Polyaryl ether sulfone

Abstract

The present invention addresses the problem of providing a novel polyaryl ether sulfone which has improved dielectric characteristics in a high frequency band. The present invention provides, as a means for solving the problem, a polyaryl ether sulfone which has a repeating unit represented by general formula (1). (In the formula, each of R1 independently represents a hydrocarbon group that comprises a cyclic structure having 5 to 7 carbon atoms, each of R2 and R3 independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and m represents 0 or 1.)

Description

Polyarylethersulfone

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

[0002] Polyarylethersulfone (PAES) resin is known as a thermoplastic plastic that possesses characteristics such as heat resistance, dimensional stability, mechanical properties, and flame retardancy. 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 more sophisticated and specialized.

[0003] In recent years, the transmission speed and frequency of electrical signals transmitted through wireless Internet devices and communication devices have become extremely high, and the insulating parts that insulate the metal wiring of these devices are also required to accommodate higher frequencies. In particular, higher frequency radio waves such as centimeter waves (SHF: Super High Frequency) and millimeter waves (EHF: Extremely High Frequency) are used to perform even faster data communications. The higher the frequency, the greater the dielectric loss in the insulating parts, resulting in attenuation of the transmitted electrical signals. Therefore, to accommodate higher frequencies, materials with excellent dielectric properties that can reduce dielectric loss are required. Meanwhile, excellent heat resistance is also required in the manufacture and use of electrical and electronic components, and electronic devices and electronic equipment using these components, and materials with improved heat resistance are also desired. Resins that are primarily used for this purpose include liquid crystal polymers (LCPs) and polyaryl ether ketones (PAEKs), and PAES has not received much attention at present.

[0004] Regarding PAES using bis[1-(4-hydroxyphenyl)-1-methylethyl]benzenes as a raw material, Patent Document 1 describes that PAES obtained by polymerizing 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene (α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene) with dichlorodiphenyl sulfone has a low melt viscosity and excellent processability despite a high heat distortion temperature. Furthermore, Patent Document 2 describes that PAES obtained by polymerizing 1,3-bis(4-hydroxy-1-isopropylidenephenyl)benzene and 1,4-bis(4-hydroxy-1-isopropylidenephenyl)benzene with a dihalodiphenyl sulfone compound has excellent heat resistance, melt fluidity, and solvent resistance, and is therefore useful for precision parts applications.

[0005] US Patent No. 3554972 Publication JP 01-256523 Publication

[0006] The dielectric properties of PAES in the high frequency band have not been known until now, and it is unclear whether it is suitable as a resin material for use in electronic devices and electronic devices used therein (hereinafter collectively referred to as "electronic devices / devices"), particularly electronic devices / devices used in high-speed communications using high-frequency radio waves, which are in demand these days (hereinafter sometimes referred to as "high-frequency communication electronic devices / devices"). Furthermore, the dielectric properties of PAES using bis[1-(4-hydroxyphenyl)-1-methylethyl]benzenes as a raw material have also not been known at all until now. The inventors synthesized PAES (polyphenylsulfone: PPSU) obtained using 4,4'-biphenol as the raw 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 dielectric constant and dielectric loss tangent were high, resulting in poor dielectric properties for use as a resin material in electronic devices / 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.

[0007] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that, among bis[1-(4-hydroxyphenyl)-1-methylethyl]benzenes used as raw materials for PAES, PAES having a hydrocarbon group containing a specific cyclic structure has improved heat resistance as well as improved dielectric properties in the high frequency band, and have completed the present invention.

