass or more, 35 ppm by mass or more, or 50 ppm by mass or more, and is 200 ppm by mass or less, 100 ppm by mass or less, 85 ppm by mass or less, or 70 ppm by mass or less. In one embodiment, the content of inorganic chlorine (Cl-2) in the aromatic polyether is 0 to 200 ppm by mass, 10 to 100 ppm by mass, 20 to 85 ppm by mass, or 35 to 70 ppm by mass. In one embodiment, the total chlorine content (Cl-3) in the aromatic polyether is 10 mass ppm or more, 50 mass ppm or more, 100 mass ppm or more, 500 mass ppm or more, 1000 mass ppm or more, or 2000 mass ppm or more, and 10000 mass ppm or less, 6000 mass ppm or less, 5000 mass ppm or less, or 4000 mass ppm or less. In one embodiment, the total chlorine content (Cl-3) in the aromatic polyether is 10 to 10000 mass ppm, 100 to 10000 mass ppm, 500 to 6000 mass ppm, 1000 to 5000 mass ppm, or 2000 to 4000 mass ppm.

[0021] In one embodiment, the amount of fluorine atoms bonded to the aromatic polyether (F-1) is 10 mass ppm or more, 50 mass ppm or more, 100 mass ppm or more, 300 mass ppm or more, 500 mass ppm or more, or 1000 mass ppm or more, and 10000 mass ppm or less, 5000 mass ppm or less, 2500 mass ppm or less, 2000 mass ppm or less, 1500 mass ppm or less, or 1200 mass ppm or less. In one embodiment, the amount of fluorine atoms bonded to the aromatic polyether (F-1) is 10 to 10000 mass ppm, 100 to 5000 mass ppm, 300 to 2500 mass ppm, 500 to 2000 mass ppm, 500 to 1500 mass ppm, or 500 to 1200 mass ppm. In one embodiment, the content of inorganic fluorine (F-2) in the aromatic polyether is 0 ppm by mass, 0 ppm by mass or more, 10 ppm by mass or more, 20 ppm by mass or more, 30 ppm by mass or more, or 50 ppm by mass or more, and is 200 ppm by mass or less, 100 ppm by mass or less, 90 ppm by mass or less, or 85 ppm by mass or less. In one embodiment, the content of inorganic fluorine (F-2) in the aromatic polyether is 0 to 200, 20 to 200 ppm by mass, 30 to 100 ppm by mass, 50 to 100 ppm by mass, or 50 to 90 ppm by mass. In one embodiment, the total fluorine content (F-3) in the aromatic polyether is 10 mass ppm or more, 50 mass ppm or more, 100 mass ppm or more, 300 mass ppm or more, 500 mass ppm or more, or 1000 mass ppm or more, and is 10000 mass ppm or less, 5000 mass ppm or less, 2500 mass ppm or less, 2000 mass ppm or less, 1500 mass ppm or less, or 1200 mass ppm or less. In one embodiment, the total fluorine content (F-3) in the aromatic polyether is 10 to 10000 mass ppm, 50 to 5000 mass ppm, 100 to 2500 mass ppm, 100 to 2000 mass ppm, 300 to 2000 mass ppm, 300 to 1500 mass ppm, 500 to 1500 mass ppm, or 500 to 1200 mass ppm.

[0022] In one embodiment, the amount of potassium atoms contained as free components in the aromatic polyether is 20 ppm by mass or more, 30 ppm by mass or more, or 50 ppm by mass or more, and 150 ppm by mass or less, 100 ppm by mass or less, or 80 ppm by mass or less. In one embodiment, the amount of potassium atoms contained as free components in the aromatic polyether is 20 to 150 ppm by mass, 30 to 100 ppm by mass, or 30 to 80 ppm by mass. In one embodiment, the amount of sodium atoms contained as free components in the aromatic polyether is 20 ppm by mass or more, 30 ppm by mass or more, or 50 ppm by mass or more, and 150 ppm by mass or less, 100 ppm by mass or less, or 90 ppm by mass or less. In one embodiment, the amount of sodium atoms contained as free components in the aromatic polyether is 20 to 150 ppm by mass, 30 to 100 ppm by mass, or 50 to 90 ppm by mass.

[0023] The aromatic polyether may contain an aromatic polyether having a chlorine atom bonded thereto (hereinafter, sometimes referred to as an (a-1) component) and an aromatic polyether having a fluorine atom bonded thereto (hereinafter, sometimes referred to as an (a-2) component). The amount of chlorine atoms bonded to the component (a-1) is, for example, 10 ppm by mass or more, 50 ppm by mass or more, 100 ppm by mass or more, 500 ppm by mass or more, 1000 ppm by mass or more, or 2000 ppm by mass or more, and 10000 ppm by mass or less, 6000 ppm by mass or less, 5000 ppm by mass or less, or 4000 ppm by mass or less. The amount of chlorine atoms bonded to the component (a-1) is, for example, 10 to 10000 ppm by mass, 500 to 6000 ppm by mass, 1000 to 5000 ppm by mass, or 2000 to 4000 ppm by mass. The amount of fluorine atoms bonded to the component (a-2) is, for example, 10 ppm by mass or more, 50 ppm by mass or more, 100 ppm by mass or more, 300 ppm by mass or more, 500 ppm by mass or more, or 1000 ppm by mass or more, and 10000 ppm by mass or less, 5000 ppm by mass or less, 2500 ppm by mass or less, 2000 ppm by mass or less, 1500 ppm by mass or less, or 1200 ppm by mass or less. The amount of fluorine atoms bonded to the component (a-2) is, for example, 10 to 10000 ppm by mass, 50 to 5000 ppm by mass, 100 to 2500 ppm by mass, 100 to 2000 ppm by mass, 300 to 2000 ppm by mass, 300 to 1500 ppm by mass, 500 to 1500 ppm by mass, or 500 to 1200 ppm by mass. In one embodiment, the mass ratio of the (a-1) component to the (a-2) component is preferably 1:99 to 99:1, 21:79 to 99:1, 25:75 to 95:5, 30:70 to 90:10, or further preferably 40:60 to 80:20.

