JP6690120B2 - Benzoxazine compound, benzoxazine resin, method for producing benzoxazine compound, curable resin composition, cured product thereof, FRP material, semiconductor encapsulating material, varnish, circuit board, prepreg, and build-up film - Google Patents

Description

  The present invention provides a benzoxazine compound, a benzoxazine resin, a method for producing a benzoxazine compound, a curable resin composition, and a cured product thereof which are excellent in heat resistance, thermal decomposition resistance, flame retardancy and dielectric properties of the resulting cured product. Objects, FRP materials, semiconductor encapsulation materials, varnishes, circuit boards, prepregs, and build-up films.

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

  As a typical benzoxazine compound, Patent Document 1 describes a compound obtained by reacting bisphenol F (or bisphenol A) with aniline and formalin. However, when the benzoxazine compound is applied to a printed wiring board, the printed wiring board has a low dielectric constant because it can withstand high-speed communication, reduce transmission loss, and even when the operating environment temperature rises. Although it is required to have high heat resistance and high thermal decomposition resistance while having characteristics such as a high dielectric constant and a low dielectric loss tangent, the benzoxazine compound has not been able to sufficiently satisfy these characteristics. Furthermore, since the benzoxazine compound is inferior in flame retardance as compared with conventional benzoxazine resins and the like, it is necessary to blend a large amount of various flame retardants, but the benzoxazine compound is blended in a large amount of various flame retardants. As a result, the workability is deteriorated and the glass transition temperature is lowered, so that it cannot be used at all for a circuit board material which is becoming thinner and a FRP composite material having a complicated shape.

Japanese Patent Laid-Open No. 11-12258

  Therefore, the problem to be solved by the present invention is to provide a cured product having heat resistance, thermal decomposition resistance, flame retardancy, and a benzoxazine resin having excellent physical properties such as dielectric properties, a benzoxazine resin, and a method for producing a benzoxazine compound. A curable resin composition, a cured product thereof, an FRP material, a semiconductor encapsulating material, a varnish, a circuit board, a prepreg, and a build-up film are provided.

  As a result of intensive studies to solve the above problems, the present inventors have found that a phenol compound having a diarylene [b, d] furan structure in which aromatic rings are bonded to each other without interposing a methylene chain, a monoamine compound and formaldehyde, It was found that the benzoxazine compound obtained by reacting with is excellent in various physical properties such as heat resistance, thermal decomposition resistance, flame retardancy and dielectric properties in the obtained cured product, and has completed the present invention.

  That is, the present invention has a diarylene [b, d] furan structure, and at least one of the two arylene groups forming the diarylene [b, d] furan structure has a naphthylene skeleton, and The present invention relates to a benzoxazine compound obtained by reacting a phenol compound in which each of the two arylene groups has a hydroxyl group on its aromatic ring with a monoamine compound and formaldehyde.

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

  The present invention comprises a step of reacting a compound (Q) having a quinone structure in the molecular structure with a compound (P) having a phenolic hydroxyl group in the molecular structure in the presence of an acid catalyst to obtain a phenol compound; And the step of reacting the monoamine compound and formaldehyde obtained in (1) with at least one of the compound (Q) having the quinone structure or the compound (P) having a phenolic hydroxyl group in the molecular structure. The compound relates to a method for producing a benzoxazine compound having a naphthalene ring in the molecule.

  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 contains 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. Regarding 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 the varnish formed into a plate shape on a copper foil, and heat-pressing the varnish.

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

  The present invention further relates to a build-up film obtained by applying the curable resin composition on a substrate and then curing the composition.

  According to the present invention, the resulting cured product has excellent heat resistance, thermal decomposition resistance, flame retardancy and various physical properties such as dielectric properties, a benzoxazine resin, a method for producing a benzoxazine compound, a curable resin composition, The cured product, FRP material, semiconductor encapsulating 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 GPC chart of the phenol resin (B) obtained in Example 2. 3 is a GPC chart of a phenol resin (C) obtained in Example 3.

Hereinafter, the present invention will be described in detail.
The benzoxazine compound of the present invention has a diarylene [b, d] furan structure, and at least one of the two arylene groups forming the diarylene [b, d] furan structure has a naphthylene skeleton, Further, it is a compound obtained by reacting a phenol compound having a hydroxyl group on each of its two arylene groups, a monoamine compound and formaldehyde.

