JP6410097B2 - Benzoxazine compound, benzoxazine resin, method for producing benzoxazine resin, curable resin composition, cured product thereof, FRP material, semiconductor sealing material, varnish, circuit board, prepreg, and build-up film - Google Patents

Description

  The present invention relates to a benzoxazine compound, a benzoxazine resin, a method for producing a benzoxazine resin, a curable resin composition, and its curing, which are excellent in various physical properties such as heat resistance, heat decomposition resistance, flame retardancy and dielectric properties in the obtained cured product. Product, FRP material, semiconductor sealing material, varnish, circuit board, prepreg, and buildup film.

  Benzoxazine resins are used to produce prepregs, laminates, circuit boards, molding compounds, adhesives, sintered powders, castings, FRP matrix resins, and precision instrument parts. Such a resin is dimensionally stable, exhibits good electrical resistance and mechanical resistance, low shrinkage, low hygroscopicity, glass transition temperature in a cured product, and also exhibits good holding characteristics with respect to mechanical properties.

  As a typical benzoxazine compound, Patent Document 1 describes a compound obtained by reacting bisphenol F (or bisphenol A), aniline and formalin. Note that when the benzoxazine compound or the like is applied to a printed wiring board, the printed wiring board can withstand high-speed communication and low transmission loss, and even when the use environment temperature rises. Although it has been required to have high heat resistance and high heat decomposability while having characteristics such as dielectric constant and low dielectric loss tangent, the benzoxazine compound has not been able to satisfy these characteristics. Furthermore, since the benzoxazine compound is inferior in flame retardancy compared to conventional benzoxazine resins, it is necessary to blend a large amount of various flame retardants, but when a large amount of various flame retardants are blended with the benzoxazine compound. The processability deteriorates and the glass transition temperature decreases, and it cannot be used at all for, for example, circuit board materials that are becoming thinner or FRP composite materials having complicated shapes.

Japanese Patent Laid-Open No. 11-12258

  Therefore, the problem to be solved by the present invention is a benzoxazine compound, a benzoxazine resin, a method for producing a benzoxazine resin, which are excellent in various physical properties such as heat resistance, heat decomposability, flame retardancy and dielectric properties in the obtained cured product, The object is to provide a curable resin composition, a cured product thereof, an FRP material, a semiconductor sealing material, a varnish, a circuit board, a prepreg, and a buildup film.

  As a result of intensive studies to solve the above problems, the present inventors have reacted a phenol compound in which aromatic rings are bonded to each other without a methylene chain, a diamine compound, an aromatic monohydroxy compound, and formaldehyde. The benzoxazine compound obtained in this way has been found to be excellent in various physical properties such as heat resistance, heat decomposition resistance, flame retardancy and dielectric properties in the obtained cured product, and the present invention has been completed.

  That is, the present invention relates to a benzoxazine compound obtained by reacting a phenol compound having a molecular structure represented by the following general formula (I) with a diamine compound, an aromatic monohydroxy compound, and formaldehyde.

［式（Ｉ）中、Ｘは下記構造式（ｘ１）又は（ｘ２）で表される構造部位である。］

[In formula (I), X is a structural site represented by the following structural formula (x1) or (x2). ]

［式（ｘ１）又は（ｘ２）中、Ｒ^１及びＲ^２はそれぞれ炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、アリール基又はアラルキル基の何れかであり、ｌは０〜１の整数、ｎは０〜３の整数である。ｎが２以上の整数の場合、複数のＲ^２は同一であっても良いし、それぞれ異なっていても良い。また、ｋは１〜３の整数、ｍは１〜２の整数であり、Ａｒは下記構造式（Ａｒ１）又は（Ａｒ２）で表される構造部位である。ｋ又はｍが２以上の整数の場合、複数のＡｒは同一であっても良いし、それぞれ異なっていても良い。式（ｘ２）における、Ｒ^２、Ａｒは、２つの芳香環のうち何れの芳香環に結合していてもよい。］

[In Formula (x1) or (x2), R ¹ and R ² are each an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group; Is an integer from 0 to 1, and n is an integer from 0 to 3. When n is an integer of 2 or more, the plurality of R ² may be the same or different from each other. K is an integer of 1 to 3, m is an integer of 1 to 2, and Ar is a structural moiety represented by the following structural formula (Ar1) or (Ar2). When k or m is an integer of 2 or more, the plurality of Ars may be the same or different. In the formula (x2), R ² and Ar may be bonded to any aromatic ring of the two aromatic rings. ]

［式（Ａｒ１）又は（Ａｒ２）中、Ｒ^３及びＲ^４はそれぞれ炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、アリール基又はアラルキル基の何れかであり、Ｒ^４は２つの芳香環のうち何れの芳香環に結合していてもよい。ｑは０〜３の整数、ｓは０〜５の整数である。ｑ又はｓが２以上の整数の場合、複数のＲ^３又はＲ^４は同一であっても良いし、それぞれ異なっていても良い。またｐ、ｒはそれぞれ１〜２の整数である。式（Ａｒ２）における、Ｒ^４、ＯＨ基は、２つの芳香環のうち何れの芳香環に結合していてもよい。］

[In the formula (Ar1) or (Ar2), R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and R ⁴ may be bonded to any of the two aromatic rings. q is an integer of 0 to 3, and s is an integer of 0 to 5. When q or s is an integer of 2 or more, a plurality of R ³ or R ⁴ may be the same or different from each other. P and r are integers of 1 to 2, respectively. In the formula (Ar2), the R ⁴ and OH groups may be bonded to any of the two aromatic rings. ]

  The present invention further relates to a benzoxazine resin containing the benzoxazine compound.

  In the present invention, the compound (Q) having a quinone structure in the molecular structure and the compound (P) having a phenolic hydroxyl group in the molecular structure are reacted to obtain a phenol compound. The present invention relates to a method for producing a benzoxazine resin in which a compound, an aromatic monohydroxy compound, and formaldehyde are reacted.

  The present invention further relates to a curable resin composition containing the benzoxazine compound or the benzoxazine resin as an essential component.

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

  The present invention further relates to an FRP material comprising the curable resin composition.

  The present invention further includes the curable resin composition and an inorganic filler, and the content of the inorganic filler is in the range of 30 to 95 parts by mass per 100 parts by mass of the curable resin composition. It relates to a stop material.

  The present invention further relates to a varnish obtained by adding an organic solvent to the curable resin composition.

  The present invention further relates to a circuit board obtained by laminating a varnish shaped like a plate with a copper foil, followed by heating and pressing.

  The present invention further relates to a prepreg obtained by impregnating a reinforcing substrate with the varnish and then semi-curing it.

  The present invention further relates to a build-up film obtained by applying a varnish on a substrate and then curing it.

  According to the present invention, a benzoxazine compound, a benzoxazine resin, a method for producing a benzoxazine resin, a curable resin composition excellent in various physical properties such as heat resistance, heat decomposition resistance, flame retardancy, and dielectric properties in the obtained cured product, The cured product, FRP material, semiconductor sealing material, varnish, circuit board, prepreg, and build-up film can be provided.

1 is a GPC chart of a phenol resin (A) obtained in Example 1. 3 is a ¹³ C NMR chart of the phenol resin (A) obtained in Example 1. FIG. 2 is an MS spectrum of the phenol resin (A) obtained in Example 1. 2 is a GPC chart of a phenol resin (B) obtained in Example 2. 3 is a ¹³ C NMR chart of the phenol resin (B) obtained in Example 2. FIG. 3 is an MS spectrum of the phenol resin (B) obtained in Example 2. 4 is a GPC chart of a phenol resin (C) obtained in Example 3. 6 is a GPC chart of a phenol resin (D) obtained in Example 4. 4 is a ¹³ C NMR chart of the phenol resin (D) obtained in Example 4. 4 is an MS spectrum of the phenol resin (D) obtained in Example 4. 6 is a GPC chart of a phenol resin (E) obtained in Example 5. 6 is a ¹³ C NMR chart of the phenol resin (E) obtained in Example 5. FIG. 4 is an MS spectrum of the phenol resin (E) obtained in Example 5. 6 is a GPC chart of a phenol resin (F) obtained in Example 6. 4 is an MS spectrum of the phenol resin (F) obtained in Example 6.

  Hereinafter, the present invention will be described in detail.

  That is, the benzoxazine compound of the present invention is a compound obtained by reacting a phenol compound having a molecular structure represented by the following general formula (I), a diamine compound, an aromatic monohydroxy compound, and formaldehyde. is there.

［式（Ｉ）中、Ｘは下記構造式（ｘ１）又は（ｘ２）で表される構造部位である。］

[In formula (I), X is a structural site represented by the following structural formula (x1) or (x2). ]

［式（ｘ１）又は（ｘ２）中、Ｒ^１及びＲ^２はそれぞれ炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、アリール基又はアラルキル基の何れかであり、ｌは０〜１の整数、ｎは０〜３の整数である。ｎが２以上の整数の場合、複数のＲ^２は同一であっても良いし、それぞれ異なっていても良い。また、ｋは１〜３の整数、ｍは１〜２の整数であり、Ａｒは下記構造式（Ａｒ１）又は（Ａｒ２）で表される構造部位である。ｋ又はｍが２以上の整数の場合、複数のＡｒは同一であっても良いし、それぞれ異なっていても良い。式（ｘ２）における、Ｒ^２、Ａｒは、２つの芳香環のうち何れの芳香環に結合していてもよい。］

[In Formula (x1) or (x2), R ¹ and R ² are each an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group; Is an integer from 0 to 1, and n is an integer from 0 to 3. When n is an integer of 2 or more, the plurality of R ² may be the same or different from each other. K is an integer of 1 to 3, m is an integer of 1 to 2, and Ar is a structural moiety represented by the following structural formula (Ar1) or (Ar2). When k or m is an integer of 2 or more, the plurality of Ars may be the same or different. In the formula (x2), R ² and Ar may be bonded to any aromatic ring of the two aromatic rings. ]

