Polyaryl ether sulfone

Abstract

To provide a novel aryl ether sulfone that exhibits enhanced dielectric characteristics in high-frequency ranges.SOLUTION: There is provided a polyaryl ether sulfone having a repeating unit represented by general formula (1). (In the formula, Z represents an oxygen atom, a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 15 carbon atoms, a fluorine-containing alkylidene group having 2 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a phenylmethylidene group, a phenylethylidene group, a phenylene group, or a fluorenylidene group. R1 and R2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms. m represents 0 or 1.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel polyarylethersulfone (PAES), and more particularly to a PAES obtained by using a specific bisphenol as a raw material, which has heat resistance and improved dielectric properties in the high frequency band. [Background technology]

[0002] Polyarylethersulfone (PAES) resin is a thermoplastic that boasts heat resistance, dimensional stability, mechanical properties, and flame retardancy, and is known as a type of super engineering plastic. For this reason, PAES resin is used as a material in the electrical and electronic fields, such as relay parts, coil bobbins, and switches; in office and audiovisual parts, such as various parts for copiers and printers; in heat-resistant tableware, such as trays for in-flight meals; and in the medical field, such as dental instruments. The use of PAES in these applications is becoming increasingly sophisticated and specialized.

[0003] In recent years, the transmission speed and frequency of electrical signals transmitted through wireless internet and communication devices have become increasingly high. This has created a demand for higher-frequency insulation for the metal wiring in these devices. In particular, higher-frequency radio waves, such as centimeter waves (SHF: Super High Frequency) and millimeter waves (EHF: Extremely High Frequency), are used for even faster data communications. As frequencies increase, dielectric loss in insulation increases, resulting in attenuation of the transmitted electrical signal. Therefore, materials with excellent dielectric properties that can reduce dielectric loss are needed to accommodate higher frequencies. Meanwhile, excellent heat resistance is also required for the manufacture and use of electrical and electronic components, as well as electronic devices and electronic equipment that use these components. Materials with improved heat resistance are also needed. Resins such as liquid crystal polymers (LCPs) and polyaryletherketones (PAEKs) are predominantly used for this purpose, while PAES has received little attention.

[0004] Among PAES obtained from bisphenol compounds and dihalogenated diphenyl sulfones, PAES obtained from 4,4'-methylenebis(2,6-dimethylphenol), a bisphenol having hydrocarbon groups at the two ortho positions of the hydroxy group, and 4,4'-dichlorodiphenyl sulfone is known to have improved heat resistance (Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Unexamined Patent Publication No. 58-101114 Summary of the Invention [Problem to be solved by the invention]

[0006] The dielectric properties of the PAES described in Patent Document 1 have not been known at all until now, and it has not been known at all whether or not it is suitable as a resin material to be used in electronic devices and electronic devices used therein (hereinafter, these may be collectively referred to as electronic devices and devices), particularly in electronic devices and devices used for high-speed communications using radio waves in high frequency bands such as centimeter waves and millimeter waves, which are in demand these days (hereinafter, these may be referred to as high-frequency communication electronic devices and devices). The present inventors synthesized PAES (polyphenylsulfone: PPSU) obtained using 4,4'-biphenol as the raw material bisphenol, which is a commonly used PAES, and PAES (polysulfone: PSU) obtained using 2,2-bis(4-hydroxyphenyl)propane, and evaluated their dielectric properties in the high frequency band. They found that the relative permittivity and dielectric loss tangent were high, and that the dielectric properties were poor for use as a resin material in electronic devices. In this situation, an object of the present invention is to provide a novel PAES having improved dielectric properties in the high frequency band. [Means for solving the problem]

[0007] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that PAES having specific hydrocarbon groups at the 2- and 5-positions relative to the oxygen atoms in the structural portion derived from the phenol moiety in the repeating unit has not only the excellent heat resistance inherent to PAES but also improved dielectric properties in the high frequency band, and have completed the present invention.

[0008] The present invention is as follows. 1. Polyaryl ether sulfone having a repeating unit represented by general formula (1). [ka] (In the formula, Z represents an oxygen atom, a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 15 carbon atoms, a fluorine-containing alkylidene group having 2 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a phenylmethylidene group, a phenylethylidene group, a phenylene group, or a fluorenylidene group; R1 and R2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms; and m represents 0 or 1.) 2. The polyaryl ether sulfone according to 1., wherein the repeating unit represented by general formula (1) is a repeating unit represented by chemical formula (1a). [ka] 3. The polyarylethersulfone according to 2., wherein the content of the repeating unit represented by chemical formula (1a) is 60 mol % or more of the entire polyarylethersulfone. 4. A molded article of polyarylethersulfone according to 1. 5. A polyarylethersulfone resin material for use in electronic devices and devices, comprising the polyarylethersulfone according to 1. A polyarylethersulfone resin material for use in electronic equipment and devices for high-frequency communication in the range of 1 GHz or more and 300 GHz or less, comprising the polyarylethersulfone described in 6.1. 7. Electronic devices using the polyarylethersulfone described in 1. 8. Electronic equipment and devices for high-frequency communication in the range of 1 GHz to 300 GHz, using the polyarylethersulfone described in 1. 9. A method for using the polyarylethersulfone according to 1. in an electronic device. 10. A method for using the polyarylethersulfone according to 1. in electronic equipment and devices for high-frequency communication in the range of 1 GHz or more and 300 GHz or less. 11. A polyarylethersulfone resin composition comprising the polyarylethersulfone according to 1. above and one or more additives selected from the group consisting of flame retardants, heat stabilizers, oxidation stabilizers, weather resistance stabilizers, antistatic agents, lubricants, and plasticizers. A molded article of the polyarylethersulfone resin composition according to 12.11. 13. An electronic device using the polyarylethersulfone resin composition according to 11. 14. The polyaryl ether sulfone according to 1., wherein the structure at both ends of the polymer chain of the polyaryl ether sulfone is any one of the structures (i) to (iii). (i) Both are one group selected from the groups represented by general formula (4) or chemical formula (5). (ii) One is a group selected from the groups represented by general formula (4) or chemical formula (5), and the other is a halogen atom. (iii) One is a group selected from the groups represented by general formula (4) or chemical formula (5), and the other is a hydroxy group. [ka] (In the formula, R3 represents a hydrogen atom or a methyl group, and * represents the bonding site to the end of the polymer chain.) 15. The polyaryl ether sulfone according to 14, having a weight average molecular weight (Mw) in the range of 2,000 or more and 100,000 or less. [Effects of the Invention]

[0009] The polyarylethersulfone of the present invention has the excellent heat resistance of conventional PAES and also has improved dielectric properties in the high-frequency band, making it suitable as a resin material for use in electronic devices and devices, particularly those used in high-speed communications using radio waves in the high-frequency band ranging from 1 GHz to 300 GHz (electronic devices and devices for high-frequency communications in the range from 1 GHz to 300 GHz). DETAILED DESCRIPTION OF THE INVENTION

