Resin composition, resin film, prepreg and metal-clad laminate

Abstract

To provide a resin composition which comprises a polyphenylene ether having excellent solvent solubility and has excellent electrical properties, heat resistance and solvent resistance.SOLUTION: There is provided a resin composition which comprises (A) a polyphenylene ether, (B) a triallyl isocyanurate and / or a triallyl cyanurate, (C) a polyfunctional methacrylate compound, (C') a crosslinking agent other than a triallyl isocyanurate, a triallyl cyanurate and a polyfunctional methacrylate compound as optional components and (D) an organic peroxide, wherein the polyphenylene ether (A) contains a repeating unit derived from phenol of the following formula (1) and a repeating unit derived from phenol of the following formula (2) in a predetermined amount, has a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) of 2.0 to 6.0, a number of OH groups per gram of 100 to 450 μmol / g and a number of OH groups per molecule of 0.8 to 2.5 pieces / molecule.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition, a resin film, a prepreg, and a metal-clad laminate.

Background Art

[0002] Polyphenylene ether (hereinafter also referred to as "PPE") has excellent high-frequency characteristics, flame retardancy, and heat resistance, and thus is widely used as a material for products and parts in the fields of electric and electronic, automotive, food and packaging, and other various industrial material fields. In particular, in recent years, taking advantage of its low dielectric characteristics and heat resistance, its application as a modifier in various applications including electrical and electronic applications such as substrate materials has been promoted.

[0003] However, generally, high-molecular-weight polyphenylene ether having repeating units derived from monohydric phenols typified by 2,6-dimethylphenol dissolves in highly toxic solvents such as chloroform, but is hardly soluble in aromatic solvents such as toluene known as good solvents at high concentrations at room temperature, and is insoluble in ketone solvents such as methyl ethyl ketone. Therefore, for example, when used as a wiring board material, it is difficult to handle with resin varnish solutions such as toluene and methyl ethyl ketone.

[0004] 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. Further, Patent Document 2 discloses a resin composition containing a low-molecular-weight polyphenylene ether component obtained by subjecting a high-molecular polyphenylene ether and a monofunctional or polyfunctional phenol to a redistribution reaction, a crosslinking agent, and an organic peroxide. Patent Document 3 discloses a thermosetting composition containing a polyphenylene ether having a specific molecular weight and an ethenylbenzyl group at the terminal, a polyphenylene ether having a specific molecular weight, and trialkenyl isocyanurate.

Prior Art Documents

Patent Document

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in the method described in Patent Document 1, there is concern about the volatilization of the organic solvent, and temperature adjustment is also required during varnish coating. In addition, polyphenylene ether obtained by a redistribution reaction as disclosed in Patent Document 2 generally contains an organic peroxide used in the redistribution reaction, and the organic peroxide remaining in the product may have an adverse effect on the dielectric properties of the substrate. Furthermore, the composition disclosed in Patent Document 3 had further problems with solubility when made into a varnish.

[0007] The present invention has been made in view of the above problems, and an object thereof is to provide a resin composition containing a polyphenylene ether excellent in solvent solubility and also excellent in electrical properties, heat resistance, and solvent resistance. Another object of the present invention is to provide a resin film, a prepreg, and a metal-clad laminate formed using the resin composition.

Means for Solving the Problems

[0008] 〔1〕(A) Polyphenylene ether, (B) Triallyl isocyanurate and / or triallyl cyanurate, (C) Polyfunctional methacrylic compound, and, As an optional component, (C’) triallyl isocyanurate, triallyl cyanurate, a crosslinking agent other than a polyfunctional methacrylic compound, and (D) a resin composition containing an organic peroxide, wherein the (A) polyphenylene ether contains a repeating unit derived from a phenol of the following formula (1) and a repeating unit derived from a phenol of the following formula (2), with respect to a total of 100 mol% of the repeating units of the following formula (1) and the following formula (2), the content of the repeating unit derived from the phenol of the following formula (1) is 55 mol% or more and less than 90 mol%, and the content of the repeating unit derived from the phenol of the following formula (2) is more than 10 mol% and 45 mol% or less, the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 2.0 to 6.0, the number of OH groups per gram is 100 to 450 μmol / g, and the number of OH groups per molecule is 0.8 to 2.5 per molecule, and the resin composition is characterized in that.

Chemical formula

Chemical formula

Chemical formula

[10] A resin film, characterized in that it contains the resin composition according to any one of [1] to [9].

[11] A prepreg, characterized in that it is a composite of a base material and the resin composition according to any one of [1] to [9].

[12] The prepreg according to

[11] , characterized in that the base material is a glass cloth.

[11] A metal-clad laminate, characterized in that it is a laminate of a cured product of the resin film according to

[10] and a metal foil.

[14] A metal-clad laminate, characterized in that it is a laminate of a cured product of the prepreg according to

[11] and a metal foil. [Advantages of the Invention]

[0009] According to the present invention, a polyphenylene ether resin composition excellent in electrical properties, heat resistance, and solvent resistance can be provided. Also, according to the present invention, it is also possible to provide an electronic circuit board material, a resin film, a prepreg, and a metal-clad laminate formed using the resin composition.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following present embodiment is an exemplification for explaining the present invention, and the present invention is not limited only to this present embodiment, and the present invention can be appropriately modified and implemented within the scope of its gist.

[0011] In the present embodiment, polyphenylene ether in which some or all of the hydroxyl groups contained in the polyphenylene ether may be simply expressed as "polyphenylene ether". Therefore, when expressed as "polyphenylene ether", unless there is a particular contradiction, both unmodified polyphenylene ether and modified polyphenylene ether are included.

[0012] In this specification, A (numerical value) to B (numerical value) means A or more and B or less. Further, in this specification, the substituent refers to, for example, a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogen atom, and the like.

[0013] <Resin Composition> The resin composition of the present embodiment is a resin composition containing (A) polyphenylene ether, (B) triallyl isocyanurate and / or triallyl cyanurate, (C) a polyfunctional methacrylic compound, and as optional components, (C') a crosslinking agent other than triallyl isocyanurate, triallyl cyanurate, and the polyfunctional methacrylic compound, and (D) an organic peroxide.

[0014] (Polyphenylene Ether) The polyphenylene ether contains at least a repeating unit derived from the phenol of the following formula (1) and a repeating unit derived from the phenol of the following formula (2), and may consist only of the repeating unit derived from the phenol of the following formula (1) and the repeating unit derived from the phenol of the following formula (2). [Chemical formula] (In formula (1), R 11 is each independently an optionally substituted saturated hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a halogen atom, and R 12 is each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a halogen atom.) [Chemical formula] (In formula (2), R 22 is each independently a hydrogen atom, an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a halogen atom, and two R 22 are not both hydrogen atoms, and R 21 is a partial structure represented by the following formula (3). [Chemical formula] (In formula (3), R 31 is each independently an optionally substituted linear alkyl group having 1 to 8 carbon atoms, or a cyclic alkyl structure having 1 to 8 carbon atoms to which two R 31 are bonded, and R 32 is each independently an optionally substituted alkylene group having 1 to 8 carbon atoms, b is each independently 0 or 1, and R 33 is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted phenyl group.))

[0015] In the above formula (1), R 11is preferably, independently of each other, a saturated hydrocarbon group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably a methyl group or a phenyl group, and even more preferably a methyl group. In formula (1), two Rs 11 are preferably both of the same structure.

[0016] In the above formula (1), R 12 is preferably, independently of each other, a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group. In formula (1), two Rs 12 are preferably different, and it is more preferable that one is a hydrogen atom and the other is a hydrocarbon group having 1 to 6 carbon atoms (preferably a methyl group).

[0017] In the above formula (2), R 22 is preferably, independently of each other, 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 which may be substituted with 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 which may be substituted with an alkyl group having 1 to 6 carbon atoms, and even more preferably a hydrogen atom or a methyl group. In formula (2), two Rs 22 are preferably different, and it is more preferable that one is a hydrogen atom and the other is a hydrocarbon group having 1 to 6 carbon atoms (preferably a methyl group).

[0018] The partial structure represented by the above formula (3) is preferably a group containing a secondary and / or tertiary carbon, for example, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, a 2,2-dimethylpropyl group, a cyclohexyl group, and structures having a phenyl group at the ends thereof, etc., more preferably a tert-butyl group, a cyclohexyl group, and even more preferably a tert-butyl group.

[0019] In this embodiment, the structure of the polyphenylene ether can be identified by analyzing it using methods such as NMR and mass spectrometry. As a specific method for identifying the structure of the polyphenylene ether, it is known that field desorption mass spectrometry (FD-MS), which is less likely to cause fragmentation, can be performed, and the repeating unit can be estimated based on the interval of the detected ions. Furthermore, there is a method of estimating the structure of the polyphenylene ether by combining peak analysis of fragment ions by electron ionization method (EI) and structure analysis by NMR.