[0024] In one embodiment, the composition contains, as aromatic polyethers, an aromatic polyether formed using 4,4'-dichlorobenzophenone as a monomer component (hereinafter, sometimes referred to as component (a-1')) and an aromatic polyether formed using 4,4'-difluorobenzophenone as a monomer component (hereinafter, sometimes referred to as component (a-2')). The mass ratio of the component (a-1') to the component (a-2') is preferably 1:99 to 99:1, 21:79 to 99:1, 25:75 to 95:5, 30:70 to 90:10, or further preferably 40:60 to 80:20.

[0025] In one embodiment, the 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 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, the 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 end structure bonded to the structural unit may be, for example, a hydrogen atom (H) or the like (when the end 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 chlorine atom (Cl) or hydroxyl group is replaced with a hydrogen atom (H), etc. The terminal structure may have a structure other than those exemplified above.

[0026] In one embodiment, the aromatic polyether comprises a repeating unit represented by formula (3): [ka]

[0027] The structural unit represented by formula (3) is a linkage between a structural unit represented by formula (1) and a structural unit represented by formula (2).

[0028] In one embodiment, the aromatic polyether does not contain any other structure other than the structural units represented by formula (1) and formula (2).

[0029] In one embodiment, the aromatic polyether contains a structure other than the structural units represented by formula (1) and formula (2) as long as the effect of the present invention is not impaired.

[0030] In one embodiment, based on all monomers subjected to the reaction, the total proportion (mass%) of the structural unit represented by formula (1) and the structural unit represented by formula (2) contained in all monomers is 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, and is 100 mass% or less, 99.9 mass% or less, or 100 mass%.

[0031] 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 larger than, smaller than, or the same as the number of moles of the structural unit represented by formula (2).

[0032] In one embodiment, the aromatic polyether is 1 In H-NMR measurements, 1 The peaks at the α-position of the hydroxyl group relative to the peaks attributable to H 1 The area ratio of the peak attributable to H (hereinafter sometimes referred to as "area ratio X") is less than 0.1%. The area ratio X is described in the Examples. 1 This value was determined by H-NMR measurement.

[0033] In one embodiment, the aromatic polyether consists of one aromatic polyether having equal area ratio X.

[0034] In one embodiment, the aromatic polyether according to the present invention is a mixture of two or more aromatic polyethers having different area ratios X. In this case, 1 In the H-NMR measurement, the above-mentioned area ratio X can be achieved. Here, the two or more aromatic polyethers may or may not include an aromatic polyether having an area ratio X of 0.1% or more. The area ratio X of the aromatic polyether having an area ratio X of 0.1% or more may be, for example, 0.12% or more or 0.14% or more, or 2.0% or less, 1.8% or less, or 1.6% or less. The area ratio X of the aromatic polyether having an area ratio X of 0.1% or more may be, for example, 0.10 to 2.0%, 0.12 to 1.8%, or 0.14 to 1.6%.

[0035] In one embodiment, when synthesizing an aromatic polyether using 4,4'-dichlorobenzophenone and hydroquinone, the above-mentioned area ratio X can be made less than 0.1% by making the molar ratio of 4,4'-dichlorobenzophenone to hydroquinone greater than 1.00.

[0036] In one embodiment, when an aromatic polyether is synthesized using 4,4'-difluorobenzophenone and hydroquinone, the molar ratio of 4,4'-difluorobenzophenone to hydroquinone is made larger than 1.00, so that the above-mentioned area ratio X can be made less than 0.1%.

[0037] The method for producing the aromatic polyether is not particularly limited. In one embodiment, the method for producing an aromatic polyether comprises the steps of: Producing component (a-1'); Producing component (a-2'), and Mixing component (a-1') and component (a-2') Includes.

[0038] There are no particular limitations on the method for producing component (a-1'). In one embodiment, the method for producing component (a-1') includes reacting 4,4'-dichlorobenzophenone with hydroquinone.

[0039] 4,4'-Dichlorobenzophenone and hydroquinone are monomers for polymerizing the component (a-1'). Through a step of reacting 4,4'-dichlorobenzophenone and hydroquinone, a copolymer of these compounds (monomer units), (a-1'), can be obtained. 4,4'-Dichlorobenzophenone and hydroquinone are also available as commercial products.

[0040] In the following description, the "reaction mixture" refers to a reaction system from the start of the reaction between 4,4'-dichlorobenzophenone and hydroquinone to the completion of the reaction, and is preferably in the form of a solution containing these monomers as well as a solvent described below. The composition of the reaction mixture may change as the reaction progresses. Usually, as the reaction progresses, the concentration of the reactants (4,4'-dichlorobenzophenone and hydroquinone) in the reaction mixture decreases, and the concentration of the product (component (a-1')) increases.

[0041] Moreover, the "maximum temperature" of the reaction mixture is the maximum temperature (maximum reached temperature) that the reaction mixture reaches during the process from the start of the reaction between 4,4'-dichlorobenzophenone and hydroquinone to the completion of the reaction.

[0042] In one embodiment, the maximum temperature of the reaction mixture may be 260°C or higher, 265°C or higher, 270°C or higher, 275°C or higher, 280°C or higher, 285°C or higher, 290°C or higher, more than 290°C, 295°C or higher, 300°C or higher, 305°C or higher, 310°C or higher, 315°C or higher, 320°C or higher, 325°C or higher, 330°C or higher, or 335°C or higher. The upper limit is not particularly limited, and is, for example, 360°C or lower. The maximum temperature of the reaction mixture is, for example, 260 to 360°C, preferably more than 290°C and 360°C or lower, more preferably 295 to 360°C.

[0043] In one embodiment, the method for producing the component (a-1') includes heating the reaction mixture to 150° C. or higher and then maintaining the temperature. The temperature during the temperature maintenance is not particularly limited and may be, for example, 150 to 360° C. The time for which the temperature is maintained is not particularly limited and may be, for example, 0.1 to 12 hours.

[0044] In one embodiment, the method for producing component (a-1') includes heating the reaction mixture to 150°C or higher, and then either heating the reaction mixture once and holding the temperature, or repeating heating the reaction mixture and holding the temperature multiple times. The number of times the reaction mixture is repeated is not particularly limited, and may be, for example, 2, 3, 4, 5, 6, 7, 8, 9, or 10 times. By repeating the temperature increase and temperature maintenance several times, the reaction can proceed efficiently.

