JP2016121267A - Polyarylene ether resin, manufacturing method of polyarylene ether resin, curable resin material, cured article thereof, semiconductor encapsulation material, semiconductor device, prepreg, print circuit board, build-up film, build-up substrate, fiber-reinforced composite material and fiber-reinforced molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylene ether resin excellent in various physical properties of heat resistance, pyrolytic property, moisture resistance and solder resistance, flame retardancy and dielectric property, a manufacturing method of the resin, a cured article thereof, a semiconductor encapsulation material, a semiconductor device, a prepreg, a print circuit board, a build-up film, a build-up substrate, a fiber-reinforced composite material and a fiber-reinforced molded article.SOLUTION: There is provided a polyarylene ether resin having a polyarylene ether structure in a molecular structure, where at least one aromatic nuclear thereof has a naphthalene ring structure and at least one aromatic nuclear thereof has two benzoxazine skeletons obtained by reacting the polyarylene ether, an aromatic monohydroxy compound, a diamine compound and formaldehyde.SELECTED DRAWING: None

Description

  The present invention relates to a polyarylene ether resin excellent in various physical properties such as heat resistance, heat decomposition resistance, moisture resistance and solder resistance, flame retardancy and dielectric properties in a cured product, a method for producing a polyarylene ether resin, a curable resin material, and its curing The present invention relates to an article, a semiconductor sealing material, a semiconductor device, a prepreg, a printed circuit board, a buildup film, a buildup board, a fiber reinforced composite material, and a fiber reinforced molded product.

  Various resins such as epoxy resins, cyanate ester resins, bismaleimide-triazine resins, and benzoxazine resins are used as resin materials for electronic components used for semiconductor sealing materials and multilayer printed circuit board insulating layers. These resin materials are required to have excellent performance in heat resistance, heat decomposition resistance, flame resistance, moisture resistance, solder resistance, dielectric properties, and the like.

  Of the various resin materials, the benzoxazine resin is characterized by excellent heat resistance and dielectric properties in the cured product. As such a benzoxazine resin, specifically, a benzoxazine resin obtained by reacting bisphenol, formalin and aniline (see Patent Document 1), or a polymer compound having a benzoxazine ring in the main chain (patent Document 2 and Patent Document 3) are known. However, the benzoxazine resin described in Patent Document 1 is not sufficient in heat decomposition resistance, flame retardancy, and moisture resistance and solder resistance, and the benzoxazine resin based on the high molecular weight compounds described in Patent Documents 2 and 3 However, there was a problem that the heat resistance was insufficient. Therefore, there has been a demand for the development of a resin material with good performance balance that is excellent in all of heat resistance, heat decomposition resistance, moisture resistance, solder resistance, flame retardancy, dielectric properties, and the like in the cured product.

Japanese Patent Laid-Open No. 11-12258 JP 2003-64180 A JP 2008-291070 A

  Accordingly, the problem to be solved by the present invention is that polyarylene ether resins and polyarylene ether resins having excellent physical properties such as heat resistance, heat decomposition resistance, moisture resistance and solder resistance, flame resistance and dielectric properties in the obtained cured product. To provide a manufacturing method, a curable resin material, a cured product thereof, a semiconductor sealing material, a semiconductor device, a prepreg, a printed circuit board, a buildup film, a buildup board, a fiber reinforced composite material, and a fiber reinforced molded product. .

  As a result of intensive studies to solve the above problems, the present inventors have a polyarylene ether structure, and at least one of the aromatic nuclei in the polyarylene ether structure is a naphthalene ring structure, and the polyarylene ether structure The polyarylene ether resin having a dihydrooxazine structure moiety introduced into the aromatic nucleus is excellent in various physical properties such as heat resistance, heat decomposition resistance, moisture solder resistance, flame resistance and dielectric properties in the obtained cured product. As a result, the present invention has been completed.

That is, the present invention
It has a polyarylene ether structure (α) in the molecular structure, at least one of the aromatic nuclei in the polyarylene ether structure (α) has a naphthalene ring structure, and the polyarylene ether structure (α) That at least one of the aromatic nuclei has a structural site (β) represented by the following structural formula (1) or a structural site (γ) represented by the following structural formula (2) on the aromatic nucleus. The polyarylene ether resin is characterized.

In formula (1),
L ¹ is a divalent hydrocarbon group or a divalent linking group in which one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom, Either
Ar ¹ is each an aromatic nucleus,
R ¹ is independently a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or one or more hydrogen atoms contained in a hydrocarbon group or an alkoxy group is an alkoxy group, a hydroxyl group, or a halogen atom. Any of the structures substituted with,
O ^{* 1} atom and C ^{* 1} atom are respectively an oxygen atom and a carbon atom that are bonded to adjacent carbon atoms in the aromatic nucleus represented by Ar ¹ .
a is an integer of 0 to 4, i is an integer of 0 to 3, j is an integer of 0 to 4,
x and y each represent a bonding point with a carbon atom on the aromatic nucleus in the polyarylene ether structure (α).

In formula (2),
L ² represents a divalent hydrocarbon group, or a divalent linking group in which one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom, Either
Ar ² is each an aromatic nucleus,
R ² is independently a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or one or more hydrogen atoms contained in a hydrocarbon group or an alkoxy group is an alkoxy group, a hydroxyl group, or a halogen atom. Any of the structures substituted with,
O ^{* 2} atom and C ^{* 2} atom are respectively an oxygen atom and a carbon atom that are bonded to carbon atoms adjacent to each other in the aromatic nucleus represented by Ar ² .
b is an integer of 0-4, k is an integer of 0-3, l is an integer of 0-4,
* 1 indicates a bond with a carbon atom on the aromatic nucleus in the polyarylene ether structure (α).

  Process for producing a polyarylene ether resin obtained by reacting an aromatic dihydroxy compound and an aralkylating agent under an acid catalyst condition with an aromatic monohydroxy compound, a diamine compound and formaldehyde About.

  The present invention further relates to a curable resin material containing the polyarylene ether resin.

  The present invention further relates to a cured product obtained by curing the curable resin material.

  The present invention further relates to a semiconductor sealing material containing the curable resin material and an inorganic filler.

  The present invention further relates to a semiconductor device obtained by heat curing the semiconductor sealing material.

  The present invention further relates to a prepreg obtained by impregnating a reinforced resin material diluted with an organic solvent into a reinforcing base material and then semi-curing it.

  The present invention further relates to a printed circuit board obtained by laminating the prepreg and a copper foil and thermocompression bonding.

  The present invention further relates to a build-up film obtained by applying a material obtained by diluting the curable resin material in an organic solvent on a support film and drying it.

  The present invention further relates to a build-up substrate obtained by applying a plating treatment to a circuit substrate obtained by applying the build-up film to a circuit substrate on which a circuit is formed and heat-curing the circuit substrate.

  The present invention further relates to a fiber-reinforced composite material containing the curable resin material and reinforcing fibers.

  The present invention further relates to a fiber reinforced molded product obtained by curing the fiber reinforced composite material.

  According to the present invention, polyarylene ether resin having excellent physical properties such as heat resistance, heat decomposition resistance, moisture solder resistance, flame retardancy and dielectric properties in a cured product, a method for producing polyarylene ether resin, a curable resin material, The cured product, semiconductor sealing material, semiconductor device, prepreg, printed circuit board, build-up film, build-up board, fiber reinforced composite material, and fiber reinforced molded product can be provided.

FIG. 1 is a GPC chart of the polyarylene ether intermediate (A-1) obtained in Synthesis Example 1. FIG. 2 is an FD-MS spectrum of the polyarylene ether intermediate (A-1) obtained in Synthesis Example 1. FIG. 3 is an FD-MS spectrum of a trimethylsilylated polyarylene ether intermediate (A-1) obtained in Synthesis Example 1. FIG. 4 is a GPC chart of the polyarylene ether intermediate (A-2) obtained in Synthesis Example 2. FIG. 5 is an FT-IR chart of the polyarylene ether intermediate (A-2) obtained in Synthesis Example 2. FIG. 6 is an FD-MS spectrum of the polyarylene ether intermediate (A-2) obtained in Synthesis Example 2. FIG. 7 is an FD-MS spectrum of the trimethylsilylated product of the polyarylene ether intermediate (A-2) obtained in Synthesis Example 2. FIG. 8 is a GPC chart of the polyarylene ether resin (B-1) obtained in Example 1. FIG. 9 is a ¹³ C-NMR chart of the polyarylene ether resin (B-1) obtained in Example 1.

Hereinafter, the present invention will be described in detail.
The polyarylene ether resin of the present invention has a polyarylene ether structure (α) in the molecular structure, and at least one of the aromatic nuclei in the polyarylene ether structure (α) has a naphthalene ring structure, and , At least one of the aromatic nuclei in the polyarylene ether structure (α) is represented by the structural site (β) represented by the following structural formula (1) or the following structural formula (2) on the aromatic nucleus. It has a structural part (γ).

In formula (1), L ¹ is a divalent hydrocarbon group, or one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom. valent linking group, either, Ar ¹ are each aromatic nucleus, R ¹ is each independently a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or a hydrocarbon group or One or more hydrogen atoms contained in the alkoxy group are any of a structure in which any one of an alkoxy group, a hydroxyl group, or a halogen atom is substituted, and each of the O ^{* 1} atom and the C ^{* 1} atom is the Ar ¹ An oxygen atom and a carbon atom bonded to carbon atoms adjacent to each other in the aromatic nucleus represented by: a is an integer of 0 to 4, i is an integer of 0 to 3, j is an integer of 0 to 4, and x , Y is the polyarylene agent A point of attachment to the aromatic nucleus in Le structure (alpha), indicating that the binding to carbon atoms adjacent to each other of the aromatic nucleus.

In the formula (2), L ² is a divalent hydrocarbon group, or one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom. valent linking group, either, Ar ² are each aromatic nucleus, R ² are each independently hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or a hydrocarbon group or One or more hydrogen atoms contained in the alkoxy group are any of the structures in which any one of an alkoxy group, a hydroxyl group, or a halogen atom is substituted, and the O ^{* 2} atom and the C ^{* 2} atom are each Ar ^2. An oxygen atom and a carbon atom bonded to carbon atoms adjacent to each other in the aromatic nucleus represented by: b is an integer of 0 to 4, k is an integer of 0 to 3, l is an integer of 0 to 4, * 1 is the polyarylene ether It indicates the point of attachment to the carbon atoms on the aromatic nucleus in the structure (alpha).

  The structural part (β) represented by the structural formula (1) and the six-membered ring structure in the structural part (γ) represented by the structural formula (2) are so-called dihydrooxazine structures. As described above, the resin having such a dihydrooxazine structure is characterized by excellent heat resistance and dielectric properties in the obtained cured product, but has sufficient heat decomposition resistance, flame resistance, and moisture resistance and solder resistance. is not. Therefore, in the present invention, the polyarylene ether structure (α) is introduced into the structural site (β) represented by the structural formula (1) and the structural site (γ) represented by the structural formula (2). Thus, the obtained cured product has succeeded in obtaining a resin excellent in various physical properties such as heat resistance, heat decomposition resistance, moisture solder resistance, flame retardancy and dielectric properties.

