Polyarylether sulfone resin material for electronic equipment and devices, electronic equipment and devices using the same, and method for using polyarylether sulfone in electronic equipment and devices

Abstract

To provide a polyarylether sulfone resin material that exhibits superior dielectric performance in high-frequency ranges and is suitable for use as a material in electronic equipment and devices, especially for high-frequency communication.SOLUTION: There is provided a polyarylether sulfone resin material for electronic equipment and devices, having a glass transition temperature of 150°C or more and a weight-average molecular weight (Mw) in the range of 2,000 or more and 1,000,000 or less, and containing polyarylether sulfone having a repeating unit represented by general formula (1). (In the formula, R1 each independently represents a hydrocarbon group having 1 to 6 carbon atoms, R2 each independently represents a hydrocarbon group having 1 to 6 carbon atoms, n each independently represents 0, 1, 2, or 3, m represents 0 or 1, and p represents an integer of 0 or from 1 to 6.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyarylethersulfone resin material obtained by using a specific bisphenol compound as a raw material, suitable for use as a material for electronic devices and electronic devices used therein, and to an electronic device and an electronic device using the same. The present invention also relates to a method for using the polyarylethersulfone obtained by using the specific bisphenol compound as a raw material for electronic devices and electronic devices used therein. [Background technology]

[0002] Polyarylethersulfone (PAES) resin is a thermoplastic plastic 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 more sophisticated and specialized, and improved heat resistance is also required.

[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. Therefore, materials with improved heat resistance are also needed. Resins primarily used for this purpose include liquid crystal polymers (LCPs) and polyaryl ether ketones (PAEKs), while PAES has received little attention.

[0004] Commonly used PAES include polyphenylsulfone (PPSU), which is a PAES obtained using 4,4'-biphenol as the raw material bisphenol, and polysulfone (PSU), which is a PAES obtained using 2,2-bis(4-hydroxyphenyl)propane, and attempts are being made to develop various improved functions by changing the raw material bisphenol. For example, it has been known that PAES obtained using 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, which is a type of bis(hydroxyphenyl)cycloalkane, is a thermoplastic resin having a high heat strain point (Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2-166122 Summary of the Invention [Problem to be solved by the invention]

[0006] The dielectric properties of PAES in the high frequency band have not been known until now, and it is unclear whether they are suitable as materials for use in electronic devices and the electronic devices used therein (hereinafter collectively referred to as electronic devices and devices), particularly for electronic devices and devices used in high-speed communications using high-frequency radio waves, which are in demand these days (hereinafter referred to as high-frequency communication electronic devices and devices). The present inventors synthesized polyphenylsulfone (PPSU), a PAES obtained using 4,4'-biphenol as the raw material bisphenol, a commonly used PAES, and polysulfone (PSU), a PAES obtained using 2,2-bis(4-hydroxyphenyl)propane, and evaluated their dielectric properties in the high frequency band. As a result, they found that the relative dielectric constant and dielectric loss tangent were high, and that their dielectric properties were poor for use as resin materials in electronic devices. An object of the present invention is to provide a PAES resin material that has both excellent dielectric properties in high frequency bands and heat resistance, and can be suitably used as a material for electronic devices and devices, particularly for high frequency communication electronic devices and devices. [Means for solving the problem]

[0007] As a result of extensive research into solving the above-mentioned problems, the present inventors have found that PAES made from hydrocarbon group-substituted 1,1-bis(4-hydroxyphenyl)cyclohexanes, which have a hydrocarbon group as a substituent on the phenol moiety, as a raw material has excellent heat resistance, as well as excellent dielectric properties in the high frequency band, and is suitable as a material for use in electronic devices and devices, particularly for use in high frequency communication electronic devices and devices, and have completed the present invention.