［式（Ａｒ１）又は（Ａｒ２）中、Ｒ^３及びＲ^４はそれぞれ炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、アリール基又はアラルキル基の何れかであり、Ｒ^４は２つの芳香環のうち何れの芳香環に結合していてもよい。ｑは０〜３の整数、ｓは０〜５の整数である。ｑ又はｓが２以上の整数の場合、複数のＲ^３又はＲ^４は同一であっても良いし、それぞれ異なっていても良い。またｐ、ｒはそれぞれ１〜２の整数である。式（Ａｒ２）における、Ｒ^４、ＯＨ基は、２つの芳香環のうち何れの芳香環に結合していてもよい。］

[In the formula (Ar1) or (Ar2), R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and R ⁴ may be bonded to any of the two aromatic rings. q is an integer of 0 to 3, and s is an integer of 0 to 5. When q or s is an integer of 2 or more, a plurality of R ³ or R ⁴ may be the same or different from each other. P and r are integers of 1 to 2, respectively. In the formula (Ar2), the R ⁴ and OH groups may be bonded to any of the two aromatic rings. ]

  A benzoxazine compound obtained by reacting a diamine compound, an aromatic monohydroxy compound, and formaldehyde with a phenol compound having a molecular structure represented by the general formula (I) is an aromatic compound without using a methylene chain. Since the rings are bonded to each other, it has a rigid molecular structure and a high concentration of aromatic ring and benzoxazine ring in the compound. That is, since the benzoxazine compound of the present invention has a molecular structure that does not have a methylene chain that easily undergoes thermal decomposition as compared with an aromatic ring as described above, the obtained cured product has a feature of high thermal decomposition resistance. Have. Furthermore, since the benzoxazine compound of the present invention has a rigid molecular structure in which aromatic rings are bonded to each other as described above, molecular motion is suppressed, and the resulting cured product has a low dielectric constant and dielectric loss tangent, resulting in a dielectric property. It has the feature of being excellent. Furthermore, since the benzoxazine compound of the present invention has a high aromatic ring concentration in the compound in addition to the rigid molecular structure as described above, it has a feature that the obtained cured product is excellent in flame retardancy. In addition to the rigid molecular structure as described above, the benzoxazine compound of the present invention is characterized by high crosslink density and excellent heat resistance in the resulting cured product since the concentration of the benzoxazine ring is high. That is, a benzoxazine compound obtained by reacting a phenol compound having a molecular structure represented by the general formula (I), a diamine compound, an aromatic monohydroxy compound, and formaldehyde is obtained in a cured product obtained. It has characteristics such as excellent heat resistance, heat decomposition resistance, flame retardancy and dielectric properties.

  In the structural formula (x1) or (x2), k is an integer of 1 to 3, and m is an integer of 1 to 2. Here, the compound corresponding to the case where the value of k or m is 1 (hereinafter abbreviated as “binuclear compound (α1)”) is heat resistance, heat decomposition resistance, flame retardancy, and dielectric in a cured product. It has characteristics such as excellent characteristics. On the other hand, a compound corresponding to a value of k or m of 2 (hereinafter abbreviated as “trinuclear compound (α2)”) or a compound corresponding to a value of k of 3 (hereinafter “tetranuclear compound”). Compound (α3) ”) is characterized by higher rigidity of the molecular skeleton and higher aromatic ring concentration, and thus more excellent heat resistance, heat decomposition resistance, flame retardancy and dielectric properties in the cured product. Have

  The benzoxazine resin or the benzoxazine resin containing a plurality of types of the benzoxazine compound includes, for example, a compound (Q) having a quinone structure in the molecular structure and a compound (P) having a phenolic hydroxyl group in the molecular structure. After reaction in a temperature range of 40 to 180 ° C. under non-catalytic or acid catalyst conditions to obtain a phenol compound or a phenol resin containing a plurality of the phenol compounds, the phenol compound or the phenol resin, a diamine compound, and an aroma It can manufacture by making a group monohydroxy compound and formaldehyde react. According to the method, an arbitrary benzoxazine compound can be selectively produced according to reaction conditions, or a benzoxazine resin that is a mixture of a plurality of types of benzoxazine compounds can be produced. In addition, arbitrary benzoxazine compounds can be isolated from the benzoxazine resin which is a mixture.

  Examples of the compound (Q) having a quinone structure include compounds represented by the following structural formula (Q1) or (Q2). Specifically, parabenzoquinone, 2-methylbenzoquinone, 2, 3, 5 -Trimethyl-benzoquinone, naphthoquinone, etc. are mentioned. These may be used alone or in combination of two or more.

In formula (Q1) or (Q2), R ¹ and R ² are each an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and l is An integer from 0 to 1, n is an integer from 0 to 3. When n is an integer of 2 or more, the plurality of R ² may be the same or different from each other.

  Examples of the compound (P) having a phenolic hydroxyl group include compounds represented by the following structural formula (P1) or (P2).

In Formula (P1) or (P2), R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and q is An integer of 0 to 3, and s is an integer of 0 to 5. When q or s is an integer of 2 or more, a plurality of R ³ or R ⁴ may be the same or different from each other. P and r are integers of 1 to 2, respectively.

  As the compound (P) having such a phenolic hydroxyl group, specifically, phenol, orthocresol, metacresol, paracresol, 2,6-dimethylphenol, 2,5-dimethylphenol, 2,4-dimethylphenol 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 3,4,5- Trimethylphenol, 4-isopropylphenol, 4-tert-butylphenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-methoxy-4-methylphenol, 2-tert-butyl-4-methoxyphenol, 2 , 6-Dimethoxyphenol, 3,5-di Toxiphenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 4-benzylphenol, 1,2-dihydroxybenzene, 1,3-dihydroxy Benzene, 1,4-dihydroxybenzene, 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxy And naphthalene. These may be used alone or in combination of two or more.

  The reaction between the compound (Q) having a quinone structure and the compound (P) having a phenolic hydroxyl group proceeds under non-catalytic conditions because of its high reactivity, but may be appropriately performed using an acid catalyst. . Examples of the acid catalyst used here include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Lewis acids such as When these acid catalysts are used, it is preferably used in an amount of 5.0% by mass or less based on the total mass of the compound (Q) having the quinone structure and the compound (P) having the phenolic hydroxyl group.

  The reaction is preferably performed under solvent-free conditions, but may be performed in an organic solvent as necessary. Examples of the organic solvent used here include methyl cellosolve, isopropyl alcohol, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. When these organic solvents are used, since the reaction efficiency is improved, the organic solvent is used for 100 parts by mass in total of the compound (Q) having a quinone structure and the compound (P) having a phenolic hydroxyl group in the molecular structure. It is preferable to use it in the ratio which becomes the range of 50-200 mass parts.

  By reacting the compound (Q) having the quinone structure with the compound (P) having the phenolic hydroxyl group, a plurality of phenol compounds having the molecular structure represented by the general formula (I) and the phenol compound are obtained. A seed-containing phenolic resin can be obtained.

  Next, the obtained phenol compound or the phenol resin, a diamine compound, an aromatic monohydroxy compound, and formaldehyde are reacted. Examples of the diamine compound include those represented by the following structural formula (R).

  In the formula (R), L represents a structure represented by the following structural formula (R1), a structure represented by the following structural formula (R2), a divalent aliphatic hydrocarbon group, and a divalent aromatic hydrocarbon group. Or one or more hydrogen atoms of the divalent aliphatic hydrocarbon group or the divalent aromatic hydrocarbon group are substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom. It is.

However, in the formula (R1), L ¹ is a divalent linking group. R ⁵ 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 substituted with either a hydroxyl group or a halogen atom. One of the structures. a is an integer of 1-4. ^* Is the point of attachment to the nitrogen atom in the formula (R).

Examples of the divalent linking group represented by L ¹ 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 these, L ¹ is preferably composed of any one of an alkylene group and an ether group because of excellent flame retardancy and dielectric properties in the cured product.

  As a structure in which a divalent aliphatic hydrocarbon group represented by L, a divalent aromatic hydrocarbon group, or one or more hydrogen atoms which they have is substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom, Specifically, alkylene groups such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group and cyclohexylene group; alkenylene groups such as arylene group; alkynylene groups such as propargylene group; hydroxyethylene group Hydroxyl group-containing alkylene groups such as hydroxypropylene group; alkoxy group-containing alkylene groups such as methoxyethylene group, methoxypropylene group, allyloxymethylene group, allyloxypropylene group, propargyloxymethylene group, propargyloxypropylene group; Chloroethylene group, chloropro Halogenated alkylene groups such as lene group, bromomethylene group, bromoethylene group, bromopropylene group, fluoromethylene group, fluoroethylene group and fluoropropylene group; arylene groups such as phenylene group, tolylene group, xylylene group and naphthylene group; hydroxy Hydroxyl-containing arylene groups such as phenylene group and hydroxynaphthylene group; Alkylene-containing arylene groups such as methoxyphenylene group, ethoxyphenylene group, allyloxyphenylene group, and propargyloxyphenylene group; vinylphenylene group, allylphenylene group, ethynylphenylene group , Unsaturated hydrocarbon group-containing arylene groups such as propargylphenylene group; chlorophenylene group, bromophenylene group, fluorophenylene group, chloronaphthylene group, bromonaphthylene group, full And halogenated arylene group such as Ronafuchiren group. These diamine 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, and flame retardancy in a cured product.

As described above, R ⁵ is 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, either a hydroxyl group or a halogen atom. It is composed of any of the substituted structures.

When R ⁵ is composed of a hydrocarbon group, examples of R ⁵ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group.

  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, 1-methylvinyl group, propenyl group, butenyl group, and pentenyl group. 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.

When R ⁵ is composed of an alkoxy group, examples of R ⁵ include a methoxy group, an ethoxy group, a proxy group, a butoxy group, a pentanoxy group, a hexanoxy group, and a cyclohexanoxy group.

When R ⁵ is composed of a structure in which one or more hydrogen atoms contained in the hydrocarbon group are substituted with either a hydroxyl group or a halogen atom, R ⁵ is a hydroxyl group-containing alkyl group or a halogenated alkyl group. Hydroxyl group-containing alkenyl group, halogenated alkenyl group, hydroxyl group-containing alkynyl group, halogenated alkynyl group, hydroxyl group-containing aryl group, halogenated aryl group, hydroxyl group-containing aralkyl group, halogenated aralkyl group, and the like.

  Examples of the hydroxyl group-containing alkyl group include a hydroxyethyl group and a hydroxypropyl 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.