[0008] The present invention is as follows: 1. A polyarylethersulfone having a repeating unit represented by general formula (1). (In the formula, R １ each independently represents a hydrocarbon group containing a cyclic structure having 5 to 7 carbon atoms; R ２ and R ３ each independently represents a hydrogen atom or 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) or (1d): 3. A molded article of the polyarylethersulfone described in 1. 4. A polyarylethersulfone resin material for electronic devices and devices, comprising the polyarylethersulfone described in 1. 5. A polyarylethersulfone resin material for electronic devices and devices for high-frequency communication in the range of 1 GHz to 300 GHz, comprising the polyarylethersulfone described in 1. 6. An electronic device and device using the polyarylethersulfone described in 1. 7. An electronic device and device for high-frequency communication in the range of 1 GHz to 300 GHz, using the polyarylethersulfone described in 1. 8. A method for using the polyarylethersulfone described in 1. in an electronic device and device. 9. A method for using the polyarylethersulfone described in 1. in an electronic device and device for high-frequency communication in the range of 1 GHz to 300 GHz. 10.1. 11. A polyarylethersulfone resin composition comprising the polyarylethersulfone described in 1. above and one or more additives selected from the group consisting of flame retardants, heat stabilizers, oxidation stabilizers, weathering stabilizers, antistatic agents, lubricants, and plasticizers. 11. A molded article of the polyarylethersulfone resin composition described in 10. 12. An electronic device or device using the polyarylethersulfone resin composition described in 10. 13. The polyarylethersulfone described in 1. above, wherein both ends of the polymer chain of the polyarylethersulfone have any of the structures (i) to (iii). (i) Both are a group selected from the group represented by general formula (4) or chemical formula (5). (ii) One is a group selected from the group represented by general formula (4) or chemical formula (5), and the other is a halogen atom. (iii) One is a group selected from the group represented by general formula (4) or chemical formula (5), and the other is a hydroxy group. (In the formula, R ７ represents a hydrogen atom or a methyl group, and * represents a bonding site at the end of a polymer chain.) 14. The polyaryl ether sulfone according to 13., having a weight average molecular weight (Mw) in the range of 2,000 or more and 100,000 or less.

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

[0010] (PAES of the Invention) The PAES of the invention has a repeating unit represented by general formula (1). (In the formula, R １ , R ２ , R ３ and m each independently represent a hydrocarbon group containing a cyclic structure having 5 to 7 carbon atoms; R ２ and R ３ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and m represents 0 or 1. Of the repeating units represented by general formula (1), repeating units represented by general formula (1-1) or (1-2) are preferred. (In the formula, R １ The definitions of and m are the same as in general formula (1). In general formula (1), R １ each independently represents a hydrocarbon group containing a cyclic structure having 5 to 7 carbon atoms. Specific examples include a cyclopentyl group, a methylcyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a phenyl group. Among these, a cyclopentyl group, a cyclohexyl group, or a phenyl group is preferred, a cyclohexyl group or a phenyl group is more preferred, and a cyclohexyl group is particularly preferred. The same applies to general formulas (1-1) and (1-2), and the same applies hereinafter. In general formula (1), R ２ and R ３ are each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Specific examples of hydrocarbon groups having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a 2-methylpentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, and a phenyl group. R２ and R ３ are each independently preferably a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, a cyclic aliphatic hydrocarbon group having 5 or 6 carbon atoms, or a phenyl group (aromatic hydrocarbon group having 6 carbon atoms), more preferably a hydrogen atom, a methyl group, a t-butyl group, a cyclohexyl group, or a phenyl group, and further preferably a hydrogen atom or a methyl group; R ２ is a hydrogen atom and R ３ It is particularly preferred that m is a methyl group or that all m are hydrogen atoms. In 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 (1f) include structures of chemical formulae (1a) to (1f). 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 (1f), more preferable to have a repeating unit selected from the repeating units represented by chemical formulae (1a), (1c), (1d) and (1f), even more preferable to have a repeating unit represented by chemical formula (1a) or (1d), and particularly preferable to have a repeating unit selected from the repeating unit represented by chemical formula (1a). In the general formula (1), when m is 1, specific examples of the repeating unit represented by the formula (1g) to (1r) include structures of the formulae (1g) to (1r), and it is preferable to have a repeating unit selected from the repeating units represented by the formulae (1g) to (1r). 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 (1g) to (1i) and (1m) to (1o).

[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 they contain the repeating units 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 units represented by general formula (1) is 100 mol%, i.e., that no other repeating units are contained. When other repeating units are contained, the content of the repeating units represented by general formula (1) is preferably 50 mol% or more of the total PAES, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more. The repeating units represented by general formula (1) and the other repeating units may be arranged regularly or randomly. PAES having a repeating unit represented by general formula (1) and other repeating units can be produced by carrying out a polycondensation reaction described later using a bisphenol compound represented by general formula (3) described later and an aromatic dihydroxy compound in combination.