In the structural formula (1) and the structural formula (2), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, a hydrocarbon group or an alkoxy group. One or more hydrogen atoms contained are composed of any of a structure in which any one of an alkoxy group, a hydroxyl group, and a halogen atom is substituted.

  Examples of the hydrocarbon group include aliphatic hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, aromatic hydrocarbon groups such as aryl groups, aralkyl groups in which aliphatic hydrocarbons and aromatic hydrocarbon groups are combined, and the like. Can be mentioned. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. Examples of the alkenyl group include a vinyl group and a 1-methylvinyl group. , Propenyl group, butenyl group, butenyl group, pentenyl group, pentenyl group and the like. Examples of the alkynyl group include ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group and the like.

  Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Aralkyl groups include benzyl, phenylethyl, phenylpropyl, tolylmethyl, tolylethyl, tolylpropyl, xylylmethyl, xylylethyl, xylylpropyl, naphthylmethyl, naphthylethyl, naphthylpropyl, etc. Can be mentioned.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentanoxy group, a hexanoxy group, and a cyclohexanoxy group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.

  The structure in which one or more hydrogen atoms of a hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom includes a hydroxyl group-containing alkyl group, an alkoxy group-containing alkyl group, a halogenated alkyl group, and a hydroxyl group-containing alkenyl. Group, alkoxy group-containing alkenyl group, halogenated alkenyl group, hydroxyl group-containing alkynyl group, alkoxy group-containing alkynyl group, halogenated alkynyl group, hydroxyl group-containing aryl group, alkoxy group-containing aryl group, halogenated aryl group, hydroxyl group-containing aralkyl group, Examples thereof include an alkoxy group-containing aralkyl group and a halogenated aralkyl group.

  Examples of the hydroxyl group-containing alkyl group include a hydroxyethyl group and a hydroxypropyl group. Examples of the alkoxy group-containing alkyl group include a methoxyethyl group, a methoxypropyl group, an allyloxymethyl group, an allyloxypropyl group, a propargyloxymethyl group, and a propargyloxypropyl group. Examples of the halogenated alkyl group include a chloromethyl group, a chloroethyl group, a chloropropyl group, a bromomethyl group, a bromoethyl group, a bromopropyl group, a fluoromethyl group, a fluoroethyl group, and a fluoropropyl group. Examples of the hydroxyl group-containing alkenyl group include 1-hydroxy-2,3-propenyl group and 2-hydroxy-4,5-pentenyl group. Examples of the halogenated alkenyl group include a 1-chloro-3,4-butenyl group and a 2-bromo-4,5-hexenyl group. Examples of the hydroxyl group-containing alkynyl group include 2-hydroxy-4,5-pentynyl group and 2-hydroxy-3,4-hexynyl. Examples of the halogenated alkynyl group include a 1-chloro-3,4-butynyl group and a 3-bromo-5,6-hexynyl group. Examples of the hydroxyl group-containing aryl group include a hydroxyphenyl group and a hydroxynaphthyl group. Examples of the halogenated aryl group include a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloronaphthyl group, a bromonaphthyl group, and a fluoronaphthyl group. Examples of the hydroxyl group-containing aralkyl group include a hydroxybenzyl group and a hydroxyphenethyl group. Examples of the halogenated aralkyl group include a chlorobenzyl group and a bromophenethyl group.

Among these, R ¹ and R ² are preferably composed of any one of a hydrogen atom, an alkyl group, an aryl group, and an aralkyl group from the viewpoint of improving heat resistance. From the viewpoint of improvement, a hydrogen atom or an aralkyl group is more preferable.

  In the structural formula (1) and the structural formula (2), L1 and L2 represent a divalent linking group. The divalent linking group represented by L1 or L2 is a divalent hydrocarbon group or one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom. And the like, and the like. The “divalent hydrocarbon group” referred to in the present invention refers to a hydrocarbon obtained by removing two hydrogens from a hydrocarbon group, and represents “—R— (R is a hydrocarbon)”. The “hydrocarbon” indicates an aliphatic saturated hydrocarbon, an aliphatic unsaturated hydrocarbon, an aromatic hydrocarbon, or a combination thereof.

When L1 and L2 represent a divalent hydrocarbon group, L1 and L2 are an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, an aralkylene group (a divalent group having an alkylene group and an arylene group). For example, “—R—Ar—R— (wherein R is an aliphatic hydrocarbon group, Ar is an aromatic hydrocarbon group)” can be used.

  In such a case, examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. Examples of the alkenylene group include a vinylene group, a 1-methylvinylene group, a propenylene group, a butenylene group, and a pentenylene group. Examples of the alkynylene group include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, and a hexynylene group. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group. Examples of the arylene group include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group. The aralkylene group is represented by “—R—Ar—R— (wherein R is an aliphatic hydrocarbon group, Ar is an aromatic hydrocarbon group)”, and has 7 to 20 carbon atoms having the alkylene group and the arylene group. Groups and the like.

When L ¹ and L ² represent a divalent group in which one or more hydrogen atoms contained in a hydrocarbon group are substituted with a hydroxyl group, an alkoxy group, or a halogen atom, L ¹ and L ² include a hydroxyl group Alkylene group, alkoxy group-containing alkylene group, halogenated alkylene group, hydroxyl group-containing alkenylene group, alkoxy group-containing alkenylene group, halogenated alkenylene group, hydroxyl group-containing alkynylene group, alkoxy group-containing alkynylene group, halogenated alkynylene group, hydroxyl group-containing cycloalkylene Groups, alkoxy group-containing cycloalkylene groups, halogenated cycloalkylene groups, hydroxyl group-containing arylene groups, alkoxy group-containing arylene groups, halogenated arylene groups, hydroxyl group-containing aralkylene groups, alkoxy group-containing aralkylene groups, and halogenated aralkylene groups.

Examples of the hydroxyl group-containing alkylene group include a hydroxyethylene group and a hydroxypropylene group. Examples of the alkoxy group-containing alkylene group include a methoxyethylene group, a methoxypropylene group, an allyloxymethylene group, an allyloxypropylene group, a propargyloxymethylene group, and a propargyloxypropylene group. Examples of the halogenated alkylene group include a chloromethylene group, a chloroethylene group, a chloropropylene group, a bromomethylene group, a bromoethylene group, a bromopropylene group, a fluoromethylene group, a fluoroethylene group, and a fluoropropylene group.
Examples of the hydroxyl group-containing alkenylene group include a hydroxybutenylene group and a hydroxypentenylene group. Examples of the alkoxy group-containing alkenylene group include a methoxybutenylene group and an ethoxyhexenylene group. Examples of the halogenated alkenylene group include a chloropropenylene group and a bromopentenylene group.
Examples of the hydroxyl group-containing alkynylene group include a hydroxypentynylene group and a hydroxyhexynylene group. Examples of the alkoxy group-containing alkynylene group include an ethoxyhexynylene group and a methoxyheptynylene group. Examples of the halogenated alkynylene group include a chlorohexynylene group and a fluorooctynylene group.
Examples of the hydroxyl group-containing cycloalkylene group include a hydroxycyclohexanylene group. Examples of the alkoxy group-containing cycloalkylene group include a methoxycyclopentanylene group. Examples of the halogenated cycloalkylene group include a dichlorocyclopentanylene group.

Examples of the hydroxyl group-containing arylene group include a hydroxyphenylene group. Examples of the alkoxy group-containing arylene group include a methoxyphenylene group, an ethoxyphenylene group, an allyloxyphenylene group, and a propargyloxyphenylene group. Examples of the halogenated arylene group include a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloronaphthyl group, a bromonaphthyl group, and a fluoronaphthyl group.
In addition to the above, an unsaturated hydrocarbon group-containing arylene group may be used as L ¹ and L ² . Examples of the unsaturated hydrocarbon group-containing arylene group include vinyl phenylene, allyl phenylene, ethynyl phenylene, and propargyl phenylene.

In addition to L ¹ and L ² , the L ¹ and L ² are structures represented by the following structural formula (L-1) and structures represented by the following structural formula (L-2). Also good.

However, in the formulas (L-1) and (L-2), L ³ represents a divalent linking group. R ⁴ each independently represents a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, or any substituent selected from a halogen atom, or one or more hydrogen atoms contained in the hydrocarbon group or the alkoxy group Represents a substituent substituted with either a hydroxyl group or a halogen atom. Moreover, p has shown the integer of 1-4. * Indicates a bonding point with a nitrogen atom in the structural formulas (1) and (2).

As described above, L ³ is composed of a divalent linking group. Examples of the divalent linking group represented by L ³ include an alkylene group, an ether group (—O— group), a carbonyl group (—CO— group), an ester group (—COO— group), and an amide group (—CONH— group). , An imino group (—C═N— group), an azo group (—N≡N— group), a sulfide group (—S— group), a sulfone group (—SO ₃ — group), and the like.

Among the above, L ³ is preferably composed of either an alkylene group or an ether group because it is excellent in flame retardancy and dielectric properties in a cured product.

The L ¹ and L ² are any of the structure represented by the structural formula (L-1), the structure represented by the structural formula (L-2), an alkylene group, an arylene group, or an aralkylene group. It is preferable that it is a bivalent coupling group shown by these.

In the structural formula (1) and the structural formula (2), Ar ¹ and Ar ² represent aromatic nuclei such as a benzene ring, a naphthalene ring, and an anthracene ring.

  In the polyarylene ether resin of the present invention, at least one of the aromatic nuclei in the polyarylene ether structure (α) has a naphthalene ring structure, and the structural site (β) or the structural site (γ) is aromatic. Any polyarylene ether resin may be used as long as it is introduced into the nucleus. For example, a polyarylene ether resin having a molecular structure represented by the following structural formula (3) is preferable.

In formula (3), Ar ³ and Ar ⁴ are aromatic nuclei, but at least one of the aromatic nuclei represented by Ar ³ and Ar ⁴ present in the molecule is a naphthalene ring. Ar ³ has, as a substituent, either a structural site (β) represented by the following structural formula (1) or a hydroxyl group on the aromatic nucleus, but at least one of Ar ^{3 in} the molecule has the following structural formula. It has the structural moiety (β) represented by (1) as a substituent. R ³ is each independently one or more hydrogen atoms contained in the structural moiety (γ) represented by the following structural formula (2), a hydrocarbon group, an alkoxy group, a halogen atom, a hydrogen atom, or a hydrocarbon group Any of the structures in which the atom is substituted with any of a hydroxyl group, an alkoxy group, an aryl group, or a halogen atom. m is an integer of 1 to 3, and n is an integer of 0 to 4.