When R ⁵ is composed of a substituent in which one or more hydrogen atoms contained in the alkoxy group are substituted with either a hydroxyl group or a halogen atom, R ⁵ includes a hydroxyl group-containing alkoxy group, a halogenated alkoxy group. Etc.

  A hydroxyethyloxy group etc. are mentioned as a hydroxyl-containing alkoxy group. A chloropropyloxy group etc. are mentioned as a halogenated alkoxy group.

When R ⁵ is composed of a halogen atom, examples of R ⁵ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In addition to the above, R ⁵ may be an alkoxy group-containing alkyl group, an alkoxy group-containing aryl group, or an unsaturated hydrocarbon group-containing aryl 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 alkoxy group-containing aryl group include a methoxyphenyl group, an ethoxyphenyl group, an allyloxyphenyl group, and a propargyloxyphenyl group. Examples of the unsaturated hydrocarbon group-containing aryl group include vinylphenyl, allylphenyl, ethynylphenyl, propargylphenyl and the like.

Among them, R ⁵ is preferably a hydrogen atom, an alkyl group, or an aralkyl group, and a resin having a benzoxazine structure having excellent heat resistance can be obtained. Therefore, R ⁵ is composed of a hydrogen atom. Is more preferable.

In the structural formula (R1), the linking group L ¹ linking two aromatic rings may be bonded to any carbon atom constituting the aromatic ring, but flame retardancy and dielectric properties in the cured product. Therefore, it is preferable that the linking group L ¹ is bonded to the position of the para position or the meta position with respect to N ^* . More preferably, the linking group L ¹ is bound to the para position with respect to N ^* .

In the structural formula (R2), the bonding positions of the two aromatic rings on the biphenyl skeleton may be any, but since the flame retardancy and dielectric properties of the cured product are excellent, the two aromatic rings are , N ^* are preferably bonded to the para position or both to the meta position. More preferably, both are bonded to the para position.

  As a structure in which a divalent aliphatic hydrocarbon group represented by L, a divalent aromatic hydrocarbon group, or one or more hydrogen atoms which they have is substituted with any of a hydroxyl group, an alkoxy group, or a halogen atom, Specifically, alkylene groups such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group and cyclohexylene group; alkenylene groups such as arylene group; alkynylene groups such as propargylene group; hydroxyethylene group Hydroxyl group-containing alkylene groups such as hydroxypropylene group; alkoxy group-containing alkylene groups such as methoxyethylene group, methoxypropylene group, allyloxymethylene group, allyloxypropylene group, propargyloxymethylene group, propargyloxypropylene group; Chloroethylene group, chloropro Halogenated alkylene groups such as lene group, bromomethylene group, bromoethylene group, bromopropylene group, fluoromethylene group, fluoroethylene group and fluoropropylene group; arylene groups such as phenylene group, tolylene group, xylylene group and naphthylene group; hydroxy Hydroxyl-containing arylene groups such as phenylene group and hydroxynaphthylene group; Alkylene-containing arylene groups such as methoxyphenylene group, ethoxyphenylene group, allyloxyphenylene group, and propargyloxyphenylene group; vinylphenylene group, allylphenylene group, ethynylphenylene group , Unsaturated hydrocarbon group-containing arylene groups such as propargylphenylene group; chlorophenylene group, bromophenylene group, fluorophenylene group, chloronaphthylene group, bromonaphthylene group, full And halogenated arylene group such as Ronafuchiren group. These diamine 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, and flame retardancy in a cured product.

  Examples of the aromatic monohydroxy compound include those represented by the following structural formulas (S1) and (S2).

In formulas (S1) and (S2), each R ⁶ independently represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or one or more hydrogen atoms contained in these, a hydroxyl group, an alkoxy group, or a halogen atom. Any of the structures substituted with any of the above. b is an integer of 0 to 4, and c is 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.

  As the formaldehyde, formalin which is in a solution state or paraformaldehyde which is in a solid state can be used, and any of them may be used.

  The reaction ratio of the phenol compound or phenol resin, the diamine compound, the aromatic monohydroxy compound, and formaldehyde is such that the phenol compound or the phenol resin is 0.25 to 0.90 equivalent relative to 1 equivalent of the amino group of the diamine compound. A resin having a target benzoxazine structure, wherein the aromatic monohydroxy compound is in the range of 0.10 to 0.75 equivalent and the formaldehyde is in the range of 1.5 to 2.5 equivalent Is preferable because it is more efficiently produced.

  You may perform reaction of a phenol compound or a phenol resin, an aromatic monohydroxy compound, a diamine compound, and formaldehyde in presence of a catalyst as needed. Specific examples of the catalyst used herein include amide compounds such as N, N-dimethylformamide; pyridine compounds such as pyridine and N, N-dimethyl-4-aminopyridine; amine compounds such as triethylamine and tetramethylethylenediamine; Quaternary ammonium salts such as butylammonium bromide; Organic acid compounds such as acetic acid, trifluoroacetic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid; Alkali metal hydroxides or carbonates such as potassium hydroxide, potassium carbonate and sodium carbonate Phenolic compounds such as dibutylhydroxytoluene; metal catalysts such as palladium, tetrakis (triphenylphosphine) palladium, copper iodide, tin tetrachloride, nickel, platinum and the like. These may be used alone or in combination of two or more.

  You may perform reaction of a phenol compound or a phenol resin, an aromatic monohydroxy compound, a diamine compound, and formaldehyde in an organic solvent as needed. 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; acetate compounds such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate; carbitol compounds such as cellosolve, 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 phenol compound or the phenol resin, the diamine compound, the aromatic monohydroxy compound, and formaldehyde can be performed under a temperature condition of 50 to 150 ° C., for example. After completion of the reaction, the aqueous layer and the organic layer are separated, and then the organic solvent is dried under reduced pressure from the organic layer to obtain a benzoxazine resin in which a plurality of types of benzoxazine compounds are mixed. In order to obtain the target benzoxazine compound from the benzoxazine resin, it may be isolated by, for example, purification of the mixture by a known crystallization or solvent washing technique or a chromatography method.

  Examples of the benzoxazine compound thus obtained include those represented by the following structural formulas (II) to (V).

In formulas (II) to (V), R ^{1 to} R ⁴ are each independently any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, and an aralkyl group. It is. Y and Z are bonded to adjacent carbon atoms on the aromatic ring, and each constitutes a pair represented by a hydroxyl group and a hydrogen atom, or a structural site represented by the following structural formulas (VI) to (VII). Although it is a group, at least one group is a group constituting a structural portion represented by the following structural formula (VI) or (VII). k is an integer of 1 to 3, l is an integer of 0 to 1, m is an integer of 1 to 2, n is an integer of 0 to 3, p is an integer of 1 to 2, q is an integer of 0 to 3, r is Integer of 1-2, s is an integer of 0-5. When l, n, q, or s is an integer of 2 or more, R ¹ , R ² , R ³ , and R ⁴ may be the same or different from each other. Further, in the formulas (III) and (V), R ² and R ⁴ may be bonded to any of the two aromatic rings constituting the naphthalene ring, and Y and Z are in parentheses. It may be bonded to any aromatic ring out of the two aromatic rings constituting the naphthalene ring described in.

In the formulas (VI) to (VII), * Y and * Z are the bonding points with the carbon atom to which Y is bonded in the compounds represented by the structural formulas (II) to (V), respectively. Is the point of attachment to the carbon atom. L is a structure represented by the structural formula (R1), a structure represented by the structural formula (R2), a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, or the divalent One of the structures in which one or more hydrogen atoms of the aliphatic hydrocarbon group or the divalent aromatic hydrocarbon group is substituted with any one of a hydroxyl group, an alkoxy group, and a halogen atom. R ⁶ is any one of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a structure in which one or more hydrogen atoms contained therein are substituted with any one of a hydroxyl group, an alkoxy group, and a halogen atom. b is an integer of 0 to 4, and c is an integer of 0 to 6. Specific R ⁶ and L are as described above.

  In the structural formulas (II) to (V), k is an integer of 1 to 3, and m is an integer of 1 to 2. Here, the binuclear compound (β1) having a k or m value of 1 is a binuclear compound obtained by reacting the binuclear compound (α1) described above with a diamine compound, an aromatic monohydroxy compound, and formaldehyde. Is a trinuclear compound (β2) having a k or m value of 2, the trinuclear compound (α2) described above is a diamine compound, an aromatic monohydroxy compound, and formaldehyde Is a trinuclear benzoxazine compound that reacts with the tetranuclear compound (β3) having a k value of 3, and the tetranuclear compound (α3) described above is a diamine compound or an aromatic monohydroxy compound And a tetranuclear benzoxazine compound reacted with formaldehyde.

  The benzoxazine compound or benzoxazine resin of the present invention is obtained by reacting a phenol compound having a molecular structure represented by the general formula (I), a diamine compound, an aromatic monohydroxy compound, and formaldehyde. In any case, if it is a compound, the obtained cured product has an effect of being excellent in various physical properties such as heat resistance, heat decomposition resistance, flame retardancy and dielectric properties. Hereinafter, the phenol compound or phenol resin used for obtaining the benzoxazine compound or benzoxazine resin of the present invention will be described in more detail.

<Phenol compound or phenol resin>
As a phenol compound, the phenol compound represented by the said general formula (I) can be used. A phenol resin containing a plurality of types of the phenol compounds can also be used. As a typical phenol compound represented by the general formula (I), a phenol compound represented by any one of the following structural formulas (I-1) to (I-3) can be used.

  In formulas (I-1) to (I-3), k is an integer of 1 to 3, m is an integer of 1 to 2, and Ar is a structural moiety represented by the following structural formula (Ar1) or (Ar2) It is. When k or m is an integer of 2 or more, the plurality of Ars may be the same or different.

In formula (Ar1) or (Ar2), p and r are each an integer of 1 to 2. R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, q is an integer of 0 to 3, and s is 0 to 0. It is an integer of 5. When q or s is an integer of 2 or more, a plurality of R ³ or R ⁴ may be the same or different from each other. In the formula (Ar2), the R ⁴ and OH groups may be bonded to any of the two aromatic rings.