  The benzoxazine compound of the present invention obtained as described above has a diarylene [b, d] furan structure in which aromatic rings are bonded to each other without interposing a methylene chain, and thus is rigid and has no aromatic ring in the compound. And is characterized by a high concentration of benzoxazine rings. That is, since the benzoxazine compound of the present invention has a molecular structure that does not have a methylene chain that is easily decomposed by heat as described above, the cured product obtained is characterized by high thermal decomposition resistance. 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, the molecular motion is suppressed, and the resulting cured product has a low dielectric constant and a low dielectric loss tangent, resulting in poor dielectric properties. It has the feature of being excellent. Further, the benzoxazine compound of the present invention has a feature that, in addition to the rigid molecular structure as described above, and the aromatic ring concentration in the compound is high, the resulting cured product has excellent flame retardancy. Further, the benzoxazine compound of the present invention has a feature that, in addition to the rigid molecular structure as described above, the concentration of the benzoxazine ring is high, so that the obtained cured product has a high crosslink density and excellent heat resistance. That is, a benzoxazine compound obtained by reacting the phenol compound with a monoamine compound and formaldehyde is characterized in that the resulting cured product has excellent heat resistance, thermal decomposition resistance, flame retardancy, and dielectric properties. I have.

  Generally, in order to improve the heat resistance of the cured product, a method of polyfunctionalizing an aromatic ring with a knot group such as formaldehyde is known, but a compound polyfunctionalized by such a method is known. Since the aromatic rings are knotted by only one knot group, the knot group is easily cleaved at the time of combustion, and the flame retardancy is low. On the other hand, the benzoxazine compound of the present invention has a diarylene [b, d] furan structure in which aromatic rings are fixed by two bonds, an ether bond and a direct bond, and therefore, aromatic rings are not formed during combustion. These binding bonds are not easily cleaved, and a cured product exhibits high flame retardancy. Furthermore, since at least one of the two arylene groups has a naphthalene skeleton, the aromatic ring concentration is further increased, and the resulting cured product exhibits extremely excellent flame retardancy.

  Since the benzoxazine compound of the present invention is further excellent in reactivity and is excellent in heat resistance, heat decomposition resistance and flame retardancy in a cured product, the phenol compound has the diarylene [b, d] furan structure. However, at least one of the two arylene groups forming the diarylene [b, d] furan structure has a naphthylene skeleton, and each of the two arylene groups has a hydroxyl group on its aromatic ring. It is preferable that at least one of the two arylene groups has a hydroxyl group at the para position of the carbon atom to which the oxygen atom forming the furan ring is bonded.

  Examples of the benzoxazine compound of the present invention obtained by reacting the above phenol compound with a monoamine compound and formaldehyde include compounds represented by the following structural formulas (III) to (VI).

In formulas (III) to (VI), each R ² is independently 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 0 to 4, and n is an integer of 0 to 3. When m or n is 2 or more, R ² may be the same or different. Y and Z are bonded to adjacent carbon atoms on the aromatic ring and are a pair represented by a hydroxyl group and a hydrogen atom, respectively, or a pair constituting a structural site represented by the following structural formula (VII). However, at least one set of Y and Z in the molecule is one set that constitutes a structural site represented by the following structural formula (VII). Furthermore, in formulas (III) to (V), R ² may be bonded to any aromatic ring of the two aromatic rings forming the naphthalene ring, and Y bonded to the naphthalene ring to which R ² is bonded. And Z may be bonded to any of the two aromatic rings forming the naphthalene ring.

In formula (VII), * Y and * Z are respectively the point of attachment to the carbon atom to which Y is bonded and the carbon atom to which Z is bonded in the compounds represented by structural formulas (III) to (VI). R ³ is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or one or more hydrogen atoms contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group is a hydroxyl group, an alkoxy group or a halogen atom. The structure is replaced by any of the above.

Specific examples of R ³ include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and cyclohexyl group; alkenyl groups such as allyl group; alkynyl groups such as propargyl group. Group; hydroxy group-containing alkyl group such as hydroxyethyl group, hydroxypropyl group; methoxyethyl group, methoxypropyl group, allyloxymethyl group, allyloxypropyl group, propargyloxymethyl group, alkoxy group-containing alkyl group such as propargyloxypropyl group A halogenated alkyl group such as chloromethyl group, chloroethyl group, chloropropyl group, bromomethyl group, bromoethyl group, bromopropyl group, fluoromethyl group, fluoroethyl group, fluoropropyl group; phenyl group, tolyl group, xylyl group, naphthyl Aryl groups such as groups; Hydroxyl group-containing aryl groups such as droxyphenyl group and hydroxynaphthyl group; alkoxy group-containing aryl groups such as methoxyphenyl group, ethoxyphenyl group, allyloxyphenyl group, propargyloxyphenyl group; vinylphenyl group, allylphenyl group, ethynylphenyl Group, an aryl group containing an unsaturated hydrocarbon group such as a propargylphenyl group, and a halogenated aryl group such as a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloronaphthyl group, a bromonaphthyl group, and a fluoronaphthyl group.