[0020] And in this embodiment, the polyphenylene ether contains a repeating unit derived from the phenol of the above formula (1) and a repeating unit derived from the phenol of the above formula (2). With respect to a total of 100 mol% of the repeating units of the above formula (1) and the above formula (2), the content of the repeating unit derived from the phenol of the above formula (1) is 55 mol% or more and less than 90 mol%, and the content of the repeating unit derived from the phenol of the above formula (2) is more than 10 mol% and 45 mol% or less. By containing the repeating unit derived from the phenol of the above formula (1) and the repeating unit derived from the phenol of the above formula (2) in the above ratio, in addition to the polyphenylene ether having excellent solvent solubility, the electrical properties, heat resistance, and solvent resistance of the resin composition and its cured product are improved.

[0021] From the same perspective, with respect to a total of 100 mol% of the repeating units of the above formula (1) and the above formula (2), it is more preferable that the content of the repeating unit derived from the phenol of the above formula (1) is 60 mol% or more and less than 85 mol%, and the content of the repeating unit derived from the phenol of the above formula (2) is more than 15 mol% and 40 mol% or less.

[0022] Since the phenol of the above formula (1) does not have an unsubstituted ortho position (that is, since hydrogen atoms are not bonded to the two carbon atoms at the ortho positions of the carbon atom to which the hydroxyl group is bonded), it can react with another phenolic monomer only at the phenolic hydroxyl group and the para-position carbon atom. Therefore, the repeating unit derived from the above formula (1) includes a repeating unit having the structure of the following formula (4).

Chemical formula

[0023] The phenol of the above formula (2) can react with another phenolic monomer at either the ortho position or the para position of the phenol in addition to the phenolic hydroxyl group. Therefore, the repeating unit derived from the phenol of the above formula (2) has the structure of the following formula (5), the structure of the following formula (6), or a combination thereof.

Chemical formula

Chemical formula

[0024] In addition, the polyphenylene ether can include a structural unit derived from the phenol of the following formula (7).

Chemical formula

[0025] In the above formula (7), R 4 is each independently either a linear alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, or the partial structure represented by the above formula (3), and is preferably a methyl group or the structure of the above formula (3). Each of the a partial structures may have the same structure or different structures. Among them, from the viewpoint of achieving a polyphenylene ether that is even more excellent in solubility in a solvent and has an even higher glass transition temperature after curing, it is preferable that each of the a partial structures has the same structure.

[0026] In the above formula (7), k is an integer of 1 to 4, and preferably an integer of 2 to 4.

[0027] Also, in the above formula (7), R 4 is bonded to at least one of the carbon atoms at the 2-position and the 6-position with the carbon atom of the benzene ring to which -O- is bonded as the 1-position, and when R 3 bonded to the 2-position and / or the 6-position is a linear alkyl group having 1 to 8 carbon atoms, it is preferably bonded to both the 2-position and the 6-position, and when R 4 bonded to the 2-position and / or the 6-position is the partial structure represented by the formula (3), it is preferably bonded to only one of the 2-position or the 6-position.

[0028] The polyphenylene ether can also contain a repeating unit derived from the above formula (7), and a repeating unit derived from the phenol of the above formula (1) and / or a repeating unit derived from the phenol of the above formula (2). At this time, R 21 in the above formula (2) and R 4When all of them are substructures (functional groups) represented by formula (3) (when the substructure (functional group) represented by the above formula (3) is substituted in both the phenol compound represented by the above formula (2) and the phenol compound represented by the above formula (7)), the structures of the substructures (functional groups) represented by the respective formulas (3) may be the same or different.

[0029] In the above formula (7), X is an a-valent arbitrary linking group, which is not particularly limited. For example, 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 combining these, etc. may be mentioned. X may be a linking group excluding a single bond. X may be a linking group that links a number of substructures to each other.

[0030] As the above X, an a-valent alkyl skeleton bonded to the benzene ring to which R is bonded via a single bond or an ester bond, etc., an a-valent aryl skeleton bonded to the benzene ring to which R is bonded via a single bond or an ester bond, etc., an a-valent heterocyclic skeleton bonded to the benzene ring to which R is bonded via a single bond or an ester bond, etc. may be mentioned. 4 is bonded, an a-valent aryl skeleton bonded to the benzene ring to which R is bonded via a single bond or an ester bond, etc., an a-valent heterocyclic skeleton bonded to the benzene ring to which R is bonded via a single bond or an ester bond, etc. may be mentioned. 4 is bonded, an a-valent aryl skeleton bonded to the benzene ring to which R is bonded via a single bond or an ester bond, etc., an a-valent heterocyclic skeleton bonded to the benzene ring to which R is bonded via a single bond or an ester bond, etc. may be mentioned. 4 is bonded, an a-valent heterocyclic skeleton bonded to the benzene ring to which R is bonded via a single bond or an ester bond, etc. may be mentioned.

[0031] Here, the alkyl skeleton is not particularly limited. For example, a branched terminal of a chain hydrocarbon (for example, a chain saturated hydrocarbon) having at least a number of carbon atoms of 2 to 6 and branched is directly bonded to the benzene ring of the substructure (it is sufficient that the benzene ring is bonded to a number of branched terminals, and there may be a branched terminal to which the benzene ring is not bonded).) etc. may be mentioned. Further, as the aryl skeleton, it is not particularly limited. For example, a benzene ring, a mesitylene group, or a 2-hydroxy-5-methyl-1,3-phenylene group is bonded to the benzene ring to which R is bonded via a single bond or an alkyl chain. 4 is bonded, a skeleton etc. may be mentioned. Further, as the heterocyclic skeleton, it is not particularly limited. For example, a triazine ring is bonded to the benzene ring to which R is bonded via a single bond or an alkyl chain. 4 is bonded, a skeleton etc. may be mentioned.

[0032] In the above formula (7), a is an integer of 2 to 6, preferably an integer of 2 to 4.

[0033] When the phenol of formula (7) does not have an unsubstituted ortho position, the structural unit derived from the phenol of formula (7) has the structure of the following formula (8). When the phenol of formula (7) has an unsubstituted ortho position, the structural unit derived from the phenol of formula (7) has the structure of the following formula (8), the structure of the following formula (9), or a combination thereof.

[0034]

Chemical formula

Chemical formula

[0035] Also, the polyphenylene ether preferably has a reduced viscosity (ηsp / c) measured in a chloroform solution with a concentration of 0.5 g / dL at 30°C of 0.13 to 0.30 dL / g, more preferably 0.15 to 0.28 dL / g, and even more preferably 0.17 to 0.25 dL / g. When the reduced viscosity (ηsp / c) measured in a chloroform solution with a concentration of 0.5 g / dL at 30°C is 0.13 dL / g or more, high heat resistance and excellent dielectric properties derived from the polyphenylene ether structure tend to be obtained. When the reduced viscosity (ηsp / c) is 0.30 dL / g or less, solubility in solvents such as toluene and methyl ethyl ketone can tend to be ensured. The reduced viscosity can be measured by the method described in the examples below.

[0036] In addition, the polyphenylene ether has a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) of 2.0 to 6.0, preferably 2.5 to 5.5 or less, and more preferably 3.0 to 5.0. When the molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 2.0 or more, the fluidity of the polyphenylene ether is improved and the reactivity during thermosetting is enhanced. When the molecular weight distribution (Mw / Mn) is 6.0 or less, the toughness of the polyphenylene ether is improved, and excellent copper foil peel strength and solvent resistance of the cured product can be obtained.

[0037] As means for making the molecular weight distribution of the polyphenylene ether fall within the above range, adjustment of the polymerization temperature, adjustment of the catalyst equivalent, adjustment of the monomer concentration in the reaction system, etc. can be mentioned from the viewpoint of controlling the polymerization reactivity. Among them, as a method for adjusting the monomer concentration in the reaction system, a method of gradually adding the monomer to the reaction system is preferable. When the monomer concentration in the reaction system is high from the beginning, it is difficult to control the molecular weight of the polymer produced because the reaction rate between the monomers is high. On the other hand, by the method of adding the monomer to the reaction system at 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 having a molecular weight distribution in a preferable range can be obtained.

[0038] And in this embodiment, the polyphenylene ether has an OH group number of 100 to 450 μmol / g, preferably 100 to 430 μmol / g, and more preferably 100 to 400 μmol / g. When the OH group number is 100 μmol / g or more, the adhesiveness to the copper foil is improved, and when it is 330 μmol / g or less, the heat resistance and dielectric properties of the substrate are improved. The OH group number of the polyphenylene ether can be measured by the method described in the examples below.

[0039] The polyphenylene ether has 0.8 to 3.0 OH groups per molecule, preferably 0.8 to 2.8 OH groups per molecule, more preferably 1.0 to 2.5 OH groups per molecule. When the number of OH groups per molecule is 0.8 or more, the adhesiveness to the copper foil is improved. When the number of OH groups per molecule is 3.0 or less, the heat resistance and dielectric properties of the substrate are improved, and the production stability of the polyphenylene ether can be ensured.

