Polyarylene ether sulfone

Abstract

To provide a novel polyarylene ether sulfone having improved dielectric properties in a high frequency band. As a solution, a polyarylene ether sulfone having a repeating unit represented by general formula (1) is provided. In the formula, R1 each independently represents a hydrocarbon group containing a cyclic structure having 5 to 7 carbon atoms, R2 and R3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and m represents 0 or 1.

Description

Technical Field

[0001] This invention relates to a novel polyarylene ether sulfone (PAES), and more specifically, to a PAES obtained using a specific bisphenol as a raw material, which has improved heat resistance and improved dielectric properties in the high-frequency range. Background Technology

[0002] Polyarylene ether sulfone (PAES) resin is well-known as a thermoplastic with characteristics such as heat resistance, dimensional stability, mechanical properties, and flame retardancy. Therefore, PAES resin is used as a raw material in electrical and electronic fields such as relay components, coil frames, and switches; in OA and AV components such as various parts of copiers or printers; in heat-resistant tableware such as in-flight dining trays in aircraft; and in medical fields such as dental instruments. The application of PAES in these applications shows a trend towards further high performance and specialization.

[0003] In recent years, with the development of extremely high-speed and high-frequency mobile signal transmission in wireless internet and communication devices, the insulation components that insulate the metal wiring of these devices also need to cope with high-frequency demands. In particular, higher-frequency radio waves such as centimeter waves (SHF: Super High Frequency) and millimeter waves (EHF: Extremely High Frequency) are used for higher-speed data communication. The higher the frequency, the greater the dielectric loss of the insulation components, and the more the mobile signal attenuates. Therefore, as a measure to cope with high-frequency demands, materials with excellent dielectric properties that can reduce dielectric loss are needed. On the other hand, in the manufacturing and use of electrical and electronic components, electronic devices, and electronic equipment using them, excellent heat resistance is also required, necessitating materials with further improved heat resistance. Resins specifically used in this application include liquid crystal polymers (LCP) or polyaryletherketones (PAEK), but PAEK has currently received almost no attention.

[0004] For PAES using bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene as raw material, Patent Document 1 describes a PAES obtained by polymerizing 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene (α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene) with dichlorodiphenyl sulfone. Although it has a high heat distortion temperature, it has a lower melt viscosity and excellent processability.

[0005] In addition, Patent Document 2 describes a PAES obtained by polymerizing 1,3-bis(4-hydroxy-1-isopropylphenyl)benzene and 1,4-bis(4-hydroxy-1-isopropylphenyl)benzene with a dihalodiphenyl sulfone compound. Due to its excellent heat resistance, melt flowability and solvent resistance, it can be used for precision parts applications.

[0006] Patent documents Patent Document 1: U.S. Patent No. 3,554,972 Patent Document 2: Japanese Patent Application Publication No. 01-256523 Summary of the Invention In PAES, the dielectric properties at high frequencies were previously unknown, and it was unclear whether it was a suitable resin material for use in electronic devices or electronic components (hereinafter sometimes collectively referred to as electronic devices and components), especially for use in high-speed communication electronic devices and components that currently require high-frequency radio waves (hereinafter sometimes referred to as high-frequency communication electronic devices and components). Furthermore, the dielectric properties of PAES using bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene as a raw material were also previously completely unknown.

[0007] As a widely used PAES, the inventors synthesized PAES (polyphenyl sulfone: PPSU) obtained from bisphenol using 4,4'-biphenol as a raw material and PAES (polysulfone: PSU) obtained from 2,2-bis(4-hydroxyphenyl)propane. They evaluated their dielectric properties in the high-frequency range and found the following problems: high relative dielectric constant and dielectric loss tangent, resulting in poor dielectric properties as a resin material for electronic devices and electronic components.

[0008] In this case, the objective of the present invention is to provide a novel PAES with improved dielectric properties in the high-frequency range.

[0009] The inventors conducted in-depth research to solve the above-mentioned problems and found that, among the bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene used as PAES raw materials, PAES with hydrocarbon groups containing specific cyclic structures not only have improved heat resistance, but also have improved dielectric properties in the high-frequency range, thus completing the present invention.

[0010] The present invention is as follows.

[0011] 1. A polyarylether sulfone, characterized in that it has repeating units represented by general formula (1), [Chemistry 1]

[0012] In the formula, R1 independently represents a hydrocarbon group containing a cyclic structure with 5 to 7 carbon atoms, R2 and R3 independently represent a hydrocarbon group with 1 to 6 carbon atoms or a hydrogen atom, and m represents 0 or 1.

[0013] 2. The polyarylether sulfone according to 1, characterized in that the repeating unit represented by general formula (1) is the repeating unit represented by chemical formula (1a) or (1d), [Chemistry 2]

[0014] .

[0015] 3. A molded article, characterized in that it is a molded article of the polyarylether sulfone described in 1.

[0016] 4. A polyarylether sulfone resin material for electronic devices and electronic components, characterized in that it comprises the polyarylether sulfone described in 1.

[0017] 5. A polyarylether sulfone resin material for high-frequency communication electronic devices and electronic components in the range of 1 GHz to 300 GHz, characterized in that it comprises the polyarylether sulfone described in 1.

[0018] 6. An electronic device and electronic component, characterized in that it uses the polyarylether sulfone described in 1.

[0019] 7. A high-frequency communication electronic device and electronic component in the range of 1 GHz to 300 GHz, characterized in that it uses the polyarylether sulfone described in 1.

[0020] 8. A method, characterized in that it is a method of using the polyarylether sulfone described in 1. in electronic devices and electronic components.

[0021] 9. A method characterized in that it is a method of using the polyarylether sulfone described in 1. in high-frequency communication electronic equipment and electronic devices in the range of 1 GHz to 300 GHz.

[0022] 10. A polyarylether sulfone resin composition, characterized in that it comprises the polyarylether sulfone of 1. and one or more additives selected from flame retardants, heat stabilizers, antioxidants, weather stabilizers, antistatic agents, lubricants and plasticizers.

[0023] 11. A molded article, characterized in that it is a molded article of the polyarylether sulfone resin composition described in 10.