  More specifically, the phenol compound represented by the structural formula (I-1) includes a phenol compound represented by any one of the following structural formulas (1) to (7). Each will be described in detail below.

In formulas (1) to (7), k is an integer of 1 to 3. R ⁷ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and u is an integer of 1 to 4. When u is an integer of 2 or more, the plurality of R ⁷ may be the same or different.

  The phenol compound represented by the following structural formula (1) reacts with a diamine compound, an aromatic monohydroxy compound, and formaldehyde among the phenol compounds represented by the general formula (I). It has the characteristic that a benzoxazine compound that is particularly excellent in the balance of heat resistance, heat decomposability, and flame retardancy can be obtained.

  In formula (1), k is an integer of 1-3.

  As a phenol resin containing the phenol compound represented by the structural formula (1), by reacting with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, heat resistance, heat decomposition resistance, and flame retardancy in a cured product are obtained. From the point that a benzoxazine resin containing a benzoxazine compound (hereinafter abbreviated as “benzoxazine resin”) containing a benzoxazine compound that is even more excellent is obtained. And a trinuclear compound (α2) having a k value of 2 are preferable, and among them, the content of the dinuclear compound (α1) is 10 to 50 in terms of area ratio in GPC measurement. And the content of the trinuclear phenol compound (α2) is in the range of 10 to 50% in terms of area ratio in GPC measurement. Le resin is more preferable.

  In particular, by reacting with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, a benzoxazine resin having further excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained. In addition to the compound (α1) and the trinuclear compound (α2), a tetranuclear compound (α3) having a k value of 3, or a tetranuclear compound (α3 ′) represented by the following structural formula (1 ′) Among them, the total content of the tetranuclear compound (α3) and the tetranuclear compound (α3 ′) is in the range of 2 to 20% as an area ratio in GPC measurement. More preferred is a phenolic resin.

  In addition, the content rate of the said binuclear compound ((alpha) 1) etc. in a phenol resin is substantially the same as the content rate of the binuclear compound ((beta) 1) etc. in the benzoxazine resin obtained by subsequent reaction. Therefore, when it is desired to obtain a benzoxazine resin that can exhibit excellent heat resistance, heat decomposition resistance, and flame retardancy in the obtained cured product, the content of the binuclear compound (α1) and the like in the phenol resin Is important. The same applies to what will be described below.

In the present invention, the contents of the binuclear compound (α1), the trinuclear compound (α2), the tetranuclear compound (α3), and the tetranuclear compound (α3 ′) are as follows: It is the ratio of the peak area of each said component with respect to the total peak area of a phenol resin computed from the GPC measurement data by conditions.
<GPC measurement 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 refractometer)
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).

  The phenol compound represented by the structural formula (1) can be produced, for example, by reacting parabenzoquinone and phenol. Since the reaction ratio of parabenzoquinone and phenol can produce a phenol resin that can easily adjust the content ratio of the binuclear compound (α1) and the trinuclear compound (α2) to the preferred range described above, It is preferable that the ratio of phenol is in the range of 0.1 to 10.0 mol with respect to 1 mol of parabenzoquinone.

  Examples of the phenol compound represented by the structural formula (1) include a phenol compound represented by any one of the following structural formulas (1-1) to (1-9).

  In formulas (1-1) to (1-9), k is an integer of 1 to 3.

  The phenol compound represented by the following structural formula (2) reacts with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, so that among the phenol compounds represented by the general formula (I), particularly in a cured product. It has the characteristic that the benzoxazine compound which is excellent in heat resistance, heat-resistant decomposition property, and a flame retardance can be obtained.

  In formula (2), k is an integer of 1-3.

  As a phenol resin containing the phenol compound represented by the structural formula (2), by reacting with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, heat resistance, heat decomposition resistance, and flame retardancy in a cured product are obtained. A binuclear compound (α1) having a k value of 1 in the structural formula (2) and a k value of 2 in the structural formula (2). A phenol resin containing a nuclear compound (α2) is preferable, and among them, the content of the binuclear compound (α1) is in the range of 2 to 50% in terms of area ratio in GPC measurement, and the three nuclei are included. A phenol resin in which the content ratio of the body compound (α2) is in the range of 10 to 90% in terms of area ratio in GPC measurement is more preferable. Furthermore, among them, the content of the binuclear compound (α1) is in the range of 2 to 25% in terms of the area ratio in GPC measurement, and the content of the trinuclear compound (α2) is the area in GPC measurement. Phenol resins having a ratio in the range of 25 to 90% are particularly preferable.

  In particular, the dinuclear compound (α1) and the trinuclear compound are obtained by reacting a benzoxazine resin, which is further excellent in heat resistance in a cured product, with a diamine compound, an aromatic monohydroxy compound, and formaldehyde. In addition to the compound (α2), a tetranuclear compound (α3) having a k value of 3 in the structural formula (2) or a tetranuclear compound (α3 ′) represented by the following structural formula (2 ′) The phenol resin to be contained is preferable. Among them, the total content of the tetranuclear compound (α3) and the tetranuclear compound (α3 ′) is in the range of 2 to 20% in terms of area ratio in GPC measurement. Phenol resin is preferred.

  In the formula (2 ′), k is an integer of 1 to 3.

  The phenol compound represented by the structural formula (2) can be produced, for example, by reacting parabenzoquinone and cresol. Since the reaction ratio of parabenzoquinone and cresol can produce a phenol resin that can easily adjust the content ratio of the binuclear compound (α1) and the trinuclear compound (α2) to the above-mentioned preferred range, parabenzoquinone It is preferable that the ratio is such that cresol is in the range of 0.1 to 10.0 mol with respect to 1 mol.

  The cresol used here may be any of ortho-cresol, meta-cresol, and para-cresol, and a plurality of types may be used in combination. Among them, by reacting with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, a phenol resin that gives a benzoxazine resin excellent in heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained. Orthocresol is preferred.

  Examples of the phenol compound represented by the structural formula (2) include a phenol compound represented by any one of the following structural formulas (2-1) to (2-31).

  The phenol compound represented by the following structural formula (3) is a cured product by reacting with a diamine compound, an aromatic monohydroxy compound, and formaldehyde among the phenol compounds represented by the general formula (I). The benzoxazine compound is excellent in heat resistance, heat decomposition resistance, and flame retardancy.

  In formula (3), k is an integer of 1-3.

  As a phenol resin containing the phenol compound represented by the structural formula (3), by reacting with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, heat resistance, heat decomposition resistance, and flame retardancy in a cured product are obtained. A binuclear compound (α1) having a k value of 1 in the structural formula (3) and a k value of 2 in the structural formula (3). A phenol resin containing a nuclear compound (α2) is preferable, and among them, the content of the binuclear compound (α1) is in the range of 2 to 50% in terms of area ratio in GPC measurement, and the three nuclei are included. A phenol resin in which the content ratio of the body compound (α2) is in the range of 10 to 95% in terms of area ratio in GPC measurement is more preferable. Further, among them, the content of the binuclear compound (α1) is in the range of 2 to 25% in terms of the area ratio in GPC measurement, and the content of the trinuclear compound (α2) is the area in GPC measurement. Even more preferred is a phenolic resin in the range of 50-95% by ratio.

  In particular, the dinuclear compound (α1) and the trinuclear compound are obtained by reacting a benzoxazine resin, which is further excellent in heat resistance in a cured product, with a diamine compound, an aromatic monohydroxy compound, and formaldehyde. In addition to the compound (α2), a tetranuclear compound (α3) having a value of k of 3 in the structural formula (3) or a tetranuclear compound (α3 ′) represented by the following structural formula (3 ′) The phenol resin to be contained is preferable. Among them, the total content of the tetranuclear compound (α3) and the tetranuclear compound (α3 ′) is in the range of 0.5 to 10% in terms of area ratio in GPC measurement. Particularly preferred is a phenolic resin.

  The phenol compound represented by the structural formula (3) can be produced, for example, by reacting parabenzoquinone and dimethylphenol. Since the reaction ratio of parabenzoquinone and dimethylphenol can produce a phenol resin that can easily adjust the content of the binuclear compound (α1) and the trinuclear compound (α2) to the above-described preferred range, It is preferable that dimethylphenol is in a range of 0.1 to 10.0 mol with respect to 1 mol of benzoquinone.

  The dimethylphenol used here may be any positional isomer such as 2,6-dimethylphenol, 2,5-dimethylphenol, 2,4-dimethylphenol, 3,5-dimethylphenol. Among them, by reacting with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, a phenol resin that gives a benzoxazine resin excellent in heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained. 2,6-dimethylphenol is preferred.

  Examples of the phenol compound represented by the structural formula (3) include a phenol compound represented by any one of the following structural formulas (3-1) to (3-3).

  The phenol compound represented by the following structural formula (4) can be produced, for example, by reacting parabenzoquinone with dihydroxybenzene. The reaction ratio of parabenzoquinone and dihydroxybenzene gives a benzoxazine resin that is more excellent in heat resistance, heat decomposition resistance, and flame retardancy in cured products by reacting with diamine compounds, aromatic monohydroxy compounds, and formaldehyde. Since a phenol resin is obtained, it is preferable that dihydroxybenzene is in a range of 0.1 to 10.0 mol with respect to 1 mol of parabenzoquinone.

  The dihydroxybenzene used here may be any positional isomer such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene and the like. Among them, by reacting with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, a phenol resin that gives a benzoxazine resin excellent in heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained. 1,3-dihydroxybenzene is preferred.

  In formula (4), k is an integer of 1-3.

  Examples of the phenol compound represented by the structural formula (4) include a phenol compound represented by any one of the following structural formulas (4-1) to (4-3).

  In formulas (4-1) to (4-3), k is an integer of 1 to 3.

  The phenol resin containing the phenol compound represented by the structural formula (4) may further contain other phenol compounds. Examples of other phenol compounds include phenol compounds represented by any of the following structural formulas (4′-1) to (4′-8).

  In formulas (4′-1) to (4′-8), u and v are each an integer of 1 to 2.

