Terminal (METH)acrylate polyphenylene ether oligomer, and polyphenylene ether resin composition, varnish, prepreg, and cured product comprising the same

Abstract

To provide a polyphenylene ether resin that enables production of a cured product having superior dielectric properties and heat resistance compared to conventional cured products based on a polyphenylene ether resin.SOLUTION: There is provided a terminal (meth)acrylate polyphenylene ether oligomer represented by a general formula (1) and / or (2), having weight-average molecular weight (Mw) in a range of 700 or more and 30,000 or less.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a (meth)acrylate-terminated polyphenylene ether oligomer, and a polyphenylene ether resin composition, varnish, prepreg, and cured product containing the same. [Background technology]

[0002] Polyphenylene ether (PPE) has a low dielectric constant and a low dielectric dissipation factor, and is known to be suitable as a material for electronic devices such as printed wiring boards. In addition to the traditional properties required for printed wiring board substrate materials, such as flame retardancy, heat resistance, and peel strength with silver foil, low dielectric constant and low dielectric dissipation factor are also required, and therefore improvements to polyphenylene ether (PPE) used as substrate materials for printed wiring boards and other substrates are being investigated. In this field, polyphenylene ether (PPE) in which the ends of poly(2,6-dimethyl-1,4-phenylene oxide) are modified with methacryl groups is one of the widely used materials. Poly(2,3,6-trialkyl-substituted-1,4-phenylene oxide) obtained by polymerization of phenol substituted with alkyl groups at the 2-, 3-, and 6-positions is also known. For example, Non-Patent Document 1 describes poly(alkyl-1,4-phenylene oxide) obtained by using alkylphenol, and epoxidized poly(alkylphenylene oxide) (EPPO) in which the polymerization terminals are epoxy-modified, and describes that the glass transition temperatures of these poly(alkyl-1,4-phenylene oxide)s are higher in the order 2,6->2,3,6->2,5-depending on the difference in the substitution positions of the alkyl groups of the alkylphenols. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Eur. Polym. J.,Vol.46,P.1488-1497,2010. Summary of the Invention [Problem to be solved by the invention]

[0004] In view of the above circumstances, an object of the present invention is to provide a polyphenylene ether resin which can provide a cured product having superior dielectric properties and heat resistance compared to cured products based on conventional polyphenylene ether resins. [Means for solving the problem]

[0005] Means for Solving the Problems The present inventors have conducted intensive research to solve the above-mentioned problems, and as a result have found that a (meth)acrylate-terminated polyphenylene ether oligomer represented by general formula (1) and / or (2), which has a bisphenol as the central structure and has a poly(2,3,6-trimethyl-1,4-phenylene oxide) moiety, can provide a cured product having excellent dielectric properties, heat resistance and thermal dimensional stability, thereby completing the present invention.

[0006] The present invention is as follows. 1. A (meth)acrylate-terminated polyphenylene ether oligomer represented by general formula (1) and / or (2) and having a weight average molecular weight (Mw) in the range of 700 or more and 30,000 or less. [ka] [ka] (In the formula, each R1 independently represents a hydrogen atom or a methyl group, each R2 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 an alkenyl group having 2 to 6 carbon atoms, each n independently represents an integer of 1 or more, each m independently represents 0, 1, 2, or 3, and each X independently represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a divalent group represented by general formula (1a), (1b), or (1c).) [ka] (In general formulae (1a), (1b), and (1c), R3 and R4 each independently represent 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; R3 and R4 may be bonded to each other to form a cycloalkylidene group having 5 to 20 carbon atoms as a whole; R5 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, Ar1 and Ar2 each independently represent an aryl group having 6 to 12 carbon atoms, and * indicates a bonding position.) 2. A polyphenylene ether resin composition comprising component (A) containing component (A-1) and component (A-2) in a weight ratio of component (A-1) to component (A-2) in the range of 25:75 to 100:0, and component (B). Component (A-1): The (meth)acrylate-terminated polyphenylene ether oligomer described in 1. Component (A-2): A polyphenylene ether resin other than the (meth)acrylate-terminated polyphenylene ether oligomer described in 1. Component (B): Crosslinking agent 3. The polyphenylene ether resin composition according to 2., wherein the component (A-2) is a polyphenylene ether resin having a repeating unit represented by general formula (6). [ka] (In the formula, each R6 independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, a phenyl group, or a halogen atom; each p independently represents 0, 1, 2, or 3; and each q independently represents an integer of 1 or greater.) 4. The polyphenylene ether resin composition according to 2., further comprising component (C): a reaction initiator. 5. A varnish comprising the polyphenylene ether resin composition according to 2. or 4., and component (E): a solvent. 6. A cured product of the polyphenylene ether resin composition according to 2. or 4. 7. A prepreg comprising the polyphenylene ether resin composition according to 2. or 4., and component (F): reinforcing fibers. A cured product of the prepreg described in 8.7. 9. The polyphenylene ether resin composition according to 2. or 4., further comprising component (D): a filler. A varnish comprising the polyphenylene ether resin composition according to 10.9. and component (E): a solvent. A cured product of the polyphenylene ether resin composition according to 11.9. Effect of the Invention

[0007] The (meth)acrylate-terminated polyphenylene ether oligomer of the present invention, when used in combination with a conventional polyphenylene ether resin, can improve the dielectric properties, heat resistance and thermal dimensional stability of the resulting cured product. The polyphenylene ether resin composition, varnish and prepreg containing a specific amount of the (meth)acrylate-terminated polyphenylene ether oligomer of the present invention can give a cured product having improved dielectric properties, heat resistance and thermal dimensional stability. Therefore, the (meth)acrylate-terminated polyphenylene ether oligomer of the present invention, and the polyphenylene ether resin composition, varnish, prepreg and cured product containing the same are suitable for applications such as heat resistance modifiers for composite materials such as substrate materials, laminates and fiber-reinforced resins. [Brief description of the drawings]