[0013] The PAES of the present invention preferably does not have, in its polymer chain, any one or more of a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a carboxyl group or a salt thereof, an ester-derived group of a sulfonic acid group, a phosphoric acid group or a carboxyl group with an alcohol, an amide-derived group of a sulfonic acid group, a phosphoric acid group or a carboxyl group with an amine, and an ionic group. The chemical structures of the sulfonic acid group, the phosphoric acid group, and the carboxyl group are groups represented by the following chemical formulas, respectively.

[0014] (Structure of Both Terminals of Polymer Chain of PAES According to the Present Invention) The structure of both terminals of the polymer chain of the PAES according to the present invention is not particularly limited. The terminal structure may be a halogen atom derived from a dihalogen compound represented by general formula (2) described below, a hydroxy group derived from a bisphenol compound represented by general formula (3), or a terminal structure in which this hydroxy group has been modified with a reactive functional group, specifically, 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). (In the formula, R ７ represents a hydrogen atom or a methyl group, and * represents a 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 such terminal structures are (i) both halogen atoms, (ii) both hydroxy groups, or (iii) one halogen atom and the other a hydroxy group, the polyarylethersulfone of the present invention can be used as a thermoplastic resin. By applying conventional molding and processing methods for thermoplastic resins (e.g., melt molding methods such as injection molding, extrusion molding, and compression molding), molded articles for use in electronic devices can be produced, and electronic 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 hydroxy group, at least one of the terminal structures has a reactive functional group, and therefore the polyarylethersulfone of the present invention can be used as a curable resin. By applying a conventional molding or processing method for curable resins (e.g., compression molding or transfer molding), it is possible to produce molded articles for use in electronic devices and devices, or to manufacture electronic devices and devices.

[0015] (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 end 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 to 500,000, even more preferably 20,000 to 200,000, and particularly preferably 30,000 to 150,000. When the terminal structures of a 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 2,000 to 50,000, more preferably 2,000 to 30,000, and particularly preferably 2,000 to 10,000. The ratio Mw / Mn, which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is preferably in the range of 1.2 to 20, more preferably 1.2 to 15, even more preferably 1.2 to 10, and particularly preferably 1.2 to 8.

[0016] (Glass transition temperature) The glass transition temperature of the PAES of the present invention is preferably 150°C or higher, more preferably 170°C or higher, even more preferably 190°C or higher, and particularly preferably 210°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 production and in use, particularly for electronic devices and devices for high-frequency communication in the range of 1 GHz to 300 GHz.

[0017] (Dielectric Dissipation Factor) The dielectric dissipation factor of the PAES of the present invention measured at a frequency of 10 GHz is preferably 0.005 or less. If the dielectric dissipation factor 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 dissipation factor is more preferably 0.004 or less, even more preferably 0.0035 or less, and particularly preferably 0.003 or less. Since a lower dielectric dissipation factor is preferable, the lower limit is not particularly limited, but it may be 0.001 or more. Furthermore, the dielectric dissipation factor measured at a frequency of 1 GHz is preferably 0.005 or less. The dielectric dissipation factor is more preferably 0.004 or less, even more preferably 0.0035 or less, and particularly preferably 0.003 or less. Since a lower dielectric dissipation factor is preferable, the lower limit is not particularly limited, but it may be 0.001 or more.

[0018] (Dielectric Constant) The 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 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 dielectric constant is more preferably 3.2 or less, even more preferably 3.0 or less, and particularly preferably 2.7 or less. The lower the dielectric constant, the better, so there is no particular restriction on the lower limit, but it may be 2.0 or more.

[0019] (Method for producing PAES of the present invention) The method for producing PAES of the present invention is not particularly limited, and for example, 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. (In the formula, each X independently represents a halogen atom, and m is defined as in general formula (1).) (In the formula, R １ , R ２ and R ３ is defined as in general formula (1).

[0020] As a specific example, when 4,4'-dichlorodiphenyl sulfone (2a) is used as the dihalogen compound represented by general formula (2), 1,3-bis[1-(4-hydroxy-5-cyclohexyl-2-methylphenyl)-1-methylethyl]benzene (3a) is used as the bisphenol compound represented by general formula (3), and potassium carbonate is used as the alkali metal compound, a polyaryl ether sulfone having a repeating unit represented by chemical formula (1a) can be produced. The reaction formulas are shown below.

[0021] (Dihalogen Compound Represented by General Formula (2)) X in General Formula (2) specifically 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.