  As the benzoxazine resin containing the benzoxazine compound of the present invention, in addition to the benzoxazine compounds represented by the structural formulas (III) to (VI), for example, the following structural formulas (III-1) to (VI- The compound etc. which are represented by 2) may be contained.

In formulas (III-1) to (VI-2), s is an integer of 0 to 4, t is an integer of 0 to 2, and k is an integer of 1 to 2. x and y represent a bonding point with the naphthalene ring, and represent bonding with carbons adjacent to each other so as to form a furan ring. R ² is each independently 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 s or t is an integer of 2 or more. , R ² may be the same or different. Y and Z are bonded to adjacent carbon atoms on the aromatic ring and are a pair represented by a hydroxyl group and a hydrogen atom, respectively, or constitute a structural moiety represented by the structural formula (VII-2). At least one set is a set forming the structural site represented by the structural formula (VII-2). Further, in formulas (III-1) to (V-2), R ² may be bonded to any aromatic ring of the two aromatic rings forming the naphthalene ring. Y and Z bonded to the naphthalene ring to which R ² is bonded may be bonded to any of the two aromatic rings forming the naphthalene ring.

In formula (VII-1), ** Y and ** Z are the bonding points with the carbon atom to which Y is bonded in the compounds represented by the structural formulas (III-1) to (VI-2). , Z is a point of attachment to the carbon atom to which R is bonded, and R ³ is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or one or more hydrogen atoms contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group. Is a structure substituted with any of a hydroxyl group, an alkoxy group or a halogen atom. The specific group represented by R ³ is as described above.

  In the structural formulas (III-1), (V-1), (VI-1), and (VI-2), k is an integer of 1 to 2. Here, the benzoxazine compound corresponding to the case where the value of k is 1 (hereinafter abbreviated as “dinuclear compound (α1)”) is a cured product having heat resistance, thermal decomposition resistance, flame retardancy and dielectric properties. Excellent in. Furthermore, since the benzoxazine compound corresponding to the case where the value of k is 2 (hereinafter abbreviated as “trinuclear compound (α2)”) has higher rigidity of the molecular skeleton and high aromatic ring concentration, The cured product is more excellent in heat resistance.

  The above-mentioned benzoxazine compound or benzoxazine resin specifically comprises a compound (Q) having a quinone structure in the molecular structure and a compound (P) having a phenolic hydroxyl group in the molecular structure without catalyst. Alternatively, a step of reacting under acid catalyst conditions in a temperature range of 40 to 180 ° C. to obtain a phenol compound or a phenol resin, and a step of reacting the phenol compound or phenol resin obtained in the above step with a monoamine compound and formaldehyde. The manufacturing method, wherein at least one of the compound (Q) having a quinone structure and the compound (P) having a phenolic hydroxyl group in the molecular structure is a compound having a naphthalene ring in the molecule. Manufactured by.

  Examples of the compound (Q) having a quinone structure include compounds represented by the following structural formula (Q1) or (Q2).

In formula (Q1) or (Q2), each R ¹ is independently a hydrogen atom, 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. It is.

  Specific examples of the compound represented by the structural formula (Q1) or (Q2) include parabenzoquinone, 2-methylbenzoquinone, 2,3,5-trimethyl-benzoquinone, naphthoquinone, and benzoquinone and naphthoquinone. Examples thereof include compounds having 1 to 2 or more alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, aryl groups, and aralkyl groups. These may be used alone or in combination of two or more. Above all, it is preferable to use naphthoquinone because a benzoxazine compound or the above benzoxazine resin having excellent heat resistance, thermal decomposition resistance, and flame retardancy in a cured product can be obtained.

  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), each R ² is independently 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 0 to 4, n is an integer of 0 to 3, and p and q are integers of 2 or more. When m or n is 2 or more, R ² may be the same or different. In the formula (P2), the hydroxyl group bonded to the naphthalene ring may be bonded to any aromatic ring among the aromatic rings forming the naphthalene ring.

