polyphenylene ether, polyphenylene ether solution, resin film, prepreg, and metal-clad laminate

Abstract

The present invention relates to a polyphenylene ether, a polyphenylene ether solution, a resin film, a prepreg, and a metal-clad laminate. A polyphenylene ether comprising a prescribed amount of repeating units derived from a phenol of the following formula (1), and repeating units derived from a phenol of the following formula (2), a molecular weight distribution (Mw / Mn) of 2.0 to 6.0, and an OH group number of 0.8 to 2.5 per 1 molecule.

Description

[0001] This application is a divisional application. The original application has the application number 202411465436.8, the application date is October 21, 2024, and the invention title is "Resin Composition, Resin Film, Prepreg and Metal-Clad Laminate". Technical Field

[0002] This invention relates to resin compositions, resin films, prepregs, and metal-coated laminates. Background Technology

[0003] Polyphenylene oxide (hereinafter also referred to as "PPE") possesses excellent high-frequency properties, flame retardancy, and heat resistance, and is therefore widely used as a material for products / components in the electrical and electronic, automotive, and food and packaging industries, as well as in various other industrial materials fields. In recent years, in particular, its low dielectric properties and heat resistance have led to its application as a modifier in various electrical and electronic applications, including substrate materials.

[0004] However, high-molecular-weight polyphenylene ethers, which typically have repeating units derived from monophenols such as 2,6-dimethylphenol, while soluble in highly toxic solvents like chloroform, suffer from the following problems: they are difficult to dissolve in high concentrations at room temperature even in aromatic solvents such as toluene, which are known to be good solvents, and they are insoluble in ketone solvents such as methyl ethyl ketone. Therefore, for example, when used as a wiring board material, it is difficult to process them in resin varnish solutions such as toluene and methyl ethyl ketone.

[0005] Patent Document 1 discloses a resin composition in which a varnish is prepared by heating and melting polyphenylene ether in an aromatic solvent in order to improve the solubility and dispersibility of polyphenylene ether.

[0006] In addition, Patent Document 2 discloses a polyphenylene ether with excellent solubility in general ketone solvents, and a thermosetting composition using the polyphenylene ether.

[0007] Furthermore, Patent Document 3 discloses a resin composition containing low-molecular-weight polyphenylene ether, a crosslinking agent, and an organic peroxide, obtained by redistribution reaction of high-molecular-weight polyphenylene ether with monofunctional or polyfunctional phenol.

[0008] Patent document 4 discloses a thermosetting composition comprising a polyphenylene ether of a specific molecular weight and having an ethylidene benzyl group at the end, a polyphenylene ether of a specific molecular weight, and a triallenyl isocyanurate.

[0009] Furthermore, Patent Document 5 discloses a resin composition containing high molecular weight polyphenylene ether, a crosslinking agent, and an organic peroxide, which is obtained by redistribution reaction of high molecular weight polyphenylene ether with monofunctional or polyfunctional phenol and end-modified.

[0010] Patent document 6 discloses a resin composition comprising two end-modified low molecular weight polyphenylene ethers with different backbones and a cross-linking curing agent.

[0011] Existing technical documents

[0012] Patent documents

[0013] Patent Document 1: Japanese Patent No. 3151397

[0014] Patent Document 2: International Publication No. 2022 / 158180

[0015] Patent Document 3: Japanese Patent No. 7202920

[0016] Patent Document 4: Japanese Patent No. 4900315

[0017] Patent Document 5: Japanese Patent No. 4211784

[0018] Patent Document 6: Japanese Patent No. 7203386 Summary of the Invention

[0019] The problem that the invention aims to solve

[0020] However, even when using the resin composition described in Patent Document 1, a resin composition containing polyphenylene ether that is soluble in toluene at room temperature (having solvent solubility) cannot be obtained, and there are further problems to be solved regarding the copper foil peel strength and toluene resistance of the cured resin composition.

[0021] In addition, when using the resin composition described in Patent Document 2, polyphenylene ether with excellent solubility in organic solvents such as toluene and methyl ethyl ketone can be obtained, but there is no disclosure regarding the copper foil peel strength and toluene resistance of the cured resin composition.

[0022] In addition, the polyphenylene ether obtained by redistribution reaction disclosed in Patent Document 3 usually contains organic peroxides used for redistribution reaction, and the organic peroxides remaining in the product may have an adverse effect on the dielectric properties of the substrate.

[0023] Furthermore, the solubility of the composition disclosed in Patent Document 4 when used to make a varnish presents a further problem to be solved.

[0024] Furthermore, the polyphenylene ether obtained by redistribution reaction disclosed in Patent Document 5 typically contains organic peroxides used in the redistribution reaction, and the organic peroxides remaining in the product may adversely affect the dielectric properties of the substrate.

[0025] In the resin composition disclosed in Patent Document 6, compared with the resin composition that uses each end-modified low molecular weight polyphenylene ether alone, there is simply a trade-off relationship, and no improvement in dielectric properties, copper foil peel strength, etc., resulting from the combined use of the two end-modified low molecular weight polyphenylene ethers was observed.

[0026] The present invention was made in view of the above-mentioned problems, and its object is to provide a resin composition comprising polyphenylene ether with excellent solvent solubility and excellent copper foil peel strength, toluene resistance, dielectric properties and heat resistance.

[0027] In addition, the present invention aims to provide resin films, prepregs, and metal-coated laminates formed using the resin composition.

[0028] Methods for solving problems

[0029] That is, the present invention is as follows.

[0030] (1) A resin composition comprising:

[0031] (A) Polyphenylene ether A;

[0032] (B) Triallyl isocyanurate and / or triallyl cyanurate;

[0033] (B') as an optional component, a crosslinking agent other than triallyl isocyanurate and triallyl cyanurate; and

[0034] (C) Organic peroxides,

[0035] The resin composition is characterized in that,

[0036] The above-mentioned (A) polyphenylene ether A comprises repeating units of phenol derived from formula (1) below and repeating units of phenol derived from formula (2) below.

[0037] The content of repeating units derived from formula (1) and formula (2) is 55 mol% or more and less than 90 mol%, relative to the total of 100 mol% of the repeating units in formula (1) and formula (2) below, and the content of repeating units derived from formula (2) is greater than 10 mol% and less than 45 mol%.

[0038] The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is below 2.0 to 6.0.

[0039] The number of OH groups per molecule is 0.8 to 2.5.

[0040] [Chemistry 1]

[0041]

[0042] (In equation (1), R) 11 Each is independently a saturated hydrocarbon group with 1 to 6 carbon atoms, with or without substituents; an aryl group with 6 to 12 carbon atoms, with or without substituents; or a halogen atom, R. 12 Each of the following groups is independently a hydrogen atom, a hydrocarbon group with 1 to 6 carbon atoms (with or without substituents), an aryl group with 6 to 12 carbon atoms (with or without substituents), or a halogen atom.

[0043] [Chemistry 2]

[0044]

[0045] (In equation (2), R) 22 Each of the following groups is independently a hydrogen atom, a saturated or unsaturated hydrocarbon group with or without substituents (1 to 20 carbon atoms), an aryl group with or without substituents (6 to 12 carbon atoms), or a halogen atom, with two R groups. 22 R is not simultaneously a hydrogen atom. 21 It is the partial structure represented by the following formula (3).

[0046] [Chemistry 3]

[0047]

[0048] (In equation (3), R) 31 Each is independently a straight-chain alkyl group having 1 to 8 carbon atoms, with or without substituents, or with 2 R groups. 31 A cyclic alkyl structure with 1 to 8 carbon atoms bonded together, R 32 Each is an alkylene group having 1 to 8 carbon atoms, with or without substituents; b is independently 0 or 1; R 33 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms with or without substituents, or a phenyl group having or without substituents.

[0049] (2) The resin composition as described in (1) is characterized in that, in the polyphenylene ether A above (A), the content of the repeating unit of phenol derived from formula (1) is more than 70 mol% and less than 85 mol% relative to the total 100 mol% of the repeating units of formula (1) and formula (2), and the content of the repeating unit of phenol derived from formula (2) is more than 15 mol% and less than 30 mol%.

[0050] (3) The resin composition as described in (1) or (2), characterized in that the partial structure represented by the above formula (3) is tert-butyl.

[0051] (4) The resin composition according to any one of (1) to (3), characterized in that the specific viscosity (ηsp / c) of the above-mentioned (A) polyphenylene ether A in a chloroform solution with a concentration of 0.5 g / dL at 30°C is 0.13 to 0.30 dL / g.

[0052] (5) The resin composition as described in any one of (1) to (4), characterized in that the number of OH groups in each 1g of the above (A) polyphenylene ether A is 100 to 450 μmol / g.

[0053] (6) The resin composition as described in any one of (1) to (4) is characterized in that the number of OH groups in each 1g of the above (A) polyphenylene ether A is 100 to 300 μmol / g.

[0054] (7) The resin composition as described in any one of (1) to (6), characterized in that the mass ratio (A:B) of the above-mentioned (A) polyphenylene ether A to the above-mentioned (B) triallyl isocyanurate and / or triallyl cyanurate is 50:50 to 80:20.

[0055] (8) The resin composition of any one of (1) to (7) is characterized in that, relative to 100 parts by weight of the total of (A) polyphenylene ether A, (B) triallyl isocyanurate and / or triallyl cyanurate and (B') crosslinking agent other than triallyl isocyanurate and triallyl cyanurate, it contains 0.05 to 10 parts by weight of the organic peroxide (C) mentioned above.

[0056] (9) The resin composition according to any one of (1) to (7) is characterized in that, relative to 100 parts by weight of the total of (A) polyphenylene ether A, (B) triallyl isocyanurate and / or triallyl cyanurate and (B') crosslinking agent other than triallyl isocyanurate and triallyl cyanurate, it contains 1.0 to 5.0 parts by weight of the organic peroxide (C) mentioned above.

[0057] (10) The resin composition according to any one of (1) to (9) is characterized in that, relative to 100 parts by weight of the total of (B) triallyl isocyanurate and / or triallyl cyanurate and (B') crosslinking agent other than triallyl isocyanurate and triallyl cyanurate, it contains 0.1 to 50 parts by weight of the above-mentioned (C) organic peroxide.

[0058] (11) The resin composition as described in any one of (1) to (10), characterized in that the 1-minute half-life temperature of the above-mentioned (C) organic peroxide is 155°C to 195°C.

[0059] (12) The resin composition of any one of (1) to (11) is characterized in that it further comprises (D) a polyfunctional methacrylic acid compound.

[0060] (13) The resin composition as described in (12) is characterized in that, relative to 100 parts by mass of the total amount of (A) polyphenylene ether A, (B) triallyl isocyanurate and / or triallyl cyanurate and (D) polyfunctional methacrylate compound, the content of (A) polyphenylene ether A is 40% by mass or more and 80% by mass or less.

[0061] (14) The resin composition as described in (12) or (13) is characterized in that, relative to 100 parts by mass of the total amount of the above-described (B) triallyl isocyanurate and / or triallyl cyanurate and the above-described (D) polyfunctional methacrylate compound, the content of the above-described (D) polyfunctional methacrylate compound is 20% by mass or more and 80% by mass or less.

[0062] (15) The resin composition of any one of (1) to (14) is characterized in that it further comprises (E) polyphenylene ether B, which comprises repeating units of phenol derived from the above formula (1) and has at least one partial structure in the molecular backbone selected from the group consisting of formula (4), formula (5), formula (6) and formula (7) (but does not include the structure equivalent to the above polyphenylene ether A).

[0063] [Chemistry 4]

[0064]

[0065] [Chemistry 5]

[0066]

[0067] [Chemistry 6]

[0068]

[0069] (In equation (6), R) 6 It consists of a hydrogen atom or a saturated or unsaturated hydrocarbon group with 1 to 10 carbon atoms. These saturated or unsaturated hydrocarbons may contain substituents as long as they satisfy the condition of having 1 to 10 carbon atoms.

[0070] [Chemistry 7]

[0071]

[0072] (In equation (7), R) 7 It is a divalent hydrocarbon group with 1 to 10 carbon atoms, either saturated or unsaturated. This saturated or unsaturated divalent hydrocarbon can also contain substituents, provided it satisfies the condition of 1 to 10 carbon atoms. R8 It consists of a hydrogen atom or a saturated or unsaturated hydrocarbon group with 1 to 10 carbon atoms. The saturated or unsaturated hydrocarbon may also contain substituents, provided it satisfies the requirement of having 1 to 10 carbon atoms.

[0073] (16) The resin composition as described in (15) is characterized in that the above-mentioned (E) polyphenylene ether B further comprises a phenolic structural unit derived from the following formula (8).

[0074] [Chemistry 8]

[0075]

[0076] (In formula (8), X is any linking group with a valence of a, where a is an integer from 2 to 6, and R 9 For any of the linear alkyl groups having 1 to 8 carbon atoms and the partial structure represented by formula (3) above, with the carbon atom of the benzene ring bonded to -O- taken as the 1-position, the R 9 It is bonded to at least one carbon atom at position 2 or 6, where k is an independent integer from 1 to 4.

[0077] R in equation (8) above 9 The partial structure represented by the above formula (3) and R as the above formula (2) 21 The structures represented by the above equation (3) can be the same or different.

[0078] (17) The resin composition as described in (15) or (16) is characterized in that the (E) polyphenylene ether B further comprises a repeating unit of phenol derived from the above formula (2).

[0079] (18) The resin composition as described in any one of (15) to (17), characterized in that the mass ratio (A:E) of the above-mentioned (A) polyphenylene ether A to the above-mentioned (E) polyphenylene ether B is 80:20 to 20:80.

[0080] (19) A resin film, characterized in that it comprises any one of (1) to (18) resin compositions.

[0081] (20) A prepreg, characterized in that it is a composite of a substrate and a resin composition as described in any one of (1) to (18).

[0082] (21) The prepreg as described in (20) is characterized in that the substrate is glass cloth.

[0083] (22) A metal-coated laminate, characterized in that it is a laminate of a cured resin film and a metal foil as described in (19).

[0084] (23) A metal-clad laminate, characterized in that it is a laminate of a cured prepreg of (20) or (21) and a metal foil.

[0085] The effects of the invention

[0086] According to the present invention, a polyphenylene ether resin composition with excellent copper foil peel strength, toluene resistance, dielectric properties and heat resistance can be provided.

[0087] In addition, according to the present invention, electronic circuit board materials, resin films, prepregs and metal-clad laminates formed using the above-described polyphenylene ether resin composition can also be provided. Detailed Implementation

[0088] The following provides a detailed description of specific embodiments of the present invention (hereinafter referred to as "this embodiment"). This embodiment is merely an example to illustrate the present invention, and the present invention is not limited to this embodiment; it can be suitably modified and implemented within the scope of its key points.

[0089] In this embodiment, polyphenylene ether formed by modifying some or all of the hydroxyl groups contained in the polyphenylene ether is sometimes simply referred to as "polyphenylene ether". Therefore, when referred to as "polyphenylene ether", it includes both unmodified polyphenylene ether and modified polyphenylene ether, unless there is a particular contradiction.