[0045] In one embodiment, the method for producing the component (a-1') includes holding the reaction mixture at 180 to 220°C for 0.5 to 2 hours, preferably 0.6 to 1.8 hours, and more preferably 0.7 to 1.5 hours (hereinafter also referred to as "temperature holding (i)"). This makes it possible to promote the reaction while suppressing the volatilization of the raw materials, and to obtain the component (a-1') with a higher molecular weight. In one embodiment, the method for producing the component (a-1') includes holding the reaction mixture at 230 to 270°C for 0.5 to 2 hours, preferably 0.6 to 1.8 hours, and more preferably 0.7 to 1.5 hours (hereinafter also referred to as "temperature holding (ii)"). This makes it possible to promote the reaction while suppressing the volatilization of the raw materials, and to obtain the component (a-1') with a higher molecular weight. In one embodiment, the method for producing the component (a-1') includes holding the reaction mixture at 280 to 360°C for 1 to 8 hours, preferably 1 to 6 hours, and more preferably 1 to 4 hours (hereinafter also referred to as "temperature holding (iii)"). This allows the component (a-1') to have the desired molecular weight. In one embodiment, the method for producing the component (a-1') may include two or three selected from the group consisting of the above temperature holds (i) to (iii). The two or three temperature holds are preferably performed in ascending order of temperature. Between the two or three temperature holds, the reaction mixture may be heated.

[0046] The heating rate when heating the reaction mixture is not particularly limited and may be, for example, 0.1 to 15° C. / min, 0.1 to 10° C. / min, 0.1 to 8° C. / min, or 0.1 to 5° C. / min. This makes it possible to promote the reaction while suppressing the volatilization of the raw materials, and to obtain the (a-1') component with a higher molecular weight.

[0047] In one embodiment, in the method for producing the component (a-1'), the time from when the temperature of the reaction mixture reaches 150°C to when it reaches the maximum temperature is 2.0 to 10 hours.

[0048] In one embodiment, the reaction mixture includes a solvent. The reaction mixture including the solvent may be in the form of a solution. The solution may include 4,4'-dichlorobenzophenone and hydroquinone dissolved in the solvent. The solvent is not particularly limited, and for example, an aprotic polar solvent can be used. Examples of the aprotic polar solvent include N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dipropylacetamide, N,N-dimethylbenzoic acid amide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, Nn-propyl-2-pyrrolidone, Nn-butyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, Examples of such sulfuric acid include N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-6-methyl-2-piperidone, N-methyl-3-ethylpiperidone, dimethyl sulfoxide, diethyl sulfoxide, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, N,N'-dimethylimidazolidinone, and diphenyl sulfone.

[0049] In one embodiment, the reaction mixture contains an aromatic sulfone, and the content of the solvent having a boiling point of 270 to 330° C. is 0 part by mass or more and less than 1 part by mass relative to 100 parts by mass of the aromatic sulfone, which makes it easy to control the reaction temperature.

[0050] The reaction mixture may contain one or more solvents, and it is particularly preferred that the reaction mixture contains only one type of solvent (single solvent), which can simplify the process.

[0051] In one embodiment, the reaction mixture includes a base, which facilitates the reaction. The base is not particularly limited, and is preferably, for example, an alkali metal salt, etc. The alkali metal salt is not particularly limited, and examples thereof include an alkali metal carbonate, an alkali metal hydrogen carbonate, an alkali metal hydride, an alkali metal hydroxide, etc. Examples of the alkali metal carbonate include potassium carbonate, sodium carbonate, lithium carbonate, rubidium carbonate, and cesium carbonate. Examples of the alkali metal hydrogen carbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate. Among these, potassium carbonate is particularly preferred. These bases may be used alone or in combination of two or more.

[0052] In one embodiment, the reaction mixture includes potassium carbonate. In one embodiment, the reaction mixture includes bases other than potassium carbonate. These bases may be used in combination with potassium carbonate. For example, potassium carbonate may be used in combination with sodium carbonate.

[0053] The total concentration of the base in the reaction mixture is not particularly limited. In one embodiment, the total amount of the base in the reaction mixture is 100 mol parts or more, and 180 mol parts or less, 160 mol parts or less, 140 mol parts or less, or 120 mol parts or less, relative to 100 mol parts of hydroquinone to be added to the reaction mixture. If the total amount of the base is 100 mol parts or more, the reaction time can be shortened. If the total amount of the base is 180 mol parts or less, the generation of a gel component can be suppressed. In addition, the total amount of the base in the reaction mixture is, for example, 100 to 180 mol parts, preferably 100 to 140 mol parts, and more preferably 100 to 120 mol parts, relative to 100 mol parts of hydroquinone to be added to the reaction mixture. In one embodiment, potassium carbonate is blended as a base in the above blending amount.

[0054] The molar ratio ([DCBP]:[HQ]) of 4,4'-dichlorobenzophenone (DCBP) and hydroquinone (HQ) to be reacted is not particularly limited. The molar ratio ([DCBP]:[HQ]) can be appropriately adjusted for the purpose of controlling the molecular weight of the resulting component (a-1'), etc. In one embodiment, the molar ratio ([DCBP]:[HQ]) 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 4,4'-dichlorobenzophenone (DCBP) may be greater than, less than, or equal to the number of moles of hydroquinone (HQ).

[0055] In one embodiment, the total concentration (based on the amount of blend) of 4,4'-dichlorobenzophenone and hydroquinone in the reaction mixture is not particularly limited, and is, for example, 1.0 mol / l or more, 1.2 mol / l or more, 1.3 mol / l or more, 1.4 mol / l or more, or 1.5 mol / l or more, and 6.0 mol / l or less, 5.0 mol / l or less, or 4.0 mol / l or less. The total concentration (based on the amount of blend) of 4,4'-dichlorobenzophenone and hydroquinone in the reaction mixture is, for example, 1.0 to 6.0 mol / l, preferably 1.3 to 5.0 mol / l, more preferably 1.5 to 4.0 mol / l.