[0040] (Method for producing polyphenylene ether) The polyphenylene ether is obtained, for example, by a method that includes at least a step of subjecting a monohydric phenol compound represented by the above formula (1) or the above formula (2), or a monohydric or polyhydric phenol compound represented by the above formula (1) and the above formula (7) to oxidative polymerization. In the step of performing the oxidative polymerization, it is preferable to subject a raw material containing at least the phenol of the above formula (1) and the phenol of the above formula (2), or the phenol of the above formula (1) and the phenol of the above formula (7) to oxidative polymerization.

[0041] Examples of the monohydric phenol compound represented by the above formula (1) 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-ditolylphenol, 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-t-butylphenol, and the like. Among them, 2,6-dimethylphenol, 2,3,6-trimethylphenol, and 2,6-diphenylphenol are particularly preferable because they are inexpensive and easily available. The monohydric phenol compound represented by the above formula (1) may be used alone or in combination of two or more.

[0042] Examples of the monohydric phenol compound represented by the above formula (2) include 2-isopropyl-5-methylphenol, 2-cyclohexyl-5-methylphenol, 2-tert-butyl-5-methylphenol, 2-isobutyl-5-methylphenol, and the like. 2-t-butyl-5-methylphenol and 2-cyclohexyl-5-methylphenol, which are bulky substituents, are more preferable from the viewpoints of suppressing disproportionation and gelation. The monohydric phenol compound represented by the above formula (2) may be used alone or in combination of two or more.

[0043] Among the polyvalent phenol compounds represented by the above formula (7), examples of the phenol compound having two phenol 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, 1,1-bis(2-methyl-4-hydroxy-5-t-butylphenyl)butane, and the like. Among them, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane and 1,1-bis(2-methyl-4-hydroxy-5-t-butylphenyl)butane are preferred because they are particularly inexpensive and easily available.

[0044] Furthermore, among the polyvalent phenolic compounds represented by the above formula (7), examples of the phenolic compounds having three or more phenolic units in 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), 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]ethylidene]bis(2,6-dimethylphenol), 4,4'-[1-[4-[1-(4-hydroxy-3-fluorophenyl)-1-methylethyl]phenyl]ethylidene]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 - cyclohexylphenol, 2,4 - bis[(4 - hydroxy - 2,3,6 - trimethylphenyl)methyl] - 6 - cyclohexylphenol, 3,6 - bis[(4 - hydroxy - 3,5 - dimethylphenyl)methyl] - 1,2 - benzenediol, 4,6 - bis[(4 - hydroxy - 3,5 - dimethylphenyl)methyl] - 1,3 - benzenediol, 2,4,6 - tris[(4 - hydroxy - 3,5 - dimethylphenyl)methyl] - 1,3 - benzenediol, 2,4,6 - tris[(2 - hydroxy - 3,5 - dimethylphenyl)methyl] - 1,3 - benzenediol, 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], 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 - benzenetriol], 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'-cyclohexylidenebis[2-cyclohexyl-6-[(2,3,4-trihydroxyphenyl)methyl]phenol], 4,4',4'',4'''-(1,2-ethanediylidene)tetrakis(2,6-dimethylphenol), 4,4',4'',4'''-(1,4-phenylenedimethylidene)tetrakis(2,6-dimethylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, and the like can be mentioned. Among them, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane is preferable because it is particularly inexpensive and easily available., The polyvalent phenol compound represented by the above formula (7) may be used alone or in combination of a plurality of kinds.

[0045] The number of phenolic hydroxyl groups in the polyvalent phenol compound represented by the above formula (7) is not particularly limited as long as it is 2 to 6, but from the viewpoint of making it easier to control the thermosetting rate, it is preferably 2 to 4.

[0046] Generally, the oxidative polymerization of phenols having a hydrogen atom at the ortho position (for example, 2-methylphenol, 2,5-dimethylphenol, 2-phenylphenol) can form an ether bond even at the ortho position, so it is difficult to control the bonding position of the phenol compound during oxidative polymerization, and a high molecular weight polymer polymerized in a branched form with an average number of hydroxyl groups of 3.5 or more per molecule is obtained, and finally a gel component insoluble in the solvent is generated.

[0047] On the other hand, when a bulky substituent is present at the ortho position on one side of the phenol represented by the above formula (2), although a hydrogen atom is present at the ortho position on the opposite side, it becomes possible to control the bonding position of the phenol compound during oxidative polymerization, and polyphenylene ether with an average number of hydroxyl groups of less than 3.0 per molecule can be obtained.

[0048] Furthermore, when a bulky substituent is present at the ortho-position on one side of the phenol represented by the above formula (2), even when a monohydric phenol having a non-bulky substituent (e.g., a hydrogen atom, an allyl group, a methyl group, an ethyl group, a methoxy group, etc.) at the ortho-position of the oxygen atom of the phenol is used as the third component, gelation does not occur, and a polyphenylene ether having an average number of hydroxyl groups of less than 3.0 per molecule can be obtained.

[0049] Also, the molecular weight of the polyphenylene ether can be adjusted, for example, by the molar ratio of the structure of the above formula (2) to the total of the structures of the above formula (1) and the above formula (2), or by the molar ratio of the structure of the above formula (7) to the total of the structures of the above formula (1) and the above formula (7). That is, when the molar ratio of the structure of the above formula (2) or the above formula (7) is high, the achievable molecular weight (reduced viscosity) can be lowered, and when the molar ratio of the structure of the above formula (2) or the above formula (7) is low, the molecular weight (reduced viscosity) can be adjusted to be high.

[0050] Here, in the method for producing polyphenylene ether, in the oxidative polymerization step, an aromatic solvent, which is a good solvent for polyphenylene ether, can be used as the polymerization solvent.

[0051] The good solvent for the polyphenylene ether is a solvent capable of dissolving the polyphenylene ether. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, xylene (including o-, m-, and p-isomers), ethylbenzene, and halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; nitro compounds such as nitrobenzene; and the like.

[0052] As the polymerization catalyst used in this embodiment, a known catalyst system that can generally be used for the production of polyphenylene ether can be used. As a generally known catalyst system, one composed of a transition metal ion having redox ability and an amine compound capable of forming a complex with the transition metal ion is known. For example, a catalyst system composed of a copper compound and an amine compound, a catalyst system composed of a manganese compound and an amine compound, a catalyst system composed of a cobalt compound and an amine compound, and the like. Since the polymerization reaction proceeds efficiently under slightly alkaline conditions, a slight amount of alkali or a further amine compound may be added here.

[0053] Further, a preferably used polymerization catalyst is a catalyst composed of a copper compound, a halogen compound, and an amine compound as constituent components of the catalyst, and more preferably, a catalyst containing a diamine compound represented by the following formula (10) as the amine compound.

Chemical formula

[0054] List the examples of copper compounds of the catalyst components described herein. As suitable copper compounds, cuprous compounds, cupric compounds or mixtures thereof can be used. Examples of cupric compounds include, for example, cupric chloride, cupric bromide, cupric sulfate, cupric nitrate, etc. Examples of cuprous compounds include, for example, cuprous chloride, cuprous bromide, cuprous sulfate, cuprous nitrate, etc. Among these, particularly preferred metal compounds are cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide. These copper salts may also be synthesized from the corresponding halogen or acid with oxides (such as cuprous oxide), carbonates, hydroxides, etc. at the time of use. A frequently used method is to mix the previously exemplified cuprous oxide with hydrogen halide (or a solution of hydrogen halide) for preparation.

[0055] Examples of the halogen compound include, for example, 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, tetraethylammonium iodide, etc. Also, these can be used as an aqueous solution or a solution using an appropriate solvent. These halogen compounds can be used alone as a component or in combination of two or more. Preferred halogen compounds are aqueous solutions of hydrogen chloride and aqueous solutions of hydrogen bromide.

[0056] The usage amounts of these compounds are not particularly limited, but it is preferably 2 times or more and 20 times or less as a halogen atom relative to the molar amount of copper atoms. The preferred usage amount of copper atoms is in the range of 0.02 mol to 0.6 mol relative to 100 mol of the phenol compound added to the polymerization reaction.

[0057] Regarding the diamine compound of the catalyst component, for example, 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-ethylethylenediamine, N,N-dimethyl-N’-ethylethylenediamine, N,N’-dimethyl-N-ethylethylenediamine, N-n-propylethylenediamine, N,N’-n-propylethylenediamine, N-i-propylethylenediamine, N,N’-i-propylethylenediamine, N-n-butylethylenediamine, N,N’-n-butylethylenediamine, N-i-butylethylenediamine, N,N’-i-butylethylenediamine, N-t-butylethylenediamine, N,N’-t-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. can be mentioned. The diamine compound preferable for this embodiment is one in which the number of carbon atoms of the alkylene group connecting two nitrogen atoms is 2 or 3. The usage amount of these diamine compounds is not particularly limited, but a range of 0.01 mol to 10 mol is preferable with respect to 100 mol of the phenol compound added to the polymerization reaction.

[0058] In addition, as a constituent component of the polymerization catalyst, a primary amine and a secondary monoamine can be included. Examples of the secondary monoamine include, but are not limited to, dimethylamine, diethylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-t-butylamine, dipentylamines, dihexylamines, dioctylamines, didecylamines, dibenzylamines, 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, diphenylamine, and the like.