[0024] 12. An electronic device and electronic component, characterized in that it is an electronic device and electronic component using the polyarylether sulfone resin composition described in 10.

[0025] 13. The polyarylene ether sulfone according to 1, characterized in that the structures at both ends of the polymer chain of the polyarylene ether sulfone are any one of (i) to (iii), (i) Both are one type of base selected from those represented by general formula (4) or chemical formula (5); (ii) One side is a base selected from the bases represented by general formula (4) or chemical formula (5), and the other side is a halogen atom; (iii) One of the groups is selected from the groups represented by general formula (4) or chemical formula (5), and the other is a hydroxyl group; [Chemistry 3] In the formula, R7 represents a hydrogen atom or a methyl group. This indicates the bonding site at the end of the polymer chain.

[0026] 14. The polyarylether sulfone according to 13, characterized in that the weight-average molecular weight (Mw) is in the range of 2,000 to 100,000.

[0027] In addition to improved heat resistance, the polyarylether sulfone of the present invention also has improved dielectric properties at high frequencies. Therefore, it is suitable as a resin material for electronic devices and electronic components, and is particularly suitable as a resin material for high-speed communication electronic devices and electronic components that use high-frequency radio waves in the range of 1 GHz to 300 GHz. Detailed Implementation

[0028] (PAES of the present invention) The PAES of the present invention has repeating units represented by general formula (1).

[0029] [Chemistry 4]

[0030] (In the formula, R1 independently represents a hydrocarbon group containing a cyclic structure with 5 to 7 carbon atoms, R2 and R3 independently represent a hydrocarbon group with 1 to 6 carbon atoms or a hydrogen atom, and m represents 0 or 1.) Among the repeating units represented by general formula (1), the repeating units represented by general formula (1-1) or (1-2) are preferred.

[0031] [Chemistry 5]

[0032]

[0033] (In the formula, the definitions of R1 and m are the same as in general formula (1).) In general formula (1), R1 independently represents a hydrocarbon group containing a cyclic structure with 5 to 7 carbon atoms. Specifically, examples include cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl, and phenyl. Among these, cyclopentyl, cyclohexyl, or phenyl are preferred, cyclohexyl or phenyl are more preferred, and cyclohexyl is particularly preferred. The same applies to general formulas (1-1) and (1-2), and the same applies below.

[0034] In general formula (1), R2 and R3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Examples of hydrocarbon groups having 1 to 6 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, 2-methylpentyl, hexyl, cyclopentyl, cyclohexyl, and phenyl. R2 and R3 are preferably each independently a straight-chain 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 (an aromatic hydrocarbon group having 6 carbon atoms). More preferably, each independently is a hydrogen atom, methyl, tert-butyl, cyclohexyl, or phenyl. Even more preferably, each independently is a hydrogen atom or a methyl group. Particularly preferred is R2 being a hydrogen atom and R3 being a methyl group, or all being hydrogen atoms.

[0035] In general formula (1), m represents 0 or 1. From the perspective of raw material availability, 0 is preferred.

[0036] In general formula (1), the repeating unit represented when m is 0 can specifically be listed as the structure of chemical formulas (1a) to (1f). Among the repeating units represented by general formula (1), it is preferable to have repeating units selected from repeating units represented by chemical formulas (1a) to (1f), more preferably to have repeating units selected from repeating units represented by chemical formulas (1a), (1c), (1d) and (1f), even more preferably to have repeating units represented by chemical formula (1a) or (1d), and particularly preferably to have repeating units represented by chemical formula (1a).

[0037] [Chemistry 6]

[0038] [Chemistry 7]

[0039] In general formula (1), the repeating unit represented when m is 1 can specifically be exemplified by structures of chemical formulas (1g) to (1r), and preferably has repeating units selected from repeating units represented by chemical formulas (1g) to (1r). From the perspective of the heat resistance of the obtained PAES, it is more preferable to have repeating units selected from repeating units represented by chemical formulas (1g) to (1i) and (1m) to (1o).

[0040] [Chemistry 8]

[0041] [Chemistry 9]

[0042] [Chemistry 10]

[0043] [Chemistry 11]

[0044] In addition to having one structure selected from the repeating units represented by general formula (1), the PAES of the present invention may also have two or more structures selected from the repeating units represented by general formula (1). Preferably, it has one structure selected from the repeating units represented by general formula (1).

[0045] The PAES of the present invention may have other repeating units as long as they have the repeating unit represented by the general formula (1), without impairing the effect of the present invention. However, it is preferred that the content of the repeating unit represented by the general formula (1) is 100 mol%, that is, it does not have other repeating units.

[0046] When other repeating units are present, in terms of the content of the repeating units represented by general formula (1), it is preferable to contain 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 other repeating units can be arranged regularly or exist randomly. PAES having the repeating units represented by general formula (1) and other repeating units can be manufactured by combining a bisphenol compound represented by general formula (3) (described later) with an aromatic dihydroxy compound and performing the polycondensation reaction (described later).

[0047] The PAES of the present invention preferably does not contain any one or more of the following in its polymer chain: a sulfonic acid group or its salt, a phosphate group or its salt, a carboxyl group or its salt, an ester derivative derived from an alcohol of a sulfonic acid group, a phosphate group, or a carboxyl group, an amide derivative derived from an amine of a sulfonic acid group, a phosphate group, or a carboxyl group, or an ionic group. The chemical structures of the sulfonic acid group, the phosphate group, and the carboxyl group are represented by the following chemical formulas.

[0048] [Chemistry 12]

[0049] (The present invention relates to the structure of the two ends of the polymer chain of PAES) There are no particular limitations on the structure of the two ends of the polymer chain of PAES of the present invention. It may have halogen atoms from dihalogen compounds represented by general formula (2), hydroxyl groups from bisphenol compounds represented by general formula (3), or modified hydroxyl groups with reactive functional groups, specifically, for example, the end structures of the group represented by general formula (4) (specifically acryloyloxy, methacryloyloxy) or the group represented by chemical formula (5) (glycidyl ether group).