In formula (1), L ¹ is a divalent hydrocarbon group, or one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom. valent linking group, either, Ar ¹ are each aromatic nucleus, R ¹ is each independently a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or a hydrocarbon group or One or more hydrogen atoms contained in the alkoxy group are any of a structure in which any one of an alkoxy group, a hydroxyl group, or a halogen atom is substituted, and each of the O ^{* 1} atom and the C ^{* 1} atom is the Ar ¹ An oxygen atom and a carbon atom bonded to carbon atoms adjacent to each other in the aromatic nucleus represented by: a is an integer of 0 to 4, i is an integer of 0 to 3, j is an integer of 0 to 4, and x , Y is an aromatic group represented by Ar ^3. It is the point of attachment to adjacent carbon atoms in the scented nucleus. ^{Incidentally, L 1, Ar 1, R} 1, represents, for a specific structure or the like, are similar to those described above.

In the formula (2), L ² is a divalent hydrocarbon group, or one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom. valent linking group, either, Ar ² are each aromatic nucleus, R ² are each independently hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or a hydrocarbon group or One or more hydrogen atoms contained in the alkoxy group are any of the structures in which any one of an alkoxy group, a hydroxyl group, or a halogen atom is substituted, and the O ^{* 2} atom and the C ^{* 2} atom are each Ar ^2. An oxygen atom and a carbon atom bonded to carbon atoms adjacent to each other in the aromatic nucleus represented by: b is an integer of 0 to 4, k is an integer of 0 to 3, l is an integer of 0 to 4, * Table 1, the ^Ar 3, Ar ⁴ It indicates the point of attachment to the carbon atoms on the aromatic nucleus. The specific structure represented by L ² , Ar ² , and R ² is the same as that described above.

In the structural formula (3), Ar ³ and Ar ⁴ are aromatic nuclei, and at least one of Ar ³ and Ar ⁴ present in the molecule is a naphthalene ring. Examples of the aromatic nucleus other than the naphthalene ring represented by Ar ³ and Ar ⁴ include a benzene ring and an anthracene ring.

In the structural formula (3), each R ³ independently represents a structural site (γ) represented by the structural formula (2), a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or a carbon atom. One or more hydrogen atoms contained in a hydrogen group or an alkoxy group is any one of the structures in which any one of an alkoxy group, a hydroxyl group, and a halogen atom is substituted. This is the same as that described in. Among these, R ³ is excellent in curability, and the cured product obtained has excellent physical properties such as heat resistance, heat decomposability, flame retardancy and moisture solder resistance. It is preferably any of a group, a hydroxy naphthyl group, a benzyl group, a naphthylmethyl group, or a structural site (γ) represented by the structural formula (2).

  The polyarylene ether structure (α) of the polyarylene ether resin has a structure such as a benzene ring or an anthracene ring as long as at least one of the aromatic nuclei in the structure has a naphthalene ring structure. It may have. Among them, since the resulting cured product becomes a polyarylene ether resin having excellent heat resistance and flame retardancy, 50 mol% or more of aromatic nuclei in the polyarylene ether structure (α) have a naphthalene ring structure. Preferably, the polyarylene ether structure (α) is more preferably a polynaphthylene ether structure.

  When the polyarylene ether structure (α) is a polynaphthylene ether structure, examples of a more preferable structure of the polyarylene ether resin of the present invention include those having a structure represented by the following structural formula (4). It is done.

In the formula (4), X and Y represent bonding to adjacent carbon atoms in the aromatic nucleus, and X is a hydroxyl group and Y is a hydrogen atom, or the following structural formula (5) In which at least one pair of X and Y in the molecule has a structural site (β) represented by the following structural formula (5). In addition, each R ⁴ independently represents a structural moiety (γ) represented by the following structural formula (6), a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or a hydrocarbon group or an alkoxy group. One or more hydrogen atoms contained are any one of structures substituted with any of an alkoxy group, a hydroxyl group or a halogen atom, and at least one of R ^{4 in} the molecule is represented by the following structural formula (6) It is a structural site (γ) represented by s is an integer of 1 to 5, and t is an integer of 0 to 4. The specific structure and the like represented by R ⁴ are the same as those described above.

In formula (5), L ^{1 ′} is a divalent hydrocarbon group, or one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with either a hydroxyl group, an alkoxy group or a halogen atom. One of divalent linking groups, and each R ^{1 ′} is independently one or more contained in a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or a hydrocarbon group or an alkoxy group. In which a hydrogen atom is substituted with an alkoxy group, a hydroxyl group or a halogen atom, a ^′ is an integer of 0 to 4, i ^′ is an integer of 0 to 5, and j ^′ is an integer of 1 to 1. And x and y are points of attachment to the carbon atom to which X and Y in the structural formula (4) are bonded. * Is a point of attachment to the naphthalene ring and represents bonding to adjacent carbon atoms on the naphthalene ring. Specific structures and the like indicated by L ^{1 ′} and R ^{1 ′} are the same as those described for L ¹ and R ¹ , respectively.

In formula (6), L ^{2 ′} is a divalent hydrocarbon group, or one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with either a hydroxyl group, an alkoxy group or a halogen atom. Each of R ^{2 ′} independently represents a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or one or more hydrogen atoms contained in a hydrocarbon group or an alkoxy group. , An alkoxy group, a structure substituted with a hydroxyl group or a halogen atom, b ^′ is an integer of 0 to 4, k ^′ is an integer of 0 to 5, and l ^′ is an integer of 1 to 6. Yes, * 1 ^′ indicates the point of attachment to the carbon atom on the naphthalene ring in the structural formula (4). * Is a point of attachment to the naphthalene ring and represents bonding to adjacent carbon atoms on the naphthalene ring. Specific structures and the like shown by L ^{2 ′} and R ^{2 ′} are the same as those described for L ² and R ² , respectively.

  The bonding position of the oxygen atom on the naphthalene ring in the naphthylene ether structure in the structural formula (4) is, for example, 1,2-position, 1,4-position, 1,5-position, 1,6-position, It may be bonded to any carbon atom on the aromatic nucleus such as 1,7-position, 2,3-position, 2,6-position, 2,7-position. Especially, since it is excellent in the flame retardance and dielectric property in hardened | cured material, it is preferable that it is 1,6-position or 2,7-position, and it is especially preferable that it is 2,7-position.

  In the structural formula (3) and the structural formula (4), n and t are integers of 0 to 4, respectively. Among them, it is preferable to contain a resin component in which n and t are 0 or 1 because the viscosity is low and both the flame retardancy and moisture resistance and solder resistance of the cured product are excellent.

Moreover, the sum of the aromatic nuclei contained in the polyarylene ether resin represented by the structural formula (3) (the sum of the aromatic nuclei represented by Ar ² , Ar ³ , and R ³ ) has a low viscosity, Since it is excellent in both flame retardance and moisture resistance and solder resistance, the range of 4 to 12 is preferable.

  In the polyarylene ether resin of the present invention, the dihydrooxazine structure in the structural moiety (β) represented by the structural formula (1) or the structural moiety (γ) represented by the structural formula (2), and a phenolic hydroxyl group The functional group equivalent when the total amount is the functional group is excellent in reactivity, and is excellent in various physical properties such as heat resistance, heat decomposition resistance, flame retardancy, and moisture solder resistance in the cured product. A range of / eq is preferable.

  In the polyarylene ether resin of the present invention, the structural site (β) and the structural site (γ) with respect to the total number of phenolic hydroxyl groups, the structural site (β) and the structural site (γ) present in the resin. The ratio of the total number is preferably 50% or more, because it is excellent in reactivity and excellent in various physical properties such as heat resistance, heat decomposition resistance, flame retardancy and moisture resistance and solder resistance in a cured product. It is particularly preferred that

<Method for producing polyarylene ether resin>
The polyarylene ether resin of the present invention can be produced, for example, by the following method.
Method 1: An aromatic dihydroxy compound and an aralkylating agent are reacted under an acid catalyst condition to obtain a polyarylene ether intermediate, and the polyarylene ether intermediate is reacted with an aromatic monohydroxy compound, a diamine compound and formaldehyde. Method.
Method 2: A method in which an aromatic dihydroxy compound is reacted under alkaline catalyst conditions to obtain a polyarylene ether intermediate, and this polyarylene ether intermediate is reacted with an aromatic monohydroxy compound, a diamine compound and formaldehyde.

<Method 1>
Method 1 will be described below. Method 1 is specifically composed of the following two steps.
Step 1: A step of reacting an aromatic dihydroxy compound and an aralkylating agent under acid catalyst conditions to obtain a polyarylene ether intermediate.
Step 2: A step of reacting a polyarylene ether intermediate, a diamine compound, an aromatic monohydroxy compound, and formaldehyde.

  Step 1 will be described. The aromatic dihydroxy compound used in Step 1 is, for example, 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol or other dihydroxybenzene; 1,2-dihydroxynaphthalene, 1,4-dihydroxynaphthalene 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like. . These may be used alone or in combination of two or more. Among them, dihydroxynaphthalene is preferable because it is excellent in flame retardancy and dielectric properties in the cured product, 1,6-dihydroxynaphthalene or 2,7-dihydroxynaphthalene is more preferable, and 2,7-dihydroxynaphthalene is particularly preferable.

  Examples of the aralkylating agent used in Step 1 include benzyl chloride, benzyl bromide, benzyl iodide, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, p-ethylbenzyl chloride, p-isopropylbenzyl chloride. , P-tert-butylbenzyl chloride, p-phenylbenzyl chloride, 5-chloromethylacenaphthylene, 2-naphthylmethyl chloride, 1-chloromethyl-2-naphthalene and their nucleus-substituted isomers, α-methylbenzyl chloride And halide compounds such as α, α-dimethylbenzyl chloride; benzyl methyl ether, o-methyl benzyl methyl ether, m-methyl benzyl methyl ether, p-methyl benzyl methyl ether, p Ether compounds such as ethyl benzyl methyl ether and nucleo-substituted isomers thereof, benzyl ethyl ether, benzyl propyl ether, benzyl isobutyl ether, benzyl n-butyl ether, p-methyl benzyl methyl ether and nucleo-substituted isomers thereof; benzyl alcohol, o -Methylbenzyl alcohol, m-methylbenzyl alcohol, p-methylbenzyl alcohol, p-ethylbenzyl alcohol, p-isopropylbenzyl alcohol, ptert-butylbenzyl alcohol, p-phenylbenzyl alcohol, α-naphthylmethanol and their nuclear substitutions Isomers, alcohol compounds such as α-methylbenzyl alcohol and α, α-dimethylbenzyl alcohol; styrene, o-methylstyrene, m-methylstyrene, p -Styrene compounds, such as methylstyrene, (alpha) -methylstyrene, (beta) -methylstyrene, etc. are mentioned. These may be used alone or in combination of two or more. Among these, benzyl chloride, benzyl bromide, and benzyl alcohol are preferable because a benzoxazine resin excellent in dielectric properties and moisture resistance and solder resistance in a cured product can be obtained.

  The reaction ratio between the aromatic dihydroxy compound and the aralkylating agent is such that the molar ratio of the two [dihydroxy compound / aralkylating agent] is 1.0 / 0.1 to 1.0 / 1.0. It is preferable because a polyarylene ether resin excellent in flame retardancy and moisture and solder resistance in a cured product can be obtained.