[0008] The present invention is as follows. 1. A polyarylethersulfone resin material for electronic devices, which has a glass transition temperature of 150°C or higher, a weight average molecular weight (Mw) in the range of 2,000 to 1,000,000, and contains polyarylethersulfone having a repeating unit represented by general formula (1). [ka] (In the formula, each R1 independently represents a hydrocarbon group having 1 to 6 carbon atoms, each R2 independently represents a hydrocarbon group having 1 to 6 carbon atoms, each n independently represents 0, 1, 2, or 3, m represents 0 or 1, and p represents 0 or an integer of 1 to 6.) 2. The polyarylethersulfone resin material for electronic devices and devices according to 1., wherein the repeating unit represented by general formula (1) is at least one selected from the repeating units represented by chemical formulas (1-1) to (1-8). [ka] [ka] 3. The polyarylethersulfone resin material for electronic devices and devices described in 1., wherein the polyarylethersulfone further has a dielectric loss tangent measured at frequencies of 1 GHz and 10 GHz of 0.005 or less, and a relative dielectric constant measured at frequencies of 1 GHz and 10 GHz of 3.5 or less. 4. The polyarylethersulfone resin material for electronic devices and devices according to 1., wherein the electronic devices and devices are electronic devices and devices for high-frequency communication in the range of 1 GHz or more and 300 GHz or less. 5. An electronic device or device using the polyarylethersulfone resin material for electronic devices or devices according to 1. 6. A circuit board, semiconductor encapsulant, or antenna element member for an electronic device or device, using the polyarylethersulfone resin material for electronic devices and devices described in 1. 7. An electronic device or device for high-frequency communication in the range of 1 GHz or more and 300 GHz or less, which uses the polyarylethersulfone resin material for electronic devices or devices described in 1. 8. A method for using polyarylethersulfone having a repeating unit represented by general formula (1), which has a glass transition temperature of 150°C or higher and a weight average molecular weight (Mw) in the range of 2,000 to 1,000,000, inclusive, in an electronic device or device. [ka] (In the formula, each R1 independently represents a hydrocarbon group having 1 to 6 carbon atoms, each R2 independently represents a hydrocarbon group having 1 to 6 carbon atoms, each n independently represents 0, 1, 2, or 3, m represents 0 or 1, and p represents 0 or an integer of 1 to 6.) 9. A method for using the polyaryl ether sulfone according to 8. in an electronic device, wherein the repeating unit represented by the general formula (1) is at least one selected from the repeating units represented by chemical formulas (1-1) to (1-8). [ka] [ka] 10. A method for using the polyarylethersulfone according to 8. in an electronic device, wherein the polyarylethersulfone further has a dielectric loss tangent of 0.005 or less when measured at frequencies of 1 GHz and 10 GHz, and a relative dielectric constant of 3.5 or less when measured at frequencies of 1 GHz and 10 GHz. 11. A method for using the polyarylethersulfone according to 8. in an electronic device or device, wherein the electronic device or device is an electronic device or device for high-frequency communication in the range of 1 GHz or more and 300 GHz or less. 12. A method for using the polyarylethersulfone according to 8. in an electronic device or device, wherein the polyarylethersulfone is used in a circuit board, a semiconductor encapsulant, or an antenna element member of the electronic device or device. [Effects of the Invention]

[0009] The polyarylethersulfone resin material according to the present invention has excellent dielectric properties in the high frequency band and is therefore suitable as a resin material for use in electronic devices and electronic equipment, particularly in high frequency communication electronic devices and devices. DETAILED DESCRIPTION OF THE INVENTION

[0010] (Repeating unit of PAES according to the present invention) The PAES according to the present invention has a repeating unit represented by general formula (1). [ka] (In the formula, each R1 independently represents a hydrocarbon group having 1 to 6 carbon atoms, each R2 independently represents a hydrocarbon group having 1 to 6 carbon atoms, each n independently represents 0, 1, 2, or 3, m represents 0 or 1, and p represents 0 or an integer of 1 to 6.) Specific examples of the hydrocarbon group having 1 to 6 carbon atoms in R1 of general formula (1) 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. R1 is preferably a methyl group, a t-butyl group, a cyclohexyl group or a phenyl group, more preferably a methyl group, a cyclohexyl group or a phenyl group, and particularly preferably a methyl group or a phenyl group. In general formula (1), n ​​is preferably 0, 1 or 2, and more preferably 0. When n is 1, the bonding positions of R1 are preferably the 2nd position, with the bonding position of the oxygen atom of the benzene ring to which R1 is bonded being the 1st position. Similarly, when n is 2, the bonding positions are preferably the 2nd and 6th positions or the 2nd and 5th positions, and more preferably the 2nd and 6th positions. When n is 3, the bonding positions are preferably the 2nd, 3rd, and 6th positions. In general formula (1), m is preferably 0 from the viewpoint of availability of raw materials. In general formula (1), p is preferably 0 or 1 to 3, more preferably 0, 1 or 3, even more preferably 0 or 3, and particularly preferably 3. In general formula (1), specific examples of the hydrocarbon group having 1 to 6 carbon atoms for R2 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 is preferably a methyl group, a t-butyl group, a cyclohexyl group or a phenyl group, more preferably a methyl group, a cyclohexyl group or a phenyl group, and particularly preferably a methyl group.