[0090] It should be noted that in this specification, A (numerical value) to B (numerical value) refers to values ​​above A and below B. Additionally, in this specification, substituents refer to, for example, saturated or unsaturated hydrocarbon groups with 1 to 10 carbon atoms, aryl groups with 6 to 10 carbon atoms, halogen atoms, etc.

[0091] <Resin Composition>

[0092] The resin composition of this embodiment is a resin composition comprising (A) polyphenylene ether A, (B) triallyl isocyanurate and / or triallyl cyanurate, (B') a crosslinking agent other than triallyl isocyanurate and triallyl cyanurate as an optional component, and (C) an organic peroxide.

[0093] (Polyphenylene ether A)

[0094] The aforementioned polyphenylene ether A comprises at least repeating units of phenol derived from formula (1) and repeating units of phenol derived from formula (2), and may consist solely of repeating units of phenol derived from formula (1) and repeating units of phenol derived from formula (2).

[0095] [Chemistry 9]

[0096]

[0097] (In equation (1), R)11 Each is independently a saturated hydrocarbon group with 1 to 6 carbon atoms, with or without substituents; an aryl group with 6 to 12 carbon atoms, with or without substituents; or a halogen atom, R. 12 Each of the following groups is independently a hydrogen atom, a hydrocarbon group with 1 to 6 carbon atoms (with or without substituents), an aryl group with 6 to 12 carbon atoms (with or without substituents), or a halogen atom.

[0098] [Chemistry 10]

[0099]

[0100] (In equation (2), R) 22 Each of the following groups is independently a hydrogen atom, a saturated or unsaturated hydrocarbon group with or without substituents (1 to 20 carbon atoms), an aryl group with or without substituents (6 to 12 carbon atoms), or a halogen atom, with two R groups. 22 R is not simultaneously a hydrogen atom. 21 It is the partial structure represented by the following formula (3).

[0101] [Chemistry 11]

[0102]

[0103] (In equation (3), R) 31 Each is independently a straight-chain alkyl group having 1 to 8 carbon atoms, with or without substituents, or with 2 R groups. 31 A cyclic alkyl structure with 1 to 8 carbon atoms bonded together, R 32 Each is an alkylene group having 1 to 8 carbon atoms, with or without substituents; b is independently 0 or 1; R 33 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms with or without substituents, or a phenyl group having or without substituents.

[0104] In the above formula (1), R 11 Each of the two R groups is preferably a saturated hydrocarbon group with 1 to 6 carbon atoms or an aryl group with 6 to 12 carbon atoms, more preferably methyl or phenyl, and even more preferably methyl. In formula (1), the two R groups are... 11 Ideally, all should have the same structure.

[0105] In the above formula (1), R 12 Each is preferably a hydrocarbon group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or a methyl group. In formula (1), the two R groups... 12 The preferred components are different, and more preferably one component is a hydrogen atom and the other is a hydrocarbon group with 1 to 6 carbon atoms (preferably methyl).

[0106] In equation (2) above, R 22Each of the following is preferably a hydrogen atom, a saturated or unsaturated hydrocarbon group having 1 to 15 carbon atoms, or an aryl group having 6 to 12 carbon atoms that can be substituted by an alkyl group having 1 to 6 carbon atoms; more preferably a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms that can be substituted by an alkyl group having 1 to 6 carbon atoms; and even more preferably a hydrogen atom or a methyl group. In formula (2), the two R atoms... 22 The preferred components are different, and more preferably one component is a hydrogen atom and the other is a hydrocarbon group with 1 to 6 carbon atoms (preferably methyl).

[0107] As part of the structure represented by the above formula (3), it is preferred to have a group containing a secondary carbon and / or a tertiary carbon, such as isopropyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, 2,2-dimethylpropyl, cyclohexyl, and structures having a phenyl group at their ends, etc., more preferably tert-butyl or cyclohexyl, and even more preferably tert-butyl.

[0108] In this embodiment, the structure of the aforementioned polyphenylene ether A can be identified by analysis using methods such as NMR and mass spectrometry. Specifically, field desorption mass spectrometry (FD-MS), which is known to be less prone to fragmentation, can be performed to estimate repeating units based on the spacing of the detected ions. Furthermore, a method can be employed to estimate the structure of polyphenylene ether A by combining peak analysis of fragment ions using electron ionization (EI) with NMR-based structural analysis.

[0109] Furthermore, in this embodiment, the polyphenylene ether A comprises repeating units of phenol derived from formula (1) and repeating units of phenol derived from formula (2). Relative to the total of 100 mol% of repeating units of formula (1) and formula (2), the content of repeating units of phenol derived from formula (1) is 55 mol% or more and less than 90 mol%, and the content of repeating units of phenol derived from formula (2) is greater than 10 mol% and less than 45 mol%.

[0110] In the above-mentioned polyphenylene ether A, by including repeating units of phenol derived from the above formula (1) and repeating units of phenol derived from the above formula (2) in the above proportion, polyphenylene ether A has excellent solvent solubility, and the copper foil peel strength and toluene resistance of the substrate are improved.

[0111] From the same perspective, in the above-mentioned polyphenylene ether A, relative to the total 100 mol% of the repeating units of the above-mentioned formula (1) and formula (2), it is preferable that the content of the repeating units of phenol derived from the above-mentioned formula (1) is 60 mol% or more and less than 85 mol%, and the content of the repeating units of phenol derived from the above-mentioned formula (2) is greater than 15 mol% and less than 40 mol%; more preferably, the content of the repeating units of phenol derived from the above-mentioned formula (1) is 70 mol% or more and less than 85 mol%, and the content of the repeating units of phenol derived from the above-mentioned formula (2) is greater than 15 mol% and less than 30 mol%; even more preferably, the content of the repeating units of phenol derived from the above-mentioned formula (1) is... The content of repeating units is 72 mol% or more and 84 mol% or less, and the content of repeating units of phenol derived from the above formula (2) is 16 mol% or more and 28 mol% or less; more preferably, the content of repeating units of phenol derived from the above formula (1) is 74 mol% or more and 83.5 mol% or less, and the content of repeating units of phenol derived from the above formula (2) is 16.5 mol% or more and 26 mol% or less; particularly preferably, the content of repeating units of phenol derived from the above formula (1) is 75 mol% or more and 83 mol% or less, and the content of repeating units of phenol derived from the above formula (2) is 17 mol% or more and 25 mol% or less.

[0112] Since the phenol of formula (1) above does not have unsubstituted ortho positions (i.e., since no hydrogen atoms are bonded to the two ortho carbon atoms of the carbon atom bonded to the hydroxyl group), it can only react with other phenolic monomers at the carbon atom opposite to the phenolic hydroxyl group. Therefore, the repeating unit derived from formula (1) above contains repeating units having the structure of formula (9) below.

[0113] [Chemistry 12]

[0114]

[0115] (In equation (9), R) 11 and R 12 Same as in equation (1).

[0116] In the phenol of formula (2) above, except for the phenolic hydroxyl group, it can react with other phenolic monomers at any position, either ortho or para. Therefore, the repeating unit of the phenol derived from formula (2) has the structure of formula (10), formula (11) below, or a combination thereof.

[0117] [Chemistry 13]

[0118]

[0119] [Chemistry 14]

[0120]

[0121] R in equations (10) and (11) 21 R 22 Same as in equation (2).

[0122] In addition, the polyphenylene ether A described above may contain phenol structural units derived from the following formula (8).

[0123] [Chemistry 15]

[0124]

[0125] (In formula (8), X is any linking group with valence α, a is an integer from 2 to 6, and R...) 9 For any of the linear alkyl groups having 1 to 8 carbon atoms and the partial structure represented by formula (3) above, with the carbon atom of the benzene ring bonded to -O- taken as the 1-position, the R 9 It is bonded to at least one carbon atom at position 2 or 6, where k is an independent integer from 1 to 4.

[0126] In equation (8) above, R 9 Each of the components is independently a straight-chain alkyl group with 1 to 8 carbon atoms, such as methyl, ethyl, or n-propyl, and any of the partial structures represented by formula (3) above, preferably methyl or the structure of formula (3) above. The structures of each of the a components can be the same or different. Among them, from the viewpoint of producing polyphenylene ether A with better solubility in solvents and a higher glass transition temperature after curing, it is preferred that the structures of each of the a components are the same.

[0127] In the above formula (8), k is an integer from 1 to 4, preferably an integer from 2 to 4.

[0128] Furthermore, in the above formula (8), the carbon atom of the benzene ring bonded by -O- is taken as the 1 position, R 9 Bonded to at least one carbon atom at positions 2 and 6, bonded to R at positions 2 and / or 6. 9 In the case of a straight-chain alkyl group having 1 to 8 carbon atoms, it is preferable to bond to the 2- and 6-positions, and to bond the R to the 2- and / or 6-positions. 9 In the case of the partial structure represented by equation (3), it is preferable to bond only to any position of 2 or 6 bits.

[0129] The polyphenylene ether A may also contain repeating units derived from formula (8) above, repeating units of phenol derived from formula (1) above, and / or repeating units of phenol derived from formula (2) above.

[0130] At this point, R in equation (2) above 21 R in equation (8) above 9In the case where both are partial structures (functional groups) represented by formula (3) (where both the phenol compound represented by formula (2) and the phenol compound represented by formula (8) are replaced by partial structures (functional groups) represented by formula (3), the structures of the partial structures (functional groups) represented by each formula (3) may be the same or different.

[0131] Furthermore, in the above formula (8), X is any linking group with a valence of α. Although there are no particular restrictions, examples include: hydrocarbon groups such as chain hydrocarbons and cyclic hydrocarbons; hydrocarbon groups containing one or more atoms selected from nitrogen, phosphorus, silicon, and oxygen; atoms such as nitrogen, phosphorus, and silicon; or groups formed by combining them. X can be a linking group other than a single bond. X can be a linking group that connects the α partial structures to each other.

[0132] As for X mentioned above, examples include: bonding to R via single bonds or ester bonds, etc. 9 The α-alkyl skeleton on the bonded benzene ring; bonded to R by single bonds or ester bonds, etc. 9 The α-valent aryl skeleton on the bonded benzene ring; bonded to R by single bonds or ester bonds, etc. 9 The α-valent heterocyclic skeleton on the bonded benzene ring; etc.

[0133] Here, there are no particular limitations on the alkyl skeleton. For example, a chain hydrocarbon (e.g., a chain saturated hydrocarbon) with 2 to 6 carbon atoms and at least 'a' branches can have its branch ends directly bonded to a benzene ring of part of the structure (the benzene ring only needs to be bonded to the 'a' branch ends, or it can have branch ends without a bonded benzene ring). Similarly, there are no particular limitations on the aryl skeleton. For example, a benzene ring, a trimethylyl group, or a 2-hydroxy-5-methyl-1,3-phenylene group can be bonded to R by a single bond or an alkyl chain. 9 The skeleton on the bonded benzene ring, etc. Furthermore, there are no particular limitations on the heterocyclic skeleton; for example, a triazine ring bonded to R by a single bond or alkyl chain can be cited. 9 The skeleton on the bonded benzene ring, etc.

[0134] In the above formula (8), a is an integer from 2 to 6, preferably an integer from 2 to 4.

[0135] If the phenol of formula (8) does not have an unsubstituted ortho position, the structural unit of the phenol derived from formula (8) has the structure of formula (12) below. If the phenol of formula (8) has an unsubstituted ortho position, the structural unit of the phenol derived from formula (8) has the structure of formula (12) below, the structure of formula (13) below, or a combination thereof.

[0136] [Chemistry 16]

[0137]

[0138] [Chemistry 17]

[0139]

[0140] R in equations (12) and (13) 9 Same as in equation (8).

[0141] In addition, the specific viscosity (ηsp / c) of the above-mentioned polyphenylene ether A in a chloroform solution with a concentration of 0.5 g / dL at 30°C is 0.13 to 0.30 dL / g, preferably 0.15 to 0.28 dL / g, and more preferably 0.17 to 0.25 dL / g.

[0142] By achieving a specific viscosity (ηsp / c) of 0.13 dL / g or higher in a chloroform solution with a concentration of 0.5 g / dL at 30°C, high heat resistance and excellent dielectric properties derived from the polyphenylene ether A structure can be obtained. By achieving a specific viscosity (ηsp / c) of 0.30 dL / g or lower, solubility in solvents such as toluene and methyl ethyl ketone can be ensured.

[0143] The specific viscosity described above can be determined by the method described in the examples below.

[0144] In addition, the molecular weight distribution (Mw / Mn) of the polyphenylene ether A obtained by gel permeation chromatography (GPC) is 2.0 to 6.0, preferably 2.5 to 5.5 or less, and more preferably 3.0 to 5.0.

[0145] By achieving a molecular weight distribution (Mw / Mn) of 2.0 or higher as determined by gel permeation chromatography (GPC), the flowability of polyphenylene ether A can be improved, and its reactivity during thermosetting can be enhanced. By achieving a molecular weight distribution (Mw / Mn) of 6.0 or lower, the toughness of polyphenylene ether A can be improved, resulting in excellent copper foil peel strength and solvent resistance of the cured product.

[0146] As a means to achieve the aforementioned molecular weight distribution of polyphenylene ether A within the specified range, from the perspective of controlling polymerization reactivity, examples include adjusting the polymerization temperature, adjusting the catalyst equivalence, and adjusting the monomer concentration in the reaction system. Among these, the method of slowly adding monomers to the reaction system is preferred for adjusting the monomer concentration. When the monomer concentration in the reaction system is high from the initial stage, the reaction rate between monomers is fast, making it difficult to control the molecular weight of the resulting polymer. On the other hand, by adding monomers to the reaction system using an appropriate flow rate, the monomer concentration in the reaction system can be controlled, and the reaction rate can be easily controlled. As a result, a polymer with a molecular weight distribution within the preferred range can be obtained.

[0147] Furthermore, in this embodiment, the OH base number of the above-mentioned polyphenylene ether A is 100 to 330 μmol / g, preferably 100 to 310 μmol / g, and more preferably 100 to 300 μmol / g.

[0148] By setting the OH base number to 100 μmol / g or higher, the adhesion to copper foil can be improved; by setting the OH base number to 330 μmol / g or lower, the heat resistance and dielectric properties of the substrate can be improved.

[0149] It should be noted that the OH radical of the above-mentioned polyphenylene ether A can be determined by the method described in the examples below.

[0150] In the above-mentioned polyphenylene ether A, the number of OH groups per molecule is 0.3 to 3.0 per molecule, preferably 0.8 to 3.0 per molecule, more preferably 0.8 to 2.8 per molecule, and even more preferably 1.0 to 2.5 per molecule.