  Examples of the acid catalyst used in Step 1 include inorganic acids such as phosphoric acid, sulfuric acid, and hydrochloric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and organic acids such as fluoromethanesulfonic acid, aluminum chloride, Examples include Friedel-Crafts catalysts such as zinc chloride, stannic chloride, ferric chloride, and diethyl sulfate. These may be used alone or in combination of two or more.

  The amount of the acid catalyst used is preferably in the range of 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the aromatic dihydroxy compound raw material in the case of an inorganic acid or an organic acid. Is preferably used in the range of 0.2 to 3.0 mol per mol of the aromatic dihydroxy compound raw material.

  The reaction of the aromatic dihydroxy compound and the aralkylating agent may be performed in an organic solvent as necessary. Examples of the organic solvent used herein include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, butyl carbitol, and the like. Examples thereof include carbitol solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. Each of these may be used alone, or two or more kinds of mixed solvents may be used.

  The reaction between the aromatic dihydroxy compound and the aralkylating agent can be performed, for example, under a temperature condition of 100 to 180 ° C., and after completion of the reaction, the reaction system is filled with an alkali compound such as an alkali metal hydroxide. After neutralization, the water and organic solvent produced in the reaction can be dried under reduced pressure to obtain a polyarylene ether intermediate.

  The polyarylene ether intermediate obtained in step 1 has a hydroxyl group equivalent in the range of 150 to 200 g / eq, low viscosity and excellent curability, heat resistance in the cured product, thermal decomposition resistance, flame retardancy, A polyarylene ether resin excellent in various physical properties such as moisture resistance and solder resistance can be obtained, which is preferable.

  Step 2 will be described. In step 2, the obtained polyarylene ether intermediate, diamine compound, aromatic monohydroxy compound, and formaldehyde are reacted.

  Examples of the diamine compound include those represented by the following structural formula (7).

  In the formula (7), L is a divalent hydrocarbon group, or a divalent hydrocarbon group in which one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom. Any one of linking groups;

  Specific examples of L include alkylene groups such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group and cyclohexylene group; alkenylene groups such as propenylene group and butenylene group; propargylene group and the like Alkynylene group; hydroxyl group-containing alkylene group such as hydroxyethylene group and hydroxypropylene group; alkoxy group-containing alkylene such as methoxyethylene group, methoxypropylene group, allyloxymethylene group, allyloxypropylene group, propargyloxymethylene group and propargyloxypropylene group Group: halogenated chloromethylene group, chloroethylene group, chloropropylene group, bromomethylene group, bromoethylene group, bromopropylene group, fluoromethylene group, fluoroethylene group, fluoropropylene group, etc. Alkylene group; arylene groups such as phenylene group, tolylene group, xylylene group and naphthylene group; hydroxyl group-containing arylene groups such as hydroxyphenylene group and hydroxynaphthylene group; methoxyphenylene group, ethoxyphenylene group, allyloxyphenylene group and propargyloxyphenylene Alkoxy group-containing arylene groups such as vinyl groups; arylene groups containing unsaturated hydrocarbon groups such as vinylphenylene groups, allylphenylene groups, ethynylphenylene groups, propargylphenylene groups; chlorophenylene groups, bromophenylene groups, fluorophenylene groups, chloronaphthylenes And halogenated arylene groups such as a bromonaphthylene group and a fluoronaphthylene group. These monoamine compounds may be used alone or in combination of two or more. Among them, an arylene group is preferable and a phenylene group is more preferable because of excellent reactivity and excellent physical properties such as heat resistance, heat decomposition resistance, flame resistance, and moisture resistance and solder resistance in a cured product.

  Examples of the aromatic monohydroxy compound include compounds represented by the following structural formulas (8) and (9).

In formulas (8) and (9), each R ¹ independently represents one or more hydrogen atoms contained in a hydrogen atom, hydrocarbon group, alkoxy group, hydroxyl group, halogen atom, or hydrocarbon group or alkoxy group. Is an alkoxy group, a hydroxyl group or a structure substituted with any one of a halogen atom, m represents an integer of 0 to 4, and n represents an integer of 0 to 6.

  Examples of such aromatic monohydroxy compounds include phenol and naphthol. These may be used alone or in combination of two or more. Among these, naphthol is preferable because it is excellent in flame retardancy and dielectric properties in a cured product.

  The formaldehyde may be used in the form of either formalin in a solution state or paraformaldehyde in a solid state.

  The reaction ratio between the polyarylene ether intermediate, the diamine compound, and the aromatic monohydroxy compound is such that the aromatic monohydroxy compound is 0.7 to 1.3 mol and the diamine with respect to 1 mol of the hydroxyl group in the polyarylene ether intermediate. It is preferable that the compound is in the range of 0.8 to 1.2 mol because the target polyarylene ether resin is more efficiently produced. In addition, the reaction ratio of the polyarylene ether intermediate and the formaldehyde is such that the formaldehyde is in the range of 3.4 to 4.6 mol with respect to 1 mol of the hydroxyl group in the polyarylene ether intermediate. The ether resin is preferable because it is generated more efficiently.

  The reaction of the polyarylene ether intermediate, the aromatic monohydroxy compound, the diamine compound, and formaldehyde may be performed in the presence of a catalyst as necessary. Examples of the catalyst used here include various catalysts usually used in the production of dihydrooxazine compounds. Specifically, amide compounds such as N, N-dimethylformamide; pyridine, N, N-dimethyl-4- Pyridine compounds such as aminopyridine; amine compounds such as triethylamine and tetramethylethylenediamine; quaternary ammonium salts such as tetrabutylammonium bromide; organic acid compounds such as acetic acid, trifluoroacetic acid, paratoluenesulfonic acid and trifluoromethanesulfonic acid; water Alkali metal hydroxides or carbonates such as potassium oxide, potassium carbonate, sodium carbonate; phenolic compounds such as dibutylhydroxytoluene; palladium, tetrakis (triphenylphosphine) palladium, copper iodide, tin tetrachloride, nickel, platinum, etc. Gold Catalyst and the like. These may be used alone or in combination of two or more.

  The reaction of the polyarylene ether intermediate, the aromatic monohydroxy compound, the diamine compound, and formaldehyde may be performed in an organic solvent as necessary. Examples of the organic solvent used herein include alcohol compounds such as water, methanol, ethanol, and isopropanol; ether compounds such as dioxane, tetrahydrofuran, and diethyl ether; acetic acid compounds such as acetic acid and trifluoroacetic acid; acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketone compounds such as cyclohexanone; Acetic ester compounds such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; Carbitol compounds such as cellosolve and butyl carbitol; Dichloromethane, chloroform, carbon tetrachloride, dichloroethane Chlorinated hydrocarbon compounds such as chlorobenzene; Hydrocarbon compounds such as cyclohexane, benzene, toluene and xylene; Dimethylforma De, dimethyl acetamide, amide compounds such as N- methylpyrrolidone; amine compounds such as aniline; dimethyl sulfoxide, acetonitrile and the like. These may be used alone or as a mixed solvent of two or more.

  The reaction of the polyarylene ether intermediate, the aromatic monohydroxy compound, the diamine compound, and formaldehyde can be performed, for example, at a temperature of 50 to 100 ° C. After the reaction is completed, the aqueous layer and the organic layer are separated. The polyarylene ether resin can be obtained by drying the organic solvent under reduced pressure from the organic layer.

  Examples of the polyarylene ether resin obtained by the above method include 2,7-dihydroxynaphthalene as an aromatic dihydroxy compound, benzyl alcohol as an aralkylating agent, phenol as an aromatic monohydroxy compound, and 4,4 as a diamine compound. When '-diaminodiphenylmethane is used, those represented by any one of the following structural formulas (10-1) to (10-23) are exemplified.

  In formulas (11-1) to (11-23), Bn represents a benzyl group.

  Further, when 1,6-dihydroxynaphthalene is used as the aromatic dihydroxy compound, benzyl alcohol is used as the aralkylating agent, phenol is used as the aromatic monohydroxy compound, and 4,4′-diaminodiphenylmethane is used as the diamine compound. Include those represented by any of the following structural formulas (11-1) to (11-23).

  In formulas (11-1) to (11-23), Bn represents a benzyl group, and Ar represents a structure represented by the following structural formula (11-24).

  In formula (11-24), * represents a bonding point with a nitrogen atom bonded to Ar in the compounds represented by formulas (11-1) to (11-23).

<Method 2>
Method 2 will be described below. Method 2 is specifically composed of the following two steps.
Step 1: A step of polycondensation reaction of an aromatic dihydroxy compound under alkaline catalyst conditions to obtain a polyarylene ether intermediate.
Step 2: A step of reacting a polyarylene ether intermediate, a diamine compound, an aromatic monohydroxy compound, and formaldehyde.

  Step 1 will be described. The aromatic dihydroxy compound used in Step 1 is the same as that described in the description of Method 1 above.

  Examples of the alkali catalyst used in Step 1 include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, alkali metal carbonates such as potassium carbonate and sodium carbonate, and phosphorus compounds such as triphenylphosphine. These may be used alone or in combination of two or more. Among these, alkali metal hydroxides are preferable because they are more excellent in reactivity.

  The amount of these alkali catalysts used is preferably in the range of 0.1 to 3.0 mol per 1 mol of the aromatic dihydroxy compound raw material.

  The condensation polymerization reaction of the aromatic dihydroxy compound may be performed in an organic solvent as necessary. Examples of the organic solvent used herein include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, butyl carbitol, and the like. Examples thereof include carbitol solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. These may be used alone or in combination of two or more.

  The polycondensation reaction of the aromatic dihydroxy compound can be performed, for example, at a temperature of 150 to 210 ° C. After the reaction is completed, the aqueous layer and the organic layer are separated, and then the organic solvent is dried from the organic layer under reduced pressure. Thus, a polyarylene ether intermediate can be obtained.

  The polyarylene ether intermediate obtained in Step 1 has a hydroxyl group equivalent in the range of 100 to 150 g / eq, low viscosity and excellent curability, heat resistance, thermal decomposition resistance, flame retardancy in the cured product, A polyarylene ether resin excellent in various physical properties such as moisture resistance and solder resistance can be obtained, which is preferable.

  Next, in step 2, the obtained polyarylene ether intermediate, diamine compound, aromatic monohydroxy compound, and formaldehyde are reacted.

  The diamine compound, aromatic monohydroxy compound, and formaldehyde used here are the same as those described in the description of the method 1.

  The reaction rate of the polyarylene ether intermediate and the diamine compound is such that the aromatic monohydroxy compound is 0.7 to 1.3 mol and the diamine compound is 0.8 mol per mol of the hydroxyl group in the polyarylene ether intermediate. The range of ˜1.2 mol is preferable because the target polyarylene ether resin is more efficiently produced. In addition, the reaction ratio of the polyarylene ether intermediate and the formaldehyde is such that the formaldehyde is in the range of 3.4 to 4.6 mol with respect to 1 mol of the hydroxyl group in the polyarylene ether intermediate. An arylene ether resin is preferable because it is more efficiently generated.