[0056] In one embodiment, no other monomers than 4,4'-dichlorobenzophenone and hydroquinone are used as monomers subjected to the above-mentioned reaction.

[0057] In one embodiment, in the above-mentioned reaction, a monomer other than 4,4'-dichlorobenzophenone and hydroquinone is used in combination within a range that does not impair the effects of the present invention.

[0058] In one embodiment, the total proportion (mass%) of 4,4'-dichlorobenzophenone and hydroquinone based on all monomers subjected to the reaction is 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 100 mass%.

[0059] In one embodiment, at the start of the reaction, 70% by weight or more, 80% by weight or more, 90% by weight or more, 95% by weight or more, 99% by weight or more, 99.5% by weight or more, 99.9% by weight or more, or substantially 100% by weight of the reaction mixture is 4,4'-dichlorobenzophenone, hydroquinone, alkali metal salts and solvents, one or more alkali metal salts selected from the group consisting of 4,4'-dichlorobenzophenone, hydroquinone, potassium carbonate and sodium carbonate, and diphenyl sulfone, or 4,4'-dichlorobenzophenone, hydroquinone, potassium carbonate and diphenyl sulfone. Incidentally, in the case of "substantially 100% by mass", unavoidable impurities may be contained.

[0060] The reaction between 4,4'-dichlorobenzophenone and hydroquinone can be carried out in an inert gas atmosphere, which is not particularly limited and may be, for example, nitrogen or argon gas.

[0061] There are no particular limitations on the method for producing component (a-2'). In one embodiment, the method for producing component (a-2') includes reacting 4,4'-difluorobenzophenone with hydroquinone. The component (a-2') can also be produced in the same manner as in producing the component (a-1') described above, except that 4,4'-difluorobenzophenone is used instead of 4,4'-dichlorobenzophenone.

[0062] In one embodiment, component (a-1') is component (a-1). In one embodiment, the (a-2') component is the (a-2) component.

[0063] A mixture of the (a-1') component and the (a-2') component can be used as the aromatic polyether. When using the mixture, the mixing ratio (mass ratio) of the (a-1') component and the (a-2') component can be adjusted to obtain an aromatic polyether having a bonded chlorine atom content of 10 to 10,000 ppm and a bonded fluorine atom content of 10 to 10,000 ppm. The method of mixing the (a-1') component and the (a-2') component is not particularly limited, and examples thereof include mixing with a known mixer and melt kneading with an extruder or the like. Specifically, for example, the (a-1') component and the (a-2') component can be kneaded with a twin-screw kneader or the like in a melted state by heating to 360°C to 440°C. At this time, the (a-1') component and the (a-2') component may be kneaded to obtain an aromatic polyether, and then an inorganic filler may be kneaded with the aromatic polyether, or the (a-1') component, the (a-2') component, and the inorganic filler may be kneaded together.

[0064] Regarding the mixing ratio of the (a-1') component and the (a-2') component, by increasing the proportion of the (a-1') component, the amount of chlorine atoms bonded to the aromatic polyether in the mixture (aromatic polyether) can be increased and the amount of fluorine atoms bonded to the aromatic polyether can be decreased.

[0065] (Inorganic filler) In one embodiment, the inorganic filler comprises one or more selected from the group consisting of glass fibers and carbon fibers. In one embodiment, the inorganic filler is in the form of one or more selected from the group consisting of chopped strands, woven fabrics, nonwoven fabrics, and unidirectional materials (also called "UD materials"). This further improves the strength of the composition.

[0066] In one embodiment, the composition may be a fiber composite material including an aromatic polyether as a matrix and an inorganic filler as a reinforcing fiber. The fiber composite material may be a so-called fiber reinforced thermoplastic (FRTP).

[0067] In one embodiment, when the inorganic filler is a fiber, the average fiber length is 0.5 to 20 mm, 0.5 to 10 mm, 1 to 7 mm, or 2 to 6 mm. The average fiber length of the inorganic filler is determined as the arithmetic average of values ​​measured with a vernier caliper.

[0068] In one embodiment, when the inorganic filler is a fiber, the average fiber diameter is 1 to 30 μm. From the viewpoints of dispersibility of the inorganic filler in the aromatic polyether, surface smoothness and mechanical strength of the molded article, the average fiber diameter of the inorganic filler is preferably 3 to 25 μm, 6 to 20 μm, or further 6 to 13 μm. The average fiber diameter of the inorganic filler is determined as the arithmetic average of values ​​measured in accordance with JIS R 7607:2000.

[0069] The carbon fiber may be treated with a sizing agent. The inorganic filler can be bound into a bundle by the sizing agent. The inorganic filler treated with the sizing agent has the sizing agent attached to its surface. The sizing agent is not particularly limited, and examples thereof include epoxy-based sizing agents, urethane-based sizing agents, polyamide-based sizing agents, and the like. Aromatic polyethers can also be used as the sizing agent. As the sizing agent, one of these may be used alone, or two or more may be used in combination. As the inorganic filler, one that has not been treated with a sizing agent may be used. The sizing agent may be used in combination with a silane coupling agent such as aminosilane, isocyanate silane, or acrylic silane.

[0070] 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 according to 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 single fiber can be used.

[0071] The glass fiber may also be treated with a sizing agent. The glass fiber can be bound into a bundle by the sizing agent. The glass fiber treated with the sizing agent has the sizing agent attached to its surface. 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 the sizing agent. As the sizing agent, one of these may be used alone, or two or more may be used in combination. As the glass fiber, one that has not been treated with a sizing agent may be used. The sizing agent may be used in combination with a silane coupling agent such as aminosilane, isocyanate silane, or acrylic silane.

[0072] The content of the inorganic filler in the composition is not particularly limited. In one embodiment, the content of the inorganic filler is 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, or 40 parts by mass or more, and is 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 55 parts by mass or less, or 50 parts by mass or less, relative to 100 parts by mass of the aromatic polyether. In one embodiment, the content of the inorganic filler is 5 to 100 parts by mass, 5 to 80 parts by mass, 5 to 60 parts by mass, 10 to 60 parts by mass, 20 to 55 parts by mass, 30 to 50 parts by mass, or 40 to 50 parts by mass, relative to 100 parts by mass of the aromatic polyether. By the content of the inorganic filler being 5 parts by mass or more, the reinforcing effect of the inorganic filler can be more suitably obtained, and by the content being 100 parts by mass or less, or even 60 parts by mass or less, the suitability of the composition when kneading and molding is further improved.