[0151] By increasing the number of OH groups per molecule to 0.3 or more, the adhesion to copper foil can be improved. By increasing the number of OH groups per molecule to 3.0 or less, the heat resistance and dielectric properties of the substrate can be improved, thus ensuring the manufacturing stability of polyphenylene ether A.

[0152] (Polyphenylene ether B)

[0153] Furthermore, the resin composition of this embodiment preferably further comprises (E) polyphenylene ether B, which contains repeating units of phenol derived from the above formula (1) and has at least one partial structure in the molecular backbone selected from the group consisting of the following formulas (4), (5), (6) and (7) (excluding the structure equivalent to the above polyphenylene ether A).

[0154] [Chemistry 18]

[0155]

[0156] (In the above formula (6), R) 6 It is a saturated or unsaturated hydrocarbon group with 1 to 10 carbon atoms or hydrogen atoms. The saturated or unsaturated hydrocarbons mentioned above can also have substituents as long as they meet the condition of 1 to 10 carbon atoms.

[0157] In equation (7) above, R 7 It is a divalent hydrocarbon group with 1 to 10 carbon atoms, either saturated or unsaturated. This saturated or unsaturated divalent hydrocarbon can also contain substituents, provided it satisfies the condition of 1 to 10 carbon atoms. R 8 It consists of a hydrogen atom or a saturated or unsaturated hydrocarbon group with 1 to 10 carbon atoms. The saturated or unsaturated hydrocarbon may also contain substituents, provided it satisfies the requirement of having 1 to 10 carbon atoms.

[0158] It should be noted that the partial structure represented by at least one of the above formulas (4), (5), (6), and (7) can be directly bonded to the oxygen of the hydroxyl group contained in polyphenylene ether B.

[0159] In addition, the above-mentioned polyphenylene ether B may further include phenolic structural units derived from the following formula (8).

[0160] [Chemistry 19]

[0161]

[0162] (In the above formula (8), X is any linking group with valence α, a is an integer from 2 to 6, R 9 For any of the linear alkyl groups having 1 to 8 carbon atoms and the partial structure represented by formula (3) above, with the carbon atom of the benzene ring bonded to -O- taken as the 1-position, the R 9 It is bonded to at least one carbon atom at position 2 or 6, where k is an independent integer from 1 to 4.

[0163] In equation (8) above, R 9 Each of the components is independently a straight-chain alkyl group with 1 to 8 carbon atoms, such as methyl, ethyl, or n-propyl, and any of the partial structures represented by formula (3) above, preferably methyl or the structure of formula (3) above. The structures of each component can be the same or different. Among them, from the viewpoint of becoming a polyphenylene ether with better solubility in solvents and a higher glass transition temperature after curing, it is preferred that the structures of each component are the same.

[0164] In the above formula (8), k is an integer from 1 to 4, preferably an integer from 2 to 4.

[0165] Furthermore, in the above formula (8), the carbon atom of the benzene ring bonded by -O- is taken as the 1 position, R 9 Bonded to at least one carbon atom at positions 2 and 6, and bonded to R at positions 2 and / or 6. 9 In the case of a straight-chain alkyl group having 1 to 8 carbon atoms, it is preferred that the R bond is applied to the 2nd and 6th positions. 9 In the case of the partial structure represented by equation (3), it is preferable to bond only to any position of 2 or 6 bits.

[0166] It should be noted that R in equation (2) above 21 R in equation (8) above 9In the case where both are partial structures (functional groups) represented by formula (3) (where both the phenol compound represented by formula (2) and the phenol compound represented by formula (8) are replaced by partial structures (functional groups) represented by formula (3), the structures of the partial structures (functional groups) represented by each formula (3) may be the same or different.

[0167] In the above formula (8), X is any linking group with a valence of α. Although there are no particular restrictions, examples include: chain hydrocarbons, cyclic hydrocarbons, and other hydrocarbon groups; hydrocarbon groups containing one or more atoms selected from nitrogen, phosphorus, silicon, and oxygen; nitrogen, phosphorus, silicon, and other atoms; or groups formed by combining them. X can be a linking group other than a single bond. X can be a linking group that connects the α partial structures to each other.

[0168] It should be noted that, as for X mentioned above, examples include: bonds formed by single bonds or ester bonds in R. 9 The α-alkyl skeleton on the bonded benzene ring; bonded to R by single bonds or ester bonds, etc. 9 The α-valent aryl skeleton on the bonded benzene ring; bonded to R by single bonds or ester bonds, etc. 9 The α-valent heterocyclic skeleton on the bonded benzene ring; etc.

[0169] Here, there are no particular limitations on the alkyl skeleton. For example, a chain hydrocarbon (e.g., a chain saturated hydrocarbon) with 2 to 6 carbon atoms and at least 'a' branches can have its branch ends directly bonded to a benzene ring of part of the structure (the benzene ring only needs to be bonded to the 'a' branch ends, or it can have branch ends without a bonded benzene ring). Similarly, there are no particular limitations on the aryl skeleton. For example, a benzene ring, a trimethylyl group, or a 2-hydroxy-5-methyl-1,3-phenylene group can be bonded to R by a single bond or an alkyl chain. 9 The skeleton on the bonded benzene ring, etc. Furthermore, there are no particular limitations on the heterocyclic skeleton; for example, a triazine ring bonded to R by a single bond or alkyl chain can be cited. 9 The skeleton on the bonded benzene ring, etc.

[0170] In the above formula (8), a is an integer from 2 to 6, preferably an integer from 2 to 4.

[0171] In addition, if the phenol of formula (8) does not have an unsubstituted ortho position, the structural unit of the phenol derived from formula (8) has the structure of formula (12) below. If the phenol of formula (8) has an unsubstituted ortho position, the structural unit of the phenol derived from formula (8) has the structure of formula (12) below, the structure of formula (13) below, or a combination thereof.

[0172] [Chemistry 20]

[0173]

[0174] [Chemistry 21]

[0175]

[0176] R in equations (12) and (13) 9 Same as in equation (8).

[0177] Furthermore, the aforementioned polyphenylene ether B may further comprise repeating units of phenol derived from formula (2) above. Wherein, the aforementioned polyphenylene ether B does not include substances equivalent to polyphenylene ether A in formula (A) above.

[0178] In addition, the number average molecular weight of the above-mentioned polyphenylene ether B is preferably 1,000 or more and 30,000 or less, more preferably 1,500 or more and 25,000 or less, and even more preferably 1,500 or more and 20,000 or less.

[0179] By making the number average molecular weight of polyphenylene ether B 1000 or more, toughness can be imparted to the resin composition and its cured product, and the peel strength of copper foil can be improved. In addition, by making the number average molecular weight of polyphenylene ether B 30000 or less, the viscosity of the varnish can be reduced and the processability improved by mixing the resin composition with the solvent, thereby reducing the melt viscosity of the resin composition in the thermosetting process and increasing the crosslinking reaction rate.

[0180] The number-average molecular weight of the aforementioned polyphenylene ether B can be a value determined by common molecular weight determination methods, specifically, values ​​determined using GPC, etc.

[0181] In this embodiment, the structure of polyphenylene ether B can also be identified by analysis using methods such as NMR and mass analysis. The specific method for identifying the structure of polyphenylene ether is the same as that for polyphenylene ether A described above.

[0182] (Manufacturing method of polyphenylene ether)

[0183] The above-mentioned (A) polyphenylene ether A and (E) polyphenylene ether B are obtained, for example, by a method including at least the following steps: oxidative polymerization of monophenolic compounds represented by formulas (1) and (2); or oxidative polymerization of monophenolic and polyphenolic compounds represented by formulas (1) and (8). In the above-mentioned oxidative polymerization steps, it is preferable to oxidatively polymerize a raw material containing at least the phenol of formula (1) and the phenol of formula (2), or the phenol of formula (1) and the phenol of formula (8).

[0184] Examples of monophenol compounds represented by formula (1) above include 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2- Ethyl-6-chlorophenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2-methyl-6-tolylphenol, 2,6-xylylphenol, 2,3,6-trimethylphenol, 2,3-diethyl-6-n-propylphenol, 2,3,6-tributylphenol, 2,6-di-n-butyl-3-methylphenol, 2,6-dimethyl-3-n-butylphenol, 2,6-dimethyl-3-tert-butylphenol, etc. Among these, 2,6-dimethylphenol, 2,3,6-trimethylphenol, and 2,6-diphenylphenol are preferred, especially due to their low cost and ease of availability.

[0185] The monophenol compound represented by formula (1) above can be used alone or in combination of two or more.

[0186] Examples of monophenol compounds represented by formula (2) above include 2-isopropyl-5-methylphenol, 2-cyclohexyl-5-methylphenol, 2-tert-butyl-5-methylphenol, and 2-isobutyl-5-methylphenol. From the viewpoint of suppressing multibranching and gelation, 2-tert-butyl-5-methylphenol and 2-cyclohexyl-5-methylphenol, which are bulky substituents, are more preferred.

[0187] The monophenol compound represented by formula (2) above can be used alone or in combination of two or more.

[0188] Among the polyphenolic compounds represented by formula (8) above, examples of phenolic compounds having two phenolic units in the molecule include 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4'-methylenebis(2,6-dimethylphenol), bis(4-hydroxy-3-methylphenyl)sulfide, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, α,α'-bis(4-hydroxy-3,5-dimethylphenyl)-1,4-diisopropylbenzene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, and 1,1-bis(2-methyl-4-hydroxy-5-tert-butylphenyl)butane. Among them, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane and 1,1-bis(2-methyl-4-hydroxy-5-tert-butylphenyl)butane are preferred, especially for their low cost and easy availability.

[0189] Furthermore, among the polyphenolic compounds represented by formula (8) above, examples of phenolic compounds having three or more phenolic units within the molecule include 4,4'-[(3-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(3-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4'-[(2-hydroxy-3-methoxyphenyl)methylene]bis(2,6-dimethylphenol), and 4,4'-[(4-hydroxy-3-ethoxyphenyl)methylene]bis(2,3,6-trimethylphenol). ethylphenol), 4,4'-[(3,4-dihydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(3,4-dihydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 2,2'-[(4-hydroxyphenyl)methylene]bis(3,5,6-trimethylphenol), 4,4'-[4-(4-hydroxyphenyl)cyclohexylidene]bis(2,6-dimethylphenol), 4,4'-[(2-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4'-[1-[4-[1-(4-hydroxy-3,5-dimethylphenyl)-1-methylethyl]phenyl]ethidene]bis(2,6-dimethylphenol), 4,4'-[1-[4-[1-(4-hydroxy-3,5-dimethylphenyl)-1-methylethyl]phenyl]ethidene]bis(2,6-dimethylphenol), 4,4'-[1-[4-[1-(4-hydroxy-3,5-dimethylphenyl]-1-methylethyl]phenyl]ethidene]bis(2,6-dimethylphenol), [-hydroxy-3-fluorophenyl)-1-methylethyl]phenyl]ethoxy]bis(2,6-dimethylphenol), 2,6-bis[(4-hydroxy-3,5-dimethylphenyl)ethyl]-4-methylphenol, 2,6-bis[(4-hydroxy-2,3,6-trimethylphenyl)methyl]-4-methylphenol, 2,6-bis[(4-hydroxy-3,5,6-trimethylphenyl)methyl]-4-ethylphenol, 2,4-bis[(4-hydroxy-3-methylphenyl)methyl]-6-methylphenol, 2,6-bis[(4-hydroxy-3-methylphenyl)methyl]-4-methylphenol, 2,4-bis[(4-hydroxy-3-cyclohexylphenyl)methyl]-6-methylphenol, 2,4-bis[(4-hydroxy-3-methyl ... [(2-hydroxy-5-methylphenyl)methyl]-6-cyclohexylphenol, 2,4-bis[(4-hydroxy-2,3,6-trimethylphenyl)methyl]-6-cyclohexylphenol, 3,6-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,2-phenylene glycol, 4,6-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,3-phenylene glycol, 2,4,6-tris[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,3-phenylene glycol, 2,4,6-tris[(2-hydroxy-3,5-dimethylphenyl)methyl]-1,3-phenylene glycol, 2,2'-methylenebis[6-[(4 / 2-hydroxy-2,5 / 3,3-dimethylphenyl)methyl]-6-cyclohexylphenol, 3,4-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,2-phenylene glycol, 4,6-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,3-phenylene glycol, 2,2'-methylenebis[6-[(4 / 2-hydroxy-2,5 / 3,3 ...[6-Dimethylphenyl)methyl]-4-methylphenol], 2,2'-methylenebis[6-[(4-hydroxy-3,5-dimethylphenyl)methyl]-4-methylphenol], 2,2'-methylenebis[6-[(4 / 2-hydroxy-2,3,5 / 3,4,6-trimethylphenyl)methyl]-4-methylphenol], 2,2'-methylenebis[6-[(4-hydroxy-2,3,5-trimethylphenyl)methyl]-4-methylphenol], 4, 4'-Methylenebis[2-[(2,4-dihydroxyphenyl)methyl]-6-methylphenol], 4,4'-Methylenebis[2-[(2,4-dihydroxyphenyl)methyl]-3,6-dimethylphenol], 4,4'-Methylenebis[2-[(2,4-dihydroxy-3-methylphenyl)methyl]-3,6-dimethylphenol], 4,4'-Methylenebis[2-[(2,3,4-trihydroxyphenyl)methyl]-3,6-dimethylphenol], 6,6'-Methylenebis[4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,2,3-phenylpyrogallol], 4,4'-cyclohexylidenebis[2-cyclohexyl-6-[(2-hydroxy-5-methylphenyl)methyl]phenol], 4,4'-cyclohexylidenebis[2-cyclohexyl-6-[(4-hydroxy-3,5-dimethylphenyl)methyl]phenol], 4,4'-cyclohexylidenebis[2-cyclohexyl-6-[(4-hydroxy-2-methyl- [5-Cyclohexylphenyl]methyl[phenol], 4,4'-cyclohexylidene bis[2-cyclohexyl-6-[(2,3,4-trihydroxyphenyl)methyl]phenol], 4,4',4”,4”'-(1,2-ethadiene)tetra(2,6-dimethylphenol), 4,4',4”,4”'-(1,4-phenylene dimethylidene)tetra(2,6-dimethylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, etc. Among these, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane is preferred, particularly due to its low cost and ease of availability.

[0190] The polyphenol compound represented by formula (8) above can be used alone or in combination of two or more.

[0191] There is no particular limitation on the number of phenolic hydroxyl groups in the polyphenol compound represented by the above formula (8), as long as it is 2 to 6. From the perspective of making it easier to control the thermosetting speed, it is preferred to have 2 to 4 hydroxyl groups.

[0192] Typically, since the oxidative polymerization of phenols with hydrogen atoms in the ortho position (e.g., 2-methylphenol, 2,5-dimethylphenol, 2-phenylphenol) can also form ether bonds in the ortho position, it becomes difficult to control the bonding position of phenol compounds during oxidative polymerization. This results in high molecular weight polymers with an average number of hydroxyl groups of 3.5 or more per molecule that are polymerized into branched structures, ultimately producing gel components that are insoluble in solvents.