[0010] (PAES of the present invention) The PAES of the present invention has a repeating unit represented by general formula (1). [ka] (In the formula, Z represents an oxygen atom, a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 15 carbon atoms, a fluorine-containing alkylidene group having 2 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a phenylmethylidene group, a phenylethylidene group, a phenylene group, or a fluorenylidene group; R1 and R2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms; and m represents 0 or 1.) In general formula (1), Z represents an oxygen atom, a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 15 carbon atoms, a fluorine-containing alkylidene group having 2 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a phenylmethylidene group, a phenylethylidene group, a phenylene group, or a fluorenylidene group. Among these, a sulfonyl group, an alkylidene group having 1 to 15 carbon atoms, a fluorine-containing alkylidene group having 2 to 15 carbon atoms, or a fluorenylidene group is preferred, a sulfonyl group, an alkylidene group having 1 to 15 carbon atoms, or a fluorenylidene group is more preferred, a sulfonyl group or an alkylidene group having 1 to 15 carbon atoms is even more preferred, and an alkylidene group having 1 to 15 carbon atoms is particularly preferred. In an alkylidene group having 1 to 15 carbon atoms, both of the two bonding positions are preferably positions 1. Among these, an alkylidene group having 1 to 12 carbon atoms and both of the two bonding positions being positions 1 is preferred, an alkylidene group having 1 to 8 carbon atoms and both of the two bonding positions being positions 1 is more preferred, an alkylidene group having 1 to 6 carbon atoms and both of the two bonding positions being positions 1 is even more preferred, and an alkylidene group having 1 carbon atom and both of the two bonding positions being positions 1, i.e., a methylene group, is particularly preferred. Specific examples of the alkylidene group having 1 to 15 carbon atoms include a methylene group, a 1,1-ethylidene group, a 1,1-propylidene group, a 2,2-propylidene group, a 1,1-butylidene group, a 2,2-butylidene group, a 1,1-pentylidene group, a 2,2-pentylidene group, a 4-methyl-2,2-pentylidene group, a 2-ethyl-1,1-hexylidene group, and a 1,1-decylidene group. Among these, preferred are methylene, 1,1-ethylidene, 1,1-propylidene, 1,1-butylidene, 1,1-pentylidene, 2-ethyl-1,1-hexylidene, and 1,1-decylidene groups, in which both of the two bonding positions of the alkylidene group are 1-positions, and more preferred among these are methylene, 1,1-ethylidene, 1,1-propylidene, 1,1-butylidene, and 1,1-pentylidene groups. The cycloalkylidene group having 5 to 15 carbon atoms may contain an alkyl group as a branched chain. Specific examples of the cycloalkylidene group include a cyclopentylidene group (5 carbon atoms), a cyclohexylidene group (6 carbon atoms), a 3-methylcyclohexylidene group (7 carbon atoms), a 4-methylcyclohexylidene group (7 carbon atoms), a 3,3,5-trimethylcyclohexylidene group (9 carbon atoms), a cycloheptylidene group (7 carbon atoms), and a cyclododecanylidene group (12 carbon atoms). In general formula (1), R1 and R2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms. The hydrocarbon group having 1 to 6 carbon atoms is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 to 6 carbon atoms, or a phenyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 5 to 6 carbon atoms, or a phenyl group, still more preferably a linear or branched alkyl group having 1 to 4 carbon atoms or a phenyl group, and particularly preferably an alkyl group having 1 carbon atom, i.e., a methyl group. Specific examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, pentyl, 2-methylpentyl, and hexyl. Among these, methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl are preferred, methyl, ethyl, isopropyl, and t-butyl are more preferred, and methyl is particularly preferred. Specific examples of the cyclic alkyl group having 5 to 6 carbon atoms include a cyclopentyl group and a cyclohexyl group, with the cyclohexyl group being preferred. In the general formula (1), m represents 0 or 1, and 0 is preferred from the viewpoint of availability of raw materials.

[0011] In general formula (1), when m is 0, specific examples of the repeating unit represented by chemical formulae (1a) to (1h) include structures of chemical formulae (1a) to (1h). Among the repeating units represented by general formula (1), it is preferable to have a repeating unit selected from the repeating units represented by chemical formulae (1a) to (1h), more preferable to have a repeating unit selected from the repeating units represented by chemical formulae (1a) to (1d) and (1h), even more preferable to have a repeating unit selected from the repeating units represented by chemical formulae (1a), (1b), (1d) and (1h), and particularly preferable to have a repeating unit selected from the repeating unit represented by chemical formula (1a). [ka] [ka] In the general formula (1), when m is 1, specific examples of the repeating unit represented by the formula (1i) to (1x) include structures of the formulae (1i) to (1x), and it is preferable to have a repeating unit selected from the repeating units represented by the formulae (1i) to (1x). From the viewpoint of the heat resistance of the resulting PAES, it is more preferable to have a repeating unit selected from the repeating units represented by the formulae (1i) to (1p). [ka] [ka] [ka] [ka]

[0012] The PAES of the present invention may have one structure selected from the repeating units represented by general formula (1), or may have two or more structures selected from the repeating units represented by general formula (1). An embodiment having one structure selected from the repeating units represented by general formula (1) is preferred. The PAES of the present invention may contain other repeating units as long as it contains the repeating unit represented by general formula (1), as long as the effects of the present invention are not impaired. However, it is preferred that the content of the repeating unit represented by general formula (1) is 100 mol %, i.e., that the PAES does not contain any other repeating units. When other repeating units are contained, the lower limit of the content of the repeating units represented by general formula (1) is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more of the total PAES. The upper limit is preferably less than 100 mol%, more preferably 99.9 mol% or less. The above lower and upper limits of the content of the repeating units represented by general formula (1) may be combined. The repeating units represented by general formula (1) and other repeating units may be arranged regularly or randomly. A PAES having the repeating units represented by general formula (1) and other repeating units can be produced by performing the polycondensation reaction described below using a bisphenol compound represented by general formula (3) described below and an aromatic dihydroxy compound in combination.

[0013] In the repeating unit represented by general formula (1), when Z is a methylene group, R1 and R2 are methyl groups, and m is 0, it is represented by chemical formula (1a). [ka] The PAES having a repeating unit represented by chemical formula (1a) preferably accounts for 50 mol % or more of the total PAES, more preferably 60 mol % or more, even more preferably 80 mol % or more, and particularly preferably 92 mol % or more.