[0050] [Chemistry 13]

[0051] (In the formula, R7 represents a hydrogen atom or a methyl group,) This indicates the bonding site at the end of the polymer chain. The reactive functional group is preferably selected from one of the groups represented by general formula (4) (specifically acryloyloxy, methacryloyloxy) and the group represented by chemical formula (5) (glycidyl ether group).

[0052] When the terminal structure is (i) both sides are halogen atoms; (ii) both sides are hydroxyl groups; (iii) one side is a halogen atom and the other side is a hydroxyl group, the polyarylether sulfone of the present invention can be used as a thermoplastic resin. By applying common molding and processing methods of thermoplastic resins (e.g., injection molding, extrusion molding, compression molding, and other melt molding methods), molded articles for use in electronic devices and electronic components can be manufactured, thereby manufacturing electronic devices and electronic components.

[0053] Furthermore, when the terminal structure is (i) both sides are reactive functional groups; (ii) one side is a reactive functional group and the other side is a halogen atom; (iii) one side is a reactive functional group and the other side is a hydroxyl group, since at least one of the terminal structures has a reactive functional group, the polyarylether sulfone of the present invention can be used as a curable resin. By applying common methods of molding and processing of curable resins (e.g., compression molding or transfer molding), molded articles for use in electronic devices and electronic components can be manufactured, for example, thereby manufacturing electronic devices and electronic components.

[0054] (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 in the range of 10,000 to 500,000, even more preferably in the range of 20,000 to 200,000, and particularly preferably in the range of 30,000 to 150,000.

[0055] When the polymer chain of the PAES of the present invention has two end structures that are (i) both halogen atoms, (ii) both hydroxyl atoms, or (iii) one halogen atom and the other hydroxyl atom, in order to give it sufficient mechanical strength, the weight-average molecular weight (Mw) is preferably in the range of 10,000 to 500,000, more preferably in the range of 20,000 to 200,000, and particularly preferably in the range of 30,000 to 150,000.

[0056] When the terminal structure of the PAES of the present invention is (i) both sides are reactive functional groups; (ii) one side is a reactive functional group and the other side is a halogen atom; (iii) one side is a reactive functional group and the other side is a hydroxyl group, in order to make it have good processability, 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.

[0057] The ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn), i.e., Mw / Mn, is preferably in the range of 1.2 to 20, more preferably in the range of 1.2 to 15, even more preferably in the range of 1.2 to 10, and particularly preferably in the range of 1.2 to 8.

[0058] (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. A higher glass transition temperature results in better heat resistance, and is therefore preferred. Thus, there is no particular limitation on the upper limit, and it can be 300°C or lower.

[0059] The PAES of the present invention is suitable for use in manufacturing processes exposed to high temperatures and in electronic devices and electronic components used in high-temperature environments, especially polyarylether sulfone resin materials for high-frequency communication electronic devices and electronic components in the range of 1 GHz to 300 GHz.

[0060] (Dielectric loss tangent) The dielectric loss tangent of the PAES of the present invention, measured at a frequency of 10 GHz, is preferably 0.005 or less. If the dielectric loss tangent is 0.005 or less, it is suitable for use as a polyarylether sulfone resin material for electronic devices and components, particularly for high-frequency communication electronic devices and components in the range of 1 GHz to 300 GHz. More preferably, the dielectric loss tangent is 0.004 or less, even more preferably 0.0035 or less, and particularly preferably 0.003 or less. The lower the dielectric loss tangent, the better; therefore, there is no particular limitation on the lower limit value, and it can be 0.001 or more.

[0061] The dielectric loss tangent, measured at a frequency of 1 GHz, is preferably 0.005 or less. More preferably, it is 0.004 or less; even more preferably, 0.0035 or less; and particularly preferably, 0.003 or less. Since lower is better, there is no particular limitation on the lower limit value, which can be 0.001 or more.

[0062] (Relative permittivity) The relative permittivity of the PAES of the present invention, measured at frequencies of 1 GHz and 10 GHz, is preferably 3.5 or less. If the relative permittivity is 3.5 or less, it is suitable for use as a polyarylether sulfone resin material for electronic devices and components, particularly for high-frequency communication electronic devices and components in the range of 1 GHz to 300 GHz. More preferably, the relative permittivity is 3.2 or less; even more preferably, 3.0 or less; and particularly preferably, 2.7 or less. The lower the relative permittivity, the better; therefore, there is no particular limitation on its lower limit, and it can be 2.0 or more.

[0063] (The method for manufacturing PAES of the present invention) There are no particular limitations on the manufacturing method of PAES of the present invention. For example, it can be manufactured by desalting and polycondensing a dihalogen compound represented by general formula (2) with a bisphenol compound represented by general formula (3) in the presence of an alkali metal compound.

[0064] [Chemistry 14]

[0065] (In the formula, X represents each halogen atom independently, and m is defined in the same way as in general formula (1).) [Chemistry 15]

[0066] (In the formula, R1, R2 and R3 are defined in the same way as in general formula (1).) In 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 polyarylene sulfone having repeating units represented by chemical formula (1a) can be produced. The reaction formulas are shown below.

[0067] [Chemistry 16]

[0068] (Dihalogen compounds represented by general formula (2)) In general formula (2), X specifically represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, wherein a fluorine atom or a chlorine atom is preferred, and a chlorine atom is particularly preferred.

[0069] In general formula (2), from the perspective of availability, m is preferably 0.

[0070] As dihalogen compounds represented by general formula (2), examples 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, 1,3-bis[(4-iodophenyl)sulfonyl]benzene.

[0071] Among them, 4,4'-difluorodiphenyl sulfone and 4,4'-dichlorodiphenyl sulfone are preferred, and 4,4'-dichlorodiphenyl sulfone is particularly preferred.

[0072] (The bisphenol compound represented by general formula (3)) Among the bisphenol compounds represented by general formula (3), the repeating unit represented by general formula (3-1) or (3-2) is preferred.

[0073] [Chemistry 17]

[0074] (In the formula, the definitions of R1, R2 and R3 are the same as in general formula (1).) For R1, R2 and R3 in general formula (3), their specific examples and preferred forms are the same as those in general formula (1). The same applies to general formulas (3-1) and (3-2).