[0193] On the other hand, when the phenol represented by the above formula (2) has a large volume substituent on one side of the ortho position, even if there is a hydrogen atom on the opposite side of the ortho position, the bonding position of the phenol compound during oxidative polymerization can be controlled, and polyphenylene ether with an average of less than 3.0 hydroxyl groups per molecule can be obtained.

[0194] Furthermore, when the phenol represented by the above formula (2) has a large substituent on one side of the ortho position, a polyphenylene ether with an average of less than 3.0 hydroxyl groups per molecule can also be obtained when a monophenol with a non-large substituent (e.g., hydrogen atom, allyl, methyl, ethyl, methoxy, etc.) on the ortho position of the oxygen atom of the phenol is used as the third component.

[0195] Furthermore, the molecular weight of the aforementioned polyphenylene ether can be adjusted, for example, by the molar ratio of the structure of formula (2) to the total molar ratio of the structures of formula (1) and formula (2), or by the molar ratio of the structure of formula (8) to the total molar ratio of the structures of formula (1) and formula (8). That is, when the molar ratio of the structures of formula (2) or formula (8) is high, the achieved molecular weight (specific viscosity) can be reduced, and when the molar ratio of the structures of formula (2) or formula (8) is low, the molecular weight (specific viscosity) can be adjusted to be higher.

[0196] Here, in the manufacturing method of polyphenylene ether, in the oxidative polymerization step, an aromatic solvent that is a good solvent for polyphenylene ether can be used as the polymerization solvent.

[0197] Here, in the polyphenylene ether manufacturing method of this embodiment, in the oxidative polymerization step, an aromatic solvent, which is a good solvent for polyphenylene ether, can be used as the polymerization solvent.

[0198] The aforementioned good solvents for polyphenylene ethers refer to solvents that can dissolve polyphenylene ethers. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene (including isomers of o-xylene, m-xylene, and p-xylene), and ethylbenzene; halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; nitro compounds such as nitrobenzene; and so on.

[0199] It should be noted that the polymerization catalyst used in the polyphenylene ether manufacturing method of this embodiment can be a known catalyst system commonly used in the manufacture of polyphenylene ether. Commonly known catalyst systems include those consisting of a transition metal ion with redox capabilities and an amine compound capable of forming a complex with that transition metal ion, such as catalyst systems consisting of copper compounds and amine compounds, catalyst systems consisting of manganese compounds and amine compounds, and catalyst systems consisting of cobalt compounds and amine compounds. Since the polymerization reaction proceeds effectively under slightly alkaline conditions, a small amount of alkali or further amine compounds may be added.

[0200] In addition, the polymerization catalysts that are suitable for use are catalysts composed of copper compounds, halides and amine compounds as components of the catalyst, and more preferably catalysts containing a diamine compound represented by the following formula (14) as an amine compound.

[0201] [Chemistry 22]

[0202]

[0203] (In the above formula (14), R) 14 R 15 R 16 R 17 Each is an independent hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 carbon atoms, and not all of them are hydrogen atoms simultaneously. R 18 It is a straight-chain alkylene group with 2 to 5 carbon atoms or a methyl branch.

[0204] Examples of copper compounds that form the catalyst components described above are given here. Suitable copper compounds can be monovalent copper compounds, divalent copper compounds, or mixtures thereof. Examples of divalent copper compounds include copper chloride, copper bromide, copper sulfate, and copper nitrate. Examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous sulfate, and cuprous nitrate. Among these, cuprous chloride, copper chloride, cuprous bromide, and copper bromide are particularly preferred metal compounds. Furthermore, these copper salts can also be synthesized in use from oxides (e.g., cuprous oxide), carbonates, hydroxides, etc., with the corresponding halogens or acids. A commonly used method is the method described above, which involves mixing cuprous oxide with hydrogen halide (or a solution of hydrogen halide).

[0205] Examples of the aforementioned halides include hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium chloride, sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, and tetraethylammonium iodide. Furthermore, they can be used in the form of aqueous solutions or solutions using suitable solvents. These halides can be used alone or in combination of two or more. Preferred halides are aqueous solutions of hydrogen chloride and hydrogen bromide.

[0206] The amount of these compounds is not particularly limited, but is preferably more than 2 to 20 times the molar amount of copper atoms, in terms of halogen atoms, and is in the range of 0.02 to 0.6 molar amounts of copper atoms, in terms of 100 molar amounts of phenol compound added to the polymerization reaction.

[0207] Examples of diamine compounds used as catalyst components include N,N,N',N'-tetramethylethylenediamine, N,N,N'-trimethylethylenediamine, N,N'-dimethylethylenediamine, N,N-dimethylethylenediamine, N-methylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N'-triethylethylenediamine, N,N'-diethylethylenediamine, N,N'-diethylethylenediamine, N,N-diethylethylenediamine, N-ethylethylenediamine, N,N-dimethyl-N'-ethylethylenediamine, N,N'-dimethyl-N-ethylethylenediamine, N-n-propylethylenediamine, N,N'-n-propylethylenediamine, N-isopropylethylenediamine, N,N'-isopropylethylenediamine, N-n-butylethylenediamine, N,N' - n-Butylethylenediamine, N-isobutylethylenediamine, N,N'-isobutylethylenediamine, N-tert-butylethylenediamine, N,N'-tert-butylethylenediamine, N,N,N',N'-tetramethyl-1,3-diaminopropane, N,N,N'-trimethyl-1,3-diaminopropane, N,N'-dimethyl-1,3-diaminopropane, N-methyl-1,3-diaminopropane, N,N,N',N'-tetramethyl-1,3-diamino-1-methylpropane, N,N,N',N'-tetramethyl-1,3-diamino-2-methylpropane, N,N,N',N'-tetramethyl-1,4-diaminobutane, N,N,N',N'-tetramethyl-1,5-diaminopentane, etc. In this embodiment, the preferred diamine compound is a diamine compound in which the alkylene group connected to two nitrogen atoms has two or three carbon atoms. The amount of these diamine compounds is not particularly limited, but is preferably in the range of 0.01 to 10 moles relative to 100 moles of phenol compound added in the polymerization reaction.

[0208] Furthermore, the components of the polymerization catalyst may include primary amines and secondary monoamines. Examples of secondary monoamines include, but are not limited to, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-tert-butylamine, dipentylamine, dihexylamine, dioctylamine, didecylamine, dibenzylamine, methylethylamine, methylpropylamine, methylbutylamine, cyclohexylamine, N-phenylmethanolamine, N-phenylethanolamine, N-phenylpropanolamine, N-(m-methylphenyl)ethanolamine, N-(p-methylphenyl)ethanolamine, N-(2',6'-dimethylphenyl)ethanolamine, N-(p-chlorophenyl)ethanolamine, N-ethylaniline, N-butylaniline, N-methyl-2-methylaniline, N-methyl-2,6-dimethylaniline, and diphenylamine.

[0209] As a component of the aforementioned polymerization catalyst, a tertiary monoamine compound may also be included. Tertiary monoamine compounds refer to aliphatic tertiary amines, including alicyclic tertiary amines. Examples include trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyl diethylamine, dimethyl n-butylamine, diethylisopropylamine, and N-methylcyclohexylamine. These tertiary monoamines can be used alone or in combination of two or more. Their amounts are not particularly limited, but are preferably in the range of 15 moles or less relative to 100 moles of phenol compound added in the polymerization reaction.

[0210] It should be noted that in this embodiment, there are no limitations on the addition of existing surfactants known to enhance polymerization activity. Examples of such surfactants include, for instance, trioctylmethylammonium chloride, known by trade names Aliquat336 and Capriquat.

[0211] In addition to pure oxygen, other oxygen-containing gases used in the above polymerization process can include gases formed by mixing oxygen with inert gases such as nitrogen in any proportion, air, and gases formed by mixing air with inert gases such as nitrogen in any proportion. Atmospheric pressure is sufficient within the system during the polymerization reaction, but depressurization or pressurization can be used as needed.

[0212] It should be noted that there is no particular limitation on the polymerization temperature, but if the temperature is too low, the reaction will be difficult to proceed. In addition, if the temperature is too high, the reaction selectivity may be reduced and gel may be formed. Therefore, the temperature range is 0 to 60°C, preferably 10 to 40°C.

[0213] In the manufacturing process of polyphenylene ether, polymerization can also be carried out in undesirable solvents such as alcohols.

[0214] Furthermore, there are no particular restrictions on the post-polymerization treatment methods in the manufacturing process of polyphenylene ether. Typically, acids such as hydrochloric acid or acetic acid, or ethylenediaminetetraacetic acid (EDTA) and its salts, hypozinotriacetic acid and its salts, are added to the reaction solution to deactivate the catalyst. Additionally, existing known methods can be used to remove the byproducts of diphenols generated during the polymerization of polyphenylene ether. If the metal ions acting as the catalyst are substantially deactivated as described above, decolorization can be achieved simply by heating the mixture. Alternatively, a method can be used by adding a necessary amount of a known reducing agent. Examples of known reducing agents include hydroquinone and sodium dithionite.

[0215] In the manufacturing process of polyphenylene ether, to extract the compounds resulting from the deactivation of the copper catalyst, water can be added to perform liquid-liquid separation, separating the organic and aqueous phases. The aqueous phase is then removed, thereby removing the copper catalyst from the organic phase. This liquid-liquid separation process is not particularly limited; methods such as static separation or separation using a centrifuge can be cited. To facilitate this liquid-liquid separation, known surfactants can be used.

[0216] Next, in the polyphenylene ether manufacturing method of this embodiment, the solvent in the organic phase containing the above-mentioned polyphenylene ether after liquid-liquid separation can be evaporated to concentrate and dry it.

[0217] There are no particular limitations on the method for evaporating the solvent contained in the organic phase. Examples include: transferring the organic phase to a high-temperature concentration tank and concentrating it by distilling off the solvent; concentrating it by distilling off toluene using equipment such as a rotary evaporator; and so on.

[0218] The drying temperature in the drying process is preferably at least 60°C or higher, more preferably 80°C or higher, further preferably 120°C or higher, and most preferably 140°C or higher. Drying polyphenylene ether at a temperature of 60°C or higher can effectively reduce the content of high-boiling-point volatile components in the polyphenylene ether powder.

[0219] To efficiently obtain the aforementioned polyphenylene ether, methods such as increasing the drying temperature, increasing the vacuum level in the drying atmosphere, and stirring during drying are effective. In particular, from a manufacturing efficiency perspective, increasing the drying temperature is preferred. The drying process preferably uses a dryer with a mixing function. Examples of mixing functions include stirred and rotary dryers. This increases throughput and maintains high productivity.

[0220] Furthermore, the resin composition of this embodiment includes the above-mentioned polyphenylene ether, triallyl isocyanurate and / or triallyl cyanurate, and organic peroxide, and may further include crosslinking agents, thermoplastic resins, flame retardants, other additives, solvents, etc., other than triallyl isocyanurate and triallyl cyanurate, as desired. The constituent elements of the resin composition of this embodiment will be described below.

[0221] (Mass ratio of polyphenylene ether A to polyphenylene ether B)

[0222] In this embodiment, the mass ratio (A:E) of the above-mentioned (A) polyphenylene ether A to the above-mentioned (E) polyphenylene ether B is preferably 80:20 to 20:80, more preferably 80:20 to 30:70, and most preferably 70:30 to 30:70.

[0223] When the above-mentioned preferred mass ratio is used, the resin composition using each polyphenylene ether alone tends to have low dielectric properties of the cured product, copper foil peel strength, and toluene resistance, which are particularly superior compared to the resin composition using each polyphenylene ether alone.

[0224] (Trylyl isocyanurate and / or triallyl cyanurate)

[0225] The resin composition of this embodiment contains (B) triallyl isocyanurate and / or triallyl cyanurate as crosslinking agents, which have the ability to initiate or promote crosslinking reactions.

[0226] From the perspective of superior compatibility of triallyl isocyanurate and / or triallyl cyanurate with polyphenylene ether A and polyphenylene ether B, coating properties of the resin composition, and characteristics of the mounted electronic circuit board, the mass ratio of the above-mentioned (A) polyphenylene ether A and the above-mentioned (E) polyphenylene ether B to triallyl isocyanurate and / or triallyl cyanurate (total mass of polyphenylene ether A + polyphenylene ether B : total mass of triallyl isocyanurate and / or triallyl cyanurate) is preferably 90:10 to 60:40, more preferably 80:20 to 70:30.

[0227] (Crossing agents other than triallyl isocyanurate and triallyl cyanurate)

[0228] The resin composition of this embodiment may contain a crosslinking agent (hereinafter sometimes simply referred to as "crosslinking agent") other than triallyl isocyanurate and triallyl cyanurate, which has the ability to initiate or promote a crosslinking reaction. The number-average molecular weight of the aforementioned crosslinking agent is preferably 4,000 or less. If the number-average molecular weight of the crosslinking agent is 4,000 or less, the increase in viscosity of the resin composition can be suppressed, and good resin flowability during heat molding can be obtained. The number-average molecular weight can be a value determined using a conventional molecular weight determination method; specifically, values ​​determined using GPC can be cited as examples.

[0229] Furthermore, from the perspective of the crosslinking reaction, it is preferable that the crosslinking agent has an average of two or more carbon-carbon unsaturated double bonds per molecule. The crosslinking agent can be composed of one compound or two or more compounds. In this specification, "carbon-carbon unsaturated double bond" refers to a double bond located at the end of a branch from the main chain when the crosslinking agent is a polymer or oligomer. Examples of carbon-carbon unsaturated double bonds include, for instance, the 1,2-vinyl bond in polybutadiene.

[0230] When the number average molecular weight of the crosslinking agent is less than 600, the number (average) of carbon-carbon unsaturated double bonds per molecule of the crosslinking agent is preferably 2 to 4. When the number average molecular weight of the crosslinking agent is 600 or more and less than 1,500, the number (average) of carbon-carbon unsaturated double bonds per molecule of the crosslinking agent is preferably 4 to 26. When the number average molecular weight of the crosslinking agent is 1,500 or more and less than 4,000, the number (average) of carbon-carbon unsaturated double bonds per molecule of the crosslinking agent is preferably 26 to 60. When the number average molecular weight of the crosslinking agent is within the above range, by making the number of carbon-carbon unsaturated double bonds above the above-mentioned specific value, the reactivity of the crosslinking agent in the resin composition of this embodiment is further improved, and the crosslinking density of the cured resin composition is further improved, resulting in superior heat resistance. On the other hand, when the number average molecular weight of the crosslinking agent is within the above range, by making the number of carbon-carbon unsaturated double bonds below the above-mentioned specific value, superior resin flowability can be imparted during heat molding.