  When the phenol resin contains the other phenol compound in addition to the compound represented by the structural formula (4), the content ratio of each component in the phenol resin is diamine compound, aromatic monohydroxy compound, and formaldehyde. By reacting, a binuclear compound (α1) having a k value of 1 in the structural formula (4) from the point of obtaining a benzoxazine resin excellent in heat resistance, heat decomposability and flame retardancy in the cured product. ) And the compound represented by the structural formula (4′-1) is in the range of 5 to 40% in area ratio in GPC measurement, and the value of k in the structural formula (4) is 2, a trinuclear compound (α2), a compound represented by the structural formula (4′-2), a compound represented by the structural formula (4′-4) or (4′-5), The total content of 10-60 % Of phenolic resin is preferred.

  The phenol compound represented by the following structural formula (5) can be produced, for example, by reacting parabenzoquinone with naphthol. The reaction ratio between parabenzoquinone and naphthol is a phenol that reacts with diamine compounds, aromatic monohydroxy compounds, and formaldehyde to give benzoxazine resins with even better heat resistance, heat decomposition resistance, and flame retardancy in cured products. Since a resin is obtained, it is preferable that naphthol is in a range of 0.1 to 10.0 mol with respect to 1 mol of parabenzoquinone.

  In formula (5), k is an integer of 1-3.

  As a phenol resin containing a phenol compound represented by the structural formula (5), it reacts with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, so that the cured product has heat resistance, heat decomposition resistance, and flame retardancy. In the structural formula (5), a binuclear compound (α1) having a k value of 1 and a k value of 2 in the structural formula (5) are obtained. A phenol resin containing a nuclear compound (α2) is preferable, and among them, the content of the binuclear compound (α1) is in the range of 5 to 60% in terms of area ratio in GPC measurement, and the three nuclei are included. A phenol resin in which the content ratio of the body compound (α2) is in the range of 5 to 50% in terms of area ratio in GPC measurement is more preferable.

  Examples of the phenol compound represented by the structural formula (5) include a phenol compound represented by any one of the following structural formulas (5-1) to (5-10).

  The phenol compound represented by the following structural formula (6) reacts with a diamine compound, an aromatic monohydroxy compound, and formaldehyde among the phenol compounds represented by the general formula (I), so that the heat resistance in the cured product is increased. Benzoxazine compounds that are particularly excellent in heat resistance, heat decomposability, and flame retardancy are obtained.

  In formula (6), k is an integer of 1-3.

  As a phenol resin containing the phenol compound represented by the structural formula (6), it reacts with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, so that the cured product has heat resistance, heat decomposition resistance, and flame retardancy. A binuclear compound (α1) having a k value of 1 in the structural formula (6) and a k value of 2 in the structural formula (6). A phenol resin containing a nuclear compound (α2) is preferable, and among them, the content of the binuclear compound (α1) is in the range of 5 to 60% in terms of area ratio in GPC measurement, and the three nuclei are included. A phenol resin in which the content ratio of the body compound (α2) is in the range of 5 to 50% in terms of area ratio in GPC measurement is more preferable.

  The phenol compound represented by any one of the structural formula (6) can be produced by reacting parabenzoquinone and dihydroxynaphthalene. The reaction ratio of parabenzoquinone and dihydroxynaphthalene gives a benzoxazine resin that is more excellent in heat resistance, heat decomposition resistance, and flame retardancy in cured products by reacting with diamine compounds, aromatic monohydroxy compounds, and formaldehyde Since a phenol resin is obtained, it is preferable that dihydroxynaphthalene is in a range of 0.1 to 10.0 mol with respect to 1 mol of parabenzoquinone.

  The dihydroxynaphthalene used here may be any positional isomer such as 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like. good. Among them, by reacting with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, a phenol resin that gives a benzoxazine resin excellent in heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained. 2,7-dihydroxynaphthalene is preferred.

  Examples of the phenol compound represented by the structural formula (6) include a phenol compound represented by any one of the following structural formulas (6-1) to (6-30).

  The phenol compound represented by the following structural formula (7) can be produced, for example, by reacting parabenzoquinone and phenylphenol in the molecular structure. The reaction rate of parabenzoquinone and phenylphenol gives a benzoxazine resin that is more excellent in heat resistance, heat decomposition resistance, and flame retardancy in cured products by reacting with diamine compounds, aromatic monohydroxy compounds, and formaldehyde. Since a phenol resin is obtained, it is preferable that phenylphenol is in a range of 0.1 to 10.0 mol with respect to 1 mol of parabenzoquinone.

  In formula (7), k is an integer of 1-3.

  Examples of the phenol compound represented by the structural formula (7) include a phenol compound represented by any one of the following structural formulas (7-1) to (7-12).

  In formulas (7-1) to (7-12), k is an integer of 1 to 3.

  More specifically, the phenol compound represented by the structural formula (I-2) includes a phenol compound represented by any one of the following structural formulas (8) to (11). Each will be described in detail below.

In formulas (8) to (11), q is an integer of 0 to 3, and r is an integer of 1 to 2. R ⁷ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and u is an integer of 1 to 4. When u is an integer of 2 or more, the plurality of R ⁷ may be the same or different.

  The phenol compound represented by the following structural formula (8) can be produced, for example, by reacting 2,4,6-trimethyl-parabenzoquinone with phenol, cresol, dimethylphenol or the like. The reaction ratio of 2,4,6-trimethyl-parabenzoquinone and phenol, cresol or dimethylphenol reacts with diamine compound, aromatic monohydroxy compound, and formaldehyde, so that the heat resistance and thermal decomposition in the cured product Therefore, phenol, cresol, dimethylphenol or the like can be added in an amount of 0.1 to 10% with respect to 1 mol of 2,4,6-trimethyl-parabenzoquinone. The ratio is preferably in the range of 0 mol.

  In formula (8), q is an integer of 0-3.

  Examples of the phenol compound represented by the structural formula (8) include a phenol compound represented by any one of the following structural formulas (8-1) to (8-9).

  In formulas (8-1) to (8-9), q is an integer of 0 to 3.

  The phenol compound represented by the following structural formula (9) can be produced, for example, by reacting 2,4,6-trimethyl-parabenzoquinone and dihydroxybenzene in the molecular structure. The reaction rate of 2,4,6-trimethyl-parabenzoquinone and dihydroxybenzene reacts with a diamine compound, aromatic monohydroxy compound, and formaldehyde, so that the cured product has heat resistance, heat decomposition resistance, and flame retardancy. Therefore, it is preferable that the amount of dihydroxybenzene is in the range of 0.1 to 10.0 mol with respect to 1 mol of 2,4,6-trimethyl-parabenzoquinone. .

  Examples of the phenol compound represented by the structural formula (9) include a phenol compound represented by the following structural formula (9-1).

  A phenol compound represented by the following structural formula (10) can be produced, for example, by reacting 2,4,6-trimethyl-parabenzoquinone with dihydroxynaphthalene or naphthol. The reaction rate of 2,4,6-trimethyl-parabenzoquinone and dihydroxynaphthalene or naphthol reacts with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, so that the cured product has heat resistance, heat decomposition resistance, and Since the phenol resin which gives the benzoxazine resin which is further excellent in flame retardancy is obtained, the ratio of dihydroxynaphthalene or naphthol in the range of 0.1 to 10.0 mol with respect to 1 mol of 2,4,6-trimethyl-parabenzoquinone It is preferable that

  In formula (10), r is an integer of 1-2.

  Examples of the phenol compound represented by the structural formula (10) include a phenol compound represented by any one of the following structural formulas (10-1) to (10-12).

  The phenol compound represented by the following structural formula (11) can be produced, for example, by reacting 2,4,6-trimethyl-parabenzoquinone with a phenylphenol compound. The reaction ratio of 2,4,6-trimethyl-parabenzoquinone and phenylphenol compound is such that it reacts with diamine compound, aromatic monohydroxy compound, and formaldehyde, so that heat resistance, heat decomposition resistance, and flame retardancy in cured products Since a phenol resin that gives a benzoxazine resin having higher properties is obtained, the molecular structure is in the range of 0.1 to 10.0 mol of phenylphenol compound with respect to 1 mol of 2,4,6-trimethyl-parabenzoquinone. A ratio is preferred.

  In formula (11), u is an integer of 1-4.

  Examples of the phenol compound represented by the structural formula (11) include a phenol compound represented by any one of the following structural formulas (11-1) to (11-3).

  More specifically, the phenol compound represented by the structural formula (I-3) includes a phenol compound represented by any one of the following structural formulas (12) to (16). Each will be described in detail below.

In formulas (12) to (16), q is an integer of 0 to 3, and m is an integer of 1 to 2. R ⁷ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, and u is an integer of 1 to 4. When u is an integer of 2 or more, the plurality of R ⁷ may be the same or different.

  The phenol compound represented by the following structural formula (12) can be produced, for example, by reacting naphthoquinone with phenol, cresol, dimethylphenol or the like. The reaction ratio between naphthoquinone and phenol, cresol, dimethylphenol, etc. is even better in heat resistance, heat decomposability, and flame retardancy in cured products by reacting with diamine compounds, aromatic monohydroxy compounds, and formaldehyde. Since a phenol resin giving a benzoxazine resin is obtained, it is preferable that phenol, cresol, dimethylphenol or the like is in a range of 0.1 to 10.0 mol with respect to 1 mol of naphthoquinone.

In formula (12), R ³ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group or an aralkyl group, m is an integer of 1 to 2, q is an integer of 0-3.

  Examples of the phenol compound represented by the structural formula (12) include a phenol compound represented by any of the following structural formulas (12-1) to (12-9).

  The phenol compound represented by the following structural formula (13) can be produced, for example, by reacting naphthoquinone with dihydroxybenzene. The reaction rate of naphthoquinone and dihydroxybenzene is a phenol that gives a benzoxazine resin that is more excellent in heat resistance, heat decomposition resistance, and flame retardancy in cured products by reacting with diamine compounds, aromatic monohydroxy compounds, and formaldehyde. Since the resin is obtained, it is preferable that dihydroxybenzene is in a range of 0.1 to 10.0 mol with respect to 1 mol of naphthoquinone.

  In formula (13), m is an integer of 1-2.

  Examples of the phenol compound represented by the structural formula (13) include a phenol compound represented by the following structural formula (13-1).