[0075] As bisphenol compounds represented by general formula (3), examples include, for instance, 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.

[0076] Preferably, 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 are 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 are particularly preferred.

[0077] (Other aromatic dihydroxy compounds) In the PAES of the present invention, in order to obtain PAES having repeating units represented by general formula (1) and other repeating units, in addition to the bisphenol compounds represented by general formula (3), other aromatic dihydroxy compounds may also be used. The other repeating units are repeating units having structures from these aromatic hydroxy compounds and structures from the dihalogen compounds represented by general formula (2).

[0078] For other aromatic dihydroxy compounds of bisphenol compounds represented by general formula (3), it is preferred to be an aromatic dihydroxy compound that does not contain a group selected from sulfonic acid group, phosphoric acid group and carboxylic acid group, and more preferably an aromatic hydroxy compound represented by general formula (6).

[0079] [Chemistry 18]

[0080] (In the formula, R represents the divalent base represented by general formula (6a) or (6b).) [Chemistry 19]

[0081] (In the formula, R4 independently represents a straight-chain or branched alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 5 or 6 carbon atoms, or a phenyl group; a independently represents an integer from 0 to 4; b represents 0 or 1; c represents 0, 1, or 2.) Each represents a bonding position. [Chemistry 20]

[0082] (In the formula, R4 independently represents a straight-chain or branched alkyl group with 1 to 6 carbon atoms, a cyclic alkyl group with 5 or 6 carbon atoms, or a phenyl group; 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 formulas (7a), (7b), or (7c); Z represents an oxygen atom, a sulfur atom, or an uncrosslinked group.) Each represents a bonding position. [Chemistry 21]

[0083] In general formulas (7a), (7b) and (7c), R5 independently represents a hydrogen atom, a straight-chain or branched alkyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 12 carbon atoms. Two R5s can be bonded to each other to form a cycloalkane group with 5 to 20 carbon atoms as a whole. R6 independently represents a hydrogen atom or a straight-chain or branched alkyl group with 1 to 6 carbon atoms. Ar1 independently represents an aryl group with 6 to 12 carbon atoms. Each represents a bonding position. Other aromatic dihydroxy compounds that can be used in combination include, specifically, 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'-dihydroxydiphenyl ether, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(3-phenyl-4-hydroxyphenyl)fluorene, 9,9-bis(3,5-diphenyl-4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)fluorene, 2,2-bis(4-hydroxy-3-phenylphenyl)propane, bisphenol Z (1,1-bis(4-hydroxyphenyl)cyclohexane), bisphenol TMC (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane), 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane. These compounds can be used in single-component or in combination of two or more.

[0084] Other repeating units are repeating units having structures derived from these aromatic hydroxyl compounds and structures derived from dihalogen compounds represented by general formula (2).

[0085] (Alkali metal compounds) As an alkali metal compound, any alkali metal compound can be used as long as it can convert the bisphenol compound shown in general formula (3) into an alkali metal salt. However, alkali metal carbonates, bicarbonates, hydroxides, etc. are generally preferred, and carbonates are particularly preferred. Examples of such alkali metals include lithium, sodium, potassium, rubidium, and cesium, with sodium and potassium being preferred, and potassium being particularly preferred.

[0086] (solvent) In the polycondensation reaction to obtain PAES, solvents can be used, and preferably solvents are used. Neutral or polar solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolinone (DMI), dimethyl sulfoxide (DMSO), sulfolane, and diphenyl sulfone are preferred as solvents. However, any solvent that can dissolve both the monomer and the polymer can be used without issue. One solvent can be used alone, or two or more solvents can be used in combination as a mixed solvent.

[0087] (Condensation reaction conditions) The amount of the dihalogen compound represented by general formula (2) used, relative to the bisphenol compound represented by general formula (3) (when used in combination with aromatic dihydroxy compounds other than general formula (3), it is the total of the bisphenol compound represented by general formula (3) and the aromatic dihydroxy compounds other than general formula (3)), varies depending on the target molecular weight. However, in order to produce high molecular weight PAES (specifically, preferably in the range of 10,000 to 500,000, more preferably in the range of 20,000 to 200,000, particularly preferably in the range of 30,000 to 150,000), it is generally in the range of 0.9 to 1.1 molar times, preferably in the range of 0.95 to 1.06 molar times, and more preferably in the range of 1.0 to 1.04 molar times.

[0088] On the other hand, in order to manufacture PAES with low 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, particularly preferably in the range of 2,000 to 10,000), the concentration is typically in the range of 0.6 to 1.4 molar ratios, preferably in the range of 0.7 to 1.3 molar ratios, and more preferably in the range of 0.8 to 1.2 molar ratios.

[0089] In PAES where the terminal structures of the polymer chains are composed of halogen atoms on both sides, the molar ratio is in the range of 1.01 to 1.1 molar times, preferably in the range of 1.01 to 1.06 molar times, and more preferably in the range of 1.01 to 1.04 molar times.

[0090] In PAES where the terminal structures of the polymer chains are both hydroxyl groups, for PAES with large molecular weights, the molar ratio is in the range of 0.9 to 0.99 molar times, preferably in the range of 0.95 to 0.99 molar times, and for PAES with small molecular weights, it 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.

[0091] The amount of alkali metal ions in the alkali metal compound used is typically in the range of 2.0 to 3.0 molar times, preferably in the range of 2.02 to 2.6 molar times, relative to the bisphenol compound represented by general formula (3) (or, when using aromatic dihydroxy compounds other than general formula (3), the total of the bisphenol compound represented by general formula (3) and the aromatic dihydroxy compounds other than general formula (3)).

[0092] The reaction temperature is typically in the range of 120~350℃, preferably in the range of 140~250℃, and the reaction time is typically in the range of 1~400 hours, preferably in the range of 2~320 hours.

[0093] These reactions are preferably carried out in an inert gas atmosphere such as nitrogen or argon. Furthermore, there are no particular restrictions on the reaction pressure; it can be any of reduced pressure, atmospheric pressure, or pressurized pressure, but it is usually carried out at atmospheric pressure.