[0011] In general formula (1), when m is 0, specific examples of the repeating unit represented by chemical formulae (1-1) to (1-8) include structures of chemical formulae (1-1) to (1-8). Among the repeating units represented by general formula (1), it is preferable to have at least one repeating unit selected from repeating units represented by chemical formulae (1-1) to (1-3) and (1-5) to (1-7), it is more preferable to have at least one repeating unit selected from repeating units represented by chemical formulae (1-1), (1-3), (1-5) and (1-7), it is even more preferable to have at least one repeating unit selected from repeating units represented by chemical formulae (1-1) and (1-5), and it is particularly preferable to have a repeating unit represented by chemical formula (1-5). [ka] [ka] In the general formula (1), when m is 1, specific examples of the repeating unit represented include structures of chemical formulas (1-9) to (1-24). From the viewpoint of the heat resistance of the resulting PAES, it is preferable to have at least one repeating unit selected from the repeating units represented by chemical formulas (1-9) to (1-16). [ka] [ka] [ka] [ka]

[0012] The PAES according to 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 according to the present invention may contain other repeating units as long as they contain 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 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 repeating units represented by general formula (1) and other repeating units may be arranged regularly or may be present 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] When the PAES of the present invention is used in electronic devices and electronic equipment described below, it is preferable that the PAES does not have a sulfonic acid group, a phosphoric acid group, or a carboxyl group in its polymer chain. 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]

[0014] (Structure of both ends of the polymer chain of PAES according to the present invention) The structures at both ends of the polymer chain of the PAES according to the present invention are 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 the 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). [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 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). When the terminal structures are (i) both halogen atoms, (ii) both hydroxy groups, or (iii) one halogen atom and the other hydroxy group, the polyarylethersulfone resin material for electronic devices of the present invention can be used as a thermoplastic resin. Molded articles for use in electronic devices and devices can be produced by applying conventional molding and processing methods for thermoplastic resins (e.g., melt molding methods such as injection molding, extrusion molding, and compression molding), 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, since either one of the terminal structures has the reactive functional group, the polyarylethersulfone resin material for electronic devices and devices 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 devices can be produced, and electronic devices and devices can be manufactured.

[0015] (molecular weight) The weight average molecular weight (Mw) of the PAES according to the present invention is in the range of 2,000 to 1,000,000, preferably 10,000 to 500,000, 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 according to the present invention are (i) both halogen atoms, (ii) both hydroxy groups, or (iii) one halogen atom and the other hydroxy group, 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, in order to provide sufficient mechanical strength when used as a thermoplastic resin. When the terminal structures of the PAES according to 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 ensure 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 1.2 or more and 20 or less, more preferably in the range of 1.2 or more and 15 or less, even more preferably in the range of 1.2 or more and 10 or less, and particularly preferably in the range of 1.2 or more and 8 or less.

[0016] (glass transition temperature) The glass transition temperature of the PAES according to the present invention is 150° C. or higher, preferably 160° C. or higher, more preferably 170° C. or higher, even more preferably 180° C. or higher, and particularly preferably 200° C. or higher. The higher the glass transition temperature, the better the heat resistance, so 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 electronic devices and devices for high-frequency communication in the range of 1 GHz or more and 300 GHz or less.

[0017] (dielectric 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 it is 0.005 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 loss tangent is more preferably 0.004 or less, even more preferably 0.0035 or less, and particularly preferably 0.0030 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.

[0018] (dielectric constant) The relative dielectric constants of the PAES of the present invention measured at frequencies of 1 GHz and 10 GHz are preferably 3.5 or less. If the relative dielectric constant is 3.5 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 relative dielectric constant is more preferably 3.0 or less, even more preferably 2.8 or less, and particularly preferably 2.7 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.