[0073] The composition may contain other components other than aromatic polyether and inorganic filler. The other components are not particularly limited, and examples thereof include other resins other than aromatic polyether. Examples of the other resins include fluororesins such as polytetrafluoroethylene. As the other components, one type may be used alone, or two or more types may be used in combination.

[0074] In one embodiment, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 97%, at least 99%, at least 99.5%, and at most 100%, at most 99.9%, or substantially 100% by weight of the composition is Aromatic polyether and inorganic filler, the aromatic polyether, the inorganic filler and the other components mentioned above. Incidentally, when it is "substantially 100% by mass", it may contain inevitable impurities.

[0075] The method for preparing the composition is not particularly limited, and examples thereof include mixing with a known mixer, melt kneading with an extruder, etc. An inorganic filler may be side-fed into the aromatic polyether using a twin-screw kneader.

[0076] Pellets of the composition may be produced and may be used as a raw material for producing molded bodies. In one embodiment, the method for producing pellets includes cutting an inorganic filler into short chopped strands and then adding an aromatic polyether to the inorganic filler. The short fibers and aromatic polyether can be mixed and pelletized to produce pellets (also referred to as "short fiber pellets"). In one embodiment, a method for producing pellets is to immerse a roving of an inorganic filler in a molten aromatic polyether, pultrusion molding the roving, and then cut the roving into a desired pellet length to produce pellets (also called "long fiber pellets"). When producing long fiber pellets as described above, breakage of the inorganic filler can be suppressed.

[0077] A molded article can be produced by molding the composition (which may be in the form of pellets as described above). For molding, known methods such as injection molding, extrusion molding, and blow molding can be used. The composition can also be press molded, and known methods such as cold press and hot press can be used. Furthermore, the composition can be used as a resin composition for 3D printers and molded by a 3D printer.

[0078] In one embodiment, the composition has a tensile strength of 1.75 times or more, more than 1.81 times, 1.82 times or more, 1.85 times or more, 1.90 times or more, or 1.95 times or more, relative to the tensile strength of the aromatic polyether alone. The upper limit of this ratio (also called "increase rate") is not particularly limited, and is, for example, 5.00 times or less or 4.00 times or less. In one embodiment, the composition has a tensile strength of 1.75 to 5.00 times, 1.85 to 5.00 times, or 1.90 to 4.00 times relative to the tensile strength of the aromatic polyether alone. In one embodiment, the composition has a tensile strength that is 1.65 to 5.00 times, 1.75 to 4.00 times, or 1.78 to 3.00 times the tensile strength of the aromatic polyether alone.

[0079] The tensile strength of the composition and the tensile strength of the aromatic polyether alone are measured by the following method. The composition (or the aromatic polyether alone) is injection molded at 400° C. using a small molding machine (MiniJet-Pro, manufactured by Haake) to prepare a dumbbell-shaped 5A specimen as specified in ISO 527-2:2012. The obtained test piece is subjected to a tensile test at a test speed of 5 mm / min and a chuck distance of 50 mm to measure the tensile strength. In preparation for the tensile test, the upper and lower chucks of the tensile tester are adjusted to the specified chuck distance (50 mm), the test piece is held by the lower chuck, and the load is adjusted to zero. After that, the test piece is also held by the upper chuck, and the tensile test is started.

[0080] In one embodiment, the tensile strength of the composition is 160 MPa or more, 170 MPa or more, 180 MPa or more, 190 MPa or more, 198 MPa or more, 200 MPa or more, or 210 MPa or more. There is no particular upper limit, and it is, for example, 400 MPa or less, 350 MPa or less, or 300 MPa or less. In one embodiment, the tensile strength of the composition is 160 to 400 MPa, 170 to 350 MPa, or 198 to 300 MPa. Furthermore, in one embodiment, the tensile strength of the composition is 160.0 to 400.0 MPa, 168.0 to 350.0 MPa, 170.0 to 300.0 MPa, or 175.0 to 250.0 MPa.

[0081] The use of the composition of the present invention is not particularly limited, and can be widely applied to various uses that require strength. The composition of the present invention is suitable for use as a metal replacement material, particularly for uses that require heat resistance, solvent resistance, and durability. More specifically, the composition is suitable for use as a bearing, gasket, structural material, etc.

[0082] The composition according to the second aspect of the present invention comprises an aromatic polyether having a structural unit represented by formula (1) and a structural unit represented by formula (2), the aromatic polyether having a total chlorine content (Cl-3) of 10 to 10,000 ppm by mass and a total fluorine content (F-3) of 10 to 10,000 ppm by mass; and an inorganic filler. According to the second aspect, the same effects as those of the first aspect can be obtained.

[0083] The composition according to the third aspect of the present invention comprises an aromatic polyether containing a structural unit represented by formula (1) and a structural unit represented by formula (2), in which the ratio of the total chlorine content (Cl-3) in the aromatic polyether to the sum of the total chlorine content (Cl-3) in the aromatic polyether and the total fluorine content (F-3) in the aromatic polyether (also referred to as "ratio (Cl / (Cl+F))")) is 40 to 95 mass%; and an inorganic filler. According to the third aspect, the same effects as those of the first aspect can be obtained.

[0084] In the third aspect, the ratio (Cl / (Cl+F)) is preferably 40 to 95 mass%, 50 to 90 mass%, or further preferably 60 to 85 mass%. In one embodiment, the ratio (Cl / (Cl+F)) may be 40 to 60 mass%.

[0085] In the second and third aspects, the total chlorine content (Cl-3) in the aromatic polyether is preferably 100-10,000 mass ppm, and the total fluorine content (F-3) in the aromatic polyether is preferably 100-10,000 mass ppm. This allows the effects of the present invention to be more effectively exhibited. The total chlorine content (Cl-3) in the aromatic polyether and the total fluorine content (F-3) in the aromatic polyether are not limited to the ranges exemplified here, and the ranges exemplified for the composition related to the first aspect can be appropriately applied.