  The phenol compound represented by the following structural formula (14) can be produced, for example, by reacting naphthoquinone with naphthol. The reaction ratio of naphthoquinone and naphthol is a phenol resin that gives a benzoxazine resin that is more excellent in heat resistance, heat decomposition resistance, and flame retardancy in cured products by reacting with diamine compounds, aromatic monohydroxy compounds, and formaldehyde Therefore, it is preferable that naphthol is in a range of 0.1 to 10.0 mol with respect to 1 mol of naphthoquinone.

  In formula (14), m is an integer of 1-2.

  Examples of the phenol compound represented by the structural formula (14) include a phenol compound represented by any one of the following structural formulas (14-1) to (14-4).

  The phenol compound represented by the following structural formula (15) is a cured product particularly by reacting with a diamine compound, an aromatic monohydroxy compound, and formaldehyde among the phenol compounds represented by the general formula (I). It has a feature that a benzoxazine compound particularly excellent in heat resistance, heat decomposition resistance, and flame retardancy can be obtained.

  The phenol compound represented by the following structural formula (15) can be produced, for example, by reacting naphthoquinone with dihydroxynaphthalene. The reaction rate of naphthoquinone and dihydroxynaphthalene is a phenol that gives a benzoxazine resin that is more excellent in heat resistance, heat decomposition resistance, and flame retardancy in cured products by reacting with diamine compounds, aromatic monohydroxy compounds, and formaldehyde. Since the resin is obtained, it is preferable that dihydroxynaphthalene is in a range of 0.1 to 10.0 mol with respect to 1 mol of naphthoquinone.

  In formula (14), m is an integer of 1-2.

  The dihydroxynaphthalene used here may be any positional isomer such as 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like. good. Among them, by reacting with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, a phenol resin that gives a benzoxazine resin excellent in heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained. 2,7-dihydroxynaphthalene is preferred.

  Examples of the phenol compound represented by the structural formula (15) include compounds represented by any of the following structural formulas (15-1) to (15-8).

  The phenol resin containing the phenol compound represented by the structural formula (15) may further contain a phenol compound other than these. Among them, a dibenzofuran compound represented by the following structural formula (15 ′) can be obtained by reacting with a diamine compound, an aromatic monohydroxy compound, and formaldehyde to obtain a benzoxazine resin excellent in flame retardancy in a cured product. It is preferable to contain. In this case, the content ratio of each component in the phenol resin is such that the content ratio of the binuclear compound (α1) whose m value is 1 in the structural formula (15) is 2 to 60% in terms of the area ratio in GPC measurement. Phenol resins that are in the range and in which the content of the dinaphthofuran compound is in the range of 1 to 60% are preferred.

  The phenol compound represented by the following structural formula (16) can be produced by reacting naphthoquinone with a phenylphenol compound. The reaction ratio of naphthoquinone and phenylphenol compound gives a benzoxazine resin that is more excellent in heat resistance, heat decomposition resistance, and flame retardancy in cured products by reacting with diamine compounds, aromatic monohydroxy compounds, and formaldehyde Since a phenol resin is obtained, it is preferable that the amount of the phenylphenol compound be in the range of 0.1 to 10.0 mol with respect to 1 mol of naphthoquinone.

In formula (16), R ⁷ is any one of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, m is an integer of 1 to 2, u is an integer of 1-4. When u is an integer of 2 or more, the plurality of R ⁷ may be the same or different.

  Examples of the phenol compound represented by the structural formula (16) include a phenol compound represented by any one of the following structural formulas (16-1) to (16-7).

  Among these exemplified phenolic compounds, it is obtained by reacting a benzoxazine compound excellent in the balance between heat resistance, heat decomposition resistance and flame retardancy in a cured product with a diamine compound, an aromatic monohydroxy compound, and formaldehyde. In terms of the point, a phenol compound represented by any one of the structural formulas (1) to (3) is preferable, and among these, the balance between heat resistance, heat decomposition resistance, and flame retardancy in a cured product is particularly excellent. To the phenol compound represented by the structural formula (1) is more preferable.

  On the other hand, in the point obtained by reacting a benzoxazine compound particularly excellent in heat resistance, heat decomposability and flame retardancy in a cured product with a diamine compound, an aromatic monohydroxy compound, and formaldehyde, the structural formula (6) Or the phenol compound represented by (15) is preferable, and the phenol compound represented by the said Structural formula (15-1) or (15-2) is more preferable at the point which is excellent in a flame retardance especially.

  The phenol resin containing the phenol compound has a hydroxyl group equivalent in the range of 125 to 300 g / eq from the point obtained by reacting a benzoxazine resin having excellent curability with a diamine compound, an aromatic monohydroxy compound, and formaldehyde. Certain phenolic resins are preferred.

  The curable resin composition of the present invention comprises the benzoxazine compound or benzoxazine resin of the present invention described in detail above as an essential component. Since the benzoxazine compound or benzoxazine resin itself can be cured, the resin component of the curable resin composition of the present invention may be composed only of the benzoxazine compound or benzoxazine resin. Other resins may be used in combination.

  Examples of other resins include epoxy resins, phenolic hydroxyl group-containing resins, active ester resins, cyanate ester resins, vinyl benzyl compounds, acrylic compounds, maleimide compounds, and copolymers of styrene and maleic anhydride.

  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 an epoxy resin is used in combination with the benzoxazine resin of the present invention, the ratio between the total number of moles (a) of the oxazine structure and the phenolic hydroxyl group in the benzoxazine resin and the number of moles (b) of the epoxy groups in the epoxy resin. [(A) / (b)] is a ratio of 1.0 / 0.1 to 1.0 / 1.0, more preferably a ratio of 1.0 / 0.1 to 1.0 / 0.5 It is preferable that a cured product having excellent heat resistance and thermal decomposition resistance in the cured product is 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 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 novolac type cyanate ester resin, cresol novolac type cyanate ester resin, triphenylmethane type cyanate ester Resin, tetraphenylethane type cyanate ester resin, DISIC Pentadiene-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 novolak type cyanate Examples include ester resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin-type cyanate ester resins, biphenyl-modified novolac-type cyanate ester resins, anthracene-type cyanate ester resins, and the like. 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).

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

In formula (ii), 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, n is an integer of 1 to 3, and m is an average of 0 to 0. 10.

  In the formula (iii), 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, n is an integer of 1 to 3, and m is an average of 0 to 0 repeating units. 10.

  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, α-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 composition 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 compositions.

  When the curable resin composition 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- And cyclic organic phosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives obtained by reacting them with compounds such as phenol resins and phenol resins.

  The amount of these phosphorus-based flame retardants is preferably, for example, in the range of 0.1 to 2.0 parts by weight in the case of using red phosphorus in 100 parts by weight of the curable resin composition. 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.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric 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, sulfuric acid such as guanylmelamine sulfate, melem sulfate, melam sulfate Examples thereof include aminotriazine compounds, aminotriazine-modified phenol resins, and aminotriazine-modified phenol resins that are further modified with tung oil, isomerized linseed oil, and the like.

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

  The blending amount of the nitrogen-based flame retardant is preferably blended in a range of 0.05 to 10 parts by weight, for example, in a range of 0.1 to 5 parts by weight in 100 parts by weight of the curable resin composition. It is more preferable.

  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.

  It is preferable to mix | blend the compounding quantity of the said silicone type flame retardant in the range of 0.05-20 mass parts in 100 mass parts of curable resin compositions, for example. 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 Sheepley (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. Glass forms such as _5- B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. A compound can be mentioned.

  The blending amount of the inorganic flame retardant is preferably blended in the range of 0.05 to 20 parts by weight, for example, in the range of 0.5 to 15 parts by weight in 100 parts by weight of the curable resin composition. It is more preferable.

  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.

  It is preferable to mix | blend the compounding quantity of the said organometallic salt type flame retardant in the range of 0.005-10 mass parts in 100 mass parts of curable resin compositions, for example.

  The curable resin composition 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 high in consideration of flame retardancy, and is particularly preferably 20% by mass or more with respect to the total mass of the curable resin composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  The curable resin composition of the present invention is optionally provided with reinforcing fibers such as glass, quartz, carbon, oriented fibers, and synthetic fibers in the normal form of short fibers, staple fibers, twisted yarns, fabrics or mats, if necessary. (Keflar, Nomex), natural fibers such as flax, burlap, sisal hemp, hemp hemp: silane coupling agent: mold release agent: pigment: dye: emulsifier and various other compounding agents can be added.

  The curable resin composition of the present invention is cured by heating and can be easily made into a cured product. Specifically, it is obtained by uniformly mixing the above-described components, and is easily cured by heating the curable resin composition at a temperature of about 100 ° C. or higher, preferably 140 to 220 ° C. It can be.

  The curable resin composition of the present invention is a known process for thermosetting resins such as phenol formaldehyde resins or epoxy resins, such as prepreg hot pressing, SMC (sheet molding compound): or molding: casting: filament winding. It is preferable to process using an injection technique or a vacuum impregnation (RTM, VaRTM) method, and since it is excellent in heat resistance, heat decomposition resistance, flame retardancy and dielectric properties in a cured product, Insulating materials for circuit boards such as resin compositions for flexible wiring boards, interlayer insulating materials for build-up boards, semiconductor sealing materials, conductive pastes, adhesive films for build-up, resin casting materials, adhesives, FRP materials, etc. It can be suitably used as various materials.

  When applied to a semiconductor sealing material, the curable resin composition is sufficiently mixed with a compounding agent such as an inorganic filler using an extruder, kneader, roll or the like as necessary until uniform. A semiconductor sealing material can be manufactured by melt-mixing. 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. The content of the inorganic filler is preferably in the range of 30 to 95 parts by mass per 100 parts by mass of the curable resin composition, and among them, improvement in flame retardancy, moisture resistance and solder crack resistance, and linear expansion In order to reduce the coefficient, the amount is more preferably 70 to 95 parts by mass, and still more preferably 80 to 95 parts by mass.

  When applied to circuit board applications, the varnish formed by adding an organic solvent to the curable resin composition of the present invention is formed into a plate shape, laminated with copper foil, and heated and pressed to form a circuit board. Can be manufactured. In addition, when applying to hard printed wiring board applications, a prepreg is obtained by impregnating a reinforcing base material with a varnish obtained by adding an organic solvent to a curable resin composition and semi-curing it, and then overlaying a copper foil thereon. And can be manufactured by a method of thermocompression bonding.