  The reaction of the polyarylene ether intermediate, the diamine compound, the aromatic monohydroxy compound, and formaldehyde may be performed in the presence of a catalyst as necessary. Examples of the catalyst used here include various catalysts usually used in the production of dihydrooxazine compounds. Specifically, amide compounds such as N, N-dimethylformamide; pyridine, N, N-dimethyl-4- Pyridine compounds such as aminopyridine; amine compounds such as triethylamine and tetramethylethylenediamine; quaternary ammonium salts such as tetrabutylammonium bromide; organic acid compounds such as acetic acid, trifluoroacetic acid, paratoluenesulfonic acid and trifluoromethanesulfonic acid; water Alkali metal hydroxides or carbonates such as potassium oxide, potassium carbonate, sodium carbonate; phenolic compounds such as dibutylhydroxytoluene; palladium, tetrakis (triphenylphosphine) palladium, copper iodide, tin tetrachloride, nickel, platinum, etc. Gold Catalyst and the like. These may be used alone or in combination of two or more.

  The reaction of the polyarylene ether intermediate, the diamine compound, the aromatic monohydroxy compound, and formaldehyde may be performed in an organic solvent as necessary. Examples of the organic solvent used herein include alcohol compounds such as water, methanol, ethanol, and isopropanol; ether compounds such as dioxane, tetrahydrofuran, and diethyl ether; acetic acid compounds such as acetic acid and trifluoroacetic acid; acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketone compounds such as cyclohexanone; Acetic ester compounds such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; Carbitol compounds such as cellosolve and butyl carbitol; Dichloromethane, chloroform, carbon tetrachloride, dichloroethane Chlorinated hydrocarbon compounds such as chlorobenzene; Hydrocarbon compounds such as cyclohexane, benzene, toluene and xylene; Dimethylforma De, dimethyl acetamide, amide compounds such as N- methylpyrrolidone; amine compounds such as aniline; dimethyl sulfoxide, acetonitrile and the like. These may be used alone or as a mixed solvent of two or more.

  The reaction of the polyarylene ether intermediate, the diamine compound, the aromatic monohydroxy compound, and formaldehyde can be performed, for example, at a temperature of 50 to 100 ° C. After the reaction is completed, the aqueous layer and the organic layer are separated. The target polyarylene ether resin can be obtained by drying the organic solvent under reduced pressure from the organic layer.

  The polyarylene ether resin obtained by Method 2 is, for example, when 2,7-dihydroxynaphthalene is used as the aromatic dihydroxy compound and 4,4′-diaminodiphenylmethane is used as the diamine compound. 12-1) to (12-12) or the like.

  In formulas (12-1) to (12-12), Ar represents a structure represented by the following structural formula (12-13).

  In formula (12-13), * represents a bonding point with a nitrogen atom bonded to Ar in the compounds represented by formulas (12-1) to (12-12).

  In addition, when 1,6-dihydroxynaphthalene is used as the aromatic dihydroxy compound and aniline is used as the monoamine compound, specifically, one represented by any of the following structural formulas (13-1) to (13-9) Etc.

  In formulas (13-1) to (13-9), Ar represents a structure represented by the following structural formula (13-10).

  In formula (13-10), * represents a bonding point with a nitrogen atom bonded to Ar in the compounds represented by formulas (13-1) to (13-9).

  The curable resin material of the present invention contains the polyarylene ether resin of the present invention as an essential component. Since the polyarylene ether resin alone can cause a curing reaction, the polyarylene ether resin may be used alone as a resin component in the curable resin material of the present invention, and other thermosetting resins. You may use together.

  Examples of the other thermosetting resins include resins having a benzoxazine structure other than the structural formula (3), epoxy resins, phenolic hydroxyl group-containing compounds, cyanate ester resins, maleimide compounds, active ester resins, vinylbenzyl compounds, Examples thereof include acrylic compounds and copolymers of styrene and maleic anhydride. When the other thermosetting resins described above are used in combination, the amount used is not particularly limited as long as the effect of the present invention is not impaired, but is in the range of 1 to 50 parts by mass in 100 parts by mass of the curable resin material. It is preferable.

  The resin having a benzoxazine structure other than those described above is not particularly limited. For example, a reaction product of bisphenol F, formalin, and aniline (Fa type benzoxazine resin), diaminodiphenylmethane, formalin, and phenol. Reaction product (Pd type benzoxazine resin), reaction product of bisphenol A, formalin and aniline, reaction product of dihydroxydiphenyl ether, formalin and aniline, reaction product of diaminodiphenyl ether, formalin and phenol, dicyclopentadiene- Examples include a reaction product of a phenol addition resin, formalin and aniline, a reaction product of phenolphthalein, formalin and aniline, a reaction product of diphenyl sulfide, formalin and aniline. These may be used alone or in combination of two or more.

  Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol sulfide type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, Biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol Addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin Resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, biphenyl-modified novolac type epoxy resin, anthracene type epoxy resin, etc. . These may be used alone or in combination of two or more.

  Among these epoxy resins, tetramethylbiphenol type epoxy resin, biphenyl aralkyl type epoxy resin, naphthylene ether type epoxy resin, polyhydroxynaphthalene type epoxy resin, novolak are particularly preferable in that a cured product having excellent flame retardancy can be obtained. It is preferable to use a type epoxy resin, and a dicyclopentadiene-phenol addition reaction type epoxy resin is preferable in that a cured product having excellent dielectric properties can be obtained.

  When the polyarylene ether resin and the epoxy resin of the present invention are used in combination, the total number of moles (p) of the dihydrooxazine structure and the phenolic hydroxyl group in the polyarylene ether resin and the number of moles of the epoxy group in the epoxy resin (q The ratio [(p) / (q)] to 1.0 / 0.1 to 1.0 / 1.0, more preferably 1.0 / 0.1 to 1.0 / 0. A ratio of 5 is preferable because a cured product having excellent heat resistance and heat decomposability in the cured product can be obtained.

  Examples of the phenolic hydroxyl group-containing compound include phenol novolak resins, cresol novolak resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, naphthylene ether resins, dicyclopentadiene phenol addition resins, phenol aralkyl resins, naphthol aralkyl resins, triphenyl resins. Methylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), Biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenol nuclei are linked by bismethylene groups), aminotriazine-modified phenol resin (melamine) Polyhydric phenol compound phenol nuclei are connected by benzoguanamine), and the like. These may be used alone or in combination of two or more.

  Among these phenolic hydroxyl group-containing compounds, those containing a large amount of an aromatic skeleton in the molecular structure are preferred because of their excellent dielectric properties and moisture absorption resistance. Specifically, phenol novolak resins, cresol novolak resins, aromatic carbonizations are preferred. Hydrogen formaldehyde resin-modified phenol resin, naphthylene ether resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, Aminotriazine modified phenolic resins are preferred.

  Examples of the cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol M type cyanate ester resin, bisphenol P type cyanate ester resin, Bisphenol Z type cyanate ester resin, bisphenol AP type cyanate ester resin, bisphenol sulfide type cyanate ester resin, phenylene ether type cyanate ester resin, naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, Polyhydroxynaphthalene-type cyanate ester resin, phenol novolat Type cyanate ester resin, cresol novolac type cyanate ester resin, triphenylmethane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type Cyanate ester resin, naphthol aralkyl-type cyanate ester resin, naphthol-phenol co-condensed novolak-type cyanate ester resin, naphthol-cresol co-condensed novolac-type cyanate ester resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin-type cyanate ester resin, biphenyl-modified novolak Type cyanate ester resin, anthracene type cyanate ester resin, etc. That. These may be used alone or in combination of two or more.

  Among these cyanate ester resins, bisphenol A-type cyanate ester resins, bisphenol F-type cyanate ester resins, bisphenol E-type cyanate ester resins, and polyhydroxynaphthalene-type cyanate ester resins are particularly preferred in that a cured product having excellent heat resistance can be obtained. Naphthalene ether type cyanate ester resin and novolak type cyanate ester resin are preferably used, and dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable in that a cured product having excellent dielectric properties can be obtained.

  Examples of the maleimide compound include various compounds represented by any of the following structural formulas (i) to (iii). These may be used alone or in combination of two or more.

（式中Ｒはｓ価の有機基であり、α及びβはそれぞれ水素原子、ハロゲン原子、アルキル基、アリール基の何れかであり、ｓは１以上の整数である。）

(In the formula, R is an s-valent organic group, α and β are each a hydrogen atom, a halogen atom, an alkyl group, or an aryl group, and s is an integer of 1 or more.)

  In the formula, R is any one of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group, and an alkoxy group, s is an integer of 1 to 3, and t is an average of 0 to 10 repeating units. .

  In the formula, R is any one of a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom, a hydroxyl group and an alkoxy group, s is an integer of 1 to 3, and t is an average of 0 to 10 repeating units.

  Although there is no restriction | limiting in particular as said active ester resin, Generally ester group with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, is in 1 molecule. A compound having two or more is preferably used. The active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or a halide thereof and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or a halide thereof and a phenol compound and / or a naphthol compound is preferred. More preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like, or a halide thereof. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m -Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin , Benzenetriol, dicyclopentadiene-phenol addition resin, and the like.

  Specific examples of the active ester resin include an active ester resin containing a dicyclopentadiene-phenol addition structure, an active ester resin containing a naphthalene structure, an active ester resin that is an acetylated product of phenol novolac, and an activity that is a benzoylated product of phenol novolac. An ester resin or the like is preferable, and an active ester resin including a dicyclopentadiene-phenol addition structure and an active ester resin including a naphthalene structure are more preferable because they are excellent in improving peel strength. More specifically, an active ester resin containing a dicyclopentadiene-phenol addition structure includes a compound represented by the following general formula (iv).

  In formula (iv), R is a phenyl group or a naphthyl group, u represents 0 or 1, and n is 0.05 to 2.5 on the average of repeating units. From the viewpoint of reducing the dielectric loss tangent of the cured resin material and improving the heat resistance, R is preferably a naphthyl group, u is preferably 0, and n is preferably 0.25 to 1.5.

  Curing of the curable resin material of the present invention proceeds even without a catalyst, but a catalyst can be used in combination. These catalysts include tertiary amine compounds such as imidazole and dimethylaminopyridine; phosphorus compounds such as triphenylphosphine; boron trifluoride amine complexes such as boron trifluoride and boron trifluoride monoethylamine complexes; thiodipropionic acid Examples thereof include organic acid compounds such as: benzoxazine compounds such as thiodiphenol benzoxazine and sulfonyl benzoxazine; sulfonyl compounds; phenolic hydroxyl group-containing compounds. Examples of the phenolic hydroxyl group-containing compound include phenol, cresol, dihydroxybenzene, bisphenol A type, bisphenol F type, bisphenol E type, bisphenol S type, bisphenol sulfide, dihydroxyphenylene ether, phenol novolac resin, cresol novolac resin, and aromatic. Hydrocarbon formaldehyde resin modified phenol resin, naphthylene ether resin, dicyclopentadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak Resin, naphthol-cresol co-condensed novolak resin, biphenyl modified phenolic resin Polyphenol compound with a polyol nucleus linked), biphenyl-modified naphthol resin (polyvalent naphthol compound with a phenol nucleus linked by a bismethylene group), aminotriazine-modified phenol resin (a compound with a phenol nucleus linked with melamine, benzoguanamine, etc.) Valent phenol compound) and the like. These may be used alone or in combination of two or more. It is preferable that the addition amount of these catalysts is 0.001-15 mass parts in 100 mass parts of curable resin materials.