[0014] The PAES of the present invention preferably does not have a sulfonic acid group, a phosphoric acid group, or a carboxyl group in its polymer chain when used in the components, members, molded articles, etc., which will be described later. The chemical structures of the sulfonic acid group, the phosphoric acid group, and the carboxyl group are groups represented by the following formulas, respectively. [ka]

[0015] The structures at both ends of the polymer chain of the PAES of the present invention are not particularly limited. They may have a halogen atom derived from a dihalogen compound represented by general formula (2) described later, a hydroxy group derived from a bisphenol compound represented by general formula (3) described later, or a terminal structure in which the hydroxy group has been modified with a reactive functional group, for example, a group represented by general formula (4) (specifically, an acryloyloxy group or a methacryloyloxy group) or a group represented by chemical formula (5) (a glycidyl ether group). [ka] (In the formula, R3 represents a hydrogen atom or a methyl group, and * represents the bonding site to the end of the polymer chain.) This reactive functional group is preferably one group selected from a group represented by general formula (4) (specifically, an acryloyloxy group or a methacryloyloxy group) and a group represented by chemical formula (5) (a glycidyl ether group). When the terminal structures are (i) both halogen atoms, (ii) both hydroxy groups, or (iii) one halogen atom and the other hydroxy group, the PAES of the present invention can be used as a thermoplastic resin. By applying a conventional molding or processing method for a thermoplastic resin (e.g., a melt molding method such as injection molding, extrusion molding, or compression molding), molded articles for use in electronic devices can be produced, and electronic devices and devices can be manufactured. Furthermore, when the terminal structures are (i) both reactive functional groups, (ii) one reactive functional group and the other a halogen atom, or (iii) one reactive functional group and the other a hydroxyl group, at least one of the terminal structures has a reactive functional group, and therefore the PAES of the present invention can be used as a curable resin. By applying conventional molding and processing methods for curable resins (e.g., compression molding and transfer molding), molded articles for use in electronic devices and electronic devices can be produced, for example.

[0016] (molecular weight) The weight-average molecular weight (Mw) of the PAES of the present invention is not particularly limited, but is preferably in the range of 2,000 to 1,000,000, more preferably 10,000 to 500,000, even more preferably 20,000 to 200,000, and particularly preferably 30,000 to 150,000. When the terminal structures of the polymer chain of the PAES of the present invention are (i) both halogen atoms, (ii) both hydroxy groups, or (iii) one halogen atom and the other hydroxy group, in order to provide sufficient mechanical strength when used as a thermoplastic resin, the weight-average molecular weight (Mw) is more preferably in the range of 10,000 or more and 500,000 or less, even more preferably in the range of 20,000 or more and 200,000 or less, and particularly preferably in the range of 30,000 or more and 150,000 or less. When the terminal structures of the PAES of the present invention are (i) both reactive functional groups, (ii) one reactive functional group and the other a halogen atom, or (iii) one reactive functional group and the other a hydroxy group, in order to provide good processability when used as a curable resin, the weight average molecular weight (Mw) is preferably in the range of 2,000 to 100,000, more preferably in the range of 2,000 to 50,000, even more preferably in the range of 2,000 to 30,000, and particularly preferably in the range of 2,000 to 10,000. The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), Mw / Mn, is preferably in the range of 1.5 or more and 20 or less, more preferably in the range of 2 or more and 15 or less, even more preferably in the range of 2 or more and 10 or less, and particularly preferably in the range of 2 or more and 8 or less.

[0017] (glass transition temperature) The glass transition temperature of the PAES of the present invention is preferably 150° C. or higher, more preferably 180° C. or higher, even more preferably 200° C. or higher, and particularly preferably 220° C. or higher. The higher the glass transition temperature, the more excellent the heat resistance, and therefore the upper limit is not particularly limited, but may be 300° C. or lower. The PAES of the present invention can be suitably used as a polyarylethersulfone resin material for electronic devices and devices that are exposed to high temperatures during manufacturing processes and in use, particularly for high-frequency communication electronic devices and devices in the range of 1 GHz or more and 300 GHz or less.

[0018] (dielectric loss tangent) The dielectric loss tangent of the PAES of the present invention measured at frequencies of 1 GHz and 10 GHz is preferably 0.005 or less. If the dielectric loss tangent is 0.005 or less, the PAES can be suitably used as a polyarylethersulfone resin material for electronic devices and devices, particularly for high-frequency communication electronic devices and devices in the range of 1 GHz to 300 GHz. The dielectric loss tangent is more preferably 0.0045 or less, and particularly preferably 0.0040 or less. The lower the dielectric loss tangent, the better, so there is no particular restriction on the lower limit, but it may be 0.001 or more.

[0019] (dielectric constant) The relative dielectric constant of the PAES of the present invention measured at frequencies of 1 GHz and 10 GHz is preferably 3.5 or less. If the relative dielectric constant is 3.5 or less, it can be suitably used as a polyarylethersulfone resin material for electronic devices and devices, particularly for high-frequency communication electronic devices and devices in the range of 1 GHz to 300 GHz. The relative dielectric constant is more preferably 3.0 or less, even more preferably 2.9 or less, and particularly preferably 2.8 or less. The lower the relative dielectric constant, the better, so there is no particular restriction on the lower limit, but it may be 2.0 or more.

[0020] (Production method of PAES of the present invention) The method for producing the PAES of the present invention is not particularly limited, and for example, the PAES can be produced by subjecting a dihalogen compound represented by general formula (2) and a bisphenol compound represented by general formula (3) to a desalting polycondensation reaction in the presence of an alkali metal compound. [ka] (In the formula, each X independently represents a halogen atom, and m is defined as in general formula (1).) [ka] (In the formula, Z, R1, and R2 are defined as in general formula (1).)

[0021] As a specific example, when 4,4'-dichlorodiphenyl sulfone (2a) is used as the dihalogen compound represented by general formula (2), bis(4-hydroxy-2,5-dimethylphenyl)methane (3a) is used as the bisphenol compound represented by general formula (3), and potassium carbonate is used as the alkali metal compound, PAES having a repeating unit represented by chemical formula (1a) can be produced. The reaction formulas are shown below. [ka]

[0022] (Dihalogen compound represented by general formula (2)) Specifically, X in the general formula (2) represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and among these, a fluorine atom or a chlorine atom is preferred, and a chlorine atom is particularly preferred. In general formula (2), m is preferably 0 from the viewpoint of availability. Specific examples of the dihalogen compound represented by general formula (2) include 4,4'-difluorodiphenyl sulfone, 4,4'-dichlorodiphenyl sulfone, 4,4'-dibromodiphenyl sulfone, 4,4'-diiododiphenyl sulfone, 1,4-bis[(4-fluorophenyl)sulfonyl]benzene, 1,4-bis[(4-chlorophenyl)sulfonyl]benzene, 1,4-bis[(4-bromophenyl)sulfonyl]benzene, 1,4-bis[(4-iodophenyl)sulfonyl]benzene, 1,3-bis[(4-fluorophenyl)sulfonyl]benzene, 1,3-bis[(4-chlorophenyl)sulfonyl]benzene, 1,3-bis[(4-bromophenyl)sulfonyl]benzene, and 1,3-bis[(4-iodophenyl)sulfonyl]benzene. Of these, 4,4'-difluorodiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone are preferred, with 4,4'-dichlorodiphenyl sulfone being particularly preferred.