[0094] <Post-reaction treatment> PAES generated by the polycondensation reaction can be recovered by commonly used methods such as condensation, solidification, washing, granulation, extraction, and solvent removal.

[0095] A method for processing PAES generated by the polycondensation reaction will be described in more detail below. A liquid containing PAES generated by the polycondensation reaction is diluted with a solvent as needed, and then mixed with a poor solvent to precipitate the precipitate, thereby obtaining PAES in powder form. In this step, to remove alkali metal salts, water is preferred as the solvent for precipitating the precipitate; acidic water containing low concentrations of hydrochloric acid, formic acid, oxalic acid, etc., can also be used. Then, to remove the raw material monomers, a solvent-based washing step is preferably performed on the obtained PAES precipitate. Methanol, ethanol, acetone, ethyl methyl sulfone, xylene, toluene, etc., are preferred as the solvent; acetone or methanol is particularly preferred from the perspective of operability or ease of distillation recovery of the reaction solvent after washing.

[0096] The conditions for the above cleaning process can be adjusted by selecting the appropriate amount of cleaning solvent, number of cleaning cycles, and cleaning temperature based on the amount of residual raw material monomers, reaction solvents, and alkali metal salts to be removed.

[0097] After cleaning with acetone or methanol, to further remove residual alkali metal salts, they can be dissolved in neutral or polar solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolinone (DMI), dimethyl sulfoxide (DMSO), sulfolane, and diphenyl sulfone, and then precipitated with water or acidic water.

[0098] In addition to cleaning tanks and pressure filters or centrifuges, multi-functional filter devices that can complete cleaning, filtration, and drying in one unit can also be used as cleaning equipment.

[0099] For PAES powder obtained after the above cleaning process, which contains moisture or solvent after cleaning, a drying process can be carried out.

[0100] The drying process can be carried out under conditions that are below the melting point of the polycondensation reactants and that allow for the removal of moisture. To minimize contact with air, it is preferable to conduct the process under an inert gas atmosphere (nitrogen, argon, etc.) or an inert gas stream under reduced pressure.

[0101] The dryer can use known devices such as evaporators, rack-type ovens, and drum dryers.

[0102] When the ends of the polymer chain of the polyarylether sulfone (PAES) of the present invention are modified with reactive functional groups such as acryloyloxy or methacryloyloxy, glycidyl ether, etc., the PAES can be obtained by modifying the hydroxyl groups of the bisphenol compound represented by general formula (3) with reactive substituents such as acryloyloxy or methacryloyloxy, glycidyl ether, etc.

[0103] The PAES of the present invention, which has a terminal structure of the group (acryloyloxy or methacryloyloxy) shown in general formula (4), can be manufactured by applying a conventionally known methacrylic acid esterification method to a polyarylene sulfone having repeating units represented by general formula (1) obtained by the above method, wherein the polyarylene sulfone contains hydroxyl groups at the end of the polymer chain.

[0104] As a method for esterifying (meth)acrylic acid, one method is to react (meth)acrylic acid and its derivatives with the terminal hydroxyl groups of a polyarylene sulfone having repeating units represented by general formula (1). When acryloyl chloride is used as a (meth)acrylic acid derivative, since chloride ions are generated in the form of hydrogen chloride, it is preferable to use a hydrogen chloride scavenger. As a hydrogen chloride scavenger, any inorganic or organic basic substance such as an alkali metal carbonate or bicarbonate, or a tertiary amine can be used. Specifically, examples of (meth)acrylic acid and its derivatives include acrylic acid, methacrylic acid, acryloyl chloride, and methacryloyl chloride.

[0105] In the esterification reaction of acrylic acid, halogenated hydrocarbons such as dichloromethane or solvents such as tetrahydrofuran, dioxane, and chlorobenzene can be used.

[0106] During the reaction, as polymerization inhibitors, hydroquinone, hydroquinone monomethyl ether, phenothiazine, 2,6-di-tert-butyl-4-methylphenol (BHT) can be added.

[0107] The PAES of the present invention, whose terminal structure is a group (glycidyl ether group) represented by chemical formula (5), can be manufactured by applying a conventionally known method of glycidyl etherification of hydroxyl compounds to a polyarylether sulfone having repeating units represented by general formula (1) obtained by the above method, wherein the polyarylether sulfone contains hydroxyl groups at the end of the polymer chain.

[0108] As a method of glycidyl etherification, glycidyl etherified PAES can be produced, for example, by reacting an epihaloalcohol with respect to the terminal hydroxyl group of a polyarylether sulfone having repeating units represented by general formula (1) 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). Specifically, epichlorohydrin and epibromohydrin can be listed as epihaloalcohols used.

[0109] <Polyaryl ether sulfone resin composition> In the PAES of the present invention, without impairing the effects of the present invention, various additives such as flame retardants, heat stabilizers, antioxidants, weather stabilizers, antistatic agents, lubricants, and plasticizers can be formulated as needed using conventional methods for incorporating additives into the raw material resin. A polyarylether sulfone resin composition comprising the PAES of the present invention and one or more additives selected from flame retardants, heat stabilizers, antioxidants, weather stabilizers, antistatic agents, lubricants, and plasticizers can be prepared.

[0110] This polyarylether sulfone resin composition can be used in the same manner as PAES of the present invention, as described later.

[0111] <Use of PAES in this invention> (Made product) The PAES of the present invention can be used to manufacture molded articles such as films, sheets, tapes, containers, wires, lenses, tubes, granules, chips, etc. by applying common molding and processing methods of thermoplastic resins (such as injection molding, extrusion molding, compression molding, and other melt molding methods) or common molding and processing methods of curable resins (such as compression molding or transfer molding).