[0231] Examples of crosslinking agents include: polyfunctional methacrylate compounds having two or more methacryloyl groups in the molecule; polyfunctional acrylate compounds having two or more acryloyl groups in the molecule; polyfunctional vinyl compounds having two or more vinyl groups in the molecule, such as polybutadiene; vinyl benzyl compounds such as divinylbenzene having a vinyl benzyl group in the molecule; polyfunctional maleimide compounds having two or more maleimide groups in the molecule, such as 4,4'-bismaleimide diphenylmethane; polyfunctional acrylates having two or more acryloyl groups in the molecule, such as tricyclodecanediethanol diacrylate; and polyfunctional methacrylates having two or more acryloyl or methacryloyl groups in the molecule, such as tricyclodecanediethanol dimethacrylate.

[0232] These crosslinking agents can be used alone or in combination of two or more. The crosslinking agent needs to contain at least one compound selected from triallyl isocyanurate and triallyl cyanurate. By including at least one compound selected from triallyl isocyanurate and triallyl cyanurate in the crosslinking agent, the resin composition tends to further improve the compatibility and coatability of the crosslinking agent with polyphenylene ether, and to exhibit superior substrate properties when mounted on an electronic circuit board.

[0233] Furthermore, in the resin composition of this embodiment, from the perspective of superior compatibility between the components, coating properties of the resin composition, and characteristics of the mounted electronic circuit board, the total content of the above-mentioned polyphenylene ether A and polyphenylene ether B (A) and (E) is preferably 40% to 80% by weight, more preferably 45% to 80% by weight, and even more preferably 50% to 80% by weight, relative to the total amount of 100 parts by weight of the above-mentioned polyfunctional methacrylate compound.

[0234] (Organic peroxides)

[0235] In the resin composition of this embodiment, in addition to the above-mentioned polyphenylene ether, triallyl isocyanurate and / or triallyl cyanurate, and optionally a crosslinking agent other than triallyl isocyanurate and triallyl cyanurate, optional (C) organic peroxides with the ability to promote polymerization reactions may also be used.

[0236] Examples of the aforementioned organic peroxides include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, di-tert-butyl peroxide, tert-butylcumyl peroxide, di(2-tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, cumyl peroxide, di-tert-butylperoxyisophthalate, tert-butyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane, di(trimethylsilyl)peroxide, trimethylsilyltriphenylsilyl peroxide, and other peroxides. It should be noted that free radical initiators such as 2,3-dimethyl-2,3-diphenylbutane can also be used as reaction initiators for resin compositions. Among them, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, di(2-tert-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane are preferred from the perspective of obtaining curing products with excellent heat resistance and mechanical properties, and thus providing curing products with low dielectric loss tangent (and preferably also low dielectric constant).

[0237] The 1-minute half-life temperature of the aforementioned organic peroxide is preferably 155–195°C, more preferably 160–195°C, and even more preferably 165–195°C. In this specification, the 1-minute half-life temperature is the temperature at which the aforementioned organic peroxide decomposes and its reactive oxygen species reach half their concentration within one minute. The 1-minute half-life temperature is a value confirmed by dissolving the organic peroxide at a concentration of 0.05–0.1 mol / L in a solvent inert to free radicals (e.g., benzene) and thermally decomposing the organic peroxide solution under a nitrogen atmosphere.

[0238] By setting the 1-minute half-life temperature of the aforementioned organic peroxide to 155°C or higher, when the aforementioned resin composition containing polyphenylene ether is subjected to heat-press molding, the reaction with the crosslinking agent is initiated after the polyphenylene ether has fully melted, thus exhibiting excellent moldability. On the other hand, by setting the 1-minute half-life temperature of the organic peroxide to 195°C or lower, the decomposition rate of the organic peroxide is sufficient under normal heat-press molding conditions (e.g., a maximum temperature of 200°C), thus enabling an effective and slow crosslinking reaction with the crosslinking agent, thereby forming a cured product with good electrical properties (especially dielectric loss tangent).

[0239] Examples of the aforementioned organic peroxides with a 1-minute half-life temperature in the range of 155–195°C include tert-hexyl isopropyl peroxide (155.0°C), tert-butyl peroxide-3,5,5-trimethylhexanoate (166.0°C), tert-butyl perlaurate (159.4°C), tert-butyl isopropyl peroxide (158.8°C), tert-butyl peroxide-2-ethylhexyl peroxide (161.4°C), tert-hexyl peroxide (160.3°C), 2,5-dimethyl-2,5-di(benzoyl peroxide)hexane (158.2°C), and tert-butyl peracetate (159.9°C). The following substances were tested: 2,2-di(tert-butylperoxy)butane (159.9℃), tert-butyl peroxybenzoate (166.8℃), n-butyl 4,4-di(tert-butylperoxy)valerate (172.5℃), di(2-tert-butylperoxyisopropyl)benzene (175.4℃), dicumyl peroxide (175.2℃), ditert-hexyl peroxide (176.7℃), 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (179.8℃), 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-yne (194.3℃), and tert-butylcumyl peroxide (173.3℃).

[0240] Regarding the content of the aforementioned organic peroxide, from the perspective of improving the reaction rate, relative to 100 parts by mass of the total crosslinking agent (including the total mass of the crosslinking agent including triallyl isocyanurate and triallyl cyanurate), it is preferably 0.05 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1.0 parts by mass or more, and particularly preferably 1.5 parts by mass or more. Furthermore, from the perspective of suppressing the dielectric constant and dielectric loss tangent of the obtained cured product to a low level, relative to 100 parts by mass of the total crosslinking agent, the content of the aforementioned organic peroxide is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and further preferably 4.5 parts by mass or less.

[0241] Furthermore, relative to 100 parts by mass of the aforementioned crosslinking agent, the content of the aforementioned organic peroxide is preferably 0.1 parts by mass or more and 50 parts by mass or less, more preferably 1.0 parts by mass or more and 25 parts by mass or less, even more preferably 2.0 parts by mass or more and 22.5 parts by mass or less, even more preferably 3.0 parts by mass or more and 21.5 parts by mass or less, and particularly preferably greater than 5.0 parts by mass and less than 20 parts by mass. By setting this content to 0.1 parts by mass or more, there is a tendency to improve the reaction rate, and by setting this content to 50 parts by mass or less, there is a tendency to suppress the dielectric constant and dielectric loss tangent of the obtained cured product to be lower.

[0242] Furthermore, relative to 100 parts by mass of the total mass of triallyl isocyanurate and / or triallyl cyanurate, the content of the aforementioned organic peroxide is preferably 0.1 parts by mass or more and 50 parts by mass or less, more preferably 1.0 parts by mass or more and 25 parts by mass or less, even more preferably 2.0 parts by mass or more and 22.5 parts by mass or less, even more preferably 3.0 parts by mass or more and 21.5 parts by mass or less, and particularly preferably greater than 5.0 parts by mass and less than 20 parts by mass. By setting this content to 0.1 parts by mass or more, there is a tendency to improve the reaction rate, and by setting this content to 50 parts by mass or less, there is a tendency to suppress the dielectric constant and dielectric loss tangent of the obtained cured product to be lower.

[0243] (Multifunctional methacrylic acid compounds)

[0244] In addition to components (A), (B), (B'), and (C) described above, the resin composition of this embodiment preferably further contains (D) a polyfunctional methacrylic acid compound. This is because it can improve the dielectric properties, heat resistance, and solvent resistance of the resin composition and its cured product.

[0245] Here, there is no particular limitation as long as the above-mentioned multifunctional methacrylic acid compounds have an average of more than one methacryloyl functional group in one molecule. From the perspective of cross-linking reaction, it is preferred that they have an average of more than two methacryloyl functional groups in one molecule. They can be composed of one compound or two or more compounds.

[0246] As the aforementioned multifunctional methacrylate compounds, examples such as tricyclodecanediethanol dimethacrylate (DCP), trimethylolpropane trimethacrylate (TMPT), ethoxylated bisphenol A dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, neopentyl glycol dimethacrylate, etc., can be used.

[0247] Furthermore, among these compounds, those selected from tricyclodecanediethanol dimethacrylate (DCP) and trimethylolpropane trimethacrylate (TMPT) are preferred due to their excellent compatibility with polyphenylene ether. Further addition of these multifunctional methacrylate compounds can further improve the dielectric properties, heat resistance, and solvent resistance of the resin composition and its cured product.

[0248] From the perspective of improving processability by reducing the viscosity of the varnish in the process of mixing the resin composition with the solvent, and from the perspective of reducing the melt viscosity of the resin composition in the thermosetting process and increasing the crosslinking reaction rate, the aforementioned polyfunctional methacrylic acid compound preferably has a molecular weight of less than 1000, more preferably less than 800, and even more preferably less than 500. By using a low molecular weight polyfunctional methacrylic acid compound, a resin composition and its cured product with excellent electrical properties, heat resistance, and solvent resistance can be obtained in this embodiment.

[0249] Furthermore, in the resin composition of this embodiment, from the viewpoint of further improving the dielectric properties, heat resistance, and solvent resistance of the resin composition and the cured product, the content of the polyfunctional methacrylic compound (D) is preferably 20% to 80% by weight or less, more preferably 25% to 75% by weight or less, and even more preferably 30% to 70% by weight or less, relative to the total amount of (B) triallyl isocyanurate and / or triallyl cyanurate and the polyfunctional methacrylic compound (D) above 100 parts by weight.

[0250] In the case of including (B') crosslinking agents other than triallyl isocyanurate and triallyl cyanurate, the resin composition of this embodiment is superior in terms of the compatibility of the crosslinking agent with polyphenylene ether, the coatability of the resin composition, and the characteristics of the mounted electronic circuit board. Relative to the total amount of (A) polyphenylene ether A and (E) polyphenylene ether B, (B) triallyl isocyanurate and / or triallyl cyanurate, (D) polyfunctional methacrylate compound, and (B') other crosslinking agents, the content of (A) polyphenylene ether A and (E) polyphenylene ether B is preferably 40% to 80% by weight, more preferably 45% to 80% by weight, and even more preferably 50% to 80% by weight.

[0251] (Thermoplastic resin)

[0252] The resin composition of this embodiment may further comprise a thermoplastic resin.

[0253] The aforementioned thermoplastic resin is preferably at least one selected from the group consisting of block copolymers of vinyl aromatic compounds and olefinic compounds and their hydrogenates (hydrogenated block copolymers obtained by hydrogenating block copolymers of vinyl aromatic compounds and olefinic compounds), and homopolymers of vinyl aromatic compounds. The content of vinyl aromatic compound units in the aforementioned block copolymers or their hydrogenates is preferably 20% by mass or more, more preferably 22% by mass or more, and can be 99% by mass or less. By making the content of vinyl aromatic compound units in the aforementioned block copolymers or their hydrogenates 20% by mass or more, there is a tendency to further improve compatibility with polyphenylene ether and further improve the adhesion strength to metal foil.

[0254] As for the aforementioned vinyl aromatic compounds, any compound that has an aromatic ring and a vinyl group within its molecule is acceptable; examples include styrene. As for olefinic compounds, any olefin that has a straight-chain or branched structure within its molecule is acceptable; examples include ethylene, propylene, butene, isobutene, butadiene, and isoprene. Among these, the thermoplastic resin, from the perspective of superior compatibility with polyphenylene ether, is preferably selected from at least one of the group consisting of styrene-butadiene block copolymers, styrene-ethylene-butadiene block copolymers, styrene-ethylene-butene block copolymers, styrene-butadiene-butene block copolymers, styrene-isoprene block copolymers, styrene-ethylene-propylene block copolymers, styrene-isobutylene block copolymers, hydrides of styrene-butadiene block copolymers, hydrides of styrene-ethylene-butadiene block copolymers, hydrides of styrene-butadiene-butene block copolymers, hydrides of styrene-isoprene block copolymers, and homopolymers of styrene (polystyrene), and more preferably one or more of the group consisting of styrene-butadiene block copolymers, hydrides of styrene-butadiene block copolymers, and polystyrene.

[0255] There is no particular limitation on the hydrogenation rate in the above hydrides, and some carbon-carbon unsaturated double bonds from olefin compounds may remain.

[0256] The weight-average molecular weight of the aforementioned thermoplastic resin is preferably 10,000 to 300,000, more preferably 20,000 to 290,000, and even more preferably 30,000 to 280,000. By having a weight-average molecular weight of 10,000 or more, the resin composition of this embodiment tends to have superior heat resistance after curing. By having a weight-average molecular weight of 300,000 or less, the resin composition of this embodiment tends to have better resin flowability during heat molding. The weight-average molecular weight is determined by the method described in the examples described later.

[0257] Based on a total of 100 parts by mass of polyphenylene ether and crosslinking agent, the content of the aforementioned thermoplastic resin is preferably 2 to 20 parts by mass, more preferably 3 to 19 parts by mass, further preferably 4 to 18 parts by mass, and particularly preferably 5 to 17 parts by mass. By setting this content to 2 parts by mass or more, the resin composition of this embodiment tends to exhibit better low dielectric constant, low dielectric loss tangent, and adhesion to metal foil after curing. By setting the content to 20 parts by mass or less, the resin composition of this embodiment tends to exhibit better resin flowability during heat molding. Furthermore, from the same perspective, based on a total of 100 parts by mass of polyphenylene ether and crosslinking agent, the content of the thermoplastic resin is preferably 2 to 20 parts by mass, more preferably 3 to 19 parts by mass.

[0258] It should be noted that the resin composition of this embodiment may also contain thermoplastic resins other than those of the types and weight-average molecular weights described above.

[0259] (Flame retardant)

[0260] The resin composition of this embodiment preferably further comprises a flame retardant.

[0261] As for the aforementioned flame retardant, from the perspective of improving heat resistance, there are no particular limitations as long as it is incompatible with other components in the resin composition after curing. Preferably, the flame retardant is incompatible with the polyphenylene ether and / or crosslinking agent in the resin composition after curing. Examples of flame retardants include: inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, and zinc borate; aromatic bromine compounds such as hexabromobenzene, decabromodiphenyl ethane, 4,4-dibromobiphenyl, and ethylene bis(tetrabromophthalimide); and phosphorus-based flame retardants such as resorcinol bis(diphenyl phosphate) and resorcinol bis(di(dimethylphenyl) phosphate). These flame retardants can be used alone or in combination of two or more. Among these, decabromodiphenyl ethane is preferred from the perspective of superior compatibility with polyphenylene ether, better coatability of the resin composition, and superior properties of the mounted electronic circuit board.

[0262] The content of the aforementioned flame retardant is not particularly limited. From the perspective of maintaining the flame retardancy rating of V-0 in UL Standard 94, the content of the flame retardant is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, relative to 100 parts by mass of the total polyphenylene ether resin and crosslinking agent. In addition, from the perspective of maintaining a low dielectric loss tangent of the obtained cured product (preferably from the perspective of further maintaining a low dielectric constant), the content of the flame retardant is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less.