[0086] The compositions according to the second and third aspects are the same as those described for the composition according to the first aspect. However, the compositions according to the second and third aspects are not limited to the composition according to the first aspect (i.e., a composition including an aromatic polyether having a structural unit represented by formula (1) and a structural unit represented by formula (2), a bonded chlorine atom amount of 10 to 10000 ppm, and a bonded fluorine atom amount of 10 to 10000 ppm, and an inorganic filler). The composition according to the present invention may satisfy any two or more of the conditions of the first, second, and third aspects. For example, the composition may be a composition that satisfies both the conditions of the first and second aspects, a composition that satisfies both the conditions of the first and third aspects, a composition that satisfies both the conditions of the second and third aspects, and a composition that satisfies both the conditions of the first, second, and third aspects. EXAMPLES

[0087] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0088] 1. Preparation of Aromatic Polyethers Aromatic polyether (A-1) Into a 300 ml four-neck flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a water collection container connected to a cooling tube, 41.220 g (0.164 mol) of 4,4'-dichlorobenzophenone, 17.809 g (0.162 mol) of hydroquinone, 25.704 g (0.186 mol) of potassium carbonate, and 140.01 g of diphenyl sulfone were placed, and nitrogen gas was passed through.

[0089] The reaction mixture was reacted under the following temperature control. <Temperature control> (1) Heat to 150°C, then heat to 200°C over 30 minutes (2) Hold at 200°C for 1 hour (3) Heat up from 200°C to 250°C (heat up rate 1.7°C / min) (4) Hold at 250°C for 1 hour (5) Heat the reaction mixture from 250°C to 300°C (maximum temperature) (heating rate 3.0°C / min). (6) Hold at 300°C (maximum temperature of the reaction mixture) for 2 hours

[0090] After the reaction was completed, the product was pulverized in a blender (Waring 7010HS), washed with acetone and then with water, and dried in a dryer at 180° C. to obtain powdered PEEK. The obtained PEEK was used as aromatic polyether (A-1).

[0091] Aromatic polyether (A-2) Commercially available PEEK (Victrex, 151G) was used as the aromatic polyether (A-2).

[0092] 2. Preparation of the Composition Example 1 Aromatic polyether (A-1), aromatic polyether (A-2), and inorganic filler (Nippon Electric Glass Co., Ltd., glass fiber, chopped strand ECS03 T-786H, average fiber diameter 10 μm, average fiber length 3 mm) were mixed at a mass ratio (A-1:A-2:inorganic filler) of 20:80:43 using a twin-screw kneader (Termo Fisher Co., Ltd., Process 11) at 400°C to obtain a composition consisting of aromatic polyethers (A-1), (A-2), and inorganic filler.

[0093] 3.Measurement method (1) Tensile strength The obtained composition was injection molded at 400° C. using a small molding machine (MiniJet-Pro, manufactured by Haake) to prepare a dumbbell-shaped 5A specimen as specified in ISO 527-2:2012. The obtained test pieces were subjected to a tensile test at a test speed of 5 mm / min and a chuck distance of 50 mm to measure the tensile strength (also referred to as "reinforced product tensile strength"). In preparation for the tensile test, the upper and lower chucks of the tensile tester were adjusted to the specified chuck distance (50 mm), the test piece was held by the lower chuck, and the load was adjusted to zero. After that, the test piece was also held by the upper chuck, and the tensile test was started. Further, the tensile strength (also referred to as "neat tensile strength") of the aromatic polyether (A) alone (neat) not containing any glass fiber was measured in the same manner as above. Furthermore, the increase rate of the reinforced tensile strength relative to the neat tensile strength (also referred to as "reinforced / neat increase rate") was calculated.

[0094] (2) Measurement of the amount of chlorine and fluorine atoms bonded to aromatic polyether The amount of chlorine atoms bonded to the aromatic polyether (Cl-1), the amount of chlorine atoms contained as free components in the aromatic polyether (Cl-2, also referred to as the "content of inorganic chlorine"), and the total amount of these chlorine atoms (Cl-3, also referred to as the "total chlorine content in the aromatic polyether") were measured by the following method. In addition, the amount of fluorine atoms bonded to the aromatic polyether (F-1), the amount of fluorine atoms contained as free components in the aromatic polyether (F-2, also referred to as the "content of inorganic fluorine"), and the total amount of these fluorine atoms (F-3, also referred to as the "total fluorine content in the aromatic polyether") were measured. In addition, the amount of potassium atoms and the amount of sodium atoms contained as free components in the aromatic polyether were measured.

[0095] <Calculation of the amount of chlorine atoms (Cl-1) bonded to aromatic polyether> a. Calculate the total chlorine content (mass ppm) (Cl-3) from the results of measuring the total chlorine content (*1: described below) of aromatic polyether. b. For aromatic polyether, calculate the potassium content (ppm by mass) from the measured potassium amount (*2: described below), and calculate the inorganic chlorine content (ppm by mass) (Cl-2) assuming that it contains an equal mole number of inorganic chlorine (chlorine atoms that are not bonded to aromatic polyether) to the potassium. c. Calculate the amount of chlorine atoms (ppm by mass) (Cl-1) bonded to the aromatic polyether by subtracting the inorganic chlorine content (ppm by mass) (Cl-2) from the total chlorine content (ppm by mass) (Cl-3).

[0096] <Calculation of the amount of fluorine atoms (F-1) bonded to aromatic polyether> a. Calculate the total fluorine content (ppm by mass) (F-3) from the results of measuring the total fluorine content (*1: described later) of the aromatic polyether. b. For aromatic polyether, calculate the sodium content (ppm by mass) from the measured sodium amount (*2: described below), and calculate the inorganic fluorine content (ppm by mass) (F-2) assuming that it contains an equal mole number of inorganic fluorine (fluorine atoms that are not bonded to aromatic polyether) to sodium. c. The amount of fluorine atoms (ppm by mass) (F-1) bonded to the aromatic polyether is calculated by subtracting the inorganic fluorine content (ppm by mass) (F-2) from the total fluorine content (ppm by mass) (F-3).