[0059] As a constituent component of the polymerization catalyst, a tertiary monoamine compound can also be included. The tertiary monoamine compound is an aliphatic tertiary amine including an alicyclic tertiary amine. For example, trimethylamine, triethylamine, tripropylamine, tributylamine, triisobutylamine, dimethylethylamine, dimethylpropylamine, allyldiethylamine, dimethyl-n-butylamine, diethylisopropylamine, N-methylcyclohexylamine, and the like can be mentioned. These tertiary monoamines can be used alone or in combination of two or more. The amount used is not particularly limited, but a range of 15 mol or less with respect to 100 mol of the phenol compound added to the polymerization reaction is preferable.

[0060] In addition, in the present embodiment, there is no limitation whatsoever on adding a surfactant known to have an effect of improving polymerization activity conventionally. Examples of such a surfactant include trioctylmethylammonium chloride known under the trade names of Aliquat336 and Capriquat.

[0061] As the oxygen-containing gas in the polymerization, in addition to pure oxygen, those obtained by mixing oxygen and an inert gas such as nitrogen at an arbitrary ratio, air, and further those obtained by mixing air and an inert gas such as nitrogen at an arbitrary ratio can be used. The pressure inside the system during the polymerization reaction is sufficient at normal pressure, but it can also be used under reduced pressure or increased pressure as necessary.

[0062] The temperature of the polymerization is not particularly limited, but if it is too low, the reaction hardly proceeds, and if it is too high, there is a risk of a decrease in reaction selectivity and formation of gel. Therefore, it is in the range of 0 to 60 °C, preferably 10 to 40 °C.

[0063] In addition, in the method for producing polyphenylene ether, polymerization can also be carried out in a poor solvent such as alcohol.

[0064] In the method for producing polyphenylene ether, there is no particular limitation on the post-treatment method after the polymerization reaction. Usually, an acid such as hydrochloric acid or acetic acid, or ethylenediaminetetraacetic acid (EDTA) and its salts, nitrilotriacetic acid and its salts, etc. are added to the reaction solution to deactivate the catalyst. Also, a method for removing by-products of divalent phenol compounds generated by the polymerization of polyphenylene ether can also be carried out using a conventionally known method. If the metal ions as the catalyst are substantially deactivated as described above, the mixture can be decolorized by simply heating it. Also, a method of adding a necessary amount of a known reducing agent is also possible. Examples of known reducing agents include hydroquinone and sodium dithionite.

[0065] In addition, in the method for producing polyphenylene ether, water may be added to extract the compound that deactivates the copper catalyst, and after performing liquid-liquid separation into an organic phase and an aqueous phase, the aqueous phase is removed to remove the copper catalyst from the organic phase. This liquid-liquid separation step is not particularly limited, but examples include methods such as static separation and separation using a centrifuge. In order to promote the above liquid-liquid separation, a known surfactant or the like may be used.

[0066] Subsequently, in the method for producing the polyphenylene ether, the organic phase containing the polyphenylene ether after liquid-liquid separation may be concentrated and dried by volatilizing the solvent.

[0067] The method for volatilizing the solvent contained in the organic phase is not particularly limited. Examples include a method of transferring the organic phase to a high-temperature concentration tank to distill off the solvent for concentration, and a method of using equipment such as a rotary evaporator to distill off toluene for concentration.

[0068] As the temperature of the drying treatment in the drying step, at least 60°C or higher is preferable, 80°C or higher is more preferable, 120°C or higher is further preferable, and 140°C or higher is most preferable. When drying the polyphenylene ether at a temperature of 60°C or higher, the content of high-boiling volatile components in the polyphenylene ether powder can be efficiently reduced.

[0069] In order to obtain the polyphenylene ether with high efficiency, methods such as increasing the drying temperature, increasing the degree of vacuum in the drying atmosphere, and performing stirring during drying are effective. In particular, the method of increasing the drying temperature is preferable from the viewpoint of production efficiency. It is preferable to use a dryer equipped with a mixing function in the drying step. Examples of the mixing function include stirrer-type and tumbling-type dryers. This can increase the throughput and maintain high productivity.

[0070] Further, the resin composition according to the present embodiment contains the above-described polyphenylene ether, triallyl isocyanurate and / or triallyl cyanurate, a polyfunctional methacrylic compound, and an organic peroxide. Optionally, it can further contain crosslinking agents other than triallyl isocyanurate and triallyl cyanurate, a polyfunctional methacrylic compound, a thermoplastic resin, a flame retardant, other additives, a solvent, etc. The components of the resin composition according to the present embodiment will be described below.

[0071] (Triallyl isocyanurate and / or triallyl cyanurate) The resin composition of this embodiment contains triallyl isocyanurate and / or triallyl cyanurate, which have the ability to cause or promote a crosslinking reaction.

[0072] (Polyfunctional methacrylic compound) In addition to the polyphenylene ether and the triallyl isocyanurate and / or triallyl cyanurate, the resin composition of this embodiment further contains a polyfunctional methacrylic compound. The polyfunctional methacrylic compound is not particularly limited as long as it has more than an average of 1 methacrylic functional group per molecule, but from the viewpoint of the crosslinking reaction, it preferably has an average of 2 or more methacrylic functional groups per molecule, and may be composed of one type of compound or two or more types of compounds.

[0073] Examples of the polyfunctional methacrylic compound include tricyclodecane dimethanol dimethacrylate (DCP), trimethylolpropane trimethacrylate (TMPT), bisphenol A ethoxylate dimethacrylate, 1,6 - hexanediol dimethacrylate, 1,9 - nonanediol dimethacrylate, 1,10 - decanediol dimethacrylate, neopentyl glycol dimethacrylate, etc. Among these, from the viewpoint of excellent compatibility with polyphenylene ether, it is preferable to contain at least one compound selected from tricyclodecane dimethanol dimethacrylate (DCP) and trimethylolpropane trimethacrylate (TMPT). By further adding these polyfunctional methacrylic compounds, the dielectric properties, heat resistance, and solvent resistance of the resin composition and its cured product can be further improved.

[0074] From the perspective of reducing the viscosity of the varnish and improving the handleability in the step of mixing the resin composition with a solvent, and from the perspective of reducing the melt viscosity of the resin composition and improving the crosslinking reaction rate in the thermosetting step, the polyfunctional methacrylic 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 compound, in this embodiment, a resin composition and a cured product thereof excellent in electrical properties, heat resistance and solvent resistance can be obtained.

[0075] (Triallyl isocyanurate, triallyl cyanurate, crosslinking agents other than polyfunctional methacrylic compounds) In the resin composition of this embodiment, a crosslinking agent other than triallyl isocyanurate, triallyl cyanurate, and polyfunctional methacrylic compounds, which has the ability to cause or promote a crosslinking reaction, can be contained. The crosslinking agent preferably has a number average molecular weight of 4,000 or less. When the number average molecular weight of the crosslinking agent is 4,000 or less, an increase in the viscosity of the resin composition can be suppressed, and good resin fluidity during heat molding can be obtained. The number average molecular weight may be a value measured by a general molecular weight measurement method, and specifically, values measured using GPC and the like can be mentioned.

[0076] Also, from the perspective of the crosslinking reaction, the crosslinking agent preferably has an average of 2 or more carbon-carbon unsaturated double bonds per molecule. The crosslinking agent may be composed of one type of compound or two or more types of compounds. The "carbon-carbon unsaturated double bond" referred to in this specification means a double bond located at the end branched from the main chain when the crosslinking agent is a polymer or oligomer. Examples of the carbon-carbon unsaturated double bond include the 1,2-vinyl bond in polybutadiene.

[0077] When the number average molecular weight of the crosslinking agent is less than 600, the number (average value) 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 value) 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 value) 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, and the number of carbon-carbon unsaturated double bonds is not less than the above specific value, the reactivity of the crosslinking agent in the resin composition of the present embodiment is further enhanced, the crosslinking density of the cured product of the resin composition is further improved, and as a result, more excellent heat resistance can be imparted. On the other hand, when the number average molecular weight of the crosslinking agent is within the above range, and the number of carbon-carbon unsaturated double bonds is not more than the above specific value, more excellent resin fluidity can be imparted during heat molding.

[0078] Examples of the crosslinking agent include polyfunctional vinyl compounds having two or more vinyl groups in the molecule such as polybutadiene, vinylbenzyl compounds such as divinylbenzene having a vinylbenzyl group in the molecule, and polyfunctional maleimide compounds having two or more maleimide groups in the molecule such as 4,4'-bismaleimidodiphenylmethane. These crosslinking agents may be used alone or in combination of two or more. Among these crosslinking agents, it is necessary to contain at least one compound selected from triallyl isocyanurate and triallyl cyanurate, and a polyfunctional methacrylic compound. By including at least one compound selected from triallyl isocyanurate and triallyl cyanurate, and a polyfunctional methacrylic compound in the crosslinking agent, the compatibility and coatability between the crosslinking agent and the polyphenylene ether can be further improved, and when mounted on an electronic circuit board, the substrate characteristics tend to be more excellent.