[0022] (Bisphenol Compound Represented by General Formula (3)) Among the bisphenol compounds represented by general formula (3), repeating units represented by general formula (3-1) or (3-2) are preferred. (In the formula, R １ , R ２ and R ３ The definition of R in general formula (3) is the same as in general formula (1). １ , R ２ , and R ３The specific examples and preferred aspects of the general formula (3) are the same as those for the general formula (1). The same applies to the general formulas (3-1) and (3-2). Specific examples of the bisphenol compound represented by the general formula (3) include 1,3-bis[1-(4-hydroxy-3-cyclohexylphenyl)-1-methylethyl]benzene, 1,3-bis[1-(4-hydroxy-5-cyclohexyl-2-methylphenyl)-1-methylethyl]benzene, 1,3-bis[1-(4-hydroxy-3-phenylphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxy-3-cyclohexylphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxy-5-cyclohexyl-2-methylphenyl)-1-methylethyl]benzene, and 1,4-bis[1-(4-hydroxy-3-phenylphenyl)-1-methylethyl]benzene. Among these, 1,3-bis[1-(4-hydroxy-5-cyclohexyl-2-methylphenyl)-1-methylethyl]benzene, 1,3-bis[1-(4-hydroxy-3-phenylphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxy-5-cyclohexyl-2-methylphenyl)-1-methylethyl]benzene or 1,4-bis[1-(4-hydroxy-3-phenylphenyl)-1-methylethyl]benzene is preferred, and 1,3-bis[1-(4-hydroxy-5-cyclohexyl-2-methylphenyl)-1-methylethyl]benzene or 1,4-bis[1-(4-hydroxy-5-cyclohexyl-2-methylphenyl)-1-methylethyl]benzene is particularly preferred.

[0023] (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 these aromatic hydroxy compounds and a repeating unit having a structure derived from the dihalogen compound represented by general formula (2). The other aromatic dihydroxy compound besides 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). (In the formula, R represents a divalent group represented by general formula (6a) or (6b).) (In the formula, R ４ each 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. (In the formula, R ４ each 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 d independently represents 0, 1, 2, or 3; 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. (In general formulas (7a), (7b) and (7c), R ５ each 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; ５ may be bonded to each other to form a cycloalkylidene group having 5 to 20 carbon atoms as a whole, and R ６ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms; Ar１ each independently represents an aryl group having 6 to 12 carbon atoms, and * indicates the 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, 1,3-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 1,4-bis[1-methyl-1-(4-hydroxyphenyl)ethyl]benzene, 2,2'-bi-1-naphthol, 1,4-bis(4-hydroxyphenyl)benzene, 1,3-bis(4-hydroxyphenyl)benzene, 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'-dihydroxybenzophenone, bis(4-hydroxyphenyl)sulfone, Examples of suitable hydroxydiphenyl ethers include 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).

[0024] (Alkali Metal Compound) Any alkali metal compound can be used as long as it can convert the bisphenol compound represented by the general formula (3) into an alkali metal salt, but usually, carbonates, hydrogen carbonates, hydroxides, etc. of alkali metals are suitably used, and carbonates are particularly preferred. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium, and among these, sodium and potassium are preferred, and potassium is particularly preferred.

[0025] (Solvent) A solvent can be used in the polycondensation reaction to obtain PAES, and its use is preferred. The solvent to be 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.

[0026] (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 of the bisphenol compound represented by general formula (3) and the other aromatic dihydroxy compound), but in order to produce a PAES with a large 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), it 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 having 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 molar ratio is usually in the range of 0.6 to 1.4 times, preferably in the range of 0.7 to 1.3 times, and more preferably in the range of 0.8 to 1.2 times. 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, preferably in the range of 1.01 to 1.06 times, and more preferably in the range of 1.01 to 1.04 times. In the case of PAES in which both terminal structures of the polymer chain of the PAES to be produced are hydroxy groups, the molar ratio is in the range of 0.9 to 0.99 times by mole for PAES with a large molecular weight, and preferably in the range of 0.95 to 0.99 times by mole, while the molar ratio is usually in the range of 0.6 to 0.95 times by mole, preferably in the range of 0.7 to 0.9 times by mole, and more preferably in the range of 0.8 to 0.9 times by mole for PAES with a small molecular weight. The amount of alkali metal ions in the alkali metal compound used is usually in the range of 2.0 to 3.0 times by mole, 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 320 hours. These reactions are preferably carried out in an inert gas atmosphere such as nitrogen or argon. There are no limitations on the reaction pressure, and the reaction may be carried out under reduced pressure, atmospheric pressure, or elevated pressure, but it is usually carried out at atmospheric pressure.