[0019] (Production method of PAES according to 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, R1, R2, n, and p are 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), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (3-5) is used as the bisphenol compound represented by general formula (3), and potassium carbonate is used as the alkali metal compound, polyarylethersulfone having a repeating unit represented by chemical formula (1-5) can be produced. The reaction formula is shown below. [ka]

[0021] (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. Among these, 4,4'-difluorodiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone are preferred, and 4,4'-dichlorodiphenyl sulfone is particularly preferred.

[0022] (Bisphenol compound represented by general formula (3)) In general formula (3), specific examples and preferred embodiments of the bonding positions of R1, n, and R2 are the same as those in general formula (1). Specific examples of the bisphenol compound represented by the general formula (3) include 1,1-bis(4-hydroxyphenyl)cyclohexane (3-1), 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (3-2), 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane (3-3), 1,1-bis(4-hydroxy-3-ethylphenyl)cyclohexane (3-4), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (3-5), 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5-trimethylcyclohexane (3-6), 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane (3-7), and 1,1-bis(4-hydroxy-3-ethylphenyl)-3,3,5-trimethylcyclohexane (3-8). At least one of these compounds may be used, and it is also possible to use only one of them or to use two or more of them in combination.

[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 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 sulfonic acid group, a phosphoric acid group, or 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; 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.) [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(4-hydroxyphenyl)benzene, 1,3-bis(4-hydroxyphenyl)benzene, 2,2-bis(4-hydroxyphenyl)propane (Bis-A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, Examples of suitable hydroxybenzophenones include 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, 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 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.

[0025] (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.

[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 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 the alkali metal compound used is usually in the range of 1.0 to 3.0 times by mole, and preferably in the range of 1.01 to 1.3 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 150 to 350°C, preferably in the range of 150 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 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.

[0027] <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.

[0028] 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.

[0029] In the case where the structure of both ends of the polymer chain of the polyarylethersulfone (PAES) according to 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) with a reactive substituent such as an acryloyloxy group, a methacryloyloxy group, or a glycidyl ether group.

[0030] The PAES according to the present invention, whose terminal structure is a group represented by general formula (4) (an acryloyl group or a methacryloyl 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-mentioned method. One example of a method for (meth)acrylation is to react the terminal hydroxy groups of 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, 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.

[0031] The PAES according to 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-mentioned method. As a method for glycidyl etherification, for example, a glycidyl etherified PAES can be produced by reacting the terminal hydroxy groups of a polyarylethersulfone 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.

[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 obtained, which contains 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, which will be described later.

[0033] <Use of PAES according to the present invention> (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 1 GHz to 100 GHz, more preferably 1 GHz to 80 GHz, and particularly preferably 1 GHz to 30 GHz.

[0034] (Polyarylethersulfone resin material for electronic devices) The PAES of the present invention has excellent dielectric properties in the high-frequency band in addition to heat resistance, which is one of the properties of PAES. 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) for use in electronic devices and devices used for high-speed communications using radio waves in the high-frequency band of 1 GHz or more and 300 GHz or less (electronic devices and devices for high-frequency communication in the range of 1 GHz or more and 300 GHz or less). The polyarylethersulfone resin material for electronic devices and devices, which contains the PAES of the present invention, may be a resin material containing only the polyarylethersulfone 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 a flame retardant, a heat stabilizer, an oxidation stabilizer, a weather stabilizer, an antistatic agent, a lubricant, and a plasticizer. As described above, the polyarylethersulfone resin material for electronic devices of the present invention can be used as a resin material for electronic devices and devices 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).