  The organic solvent used when varnishing the curable resin composition of the present invention is preferably a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol, etc. It is preferable to use in the ratio from which the non volatile matter of a conductive resin composition will be 40-80 mass%. Examples of the reinforcing base material used for the printed wiring board include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. More specifically, the varnish-like curable resin composition described above is first heated at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C. to obtain a cured prepreg. obtain. At this time, the mass ratio of the curable resin composition to be used and the reinforcing substrate is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60 mass%. Next, the prepreg obtained as described above is laminated by a conventional method, and a copper foil is appropriately stacked, and then subjected to thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa, A target circuit board can be obtained.

In order to produce a flexible wiring board from the curable resin composition of the present invention, a curable resin composition containing an organic solvent is applied to an electrical insulating film using a coating machine such as a reverse roll coater or a comma coater. Subsequently, it heats for 1 to 15 minutes at 60-170 degreeC using a heater, volatilizes a solvent, and makes curable resin composition B-stage. Next, the metal foil is thermocompression bonded to the resin layer using a heating roll or the like. At that time, the pressure is preferably ^{2 to} 200 N / cm ² and the pressure is 40 to 200 ° C. If sufficient adhesive performance can be obtained, the process may be completed here. However, when complete curing is required, it is preferably post-cured at 100 to 200 ° C. for 1 to 24 hours. The thickness of the resin layer after finally curing is preferably in the range of 5 to 100 μm.

  In order to produce a build-up film from the curable resin composition of the present invention, for example, a curable resin composition appropriately blended with rubber, filler or the like is spray-coated on a substrate such as a wiring board on which a circuit is formed, After applying using a curtain coating method or the like, it is cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. Moreover, a roughened surface is formed by heat-pressing a copper foil with a resin obtained by semi-curing a curable resin composition on a copper foil onto a wiring board on which a circuit is formed at 170 to 250 ° C. It is also possible to produce a build-up substrate by omitting this process.

  The method for producing an adhesive film for build-up from the curable resin composition of the present invention is, for example, applying a diluted curable resin composition of the present invention by adding an organic solvent on a support film, and There is a method of forming an adhesive film for a multilayer printed wiring board.

  Examples of the organic solvent used in this case 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, ethanol, propanol, butanol, and the like. Alcohol solvents, cellosolve, carbitol solvents such as butyl carbitol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are used, and the curable resin composition should be used in a ratio of 30 to 60% by mass. Is preferred.

  The adhesive film comprising the curable resin composition of the present invention is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and simultaneously with the lamination of the circuit board, via holes or through holes existing in the circuit board. It is important to show fluidity (resin flow) that can be filled with resin, 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 multilayer printed wiring 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 method for producing the adhesive film described above is, after preparing the varnish-like curable resin composition of the present invention, applying the varnish-like curable resin composition to the surface of the support film, Further, it can be produced by drying the organic solvent by heating or blowing hot air to form the layer (γ) of the curable resin composition.

  The thickness of the layer (γ) to be formed 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 layer is preferably 10 to 100 μm.

  In addition, the said layer ((gamma)) may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the resin assembly layer surface 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 above support film is peeled off after being laminated on the circuit board or after forming the insulating layer by heat curing. If the support film is peeled after the adhesive 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.

  Next, a method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (γ) is protected with a protective film, after peeling these layers ( Lamination is performed, for example, by a vacuum laminating method on one side or both sides of the circuit board so that γ) is in direct contact with the circuit board. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive 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., a pressure bonding pressure of preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m 2), Lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

  When the curable resin composition of the present invention is used as a conductive paste, for example, a method of dispersing fine conductive particles in a curable resin composition to form a composition for an anisotropic conductive film, which is liquid at room temperature. Examples thereof include a paste resin composition for circuit connection and a method of using an anisotropic conductive adhesive.

  The curable resin composition of the present invention can also be used as a resist ink. In this case, a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent are blended in the curable resin composition, and further, a pigment, talc, and filler are added to form a resist ink composition. Then, after apply | coating on a printed circuit board by a screen printing system, the method of setting it as a resist ink hardened | cured material is mentioned. Since the polyarylene ether resin alone can cause a curing reaction, in the curable resin composition of the present invention, the polyarylene aer resin may be used alone or in combination with other resins. May be.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on mass unless otherwise specified. GPC, ¹³ CNMR, and MS spectrum were measured under the following conditions.

GPC: Measurement conditions are as follows.
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 refractometer)
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).

<Measurement conditions for ¹³ C-NMR>
The measurement conditions for ¹³ C-NMR were as follows.
Device: AL-400 manufactured by JEOL Ltd.
Measurement mode: SGNNE (1H complete decoupling method of NOE elimination),
Solvent: dimethyl sulfoxide,
Pulse angle: 45 ° pulse,
Sample concentration: 30 wt%
Integration count: 10,000 times

<MS measuring device>
The following apparatus was used as the MS measurement apparatus.
Apparatus: Double convergence type mass spectrometer AX505H (FD505H) manufactured by JEOL Ltd.

<IR measurement device>
The following apparatus was used as an IR measurement apparatus.
Equipment: “FT / IR-550” manufactured by JASCO Corporation

Example 1 Production of benzoxazine resin (A-1) A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 282 g (3 mol) of phenol and 3 g of paratoluenesulfonic acid, and stirred. The temperature was raised from room temperature to 80 ° C. After reaching 80 ° C., 162 g (1.5 mol) of parabenzoquinone was added over 1 hour, and then the temperature was further raised to 130 ° C. and stirred for 1 hour to react. After completion of the reaction, the residue was dried under reduced pressure to obtain 250 g of a phenol resin (A). The GPC chart of the obtained phenol resin is shown in FIG. 1, the ¹³ C-NMR spectrum is shown in FIG. 2, and the MS spectrum is shown in FIG. The hydroxyl equivalent of the phenol resin (A) was 88 g / eq, and the softening point was 95 ° C. From the MS spectrum, 202 peaks corresponding to the following dinuclear compound (a-1), 294 peaks corresponding to the following trinuclear compound (b-1), and the following tetranuclear compound (c-1) Corresponding 386 peaks were detected. The content of the binuclear compound (a-1) equivalent component in the phenol resin calculated from the GPC chart is 37.3%, the content of the trinuclear compound (b-1) equivalent component is 30.7%, The content of the tetranuclear compound (c-1) equivalent component was 10.3%.

Then, 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) of 4,4′-diaminodiphenylmethane, phenol 94 .1 g (1.0 mol) and 88.0 g of phenolic resin (A) (hydroxyl group 1.0 equivalent) were charged and dissolved in 500 g of toluene, and then 286.0 g (4.0 mol) of 42% formaldehyde aqueous solution was added. Then, the temperature was raised to 80 ° C. while stirring, and the reaction was carried out 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 235 g of a benzoxazine resin. The IR spectrum of the obtained benzoxazine resin showed absorption at 948 cm ⁻¹ derived from the oxazine ring, and the mass spectrum showed peaks such as 1223 and 1655, so that the target benzoxazine resin (A-1) It was confirmed that

Example 2 Production of benzoxazine resin (B-1) In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer, 649 g of orthocresol (6.0 mol) and 162 g of parabenzoquinone (1. 5 mol) and 8 g of paratoluenesulfonic acid were charged, and the temperature was raised from room temperature to 120 ° C. with stirring. After reaching 120 ° C., the mixture was stirred for 2 hours. After completion of the reaction, the precipitated crystal was separated and washed twice with 200 g of water. Thereafter, it was dried under heating under reduced pressure to obtain 117 g of a phenol resin (B). FIG. 4 shows a GPC chart of the obtained phenol resin (B), FIG. 5 shows a ¹³ CNMR spectrum, and FIG. 6 shows an MS spectrum. The hydroxyl equivalent of the phenol resin (B) is 81 g / eq. From the MS spectrum, 216 peaks corresponding to the following dinuclear compound (a-2) and 322 corresponding to the following trinuclear compound (b-2) are obtained. 428 peaks corresponding to the following tetranuclear compound (c-2) were detected. The content of the binuclear compound (a-2) equivalent component in the phenol resin calculated from the GPC chart is 4.6%, the content of the trinuclear compound (b-2) equivalent component is 88.0%, The content of the tetranuclear compound (c-2) equivalent component was 5.1%.

Then, 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) of 4,4′-diaminodiphenylmethane, phenol 94 .1 g (1.0 mol) and 81.0 g of phenol resin (B) (hydroxyl group 1.0 equivalent) were charged and dissolved in 500 g of toluene, and then 286.0 g (4.0 mol) of 42% formaldehyde aqueous solution was added. Then, the temperature was raised to 80 ° C. while stirring, and the reaction was carried out 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 222 g of a benzoxazine resin. The IR spectrum of the obtained benzoxazine resin showed absorption at 948 cm ⁻¹ derived from the oxazine ring, and the mass spectrum showed peaks of 1237, 1683, etc., so that the target benzoxazine resin (B-1) It was confirmed that

Example 3 Production of benzoxazine resin (C-1) To a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, 649 g of orthocresol (6.0 mol) and 3 g of paratoluenesulfonic acid were added. The temperature was raised from room temperature to 80 ° C. while charging and stirring. After reaching 80 ° C., 162 g (1.5 mol) of parabenzoquinone was added over 1 hour, and then the temperature was further raised to 130 ° C. and stirred for 1 hour to react. After completion of the reaction, the residue was dried under reduced pressure to obtain 260 g of a phenol compound (C). A GPC chart of the resulting phenol compound (C) is shown in FIG. The hydroxyl group equivalent of the phenol compound (C) was 97 g / eq. The content of the binuclear compound (α1) equivalent component in the phenol resin calculated from the GPC chart is 25.8%, the content of the trinuclear compound (α2) equivalent component is 51.7%, and the tetranuclear compound. The content of (α3) equivalent component was 10.0%.