[0027] <Post-Reaction Treatment> PAES produced by the polycondensation reaction can be recovered by commonly used methods such as coagulation, solidification, washing, granulation, extraction, and solvent distillation. A more detailed example of a method for treating PAES produced by the polycondensation reaction is described below. A solution containing PAES produced by the polycondensation reaction is optionally diluted with a polymer-containing reaction solution, and the resulting solution is mixed with a poor solvent to precipitate a precipitate, thereby obtaining powdered PAES. In this step, to remove alkali metal salts, water is preferred as the solvent used for precipitating the precipitate. Acidic water containing low concentrations of hydrochloric acid, formic acid, oxalic acid, etc. may also be used. Next, the resulting PAES precipitate is preferably washed with a solvent to remove raw material monomers, etc. 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 washes, 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, to further remove remaining alkali metal salts, the product may be dissolved in a neutral polar solvent such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), dimethyl sulfoxide (DMSO), sulfolane, or diphenyl sulfone, followed by precipitation with water or acidic water. The washing apparatus may be a combination of a washing tank and a pressure filter or a centrifuge, or a multi-function filter capable of washing, filtering, and drying in one device.

[0028] A drying step can be carried out to dry the powdery PAES containing water and solvent after completion of washing obtained by the above washing step. The conditions for this drying step may be any conditions that allow removal of water at a temperature below the melting point of the polycondensation reaction product. To minimize contact with air, it is preferable to carry out the drying step under an inert gas (nitrogen, argon, etc.) atmosphere, under an inert gas stream, or under reduced pressure. As the dryer, known devices such as an evaporator, a tray oven, or a tumbler can be used.

[0029] In the case where the structures of both ends of the polymer chain of the aryl ether sulfone (PAES) of the present invention are terminal structures modified with reactive functional groups 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) with a reactive substituent such as an acryloyloxy group, a methacryloyloxy group, or a glycidyl ether group.

[0030] The PAES of the present invention, whose terminal structure is a group represented by general formula (4) (acryloyloxy group or methacryloyloxy group), can be produced by applying a conventionally known method for (meth)acrylation of a hydroxy compound to a polyarylethersulfone having a repeating unit represented by general formula (1) containing a hydroxy group at the end of the polymer chain obtained by the above method. For example, a (meth)acrylation method includes reacting the terminal hydroxy group of a polyarylethersulfone 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, inorganic or organic basic substances such as alkali metal carbonates or bicarbonates, tertiary amines, etc. 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, or tetrahydrofuran, dioxane, chlorobenzene, etc. may be used. During the reaction, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, phenothiazine, 2,6-di-tert-butyl-4-methylphenol (BHT), etc. may be added.

[0031] 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 a polyarylethersulfone having a repeating unit represented by general formula (1) containing a hydroxy group at the end of the polymer chain obtained by the above method. For example, the glycidyl etherification method can be carried out by reacting the terminal hydroxy group of a polyarylethersulfone having a repeating unit represented by general formula (1) with an 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) to produce a glycidyl etherified PAES. Specific examples of the epihalohydrin used include epichlorohydrin and epibromohydrin.

[0032] <Polyarylethersulfone resin composition> The PAES of the present invention can be blended with various additives, such as flame retardants, heat stabilizers, oxidation stabilizers, weathering stabilizers, antistatic agents, lubricants, and plasticizers, as desired, by a conventional method of blending additives with raw resins, within a range that does not impair the effects of the present invention. A polyarylethersulfone resin composition can be produced containing the PAES of the present invention and one or more additives selected from the group consisting of flame retardants, heat stabilizers, oxidation stabilizers, weathering stabilizers, antistatic agents, lubricants, and plasticizers. This polyarylethersulfone resin composition can be used in the same manner as the PAES of the present invention, as described below.

[0033] <Use of PAES of the Present Invention> (Molded Articles) 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 / processing method for thermoplastic resins (e.g., melt molding methods such as injection molding, extrusion molding, and compression molding) or a conventional molding / 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 electronic devices and electronic devices used therefor (electronic devices and devices) described below, and among these, electronic devices and devices used for high-speed communication using radio waves in the high-frequency band ranging from 1 GHz to 300 GHz (electronic devices and devices for high-frequency communication in the range of from 1 GHz to 300 GHz), as well as for articles such 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 equipment, 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, and can be molded into these articles.