[0079] Further, in the resin composition of the present embodiment, from the viewpoint of further improving the compatibility between the components, the coatability of the resin composition, and the characteristics of the mounted electronic circuit board, the content of the polyphenylene ether with respect to 100 parts by weight of the total amount of the polyphenylene ether, the triallyl isocyanurate and / or triallyl cyanurate, and the polyfunctional methacrylic compound is preferably 40% by weight or more and 80% by weight or less, more preferably 45% by weight or more and 80% by weight or less, and still more preferably 50% by weight or more and 80% by weight or less.

[0080] Furthermore, in the resin composition of the present 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 with respect to 100 parts by weight of the total amount of the triallyl isocyanurate and / or triallyl cyanurate and the polyfunctional methacrylic compound is preferably 20% by weight or more and 80% by weight or less, more preferably 25% by weight or more and 75% by weight or less, and still more preferably 30% by weight or more and 70% by weight or less.

[0081] When a crosslinking agent other than triallyl isocyanurate, triallyl cyanurate, and the polyfunctional methacrylic compound is included, in the resin composition of the present embodiment, from the viewpoint of further improving the compatibility between the crosslinking agent and the polyphenylene ether, the coatability of the resin composition, and the characteristics of the mounted electronic circuit board, the content of the polyphenylene ether with respect to 100 parts by weight of the total amount of the polyphenylene ether, the triallyl isocyanurate and / or triallyl cyanurate, the polyfunctional methacrylic compound, and the other crosslinking agent is preferably 40% by weight or more and 80% by weight or less, more preferably 45% by weight or more and 80% by weight or less, and still more preferably 50% by weight or more and 80% by weight or less.

[0082] (Organic peroxide) In the resin composition of the present embodiment, in addition to the polyphenylene ether, the triallyl isocyanurate and / or triallyl cyanurate, and the polyfunctional methacrylic compound, any organic peroxide having the ability to promote the polymerization reaction can be used. Examples of the organic peroxide include peroxides such as benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, di-t-butyl peroxide, t-butyl cumyl peroxide, di(2-t-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di-t-butyl peroxyisophthalate, t-butyl peroxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl) peroxide, trimethylsilyl triphenylsilyl peroxide. Radical generators such as 2,3-dimethyl-2,3-diphenylbutane can also be used as a reaction initiator for the resin composition. Among them, from the viewpoint of providing a cured product having excellent heat resistance and mechanical properties and further having a lower dielectric tangent (more preferably, a lower dielectric constant), 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, di(2-t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane are preferred.

[0083] The one-minute half-life temperature of the organic peroxide is preferably 155 to 195 °C, more preferably 160 to 195 °C, and even more preferably 165 to 195 °C. In this specification, the one-minute half-life temperature means the temperature at which the organic peroxide decomposes and the time for the amount of its active oxygen to become half is one minute. The one-minute half-life temperature is a value confirmed by a method of dissolving the organic peroxide in a solvent inert to radicals, such as benzene, etc., to a concentration of 0.05 to 0.1 mol / L and thermally decomposing the organic peroxide solution in a nitrogen atmosphere.

[0084] When the one-minute half-life temperature of the organic peroxide is 155 °C or higher, when the polyphenylene ether-containing resin composition is subjected to heat and pressure molding, the polyphenylene ether is sufficiently melted and then the reaction with the crosslinking agent starts, so it tends to have excellent moldability. On the other hand, when the one-minute half-life temperature of the organic peroxide is 195 °C or lower, since the decomposition rate of the organic peroxide under normal heat and pressure molding conditions (for example, the maximum temperature reached is 200 °C) is sufficient, the crosslinking reaction with the crosslinking agent can proceed efficiently and gently, so it is possible to form a cured product having good electrical properties (especially dielectric tangent).

[0085] Examples of the organic peroxide having a half-life temperature of 1.5 minutes within the range of 155 to 195°C include t-hexyl peroxyisopropyl monocarbonate (155.0°C), t-butyl peroxy-3,5,5-trimethylhexanoate (166.0°C), t-butyl peroxy laurate (159.4°C), t-butyl peroxyisopropyl monocarbonate (158.8°C), t-butyl peroxy 2-ethylhexyl monocarbonate (161.4°C), t-hexyl peroxybenzoate (160.3°C), 2,5-dimethyl-2,5-di(benzoylperoxy)hexane (158.2°C), t-butyl peroxyacetate (159.9°C), 2,2-di-(t-butylperoxy)butane (159.9°C), t-butyl peroxybenzoate (166.8°C), n-butyl 4,4-di-(t-butylperoxy)valerate (172.5°C), di(2-t-butylperoxyisopropyl)benzene (175.4°C), dicumyl peroxide (175.2°C), di-t-hexyl peroxide (176.7°C), 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (179.8°C), 2,5-dimethyl-2,5-bis(t-butylperoxy)hexine-3 (194.3°C), and t-butyl cumyl peroxide (173.3°C).

[0086] From the viewpoint of increasing the reaction rate, the content of the organic peroxide is preferably 0.05 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1.0 parts by mass or more, and particularly preferably 1.5 parts by mass or more, based on 100 parts by mass in total of the polyphenylene ether and the crosslinking agent (the total mass of the crosslinking agent including the triallyl isocyanurate, the triallyl cyanurate, and the polyfunctional methacrylic compound). Further, from the viewpoint of keeping the dielectric constant and the dielectric loss tangent of the resulting cured product low, the content of the organic peroxide is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, and still more preferably 4.5 parts by mass or less, based on 100 parts by mass in total of the polyphenylene ether and the crosslinking agent.

[0087] From the viewpoint of increasing the reaction rate, the content of the organic peroxide is preferably 0.05 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1.0 part by mass or more, and particularly preferably 1.5 part by mass or more, based on 100 parts by weight in total of the polyphenylene ether, the triallyl isocyanurate, the triallyl cyanurate, and the polyfunctional methacrylic compound. Further, from the viewpoint of keeping the dielectric constant and the dielectric loss tangent of the resulting cured product low, the content of the organic peroxide is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, still more preferably 4.5 parts by mass or less, based on 100 parts by weight in total of the polyphenylene ether, the triallyl isocyanurate and / or triallyl cyanurate, and the polyfunctional methacrylic compound.

[0088] Also, the content of the organic peroxide is preferably 0.1 part by mass or more and 50 parts by mass or less, more preferably 1.0 part by mass or more and 25 parts by mass or less, still more preferably 2.0 part by mass or more and 22.5 parts by mass or less, even more preferably 3.0 part by mass or more and 21.5 parts by mass or less, and particularly preferably more than 5.0 parts by mass and 20 parts by mass or less, based on 100 parts by weight of the crosslinking agent. When the content is 0.1 part by mass or more, the reaction rate tends to increase, and when it is 50 parts by mass or less, the dielectric constant and the dielectric loss tangent of the resulting cured product tend to be kept low.

[0089] Further, the content of the organic peroxide is preferably 0.1 part by mass or more and 50 parts by mass or less, more preferably 1.0 part by mass or more and 25 parts by mass or less, still more preferably 2.0 part by mass or more and 22.5 parts by mass or less, even more preferably 3.0 part by mass or more and 21.5 parts by mass or less, and particularly preferably more than 5.0 parts by mass and 20 parts by mass or less, based on 100 parts by mass in total of the triallyl isocyanurate and / or triallyl cyanurate and the polyfunctional methacrylic compound. When the content is 0.1 part by mass or more, the reaction rate tends to be increased, and when it is 50 parts by mass or less, the dielectric constant and dielectric loss tangent of the obtained cured product tend to be suppressed low.

[0090] (Thermoplastic resin) The resin composition of the present embodiment may further contain a thermoplastic resin. The thermoplastic resin is preferably at least one selected from the group consisting of a block copolymer of a vinyl aromatic compound and an olefinic alkene compound and a hydrogenated product thereof (a hydrogenated block copolymer obtained by hydrogenating a block copolymer of a vinyl aromatic compound and an olefinic alkene compound), and a homopolymer of a vinyl aromatic compound. The content of the unit derived from the vinyl aromatic compound in the block copolymer or its hydrogenated product is preferably 20% by mass or more, more preferably 22% by mass or more, and can be 99% by mass or less. When the content of the unit derived from the vinyl aromatic compound in the block copolymer or its hydrogenated product is 20% by mass or more, the compatibility with polyphenylene ether is further improved, and the adhesion strength to the metal foil tends to be further improved.