[0023] (Bisphenol compound represented by general formula (3)) The definitions and preferred embodiments of Z, R1, and R2 in general formula (3) are the same as those in general formula (1). Specific examples of the bisphenol compound represented by the general formula (3) include bis(4-hydroxy-2,5-dimethylphenyl)methane (3a), bis(4-hydroxy-2,5-diethylphenyl)methane, bis(4-hydroxy-2,5-diisopropylphenyl)methane, bis(4-hydroxy-2,5-diisobutylphenyl)methane, bis(4-hydroxy-2,5-dicyclohexylphenyl)methane, bis(4-hydroxy-2-methyl-5-cyclohexylphenyl)methane, and bis(4-hydroxy-2,5-diphenylphenyl)methane. , 1,1-bis(4-hydroxy-2,5-dimethylphenyl)ethane, 2,2-bis(4-hydroxy-2,5-dimethylphenyl)propane, bis(4-hydroxy-2,5-dimethylphenyl)sulfone, 1,1-bis(4-hydroxy-2,5-dimethylphenyl)cyclohexane, 1,1-bis(4-hydroxy-2,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, bis(4-hydroxy-2,5-dimethylphenyl)phenylmethane, and 9,9-bis(4-hydroxy-2,5-dimethylphenyl)fluorene. At least one of these compounds may be used, and it is also possible to use only one type or two or more types in combination. Among these, bis(4-hydroxy-2,5-dimethylphenyl)methane (3a), bis(4-hydroxy-2,5-diethylphenyl)methane, bis(4-hydroxy-2,5-diisopropylphenyl)methane, bis(4-hydroxy-2,5-diisobutylphenyl)methane, bis(4-hydroxy-2,5-dicyclohexylphenyl)methane, bis(4-hydroxy-2-methyl-5-cyclohexylphenyl)methane, bis(4-hydroxy-2,5-diphenylphenyl)methane, 1,1-bis(4-hydroxy-2,5-dimethylphenyl)ethane, 2,2-bis(4-hydroxy-2,5-dimethylphenyl)propane, bis(4-hydroxy-2,5-dimethylphenyl)sulfone, and 9,9-bis(4-hydroxy-2,5-dimethylphenyl)fluorene are preferred, and bis(4-hydroxy-2,5-dimethylphenyl)methane is also preferred. Bis(4-hydroxy-2,5-dimethylphenyl)methane, bis(4-hydroxy-2-methyl-5-cyclohexylphenyl)methane, 1,1-bis(4-hydroxy-2,5-dimethylphenyl)ethane, 2,2-bis(4-hydroxy-2,5-dimethylphenyl)propane, bis(4-hydroxy-2,5-dimethylphenyl)sulfone, and 9,9-bis(4-hydroxy-2,5-dimethylphenyl)fluorene are more preferred, and bis(4-hydroxy-2,5-dimethylphenyl)methane, bis(4-hydroxy-2-methyl-5-cyclohexylphenyl)methane, 1,1-bis(4-hydroxy-2,5-dimethylphenyl)ethane, 2,2-bis(4-hydroxy-2,5-dimethylphenyl)propane, and bis(4-hydroxy-2,5-dimethylphenyl)sulfone are even more preferred, with bis(4-hydroxy-2,5-dimethylphenyl)methane being particularly preferred.

[0024] (Other aromatic dihydroxy compounds) In the PAES of the present invention, in order to obtain a PAES having a repeating unit represented by general formula (1) and other repeating units, other aromatic dihydroxy compounds can be used in combination with the bisphenol compound represented by general formula (3). The other repeating units have a structure derived from the aromatic hydroxy compound and a structure derived from the dihalogen compound represented by general formula (2). The aromatic dihydroxy compound other than the bisphenol compound represented by general formula (3) is preferably an aromatic dihydroxy compound that does not contain a group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, and a carboxylic acid group, and more preferably an aromatic hydroxy compound represented by general formula (6). [ka] (In the formula, R represents a divalent group represented by general formula (6a) or (6b).) [ka] (In the formula, each R4 independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, or a phenyl group; each a independently represents an integer of 0 to 4; b represents 0 or 1; c represents 0, 1, or 2; and * represents a bonding position.) [ka] (In the formula, each R4 independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, or a phenyl group; Y represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a divalent group represented by general formula (7a), (7b), or (7c); Z represents an oxygen atom, a sulfur atom, or no crosslink; and * represents each bonding position.) [ka] (In general formulas (7a), (7b), and (7c), each R5 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; two R5s may be bonded to each other to form a cycloalkylidene group having 5 to 20 carbon atoms as a whole; each R6 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms; each Ar1 independently represents an aryl group having 6 to 12 carbon atoms; and each * indicates a bonding position.) Specific examples of other aromatic dihydroxy compounds that can be used in combination include hydroquinone, resorcinol, 2-phenylhydroquinone, 4,4'-biphenol, 3,3'-biphenol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,1'-bi-2-naphthol, 2,2'-bi-1-naphthol, 1,3-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,4-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,4-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,5-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,6-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,7-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,8-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,9-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,1'-bi-2-naphthol, 2,2'-bi-1-naphthol, 1,3-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,4-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,5-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,6-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,7-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,8-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,9-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,9-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,9-bis[1- phenyl)ethyl]benzene, 1,4-bis(4-hydroxyphenyl)benzene, 1,3-bis(4-hydroxyphenyl)benzene, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3,5-dimethylphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane (Bis-A), 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4'-dihydroxybenzophenone, bis( 4-hydroxyphenyl) sulfone, 4,4'-dihydroxydiphenyl ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(3-phenyl-4-hydroxyphenyl)fluorene, 9,9-bis(3,5-diphenyl-4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, bisphenol Z (1,1-bis(4-hydroxyphenyl)cyclohexane), bisphenol TMC (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane), 1,1-bis(4-hydroxyphenyl)cyclododecane, and 1,1-bis(4-hydroxyphenyl)-1-phenylethane. These compounds may be used alone or in combination of two or more. The other repeating units have a structure derived from these aromatic hydroxy compounds and a repeating unit having a structure derived from a dihalogen compound represented by general formula (2).

[0025] (alkali metal compounds) Any alkali metal compound can be used as long as it can convert the bisphenol compound represented by general formula (3) into an alkali metal salt, but usually, carbonates, hydrogen carbonates, hydroxides, etc. of alkali metals are suitably used, with carbonates being particularly preferred. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium, with sodium and potassium being preferred, and potassium being particularly preferred.

[0026] (solvent) A solvent can be used in the polycondensation reaction to obtain PAES, and its use is preferred. The solvent used is preferably an aprotic polar solvent such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), dimethyl sulfoxide (DMSO), sulfolane, or diphenyl sulfone, but any solvent can be used without any problems as long as it dissolves the monomer and polymer. The solvent may be used alone, or two or more types may be used in combination as a mixed solvent.