[0034] (High-Frequency Band Radio Waves) In the present invention, high-frequency band radio waves refer to radio waves having a frequency in the range of 1 GHz to 300 GHz, and include 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 in the range of 3 GHz to 100 GHz, more preferably in the range of 5 GHz to 80 GHz, and particularly preferably in the range of 5 GHz to 30 GHz.

[0035] (Polyarylethersulfone Resin Material for Electronic Devices and Devices) The polyarylethersulfone of the present invention has excellent dielectric properties in the high-frequency band in addition to heat resistance. Therefore, a resin material containing the polyarylethersulfone 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 (electronic devices and devices) used therein, 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 communication 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 containing only the PAES of the present invention, depending on the properties required for the electronic devices and devices 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 flame retardants, heat stabilizers, oxidation stabilizers, weather stabilizers, antistatic agents, lubricants, and plasticizers.

[0036] (Electronic Devices and 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 a 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 improved heat resistance and also improved dielectric properties in high-frequency bands, so it is preferable to use the PAES of the present invention in electronic devices and devices, particularly in electronic devices and devices for high-frequency communication in the range of 1 GHz to 300 GHz. 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, measuring and measurement instruments used in various industries such as automobiles, aircraft, industry, agriculture, logistics, and civil engineering, high-speed wireless communication equipment, electronic organizers, digital still cameras, video cameras, electronic paper, televisions, players, various audio equipment, in-vehicle displays such as car navigation systems and 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, measuring and measurement instruments used in various industries such as automobiles, aircraft, industry, 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 radio waves in the high-frequency band. More specifically, the PAES and polyarylethersulfone resin materials of the present invention can be suitably used, for example, for exterior members, structural members, circuit boards, semiconductor encapsulants, or antenna element members of these electronic devices and devices (preferably, electronic devices and devices for high-frequency communication in the range of 1 GHz to 300 GHz).Among these, the composition can be suitably used for circuit boards of electronic devices and devices, semiconductor encapsulants and antenna element members, and can be particularly suitably used for circuit boards of electronic devices and devices.

[0037] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0038] The analytical methods used in the present invention are as follows. <Analytical Methods> 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. Measuring apparatus: DMA850 (manufactured by TA Instruments) Heating rate: 4.0°C / min Frequency: 1 Hz Atmosphere: Air Measurement mode: Tensile Test piece: 40 mm x 7 mm x thickness 0.02 to 0.05 mm Analysis method: The peak top of tan δ was taken as the glass transition point 2. Measurement of Relative Dielectric Constant 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 cavity resonator for 1 GHz (manufactured by Kanto Electronics Application Development Co., Ltd.), CP531 cavity resonator for 10 GHz (manufactured by Kanto Electronics Application Development Co., Ltd.), PNA network analyzer N5222B (manufactured by Keysight Technologies, Inc.), cylindrical cavity resonator (material: copper, internal mirror finish) Test piece: L 80-90 × W 1.4-1.6 × t 0.03-0.06 (mm) Measurement frequency: near 1 GHz, 10 GHz Measurement environment: room temperature (23±1°C / 50±5% RH) Measurement method: conforms to IEC62810 (cavity resonator perturbation method) 3. Molecular weight measurement The molecular weight of PAES obtained in the examples and comparative examples described later was measured by gel permeation chromatography (GPC) using the following apparatus and conditions after dissolving the PAES obtained by polymerization in a solvent and passing it through a 0.45 μm membrane filter. Apparatus: 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°C Mobile phase: N-methyl-2-pyrrolidone Flow rate: 0.8 mL / min. Injection volume: 100 μL Detection: Refractive index Standard substance: Polystyrene