[0008] [Figure 1] FIG. 2 is a diagram showing a spectrum of the polyphenylene ether oligomer obtained in Synthesis Example 1 by Fourier transform infrared spectroscopy (FT-IR) analysis. [Diagram 2] FIG. 2 is a diagram showing an NMR analysis spectrum of the polyphenylene ether oligomer obtained in Synthesis Example 1. [Diagram 3] FIG. 2 is a diagram showing a Fourier transform infrared spectroscopy (FT-IR) spectrum of the methacrylate-terminated polyphenylene ether oligomer obtained in Example 1. [Figure 4] FIG. 2 is a diagram showing an NMR analysis spectrum of the methacrylate-terminated polyphenylene ether oligomer obtained in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] <(Meth)acrylate-Terminated Polyphenylene Ether Oligomer> The (meth)acrylate-terminated polyphenylene ether oligomer of the present invention is represented by general formula (1) and / or (2) and has a weight average molecular weight (Mw) in the range of 700 or more and 30,000 or less. In general formulae (1) and (2), R1 each independently represents a hydrogen atom or a methyl group, and among these, a methyl group is preferred. R2 in general formulas (1) and (2) each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms, and among these, each independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, or an alkenyl group having 2 to 4 carbon atoms, more preferably a methyl group, a t-butyl group, a cyclohexyl group, a vinyl group, or an allyl group, and particularly preferably a methyl group. In the general formulae (1) and (2), m is each independently 0, 1, 2 or 3, of which 0, 2 or 3 is preferred, 2 or 3 is more preferred, and 2 is particularly preferred. When m is 1, 2 or 3, the position at which R2 bonds to the benzene ring is preferably in the ortho position relative to the oxygen atom, since this reduces the amount of branched chain structures formed in the polymerization reaction step in the terminal (meth)acrylate polyphenylene ether oligomer of the present invention. When m is 2, the positions at which R2 is bonded to the benzene ring are preferably the 2-position and the 6-position or the 2-position and the 5-position relative to the oxygen atom, and particularly preferably the 2-position and the 6-position. When m is 2 and R2 is bonded to the benzene ring at the 2-position and the 6-position relative to the oxygen atom, the terminal (meth)acrylate polyphenylene ether oligomer of the present invention is represented by general formula (1A) and / or (2A). [ka] (In the formula, R1, R2, X, and n are defined as the same as in general formulas (1) and (2).) When m is 3, the positions at which R2 is bonded to the benzene ring are preferably the 2-position, the 3-position, and the 6-position relative to the oxygen atom. In this case, the terminal (meth)acrylate polyphenylene ether oligomer of the present invention is represented by general formula (1B) and / or (2B). [ka] (In the formula, R1, R2, X, and n are defined as the same as in general formulas (1) and (2).) From the viewpoint of the position at which m and R2 are bonded to the benzene ring, the chemical structure of the terminal (meth)acrylate polyphenylene ether oligomer of the present invention is preferably a chemical structure represented by general formula (1A) and / or (2A) or a chemical structure represented by general formula (1B) and / or (2B) among the chemical structures represented by general formula (1) and / or (2), and more preferably a chemical structure represented by general formula (1A) and / or (2A). In the general formulas (1) and (2), n is each independently an integer of at least 1. The upper limit is the degree of polymerization at which the weight average molecular weight (Mw) falls within the range of the present invention.

[0010] X in general formulas (1) and (2) each independently represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a divalent group represented by general formula (1a), (1b), or (1c). Each independently represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a divalent group represented by general formula (1a), (1b), or (1c), preferably an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a divalent group represented by general formula (1a), (1b), or (1c), more preferably a divalent group represented by general formula (1a), (1b), or (1c), even more preferably a divalent group represented by general formula (1a) or (1c), and particularly preferably a divalent group represented by general formula (1a). When X in general formulas (1) and (2) is general formula (1a), more preferred R3 and R4 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or R3 and R4 bonded to each other to form a cycloalkylidene group having 5 to 20 carbon atoms as a whole, further preferably each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, an aryl group having 6 to 8 carbon atoms, or R3 and R4 bonded to each other to form a cycloalkylidene group having 5 to 20 carbon atoms as a whole, and particularly preferably each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a cycloalkylidene group having 5 to 20 carbon atoms as a whole. R3 and R4 may be bonded to each other to form a cycloalkylidene group having 5 to 20 carbon atoms as a whole, and the cycloalkylidene group having 5 to 20 carbon atoms may contain an alkyl group as a branched chain. The cycloalkylidene group preferably has 5 to 15 carbon atoms, more preferably has 6 to 12 carbon atoms, and particularly preferably has 6 to 9 carbon atoms. This order of preference can be arbitrarily combined with the above-mentioned more preferred cycloalkylidene groups having 5 to 20 carbon atoms in R3 and R4. Specific examples of the cycloalkylidene group include a cyclopentylidene group (5 carbon atoms), a cyclohexylidene group (6 carbon atoms), a 3-methylcyclohexylidene group (7 carbon atoms), a 4-methylcyclohexylidene group (7 carbon atoms), a 3,3,5-trimethylcyclohexylidene group (9 carbon atoms), a cycloheptylidene group (7 carbon atoms), a bicyclo[2.2.1]heptane-2,2-diyl group (7 carbon atoms), a 1,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyl group (10 carbon atoms), a 4,7,7-trimethylbicyclo[2.2.1]heptane-2,2-diyl group (10 carbon atoms), a tricyclo[5.2.1.0 2,6 ]decane-8,8-diyl group (10 carbon atoms), 2,2-adamantylidene group (10 carbon atoms), cyclododecanylidene group (12 carbon atoms), etc. are preferred. Cyclohexylidene group, 3-methylcyclohexylidene group, 4-methylcyclohexylidene group, 3,3,5-trimethylcyclohexylidene group, cyclododecanylidene group are more preferred, cyclohexylidene group, 3,3,5-trimethylcyclohexylidene group, cyclododecanylidene group are particularly preferred, and cyclohexylidene group, 3,3,5-trimethylcyclohexylidene group are particularly preferred. When X in general formulas (1) and (2) is general formula (1b), preferred Ar1 and Ar2 are each independently a benzene ring or a naphthalene ring, and more preferred are both benzene rings. For example, when both Ar1 and Ar2 are benzene rings, the group represented by formula (1b) is a fluorenylidene group. When X in general formulas (1) and (2) is general formula (1c), each R5 is independently a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms, preferably a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 or 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, further preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group. In general formula (1c), the bonding position to the benzene ring is preferably the meta position or the para position.

[0011] Specific examples of the polyphenylene ether oligomer having a terminal (meth)acrylate represented by general formula (1) of the present invention include the following compounds. [ka] (In the formula, n is defined as in general formulas (1) and (2).)

[0012] Specific examples of the polyphenylene ether oligomer having a terminal (meth)acrylate represented by general formula (2) of the present invention include the following compounds. [ka] (In the formula, n is defined as in general formulas (1) and (2).)

[0013] The (meth)acrylate-terminated polyphenylene ether oligomer of the present invention has methyl groups at the 2-, 3- and 6-positions relative to oxygen atoms in the phenylene ether repeating structure, and therefore is extremely useful because it gives a cured product having excellent dielectric properties, heat resistance and thermal dimensional stability compared to conventional (meth)acrylate-terminated polyphenylene ether oligomers having methyl groups at the 2- and 6-positions.