[0263] (Silica filler)

[0264] The resin composition of this embodiment may further contain silica filler. Examples of silica fillers include natural silica, molten silica, synthetic silica, amorphous silica, AEROSIL, and hollow silica. The silica filler content may be 10 to 300 parts by weight relative to 100 parts by weight of the total polyphenylene ether and crosslinking agent. Furthermore, the silica filler may be a substance whose surface has been surface-treated using a silane coupling agent or the like.

[0265] In addition to the flame retardant and silica filler described above, the resin composition of this embodiment may further include additives such as heat stabilizers, antioxidants, UV absorbers, surfactants, and lubricants, as well as solvents. When the resin composition of this embodiment contains a solvent, it can be in the form of a varnish in which the solid components of the resin composition are dissolved or dispersed in the solvent, and a resin film can be formed from the resin composition of this embodiment.

[0266] (solvent)

[0267] The resin composition of this embodiment may further contain a solvent. From the perspective of solubility, aromatic compounds such as toluene and xylene, methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone, and chloroform are preferred as solvents. One of these solvents may be used alone, or two or more may be used in combination.

[0268] <Resin Film>

[0269] The resin film of this embodiment comprises the resin composition of this embodiment.

[0270] The method of manufacturing the membrane is not particularly limited; for example, it can be obtained by molding the resin composition of this embodiment into a membrane or sheet.

[0271] <Prepreg>

[0272] The prepreg in this embodiment is a composite of a substrate and a resin composition of this embodiment, which can be impregnated or coated onto the substrate. The method for manufacturing the prepreg is not particularly limited; for example, it can be obtained by impregnating the substrate in a resin composition (varnish) containing a solvent, followed by drying to remove the solvent components using a hot air dryer or similar method.

[0273] Examples of suitable substrates include: various glass cloths such as untwisted roving, cloth, chopped strand mat, and surface mat; asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloths; textiles or nonwovens made from liquid crystal fibers such as fully aromatic polyamide fibers, fully aromatic polyester fibers, and polybenzoxazole fibers; natural fiber cloths such as cotton cloth, linen cloth, and felt; natural cellulose substrates such as carbon fiber cloth, kraft paper, cotton paper, and cloths made from paper-glass blended filaments; polytetrafluoroethylene porous membranes; and so on. Glass cloth is preferred. These substrates can be used individually or in combination of two or more.

[0274] In this embodiment, the proportion of the solid component (components other than the solvent in the resin composition) of the prepreg is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. By setting the above proportion to 30% by mass or more, the prepreg tends to have superior insulation reliability when used in applications such as electronic substrates. By setting the above proportion to 80% by mass or less, the prepreg tends to have superior mechanical properties such as flexural modulus in applications such as electronic substrates.

[0275] Metal-coated laminates

[0276] The metal-clad laminate of this embodiment can be obtained by laminating and curing the resin composition, resin film, or prepreg of this embodiment with a metal foil. The metal-clad laminate of this embodiment preferably has a form in which a cured prepreg (hereinafter also referred to as a "cured composite") and a metal foil are laminated and bonded together, and it can be suitable as a material for electronic substrates. Examples of metal foils include aluminum foil and copper foil, among which copper foil is preferred due to its low resistance. The cured composite combined with the metal foil can be a single sheet or multiple sheets, and depending on the application, the metal foil is stacked on one or both sides of the composite and processed into a laminate.

[0277] As a method for manufacturing the metal-clad laminate of this embodiment, one example is the following method: forming a composite material (e.g., the prepreg described above) consisting of a resin composition and a substrate, overlapping it with a metal foil, and then curing the resin composition to obtain a laminate formed by laminating the cured laminate with the metal foil. One particularly preferred application of the above-described metal-clad laminate is as a printed wiring board. In the printed wiring board, it is preferable to remove at least a portion of the metal foil from the metal-clad laminate.

[0278] Printed wiring board

[0279] In the printed wiring board of this embodiment, a portion of the metal foil is removed from the metal-clad laminate of this embodiment. The printed wiring board of this embodiment is typically formed by a pressure-heat molding method using the prepreg of the present invention described above. As the substrate, the same substrate as described above for the prepreg can be cited. The printed wiring board of this embodiment, by comprising the resin composition of this embodiment, exhibits excellent copper foil peel strength and toluene resistance.

[0280] Example

[0281] The following describes this embodiment in further detail based on the embodiments, but this embodiment is not limited to the following embodiments.

[0282] <Polyphenylene ether>

[0283] (Manufacturing example)

[0284] • Manufacturing Example 1: Polyphenylene Ether 1 (PPE1)

[0285] Using a 40-liter jacketed polymerization reactor equipped with a nozzle for introducing oxygen-containing gas, a turbine agitator, and a baffle plate at the bottom, and a reflux cooler on the exhaust line at the top of the reactor, the following substances were added to the reactor while nitrogen was being blown in at a flow rate of 46.3 L / min: 3.6 g of divalent copper oxide, 27.1 g of a 47% (w / w) aqueous solution of hydrogen bromide, 8.7 g of di-tert-butylethylenediamine, 42.0 g of di-n-butylamine, 128.0 g of butyldimethylamine, 14.6 kg of toluene, and 2.0 g of trioctylmethylammonium chloride (R = C8-C). 10 A homogeneous solution was prepared. Next, using a pump, 647.8 g of 2-tert-butyl-5-methylphenol, 2352.3 g of 2,6-dimethylphenol, and 2.35 kg of toluene were added dropwise to the polymerization reactor over 35 minutes. Simultaneously, dry air was introduced into the polymerization solution from the bottom of the reactor at a rate of 31.5 L / min using a nozzle to initiate polymerization. Dry air was introduced for 240 minutes to obtain the polymerization mixture. It should be noted that the internal temperature was controlled at 40°C during polymerization. The polymerization mixture (polymer solution) at the end of polymerization was a homogeneous solution.

[0286] The drying air supply was then stopped, and 38.73 g of sodium ethylenediaminetetraacetic acid (EDTA-4) (a reagent prepared by Tongren Chemical Research Institute) was added to the polymerization mixture in the form of a 2 kg aqueous solution. The polymerization mixture was stirred at 70 °C for 240 minutes, then allowed to stand for 20 minutes, and the organic phase was separated from the aqueous phase by liquid-liquid separation. The organic phase was then concentrated using a rotary evaporator until the polymer concentration reached 30% by mass.

[0287] The concentrated solution was mixed with methanol at a mass ratio of 4 (methanol to polymer solution) to precipitate the polymer. The precipitated polyphenylene ether was obtained by vacuum filtration using a glass filter. The precipitated polyphenylene ether was then washed three times with methanol at a mass ratio of 4 (methanol to precipitated polyphenylene ether). The precipitated polyphenylene ether was then maintained at 140°C and 1 mmHg for 120 minutes to obtain dried polyphenylene ether (PPE1).

[0288] • Manufacturing Example 2: Polyphenylene oxide 2 (PPE2)

[0289] After initiating polymerization, dry air was introduced for 200 minutes, and otherwise the operation was carried out using the same method as in Manufacturing Example 1 to obtain polyphenylene ether (PPE2).

[0290] • Manufacturing Example 3: Polyphenylene oxide 3 (PPE3)

[0291] Except for the addition solution containing 928.3 g of 2-tert-butyl-5-methylphenol, 2071.7 g of 2,6-dimethylphenol and 2.07 kg of toluene, the same method as in Manufacturing Example 1 was used to obtain polyphenylene ether (PPE3).

[0292] • Manufacturing Example 4: Polyphenylene oxide 4 (PPE4)

[0293] Except for the addition solution containing 1096.6 g of 2-tert-butyl-5-methylphenol, 1903.4 g of 2,6-dimethylphenol and 1.90 kg of toluene, the same method as in Manufacturing Example 1 was used to obtain polyphenylene ether (PPE4).

[0294] • Manufacturing Example 5: Polyphenylene Ether 5 (PPE5)

[0295] Except for the addition solution containing 1417.9 g of 2-tert-butyl-5-methylphenol, 1582.1 g of 2,6-dimethylphenol and 1.58 kg of toluene, the same method as in Manufacturing Example 1 was used to obtain polyphenylene ether (PPE5).

[0296] • Manufacturing Example 6: Polyphenylene oxide 6 (PPE6)

[0297] The PPE6 uses "XYRON S203A" manufactured by Asahi Kasei Corporation.

[0298] • Manufacturing Example 7: Polyphenylene Ether 7 (PPE7)

[0299] Except for the addition solution containing 314.0 g of 2-tert-butyl-5-methylphenol, 2686.0 g of 2,6-dimethylphenol and 2.68 kg of toluene, the same method as in Manufacturing Example 1 was used to obtain polyphenylene ether (PPE7).

[0300] • Manufacturing Example 8: Polyphenylene oxide 8 (PPE8)

[0301] A 40-liter jacketed polymerization reactor, equipped with a nozzle for introducing oxygen-containing gas at the bottom, a turbine agitator, and a baffle plate, and with a reflux cooler on the exhaust line at the top, was used to prepare a homogeneous solution. This solution consisted of 2.4 g of divalent copper oxide, 18.1 g of a 47% (w / w) aqueous solution of hydrogen bromide, 5.8 g of di-tert-butylethylenediamine, 28.1 g of di-n-butylamine, 85.6 g of butyldimethylamine, 17.9 kg of toluene, 1903.4 g of 2,6-dimethylphenol, and 1096.6 g of 2-tert-butyl-5-methylphenol. Next, dry air was introduced into the reactor at a rate of 10.5 L / min using a nozzle to initiate polymerization. After 120 minutes of dry air circulation, a polymerization mixture was obtained. It should be noted that the internal temperature was controlled at 20°C during polymerization. At the end of polymerization, the polymer mixture (polymer solution) is in a homogeneous solution state.

[0302] Stop the flow of dry air and add 25.9 g of sodium ethylenediaminetetraacetic acid (EDTA-4) (a reagent prepared by Tongren Chemical Research Institute) to the polymerization mixture as an aqueous solution in 2 kg of water. Stir the polymerization mixture at 70°C for 150 minutes, then let it stand for 20 minutes to separate the organic and aqueous phases via liquid-liquid separation. Concentrate the organic phase using a rotary evaporator until the polymer concentration reaches 25% by mass.

[0303] The above solution was mixed with methanol at a ratio of 6:1 (methanol to polymer solution) to precipitate the polymer. The precipitated polyphenylene ether was obtained by vacuum filtration using a glass filter. The precipitated polyphenylene ether was then further washed with methanol at a ratio of 3:1 (methanol to precipitated polyphenylene ether). This washing operation was performed three times. The precipitated polyphenylene ether was then kept at 140°C and 1 mmHg for 120 minutes to obtain dried polyphenylene ether 8 (PPE8).

[0304] • Manufacturing Example 9: Polyphenylene Ether 9 (PPE9)

[0305] Except for the addition solution containing 1720.3 g of 2-tert-butyl-5-methylphenol, 1279.7 g of 2,6-dimethylphenol and 2.68 kg of toluene, the same method as in Manufacturing Example 1 was used to obtain polyphenylene ether 9 (PPE9).

[0306] • Manufacturing Example 9': Modified Polyphenylene Ether 9 (Modified PPE 9)

[0307] In a 500 mL three-necked flask equipped with a temperature regulator, stirrer, cooling device, and dropping funnel, 50 g of polyphenylene ether 7 (PPE7) prepared by the above-described method, 50 g of toluene, 10.2 g of chloromethylstyrene (p-chloromethylstyrene to m-chloromethylstyrene ratio of 50 / 50, manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.43 g of tetrabutylammonium bromide were added. The mixture was then stirred to dissolve, and the liquid temperature was set to 85°C. A sodium hydroxide aqueous solution (7.12 g sodium hydroxide / 7.12 g water) was added dropwise to the mixture over 1 hour, and stirring was continued at 85°C for another 5 hours.

[0308] Next, the obtained aqueous layer was removed using a separatory funnel, yielding a toluene layer (polymer solution) containing the polymer. This toluene was mixed with methanol at a ratio of 10 to the polymer solution to precipitate the polymer. The resulting wetted polyphenylene ether was obtained by vacuum filtration using a glass filter. The wetted polyphenylene ether was further cleaned using a cleaning solvent (methanol:water = 80:20) at a ratio of 2.5 to the wetted polyphenylene ether. This cleaning operation based on the methanol-water mixture was performed three times, followed by cleaning the wetted polyphenylene ether with methanol at a ratio of 2.5 to the wetted polyphenylene ether.

[0309] After performing the above methanol-based cleaning operation twice, the moistened polyphenylene ether was kept at 100°C and 1 mmHg for 8 hours to obtain the dried modified polyphenylene ether 9 (modified PPE9).

[0310] It should be noted that, to conduct 1 ¹H NMR measurements confirmed the presence of proton peaks originating from styrene-based olefins, indicating that the hydroxyl groups were modified into styrene groups.

[0311] • Manufacturing Example 10: Polyphenylene oxide 10 (PPE10)

[0312] A 1.5-liter jacketed reactor with a nozzle for introducing oxygen-containing gas at the bottom, a turbine agitator, and baffles, and a reflux cooler on the exhaust line at the top of the reactor, was used. A pre-prepared mixture of 0.10 g of cuprous oxide and 0.77 g of 47% hydrogen bromide, along with 0.25 g of N,N'-di-tert-butylethylenediamine, 3.62 g of dimethyl-n-butylamine, 1.19 g of di-n-butylamine, 894 g of toluene, 79.45 g of 2,6-dimethylphenol, and 20.55 g of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, was then introduced into the reactor via the nozzle at a rate of 1.05 L / min while vigorous stirring. Simultaneously, a heat transfer medium was circulated within the jacket to regulate the polymerization temperature and maintain it at 20°C. After introducing air for 150 minutes, the air supply was stopped, and the reactor was purged with nitrogen. Then, 1.10 g of tetrasodium ethylenediaminetetraacetate tetrahydrate (a reagent prepared by Tongjin Chemical Research Institute) was added to the polymerization mixture as an aqueous solution of 100 g of water. The mixture was then heated to 70°C and copper extraction was performed at 70°C for 2 hours. Subsequently, the mixture was separated by settling into an unmodified polyphenylene ether solution (organic phase) and an aqueous phase containing the transferred catalyst metal. The organic phase was concentrated using a rotary evaporator until the polymer concentration reached 25% by mass.

[0313] The above solution was mixed with methanol at a ratio of 6:1 (methanol to polymer solution) to precipitate the polymer. The precipitated polyphenylene ether was obtained by vacuum filtration using a glass filter. The precipitated polyphenylene ether was further washed with methanol at a ratio of 3:1 (methanol to precipitated polyphenylene ether). This washing operation was performed three times. The precipitated polyphenylene ether was then kept at 140°C and 1 mmHg for 120 minutes to obtain dried polyphenylene ether 10 (PPE10).