[0097] (*1) Measurement method for total chlorine (Cl-3) and total fluorine (F-3) content in aromatic polyethers The sample (aromatic polyether) is introduced into a combustion furnace and burned in combustion gas containing oxygen. The generated gas is collected in an absorption liquid, which is then separated and quantified using an ion chromatograph. The quantitative value is determined based on a calibration curve created from references of known concentrations. The measurement conditions are as follows: <Sample Combustion> Combustion equipment: AQF-2100H manufactured by Nitto Seiko Analytech Co., Ltd. Combustion furnace temperature setting: front stage 800℃, rear stage 1100℃ Argon flow rate: 400ml / min Oxygen flow rate: 200ml / min Absorbing liquid: Hydrogen peroxide <Ion chromatograph> Analytical equipment: Thermo Fisher Scientific Integrion Column: A guard column (Dionex IonPac AG12A) and a separation column (Dionex IonPac AS12A) were used in conjunction (both columns were manufactured by Thermo Fisher Scientific). Eluent: Na 2 CO 3 (2.7 mmol / l)+NaHCO 3 (0.3mmol / l) Flow rate: 1.5ml / min Column temperature: 30℃ Measurement mode: Suppressor method Detector: Electrical conductivity detector

[0098] (*2) Method for measuring the amount of potassium and sodium in aromatic polyether (the amount of potassium atoms and the amount of sodium atoms contained as free components in aromatic polyether) The contents of potassium atoms (K) and sodium atoms (Na) in the aromatic polyether are measured by ICP emission spectrometry in the following manner: the aromatic polyether is pretreated, and Na is measured at 589.592 nm and K is measured at 766.481 nm. 1 g of the sample is weighed onto a platinum dish, concentrated sulfuric acid is added to it, and then the dish is heated to perform a carbonization treatment. The platinum dish is then placed into an electric furnace and ashed at 550°C for 12 hours. After ashing, hydrochloric acid is added and then heat treatment is performed. After cooling, the volume is adjusted to a constant level with ultrapure water. If the sample contains an inorganic filler, after ashing, hydrofluoric acid is added and then heat treatment is performed to dryness, after cooling, hydrochloric acid is added and then heat treatment is performed. After cooling, the volume is adjusted to a constant level with ultrapure water. The quantitative value is calculated based on a calibration curve prepared from references of known concentrations. The calibration curve solution has the same hydrochloric acid concentration as the sample solution.

[0099] In addition, with regard to the above measured values, "-" in Table 1 indicates that the value is 6 ppm by mass or less.

[0100] (Supplementary Exam) Considering the possibility that 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone, which are monomers (reactants) used in the synthesis, may remain in the aromatic polyether, the amount of fluorine atoms contained in the aromatic polyether as 4,4'-difluorobenzophenone and the amount of chlorine atoms contained in the aromatic polyether as 4,4'-dichlorobenzophenone were quantified by the following method. First, the solid sample (aromatic polyether) is pulverized in a blender, washed with acetone and water in that order, and dried in an explosion-proof dryer at 180°C. When the reaction mixture (product) immediately after the reaction to produce aromatic polyether is used as the sample, the product is cooled and solidified after the reaction is completed to obtain the solid sample. The blender used is not particularly limited, and Waring 7010HS was used here. Next, about 1 g of the dried sample was weighed into a recovery flask, 100 ml of cyclohexanone and boiling stones were added thereto, and the mixture was heated under reflux with a mantle heater for 1 hour. After being allowed to cool to room temperature, the solid content was removed by filtration. The resulting solution was then measured by gas chromatography to calculate the amount of 4,4'-difluorobenzophenone (ppm by mass) and the amount of 4,4'-dichlorobenzophenone (ppm by mass) in the sample. Here, the amount of 4,4'-difluorobenzophenone (ppm by mass) and the amount of 4,4'-dichlorobenzophenone (ppm by mass) in the sample were determined based on a calibration curve created from a reference of known concentration. The measurement conditions for the gas chromatograph are shown below.

[0101] <Gas chromatograph measurement conditions> Analyzer: Agilent Technologies 8890 GC column: Agilent Technologies DB-HeavyWAX (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) Inlet temperature: 250℃ Oven temperature: 250℃ (constant) Flow rate: 1ml / min Injection volume: 1μl Split ratio: 40:1 Detector: FID Detector temperature: 250℃

[0102] The amount (ppm by mass) of fluorine atoms contained in the aromatic polyether as 4,4'-difluorobenzophenone and the amount (ppm by mass) of chlorine atoms contained in the aromatic polyether as 4,4'-dichlorobenzophenone were calculated using the following formula. Amount of fluorine atoms contained in aromatic polyether as 4,4'-difluorobenzophenone (ppm by mass) = amount of 4,4'-difluorobenzophenone in sample (ppm by mass) ÷ 218.20 (molecular weight of 4,4'-difluorobenzophenone) × 19.00 (atomic weight of fluorine) × 2 Amount of chlorine atoms contained in aromatic polyether as 4,4'-dichlorobenzophenone (ppm by mass) = amount of 4,4'-dichlorobenzophenone in sample (ppm by mass) ÷ 251.11 (molecular weight of 4,4'-dichlorobenzophenone) × 35.45 (atomic weight of chlorine) × 2

[0103] As a result of the above supplementary tests, the amount of fluorine atoms (ppm by mass) contained in the aromatic polyether as 4,4'-difluorobenzophenone and the amount of chlorine atoms (ppm by mass) contained in the aromatic polyether as 4,4'-dichlorobenzophenone were both less than 100 ppm by mass, which is the lower limit of quantification, and therefore it was confirmed that there was no effect on the calculation results of the amount of fluorine atoms bonded to the aromatic polyether (F-1) and the amount of chlorine atoms bonded to the aromatic polyether (Cl-1) described above.

[0104] In addition, the ratio of the total chlorine content in the aromatic polyether (Cl-3) to the sum of the total chlorine content in the aromatic polyether (Cl-3) and the total fluorine content in the aromatic polyether (F-3) ("ratio (Cl / (Cl+F))") was calculated from the values ​​of the total chlorine content in the aromatic polyether (Cl-3) and the total fluorine content in the aromatic polyether (F-3).