[0014] The weight average molecular weight (Mw) of the (meth)acrylate-terminated polyphenylene ether oligomer of the present invention is in the range of 700 or more and 30,000 or less, preferably in the range of 1,000 or more and 30,000 or less, more preferably in the range of 3,000 or more and 20,000 or less, and even more preferably in the range of 3,000 or more and 15,000 or less.

[0015] <Method for producing (meth)acrylate-terminated polyphenylene ether oligomer> The method for producing the (meth)acrylate-terminated polyphenylene ether oligomer of the present invention is not particularly limited, but for example, as shown in the following reaction formula, the polyphenylene ether oligomer can be produced by a method including a polymerization reaction step of reacting 2,3,6-trimethylphenol with a bisphenol (3) represented by general formula (3) to obtain a polyphenylene ether oligomer (4) represented by general formula (4), and a (meth)acrylation step of reacting the polyphenylene ether oligomer (4) represented by general formula (4) obtained by the polymerization reaction step with (meth)acrylic anhydride represented by general formula (5). [ka] (In the formula, R2, X, m, and n are the same as defined in general formulas (1) and (2).) [ka] (In the formula, R1, R2, X, m, and n are defined as the same as in general formulas (1) and (2).)

[0016] <Polymerization reaction process> (Bisphenols (3)) Specific examples of the bisphenols (3) represented by the general formula (3) include bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxy-2,3,5-trimethylphenyl)methane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)butane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)-4-methylpentane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)hexane, 1,1 -bis(4-hydroxy-3,5-dimethylphenyl)-1-phenylethane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclopentane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)cyclododecane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)adamantane, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, and the like. In the reaction, such bisphenols (3) may be used alone or in combination of two or more kinds in any desired ratio. In the general formula (3), R2, X, and m are defined the same as in the general formulas (1) and (2), and preferred embodiments are also the same. When m is 2 and R2 is bonded to the benzene ring at the 2-position and 6-position relative to the oxygen atom, the bisphenol (3) is represented by the general formula (3A). [ka] (In the formula, R2 is defined as the same as in general formulas (1) and (2).) When m is 3 and R2 is bonded to the benzene ring at the 2-, 3-, and 6-positions relative to the oxygen atom, the bisphenol (3) is represented by the general formula (3B). [ka] (In the formula, R2 is defined as the same as in general formulas (1) and (2).) In order to produce the (meth)acrylate-terminated polyphenylene ether oligomer of the present invention, which has a chemical structure represented by general formula (1A) and / or (2A) or a chemical structure represented by general formula (1B) and / or (2B), a bisphenol represented by general formula (3A) or (3B) is preferred.

[0017] The polymerization reaction step preferably uses a catalyst. Examples of the catalyst to be used include copper compounds and organic bases, and it is preferable to use them in combination to form a copper-organic base complex compound. Examples of the copper compound include copper chloride (I), copper bromide (I), copper iodide (I), copper sulfate (I), copper nitrate (I), copper chloride (II), copper bromide (II), copper iodide (II), copper sulfate (II), and copper nitrate (II). Among these, monovalent copper halides such as copper chloride (I), copper bromide (I), and copper iodide (I) are preferred, and copper chloride (I) is more preferred. Examples of the organic base include N,N'-di-tert-butylethylenediamine, N-butyldimethylamine, tetramethylethylenediamine (TMEDA), trimethylamine, diazabicycloundecene (DBU), pyridine, 2-methylpyridine, 1,4,7-triazacyclononane, quinuclidine, and tetraphenylethylenediamine. Among these, a mixture of N,N'-di-tert-butylethylenediamine and N-butyldimethylamine or tetramethylethylenediamine (TMEDA) is preferred, and tetramethylethylenediamine (TMEDA) is more preferred. The copper-organic base complex compound is preferably a complex compound obtained by combining a monovalent copper halide such as copper chloride (I), copper bromide (I), or copper iodide (I) with a mixture of N,N'-di-tert-butylethylenediamine and N-butyldimethylamine or tetramethylethylenediamine (TMEDA), and a complex compound obtained by combining copper chloride (I) with tetramethylethylenediamine (TMEDA) is particularly preferred. The copper-organic base complex compound can be obtained by mixing a copper compound and an organic base compound that can be a ligand in the presence of an inert organic solvent. The formation of the complex can be confirmed by the complete dissolution of a copper compound that is insoluble in an organic solvent in the organic solvent. The amount of catalyst used is within a range where no quality problems occur in the oligomers produced due to catalyst residues, and although the suitable amount varies depending on the type of catalyst and cannot be generally stated, it is generally within a range of, for example, 0.1 to 100 mol % per mol of bisphenols (3), preferably 0.1 to 5 mol %, and more preferably 0.1 to 1 mol %. The catalyst may be added as it is or may be dissolved in a solvent, and the solvent is preferably one that does not affect the reaction. The polymerization reaction step is preferably carried out in an environment with an oxygen concentration in the range of 20 to 100% by volume, and more preferably in an environment of pure oxygen (99% by volume or more).

[0018] In this polymerization reaction step, the solvent used may be any solvent capable of uniformly mixing the raw materials of 2,3,6-trimethylphenol and bisphenols (3) used and the catalyst used, and specifically, preferred are aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, diethylbenzene, mesitylene, and tetralin, aliphatic alkyl solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, and n-octane, and aromatic chlorine solvents such as chlorobenzene and dichlorobenzene, and among these, aromatic solvents are more preferred. Among aromatic solvents, toluene is more preferred. The amount of the solvent used is preferably in the range of 1 to 100 parts by weight, more preferably in the range of 10 to 50 parts by weight, and further preferably in the range of 10 to 20 parts by weight, per part by weight of 2,3,6-trimethylphenol used as the raw material. The reaction conditions for the polymerization reaction step are generally in the range of 30 to 100°C, preferably in the range of 40 to 80°C, and more preferably in the range of 40 to 60°C. If the reaction temperature is too low, the reaction will not proceed, whereas if the reaction temperature is too high, side reactions such as decomposition reactions will proceed, which are undesirable. Under these reaction conditions, the reaction is generally completed within about 0.5 to 10 hours.

[0019] (Polyphenylene ether oligomer represented by general formula (4)) The weight average molecular weight (Mw) of the polyphenylene ether oligomer represented by general formula (4) obtained by the polymerization reaction step is in the range of 700 to 30,000. Among them, the range of 1,000 to 30,000 is preferable, the range of 3,000 to 20,000 is more preferable, and the range of 3,000 to 15,000 is even more preferable. In the general formula (4), R2, X, and n are defined the same as in the general formulas (1) and (2), and the preferred embodiments are also the same. Among the polyphenylene ether oligomers, a polyphenylene ether oligomer having a chemical structure represented by general formula (4A) or general formula (4B) has two substituents R2 at the ortho position relative to the oxygen atom, and therefore contains a small amount of branched chain structures generated in the polymerization reaction step, and is therefore preferred in terms of reaction selectivity. [ka] (In the formula, R2, X, and n are defined as the same as in general formulas (1) and (2).) [ka] (In the formula, R2, X, and n are defined as the same as in general formulas (1) and (2).)