[0112] The PAES of the present invention, in addition to being used as electronic devices or electronic components used in the electronic devices described later, and electronic devices and electronic components for high-speed communication that use high-frequency radio waves in the range of 1 GHz to 300 GHz (electronic devices and electronic components for high-frequency communication in the range of 1 GHz to 300 GHz), can also be used as resin materials for mechanical parts (e.g., impellers, fan gears, gears, bearings, motor parts, housings), automotive parts (e.g., automotive mechanical parts, engine parts, engine compartment parts, electronic parts, interior parts), cooking utensils and appliances, dental instruments, optical instrument parts (e.g., lenses, films), medical instrument parts and materials, dental instrument parts and materials, valves, fittings, nozzles, filters, membranes, sanitary supplies, sporting goods, leisure goods, straps, and other articles, and can be molded into these articles.

[0113] (High-frequency radio waves) The term "high-frequency radio waves" in this invention refers to radio waves with frequencies ranging from 1 GHz to 300 GHz, including microwaves, centimeter waves (SHF: Super High Frequency), millimeter waves (EHF: Extremely High Frequency), etc. The frequency range of the high-frequency radio waves is preferably from 3 GHz to 100 GHz, more preferably from 5 GHz to 80 GHz, and particularly preferably from 5 GHz to 30 GHz.

[0114] (Polyaryl ether sulfone resin materials for electronic equipment and electronic devices) In addition to heat resistance, the polyarylethersulfone of the present invention also has excellent dielectric properties in the high-frequency band. Therefore, the resin material containing the polyarylethersulfone of the present invention is suitable as a polyarylethersulfone resin material for use in electronic devices or electronic devices used therein (electronic devices and electronic devices), and is particularly suitable as a polyarylethersulfone resin material for use in high-speed communication electronic devices and electronic devices that use high-frequency radio waves in the range of 1 GHz to 300 GHz (high-frequency communication electronic devices and electronic devices in the range of 1 GHz to 300 GHz).

[0115] The polyarylene ether sulfone resin material for electronic devices and electronic components incorporating the PAES of the present invention can be a resin material composed solely of the PAES of the present invention, depending on the characteristics required for the manufactured electronic devices and electronic components. Alternatively, it can be a resin material in which the PAES of the present invention contains one or more additives selected from flame retardants, heat stabilizers, antioxidants, weather stabilizers, antistatic agents, lubricants, and plasticizers.

[0116] (Electronic devices and electronic components) In this invention, electronic devices and the electronic components used therein are collectively referred to as electronic devices and electronic components. In particular, electronic devices and electronic components used in high-speed communication using high-frequency radio waves in the range of 1 GHz to 300 GHz are collectively referred to as high-frequency communication electronic devices and electronic components in the range of 1 GHz to 300 GHz.

[0117] In addition to improved heat resistance, the PAES of the present invention has improved dielectric properties in the high-frequency range. Therefore, electronic devices and electronic components using the PAES of the present invention are preferred, especially for high-frequency communication electronic devices and electronic components in the range of 1 GHz to 300 GHz.

[0118] Specifically, examples of such electronic devices include: mobile phones, smartphones, computers, mobile routers, data center communication equipment, base stations, radar, robots, drones, wearable computers, measuring and measuring equipment used in various industries such as automobiles, aircraft, industry, agriculture, logistics, and civil engineering, high-speed wireless communication equipment, electronic notebooks, digital cameras, camcorders, electronic paper, televisions, media players, various audio instruments, car navigation devices or dashboards and other in-vehicle displays, calculators, printers, scanners, copiers, refrigerators, washing machines, etc.

[0119] Among them, electronic devices used in high-speed communication using high-frequency radio waves include: mobile phones, smartphones, computers, mobile routers, data center communication equipment, base stations, radar, robots, drones, wearable computers, measuring and measurement equipment used in various industries such as automobiles, aircraft, industry, agriculture, logistics, and civil engineering, as well as high-speed wireless communication equipment.

[0120] Specifically, the electronic devices mentioned include semiconductors, electronic displays, and electrical and electronic components. Examples of such electrical and electronic components include, for example, capacitors, printed circuits, connectors, various sensors, inductors, switches, and housings. These can also be used in electronic devices employing high-speed communication using high-frequency radio waves.

[0121] More specifically, the PAES and polyarylethersulfone resin materials of the present invention are suitable for, for example, external components, structural components, circuit boards, semiconductor encapsulants, or antenna element components of electronic devices and electronic components (preferably high-frequency communication electronic devices and electronic components in the range of 1 GHz to 300 GHz). Among these, they are more suitable for use as circuit boards, semiconductor encapsulants, or antenna element components of electronic devices and electronic components, and are particularly suitable for use as circuit boards of electronic devices and electronic components.

[0122] Example The present invention will be further described in detail below through embodiments, but the present invention is not limited to these embodiments.

[0123] The analysis method in this invention is as follows.

[0124] <Analytical Methods> 1. Determination of glass transition temperature (Tg) The glass transition temperature of PAES obtained in the examples and comparative examples was determined using the following apparatus and conditions.

[0125] Measurement device: DMA850 (manufactured by TA Instruments) Heating rate: 4.0℃ / min. Frequency: 1Hz Atmosphere: air Measurement mode: Tension Test piece: 40mm × 7mm × thickness 0.02~0.05mm Analytical method: using the peak of tanδ as the glass transition point. 2. Determination of relative permittivity and dielectric loss tangent The relative permittivity and dielectric loss tangent of PAES obtained from the examples and comparative examples were determined using the following apparatus and conditions.

[0126] Measurement instruments: CP431 cavity resonator for 1GHz (manufactured by Kanto Electron Application Development Co., Ltd.), CP531 cavity resonator for 10GHz (manufactured by Kanto Electron Application Development Co., Ltd.), N5222B PNA network analyzer (manufactured by Keysight Technologies Co., Ltd.), cylindrical cavity resonator (material: copper, internal mirror finish). Test piece: L80~90×W1.4~1.6×t0.03~0.06 (mm) Measurement frequencies: around 1 GHz and 10 GHz Measurement environment: room temperature (23±1℃ / 50±5%RH) Measurement method: Based on International Electrotechnical Commission IEC 62810 (Cavity Resonator Perturbation Method) 3. Molecular weight determination The molecular weight of PAES obtained in the examples and comparative examples described below was determined by dissolving the PAES obtained from polymerization in a solvent, passing it through a 0.45 μm filter membrane, and then by gel permeation chromatography (GPC) under the following apparatus and conditions.