[0091] As the vinyl aromatic compound, it only needs to have an aromatic ring and a vinyl group in the molecule, and examples thereof include styrene. As the olefinic alkene compound, it only needs to be an alkene having a linear or branched structure in the molecule, and examples thereof include ethylene, propylene, butylene, isobutylene, butadiene, and isoprene. Among these, as the thermoplastic resin, from the viewpoint of further excellent compatibility with polyphenylene ether, styrene-butadiene block copolymer, styrene-ethylene-butadiene block copolymer, styrene-ethylene-butylene block copolymer, styrene-butadiene-butylene block copolymer, styrene-isoprene block copolymer, styrene-ethylene-propylene block copolymer, styrene-isobutylene block copolymer, hydrogenated product of styrene-butadiene block copolymer, hydrogenated product of styrene-ethylene-butadiene block copolymer, hydrogenated product of styrene-butadiene-butylene block copolymer, hydrogenated product of styrene-isoprene block copolymer, and at least one selected from the group consisting of a homopolymer of styrene (polystyrene) is preferably used, and more preferably one or more selected from the group consisting of styrene-butadiene block copolymer, hydrogenated product of styrene-butadiene block copolymer, and polystyrene.

[0092] The hydrogenation rate in the hydrogenated product is not particularly limited, and a carbon-carbon unsaturated double bond derived from the olefinic alkene compound may partially remain.

[0093] The weight average molecular weight of the thermoplastic resin is preferably 10,000 to 300,000, more preferably 20,000 to 290,000, and still more preferably 30,000 to 280,000. When the weight average molecular weight is 10,000 or more, the resin composition of this embodiment tends to have more excellent heat resistance when cured. When the weight average molecular weight is 300,000 or less, the resin composition of this embodiment tends to have better resin fluidity during heat molding. The weight average molecular weight is determined by the method described in the examples below.

[0094] The content of the thermoplastic resin is preferably 2 to 20 parts by mass, more preferably 3 to 19 parts by mass, still more preferably 4 to 18 parts by mass, and particularly preferably 5 to 17 parts by mass, based on 100 parts by mass in total of the polyphenylene ether and the crosslinking agent. When the content is 2 parts by mass or more, the resin composition of the present embodiment tends to be more excellent in low dielectric constant property, low dielectric tangent property, and adhesion to a metal foil when cured. When the content is 20 parts by mass or less, the resin composition of the present embodiment tends to have more excellent resin fluidity during heat molding. Also, from the same viewpoint, the content of the thermoplastic resin is preferably 2 to 20 parts by mass, more preferably 3 to 19 parts by mass, based on 100 parts by mass in total of the polyphenylene ether and the crosslinking agent.

[0095] In addition, the resin composition of the present embodiment can also contain a thermoplastic resin other than the thermoplastic resin having the types and weight average molecular weights described above.

[0096] (Flame retardant) The resin composition of the present embodiment preferably further contains a flame retardant. The flame retardant is not particularly limited as long as it is incompatible with other contained components in the resin composition after the curing of the resin composition from the viewpoint of improving heat resistance. Preferably, the flame retardant is incompatible with the polyphenylene ether and / or the crosslinking agent in the resin composition after the curing of the resin composition. Examples of the flame retardant include inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide, and zinc borate; aromatic bromine compounds such as hexabromobenzene, decabromodiphenylethane, 4,4-dibromobiphenyl, and ethylenebistetrabromophthalimide; and phosphorus-based flame retardants such as resorcinol bis-diphenyl phosphate and resorcinol bis-dixylenyl phosphate. These flame retardants may be used alone or in combination of two or more. Among these, the flame retardant is preferably decabromodiphenylethane from the viewpoint of being more excellent in the compatibility between the flame retardant and the polyphenylene ether, the coating property of the resin composition, and the characteristics of the mounted electronic circuit board.

[0097] Although the content of the flame retardant is not particularly limited, from the viewpoint of maintaining the flame retardancy of V-0 level of UL standard 94, it is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, based on 100 parts by mass in total of the polyphenylene ether and the crosslinking agent. Further, from the viewpoint of maintaining a low dielectric tangent of the obtained cured product (preferably from the viewpoint 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, still more preferably 40 parts by mass or less.

[0098] (Silica filler) The resin composition of the present embodiment may further contain a silica filler. Examples of the silica filler include natural silica, fused silica, synthetic silica, amorphous silica, aerosil, and hollow silica. The content of the silica filler can be 10 to 300 parts by mass based on 100 parts by mass in total of the polyphenylene ether and the crosslinking agent. Further, the silica filler may be surface-treated using a silane coupling agent or the like on its surface.

[0099] In addition to the flame retardant and the silica filler, the resin composition of the present embodiment may further contain additives such as a heat stabilizer, an antioxidant, a UV absorber, a surfactant, a lubricant, and a solvent. When the resin composition of the present embodiment contains a solvent, it can be in the form of a varnish in which the solid content in the resin composition is dissolved or dispersed in the solvent, and a resin film can be formed from the resin composition of the present embodiment.

[0100] (Solvent) The resin composition of the present embodiment may further contain a solvent. From the viewpoint of solubility, aromatic compounds such as toluene and xylene, methyl ethyl ketone (MEK), cyclopentanone, cyclohexanone, and chloroform are preferable as the solvent. These solvents may be used alone or in combination of two or more.

[0101] <Resin Film> The resin film of this embodiment contains the resin composition of this embodiment. The method for manufacturing the film is not particularly limited. For example, it can be obtained by molding the resin composition of this embodiment into a film or sheet form.

[0102] <Prepreg> The prepreg of this embodiment is a composite of a base material and the resin composition of this embodiment, and the resin composition of this embodiment may be impregnated or coated on the base material. The method for manufacturing the prepreg is not particularly limited. For example, it can be obtained by impregnating a base material into a resin composition (varnish) containing a solvent and then drying and removing the solvent component with a hot air dryer or the like.

[0103] Examples of the base material include various glass cloths such as roving cloth, cloth, chopped mat, and surfacing mat; asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloths; woven or non-woven cloths obtained from liquid crystal fibers such as wholly aromatic polyamide fibers, wholly aromatic polyester fibers, and polybenzoxazole fibers; natural fiber cloths such as cotton cloth, linen cloth, and felt; natural cellulose-based base materials such as carbon fiber cloth, kraft paper, cotton paper, and cloth obtained from paper-glass mixed fibers; polytetrafluoroethylene porous film; and the like. Among them, glass cloth is preferred. These base materials may be used alone or in combination of two or more.

[0104] The proportion of the solid content of the resin composition of this embodiment (components other than the solvent of the resin composition) in the prepreg is preferably 30 to 80% by mass, and more preferably 40 to 70% by mass. When the above proportion is 30% by mass or more, the prepreg tends to be more excellent in insulation reliability when used for electronic substrates or the like. When the above proportion is 80% by mass or less, the prepreg tends to be more excellent in mechanical properties such as flexural modulus in applications such as electronic substrates.

[0105] <Metal-clad laminate> The metal-clad laminate of the present embodiment can be obtained by laminating and curing the resin composition, the resin film, or the prepreg of the present embodiment described above, and a metal foil. The metal-clad laminate of the present embodiment preferably has a form in which a cured product of the prepreg (hereinafter, also referred to as a "cured product composite") and a metal foil are laminated and adhered, and is suitably used as a material for an electronic substrate. Examples of the metal foil include an aluminum foil and a copper foil. Among these, a copper foil is preferable because of its low electrical resistance. The cured product composite to be combined with the metal foil may be one sheet or a plurality of sheets, and a metal foil is overlapped on one side or both sides of the composite according to the application to process it into a laminate.

[0106] As a method for manufacturing a metal-clad laminate, for example, a composite (for example, the above-mentioned prepreg) composed of a resin composition and a base material is formed, and after overlapping this with a metal foil, the resin composition is cured to obtain a laminate in which a cured product laminate and a metal foil are laminated. One of the particularly preferable applications of the above metal-clad laminate is a printed wiring board. In the printed wiring board, it is preferable that at least a part of the metal foil is removed from the metal-clad laminate.

[0107] <Printed Wiring Board> In the printed wiring board of the present embodiment, a part of the metal foil is removed from the metal-clad laminate of the present embodiment. The printed wiring board of the present embodiment can typically be formed by a method of pressure heating and molding using the prepreg of the present invention described above. Examples of the base material are the same as those described above for the prepreg. The printed wiring board of the present embodiment has excellent dielectric properties, high heat resistance, and excellent solvent resistance by including the resin composition of the present embodiment.

Examples

[0108] Hereinafter, the present embodiment will be described in more detail based on examples, but the present embodiment is not limited to the following examples.