[0020] Specific examples of the polyphenylene ether oligomer represented by the general formula (4A) include the following compounds. [ka] (In the formula, n is defined as in general formulas (1) and (2).)

[0021] Specific examples of the polyphenylene ether oligomer represented by the general formula (4B) include the following compounds. [ka] (In the formula, n is defined as in general formulas (1) and (2).) The polyphenylene ether oligomer represented by general formula (4) has methyl groups at the 2-, 3-, and 6-positions in the phenylene ether repeating structure, and therefore gives a cured product having excellent dielectric properties, heat resistance, and thermal dimensional stability compared to the case of using a conventional polyphenylene ether oligomer having methyl groups at the 2- and 6-positions. Therefore, it can be usefully used as a raw material for obtaining the (meth)acrylate-terminated polyphenylene ether oligomer represented by general formula (1) and / or (2) of the present invention.

[0022] <(Meth)acrylation process> The polyphenylene ether oligomer represented by general formula (4) can be reacted with a (meth)acrylation agent such as (meth)acrylic anhydride represented by general formula (5) to obtain the (meth)acrylate-terminated polyphenylene ether oligomer represented by general formula (1) and / or (2) of the present invention. Specific examples of the (meth)acrylation agent include acrylic acid chloride, methacrylic acid chloride, acrylic acid, methacrylic acid, acrylic anhydride, methacrylic anhydride, etc. In the (meth)acrylic anhydride represented by the general formula (5), when both R1 are hydrogen atoms, it is acrylic anhydride, and when both R1 are methyl groups, it is methacrylic anhydride. When a polyphenylene ether oligomer having (meth)acrylates at both ends as represented by general formula (1) is obtained, the amount of the (meth)acrylation agent used is usually 1.0 to 2.5 times by mol, preferably 1.1 to 2.0 times by mol, and more preferably 1.15 to 1.5 times by mol based on all terminal hydroxy groups of the polyphenylene ether oligomer represented by general formula (4). When obtaining a polyphenylene ether oligomer having a (meth)acrylate at one end represented by general formula (2), the (meth)acrylation agent is usually used in an amount of 0.5 to 1.5 times by mol, preferably 0.55 to 1.25 times by mol, and more preferably 0.6 to 1.0 times by mol based on all the terminal hydroxy groups of the polyphenylene ether oligomer represented by general formula (ii).

[0023] When the polyphenylene ether oligomer represented by the general formula (4) is (meth)acrylated using (meth)acrylic anhydride as the (meth)acrylation agent, the reaction is usually carried out at a temperature in the range of 50 to 100°C for a period in the range of 1 to 20 hours. The reaction solvent that can be used may be any solvent that can uniformly mix the raw materials to be used, and specific examples thereof include halogenated hydrocarbon solvents such as methylene chloride and aromatic hydrocarbon solvents such as toluene and xylene. The amount of the solvent used is not particularly limited, but is usually 0.5 to 10 times by weight relative to the polyphenylene ether oligomer represented by the general formula (4). It is preferable to use a catalyst in the reaction. For example, an organic base compound such as triethylamine, 4-dimethylaminopyridine (DMAP), pyridine, or 1,8-diazabicyclo[5.4.0]undecen-7-ene (DBU) can be used, and among these, 4-dimethylaminopyridine is preferred. The amount of the catalyst used can be arbitrarily determined depending on the amount of the solvent used, the reaction temperature, etc., but is usually 0.01 to 0.5 times by weight relative to the polyphenylene ether oligomer represented by the general formula (4).

[0024] The case where the polyphenylene ether oligomer represented by the general formula (4) is (meth)acrylated using (meth)acrylic acid chloride as the (meth)acrylation agent will be described below. In such a case, since the reaction generates chloride ions in the form of hydrogen chloride, it is preferable to use a hydrogen chloride scavenger in combination. Any basic substance can be used as the hydrogen chloride scavenger. As inorganic basic substances, carbonates and hydrogen carbonates of alkali metals can be used. As organic basic substances, tertiary amines can be used. Examples of tertiary amines include aliphatic amines such as trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyl-diethylamine, N-ethyl-dimethylamine, N-ethyl-diamylamine, N,N-diisopropylethylamine, N,N-dimethyl-cyclohexylamine, and N,N-diethyl-cyclohexylamine; aromatic amines such as N,N-dimethylaniline and N,N-diethylaniline; heterocyclic amines such as pyridine, picoline, and N,N-dimethylaminopyridine; and alicyclic amines such as 1,8-diazabicyclo[5.4.0]undec-7-ene and 1,5-diazabicyclo[4.3.0]non-5-ene. The amount of hydrogen chloride scavenger used is usually 0.8 to 10 times the molar amount of the (meth)acrylation agent used, preferably 0.9 to 8 times the molar amount, and particularly preferably about 1.0 to 7 times the molar amount. If the amount of hydrogen chloride scavenger is less than 0.8 times the molar amount of the (meth)acrylation agent, the hydrogen chloride generated cannot be completely captured, and the raw material polyphenylene ether oligomer represented by general formula (4) and the target product terminal (meth)acrylate polyphenylene ether oligomer represented by general formula (1) or (2) may be decomposed, which may cause a decrease in the purity of the target product. In addition, if the amount of hydrogen chloride scavenger exceeds 10 times the molar amount of the (meth)acrylation agent, not only is the removal of the hydrogen chloride scavenger complicated, but it is also uneconomical, which is not preferable.

[0025] The solvent used may be any solvent capable of uniformly mixing the raw materials used, and specific examples thereof include halogenated hydrocarbons such as methylene chloride, tetrahydrofuran, dioxane, chlorobenzene, etc. The amount of the solvent used is not particularly limited, but is usually in the range of 0.5 to 100 times by weight, preferably 1 to 50 times by weight, and particularly preferably 2 to 10 times by weight, relative to the polyphenylene ether oligomer represented by general formula (4). The reaction is carried out at a relatively low temperature, usually in the range of -50 to 100°C, preferably in the range of -30 to 80°C, and more preferably in the range of -15 to 60°C. If the reaction temperature exceeds 100°C, side reactions occur, leading to a decrease in the yield of the target product. Also, if the reaction temperature is lower than -50°C, the reaction rate becomes slow and the required time becomes too long, which is not economical. The reaction procedure may be a method of mixing the polyphenylene ether oligomer represented by the general formula (4) and the (meth)acrylation agent in a solvent in advance and then adding a hydrogen chloride scavenger thereto, or a method of mixing the polyphenylene ether oligomer represented by the general formula (4) and the hydrogen chloride scavenger in a solvent in advance and then adding a (meth)acrylation agent thereto. In these methods, the hydrogen chloride scavenger and the (meth)acrylation agent to be added later may be used in a state of being diluted in a solvent.