[0127] Device: Pump: LC-10ADvp (manufactured by Shimadzu Corporation) Chromatographic column: Shodex GPC KF-806L + KF-802 (manufactured by Showa Denko Corporation) Detector: Shodex RI-71 (manufactured by Showa Denko Corporation) Temperature: 50℃ Mobile phase: N-methyl-2-pyrrolidone Flow rate: 0.8 mL / min. Injection volume: 100μL Test: Refractive index Standard material: polystyrene <Example 1> (Synthesis of PAES(1a)) To a 500 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, add 9.70 g of 4,4'-dichlorodiphenyl sulfone, 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) as monomers. Stir and dissolve the monomers under a nitrogen atmosphere. Then, heat the solution to 160 °C and allow the polymerization reaction to proceed for 312 hours.

[0128] After the reaction was complete, DMAc was added to the reaction solution in a manner that yielded a solution of approximately 10% by weight, using the total weight of the monomers used as the weight of the solute. The solution was then cooled to room temperature. This DMAc solution was mixed with approximately 10 times the volume of pure water relative to the DMAc solution, causing the polymer to precipitate. The precipitate was filtered off, and then the filtrate was mixed with methanol and filtered off again to obtain PAES powder.

[0129] In addition, the obtained PAES is a PAES having repeating units represented by chemical formula (1a).

[0130] [Chemistry 22]

[0131] (Forming of 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. Next, it was dried at 80°C for 1 hour, followed by drying 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 the PAES film.

[0132] <Example 2> (Synthesis of PAES) To a 1L four-necked flask equipped with a Diane-Stark water separator filled with toluene and fitted with a Liebig condenser at the top, a stirrer, and a nitrogen inlet, 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), 8.81 g of dried potassium carbonate, 289.10 g of dimethylacetamide (DMAc), and 51.14 g of toluene (as monomers) were added and stirred under a nitrogen atmosphere to dissolve them. The liquid temperature was then raised to 160°C, and the polymerization reaction was carried out for 120 hours while distilling off the water generated in the reaction system.

[0133] After the reaction was complete, DMAc was added to the reaction solution in a manner that yielded a solution of approximately 10% by weight, using the total weight of the monomers used as the weight of the solute. The solution was then cooled to room temperature. This DMAc solution was mixed with approximately 10 times the volume of pure water relative to the DMAc solution, causing the polymer to precipitate. The precipitate was filtered off, and then the filtrate was mixed with methanol and filtered off again to obtain PAES powder. Furthermore, the obtained PAES is PAES having repeating units represented by the chemical formula (1d).

[0134] [Chemistry 23]

[0135] (Forming of 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. Next, it was dried at 80°C for 1 hour, followed by drying 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.

[0136] <Comparative Example 1> (Synthesis of PAES) To a 500 mL four-necked flask equipped with a Diane-Stark water separator filled with toluene, a stirrer, and a nitrogen inlet, 9.91 g of 4,4'-biphenol, 7.80 g of dried potassium carbonate, 144.56 g of dimethylacetamide (DMAc), and 25.54 g of toluene (as monomers) were added, and dissolved at room temperature while purging with nitrogen. The solution was then heated to 150 °C under a nitrogen atmosphere, and the water in the solution was azeotropically dehydrated while the toluene was refluxed.

[0137] Then, under a nitrogen atmosphere, the liquid temperature was cooled to below 100°C, 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 the polymerization reaction was carried out for 120 hours while distilling the water generated from the reaction out of the reaction system.

[0138] After the reaction was complete, DMAc was added to the reaction solution in a manner that yielded a solution of approximately 10% by weight, using the total weight of the monomers used as the weight of the solute. The solution was then cooled to room temperature. This DMAc solution was mixed with approximately 10 times the volume of pure water relative to the DMAc solution, causing the polymer to precipitate. The precipitate was filtered off, and then the filtrate was mixed with methanol and filtered off again to obtain PAES powder.

[0139] In addition, the obtained PAES is a PAES having repeating units represented by the following chemical formula.

[0140] [Chemistry 24]

[0141] (Forming of 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. The substrate was then dried sequentially 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.

[0142] <Comparative Example 2> To a 500 mL four-necked flask equipped with a Diane-Stark water separator filled with toluene, a stirrer, and a nitrogen inlet, 14.33 g of 4,4'-dichlorodiphenyl sulfone, 11.17 g of 2,2-bis(4-hydroxyphenyl)propane, 7.03 g of dried potassium carbonate, 144.50 g of dimethylacetamide (DMAc), and 25.56 g of toluene (as monomers) were added and stirred until 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 in the reaction system.

[0143] After the reaction was complete, DMAc was added to the reaction solution in a solution containing approximately 10% by weight, using the total weight of the monomers used as the weight of the solute. The solution was then cooled to room temperature. This DMAc solution was mixed with approximately 10 times the volume of pure water relative to the DMAc solution, causing the polymer to precipitate. The precipitate was filtered off, and then mixed with methanol and filtered again to obtain PAES powder. Further, for washing, the filtered powder was dissolved in DMAc and mixed with 1% by weight hydrochloric acid solution to precipitate the polymer, followed by filtration. Further, to remove the hydrochloric acid, the precipitate was added to pure water and filtered to obtain washed PAES powder.

[0144] In addition, the obtained PAES is a PAES having repeating units represented by the following chemical formula.

[0145] [Chemistry 25]

[0146] (Forming of 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. Next, it was dried at 80°C for 1 hour, followed by drying 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.

[0147] <Comparative Example 3> (Synthesis of PAES) To a 1L four-necked flask equipped with a Diane-Stark water separator filled with toluene, a stirrer, and a nitrogen inlet, 23.36 g of 4,4'-dichlorodiphenyl sulfone, 27.64 g of 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 11.47 g of dried potassium carbonate, 289.19 g of dimethylacetamide (DMAc), and 51.16 g of toluene (as monomers) were added and stirred until dissolved under a nitrogen atmosphere. The solution was then heated to 160°C, and the polymerization reaction was carried out for 140 hours while distilling off the water generated during the reaction.