[0109] <Polyphenylene Ether> (Production Example) · Production Example 1: Polyphenylene Ether 1 (PPE1) A 40-liter jacketed polymerization tank equipped with a sparger for introducing oxygen-containing gas, a stirring turbine blade, and a baffle at the bottom of the polymerization tank, and a reflux condenser in the vent gas line at the upper part of the polymerization tank was charged with nitrogen gas at a flow rate of 46.3 L / min while introducing 3.6 g of cupric oxide, 27.1 g of a 47% by mass aqueous hydrogen bromide solution, 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 = C 8 -C 10 ) to form a homogeneous solution. Next, using a pump, a dropping solution of 647.8 g of 2-tert-butyl-5-methylphenol, 2352.3 g of 2,6-dimethylphenol, and 2.35 kg of toluene was started to be dropped into the polymerization tank over 35 minutes. At the same time, dry air was introduced into the polymerization solution from the bottom of the polymerization tank through the sparger at a rate of 31.5 L / min to start the polymerization. Dry air was bubbled for 240 minutes to obtain a polymerization mixture. During the polymerization, the internal temperature was controlled to be 40 °C. The polymerization mixture (polymerization solution) at the end of the polymerization was in a homogeneous solution state. Thereafter, the bubbling of dry air was stopped, and 38.73 g of ethylenediaminetetraacetic acid tetrasodium salt (reagent manufactured by Dojindo Laboratories) was added to the polymerization mixture as a 2 kg aqueous solution. The polymerization mixture was stirred at 70 °C for 240 minutes, then left standing for 20 minutes, and the organic phase and the aqueous phase were separated by liquid-liquid separation. The organic phase was concentrated by a rotary evaporator until the polymer concentration reached 30% by mass. Methanol with a mass ratio of methanol to the polymer solution of 4 was mixed with the concentrated solution to precipitate the polymer. Wet polyphenylene ether was obtained by vacuum filtration using a glass filter. Further, the wet polyphenylene ether was washed three times with methanol in an amount such that the mass ratio of methanol to the wet polyphenylene ether was 4. Thereafter, the wet polyphenylene ether was held at 140 °C and 1 mmHg for 120 minutes to obtain dry polyphenylene ether (PPE1).

[0110] · Production Example 2: Polyphenylene Ether 2 (PPE2) After starting the polymerization, the operation was carried out in the same manner as in Production Example 1 except that dry air was passed for 200 minutes to obtain polyphenylene ether (PPE2).

[0111] · Production Example 3: Polyphenylene Ether 3 (PPE3) The operation was carried out in the same manner as in Production Example 1 except that a dropping solution of 1096.6 g of 2-tert-butyl-5-methylphenol, 1903.4 g of 2,6-dimethylphenol and 1.90 kg of toluene was used to obtain polyphenylene ether (PPE3).

[0112] · Production Example 4: Polyphenylene Ether 4 (PPE4) The operation was carried out in the same manner as in Production Example 1 except that a dropping solution of 1417.9 g of 2-tert-butyl-5-methylphenol, 1582.1 g of 2,6-dimethylphenol and 1.58 kg of toluene was used to obtain polyphenylene ether (PPE4).

[0113] · Production Example 5: Polyphenylene Ether 5 (PPE5) The operation was carried out in the same manner as in Production Example 1 except that a dropping solution of 1720.3 g of 2-tert-butyl-5-methylphenol, 1279.7 g of 2,6-dimethylphenol and 2.68 kg of toluene was used to obtain polyphenylene ether (PPE5).

[0114] · Production Example 6: Polyphenylene Ether 6 (PPE6) "XYRON S203A" manufactured by Asahi Kasei Corporation was used as PPE6.

[0115] · Production Example 7: Polyphenylene Ether 7 (PPE7) A 40-liter jacketed polymerization tank equipped with a sparger, a stirring turbine blade, and a baffle for introducing an oxygen-containing gas at the bottom of the overlapping tank, and a reflux condenser in the vent gas line at the upper part of the polymerization tank was charged with 2.4 g of cupric oxide, 18.1 g of a 47% by mass aqueous hydrogen bromide solution, 5.8 g of di-t-butylethylenediamine, 28.1 g of di-n-butylamine, 85.6 g of butyldimethylamine, 17.9 kg of toluene, and 1,903.4 g of 2,6-dimethylphenol and 1,096.6 g of 2-tert-butyl-5-methylphenol while blowing nitrogen gas at a flow rate of 17.1 L / min to form a homogeneous solution. Next, dry air was introduced from the sparger into the polymerization tank at a rate of 10.5 L / min to initiate polymerization. The dry air was bubbled for 120 minutes to obtain a polymerization mixture. During the polymerization, the internal temperature was controlled to be 20°C. The polymerization mixture (polymer solution) at the end of polymerization was in a homogeneous solution state. The bubbling of dry air was stopped, and 25.9 g of sodium ethylenediaminetetraacetate (reagent manufactured by Dojindo Laboratories) was added to the polymerization mixture as a 2 kg aqueous solution. The polymerization mixture was stirred at 70°C for 150 minutes, then allowed to stand for 20 minutes, and the organic phase and the aqueous phase were separated by liquid-liquid separation. The organic phase was concentrated by a rotary evaporator until the polymer concentration reached 25% by mass. Methanol was mixed with the above solution such that the ratio of methanol to the polymer solution was 6 to precipitate the polymer. Wet polyphenylene ether was obtained by vacuum filtration using a glass filter. The wet polyphenylene ether was further washed with methanol in an amount such that the ratio of methanol to the wet polyphenylene ether was 3. The above washing operation was performed three times. Then, the wet polyphenylene ether was held at 140°C and 1 mmHg for 120 minutes to obtain dry polyphenylene ether 7 (PPE7).

[0116] (Analysis of polyphenylene ether) The following analysis was performed on PPE1 to 7 obtained in the above Production Example. The analysis results are shown in Table 1.

[0117] (1) Reduced viscosity (ηsp / c) of polyphenylene ether A 0.5 g / dL chloroform solution of polyphenylene ether was prepared, and the reduced viscosity (ηsp / c) (dL / g) at 30 °C was determined using an Ubbelohde viscometer tube.

[0118] (2) Number-average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of polyphenylene ether As a measuring device, gel permeation chromatography (manufactured by Shimadzu Corporation, LC-2030C Plus) was used. A calibration curve was created with standard polystyrene and ethylbenzene, and using this calibration curve, the number-average molecular weight (Mn) of the obtained polyphenylene ether was measured. As the standard polystyrene, those 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 were used. As the column, two K-805L columns manufactured by Showa Denko K.K. connected in series were used. As the solvent, chloroform was used, and the solvent flow rate was 1.0 mL / min, and the column temperature was measured at 40 °C. As the measurement sample, a 1 g / L chloroform solution of polyphenylene ether was prepared and used. The UV wavelength of the detector was 254 nm for standard polystyrene and 283 nm for polyphenylene ether. 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 from the ratio of the peak areas based on the curve showing the molecular weight distribution obtained by GPC.

[0119] (3) OH number of polyphenylene ether 5.0 mg of polyphenylene ether was weighed. Then, the weighed polyphenylene ether was dissolved in 25 mL of methylene chloride. To 2.0 mL of the prepared solution, 150 μL of an ethanol solution of 2 mass% tetraethylammonium hydroxide (TEAH) was added, and then the absorbance (Abs) at 318 nm was measured using a UV spectrophotometer (Hitachi, Ltd.: Model U-3210) (a cell for absorbance measurement with a cell length of 1 cm was used). Then, based on the measurement result, the number of OH groups obtained from the absorbance was determined by the following formula (1). Number of OH groups (μmol / g) = [(25 × Abs) / (ε × 5)] × 10 6 ··· Formula (1) (Here, ε represents the extinction coefficient and is 4700 L / mol·cm.)

[0120] (4) Number of OH groups per molecule of polyphenylene ether Using the number average molecular weight determined by gel permeation chromatography (details are described in the above (2)), the number of OH groups per molecule of polyphenylene ether was determined by the following formula (2). Average number of hydroxyl groups per molecule (number / molecule) = (number average molecular weight determined using gel permeation chromatography) × (number of OH groups obtained from absorbance) / 10 6 ··· Formula (2)

[0121] (5) Long-term solubility in toluene (TL solubility) 5.0 g of polyphenylene ether and 5.0 g of toluene were weighed into a transparent screw tube made of glass. They were mixed at 20 °C using a stir bar and a magnetic stirrer. After allowing one day to pass for the mixed solution, the solution was checked and judged according to the following criteria. 〇: The solution maintains transparency △: There is a slight residue of undissolved material ×: It is clearly not dissolved or there is a large amount of insoluble matter

[0122]

Table 1

[0123] <Components other than polyphenylene ether> (Triallyl isocyanurate and / or triallyl cyanurate) · Triallyl isocyanurate (Product name: TAIC, manufactured by Tokyo Chemical Industry Co., Ltd., number average molecular weight: 249.3, number of unsaturated double bonds in the molecule: 3)

[0124] (Polyfunctional methacrylic compound) · Tricyclodecane dimethanol dimethacrylate (Product name: DCP, manufactured by Tokyo Chemical Industry Co., Ltd., number average molecular weight: 332.4, number of methacrylic functional groups in the molecule: 2) · Trimethylolpropane trimethacrylate (Product name: TMPT, manufactured by Tokyo Chemical Industry Co., Ltd., number average molecular weight: 338.4, number of methacrylic functional groups in the molecule: 3)

[0125] (Organic peroxide) · Bis(1-tert-butylperoxy-1-methylethyl)benzene (Product name: Perbutyl P, manufactured by NOF Corporation, half-life temperature for 1 minute: 175.4 °C)

[0126] [Examples] As shown below, cured products of the resin compositions of each example and comparative example were prepared.