[0026] In the (meth)acrylation reaction step, for example, hydroquinone, hydroquinone monomethyl ether, phenothiazine, 2,6-di-tert-butyl-4-methylphenol (BHT) or the like may be added as a polymerization inhibitor for the (meth)acrylation agent during the reaction.

[0027] <Post-treatment and purification in the (meth)acrylation process> If the catalyst or the like used in the (meth)acrylation reaction remains in the organic solvent together with the target polyphenylene ether oligomer having a (meth)acrylate end represented by general formula (1) and / or (2), undesirable phenomena such as coloration and decomposition are likely to occur, and therefore it is preferable to remove it by a washing procedure such as washing with water after the reaction. The method for isolating the obtained polyphenylene ether oligomer having a terminal (meth)acrylate represented by the general formula (1) and / or (2) may include a method of obtaining the oligomer as a precipitate by mixing a poor solvent with the solution in which the oligomer is dissolved. Specific examples of the poor solvent include aliphatic alcohol solvents having 1 to 6 carbon atoms, such as methanol, ethanol, and propanol, and mixtures of the above aliphatic alcohol solvents with water. The precipitate that has separated out is separated by filtration, and the resulting solid matter is dried by heating at a temperature in the range of 40 to 100°C under reduced pressure, thereby obtaining the target (meth)acrylate-terminated polyphenylene ether oligomer represented by general formula (1) and / or (2).

[0028] <Polyphenylene ether resin composition> The polyphenylene ether resin composition of the present invention contains component (A) which contains component (A-1), which is a (meth)acrylate-terminated polyphenylene ether oligomer represented by general formula (1) and / or (2), and component (A-2), which is a polyphenylene ether resin other than component (A-1), in a weight ratio of component (A-1):component (A-2) in the range of 25:75 to 100:0, and component (B) which is a crosslinking agent. The weight ratio of component (A-1) to component (A-2) is preferably in the range of 25:75 to 80:20, more preferably in the range of 25:75 to 60:40, further preferably in the range of 25:75 to 50:50, and particularly preferably in the range of 25:75 to 40:60. The polyphenylene ether resin composition of the present invention may contain, as component (A-1), one type or two or more types of (meth)acrylate-terminated polyphenylene ether oligomers represented by general formula (1) and / or (2). The polyphenylene ether resin composition of the present invention uses, as component (A-2), a polyphenylene ether other than component (A-1), which is a (meth)acrylate-terminated polyphenylene ether oligomer represented by general formula (1) and / or (2), in combination. The polyphenylene ether that can be used in combination as component (A-2) is preferably a polyphenylene ether having a repeating unit represented by general formula (6), excluding the terminal (meth)acrylate polyphenylene ether oligomer represented by general formula (1) and / or (2), and more preferably a polyphenylene ether having a repeating unit represented by general formula (6-1), excluding the terminal (meth)acrylate polyphenylene ether oligomer represented by general formula (1) and / or (2). [ka] (In the formula, each R6 independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, a phenyl group, or a halogen atom; each p independently represents 0, 1, 2, or 3; and each q independently represents an integer of 1 or greater.) [ka] (In the formula, each q is independently an integer of 1 or more). Specific examples of polyphenylene ethers that can be used in combination as component (A-2) include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), copolymers of 2,6-dimethylphenol and other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.), polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols, bisphenols, or trisphenols, and polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol and other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.) with biphenols, bisphenols, or trisphenols. Also included are polyphenylene ethers in which the terminal hydroxyl groups of these polyphenylene ethers have been modified with functional groups having unsaturated double bonds, such as allyl ether, acryloyl, methacryloyl, vinyl ether, etc. For example, polyphenylene ethers that are compounds in which the terminals of a copolymer of 2,6-dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane are (meth)acrylated can be used. Among these, the polyphenylene ether that can be used in combination as component (A-2) is preferably a polyphenylene ether modified with a functional group having an unsaturated double bond, and more preferably a compound modified with a functional group having an unsaturated double bond of a polyphenylene ether copolymer obtained by coupling 2,6-dimethylphenol with a biphenol, bisphenol, or trisphenol, or a compound modified with a functional group having an unsaturated double bond of a polyphenylene ether copolymer obtained by coupling 2,6-dimethylphenol and other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.) with a biphenol, bisphenol, or trisphenol. More preferred are terminal (meth)acrylated compounds of polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols, bisphenols or trisphenols, and terminal (meth)acrylated compounds of polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol and other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.) with biphenols, bisphenols or trisphenols, and particularly preferred are terminal (meth)acrylated compounds of copolymers of 2,6-dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane.

[0029] <Component (B): Crosslinking agent> The crosslinking agent of component (B) in the polyphenylene ether resin composition of the present invention is not particularly limited as long as it can react with component (A) to form crosslinks and cure the composition. Specifically, for example, compounds having two or more unsaturated double bonds in the molecule can be mentioned. More specifically, trialkenyl isocyanurate compounds such as triallyl isocyanurate, polyfunctional allyl ether compounds having two or more allyl ether groups in the molecule, polyfunctional methacrylate compounds having two or more methacrylic groups in the molecule, polyfunctional acrylate compounds having two or more acrylic groups in the molecule, vinyl compounds (polyfunctional vinyl compounds) having two or more vinyl groups in the molecule such as polybutadiene, and vinylbenzyl compounds having two or more vinylbenzyl groups in the molecule can be mentioned. Among these, trialkenyl isocyanurate compounds, polyfunctional allyl ether compounds having two or more allyl ether groups in the molecule, polyfunctional acrylate compounds having two or more acrylic groups in the molecule, polyfunctional methacrylate compounds, and polyfunctional vinyl compounds are preferred. It is believed that the use of these will more favorably form crosslinks by the curing reaction, and the heat resistance of the cured product of the resin composition containing the terminal (meth)acrylate polyphenylene ether oligomer of the present invention can be further improved. In addition, the thermosetting curing agent may be one of the exemplified thermosetting curing agents, or two or more of them may be used in combination. In addition, as the thermosetting curing agent, the above-mentioned compound having two or more unsaturated double bonds in the molecule and a compound having one unsaturated double bond in the molecule may be used in combination. Specific examples of the compound having one unsaturated double bond in the molecule include a compound having one vinyl group in the molecule (monovinyl compound), etc. In the polyphenylene ether resin composition of the present invention, the content of the crosslinking agent of component (B) is preferably in the range of 1 to 50 parts by weight, more preferably in the range of 1 to 30 parts by weight, and even more preferably in the range of 1 to 25 parts by weight, per 100 parts by weight of component (A).