[0027] (Conditions for polycondensation reaction) The amount of the dihalogen compound represented by general formula (2) used depends on the target molecular weight relative to the bisphenol compound represented by general formula (3) (when an aromatic dihydroxy compound other than general formula (3) is used in combination, the total amount of the bisphenol compound represented by general formula (3) and the other aromatic dihydroxy compound). To produce a PAES with a high molecular weight (specifically, preferably in the range of 10,000 or more and 500,000 or less, more preferably in the range of 20,000 or more and 200,000 or less, and particularly preferably in the range of 30,000 or more and 150,000 or less), the amount is usually in the range of 0.9 to 1.1 times by mole, preferably in the range of 0.95 to 1.06 times by mole, and more preferably in the range of 1.0 to 1.04 times by mole. On the other hand, to produce PAES with a small molecular weight (specifically, preferably in the range of 2,000 to 100,000, more preferably in the range of 2,000 to 50,000, even more preferably in the range of 2,000 to 30,000, and particularly preferably in the range of 2,000 to 10,000), the amount is usually in the range of 0.6 to 1.4 times by mole, preferably in the range of 0.7 to 1.3 times by mole, and more preferably in the range of 0.8 to 1.2 times by mole. In the case of PAES in which both terminal structures of the polymer chain of the produced PAES are halogen atoms, the molar ratio is in the range of 1.01 to 1.1 times by mole, preferably in the range of 1.01 to 1.06 times by mole, and more preferably in the range of 1.01 to 1.04 times by mole. In the case of PAES in which both terminal structures of the polymer chain of the produced PAES are hydroxy groups, the molar ratio for PAES with a high molecular weight is in the range of 0.9 to 0.99 molar times, and preferably in the range of 0.95 to 0.99 molar times, while the molar ratio for PAES with a low molecular weight is usually in the range of 0.6 to 0.95 molar times, preferably in the range of 0.7 to 0.9 molar times, and more preferably in the range of 0.8 to 0.9 molar times. The amount of alkali metal ions of the alkali metal compound used is usually in the range of 2.0 to 3.0 times by mole, and preferably in the range of 2.02 to 2.6 times by mole, relative to the bisphenol compound represented by general formula (3) (when an aromatic dihydroxy compound other than general formula (3) is used in combination, the total amount of the bisphenol compound represented by general formula (3) and the other aromatic dihydroxy compound). The reaction temperature is usually in the range of 120 to 350°C, preferably in the range of 140 to 250°C, and the reaction time is usually 1 to 400 hours, preferably 2 to 160 hours. These reactions are preferably carried out in an atmosphere of an inert gas such as nitrogen or argon. There is no limitation on the reaction pressure, and the reaction may be carried out at reduced pressure, atmospheric pressure, or elevated pressure, but the reaction is usually carried out at atmospheric pressure.

[0028] <Post-reaction treatment> The PAES produced by the polycondensation reaction can be recovered by a commonly used method such as coagulation, solidification, washing, granulation, extraction, or solvent distillation. A method for treating PAES produced by the polycondensation reaction will be described in more detail below. A solution containing PAES produced by the polycondensation reaction can be obtained by mixing a solution obtained by diluting the reaction solution containing the polymer with a solvent, if necessary, with a poor solvent to precipitate PAES, thereby obtaining powdery PAES. In this process, water is a preferred solvent for removing alkali metal salts, but acidic water containing low concentrations of hydrochloric acid, formic acid, oxalic acid, or the like may also be used. The resulting PAES precipitate is then preferably washed with a solvent to remove raw material monomers and the like. Examples of suitable solvents include methanol, ethanol, acetone, methyl ethyl sulfone, xylene, and toluene. Acetone and methanol are particularly preferred due to their ease of operation and ease of distillation recovery of the reaction solvent after washing. The conditions for the above washing step may be appropriately selected, such as the amount of washing solvent used, the number of washings, and the washing temperature, depending on the amounts of the residual raw material monomer, reaction solvent, and alkali metal salt to be removed. After washing with acetone or methanol, the product may be dissolved in an aprotic polar solvent such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), dimethyl sulfoxide (DMSO), sulfolane, or diphenyl sulfone to remove any remaining alkali metal salts, followed by precipitation with water or acidic water. The equipment used for washing may be a combination of a washing tank and a pressure filter or a centrifuge, or a multi-function filter that can perform washing, filtering, and drying in one device.

[0029] A drying step can be carried out to dry the powdery PAES containing water and solvent obtained in the above washing step. The conditions for this drying step may be any conditions that allow removal of moisture at a temperature below the melting point of the polycondensation reaction product. To minimize contact with air, the step is preferably carried out in an inert gas (nitrogen, argon, etc.) atmosphere, in an inert gas stream, or under reduced pressure. The dryer may be a known device such as an evaporator, a tray oven, or a tumbler.

[0030] In the case where the structure of both ends of the polymer chain of the polyarylethersulfone (PAES) of the present invention is a terminal structure modified with a reactive functional group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyl ether group, the PAES can be obtained by modifying the hydroxy group derived from the bisphenol compound represented by general formula (3) into a reactive substituent.

[0031] The PAES of the present invention, whose terminal structure is a group represented by general formula (4) (an acryloyloxy group or a methacryloyloxy group), can be produced by applying a conventionally known method for (meth)acrylation of a hydroxy compound to a PAES having a repeating unit represented by general formula (1) containing a hydroxy group at the end of the polymer chain obtained by the above-mentioned method. One method for (meth)acrylation is, for example, to react the terminal hydroxy groups of PAES having a repeating unit represented by general formula (1) with (meth)acrylic acid or a derivative thereof. When acrylic acid chloride is used as the (meth)acrylic acid derivative, chloride ions are generated in the form of hydrogen chloride, so it is preferable to use a hydrogen chloride scavenger in combination. As the hydrogen chloride scavenger, any inorganic or organic basic substance such as an alkali metal carbonate or bicarbonate, or a tertiary amine can be used. Specific examples of (meth)acrylic acid and its derivatives include acrylic acid, methacrylic acid, acrylic acid chloride, and methacrylic acid chloride. In the acrylation reaction, a solvent such as a halogenated hydrocarbon such as methylene chloride, tetrahydrofuran, dioxane, or chlorobenzene may be used. During the reaction, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, phenothiazine, or 2,6-di-tert-butyl-4-methylphenol (BHT) may be added.

[0032] The PAES of the present invention, whose terminal structure is a group represented by chemical formula (5) (glycidyl ether group), can be produced by applying a conventionally known method for glycidyl etherifying a hydroxy compound to PAES having a repeating unit represented by general formula (1) containing a hydroxy group at the end of the polymer chain obtained by the above-mentioned method. As a method for glycidyl etherification, for example, a glycidyl etherified PAES can be produced by reacting the terminal hydroxy group of PAES having a repeating unit represented by general formula (1) with epihalohydrin in the presence of an alkali metal hydroxide (e.g., sodium hydroxide or potassium hydroxide) or a quaternary ammonium salt (e.g., tetramethylammonium chloride or tetramethylammonium bromide). Specific examples of the epihalohydrin used include epichlorohydrin and epibromohydrin.

[0033] <Polyarylethersulfone resin composition> The PAES of the present invention can be blended with various additives, such as a flame retardant, a heat stabilizer, an oxidation stabilizer, a weathering stabilizer, an antistatic agent, a lubricant, and a plasticizer, as desired, by a conventional method of blending an additive with a raw material resin, within a range that does not impair the effects of the present invention.A polyarylethersulfone resin composition can be obtained, which contains the PAES of the present invention and one or more additives selected from the group consisting of a flame retardant, a heat stabilizer, an oxidation stabilizer, a weathering stabilizer, an antistatic agent, a lubricant, and a plasticizer. This polyarylethersulfone resin composition can be used in the same manner as the PAES of the present invention described below.