  When the curable resin material of the present invention is used for applications requiring high flame retardancy such as printed wiring board applications, a non-halogen flame retardant containing substantially no halogen atoms may be blended.

  Examples of the non-halogen flame retardant include a phosphorus flame retardant, a nitrogen flame retardant, a silicone flame retardant, an inorganic flame retardant, an organic metal salt flame retardant, and the like. It is not intended to be used alone, and a plurality of the same type of flame retardants may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  The organic phosphorus compounds include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10-dihydro -9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7- Examples thereof include cyclic organic phosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The amount of these phosphorus-based flame retardants is appropriately selected depending on the type of phosphorus-based flame retardant, the other components of the curable resin material, and the desired degree of flame retardancy. For example, non-halogen flame retardants And 100 parts by mass of the curable resin material in which all other fillers and additives are blended, it is preferable to blend in the range of 0.1 to 2.0 parts by mass when using red phosphorus. Is preferably used in the range of 0.1 to 10.0 parts by mass, and more preferably in the range of 0.5 to 6.0 parts by mass.

  Also, when using the phosphorus flame retardant, the phosphorus flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boron compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (1) guanylmelamine sulfate, melem sulfate, melam sulfate (2) Cocondensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (3) (2) A mixture of a co-condensate and a phenol resin such as a phenol formaldehyde condensate, (4) those obtained by further modifying (2) and (3) above with paulownia oil, isomerized linseed oil or the like.

  Examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The amount of the nitrogen-based flame retardant is appropriately selected according to the type of the nitrogen-based flame retardant, the other components of the curable resin material, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 10 parts by mass, and in the range of 0.1 to 5 parts by mass, in 100 parts by mass of the curable resin material containing all of the fuel and other fillers and additives. More preferably.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone flame retardant is appropriately selected depending on the type of the silicone flame retardant, the other components of the curable resin material, and the desired degree of flame retardancy. It is preferable to mix in a range of 0.05 to 20 parts by mass in 100 parts by mass of the curable resin material in which all of the fuel and other fillers and additives are blended. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.

  Examples of the metal oxide include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, Examples thereof include chromium oxide, nickel oxide, copper oxide, and tungsten oxide.

  Examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Examples of the low-melting-point glass include Shipley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, and P ₂ O _5. Glassy compounds such as —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, and lead borosilicate Can be mentioned.

  The blending amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, the other components of the curable resin material, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.05 to 20 parts by mass, and in the range of 0.5 to 15 parts by mass, in 100 parts by mass of the curable resin material containing all of the fuel and other fillers and additives. More preferably.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound. And the like.

  The amount of the organic metal salt-based flame retardant is appropriately selected depending on the type of the organic metal salt-based flame retardant, the other components of the curable resin material, and the desired degree of flame retardancy. It is preferable to blend in the range of 0.005 to 10 parts by mass in 100 parts by mass of the curable resin material in which all of the non-halogen flame retardant and other fillers and additives are blended.

  The curable resin material of this invention can mix | blend an inorganic filler as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 20% by mass or more with respect to the total mass of the curable resin material. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  In addition to the above, the curable resin material of the present invention may contain various compounding agents such as a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.

  The curable resin material of the present invention is obtained by uniformly mixing the above-described components, and can be easily made into a cured product by heating. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  The curable resin material of the present invention is excellent in various physical properties such as heat resistance, heat decomposition resistance, moisture resistance, solder resistance, flame retardancy, and dielectric properties in a cured product. Therefore, a semiconductor sealing material, a semiconductor device, a prepreg, and a printed circuit It can be suitably used for substrates, build-up substrates, build-up films, fiber-reinforced composite materials, fiber-reinforced resin molded products, and conductive paste applications.

1. Semiconductor encapsulating material As a method for obtaining a semiconductor encapsulating material from the curable resin material of the present invention, the curable resin material and a compounding agent such as an inorganic filler are optionally mixed with an extruder, a kneader, a binder. -A method of sufficiently melt-mixing until uniform using a slurry or the like. At that time, fused silica is usually used as the inorganic filler, but when used as a high thermal conductive semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, nitridation having higher thermal conductivity than fused silica. High filling such as silicon, or fused silica, crystalline silica, alumina, silicon nitride, or the like may be used. As for the filling rate, it is preferable to use an inorganic filler in the range of 30 to 95% by mass per 100 parts by mass of the curable resin material, and among them, improvement in flame resistance, moisture resistance and solder crack resistance, and linear expansion coefficient In order to achieve a decrease, the amount is more preferably 70 parts by mass or more, and further preferably 80 parts by mass or more. In addition, when obtaining a semiconductor sealing material from curable resin material, you may mix | blend a hardening accelerator with curable resin material, an inorganic filler, etc. as needed.

2. Semiconductor device As semiconductor package molding for obtaining a semiconductor device from the curable resin material of the present invention, the semiconductor sealing material is molded using a casting, a transfer molding machine, an injection molding machine or the like, and further at 50 to 200 ° C. The method of heating for 2 to 10 hours is mentioned.

3. Prepreg As a method for obtaining a prepreg from the curable resin material of the present invention, a curable resin material blended with the following organic solvent and varnished and diluted is used as a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth). And a glass mat, a glass roving cloth, etc.), followed by heating at a heating temperature according to the solvent type used, preferably 50 to 170 ° C., and semi-curing. The mass ratio of the resin material and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60 mass%.

  Examples of the organic solvent used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxy propanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. For example, when a printed circuit board is further produced from a prepreg as described below, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, dimethylformamide, etc. The nonvolatile content is preferably 40 to 80% by mass.

4). Printed Circuit Board As a method for obtaining a printed circuit board from the curable resin material of the present invention, the prepreg is laminated by a conventional method, and a copper foil is appropriately stacked, and 10 to 170-300 ° C. under a pressure of 1-10 MPa. The method of heat-pressing for minutes to 3 hours is mentioned.

5). Build-up substrate The method for obtaining a build-up substrate from the curable resin material of the present invention comprises the following steps. First, a step of applying the curable resin material appropriately blended with rubber, filler or the like to a circuit board on which a circuit has been formed using a spray coating method, a curtain coating method, or the like, and then curing (step 1). Then, after drilling a predetermined through-hole part, etc., if necessary, the surface is treated with a roughening agent, the surface is washed with hot water to form irregularities, and a metal such as copper is plated (process) 2). A step of repeating such an operation sequentially as desired, and alternately building up and forming a resin insulating layer and a conductor layer having a predetermined circuit pattern (step 3). The through-hole portion is formed after the outermost resin insulating layer is formed. In addition, the build-up board of the present invention is roughened by thermocompression bonding a resin-coated copper foil obtained by semi-curing the resin material on a copper foil onto a wiring board on which a circuit is formed at 170 to 300 ° C. It is also possible to produce a build-up substrate by forming the surface and omitting the plating process.

6). Build-up film As a method for obtaining a build-up film from the curable resin material of the present invention, for example, a curable resin material is applied on a support film and then dried to form a resin material layer on the support film. A method is mentioned. When the curable resin material of the present invention is used for a build-up film, the film softens under the temperature condition of the laminate in the vacuum laminating method (usually 70 ° C. to 140 ° C.) and exists on the circuit board at the same time as the circuit board lamination. It is important to show fluidity (resin flow) that allows resin filling in the via hole or through hole to be formed, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Here, the diameter of the through hole of the circuit board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  Specifically, the above-described method for producing the build-up film is prepared by preparing the curable resin material varnished by blending the following organic solvent, and then applying the resin material to the surface of the support film (Y). Further, it can be produced by drying the organic solvent by heating or blowing hot air to form the layer (X) of the curable resin material.

  Examples of the organic solvent used herein include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolve, butyl carbitol, and the like. Carbitols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and the non-volatile content is preferably 30 to 60% by mass. preferable.

  The thickness of the formed layer (X) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer included in the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin material layer is preferably 10 to 100 μm. In addition, the layer (X) of the resin material in the present invention may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust from adhering to the surface of the resin material layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment. Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  The support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled after the curable resin material layer constituting the build-up film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

A multilayer printed circuit board can be manufactured using the buildup film obtained as described above. For example, when the layer (X) is protected with a protective film, the layer (X) is peeled and then laminated on one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. If necessary, the build-up film and the circuit board may be heated (preheated) as necessary before lamination. The laminating conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C. and a pressure bonding pressure of 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m ² ). It is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less.

7). Fiber-reinforced composite material The fiber-reinforced composite material of the present invention contains the curable resin material and reinforcing fibers. As a method for obtaining a fiber reinforced composite material from the curable resin material of the present invention, the components constituting the curable resin material are uniformly mixed to prepare a varnish, and then impregnated into a reinforced substrate made of reinforced fibers. Then, it can be produced by a polymerization reaction.

  Specifically, the curing temperature at the time of performing the polymerization reaction is preferably in the temperature range of 50 to 250 ° C., in particular, after curing at 50 to 100 ° C. to obtain a tack-free cured product, The treatment is preferably performed at a temperature of 120 to 200 ° C.

  Here, the reinforced fiber may be any of a twisted yarn, an untwisted yarn, or a non-twisted yarn, but an untwisted yarn or a non-twisted yarn is preferable because both the formability and mechanical strength of the fiber-reinforced plastic member are compatible. Furthermore, the form of a reinforced fiber can use what the fiber direction arranged in one direction, and a textile fabric. The woven fabric can be freely selected from plain weaving, satin weaving, and the like according to the site and use. Specifically, since it is excellent in mechanical strength and durability, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like can be mentioned, and two or more of these can be used in combination. Among these, carbon fiber is preferable from the viewpoint that the strength of the molded product is particularly good. As the carbon fiber, various types such as polyacrylonitrile-based, pitch-based, and rayon-based can be used. Among these, a polyacrylonitrile-based one that can easily obtain a high-strength carbon fiber is preferable. Here, the use amount of the reinforcing fiber when the varnish is impregnated into a reinforcing base material made of reinforcing fiber to form a fiber-reinforced composite material is such that the volume content of the reinforcing fiber in the fiber-reinforced composite material is 40 to 85%. The amount is preferably in the range.

8). Fiber-reinforced resin molded article The fiber-reinforced resin molded article of the present invention is obtained by curing the fiber-reinforced composite material. As a method for obtaining a fiber reinforced molded product from the curable resin material of the present invention, any of a hand lay-up method, a spray-up method, a male type and a female type in which a fiber aggregate is laid on a mold and the varnish is laminated in multiple layers. Vacuum bags that are molded in a vacuum (reduced pressure) after being sealed with a flexible mold capable of applying pressure to the molded product. The varnish is impregnated into the reinforcing fiber by the SMC press method in which the varnish containing the reinforcing fiber is formed into a sheet shape by the mold, the RTM method in which the varnish is injected into the mating die in which the fiber is laid. For example, there is a method of producing a prepreg that has been prepared and baking it in a large autoclave. In addition, the fiber reinforced resin molded product obtained above is a molded product having a reinforced fiber and a cured product of a curable resin material. Specifically, the amount of the reinforced fiber in the fiber reinforced molded product is 40 It is preferably in the range of -70% by mass, and particularly preferably in the range of 50-70% by mass from the viewpoint of strength.