[0030] <Component (C): Reaction initiator> The polyphenylene ether resin composition of the present invention preferably contains a reaction initiator as component (C) in addition to components (A) and (B). Component (C) is added to promote the crosslinking reaction of the resin composition containing components (A) and (B). Component (C) is not particularly limited as long as it accelerates the crosslinking reaction, and examples thereof include ionic catalysts such as imidazoles, tertiary amines, quaternary ammonium salts, boron trifluoride amine complexes, organophosphines, and organophosphonium salts, and radical polymerization initiators such as organic peroxides, hydroperoxides, and azoisobutyronitrile. Among these, it is preferable to use organic peroxides. Examples of organic peroxides include aliphatic organic peroxides such as di-t-butyl peroxide, dilauroyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne, and di-n-propyl peroxydicarbonate, dibenzoyl peroxide, dicumyl peroxide, and t-butyl peroxybenzyl peroxide. Examples of aromatic organic peroxides include aromatic organic peroxides containing an aromatic ring, such as benzoate, t-amyl peroxybenzoate, t-butylcumyl peroxide, bis(1-t-butylperoxy-1-methylethyl)benzene, 2-phenyl-2-[(2-phenylpropan-2-yl)peroxy]propane, α,α'-di(t-butylperoxy)diisopropylbenzene, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, and di-t-butylperoxyisophthalate. Among these, it is preferable to use aromatic organic peroxides. As the aromatic organic peroxide, dicumyl peroxide, t-butylcumyl peroxide, bis(1-t-butylperoxy-1-methylethyl)benzene, and 2-phenyl-2-[(2-phenylpropan-2-yl)peroxy]propane are more preferred, and 2-phenyl-2-[(2-phenylpropan-2-yl)peroxy]propane is particularly preferred. The polyphenylene ether resin composition of the present invention contains component (C) in an amount of preferably 0.05 to 0.9% by weight, more preferably 0.15 to 0.8% by weight, even more preferably 0.3 to 0.7% by weight, and particularly preferably 0.35 to 0.6% by weight, based on the total amount of the resin composition. The component (C) may be used alone or in combination of two or more kinds.

[0031] <Component (D): Filler> The polyphenylene ether resin composition of the present invention may contain a filler as component (D) in addition to components (A), (B) and, if necessary, (C). The component (D) is contained in an amount of preferably 10 to 150 parts by weight, and more preferably 10 to 100 parts by weight, based on 100 parts by weight of the polyphenylene ether resin composition. Component (D) is not particularly limited as long as it is a filler that is usually used in various resin compositions, and for example, inorganic fillers such as silicon oxide, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, silicon nitride, silicon carbide, and hexagonal boron nitride can be mixed and used.

[0032] <Component (E): Solvent> The polyphenylene ether resin composition of the present invention may contain a solvent as component (E), and is particularly preferably in the form of a varnish in which the solvent is dissolved or dispersed in component (E). There are no particular limitations on component (E) as long as it dissolves or disperses the polyphenylene ether resin composition, and examples thereof include aromatic compounds such as toluene and xylene, ketone compounds such as methyl ethyl ketone, cyclopentanone and cyclohexanone, and chlorine-based organic solvents such as chloroform. Among these, aromatic compounds such as toluene and xylene, and ketone compounds such as methyl ethyl ketone, cyclopentanone and cyclohexanone are preferred, aromatic compounds such as toluene and xylene are more preferred, and toluene is particularly preferred. The component (E) is contained in an amount of preferably 50 to 2000 parts by weight, and more preferably 100 to 1000 parts by weight, based on 100 parts by weight of the polyphenylene ether resin composition.

[0033] The method for preparing the polyphenylene ether resin composition of the present invention is not particularly limited, and for example, the above-mentioned components may be mixed and mixed or dispersed by a stirrer.

[0034] <Prepreg> The prepreg of the present invention can be prepared by mixing the polyphenylene ether resin composition containing components (A) and (B), and further components (C) and (D) as required, with the reinforcing fiber of component (F). Examples of the mixing method include coating or impregnating the reinforcing fiber of component (F) with a varnish.

[0035] <Component (F)> The component (F) in the present invention is not particularly limited as long as it is a reinforcing fiber that is usually used in prepregs, and for example, various inorganic or organic fibers such as carbon fiber, aramid fiber, nylon fiber, high-strength polyester fiber, glass fiber, boron fiber, alumina fiber, and silicon nitride fiber can be used. Among these, from the viewpoint of specific strength and specific elasticity, carbon fiber, aramid fiber, glass fiber, boron fiber, alumina fiber, and silicon nitride fiber are listed. Among them, carbon fiber is preferred from the viewpoint of mechanical properties and weight reduction. When carbon fiber is used as a reinforcing fiber, it may be subjected to a surface treatment with a metal. The thickness of the fiber base material is preferably 0.3 mm or less, more preferably 0.15 mm or less, and even more preferably 0.1 mm or less. The component (F) may be used alone or in combination of two or more kinds.

[0036] <Method of manufacturing the cured product> The cured product of the present invention can be obtained by curing the polyphenylene ether resin composition or prepreg of the present invention. Examples of methods for producing the cured product of the present invention include a method in which the prepreg is heated to a predetermined temperature to be cured, and a method in which the polyphenylene ether resin composition of the present invention is filled into a mold or the like, or the polyphenylene ether resin composition of the present invention is heated and melted and injected into a mold or the like, and then heated to a predetermined temperature to be cured. The heat curing temperature can be appropriately determined within the range of 100 to 300°C. EXAMPLES