[0035] (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 polyarylethersulfone resin material for electronic devices and devices of the present invention not only has heat resistance, one of the properties of PAES, but also has excellent dielectric properties in the high-frequency band, making it suitable for use in electronic devices and devices, particularly in high-frequency communication electronic devices and devices 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 in the high-speed communications field that require high frequency compatibility include mobile phones, smartphones, personal computers, mobile routers, data center communications equipment, base stations, radar, robots, drones, and wearable computers, as well as measurement and measuring instruments and their communications equipment used in various industries such as automobiles, aircraft, manufacturing, agriculture, logistics, and civil engineering. 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 polyarylethersulfone resin material for electronic devices and devices 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 devices (preferably, electronic devices and devices for high-frequency communication in the range of 1 GHz to 300 GHz). Among these, the polyarylethersulfone resin material can be suitably used in circuit boards, semiconductor encapsulants, or antenna element components of electronic devices and devices, and can be particularly suitably used in circuit boards of electronic devices and devices. [Example]

[0036] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0037] 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 tan δ 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 1GHz, 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 the PAES obtained in the examples and comparative examples was measured by dissolving PAES powder in a solvent, passing the solution through a membrane filter with a pore size of 0.45 μm, and subjecting the solution to 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

[0038] Example 1 (Synthesis of PAES (1a)) 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, 13.30 g of 4,4'-dichlorodiphenyl sulfone and 12.19 g of 1,1-bis(4-hydroxyphenyl)cyclohexane as monomers, 6.53 g of dried potassium carbonate, 144.52 g of dimethylacetamide (DMAc), and 25.55 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, and then mixed with methanol and filtered again to obtain PAES powder. The obtained PAES has a repeating unit represented by chemical formula (1-1). [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, 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.

[0039] <Example 2> (Synthesis of PAES (1-5)) A 500 mL four-neck flask equipped with a stirrer and a nitrogen inlet tube was charged with 12.38 g of 4,4'-dichlorodiphenyl sulfone as a monomer, 13.12 g of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (3-5), 6.08 g of dried potassium carbonate, and 144.58 g of dimethylacetamide (DMAc), and the mixture was stirred and dissolved under a nitrogen atmosphere. The mixture was then heated to 160°C and the polymerization reaction was carried out for 75 hours. 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, and then mixed with methanol and filtered again to obtain PAES powder. The obtained PAES has a repeating unit represented by the chemical formula (1-5). [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, 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.

[0040] <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. Next, the liquid temperature was cooled to 100°C or less under a nitrogen atmosphere, and 15.59 g of 4,4'-dichlorodiphenyl sulfone was added as a monomer and dissolved. 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 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, and then 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.

[0041] <Comparative Example 2> (Synthesis of PAES(PSU)) 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, 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 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 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 off, and the resulting residue was 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. % 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 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.

[0042] <Comparative Example 3> (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, 13.95 g of 4,4'-dichlorodiphenyl sulfone and 11.55 g of 2,2-bis(4-hydroxyphenyl)butane as monomers, 6.85 g of dried potassium carbonate, 144.58 g of dimethylacetamide (DMAc), and 25.54 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 78 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, 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 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, 13.26 g of 4,4'-dichlorodiphenyl sulfone and 12.24 g of 2,2-bis(4-hydroxyphenyl)-4-methylpentane as monomers, 6.51 g of dried potassium carbonate, 144.58 g of dimethylacetamide (DMAc), and 25.55 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 72 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 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 5> (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 25.26 g of 4,4'-dichlorodiphenyl sulfone as monomers, 25.74 g of 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 12.40 g of dried potassium carbonate, 289.06 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 140 hours while distilling off the water produced by the reaction. After the reaction was completed, DMAc was added to the mixture to make 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 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.

[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). 0.5The results are summarized in Table 1.

[0046] [Table 1]

[0047] 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. It was revealed that the PAES obtained in Examples 1 and 2, which are specific examples of the present invention, have sufficiently excellent heat resistance as PAES from their glass transition temperatures. In particular, it was revealed that the PAES obtained in Example 2 has a higher glass transition temperature than PPSU and has particularly excellent heat resistance. The PAES obtained in Examples 1 and 2 have, in comparison with the PAES obtained in Comparative Examples 1 and 2, the relative permittivity, dielectric loss tangent, and amount of dielectric loss of an electric signal at 1 GHz and the higher frequency of 10 GHz (relative permittivity) 0.5 It was found that the value of × (dielectric tangent) was very low. The PAES obtained in Comparative Examples 3, 4, and 5 were PAES obtained using, as the raw material bisphenol, bisphenols having a chain alkylidene group with 4, 6, and 8 carbon atoms, respectively. On the other hand, the PAES obtained in Examples 1 and 2 were PAES obtained using, as the raw material bisphenol, bisphenols having a cyclic alkylidene group with 6 and 9 carbon atoms, respectively. The PAES obtained in Comparative Examples 3, 4 and 5 had lower dielectric constants, dielectric loss tangents and dielectric constants than PPSU and PSU. 0.5 The value of × (dielectric tangent) is small, and the material has excellent dielectric properties, while the glass transition temperature is low. However, the PAES obtained in Examples 1 and 2, which are specific examples of the present invention, have lower dielectric constants, dielectric loss tangents, and dielectric constants than the PAES obtained in Comparative Examples 3, 4, and 5. 0.5The values ​​of × (dielectric tangent) were equivalent, and it was revealed that in addition to having excellent dielectric properties, the glass transition temperature was very high and the heat resistance was also excellent.