9. Conductive paste Examples of a method for obtaining a conductive paste from the curable resin material of the present invention include a method of dispersing fine conductive particles in the curable resin material. The conductive paste can be a paste resin material for circuit connection or an anisotropic conductive adhesive depending on the type of fine conductive particles used.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “part” and “%” are based on mass unless otherwise specified. In addition, the softening point measurement, melting | fusing point measurement, GPC measurement, < ¹³ > C-NMR, MS spectrum, and IR were measured on condition of the following.

  Softening point measurement method: compliant with JIS K7234.

  Melting point measurement method: Conforms to ASTM D4287.

GPC: Measured under the following conditions.
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

¹³ C-NMR: Measured with “JNM-ECA500” manufactured by JEOL Ltd.
Magnetic field strength: 500 MHz
Pulse width: 3.25 μsec
Integration count: 8000 times Solvent: DMSO-d6
Sample concentration: 30% by mass

FD-MS: Measured using “JMS-T100GC AccuTOF” manufactured by JEOL Ltd.
Measurement range: m / z = 4.00-2000.00
Rate of change: 51.2 mA / min
Final current value: 45 mA
Cathode voltage: -10 kV
Recording interval: 0.07 sec

  IR: Measured by KBr method using “Nicolet iS10” manufactured by Thermo Fisher Scientific.

Synthesis Example 1 Synthesis of Polyarylene Ether Intermediate (A-1) 160 g (1.0 mol) of 2,7-dihydroxynaphthalene was added to a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer. Then, 25 g (0.25 mol) of benzyl alcohol, 160 g of xylene and 2 g of paratoluenesulfonic acid monohydrate were added and stirred at room temperature while blowing nitrogen. Thereafter, the temperature was raised to 140 ° C., and the resulting water was stirred for 4 hours while distilling out of the system (xylene distilled off simultaneously was returned to the system). Thereafter, the temperature was raised to 150 ° C., and the resulting water and xylene were stirred for 3 hours while distilling out of the system. After completion of the reaction, 2 g of 20% aqueous sodium hydroxide solution was added for neutralization, and then water and xylene were removed under reduced pressure to obtain 178 g of polyarylene ether intermediate (A-1). The obtained polyarylene ether intermediate (A-1) was a brown solid, the hydroxyl group equivalent was 178 g / eq, and the softening point was 130 ° C. The GPC chart of the resulting polyarylene ether intermediate (A-1) is shown in FIG. 1, the FD-MS spectrum is shown in FIG. 2, and the FD-MS spectrum of the trimethylsilylated product of the polyarylene ether intermediate (A-1) is shown. As shown in FIG.

  From the molecular weight peaks in FIG. 2 and FIG. 3, the presence of each compound of a to f below was confirmed.

a. A peak in which one benzyl group (molecular weight Mw: 90) is added to 2,7-dihydroxynaphthalene (Mw: 160) (M ⁺ = 250), and a peak in which two benzyl groups (molecular weight Mw: 90) are further added (M ⁺ = 340) was observed, and the presence of a compound having a structure in which 1 mol of a benzyl group was bonded to 1 mol of 2,7-dihydroxynaphthalene and a compound having a structure in which 2 mol were bonded were confirmed.

b. Since a peak of 2,7-dihydroxynaphthalene dimer (M ⁺ = 302) and a peak (M ⁺ = 446) in which two trimethylsilyl groups (molecular weight Mw: 72) were added were observed, 2,7 -The presence of dihydroxynaphthalene dimer ether compound was confirmed.

c. A peak of 2,7-dihydroxynaphthalene trimer (M ⁺ = 444), a peak obtained by adding two trimethylsilyl groups (molecular weight Mw: 72) (M ⁺ = 588), and a peak added by three (M ⁺ =) 660), 2,7-dihydroxynaphthalene trimer ether compound and 2,7-dihydroxynaphthalene dimer ether were mole-dehydrated to form 1 mole of 2,7-dihydroxynaphthalene. The presence of the structure trimer compound was confirmed.

d. A peak of 2,7-dihydroxynaphthalene tetramer (M ⁺ = 586), a peak obtained by adding two trimethylsilyl groups (molecular weight Mw: 72) (M ⁺ = 730) and a peak added by three (M ⁺ = 802) was observed, and 1 mol of 2,7-dihydroxynaphthalene tetramer ether compound and 2,7-dihydroxynaphthalene trimer ether were formed by nuclear dehydration of 1 mol of 2,7-dihydroxynaphthalene. The presence of a tetrameric compound of structure was confirmed.

e. A peak of 2,7-dihydroxynaphthalene pentamer (M ⁺ = 729), a peak obtained by adding two trimethylsilyl groups (molecular weight Mw: 72) (M ⁺ = 873), and a peak added by three (M ⁺ = 944) and four added peaks (M ⁺ = 1016) were observed, and 2,7-dihydroxynaphthalene pentamer ether compound and 2,7-dihydroxynaphthalene tetramer ether were added at a rate of 2,7. -A structure of a pentamer compound formed by dehydration of 1 mol of dihydroxynaphthalene and a structure of 2 mol of 2,7-dihydroxynaphthalene dehydrated by 1 mol of 2,7-dihydroxynaphthalene trimer ether The presence of the pentamer compound was confirmed.

  f. Since a peak with one benzyl group (molecular weight Mw: 90) added and a peak with two benzyl groups (molecular weight Mw: 90) added to each of b to e, 1 to each of b to e. The presence of a compound having a structure in which 1 mol of a benzyl group was bonded to the mole and a compound having a structure having a bond of 2 mol were confirmed.

Synthesis Example 2 Synthesis of Polyarylene Ether Intermediate (A-2) 160 g (1.0 mol) of 2,7-dihydroxynaphthalene was added to a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer. The mixture was stirred and heated to 200 ° C. with stirring while blowing nitrogen, and melted. After melting, 23 g (0.2 mol) of a 48% potassium hydroxide aqueous solution was added. Thereafter, the water derived from the 48% aqueous potassium hydroxide solution and the water produced were extracted using a fractionating tube, and then reacted for another 5 hours. After completion of the reaction, 1000 g of methyl isobutyl ketone was further added, dissolved, and transferred to a separatory funnel. Subsequently, after washing with water until the washing water showed neutrality, the solvent was removed from the organic layer under heating and reduced pressure to obtain 150 g of polyarylene ether intermediate (A-2). The obtained polyarylene ether intermediate (A-2) was a brown solid, the hydroxyl group equivalent was 120 g / eq, and the melting point was 179 ° C. The GPC chart of the resulting polyarylene ether intermediate (A-2) is shown in FIG. 4, the FT-IR chart in FIG. 5, the FD-MS spectrum in FIG. 6, and the polyarylene ether intermediate (A-2). The FD-MS spectrum of the trimethylsilylated product is shown in FIG.

From the GPC chart of FIG. 4, it was confirmed that the residual ratio of the unreacted raw material (2,7-dihydroxynaphthalene) was 64% in terms of the area ratio by GPC. From the result of the FT-IR chart shown in FIG. 5, it was confirmed that the absorption (1250 cm ⁻¹ ) derived from the aromatic ether was newly generated as compared with the raw material (2,7-dihydroxynaphthalene), and the hydroxyl groups were dehydrated. It was confirmed that the etherification reaction occurred. From the results of the MS chart shown in FIG. 6, 2,7-dihydroxynaphthalene trimer structure formed by dehydration between 3 molecules of 2,7-dihydroxynaphthalene (Mw: 444) and dehydration between 5 molecules. The presence of the produced 2,7-dihydroxynaphthalene pentamer structure (Mw: 728) was confirmed.

From the FD-MS spectrum obtained by the trimethylsilylation method shown in FIG. 7, the molecular weight (Mw: 72) of the trimethylsilyl group is two (M ⁺ = 588) in the 2,7-dihydroxynaphthalene trimer structure (Mw: 444), The presence of 3 (M ⁺ = 660) compounds was confirmed.

Further, from the FD-MS spectrum obtained by the trimethylsilylation method shown in FIG. 7, 2,7-dihydroxynaphthalene was dehydrated between 5 molecules and 2,7-dihydroxynaphthalene pentamer structure (Mw: 728) was converted to trimethylsilyl. The presence of a compound having 3 (M ⁺ = 945) and 4 (M ⁺ = 1018) molecular weights (Mw: 72) of the base was confirmed.

  From the above, in the phenolic hydroxyl group-containing resin (A-2), the content of raw material 2,7-dihydroxynaphthalene is 64% of the total area ratio by GPC, and the others are represented by the following structural formula. , 7-dihydroxynaphthalene trimer ether compound;

  A trimer compound produced by dehydration of 1,7-dihydroxynaphthalene in one molecular nucleus to 2,7-dihydroxynaphthalene dimer ether represented by the following structural formula;

  It was revealed that 2,7-dihydroxynaphthalene trimer ether represented by the following structural formula is composed of a pentamer compound formed by dinuclear dehydration of 2,7-dihydroxynaphthalene. .

Example 1 Synthesis of polyarylene ether resin (B-1) 4,4′-diaminodiphenylmethane while flowing nitrogen gas through a four-necked flask equipped with a dropping funnel, thermometer, stirring device, heating device, and cooling reflux tube 198.3 g (1.0 mol), 94.1 g (1.0 mol) of phenol, and 178.0 g of polyarylene ether intermediate (A-1) synthesized in Synthesis Example 1 (hydroxyl group 1.0 mol) After being charged and dissolved in 520 g of toluene, 286.0 g (4.0 mol) of a 42% formaldehyde aqueous solution was added, the temperature was raised to 80 ° C. with stirring, and the mixture was reacted at 80 ° C. for 5 hours. After the reaction, it was transferred to a separatory funnel and the aqueous layer was removed. Thereafter, the solvent was removed from the organic layer under heating and reduced pressure to obtain 505 g of a polyarylene ether resin.

Since the IR spectrum of the obtained polyarylene ether resin showed absorption at 948 cm ⁻¹ , the polyarylene ether resin was the target polyarylene ether resin (B-1) in which a dihydrooxazine skeleton was formed. I confirmed that there was.

Example 2 Synthesis of Polyarylene Ether Resin (B-2) 178.0 g of polyarylene ether intermediate (A-1) of Example 1 (1.0 mol of hydroxyl group) was converted to polyarylene ether intermediate (A-2). A polyarylene ether resin (B-2) was obtained in the same manner as in Example 1 except that the amount was changed to 120.0 g (hydroxyl group 1.0 mol).

The IR spectrum of the obtained polyarylene ether resin showed that the IR spectrum showed absorption of the oxazine ring at 946 cm ^−1, and thus the polyarylene ether resin was the target polyarylene ether resin in which a dihydrooxazine skeleton was formed. It confirmed that it was (B-2).