[0039] Example 1 Synthesis of PAES (1a) A 500 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube was charged with 9.70 g of 4,4'-dichlorodiphenyl sulfone as a monomer, 17.30 g of 1,3-bis[1-(4-hydroxy-5-cyclohexyl-2-methylphenyl)-1-methylethyl]benzene (3a), 4.83 g of dried potassium carbonate, and 153.00 g of dimethylacetamide (DMAc), followed by stirring and dissolution under a nitrogen atmosphere. The solution was then heated to 160°C, and the polymerization reaction was carried out for 312 hours. After completion of the reaction, DMAc was added to the reaction solution to give an approximately 10 wt % solution, with the total weight of the monomers used being the weight of the solute, and 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 off, and then mixed with methanol and filtered again to obtain PAES powder. The obtained PAES is a PAES having a repeating unit represented by chemical formula (1a). (Forming into PAES film) The obtained PAES powder was dissolved in DMAc to prepare a solution, which was then cast onto a glass substrate and air-dried for 10 minutes. Thereafter, the solution was dried at 80°C for 1 hour, then at 120°C for 1 hour, 160°C for 1 hour, and 210°C for 1 hour under reduced pressure using a vacuum pump to obtain a PAES film.

[0040] Example 2 (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, 17.96 g of 4,4'-dichlorodiphenyl sulfone and 33.04 g of 1,4-bis[1-(4-hydroxy-5-cyclohexyl-2-methylphenyl)-1-methylethyl]benzene (3d) as monomers were charged, along with 8.81 g of dried potassium carbonate, 289.10 g of dimethylacetamide (DMAc), and 51.14 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 water produced by the reaction outside the reaction system. After completion of the reaction, DMAc was added to the reaction solution to form an approximately 10 wt% solution, with the total weight of the monomers used being the weight of the solute, and 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 separated by filtration, then mixed with methanol and separated by filtration again to obtain PAES powder. The obtained PAES has a repeating unit represented by chemical formula (1d). (Forming into PAES film) The obtained PAES powder was dissolved in DMAc to prepare a solution, which was then cast onto a glass substrate and air-dried for 10 minutes. Thereafter, the solution was 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 260°C for 1 hour under reduced pressure using a vacuum pump to obtain a PAES film.

[0041] Comparative Example 1 (Synthesis of PAES) A 500 mL four-neck flask equipped with a Dean-Stark tube filled with toluene and fitted with a Liebig condenser at the top, a stirrer, and a nitrogen inlet tube was charged with 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, and these were dissolved at room temperature while flowing nitrogen. Next, the solution was heated to 150°C under a nitrogen atmosphere, and the water in the solution was azeotropically dehydrated while refluxing the toluene. Next, the liquid temperature was cooled to 100°C or below under a nitrogen atmosphere, and 15.59 g of 4,4'-dichlorodiphenyl sulfone as a monomer was added and dissolved. Next, the liquid temperature was heated to 160°C, and a 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 solution to form an approximately 10 wt% solution, with the total weight of the monomers used being the weight of the solute, and 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, and then mixed with methanol and filtered again to obtain PAES powder. The resulting PAES has a repeating unit represented by the following chemical formula: (Forming into PAES film) The obtained PAES powder was dissolved in DMAc to prepare a solution, which was then cast onto a glass substrate and air-dried for 10 minutes, followed by drying 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 in this order to obtain a PAES film.

[0042] Comparative Example 2: 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 was charged with 14.33 g of 4,4'-dichlorodiphenyl sulfone and 11.17 g of 2,2-bis(4-hydroxyphenyl)propane as monomers, 7.03 g of dried potassium carbonate, 144.50 g of dimethylacetamide (DMAc), and 25.56 g of toluene, and the mixture was stirred and dissolved under a nitrogen atmosphere. The solution was then heated to 160°C, and the polymerization reaction was carried out for 75 hours while distilling off the water produced by the reaction. After completion of the reaction, DMAc was added to the reaction solution to give an approximately 10 wt. % solution, with the total weight of the monomers used being the weight of the solute. 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 off, then mixed with methanol and filtered again to obtain PAES powder. Furthermore, for washing, the filtered powder was dissolved in DMAc and then mixed with 1 wt% hydrochloric acid water to precipitate the polymer, followed by filtration. Furthermore, to remove the hydrochloric acid, the filtered powder was poured into pure water and filtered to obtain washed PAES powder. The obtained PAES has a repeating unit represented by the following chemical formula: (Forming into PAES film) The obtained PAES powder was dissolved in DMAc to prepare a solution, which was then cast onto a glass substrate and air-dried for 10 minutes. Thereafter, the solution was 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.