[0034] <Use of PAES of the present invention> (molded product) The PAES of the present invention can be used to produce molded articles such as films, sheets, tapes, containers, threads, lenses, tubes, pellets, and chips by applying a conventional molding and processing method for thermoplastic resins (e.g., melt molding methods such as injection molding, extrusion molding, and compression molding) or a conventional molding and processing method for curable resins (e.g., compression molding and transfer molding). The PAES of the present invention can be used as a resin material for and molded into articles such as electronic devices and electronic devices used therein (electronic devices and devices), which will be described later, and electronic devices and devices used for high-speed communication using radio waves in the high-frequency band of 1 GHz to 300 GHz (electronic devices and devices for high-frequency communication in the range of 1 GHz to 300 GHz), as well as machine parts (e.g., impellers, fan gears, gears, bearings, motor parts, cases), automobile parts (e.g., automobile mechanism parts, engine parts, engine room parts, electrical parts, interior parts), cooking utensils and tools, dental instruments, optical equipment parts (e.g., lenses, films), medical equipment parts and materials, dental equipment parts and materials, valves, pipes, nozzles, filters, membranes, sanitary equipment, sporting goods, leisure goods, and cable ties.

[0035] (high frequency radio waves) In the present invention, high-frequency band radio waves refer to radio waves with frequencies in the range of 1 GHz to 300 GHz, including microwaves, centimeter waves (SHF: Super High Frequency), millimeter waves (EHF: Extremely High Frequency), etc. The frequency range of such high-frequency band radio waves is preferably 3 GHz to 100 GHz, more preferably 5 GHz to 80 GHz, and particularly preferably 5 GHz to 30 GHz.

[0036] (Polyarylethersulfone resin material for electronic devices) The PAES of the present invention has heat resistance, one of the properties of PAES, and also has improved dielectric properties in the high-frequency band. Therefore, a resin material containing the PAES of the present invention is suitable as a polyarylethersulfone resin material (polyarylethersulfone resin material for electronic devices and devices) for use in electronic devices and electronic devices used therein (electronic devices and devices), and is particularly suitable as a polyarylethersulfone resin material (polyarylethersulfone resin material for high-frequency communication electronic devices and devices in the range of 1 GHz to 300 GHz) for use in electronic devices and devices used for high-speed communications using radio waves in the high-frequency band in the range of 1 GHz to 300 GHz. The polyarylethersulfone resin material for electronic devices and devices containing the PAES of the present invention may be a resin material consisting only of the PAES of the present invention, depending on the properties required for the electronic device or device to be manufactured, or may be a resin material containing the PAES of the present invention and one or more additives selected from the group consisting of a flame retardant, a heat stabilizer, an oxidation stabilizer, a weather stabilizer, an antistatic agent, a lubricant, and a plasticizer.

[0037] (Electronic devices) In the present invention, electronic devices and electronic devices used therein are collectively referred to as "electronic devices and devices." In particular, electronic devices and devices used for high-speed communication using radio waves in the high-frequency band ranging from 1 GHz to 300 GHz are collectively referred to as "electronic devices and devices for high-frequency communication in the range of 1 GHz to 300 GHz." The PAES of the present invention has heat resistance, which is one of the properties of PAES, and also has excellent dielectric properties in the high frequency band. Therefore, electronic devices and devices using the PAES of the present invention are preferred, particularly electronic devices and devices for high frequency communication in the range of 1 GHz or more and 300 GHz or less. Specific examples of the electronic devices include mobile phones, smartphones, personal computers, mobile routers, data center communication equipment, base stations, radar, robots, drones, wearable computers, measurement and measuring instruments used in various industries such as automobiles, aircraft, manufacturing, agriculture, logistics, and civil engineering, high-speed wireless communication equipment, electronic organizers, digital still cameras, video cameras, electronic paper, televisions, players, various audio equipment, car navigation devices, in-vehicle displays such as instrument panels, calculators, printers, scanners, copiers, refrigerators, and washing machines. Among these, electronic devices used for high-speed communication using high-frequency radio waves include mobile phones, smartphones, personal computers, mobile routers, data center communication equipment, base stations, radar, robots, drones, wearable computers, measurement and measuring equipment used in various industries such as automobiles, aircraft, manufacturing, agriculture, logistics, and civil engineering, and high-speed wireless communication equipment. Specific examples of the electronic devices include semiconductors, electronic displays, and electrical and electronic components. Examples of the electrical and electronic components include capacitors, printed circuits, connectors, various sensors, inductors, switches, and housings. These are also used in electronic devices used for high-speed communication using high-frequency radio waves. More specifically, the PAES and polyarylethersulfone resin materials of the present invention can be suitably used, for example, in exterior components, structural components, circuit boards, semiconductor encapsulants, or antenna element components of these electronic devices and electronic equipment (preferably, electronic devices and devices for high-frequency communication in the range of 1 GHz to 300 GHz). Among these, the PAES and polyarylethersulfone resin materials are more suitably used in circuit boards, semiconductor encapsulants, and antenna element components of electronic devices and electronic equipment, and are particularly suitably used in circuit boards of electronic devices and electronic equipment. [Example]

[0038] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0039] The analytical method in the present invention is as follows. <Analysis method> 1. Measurement of glass transition temperature (Tg) The glass transition temperatures of the PAES obtained in the examples and comparative examples were measured using the following apparatus and conditions. Measurement device: DMA850 (TA Instruments) Heating rate: 4.0℃ / min. Frequency: 1Hz Atmosphere:Air Measurement mode: Tensile Test piece: 40mm x 7mm x thickness 0.02~0.05mm Analysis method: The peak top of tanδ is taken as the glass transition point 2. Measurement of relative permittivity and dielectric loss tangent The relative dielectric constant and dielectric loss tangent of the PAES obtained in the examples and comparative examples were measured using the following apparatus and conditions. Measurement equipment: CP431 1GHz cavity resonator (Kanto Electronics Application Development Co., Ltd.), CP531 10GHz cavity resonator (Kanto Electronics Application Development Co., Ltd.), N5222B PNA network analyzer (Keysight Technologies, Inc.), cylindrical cavity resonator (material: copper, internal mirror finish) Test piece: L80~90 x W1.4~1.6 x t0.03~0.06 (mm) Measurement frequency: Around 10GHz Measurement environment: Room temperature (23±1℃ / 50±5%RH) Measurement method: IEC62810 compliant (cavity resonator perturbation method) 3.Molecular weight measurement The molecular weight of PAES obtained in the examples and comparative examples described below was measured by dissolving the PAES obtained by polymerization in a solvent, passing the solution through a 0.45 μm membrane filter, and then by gel permeation chromatography (GPC) using the following apparatus and conditions. Equipment: Pump: LC-10ADvp (Shimadzu Corporation) Column: Shodex GPC KF-806L + KF-802 (Showa Denko K.K.) Detector: Shodex RI-71 (Showa Denko K.K.) Temperature: 50℃ Mobile phase: N-methyl-2-pyrrolidone Flow rate: 0.8mL / min. Injection volume: 100μL Detection: Refractive index Standard material: polystyrene