[0127] (Example 1) According to the composition shown in Table 2, to 102 parts by mass of toluene, PPE1 synthesized by the above method was added and stirred until PPE1 was dissolved. Next, triallyl isocyanurate, polyfunctional methacrylic compound, and organic peroxide were added respectively and stirred well to obtain a varnish. After the obtained varnish was impregnated into a low-dielectric glass cloth, excess varnish was scraped off by passing it through a slit of a predetermined width and dried in a drying oven at 130 °C for a predetermined time to remove toluene, thereby obtaining a prepreg. The obtained prepreg was cut into a predetermined size, stacked in a predetermined number, and further, while copper foils (manufactured by Furukawa Electric Co., Ltd., thickness 18 μm, F1N-WS foil) were stacked on both sides of the stacked prepregs, a vacuum press was performed to obtain a copper-clad laminate. In the process of the vacuum press, first, while applying a pressure of 40 kg / cm2, the temperature was raised from 30 °C to 200 °C at a rate of 2 °C / min. After the temperature reached 200 °C, 200 °C was maintained for 60 minutes while applying a pressure of 40 kg / cm 2 was maintained. Then, the obtained copper-clad laminate was subjected to etching to remove the copper foil, thereby obtaining a laminate as a sample.

[0128] (Examples 2 to 9, Comparative Examples 1 to 13) Resin compositions, varnishes, prepregs, and copper-clad laminates were obtained respectively in the same manner as in Example 1, except that the resin composition was changed as shown in Tables 2 and 3. Regarding Comparative Example 12 using PPE6, polyphenylene ether was not completely dissolved in toluene, and prepregs and copper-clad laminates could not be produced.

[0129] <Evaluation> (1) Dielectric properties of the cured product of the resin composition Regarding the cured products of the resin compositions obtained in the above-described Examples and Comparative Examples, the dielectric constant and dielectric tangent at 10 GHz were measured by 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 Lab Co., Ltd.) were used. The cured products of the resin compositions obtained in the above-described Examples and Comparative Examples, having a thickness of about 0.5 mm, were cut into plates having a length of 50 mm and a width of 50 mm. Next, they were placed in an oven at 105 °C ± 3 °C and dried for 1 hour, and then left standing for 24 ± 2 hours in an environment of 23 °C and a relative humidity of 50 ± 2%. Thereafter, the dielectric constant and dielectric tangent were measured using the above-described measuring apparatus in an environment of 23 °C and a relative humidity of 50 ± 2%. In addition, from the perspective of reducing transmission loss, the dielectric tangent of the cured product of the measured resin composition is preferably 0.0053 or less, more preferably 0.0050 or less, still more preferably 0.0049 or less.

[0130] (2) Heat resistance (glass transition temperature) of the cured product of the resin composition For the copper-clad laminates obtained in the above-described examples and comparative examples, dynamic viscoelasticity was measured, and the temperature at which tanδ was maximum was determined as the glass transition temperature (Tg). A dynamic viscoelasticity apparatus (EPLEXOR 500N, manufactured by GABO) was used as the measuring apparatus. The cured products of the resin composition having a thickness of about 0.5 mm obtained in the above-described examples and comparative examples were cut into a length of 50 mm and a width of about 10 mm to obtain test pieces, and measurements were performed under the conditions of a tensile mode and a frequency of 5 Hz. In addition, from the perspective of dimensional stability in the processing process, the glass transition temperature of the cured product of the measured resin composition is preferably 203°C or higher, more preferably 205°C or higher, still more preferably 208°C or higher, and particularly preferably 210°C or higher.

[0131] (3) Solvent resistance (toluene immersion test) of the cured product of the resin composition The cured products of the resin composition having a thickness of about 0.5 mm obtained in the above-described examples and comparative examples were cut into a length of 50 mm and a width of 5 mm, immersed in a sufficient amount of toluene at 20°C for 24 hours, and then the mass loss was evaluated according to the following criteria. 〇: When the mass loss before and after immersion is less than 0.5% by mass △: When the mass loss before and after immersion is 0.5% by mass or more and less than 1% by mass ×: When the mass loss before and after immersion is 1% by mass or more

[0132]

Table 2

[0133]

Table 3

[0134] From the results in Tables 2 and 3, it can be seen that when PPE1 to 4 are included, the resin composition has excellent solubility in toluene, and by using them, a resin composition having excellent dielectric properties, high heat resistance, and excellent solvent resistance can be obtained. Also, for each sample in the examples, it can be seen that in terms of any of the dielectric properties, heat resistance, and solvent resistance, they are excellently balanced compared to each sample in the comparative examples.

Industrial Applicability

[0135] The resin composition containing the polyphenylene ether of the present invention and its cured product have excellent dielectric properties, heat resistance, and solvent resistance, and thus have industrial utility value as electronic material applications and modifier applications.

Claims

1. (A) polyphenylene ether, (B) triallyl isocyanurate and / or triallyl cyanurate, (C) a polyfunctional methacrylic compound, (C') a crosslinking agent other than triallyl isocyanurate, triallyl cyanurate, and polyfunctional methacrylic compounds, as an optional component; (D) a resin composition containing an organic peroxide, The polyphenylene ether (A) contains a repeating unit derived from a phenol represented by the following formula (1) and a repeating unit derived from a phenol represented by the following formula (2), the content of the repeating unit derived from phenol of the following formula (1) is 55 mol% or more and less than 90 mol%, and the content of the repeating unit derived from phenol of the following formula (2) is more than 10 mol% and 45 mol% or less, relative to 100 mol% in total of the repeating units of the following formula (1) and the following formula (2), The molecular weight distribution (Mw / Mn) determined by gel permeation chromatography (GPC) is 2.0 to 6.0; A resin composition characterized in that the number of OH groups per gram is 100 to 450 μmol / g and the number of OH groups per molecule is 0.8 to 2.5 / molecule. 【Chemistry 1】 (In formula (1), R 11 each independently represents an optionally substituted saturated hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a halogen atom; R 12 are each independently a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 6 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a halogen atom. 【Chemistry 2】 (In formula (2), R 22 are each independently a hydrogen atom, an optionally substituted saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 12 carbon atoms, or a halogen atom; 22 are not both hydrogen atoms, and R 21 is a partial structure represented by the following formula (3). 【Chemistry 3】 (In formula (3), R 31 each independently represents a linear alkyl group having 1 to 8 carbon atoms which may be substituted, or two R 31 is a cyclic alkyl structure having 1 to 8 carbon atoms bonded to R 32 each independently represents an optionally substituted alkylene group having 1 to 8 carbon atoms; each b independently represents 0 or 1; R 33 is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted phenyl group.

2. The resin composition according to claim 1, wherein the partial structure represented by the formula (3) is a t-butyl group.

3. 2. The resin composition according to claim 1, wherein the content of the polyphenylene ether (A) is 40 mass% or more and 80 mass% or less relative to 100 mass parts of the total amount of the polyphenylene ether (A), the triallyl isocyanurate and / or triallyl cyanurate (B), and the polyfunctional methacrylic compound (C).

4. The resin composition according to claim 1, characterized in that the content of the polyfunctional methacrylic compound (C) is 20 mass% or more and 80 mass% or less relative to 100 mass parts of the total amount of the (B) triallyl isocyanurate and / or triallyl cyanurate and the (C) polyfunctional methacrylic compound.

5. The resin composition according to claim 1, characterized in that the resin composition contains 0.05 parts by mass or more and 10 parts by mass or less of the organic peroxide (D) relative to a total of 100 parts by mass of the polyphenylene ether (A), the triallyl isocyanurate and / or triallyl cyanurate (B), the polyfunctional methacrylic compound (C), and the crosslinking agent other than triallyl isocyanurate and triallyl cyanurate (C').

6. The resin composition according to claim 5, characterized in that the resin composition contains 1.0 parts by mass or more and 5.0 parts by mass or less of the organic peroxide (D) relative to a total of 100 parts by mass of the polyphenylene ether (A), the triallyl isocyanurate and / or triallyl cyanurate (B), the polyfunctional methacrylic compound (C), and the crosslinking agent other than triallyl isocyanurate and triallyl cyanurate (C').

7. The resin composition according to claim 1, characterized in that the (D) organic peroxide is contained in an amount of 0.1 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the total amount of the (B) triallyl isocyanurate and / or triallyl cyanurate, the (C) polyfunctional methacrylic compound, and the (C') crosslinking agent other than triallyl isocyanurate and triallyl cyanurate.

8. The resin composition according to claim 1, wherein the organic peroxide (C) has a one-minute half-life temperature of 155°C to 195°C.

9. The resin composition according to claim 1, characterized in that the polyphenylene ether A (A) has a reduced viscosity (ηsp / c) of 0.13 to 0.30 dL / g measured in a chloroform solution having a concentration of 0.5 g / dL at 30°C.

10. A resin film comprising the resin composition according to any one of claims 1 to 9.

11. A prepreg, which is a composite of a substrate and the resin composition according to any one of claims 1 to 9.

12. The prepreg according to claim 11, characterized in that the base material is a glass cloth.

13. A metal-clad laminate comprising a laminate of the cured resin film according to claim 10 and a metal foil.

14. A metal-clad laminate comprising a cured product of the prepreg according to claim 11 and a metal foil.

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