[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, 23.36 g of 4,4'-dichlorodiphenyl sulfone and 27.64 g of 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene as monomers, 11.47 g of dried potassium carbonate, 289.19 g of dimethylacetamide (DMAc), and 51.16 g of toluene were charged and stirred to dissolve under a nitrogen atmosphere. The liquid temperature was then heated to 160°C, and the polymerization reaction was carried out for 140 hours while distilling off water produced by the reaction outside the reaction system. After completion of the reaction, DMAc was added to the reaction solution to form an approximately 10 wt% solution, with the total weight of the monomers used being the weight of the solute, and 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 separated by filtration, then mixed with methanol and separated by filtration again to obtain PAES powder. The obtained PAES has a repeating unit represented by the following chemical formula: (Forming into PAES film) The obtained PAES powder was dissolved in DMAc to prepare a solution, which was then cast onto a glass substrate and air-dried for 10 minutes. Thereafter, the solution was 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.

[0044] 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 the dielectric loss tangent × (relative dielectric constant) in the present invention. ０．５ The value of × (dielectric loss tangent) is the dielectric loss of an electrical signal, which is calculated as (proportionality constant) × (frequency) × (relative permittivity) ０．５ The results are shown in Table 1.

[0045]

[0046] The PAES obtained in Comparative Examples 1 and 2 are PAES having the same repeating units as resins generally called polyphenylsulfone (PPSU) and polysulfone (PSU), respectively. The PAES obtained in Examples 1 and 2, which are specific examples of the present invention, have very low relative permittivity and dielectric loss tangent values ​​compared to the PAES obtained in Comparative Examples 1 and 2, which indicate the amount of dielectric loss of an electrical signal (relative permittivity). ０．５ The values ​​of dielectric constant × (dielectric loss tangent) were very small, which revealed that the PAES obtained in Comparative Example 3 had improved dielectric properties. The PAES obtained in Comparative Example 3 was a PAES obtained using a bisphenol compound that did not have a substituent at the phenol moiety as a raw material, as opposed to the raw material bisphenol used in Example 1. The PAES obtained in Examples 1 and 2 had significantly improved relative permittivity, dielectric loss tangent, and (dielectric constant) values ​​compared to the PAES obtained in Comparative Example 3. ０．５ While the dielectric properties in terms of the value of × (dielectric tangent) were equivalent, the glass transition temperatures were 47°C and 81°C higher, respectively, demonstrating improved heat resistance. The polyarylethersulfone of the present invention is highly useful as a material for use in a wider range of applications in electronic devices and devices that are exposed to high temperatures during manufacturing processes and in use. From the above, it was revealed that the polyarylethersulfone of the present invention has improved heat resistance as well as improved dielectric properties in the high-frequency band compared to conventionally known PAES. It was also revealed that the polyarylethersulfone 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 to 300 GHz.

Claims

1. Polyarylethersulfone having a repeating unit represented by general formula (1). (In the formula, R １ each independently represents a hydrocarbon group containing a cyclic structure having 5 to 7 carbon atoms; R ２ and R ３ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and m represents 0 or 1.

2. The polyarylethersulfone according to claim 1, wherein the repeating unit represented by general formula (1) is a repeating unit represented by chemical formula (1a) or (1d).

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

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

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

6. Electronic devices and devices using the polyarylethersulfone described in claim 1.

7. Electronic equipment and devices for high frequency communication in the range of 1 GHz to 300 GHz, which use the polyarylethersulfone according to claim 1.

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

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

10. 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, weathering stabilizers, antistatic agents, lubricants, and plasticizers.

11. A molded article made from the polyarylethersulfone resin composition according to claim 10.

12. An electronic device or device using the polyarylethersulfone resin composition according to claim 10.

13. The polyarylethersulfone according to claim 1, wherein the structure at both ends of the polymer chain of the polyarylethersulfone is any one of structures (i) to (iii). (i) Both are a group selected from the group represented by general formula (4) or chemical formula (5). (ii) One is a group selected from the group represented by general formula (4) or chemical formula (5), and the other is a halogen atom. (iii) One is a group selected from the group represented by general formula (4) or chemical formula (5), and the other is a hydroxy group. (In the formula, R ７ indicates a hydrogen atom or a methyl group, and * indicates the bonding site to the end of the polymer chain.) 14. The polyarylethersulfone according to claim 13, having a weight average molecular weight (Mw) in the range of 2,000 to 100,000.

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