[0040] Example 1 (Synthesis of PAES) A 1 L four-necked flask reaction vessel equipped with a Dean-Stark tube filled with toluene and fitted with a Liebig condenser on top, a stirrer, and a nitrogen inlet tube was charged with 27.20 g of 4,4'-dichlorodiphenyl sulfone as monomers, 23.80 g of bis(4-hydroxy-2,5-dimethylphenyl)methane, 13.35 g of dried potassium carbonate, 289.02 g of dimethylacetamide (DMAc), and 51.00 g of toluene, and the mixture was stirred and dissolved under a nitrogen atmosphere. The liquid temperature was then heated to 160°C, and the polymerization reaction was carried out for 120 hours while distilling off the water produced by the reaction. After the reaction was completed, DMAc was added to form a solution of approximately 10 wt % (the total weight of the monomers used was considered the weight of the solute), and the solution was cooled to room temperature. The DMAc solution was mixed with approximately 10 times the amount of pure water relative to the DMAc solution to precipitate a polymer. The precipitate was separated by filtration, and the residue was then mixed with methanol and filtered again to obtain PAES powder. Furthermore, for washing, the separated powder was dissolved in DMAc and then mixed with 1 wt % aqueous hydrochloric acid to precipitate the polymer, which was then filtered. To further remove the hydrochloric acid, the residue was poured into pure water and filtered to obtain washed PAES powder. The resulting PAES has a repeating unit represented by chemical formula (1a). [ka] (Forming into PAES film) The PAES powder was dissolved in DMAc to prepare a solution, which was then cast onto a glass substrate and air-dried for 10 minutes. The solution was then dried at 80°C for 1 hour, then at 120°C for 1 hour, 160°C for 1 hour, 200°C for 1 hour, and 240°C for 1 hour under reduced pressure using a vacuum pump to obtain a PAES film.

[0041] <Comparative Example 1> (Synthesis of PAES (PPSU)) In a 500 mL four-neck flask equipped with a Dean-Stark tube filled with toluene and fitted with a Liebig condenser, a stirrer, and a nitrogen inlet, 9.91 g of 4,4'-biphenol (as a monomer), 7.80 g of dried potassium carbonate, 144.56 g of dimethylacetamide (DMAc), and 25.54 g of toluene were charged and dissolved at room temperature under a nitrogen stream. The solution was then heated to 150°C under a nitrogen atmosphere, and the water in the solution was azeotropically dehydrated overnight while refluxing the toluene. The liquid temperature was then cooled to 100°C or below under a nitrogen atmosphere, and 15.59 g of 4,4'-dichlorodiphenyl sulfone was added as a monomer and dissolved in the solution. The liquid temperature was then heated to 160°C, and the polymerization reaction was carried out for 120 hours while distilling off the water produced by the reaction outside the reaction system. After the reaction was completed, DMAc was added to the reaction mixture to form a solution of approximately 10% by weight, with the total weight of the monomers used as the solute weight. The solution was then cooled to room temperature. The DMAc solution was mixed with approximately 10 times the amount of pure water to precipitate the polymer. The precipitate was filtered, mixed with methanol, and filtered again to obtain PAES powder. The obtained PAES has a repeating unit represented by the following chemical formula. [ka] (Forming into PAES film) The PAES powder was dissolved in DMAc to prepare a solution, which was then cast onto a glass substrate and air-dried for 10 minutes.Then, the solution was dried at 80°C for 1 hour, 120°C for 1 hour, 160°C for 1 hour, 200°C for 1 hour, and 250°C for 1 hour, to obtain a PAES film.

[0042] <Comparative Example 2> (Synthesis of PAES (PUS)) A 500 mL four-necked flask reaction vessel equipped with a Dean-Stark tube filled with toluene and fitted with a Liebig condenser, a stirrer, and a nitrogen inlet tube was charged with 14.33 g of 4,4'-dichlorodiphenylsulfone and 11.17 g of 2,2-bis(4-hydroxyphenyl)propane as monomers, 7.03 g of dried potassium carbonate, 144.50 g of DMAc, and 25.56 g of toluene, and the mixture was stirred and dissolved under a nitrogen atmosphere. The temperature was then raised to 160°C, and the polymerization reaction was carried out for 75 hours while distilling off the water produced by the reaction. After the reaction was completed, DMAc was added to the reaction solution to form an approximately 10 wt. % solution, with the total weight of the monomers used considered as the solute weight. The solution was then cooled to room temperature. The DMAc solution was mixed with approximately 10 times the amount of pure water relative to the DMAc solution to precipitate a polymer. The precipitate was filtered, then mixed with methanol and filtered again to obtain PAES powder. Furthermore, for washing, the filtered powder was dissolved in DMAc and mixed with 1 wt. % aqueous hydrochloric acid to precipitate a polymer, which was then filtered. To further remove the hydrochloric acid, the filtered product was poured into pure water and filtered to obtain a washed PAES powder. The obtained PAES has a repeating unit represented by the following chemical formula. [ka] (Forming into PAES film) The PAES powder obtained by the synthesis of the above PAES was formed into a film in the same manner as in the formation of the PAES film in Example 1.

[0043] <Comparative Example 3> (Synthesis of PAES) In a 1 L four-neck flask equipped with a Dean-Stark tube filled with toluene and fitted with a Liebig condenser on top, a stirrer, and a nitrogen inlet tube, 30.29 g of 4,4'-dichlorodiphenyl sulfone as monomers, 20.71 g of bis(4-hydroxyphenyl)methane, 14.87 g of dried potassium carbonate, 289.06 g of dimethylacetamide (DMAc), and 51.01 g of toluene were charged and dissolved with stirring. The solution was then heated to 160°C under a nitrogen atmosphere, and the polymerization reaction was carried out for 26 hours while distilling off the water produced by the reaction. After the reaction was completed, DMAc was added to the reaction solution so that the total weight of the monomers used was approximately 10% by weight, assuming the weight of the solute. The solution was then cooled to room temperature. The DMAc solution was poured into pure water in an amount approximately 10 times the amount of the DMAc solution, to precipitate a polymer, and then filtered. The filtered material was then poured into methanol and filtered. Furthermore, for washing, the filtered powder was dissolved in DMAc and mixed with 1% by weight of hydrochloric acid in water, to precipitate a polymer, and then filtered. Furthermore, to remove the hydrochloric acid, the filtered material was poured into pure water and filtered, yielding a washed PAES powder. The obtained PAES has a repeating unit represented by the following chemical formula. [ka] (Forming into PAES film) The PAES powder obtained by the synthesis of the above PAES was formed into a film in the same manner as in the formation of the PAES film in Example 1.