Examples 3 to 5 Preparation of compositions and molded products Polyarylene ether resins (B-1) and (B-2) obtained in Examples 1 and 2 and a cresol novolac type epoxy resin (manufactured by DIC Corporation) as an epoxy resin “N-680”), phenol novolak resin (“TD-2131” manufactured by DIC Corporation), and fused silica (“FB3SDC” manufactured by Electrochemical Co., Ltd.) as a phenol resin are mixed as shown in Table 1 and pressed. After molding at a temperature of 200 ° C. for 10 minutes, it was post-cured at a temperature of 200 ° C. for 5 hours to obtain a cured product having a thickness of 0.8 mm. Table 1 shows the physical property evaluation results of the obtained cured product.

Comparative Example 1 Production of Composition and Molded Product A comparative benzoxazine compound (manufactured by Huntsman, reaction product of bisphenol F, formalin and aniline (indicated as “MT35700” in the table)), a cresol novolac type epoxy resin (referred to as “MT35700” in the table) As shown in Table 1, “N-680” manufactured by DIC Corporation), phenol novolac resin (“TD-2131” manufactured by DIC Corporation), and fused silica (“FB3SDC” manufactured by Electrochemical Co., Ltd.) are used as phenol resins. After mixing and molding with a press at a temperature of 200 ° C. for 10 minutes, a cured product having a thickness of 0.8 mm was obtained by post-curing at a temperature of 200 ° C. for 5 hours. Table 1 shows the measurement method.

<Glass transition temperature>
The cured product obtained above was cut into a size of 5 mm in width and 54 mm in length, and this was used as a test piece as a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., rectangular tension method: frequency 1 Hz, The temperature at which the change in elastic modulus was the maximum (the highest rate of change in tan δ) was measured as the glass transition temperature using a temperature increase rate of 3 ° C./min.

<Evaluation of thermal decomposition resistance>
The cured product obtained above was cut into a size of 6 mg, and this was used as a test piece, using a differential thermal-thermal mass simultaneous measurement device (“TGA / DSC1” manufactured by METTLER TOLEDO) with a nitrogen gas flow (100 ml). / Min), the temperature was raised at 5 ° C. per minute, and the temperature when 5% of the mass decreased was measured.

<Measurement of dielectric constant and tangent>
In accordance with JIS-C-6481, the dielectric constant at 1 GHz of the test piece after being stored in an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, Inc. for 24 hours in a room at a temperature of 23 ° C. and a humidity of 50% and The dielectric loss tangent was measured.

<Hygroscopic resistance>
The cured product obtained above was cut into a size of 25 mm in width and 75 mm in length and left as a test piece in an atmosphere of 85 ° C./85% 168 for 168 hours, and the mass change before and after the treatment was measured.

<Solder reflow properties>
Ten pieces obtained by cutting the cured product having a width of 25 mm and a length of 75 mm were prepared, and these were left in an atmosphere of 85 ° C./85% RH for 168 hours to perform a moisture absorption treatment. When the specimen after the moisture absorption treatment was immersed in a solder bath at 260 ° C. for 10 seconds, the number of specimens in which cracks occurred was measured.

<Flame retardance>
Five pieces obtained by cutting the cured product obtained in the above to 12.7 mm and a length of 127 mm were prepared, and these were used as test pieces, and a combustion test based on the UL-94 test method was performed.
* 1: Total burning time of 5 specimens (seconds)
* 2: Maximum burning time (seconds) in one flame contact

Claims (22)

It has a polyarylene ether structure (α) in the molecular structure, at least one of the aromatic nuclei in the polyarylene ether structure (α) has a naphthalene ring structure, and the polyarylene ether structure (α) That at least one of the aromatic nuclei has a structural site (β) represented by the following structural formula (1) or a structural site (γ) represented by the following structural formula (2) on the aromatic nucleus. Characteristic polyarylene ether resin.

(In the formula (1),
L ¹ is a divalent hydrocarbon group or a divalent linking group in which one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom, Either
Ar ¹ is each an aromatic nucleus,
R ¹ is independently a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or one or more hydrogen atoms contained in a hydrocarbon group or an alkoxy group is an alkoxy group, a hydroxyl group, or a halogen atom. Any of the structures substituted with,
O ^{* 1} atom and C ^{* 1} atom are respectively an oxygen atom and a carbon atom that are bonded to adjacent carbon atoms in the aromatic nucleus represented by Ar ¹ .
a is an integer of 0 to 4, i is an integer of 0 to 3, j is an integer of 0 to 4,
x and y are bonding points with the aromatic nucleus in the polyarylene ether structure (α), and indicate that they are bonded to adjacent carbon atoms in the aromatic nucleus. )

(In the formula (2),
L ² represents a divalent hydrocarbon group, or a divalent linking group in which one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom, Either
Ar ² is each an aromatic nucleus,
R ² is independently a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or one or more hydrogen atoms contained in a hydrocarbon group or an alkoxy group is an alkoxy group, a hydroxyl group, or a halogen atom. Any of the structures substituted with,
O ^{* 2} atom and C ^{* 2} atom are respectively an oxygen atom and a carbon atom that are bonded to carbon atoms adjacent to each other in the aromatic nucleus represented by Ar ² .
b is an integer of 0-4, k is an integer of 0-3, l is an integer of 0-4,
* 1 indicates the point of attachment to the carbon atom on the aromatic nucleus in the polyarylene ether structure (α). ) 2. The polyarylene ether resin according to claim 1, which has a molecular structure represented by the following structural formula (3) and has one or more of the structural site (β) or the structural site (γ) in the molecule.

(In formula (3), Ar ³ and Ar ⁴ are aromatic nuclei, but at least one of the aromatic nuclei represented by Ar ³ and Ar ⁴ present in the molecule is a naphthalene ring.
Ar ³ has, as a substituent, either a structural site (β) represented by the following structural formula (1) or a hydroxyl group on the aromatic nucleus, but at least one of Ar ^{3 in} the molecule has the following structural formula. It has the structural moiety (β) represented by (1) as a substituent.
R ³ is each independently one or more hydrogen atoms contained in the structural moiety (γ) represented by the following structural formula (2), a hydrocarbon group, an alkoxy group, a halogen atom, a hydrogen atom, or a hydrocarbon group Any of the structures in which the atom is substituted with any of a hydroxyl group, an alkoxy group, an aryl group, or a halogen atom. m is an integer of 1 to 3, and n is an integer of 0 to 4. )

(In the formula (1),
L ¹ is a divalent hydrocarbon group or a divalent linking group in which one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom, Either
Ar ¹ is each an aromatic nucleus,
R ¹ is independently a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or one or more hydrogen atoms contained in a hydrocarbon group or an alkoxy group is an alkoxy group, a hydroxyl group, or a halogen atom. Any of the structures substituted with,
O ^{* 1} atom and C ^{* 1} atom are respectively an oxygen atom and a carbon atom that are bonded to adjacent carbon atoms in the aromatic nucleus represented by Ar ¹ .
a is an integer of 0 to 4, i is an integer of 0 to 3, j is an integer of 0 to 4,
x and y each represent a bonding point with adjacent carbon atoms in the aromatic nucleus represented by Ar ³ . )

(In the formula (2),
L ² represents a divalent hydrocarbon group, or a divalent linking group in which one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom, Either
Ar ² is each an aromatic nucleus,
R ² is independently a hydrogen atom, a hydrocarbon group, an alkoxy group, a hydroxyl group, a halogen atom, or one or more hydrogen atoms contained in a hydrocarbon group or an alkoxy group is an alkoxy group, a hydroxyl group, or a halogen atom. Any of the structures substituted with,
O ^{* 2} atom and C ^{* 2} atom are respectively an oxygen atom and a carbon atom that are bonded to carbon atoms adjacent to each other in the aromatic nucleus represented by Ar ² .
b is an integer of 0-4, k is an integer of 0-3, l is an integer of 0-4,
* 1 indicates the point of attachment to the carbon atom on the aromatic nucleus represented by Ar ³ and Ar ⁴ . )   The polyarylene ether resin according to claim 1, wherein the polyarylene ether structure (α) is a polynaphthylene ether structure. The polyarylene ether resin according to claim 2, wherein Ar ¹ in the structural formula (1) and Ar ³ and Ar ⁴ in the structural formula (3) are naphthalene ring structure sites. The polyarylene ether resin according to claim ² , wherein Ar ² in the structural formula (2) and Ar ³ and Ar ⁴ in the structural formula (3) are naphthalene ring structure sites. Ar ¹ in the structural formula (1), wherein Ar ² in the structural formula (2), and ^Ar 3, Ar ⁴ of the formula (3), poly claim 2, wherein the naphthalene ring structure site Arylene ether resin.   The total number of structural sites (β) and structural sites (γ) is 50% with respect to the total number of phenolic hydroxyl groups, structural sites (β) and structural sites (γ) present in the polyarylene ether resin. The polyarylene ether resin according to claim 2, which is as described above.   The polyarylene ether intermediate formed by reacting an aromatic dihydroxy compound and an aralkylating agent under acid catalyst conditions, and an aromatic monohydroxy compound, a diamine compound, and formaldehyde, are obtained by reacting. Polyarylene ether resin.   The polyarylene ether resin according to claim 1, which is obtained by reacting a polyarylene ether intermediate obtained by reacting an aromatic dihydroxy compound under alkaline catalyst conditions with an aromatic monohydroxy compound, a diamine compound and formaldehyde.   Process for producing a polyarylene ether resin obtained by reacting an aromatic dihydroxy compound and an aralkylating agent under an acid catalyst condition with an aromatic monohydroxy compound, a diamine compound and formaldehyde . A method for producing a polyarylene ether resin obtained by reacting a polyarylene ether intermediate obtained by reacting an aromatic dihydroxy compound under alkaline catalyst conditions with an aromatic monohydroxy compound, a diamine compound and formaldehyde.   A curable resin material comprising the polyarylene ether resin according to claim 1 as an essential component.   A cured product obtained by curing the curable resin material according to claim 12.   A semiconductor sealing material containing the curable resin material according to claim 12 and an inorganic filler.   A semiconductor device obtained by heat-curing the semiconductor sealing material according to claim 14.   A prepreg obtained by impregnating a reinforced resin material according to claim 12 diluted with an organic solvent into a reinforcing base material and then semi-curing it.   A printed circuit board obtained by laminating the prepreg according to claim 16 and a copper foil and heat-pressing them.   The buildup film obtained by apply | coating what dried the curable resin material of Claim 12 in the organic solvent on a support film, and making it dry.   A build-up substrate obtained by plating a circuit substrate obtained by applying the build-up film according to claim 18 to a circuit substrate on which a circuit is formed and heat-curing the circuit substrate.   A fiber-reinforced composite material containing the curable resin material according to claim 12 and reinforcing fibers.   The fiber-reinforced composite material according to claim 20, wherein a volume content of the reinforcing fibers is in the range of 40 to 85%.   A fiber-reinforced molded product obtained by curing the fiber-reinforced composite material according to claim 20.

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