[0148] After the reaction was complete, DMAc was added to the reaction solution in a manner that yielded a solution of approximately 10% by weight, using the total weight of the monomers used as the weight of the solute. The solution was then cooled to room temperature. This DMAc solution was mixed with approximately 10 times the volume of pure water relative to the DMAc solution, causing the polymer to precipitate. The precipitate was filtered off, and then the filtrate was mixed with methanol and filtered off again to obtain PAES powder.

[0149] In addition, the obtained PAES is a PAES having repeating units represented by the following chemical formula.

[0150] [Chemistry 26]

[0151] (Forming of 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. Next, it was dried at 80°C for 1 hour, followed by drying 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.

[0152] For the PAES obtained in the examples and comparative examples, the molecular weight (weight-average molecular weight: Mw and number-average molecular weight: Mn), polydispersity index (Mw / Mn), glass transition temperature, relative permittivity, and dielectric loss tangent were determined using the above analytical methods. Furthermore, based on the measured values ​​of the relative permittivity and dielectric loss tangent, the (relative permittivity) was... 0.5 The value of × (dielectric loss tangent) is used to evaluate dielectric properties. The (relative permittivity) described in this invention... 0.5 The value of × (dielectric loss tangent) is based on the dielectric loss of the electrical signal, which can be expressed as (proportional constant) × (frequency) × (relative permittivity). 0.5 The results are calculated using the dielectric loss tangent (×). These results are summarized in Table 1.

[0153] [Table 1]

[0154] The PAES obtained in Comparative Examples 1 and 2 are PAES having the same repeating units as resins commonly referred to as polyphenylsulfone (PPSU) and polysulfone (PSU), respectively.

[0155] Compared to the PAES obtained in Comparative Examples 1 and 2, the PAES obtained in Examples 1 and 2 of the present invention have very low relative permittivity and dielectric loss tangent values, even in terms of the (relative permittivity) which represents the dielectric loss of the electrical signal. 0.5 When compared with the value of (dielectric loss tangent), it is also significantly smaller, thus clearly demonstrating that the PAES of the present invention has improved dielectric properties.

[0156] The PAES obtained in Comparative Example 3, compared to the bisphenol used in Example 1, was obtained by using a bisphenol compound with no substituents at the phenol site as the raw material.

[0157] The PAES obtained in Examples 1 and 2, compared with the PAES obtained in Comparative Example 3, show improvements in relative permittivity, dielectric loss tangent, and (relative permittivity) 0.5 In terms of dielectric properties, the values ​​of × (dielectric loss tangent) are equivalent, but the glass transition temperatures are 52°C and 83°C higher, respectively, indicating improved heat resistance. Therefore, it is highly useful as a material for manufacturing processes exposed to high temperatures and for electronic devices and components used in high-temperature environments, making it applicable to a wider range of applications.

[0158] In summary, the polyarylether sulfone of the present invention, compared with the previously known PAES, not only has improved heat resistance, but also improved dielectric properties at high frequencies.

[0159] Furthermore, it can be clearly understood that the polyarylether sulfone of the present invention is suitable as a polyarylether sulfone resin material for use in electronic devices and electronic components, especially for high-frequency communication electronic devices and electronic components in the range of 1 GHz to 300 GHz.

Claims

1. A polyarylether sulfone, characterized in that, Having repeating units as represented by general formula (1), [Chemistry 1] In the formula, R1 independently represents a hydrocarbon group containing a cyclic structure with 5 to 7 carbon atoms, R2 and R3 independently represent a hydrocarbon group with 1 to 6 carbon atoms or a hydrogen atom, and m represents 0 or 1.

2. The polyarylether sulfone according to claim 1, characterized in that, The repeating unit represented by general formula (1) is the repeating unit represented by chemical formula (1a) or (1d). [Chemistry 2] 。 3. A molded article, characterized in that, It is a molded article of polyarylether sulfone as described in claim 1.

4. A polyarylethersulfone resin material for electronic devices and electronic components, characterized in that, It includes the polyarylether sulfone as described in claim 1.

5. A polyarylethersulfone resin material for high-frequency communication electronic devices and electronic components in the range of 1 GHz to 300 GHz, characterized in that, It includes the polyarylether sulfone as described in claim 1.

6. An electronic device and electronic component, characterized in that, Use the polyarylether sulfone as described in claim 1.

7. A high-frequency communication electronic device and electronic component in the range of 1 GHz to 300 GHz, characterized in that, Use the polyarylether sulfone as described in claim 1.

8. A method, characterized in that, It is a method for using the polyarylether sulfone described in claim 1 in electronic devices and electronic components.

9. A method, characterized in that, It is a method for using the polyarylether sulfone of claim 1 in high-frequency communication electronic devices and electronic components in the range of 1 GHz to 300 GHz.

10. A polyarylethersulfone resin composition, characterized in that, It includes the polyarylether sulfone as described in claim 1 and one or more additives selected from flame retardants, heat stabilizers, antioxidants, weather stabilizers, antistatic agents, lubricants and plasticizers.

11. A molded article, characterized in that, It is a molded article of the polyarylether sulfone resin composition according to claim 10.

12. An electronic device and electronic component, characterized in that, It refers to electronic devices and electronic components using the polyarylether sulfone resin composition of claim 10.

13. The polyarylether sulfone according to claim 1, characterized in that, The structures at both ends of the polymer chain of the polyarylether sulfone are any one of the structures in (i) to (iii). (i) Both are one type of base selected from those represented by general formula (4) or chemical formula (5); (ii) One side is a base selected from the bases represented by general formula (4) or chemical formula (5), and the other side is a halogen atom; (iii) One of the groups is selected from the groups represented by general formula (4) or chemical formula (5), and the other is a hydroxyl group; [Chemistry 3] In the formula, R7 represents a hydrogen atom or a methyl group. This indicates the bonding site at the end of the polymer chain.

14. The polyarylether sulfone according to claim 13, characterized in that, The weight-average molecular weight (Mw) is in the range of 2,000 to 100,000.

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