[0044] <Comparative Example 4> (Synthesis of PAES) In a 500 mL four-neck flask equipped with a Dean-Stark tube filled with toluene and fitted with a Liebig condenser on top, a stirrer, and a nitrogen inlet tube, 13.59 g of 4,4'-dichlorodiphenyl sulfone and 11.90 g of bis(4-hydroxy-3,5-dimethylphenyl)methane as monomers, 6.67 g of dried potassium carbonate, 144.51 g of DMAc, and 25.52 g of toluene were charged and dissolved under a nitrogen atmosphere with stirring. The liquid temperature was then heated to 160°C, and the polymerization reaction was carried out for 140 hours while distilling off the water produced by the reaction. After the reaction was completed, DMAc was added to the reaction mixture to form a solution of approximately 10% by weight, with the total weight of the monomers used as the solute weight. The solution was then cooled to room temperature. The DMAc solution was mixed with approximately 10 times the amount of pure water to precipitate the polymer. The precipitate was filtered, mixed with methanol, and filtered again to obtain PAES powder. The obtained PAES has a repeating unit represented by the following chemical formula. [ka] (Forming into PAES film) The PAES powder was dissolved in DMAc to prepare a solution, which was then cast onto a glass substrate and air-dried for 10 minutes.Then, the solution was dried at 80°C for 1 hour, 120°C for 1 hour, 160°C for 1 hour, 200°C for 1 hour, and 240°C for 1 hour, to obtain a PAES film.

[0045] The PAES obtained in the Examples and Comparative Examples were measured for molecular weight (weight average molecular weight: Mw and number average molecular weight: Mn), dispersity (Mw / Mn), glass transition temperature, relative dielectric constant, and dielectric loss tangent by the above-mentioned analytical methods. 0.5 The dielectric properties were evaluated based on the value of × (dielectric loss tangent). 0.5 The value of × (dielectric loss tangent) is the dielectric loss of an electrical signal, which is (proportionality constant) × (frequency) × (relative permittivity). 0.5× (dielectric loss tangent). These results are summarized in Table 1.

[0046] [Table 1]

[0047] The PAES obtained using 4,4'-biphenol in Comparative Example 1 and the PAES obtained using 2,2-bis(4-hydroxyphenyl)propane in Comparative Example 2 are polymers having the same repeating units as polyphenylsulfone (PPSU) and polysulfone (PSU), respectively, which are known as general-purpose PAES products, but which do not have substituents in the structural portion derived from the phenol moiety in the repeating units. The PAES obtained using bis(4-hydroxyphenyl)methane in Comparative Example 3 is a polymer having no substituents in the structural portion derived from the phenol moiety in its repeating units. The PAES obtained using bis(4-hydroxy-2,5-dimethylphenyl)methane in Example 1 is a polymer having methyl groups at the 2nd and 5th positions relative to the oxygen atoms of the structural moiety derived from the phenol moiety in its repeating unit. The PAES of Example 1 is compared with the PAES of Comparative Examples 1 to 3 in terms of the relative permittivity, dielectric loss tangent, and amount of dielectric loss of the electrical signal (relative permittivity). 0.5 It was found that the value of × (dielectric tangent) was very small. Furthermore, the PAES of Comparative Example 4 obtained using bis(4-hydroxy-3,5-dimethylphenyl)methane is a polymer having methyl groups at the 2nd and 6th positions relative to the oxygen atoms in the structural portion derived from the phenol moiety in its repeating unit, and it was revealed that its dielectric properties are improved compared to the PAES of Comparative Examples 1 to 3. In contrast, the PAES of Example 1, which is a specific example of the present invention, has a dielectric loss tangent value (relative dielectric constant) greater than that of the PAES of Comparative Example 4. 0.5 The value of × (dielectric loss tangent) was smaller, revealing improved dielectric properties.

[0048] From the above, it was revealed that PAES, which has specific hydrocarbon groups at the 2nd and 5th positions relative to the oxygen atoms in the structural part derived from the phenol moiety in the repeating unit, has a low dielectric tangent in the high frequency band and therefore has improved dielectric properties in the high frequency band. It has also been revealed that the PAES of the present invention is suitable as a polyarylethersulfone resin material for electronic devices and devices, particularly for high-frequency communication electronic devices and devices in the range of 1 GHz or more and 300 GHz or less.

Claims

1. A polyaryl ether sulfone having a repeating unit represented by general formula (1). 【Chemical 1】 (wherein Z represents an oxygen atom, a sulfonyl group, a carbonyl group, an alkylidene group having 1 to 15 carbon atoms, a fluorine-containing alkylidene group having 2 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a phenylmethylidene group, a phenylethylidene group, a phenylene group, or a fluorenylidene group; R １ and R ２ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, and m represents 0 or 1.

2. The polyaryl ether sulfone according to claim 1, wherein the repeating unit represented by general formula (1) is a repeating unit represented by chemical formula (1a). 【Chemistry 2】

3. The polyarylethersulfone according to claim 2, wherein the content of the repeating unit represented by chemical formula (1a) is 60 mol% or more of the entire polyarylethersulfone.

4. A molded article of the polyarylethersulfone according to claim 1.

5. A polyarylethersulfone resin material for electronic devices, comprising the polyarylethersulfone according to claim 1.

6. A polyarylethersulfone resin material for use in electronic devices and devices for high-frequency communication in the range of 1 GHz to 300 GHz, comprising the polyarylethersulfone according to claim 1.

7. An electronic device or device using the polyarylethersulfone according to claim 1.

8. 10. An electronic device or device for high-frequency communication in the range of 1 GHz to 300 GHz, which uses the polyarylethersulfone according to claim 1.

9. A method for using the polyarylethersulfone according to claim 1 in an electronic device.

10. A method for using the polyarylethersulfone according to claim 1 in electronic devices and devices for high-frequency communication in the range of 1 GHz to 300 GHz.

11. A polyarylethersulfone resin composition comprising the polyarylethersulfone according to claim 1 and one or more additives selected from the group consisting of flame retardants, heat stabilizers, oxidation stabilizers, weather resistance stabilizers, antistatic agents, lubricants, and plasticizers.

12. A molded article made from the polyarylethersulfone resin composition according to claim 11.

13. An electronic device or device using the polyarylethersulfone resin composition according to claim 11.

14. The polyarylethersulfone according to claim 1, wherein the structure at both ends of the polymer chain of the polyarylethersulfone is any one of the structures (i) to (iii). (i) Both are one group selected from the groups represented by general formula (4) or chemical formula (5). (ii) One is a group selected from the groups represented by general formula (4) or chemical formula (5), and the other is a halogen atom. (iii) One is a group selected from the groups represented by general formula (4) or chemical formula (5), and the other is a hydroxy group. 【Chemistry 3】 (In the formula, R ３ indicates a hydrogen atom or a methyl group, and * indicates the bonding site to the end of the polymer chain.)

15. The polyarylethersulfone according to claim 14, having a weight average molecular weight (Mw) in the range of 2,000 or more and 100,000 or less.

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