[0037] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples, the weight average molecular weight (Mw) was measured by gel permeation chromatography using the following analytical method. <Analysis method> 1. High performance liquid chromatography (HPLC) measurement Measurement equipment: High-performance liquid chromatography analyzer (UFLC) (manufactured by Shimadzu Corporation) Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A (UFLC), cell length 5mm Column: HALO-C18 (column 3.0 x 75 mm, particle size 2.7 μm, manufactured by Advanced Materials Technology) [Measurement conditions] Oven temperature: 50℃ Flow rate: 0.7mL / min. Mobile phase: (A) 0.2 vol% acetic acid aqueous solution, (B) methanol Gradient conditions: (B) Volume % (time from start of analysis) 20% (0 min) → 40% (10 min) → 60% (20 min) → 100% (37 min) → 100% (40 min) Detection wavelength: 280nm Sample concentration: 5.0mg / mL Sample injection volume: 10 μL 2. Gel permeation chromatography measurement (molecular weight measurement) Equipment: Tosoh Corporation HLC-8320GPC Detector: RI (differential refractometer) [Measurement conditions] Flow rate: 1mL / min. Eluent: Tetrahydrofuran Temperature: 40℃ Wavelength: 254nm Sampling pitch: 100msec. Measurement sample: 10 mg of polyphenylene ether compound-containing composition diluted 30 times with tetrahydrofuran Injection volume: 10μL [Column] (from upstream) Guard Column HXL-L + G4000HXL + G3000HXL + G2000HXL x 2 (7.8 mm ID x 30 cm, Tosoh Corporation) [Molecular weight calculation method] The molecular weight was calculated in terms of standard polystyrene using a calibration curve of a third-order approximation curve using the following polystyrene standard samples. The measurement conditions were the same as above, except that the injection volume was changed to 10 μL. (Polystyrene standard sample) ·TSKgel Standard Polystyrene A-500:Nominal Mol.Wt. 5.9×10 2 Mw / Mn 1.19 (0005203 / Tosoh Corporation) ·TSKgel Standard Polystyrene A-2500:Nominal Mol.Wt. 2.63×10 3 Mw / Mn 1.05 (0005205 / Tosoh Corporation) ·TSKgel Standard Polystyrene A-5000:Nominal Mol.Wt. 5.06×10 3 Mw / Mn 1.02 (0005206 / Tosoh Corporation) ·TSKgel Standard Polystyrene F-1:Nominal Mol.Wt. 1.02×10 4 Mw / Mn 1.02 (0005207 / Tosoh Corporation) ·TSKgel Standard Polystyrene F-2:Nominal Mol.Wt. 1.74×10 4 Mw / Mn 1.01 (0005208 / Tosoh Corporation) ·TSKgel Standard Polystyrene F-4:Nominal Mol.Wt. 3.79×10 4 Mw / Mn 1.01 (0005209 / Tosoh Corporation) 3. Fourier transform infrared spectroscopy (FT-IR) analysis Equipment: IRPrestinge-21 [Measurement conditions] Measurement wave number range: 4000~750cm -1 Number of times: 40 4.NMR analysis Measurement equipment: Fourier transform nuclear magnetic resonance AVANCE III HD 400 (manufactured by BRUKER) The measurement sample was dissolved in deuterated chloroform. 1 H-NMR spectrum was measured. 5. Measurement of glass transition temperature (Tg) and CTE The films (sample size: width 5 mm, length 15 mm) prepared in the examples and comparative examples were used to determine the Tg and CTE of α1 (50-100°C) and α2 (250-300°C) of the films obtained from the TMA curves under the measurement conditions described below using the following equipment. Equipment: TMA 7100 (Hitachi High-Tech Science Co., Ltd.) [Measurement conditions] Conditions: Load 40mN Temperature range: 30℃~400℃ Heating rate: 5℃ / min. Measurement mode: Tensile 6. Dielectric Characterization The films (sample size: width 1.5 mm, length 8.0 mm) produced in the examples and comparative examples were measured for relative dielectric constant and dielectric loss tangent using the following device (sample size: width 1.5 mm, length 8.0 mm). Measurement equipment: PNA network analyzer N522B (Keysight Technologies, Inc.) Cavity resonator: CP531 for 10GHz (manufactured by Kanto Electronics Application Development Co., Ltd.) [Measurement conditions] Test method: Compliant with IEC 62180 (cavity resonator perturbation method) Test conditions: Frequency: 10GHz Number of measurements: n=2

[0038] <Synthesis Example 1> Synthesis of polyphenylene ether oligomer: Polymerization reaction process [ka] In a 1L four-neck flask equipped with a thermometer, stirrer, and condenser, 700g of toluene, 0.685g (6.92mmol) of copper chloride (I), and 4.10g (36.1mmol) of tetramethylethylenediamine (TMEDA) were added, and the mixture was stirred for 1 hour, after which 72.0g (529mmol) of 2,3,6-trimethylphenol (TMP) and 15.0g (52.7mmol) of 1,1-bis(4-hydroxy-3,5-dimethylphenyl)ethane were added. After the addition was completed, the reaction system was depressurized to remove air, and pure oxygen was blown in to replace the system under an oxygen atmosphere three times. The temperature was then raised to 40°C and the mixture was stirred for 5 hours. The reaction solution was analyzed by liquid chromatography, and it was confirmed that the raw material TMP was 5% or less. Then, 100g of 1N hydrochloric acid was added to the reaction solution. The reaction solution was then added to a methanol solution (1500 g) and stirred for 1 hour. Stirring was then stopped and the mixture was allowed to stand for 20 hours. After confirming that solid matter had been generated, the mixture was filtered under reduced pressure and the solid matter was collected. The collected solid matter was dried under reduced pressure at 60°C in an evaporator, and 53.4 g of dried solid matter was obtained (yield: 61%). The obtained solid matter was analyzed by gel permeation chromatography and liquid chromatography, and as a result, it was confirmed that the solid matter was a PPE oligomer having a number average molecular weight of 1,100 and a weight average molecular weight of 1,400. The FT-IR analysis of the solid fraction showed that the absorption intensity was extremely small, but the absorption intensity was in the range of 3200 to 3400 cm -1 The OH stretching vibration peak of the aromatic hydroxyl group was confirmed in the vicinity. The FT-IR spectrum is shown in Figure 1. The obtained solid 1 As a result of H-NMR analysis, peaks derived from the methyl groups of the polyphenylene ether oligomer were observed around 1.2 to 1.5 ppm and 1.7 to 2.6 ppm, and a peak derived from aromatics was confirmed around 6.0 to 7.5 ppm, and a peak derived from hydroxyl groups was confirmed around 4.4 to 4.6 ppm. 1 The H-NMR spectrum is shown in Figure 2.