[0314] • Manufacturing Example 10': Modified Polyphenylene Ether 10 (Modified PPE 10)

[0315] Using a 500 mL three-necked flask equipped with a nitrogen inlet line at the top of the reactor and a reflux cooler at the exhaust line at the top of the reactor, after purging the reactor with nitrogen, 20 g of polyphenylene ether 8 (PPE8) and 0.25 g of 4-dimethylaminopyridine, prepared using the above-described method, were added. While stirring, 5.7 mL of triethylamine was added using a syringe. Then, 2.0 mL of methacryloyl chloride was collected in the syringe and added dropwise to the system at room temperature. After the addition was complete, the flask was heated in an oil bath for 1 hour with continuous stirring at 90°C. The reaction was then further heated in an oil bath under reflux. Heating was stopped after 4 hours following the start of reflux, and the mixture was allowed to return to room temperature before adding 0.66 g of methanol to stop the reaction. The reaction solution was then filtered through a glass filter to obtain a solution free of the byproduct triethylammonium salt. This solution was mixed with methanol at a methanol-to-polymer solution ratio of 10 to precipitate the polymer. Moistened polyphenylene ether (PPE) was obtained by vacuum filtration using a glass filter. The moistened PPE was then further washed with methanol in a methanol-to-PPE ratio of 2.5. This washing operation was performed three times. The moistened PPE was then kept at 100°C and 1 mmHg for 8 hours to obtain dried modified PPE 10 (modified PPE 10). It should be noted that... 1 ¹H NMR measurements confirmed the presence of a proton peak originating from the olefin of the methacryloyl group, indicating that the hydroxyl group was modified into a methacryloyl group.

[0316] • Manufacturing Example 11: Polyphenylene oxide 11 (PPE11)

[0317] Except for using 71.92 g of 2,6-dimethylphenol and 28.08 g of 4,4'-dihydroxy-2,2',3,3',5,5'-hexamethylbiphenyl, the same method as in Manufacturing Example 8 was used to obtain polyphenylene ether 11 (PPE11).

[0318] • Manufacturing Example 11': Modified Polyphenylene Ether 11 (Modified PPE 11)

[0319] Except for using polyphenylene ether 11 (PPE11) produced by the above manufacturing method as a raw material, the modified polyphenylene ether 11 (modified PPE11) was obtained by performing the same operation as in manufacturing example 9'.

[0320] (Analysis of polyphenylene ether)

[0321] The following analysis was performed on each PPE obtained from the above manufacturing examples. The analysis results are shown in Table 1.

[0322] (1) Specific viscosity of polyphenylene ether (ηsp / c)

[0323] Prepare a chloroform solution of polyphenylene ether at a concentration of 0.5 g / dL, and determine the specific viscosity (ηsp / c) (dL / g) at 30°C using an Ubbelohde viscometer.

[0324] (2) Number-average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of polyphenylene ether

[0325] As the measuring apparatus, gel permeation chromatography (manufactured by Shimadzu Corporation, LC-2030C Plus) was used. A calibration curve was prepared using standard polystyrene and ethylbenzene, and the number-average molecular weight (Mn) of the obtained polyphenylene ether was determined using this calibration curve. Polystyrene with molecular weights of 3,650,000, 2,170,000, 1,090,000, 681,000, 204,000, 52,000, 30,200, 13,800, 3,360, 1,300, and 550 was used as the standard.

[0326] Regarding the column, a column consisting of two K-805L columns manufactured by Showa Denko Co., Ltd. connected in series was used. Chloroform was used as the solvent, and the measurement was conducted at a flow rate of 1.0 mL / min and a column temperature of 40°C. A 1 g / L chloroform solution of polyphenylene ether was prepared as the sample for the measurement. Regarding the UV wavelength of the detection section, it was 254 nm for standard polystyrene and 283 nm for polyphenylene ether.

[0327] Based on the above measurement data, the number-average molecular weight (Mn) (g / mol), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were calculated according to the proportion of the peak area of ​​the curve representing the molecular weight distribution obtained by GPC.

[0328] (3) Number of OH groups in polyphenylene ether

[0329] Weigh 5.0 mg of polyphenylene ether. Then, dissolve the weighed polyphenylene ether in 25 mL of dichloromethane. Add 150 μL of ethanol solution containing 2% tetraethylammonium hydroxide (TEAH) relative to 2.0 mL of the prepared solution, and then measure the absorbance (Abs) at 318 nm using a UV spectrophotometer (Hitachi, U-3210 type) (using an absorbance measuring dish with a dish length of 1 cm). Then, based on the measurement result, calculate the OH base number obtained from the absorbance using the following mathematical formula (1).

[0330] OH radical (μmol / g) = [(25×Abs) / (ε×5)]×10 6 ...Mathematical formula (1)

[0331] (Here, ε represents the absorptivity, which is 4700 L / mol·cm.)

[0332] (4) The number of OH groups per molecule of polyphenylene ether

[0333] Using the number-average molecular weight obtained by gel permeation chromatography (details described in (2) above), the number of OH groups per molecule of polyphenylene ether is determined by the following mathematical formula (2).

[0334] Average number of hydroxyl groups per molecule (molecule / molecule) = (number average molecular weight obtained by gel permeation chromatography) × (number of OH groups obtained from absorbance) / 10 6 ...Mathematical formula (2)

[0335] (5) Long-term solubility relative to toluene (TL solubility)

[0336] Weigh 5.0 g of polyphenylene ether and 5.0 g of toluene into a transparent glass screw-in tube. Mix at 20°C using a stir bar and a magnetic stirrer. Verify the solution after one day, judging its quality according to the following criteria.

[0337] 〇: The solution remains transparent

[0338] △: Slight presence of insoluble matter

[0339] ×: Clearly insoluble or containing a large amount of insoluble components

[0340]

[0341] <Ingredients other than polyphenylene ether>

[0342] (Trylyl isocyanurate and / or triallyl cyanurate)

[0343] • Triallyl isocyanurate (Product name: TAIC, manufactured by Tokyo Chemical Industry Co., Ltd., number average molecular weight: 249.3, number of intramolecular unsaturated double bonds: 3)

[0344] (Organic peroxides)

[0345] • Bis(1-tert-butylperoxide-1-methylethyl)benzene (product name: Perbutyl P, manufactured by Nippon Yushu Co., Ltd., 1-minute half-life temperature: 175.4℃)

[0346] (Multifunctional methacrylic acid compounds)

[0347] • Tricyclodecanediethanol dimethacrylate (Product name: DCP, manufactured by Tokyo Chemical Industry Co., Ltd., number average molecular weight: 332.4, number of intramolecular methacrylamide functional groups: 2)

[0348] • Trimethylolpropane trimethacrylate (Product name: TMPT, manufactured by Tokyo Chemical Industry Co., Ltd., number average molecular weight: 338.4, number of intramolecular methacrylamide functional groups: 3)

[0349] (Thermoplastic resin)

[0350] • Hydrogenated styrene-based thermoplastic resin (SEBS) (Product name: Tuftec H1041, manufactured by Asahi Kasei Corporation, weight average molecular weight: approx. 90,000, styrene unit content: 32% by mass)

[0351] (Flame retardant)

[0352] • Decabromodiphenyl ethane (product name: SAYTEX 8010, manufactured by Albemarle)

[0353] (filler)

[0354] • Spherical silica (product name: SO-C6, manufactured by Admatechs)

[0355] [Example A]

[0356] As shown below, cured products of the resin compositions of each embodiment and comparative example were prepared.

[0357] (Example 1)

[0358] According to the composition and solvent shown in Table 2, thermoplastic resin was added relative to 205 parts by mass of toluene, and the mixture was stirred and dissolved. Then, flame retardant, spherical silica, and PPE1 synthesized by the above method were added, and stirring was continued until PPE1 dissolved. Next, triallyl isocyanurate and organic peroxide were added to the solution, and the mixture was stirred thoroughly to obtain a varnish.

[0359] After the obtained varnish is impregnated into L-sized glass cloth, the excess varnish is scraped off by passing it through a slit of a specified width. The cloth is then dried in a drying oven at 130°C for a specified time to remove toluene, thereby obtaining the prepreg.

[0360] The obtained prepreg is cut to a specified size, and a specified number of sheets are stacked. Copper foil (manufactured by Furukawa Electric Industries, Ltd., 18μm thick, F1N-WS foil) is then stacked on both sides of the stacked prepreg. Vacuum pressing is performed in this state to obtain a copper-clad laminate. In the vacuum pressing process, firstly, a pressure of 40 kg / cm² is applied to one side... 2 The pressure was applied while the temperature was increased from 30°C to 200°C at a rate of 2°C / min. After reaching 200°C, a pressure of 40 kg / cm² was applied. 2 It is kept at 200℃ for 60 minutes under pressure.

[0361] Subsequently, the copper-clad laminate obtained above is etched to remove the copper foil, thereby obtaining a laminate as a sample.

[0362] (Examples 2-6, Comparative Examples 1-4)

[0363] Except for the changes in resin composition shown in Table 2, resin compositions, varnishes, prepregs, and copper-clad laminates were obtained under the same conditions as in Example 1.

[0364] It should be noted that for Comparative Example 1, which used PPE6, and Comparative Example 2, which used PPE7, the PPE was not completely dissolved in toluene, making it impossible to fabricate prepreg and copper-clad laminate.

[0365] <Evaluation>

[0366] The following evaluation was performed on each sample obtained in the above embodiments and comparative examples.

[0367] (1) Peel strength of the cured copper foil of the resin composition (peel strength N / mm)

[0368] The stress was measured when the copper foil of the copper-clad laminate was peeled off at a fixed speed. The copper-clad laminate obtained in the above examples and comparative examples, which used 18μm thick copper foil (manufactured by Furukawa Electric Industries, Ltd., F1N-WS foil), was cut into dimensions of 10mm width × 120mm length. Using Autograph (manufactured by Shimadzu Corporation, AG-I20kN), the average load when the copper foil was peeled off at a speed of 50mm / min at an angle of 90° relative to the removal surface was measured, and the average value of 3 measurements was obtained.

[0369] It should be noted that, from the perspective of preventing wire stripping, the calculated copper foil peel strength of the cured resin composition is preferably 0.39 N / mm or more, more preferably 0.52 N / mm or more, further preferably 0.55 N / mm or more, and particularly preferably 0.60 N / mm or more.

[0370] (2) Toluene immersion test

[0371] The cured resin compositions with a thickness of about 0.5 mm obtained in the above examples and comparative examples were cut into lengths of 50 mm and widths of 5 mm. After being impregnated in a sufficient amount of toluene at 20°C for 24 h, the reduction in mass was evaluated according to the following criteria.

[0372] 〇: The mass reduction before and after impregnation is less than 0.5% by mass.

[0373] △: Cases where the mass reduction before and after impregnation is greater than 0.5% and less than 1% by mass.

[0374] ×: Cases where the mass reduction before and after impregnation is more than 1% by mass.

[0375]

[0376] As shown in Tables 1 and 2, PPEs 1 to 4 exhibit excellent solubility in toluene, and by using them, resin compositions with excellent copper foil peel strength and toluene resistance can be obtained.

[0377] [Example B]

[0378] As shown below, cured products of the resin compositions of each embodiment and comparative example are prepared.

[0379] (Example 7)

[0380] According to the composition shown in Table 3, PPE1 synthesized by the above method was added relative to 102 parts by mass of toluene, and stirred until PPE1 dissolved. Then, triallyl isocyanurate, a polyfunctional methacrylate compound, and an organic peroxide were added separately, and stirred thoroughly to obtain a varnish.

[0381] After the obtained varnish is impregnated into the low dielectric glass cloth, the excess varnish is scraped off by passing it through a slit of a specified width. The cloth is then dried in a drying oven at 130°C for a specified time to remove toluene, thereby obtaining the prepreg.

[0382] The obtained prepreg is cut to a specified size, and a specified number of sheets are stacked. Copper foil (manufactured by Furukawa Electric Industries, Ltd., 18μm thick, F1N-WS foil) is then stacked on both sides of the stacked prepreg. Vacuum pressing is performed in this state to obtain a copper-clad laminate. In the vacuum pressing process, firstly, a pressure of 40 kg / cm² is applied to one side... 2 The pressure was applied while the temperature was increased from 30°C to 200°C at a rate of 2°C / min. After reaching 200°C, a pressure of 40 kg / cm² was applied. 2 It is kept at 200℃ for 60 minutes under pressure.

[0383] Subsequently, the copper-clad laminate obtained above is etched to remove the copper foil, thereby obtaining a laminate as a sample.

[0384] (Examples 8-15, Comparative Examples 5-17)

[0385] Except for the changes in resin composition shown in Tables 3 and 4, the resin composition, varnish, prepreg, and copper-clad laminate were obtained using the same method as in Example 7.

[0386] It should be noted that in Comparative Example 15, which used PPE6, the polyphenylene ether was not completely dissolved in toluene, making it impossible to fabricate prepreg and copper-clad laminate.

[0387] <Evaluation>

[0388] (1) Dielectric properties of the cured resin composition

[0389] For the cured resin compositions obtained in the above examples and comparative examples, the dielectric constant and dielectric loss tangent at 10 GHz were determined using the split cylinder method. As the measuring apparatus, a network analyzer (N5227B, manufactured by KEYSIGHT TECHNOLOGIES) and a split cylinder resonator (CR-710, manufactured by EM Labo Co., Ltd.) were used.

[0390] The cured resin compositions with a thickness of approximately 0.5 mm obtained in the above examples and comparative examples were cut into plates with a length of 50 mm and a width of 50 mm. These plates were then placed in an oven at 105°C ± 3°C and dried for 1 hour, followed by standing at 23°C and 50 ± 2% relative humidity for 24 ± 2 hours. Subsequently, the dielectric constant and dielectric loss tangent were measured using the aforementioned measuring apparatus at 23°C and 50 ± 2% relative humidity.

[0391] It should be noted that, from the perspective of reducing transmission loss, the dielectric loss tangent of the cured resin composition is preferably 0.0053 or less, more preferably 0.0050 or less, and even more preferably 0.0049 or less.

[0392] (2) Heat resistance (glass transition temperature) of the cured resin composition

[0393] For the copper-clad laminates obtained in the above embodiments and comparative examples, dynamic viscoelasticity was measured, and the temperature at which tanδ was maximized was determined as the glass transition temperature (Tg). A dynamic viscoelasticity apparatus (GABO EPLEXOR 500N) was used as the measuring device.

[0394] The cured resin compositions with a thickness of about 0.5 mm obtained in the above examples and comparative examples were cut into pieces with a length of 50 mm and a width of about 10 mm and used as test pieces. The test pieces were measured under tensile mode and a frequency of 5 Hz.

[0395] It should be noted that, from the perspective of dimensional stability in the processing technology, the glass transition temperature of the cured resin composition is preferably 203°C or higher, more preferably 205°C or higher, even more preferably 208°C or higher, and particularly preferably 210°C or higher.

[0396] (3) Solvent resistance of the cured resin composition (toluene immersion test)

[0397] The cured resin compositions with a thickness of about 0.5 mm obtained in the above examples and comparative examples were cut into lengths of 50 mm and widths of 5 mm. After being impregnated in a sufficient amount of toluene at 20°C for 24 h, the reduction in mass was evaluated according to the following criteria.