[0105] (3) 1 H-NMR measurement (area ratio X) The aromatic polyether (A) used in the composition was analyzed by the following procedure. 1 H-NMR measurements were performed. PEEK 1 H-NMR measurement was performed, and the ratio (area ratio X) of the area of ​​the peak at the α-position of the hydroxyl group (area from chemical shift 6.98 ppm to 7.03 ppm) to the area of ​​the main chain peak (area from chemical shift 7.32 ppm to 7.36 ppm) was calculated using the following formula. Area ratio X [%] = (Area of ​​the peak at the α-position of the hydroxyl group / Area of ​​the main chain peak) x 100 1 The measurement conditions for H-NMR measurement are as follows. < 1 H-NMR measurement conditions> NMR equipment: Bruker Japan Ascend500 Probe: 5mmφTCI cryoprobe ·NMR sample tube diameter: 5mmφ Sample solution preparation: 0.6 ml of methanesulfonic acid was added to approximately 20 mg of sample, and the mixture was stirred at room temperature for 1 hour. After that, 0.4 ml of deuterated dichloromethane was added and the mixture was stirred at room temperature for an additional 30 minutes to dissolve the sample, producing a sample solution. Observation range: 20 ppm Observation center: 6.175 ppm Number of data points: 64kB Pulse repetition time: 10 seconds Number of times: 256 Flip angle: 30° ·Measurement temperature: 25℃ Chemical shift reference: The middle peak of the three peaks of deuterated dichloromethane is set to 5.32 ppm.

[0106] The above results are shown in Table 1.

[0107] Example 2 A composition was obtained in the same manner as in Example 1, except that the aromatic polyether (A) was a mixture of the aromatic polyethers (A-1) and (A-2) in a mass ratio (A-1:A-2) of 40:60. The obtained composition was measured in the same manner as in Example 1. The results are shown in Table 1.

[0108] Example 3 A composition was obtained in the same manner as in Example 1, except that the aromatic polyether (A) was a mixture of the aromatic polyethers (A-1) and (A-2) in a mass ratio (A-1:A-2) of 60:40. The obtained composition was measured in the same manner as in Example 1. The results are shown in Table 1.

[0109] Example 4 A composition was obtained in the same manner as in Example 1, except that the aromatic polyether (A) was a mixture of the aromatic polyethers (A-1) and (A-2) in a mass ratio (A-1:A-2) of 80:20. The obtained composition was measured in the same manner as in Example 1. The results are shown in Table 1.

[0110] Comparative Example 1 A composition was obtained in the same manner as in Example 1, except that aromatic polyethers (A-1) and (A-2) were used as the aromatic polyether (A) in a mass ratio (A-1:A-2) of 0:100 (the blending of aromatic polyether (A-1) was omitted). The obtained composition was measured in the same manner as in Example 1. The results are shown in Table 1.

[0111] Comparative Example 2 A composition was obtained in the same manner as in Example 1, except that aromatic polyethers (A-1) and (A-2) were used as the aromatic polyether (A) in a mass ratio (A-1:A-2) of 100:0 (the blending of aromatic polyether (A-2) was omitted). The obtained composition was measured in the same manner as in Example 1. The results are shown in Table 1.

[0112] [Table 1]

Claims

1. An aromatic polyether comprising a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), wherein the amount of chlorine atoms bonded is 10 to 10,000 ppm by mass and the amount of fluorine atoms bonded is 10 to 10,000 ppm by mass, and an inorganic filler. 【Chemical 8】

2. The composition according to claim 1, wherein the aromatic polyether comprises an aromatic polyether (a-1) having a chlorine atom bonded thereto and an aromatic polyether (a-2) having a fluorine atom bonded thereto.

3. The composition according to claim 1 or 2, wherein the aromatic polyether comprises an aromatic polyether (a-1') formed using 4,4'-dichlorobenzophenone as a monomer component and an aromatic polyether (a-2') formed using 4,4'-difluorobenzophenone as a monomer component.

4. The composition according to claim 1 or 2, wherein the aromatic polyether comprises a repeating unit represented by the following formula (3). 【Chemical Formula 9】

5. The composition according to claim 1 or 2, wherein the average fiber length of the inorganic filler is 0.5 to 20 mm.

6. The composition according to claim 1 or 2, wherein the content of the inorganic filler is 5 to 100 parts by mass with respect to 100 parts by mass of the aromatic polyether.

7. The composition according to claim 1 or 2, wherein the tensile strength is more than 1.81 times the tensile strength of the aromatic polyether alone.

8. The composition according to claim 1 or 2, wherein the tensile strength is 1.65 to 5.00 times the tensile strength of the aromatic polyether alone.

9. An aromatic polyether comprising a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), wherein the total chlorine content in the aromatic polyether is 10 to 10,000 ppm by mass and the total fluorine content in the aromatic polyether is 10 to 10,000 ppm by mass, and an inorganic filler. 【Chemical Formula 10】

10. An aromatic polyether comprising a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2), wherein the ratio of the total chlorine content in the aromatic polyether to the total of the total chlorine content and the total fluorine content in the aromatic polyether is 40 to 95% by mass, and an inorganic filler. 【Chemical 11】

11. The composition according to claim 9 or 10, wherein the total chlorine content in the aromatic polyether is 100 to 10,000 ppm by mass and the total fluorine content in the aromatic polyether is 100 to 10,000 ppm by mass.

12. The composition according to claim 9 or 10, wherein the aromatic polyether contains a repeating unit represented by the following formula (3). 【Chemical Formula 12】

13. The composition according to claim 9 or 10, wherein the average fiber length of the inorganic filler is 0.5 to 20 mm.

14. The composition according to claim 9 or 10, wherein the content of the inorganic filler is 5 to 100 parts by mass with respect to 100 parts by mass of the aromatic polyether.

15. The composition according to claim 9 or 10, wherein the tensile strength is more than 1.81 times the tensile strength of the aromatic polyether alone.

16. The composition according to claim 9 or 10, wherein the tensile strength is 1.65 to 5.00 times the tensile strength of the aromatic polyether alone.

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