Then, 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) of 4,4′-diaminodiphenylmethane, phenol 94 .1 g (1.0 mol) and 97.0 g of phenol resin (C) (1.0 equivalent of hydroxyl group) were charged and dissolved in 500 g of toluene, and then 286.0 g (4.0 mol) of 42% formaldehyde aqueous solution was added. Then, the temperature was raised to 80 ° C. while stirring, and the reaction was carried out 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 265 g of a benzoxazine resin. The IR spectrum of the obtained benzoxazine resin showed absorption at 948 cm ⁻¹ derived from the oxazine ring, and the mass spectrum showed peaks such as 1237 and 1683, so that the target benzoxazine resin (C-1) It was confirmed that

Example 4 Production of benzoxazine resin (D-1) In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, 165 g (1.5 mol) of resorcin, 162 g of parabenzoquinone (1.5 Mol) and the temperature was raised from room temperature to 120 ° C. with stirring. After reaching 120 ° C., the mixture was stirred for 2 hours. After completion of the reaction, the mixture was heated to 180 ° C. and dried under reduced pressure to obtain 280 g of a phenol resin (D). FIG. 8 shows a GPC chart of the obtained phenol resin (D), FIG. 9 shows a ¹³ CNMR spectrum, and FIG. 10 shows an MS spectrum. The hydroxyl equivalent of the phenol resin (D) was 60 g / eq, and the softening point was 98 ° C. From the MS spectrum, 202, 218 peaks corresponding to the binuclear compound, 310, 326 peaks corresponding to the trinuclear compound, and 418, 434 peaks corresponding to the tetranuclear compound were detected. The content of the binuclear compound equivalent component in the phenol resin calculated from the GPC chart is 20.0%, the content of the trinuclear compound equivalent component is 20.8%, and the content of the tetranuclear compound equivalent component is It was 13.0%.

Then, 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) of 4,4′-diaminodiphenylmethane, phenol 94 .1 g (1.0 mol) and 60.0 g of phenol resin (D) (hydroxyl group 1.0 equivalent) were charged and dissolved in 400 g of toluene, and then 286.0 g (4.0 mol) of 42% formaldehyde aqueous solution was added. Then, the temperature was raised to 80 ° C. while stirring, and the reaction was carried out 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 178 g of a benzoxazine resin. The IR spectrum of the obtained benzoxazine resin showed absorption at 948 cm ⁻¹ derived from the oxazine ring, and the mass spectrum showed peaks such as 1579, so that the desired benzoxazine resin (D-1) was obtained. It was confirmed that

Example 5 Production of benzoxazine resin (E-1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 240 g (1.5 mol) of 2,7-dihydroxynaphthalene, parabenzoquinone 162 g (1.5 mol), 268 g of isopropyl alcohol, and 8 g of oxalic acid were charged, and the temperature was raised from room temperature to 120 ° C. with stirring. After reaching 120 ° C., the reaction was allowed to stir for 2 hours. After completion of the reaction, the mixture was heated to 180 ° C. and dried under reduced pressure to obtain 359 g of phenol resin (E). FIG. 10 shows a GPC chart of the obtained phenol resin, FIG. 11 shows a ¹³ CNMR spectrum, and FIG. 12 shows an MS spectrum. The hydroxyl equivalent of the phenol resin (E) was 68 g / eq, and the softening point was 126 ° C. From the MS spectrum, 268 peaks corresponding to the following dinuclear compound (a-4) and 426 peaks corresponding to the following trinuclear compound (b-4) were detected. The content of the binuclear compound (a-4) equivalent component in the phenol resin calculated from the GPC chart is 43.6%, and the content of the trinuclear compound (b-4) equivalent component is 30.7%. there were.

Then, 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) of 4,4′-diaminodiphenylmethane, phenol 94 .1 g (1.0 mol) and 68.0 g of phenol resin (E) (hydroxyl group 1.0 equivalent) were charged and dissolved in 400 g of toluene. Then, 143 g (2.0 mol) of a 42% formaldehyde aqueous solution was added, The temperature was raised to 80 ° C. with stirring, and the reaction was carried out 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 151 g of a benzoxazine resin. The IR spectrum of the obtained benzoxazine resin showed absorption at 948 cm ⁻¹ derived from the oxazine ring, and the mass spectrum showed a peak such as 1629. Thus, the desired benzoxazine resin (E-1) was obtained. It was confirmed that

Example 6 Production of benzoxazine resin (F-1) In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer, 2,7-dihydroxynaphthalene 160 g (1.0 mol), naphthoquinone 158 g (1.0 mol) and 318 g of methyl isobutyl ketone were charged and the temperature was raised from room temperature to 150 ° C. with stirring. After reaching 150 ° C., the reaction was allowed to stir for 3 hours. After completion of the reaction, the mixture was heated to 180 ° C. and dried under reduced pressure to obtain 300 g of a phenol resin (F). The GPC chart of the obtained phenol resin is shown in FIG. 14, and the MS spectrum is shown in FIG. The obtained phenol resin (F) had a hydroxyl group equivalent of 101 g / eq and a softening point of 130 ° C. From the MS spectrum, 318 peaks corresponding to the compound represented by the following structural formula (a-5) and 300 peaks corresponding to the compound represented by the following structural formula (d) were detected. The content of the following binuclear compound (a-5) equivalent component in the phenol resin calculated from the GPC chart is 49.7%, and the content of the naphthofuran compound represented by the following structural formula (d) is 6. 0%.

Then, 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) of 4,4′-diaminodiphenylmethane, phenol 94 .1 g (1.0 mol) and phenol resin (F) 101.0 g (hydroxyl group 1.0 equivalent) were charged and dissolved in 400 g of toluene, and then 286.0 g (4.0 mol) of 42% formaldehyde aqueous solution was added. Then, the temperature was raised to 80 ° C. while stirring, and the reaction was carried out 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 169 g of a benzoxazine resin. The IR spectrum of the obtained benzoxazine resin showed absorption at 948 cm ⁻¹ derived from the oxazine ring, and the mass spectrum showed a peak such as 980, so that the desired benzoxazine resin (F-1) was obtained. It was confirmed that

Examples 7 to 12 Production of compositions and molded products Benzoxazine resins (A-1), (B-1), (C-1), (D-1), (E) obtained in Examples 1 to 6 -1), (F-1), a phenol novolac resin (“TD-2131” manufactured by DIC Corporation), and fused silica (“FB3SDC” manufactured by Electrochemical Co., Ltd.) are mixed as shown in Table 1, After 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. The physical property results of the obtained cured product are shown in Table 1, and the measurement method is shown below.

Comparative Example 1 Production of Composition and Molded Product A benzoxazine compound (manufactured by Huntsman, reaction product of bisphenol F, formalin and aniline (denoted as “MT35700” in the table)) and phenol novolac resin (manufactured by DIC Corporation “TD” -2131 ") and fused silica (" FB3SDC "manufactured by Electrochemical Co., Ltd.) are mixed as shown in Table 1 and molded at a temperature of 200 ° C for 10 minutes with a press, and then 5 at a temperature of 200 ° C. After time, it was cured to obtain a cured product having a thickness of 0.8 mm. The physical property evaluation results of the obtained cured product are shown in Table 1, and the measurement method is shown below.

<Glass transition temperature>
A cured product having a thickness of 0.8 mm was cut into a size having a width of 5 mm and a length of 54 mm. Using this test piece 1 with a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., Ltd., rectangular tension method: frequency 1 HZ, heating rate 3 ° C./min) (The tan δ change rate is the highest) was measured as the glass transition temperature.

<Evaluation of thermal decomposition resistance>
After holding the test piece 1 at 250 ° C. for 72 hours, the mass reduction rate when compared with the initial mass was measured.

<Measurement of dielectric constant and tangent>
In accordance with JIS-C-6481, the impedance material analyzer “HP4291B” manufactured by Agilent Technologies, Inc. was used to dry the test piece 1 at 1 GHZ after being stored in a room at 23 ° C. and 50% humidity for 24 hours. The dielectric constant and tangent were measured.
<Flame retardance>
A cured product having a thickness of 0.8 mm was cut into a size of 12.7 mm in width and 127 mm in length, and the combustion test was performed using five test pieces in accordance with the UL-94 test method using the obtained test pieces. The flame retardancy was measured.

Claims (10)

A benzoxazine compound obtained by reacting a phenolic compound having a molecular structure represented by the following general formula (I) with a diamine compound, an aromatic monohydroxy compound, and formaldehyde.

[In formula (I), X is a structural site represented by the following structural formula (x1) or (x2). ]

[In Formula (x1) or (x2), R ¹ and R ² are each an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group; Is an integer from 0 to 1, and n is an integer from 0 to 3. When n is an integer of 2 or more, the plurality of R ² may be the same or different from each other. K is an integer of 1 to 3, m is an integer of 1 to 2, and Ar is a structural moiety represented by the following structural formula (Ar1) or (Ar2). When k is 2 or 3, or m is 2 , the plurality of Ar may be the same or different from each other. In the formula (x2), R ² and Ar may be bonded to any one of the two aromatic nuclei. ]

Wherein (Ar @ 1) or (Ar @ 2), ^{R 3} and ^{R 4} are each an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, Ru der either an aryl group or an aralkyl group. q is an integer of 0 to 3, and s is an integer of 0 to 5. When q or s is an integer of 2 or more, a plurality of R ³ or R ⁴ may be the same or different from each other. P and r are integers of 1 to 2, respectively. In the formula (Ar2), the R ⁴ and OH groups may be bonded to any of the two aromatic nuclei. ]   A benzoxazine resin containing the benzoxazine compound according to claim 1.   A curable resin composition comprising the benzoxazine compound according to claim 1 or the benzoxazine resin according to claim 2 as an essential component. A cured product obtained by curing the curable resin composition according to claim 3 . An FRP material comprising the curable resin composition according to claim 3 . A semiconductor encapsulant comprising the curable resin composition according to claim 3 and an inorganic filler, wherein the content of the inorganic filler is in the range of 30 to 95 parts by mass per 100 parts by mass of the curable resin composition. Stop material. A varnish obtained by adding an organic solvent to the curable resin composition according to claim 3 . A circuit board obtained by laminating a varnish according to claim 7 in a plate shape with a copper foil, followed by heat and pressure molding. A prepreg obtained by impregnating a varnish according to claim 7 into a reinforcing base material and then semi-curing it. A buildup film obtained by applying the varnish according to claim 7 on a substrate and then curing the varnish.

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