[0398] 〇: The mass reduction before and after impregnation is less than 0.5% by mass.

[0399] △: Cases where the mass reduction before and after impregnation is greater than 0.5% and less than 1% by mass.

[0400] ×: Cases where the mass reduction before and after impregnation is more than 1% by mass.

[0401]

[0402]

[0403] As shown in Tables 3 and 4, the inclusion of PPEs 1, 2, 4, and 5 indicates excellent solubility in toluene, and the use of these compounds yields resin compositions with excellent dielectric properties, high heat resistance, and excellent solvent resistance. Furthermore, it is evident that, compared to the comparative examples, each of the samples in the examples exhibits a well-balanced and superior performance in terms of dielectric properties, heat resistance, and solvent resistance.

[0404] [Example C]

[0405] As shown below, cured products of the resin compositions of each embodiment and comparative example are prepared.

[0406] (Example 16)

[0407] According to the composition and solvent shown in Table 5, thermoplastic resin was added relative to 101 parts by mass of toluene, and the mixture was stirred and dissolved. Then, flame retardant, spherical silica, and PPE1 and modified PPE10 synthesized by the above method were added, and stirring was continued until PPE1 and modified PPE10 were dissolved. Next, triallyl isocyanurate and / or triallyl cyanurate, as well as organic peroxide, were added to the solution, and the mixture was stirred thoroughly to obtain a varnish.

[0408] After the obtained varnish is impregnated into L-sized glass cloth, the excess varnish is scraped off by passing it through a slit of a specified width. The cloth is then dried in a drying oven at 130°C for a specified time to remove toluene, thereby obtaining the prepreg.

[0409] The obtained prepreg is cut to a specified size, and a specified number of sheets are stacked. Copper foil (manufactured by Furukawa Electric Industries, Ltd., 18μm thick, F1N-WS foil) is then stacked on both sides of the stacked prepreg. Vacuum pressing is performed in this state to obtain a copper-clad laminate. In the vacuum pressing process, firstly, a pressure of 40 kg / cm² is applied to one side... 2 The pressure was applied while the temperature was increased from 30°C to 200°C at a rate of 2°C / min. After reaching 200°C, a pressure of 40 kg / cm² was applied. 2 It is kept at 200℃ for 60 minutes under pressure.

[0410] Subsequently, the copper-clad laminate obtained above is etched to remove the copper foil, thereby obtaining a laminate as a sample.

[0411] (Examples 17-25, Comparative Examples 18-32)

[0412] Except for the changes in resin composition shown in Tables 5 and 6, the resin composition, varnish, prepreg and copper-clad laminate were obtained under the same conditions as in Example 16.

[0413] It should be noted that in Comparative Examples 22 and 23, which used PPE6, the PPE was not completely dissolved in toluene, making it impossible to fabricate prepreg and copper-clad laminate.

[0414] <Evaluation>

[0415] The samples obtained in the above embodiments and comparative examples were evaluated as follows. The evaluation results are shown in Tables 5 and 6.

[0416] (1) Dielectric properties of the cured resin composition

[0417] For the cured resin compositions manufactured in the examples and comparative examples, the dielectric constant and dielectric loss tangent at 10 GHz were determined using the split cylinder method. As the measuring apparatus, a network analyzer (N5227B, manufactured by KEYSIGHT TECHNOLOGIES) and a split cylinder resonator (CR-710, manufactured by EM Labo Co., Ltd.) were used.

[0418] The cured resin composition with a thickness of approximately 0.5 mm, prepared using the above method, was cut into plates with a length of 50 mm and a width of 50 mm. These plates were then placed in an oven at 105℃±3℃ and dried for 1 hour, followed by standing at 23℃ and 50±2% relative humidity for 24±2 hours. Subsequently, the dielectric constant and dielectric loss tangent were measured using the aforementioned measuring apparatus at 23℃ and 50±2% relative humidity.

[0419] It should be noted that, from the perspective of reducing transmission loss, the dielectric loss tangent of the cured resin composition is preferably less than 0.00320, more preferably less than 0.00318, further preferably less than 0.00316, and particularly preferably less than 0.00312.

[0420] (2) Peel strength of the cured copper foil of the resin composition (peel strength N / mm)

[0421] The stress was measured when the copper foil of the copper-clad laminate was peeled off at a fixed speed. The copper-clad laminate obtained in the above examples and comparative examples, which used 18μm thick copper foil (manufactured by Furukawa Electric Industries, Ltd., F1N-WS foil), was cut into dimensions of 10mm width × 120mm length. Using Autograph (manufactured by Shimadzu Corporation, AG-I20kN), the average load when the copper foil was peeled off at a speed of 50mm / min at an angle of 90° relative to the removal surface was measured, and the average value of 3 measurements was obtained.

[0422] It should be noted that, from the perspective of preventing wire stripping, the calculated copper foil peel strength of the cured resin composition is preferably 0.39 N / mm or more, more preferably 0.52 N / mm or more, further preferably 0.55 N / mm or more, and particularly preferably 0.60 N / mm or more.

[0423] (3) Solvent resistance of the cured resin composition (toluene immersion test)

[0424] Cured resin compositions with a thickness of about 0.5 mm obtained in the above examples and comparative examples were cut into lengths of 50 mm and widths of 5 mm. After being impregnated in a sufficient amount of toluene at 20°C for 24 h, their mass reduction was evaluated according to the following criteria.

[0425] 〇: The mass reduction before and after impregnation is less than 0.5% by mass.

[0426] △: Cases where the mass reduction before and after impregnation is greater than 0.5% and less than 1% by mass.

[0427] ×: Cases where the mass reduction before and after impregnation is more than 1% by mass.

[0428]

[0429]

[0430] As shown in Tables 5 and 6, by combining PPE1, 2, 4, and 5 with modified PPE9 to 11, resin compositions and their cured products with excellent dielectric properties, copper foil peel strength, and toluene resistance were obtained.

[0431] Industrial applicability

[0432] The polyphenylene ether-containing resin composition of the present invention exhibits excellent copper foil peel strength and solvent resistance, and therefore has industrial value for use as an electronic material and as a modifier.

Claims

1. A polyphenylene ether, characterized in that, It comprises repeating units of phenol derived from formula (1) below, and repeating units of phenol derived from formula (2) below. The content of repeating units derived from formula (1) and formula (2) is 70 mol% or more and less than 85 mol%, relative to the total of 100 mol% of the repeating units in formula (1) and formula (2) below, and the content of repeating units derived from formula (2) is greater than 15 mol% and less than 30 mol%. The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) ranged from 2.0 to 6.

0. The number of OH groups per molecule is 0.8–2.

5. The specific viscosity (ηsp / c) measured in a chloroform solution with a concentration of 0.5 g / dL at 30℃ is below 0.30 dL / g. [Chemistry 1] ・・・(1) In equation (1), R 11 Each is independently a saturated hydrocarbon group with 1 to 6 carbon atoms, with or without substituents; an aryl group with 6 to 12 carbon atoms, with or without substituents; or a halogen atom, R. 12 Each of the following is independently a hydrogen atom, a hydrocarbon group with 1 to 6 carbon atoms (with or without substituents), an aryl group with 6 to 12 carbon atoms (with or without substituents), or a halogen atom. [Chemistry 2] ・・・(2) In equation (2), R 22 Each of the following groups is independently a hydrogen atom, a saturated or unsaturated hydrocarbon group with or without substituents (1 to 20 carbon atoms), an aryl group with or without substituents (6 to 12 carbon atoms), or a halogen atom, with two R groups. 22 R is not simultaneously a hydrogen atom. 21 The partial structure is represented by the following equation (3). [Chemistry 3] ・・・(3) In equation (3), R 31 Each is independently a straight-chain alkyl group having 1 to 8 carbon atoms, with or without substituents, or with 2 R groups. 31 A cyclic alkyl structure with 1 to 8 carbon atoms bonded together, R 32 Each is an alkylene group having 1 to 8 carbon atoms, with or without substituents; b is independently 0 or 1; R 33 It is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms with or without substituents, or a phenyl group having or without substituents.

2. The polyphenylene ether according to claim 1, characterized in that, The partial structure represented by equation (3) is tert-butyl.

3. The polyphenylene ether according to claim 1, characterized in that, Its specific viscosity (ηsp / c) measured in a chloroform solution with a concentration of 0.5 g / dL at 30℃ is 0.13 dL / g to 0.30 dL / g.

4. The polyphenylene ether according to claim 1, characterized in that, The number of OH groups per 1g of the polyphenylene ether is 100μmol / g to 300μmol / g.

5. The polyphenylene ether as described in claim 1, wherein, The monophenol compound represented by formula (1) is selected from 2,6-dimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, and 2-ethyl-6-chlorophenol. One or more of the group consisting of phenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2-methyl-6-tolylphenol, 2,6-dimethyltolylphenol, 2,3,6-trimethylphenol, 2,3-diethyl-6-n-propylphenol, 2,3,6-tributylphenol, 2,6-di-n-butyl-3-methylphenol, 2,6-dimethyl-3-n-butylphenol, and 2,6-dimethyl-3-tert-butylphenol.

6. The polyphenylene ether according to claim 1, characterized in that, The monophenol compound represented by formula (2) is selected from one or more of the group consisting of 2-isopropyl-5-methylphenol, 2-cyclohexyl-5-methylphenol, 2-tert-butyl-5-methylphenol and 2-isobutyl-5-methylphenol.

7. The polyphenylene ether according to claim 1, characterized in that, It further comprises structural units derived from the following compounds: A phenolic compound selected from the group consisting of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4'-methylenebis(2,6-dimethylphenol), bis(4-hydroxy-3-methylphenyl)sulfide, bis(4-hydroxy-3,5-dimethylphenyl)sulfone, α,α'-bis(4-hydroxy-3,5-dimethylphenyl)-1,4-diisopropylbenzene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane and 1,1-bis(2-methyl-4-hydroxy-5-tert-butylphenyl)butane having two phenolic units within the molecule; or The following are selected from 4,4'-[(3-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(3-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(4-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4'-[(2-hydroxy-3-methoxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[(4-hydroxy-3-ethoxyphenyl)methylene]bis(2,3,6-trimethylethylphenol), 4,4'-[(3,4-dihydroxyphenyl)methylene]bis(2,6-dimethylphenol), 4,4'-[( 3,4-Dihydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 2,2'-[(4-hydroxyphenyl)methylene]bis(3,5,6-trimethylphenol), 4,4'-[4-(4-hydroxyphenyl)cyclohexylidene]bis(2,6-dimethylphenol), 4,4'-[(2-hydroxyphenyl)methylene]bis(2,3,6-trimethylphenol), 4,4'-[1-[4-[1-(4-hydroxy-3,5-dimethylphenyl)-1-methylethyl]phenyl]ethoxyne]bis(2,6-dimethylphenol), 4,4'-[1-[4-[1-(4-hydroxy-3,5-dimethylphenyl)-1-methylethyl]phenyl]ethoxyne]bis(2,6-dimethylphenol), 2,6-bis[( [4-hydroxy-3,5-dimethylphenyl)ethyl]-4-methylphenol, 2,6-bis[(4-hydroxy-2,3,6-trimethylphenyl)methyl]-4-methylphenol, 2,6-bis[(4-hydroxy-3,5,6-trimethylphenyl)methyl]-4-ethylphenol, 2,4-bis[(4-hydroxy-3-methylphenyl)methyl]-6-methylphenol, 2,6-bis[(4-hydroxy-3-methylphenyl)methyl]-4-methylphenol, 2,4-bis[(4-hydroxy-3-cyclohexylphenyl)methyl]-6-methylphenol, 2,4-bis[(4-hydroxy-3-methylphenyl)methyl]-6-cyclohexylphenol, 2,4-bis[(2-hydroxy-5-methylphenyl)methyl]-6-cyclohexyl Phenol, 2,4-bis[(4-hydroxy-2,3,6-trimethylphenyl)methyl]-6-cyclohexylphenol, 3,6-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,2-benzene glycol, 4,6-bis[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,3-benzene glycol, 2,4,6-tris[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,3-benzene glycol, 2,4,6-tris[(2-hydroxy-3,5-dimethylphenyl)methyl]-1,3-benzene glycol, 2,2'-methylenebis[6-[(4 / 2-hydroxy-2,5 / 3,6-dimethylphenyl)methyl]-4-methylphenol], 2,2'-methylenebis[6-[(4-hydroxy-3,5-dimethylphenyl)methyl]-4-methylphenol],5-Dimethylphenyl)methyl]-4-methylphenol], 2,2'-methylenebis[6-[(4 / 2-hydroxy-2,3,5 / 3,4,6-trimethylphenyl)methyl]-4-methylphenol], 2,2'-methylenebis[6-[(4-hydroxy-2,3,5-trimethylphenyl)methyl]-4-methylphenol], 4,4'-methylenebis[2-[(2,4-dihydroxyphenyl)methyl]-6-methylphenol], 4,4'- Methylenebis[2-[(2,4-dihydroxyphenyl)methyl]-3,6-dimethylphenol], 4,4'-methylenebis[2-[(2,4-dihydroxy-3-methylphenyl)methyl]-3,6-dimethylphenol], 4,4'-methylenebis[2-[(2,3,4-trihydroxyphenyl)methyl]-3,6-dimethylphenol], 6,6'-methylenebis[4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-1,2 [3-Phenylephrine], 4,4'-cyclohexylidene bis[2-cyclohexyl-6-[(2-hydroxy-5-methylphenyl)methyl]phenol], 4,4'-cyclohexylidene bis[2-cyclohexyl-6-[(4-hydroxy-3,5-dimethylphenyl)methyl]phenol], 4,4'-cyclohexylidene bis[2-cyclohexyl-6-[(4-hydroxy-2-methyl-5-cyclohexyl ... Phenolic compounds having three or more phenolic units within the group consisting of [(2,3,4-trihydroxyphenyl)methyl]phenol, 4,4',4'',4'''-(1,2-ethadiene)tetra(2,6-dimethylphenol), 4,4',4'',4'''-(1,4-phenylenedimethylidene)tetra(2,6-dimethylphenol), and 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane.

8. A polyphenylene ether solution, characterized in that, It includes: The polyphenylene ether according to any one of claims 1 to 7; and The solvent is selected from one or more solvents in the group consisting of toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, and chloroform.

9. A resin film, characterized in that, It comprises polyphenylene ether according to any one of claims 1 to 7.

10. A prepreg, characterized in that, It is a composite of a substrate and the polyphenylene ether according to any one of claims 1 to 7.

11. The prepreg as described in claim 10, characterized in that, The substrate is glass cloth.

12. A metal-clad laminate, characterized in that, It is a laminate of the cured resin film of claim 9 and the metal foil.

13. A metal-clad laminate, characterized in that, It is a laminate of the cured prepreg of claim 10 and the metal foil.

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