[0039] <Example 1> (Synthesis of (meth)acrylate-terminated PPE oligomer: (meth)acrylation step) [ka] In a 1L four-neck flask equipped with a thermometer, a stirrer, and a condenser, 30 g of the PPE oligomer obtained in Synthesis Example 1, 150 g of toluene, and 0.35 g (2.87 mmol) of 4-dimethylaminopyridine (DMAP) were added, and the temperature was raised to 80°C. Then, 8.75 g (48.7 mmol) of methacrylic anhydride and 22.5 g of toluene were added to a 100 mL dropping funnel, and this was dropped over 20 minutes. Then, the reaction temperature was raised to 90°C, and stirring was carried out for 4 hours. A portion of the reaction liquid was taken out and dried, and the solid content was subjected to FT-IR analysis, which showed that the peak peak was 3200-3400 cm -1 Disappearance of aromatic hydroxyl groups near 1700cm -1 A peak derived from the carbonyl moiety of the methacryl group near the mercury atom was confirmed. From this result, it was determined that the reaction had ended, and the temperature of the reaction solution was lowered to 25°C. Thereafter, the reaction solution was added to 600g of methanol, stirred for 1 hour, and allowed to stand for 20 hours. After confirming that a precipitate had formed, the solid matter was collected by vacuum filtration. The collected solid matter was dried under reduced pressure at 80°C in an evaporator, and 32.8g of dried solid matter was obtained. The FT-IR analysis of the solid obtained showed that -1 Since a peak derived from the carbonyl moiety of the methacryl group was observed near the peak, it was confirmed that a methacrylated PPE oligomer (hereinafter referred to as TMP-PPE) was obtained. The FT-IR spectrum is shown in Figure 3. The obtained solid 1As a result of 1 H-NMR analysis, disappearance of the hydroxyl group peak at 4.5 ppm was confirmed, and appearance of peaks derived from methacrylic acid was confirmed at around 4.3 to 4.5 and 5.6 ppm. 1 The H-NMR spectrum is shown in Figure 4.

[0040] (Preparation of polyphenylene ether resin composition varnish and preparation of cured material (film)) As component (A), 1.5 g of the TMP-PPE obtained in Example 1, 3.5 g of a compound in which the terminal of a PPE oligomer, which is a copolymer of 2,6-dimethylphenol and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, is acrylated (hereinafter referred to as 26XL-PPE) (weight ratio of TMP-PPE:26XL-PPE=30:70), 40.0 g of toluene, 1.42 g of triallylisocyanurate (crosslinking agent 1) as component (B), and 0.06 g of dicumyl peroxide (manufactured by Nippon Oil & Fats Co., Ltd.: trade name "Percumyl D", reaction initiator 1) as component (C) were placed in a vial and allowed to stand until completely dissolved. The completely dissolved polyphenylene ether oligomer solution was applied to a polyimide film and dried at 105°C for 2 hours in a vacuum dryer. Thereafter, the film was cured in a heat press tester at 10 MPa under conditions of 105°C / 30 minutes, 150°C / 1 hour, 200°C / 1 hour, 250°C / 1 hour, and 270°C / 1 hour to obtain a film.

[0041] <Comparative Examples 1 to 3> The films were produced under the same conditions as in Example 1, except that no TMP-PPE was used and only 26XL-PPE was used (weight ratio of TMP-PPE:26XL-PPE = 0:100, Comparative Example 1), the weight ratio of TMP-PPE:26XL-PPE was 10:90 (Comparative Example 2), and the weight ratio of TMP-PPE:26XL-PPE was 20:80 (Comparative Example 3).

[0042] The glass transition temperature (Tg) and CTE were measured and the dielectric properties were evaluated under the above-mentioned analysis conditions for the films obtained in Example 1 and Comparative Examples 1 to 3. The results are summarized in Table 1. [Table 1]

[0043] Non-Patent Document 1 listed in the Background Art section describes that the glass transition temperature of the resulting polyphenylene ether was high in the order of 2,6->2,3,6->2,5-, depending on the substitution position of the alkyl group in the alkylphenol. However, it has been revealed that the addition of the (meth)acrylate-terminated polyphenylene ether oligomer of the present invention to a conventional polyphenylene ether resin in which the substitution positions of the alkyl groups are 2 and 6 increases the Tg of the cured product of the resulting polyphenylene ether resin composition. In other words, it has been revealed that the (meth)acrylate-terminated polyphenylene ether oligomer of the present invention can improve the heat resistance of the resulting cured product. Furthermore, it was revealed that the (meth)acrylate-terminated polyphenylene ether oligomer of the present invention has a small CTE at α2 and a small relative dielectric constant, and therefore the thermal dimensional stability and dielectric properties can also be improved. From the above, it has become clear that the (meth)acrylate-terminated polyphenylene ether oligomer of the present invention, when used in combination with a conventional polyphenylene ether resin, can improve the dielectric properties, heat resistance, and thermal dimensional stability of the resulting cured product. It has also been revealed that a polyphenylene ether resin composition, varnish, and prepreg containing a specific amount of the (meth)acrylate-terminated polyphenylene ether oligomer of the present invention can give a cured product having improved dielectric properties, heat resistance, and thermal dimensional stability.

Claims

1. A (meth)acrylate-terminated polyphenylene ether oligomer represented by general formula (1) and / or (2), characterized in that the weight average molecular weight (Mw) is in the range of 700 or more and 30,000 or less. 【Chemistry 1】 【Chemistry 2】 (In the formula, R １ each independently represents a hydrogen atom or a methyl group; R ２ each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms; each n independently represents an integer of 1 or more; each m independently represents 0, 1, 2, or 3; and each X independently represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or a divalent group represented by general formula (1a), (1b), or (1c). 【Chemistry 3】 (In general formulas (1a), (1b) and (1c), R ３ and R ４ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; R ３ and R ４ may be bonded to each other to form a cycloalkylidene group having 5 to 20 carbon atoms as a whole, R ５ each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms; Ar １ and Ar ２ each independently represents an aryl group having 6 to 12 carbon atoms, and * indicates the bonding position.)

2. A polyphenylene ether resin composition comprising component (A) containing component (A-1) and component (A-2) in a weight ratio of component (A-1) to component (A-2) in the range of 25:75 to 100:0, and component (B). Component (A-1): The (meth)acrylate-terminated polyphenylene ether oligomer according to claim 1 Component (A-2): A polyphenylene ether resin other than the (meth)acrylate-terminated polyphenylene ether oligomer according to claim 1. Component (B): Crosslinking agent

3. The polyphenylene ether resin composition according to claim 2, wherein the component (A-2) is a polyphenylene ether resin having a repeating unit represented by general formula (6). 【Chemistry 4】 (In the formula, R ６ each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 5 or 6 carbon atoms, a phenyl group, or a halogen atom; each p independently represents 0, 1, 2, or 3; and each q independently represents an integer of 1 or greater.

4. The polyphenylene ether resin composition according to claim 2 , further comprising a component (C): a reaction initiator.

5. A varnish comprising the polyphenylene ether resin composition according to claim 2 or 4 and component (E): a solvent.

6. A cured product of the polyphenylene ether resin composition according to claim 2 or 4.

7. A prepreg comprising the polyphenylene ether resin composition according to claim 2 or 4 and component (F): reinforcing fibers.

8. A cured product of the prepreg according to claim 7.

9. The polyphenylene ether resin composition according to claim 2 or 4, further comprising a component (D): a filler.

10. A varnish comprising the polyphenylene ether resin composition according to claim 9 and component (E): a solvent.

11. A cured product of the polyphenylene ether resin composition according to claim 9.

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