[0048] From the above, it has become clear that the PAES of the present invention not only has excellent heat resistance as a PAES, but also has excellent dielectric properties in the high-frequency band, and therefore can be suitably used as a polyarylethersulfone resin material for electronic devices and devices, particularly as a PAES resin material for high-frequency communication electronic devices and devices in the range of 1 GHz or more and 300 GHz or less.

Claims

1. A polyarylethersulfone resin material for electronic devices, comprising polyarylethersulfone having a glass transition temperature of 150°C or higher, a weight average molecular weight (Mw) in the range of 2,000 to 1,000,000, and having a repeating unit represented by general formula (1): 【Chemical 1】 (In the formula, R １ each independently represents a hydrocarbon group having 1 to 6 carbon atoms; R ２ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, each n independently represents 0, 1, 2, or 3, m represents 0 or 1, and p represents 0 or an integer of 1 to 6.

2. The repeating unit represented by the general formula (1) is at least one selected from the repeating units represented by chemical formulas (1-1) to (1-8). A polyarylethersulfone resin material for electronic devices and devices according to claim 1. 【Chemistry 2】 【Chemistry 3】

3. 2. The polyarylethersulfone resin material for electronic devices and devices according to claim 1, wherein the polyarylethersulfone further has a dielectric loss tangent measured at frequencies of 1 GHz and 10 GHz of 0.005 or less, and a relative dielectric constant measured at frequencies of 1 GHz and 10 GHz of 3.5 or less.

4. The polyarylethersulfone resin material for electronic devices and devices according to claim 1, wherein the electronic devices and devices are electronic devices and devices for high-frequency communication in the range of 1 GHz to 300 GHz.

5. An electronic device or device using the polyarylethersulfone resin material for electronic devices or devices according to claim 1.

6. A circuit board, a semiconductor sealing material, or an antenna element member for an electronic device or device, which uses the polyarylethersulfone resin material for electronic devices or devices according to claim 1.

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

8. A method for using a polyarylethersulfone having a glass transition temperature of 150°C or higher and a weight average molecular weight (Mw) in the range of 2,000 to 1,000,000, in an electronic device or device. 【Chemistry 4】 (In the formula, R １ each independently represents a hydrocarbon group having 1 to 6 carbon atoms; R ２ each independently represents a hydrocarbon group having 1 to 6 carbon atoms, each n independently represents 0, 1, 2, or 3, m represents 0 or 1, and p represents 0 or an integer of 1 to 6.

9. The repeating unit represented by the general formula (1) is at least one selected from the repeating units represented by chemical formulas (1-1) to (1-8). A method for using the polyarylethersulfone according to claim 8 in an electronic device or device. 【Chemistry 5】 【Chemistry 6】

10. 9. The method for using the polyarylethersulfone according to claim 8 in an electronic device or apparatus, wherein the polyarylethersulfone further has a dielectric loss tangent of 0.005 or less measured at frequencies of 1 GHz and 10 GHz, and a relative dielectric constant of 3.5 or less measured at frequencies of 1 GHz and 10 GHz.

11. 9. A method for using the polyarylethersulfone according to claim 8 in an electronic device or device, wherein the electronic device or device is a high-frequency communication electronic device or device in the range of 1 GHz to 300 GHz.

12. 9. The method for using the polyarylethersulfone according to claim 8 in an electronic device or device, wherein the polyarylethersulfone is used for a circuit board, a semiconductor encapsulant, or an antenna element member of the electronic device or device.

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