  As the compound represented by the structural formula (P1) or (P2), specifically, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and dihydroxybenzenes and dihydroxynaphthalene of which alkyl groups having 1 to 4 carbon atoms and carbon atoms Examples thereof include compounds in which one or more alkoxy groups, aryl groups, and aralkyl groups of the formulas 1 to 4 are substituted. These may be used alone or in combination of two or more. Among them, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6 can be obtained because a benzoxazine compound having excellent heat resistance, thermal decomposition resistance, and flame retardancy in a cured product can be obtained. -Dihydroxynaphthalene or 2,7-dihydroxynaphthalene is preferable, and 2,7-dihydroxynaphthalene is particularly preferable.

  The reaction of the compound (Q) having a quinone structure with the compound (P) having a phenolic hydroxyl group proceeds under non-catalyst conditions because of its high reactivity, but it is preferable to appropriately use 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 acid and the like. When these acid catalysts are used, they are 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 a phenolic hydroxyl group in the molecular structure. Is preferred.

  Further, the above reaction is preferably carried out under a solvent-free condition, but may be carried out in an organic solvent if 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 added to 100 parts by mass 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 a ratio of 50 to 200 parts by mass.

  After completion of the reaction between the compound (Q) having a quinone structure in the molecular structure and the compound (P) having a phenolic hydroxyl group in the molecular structure, a phenol compound or a phenol resin may be obtained by drying under reduced pressure. I can.

  Examples of such a phenol compound or a phenol compound contained in the phenol resin include compounds having a structure represented by the following structural formulas (1) to (4).

In formulas (1) to (4), each R ² is independently 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 0 to 4, and n is an integer of 0 to 3. When m or n is 2 or more, R ² may be the same or different. x and y represent the bonding points with the naphthalene ring, and represent that they are bonded to adjacent carbon atoms of the naphthalene ring so as to form a furan ring with the oxygen atom. In formulas (1) to (3), R ² bonded to the naphthalene ring and the hydroxyl group bonded to the naphthalene ring to which R ² is linked are each an aromatic ring among the aromatic rings forming the naphthalene ring. May be bound to.

  In the reaction, in addition to the compounds represented by the structural formulas (1) to (4), for example, compounds represented by the following structural formulas (1 ′) to (4 ′) can be obtained. The phenol resin contains, for example, compounds represented by the following structural formulas (1 ′) to (4 ′) in addition to the phenol compounds represented by the structural formulas (1) to (4). Good.

  In formulas (1 ') to (4'), k and i are integers of 1 to 2, respectively. x and y represent a bonding point with the naphthalene ring, and represent bonding with carbons adjacent to each other so as to form a furan ring.

  In the structural formula (1 ′), (3 ′), or (4 ′), k is an integer of 1 to 2. Here, the binuclear phenol compound (β1) corresponding to the case where the value of k is 1 gives the binuclear compound (α1) by reacting with the monoamine compound and formaldehyde. On the other hand, the trinuclear phenol compound (β2) corresponding to the case where the value of k is 2 gives the trinuclear compound (α2).

  When the phenol resin contains the binuclear phenol compound (β1) or the trinuclear phenol compound (β2) represented by the above structure, the binuclear phenol compound (β1) or the trinuclear phenol compound The content of the compound (β2) in the whole resin is maintained in the subsequent reaction, and in the finally obtained benzoxazine resin, the dinuclear compound (α1) or the trinuclear compound in the whole benzoxazine resin is contained. It is almost the same as the content rate of (α2). Therefore, in order to obtain a benzoxazine resin having excellent heat resistance, thermal decomposition resistance, flame retardancy, and dielectric properties in a cured product, a binuclear phenol compound (β1) or a 33-nuclear phenol compound (β1) contained in a phenol resin ( The content rate of β2) is important.

  Then, the obtained phenol compound or the monoamine compound for reacting with the phenol resin is reacted with formaldehyde. Examples of the monoamine compound include those represented by the following structural formula (R).

In formula (R), R ³ is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or one or more hydrogen atoms contained in the aliphatic hydrocarbon group or aromatic hydrocarbon group is a hydroxyl group, an alkoxy group or a halogen atom. Or a structure substituted with any of the above. Specific groups for R ³ are as described above.

Among them, R ³ is preferably an aryl group, and more preferably a phenyl group, because of its excellent reactivity and excellent heat resistance and thermal decomposition resistance in the cured product.

  As the formaldehyde, formalin in a solution state or paraformaldehyde in a solid state can be used, but either may be used.

  The reaction of the phenol compound or the phenol resin with the monoamine compound produces the desired benzoxazine resin efficiently, so that 1 mol of the monoamine compound is added to 1 mol of the hydroxyl group in the phenol compound or the phenol resin. It is preferable to react in the range of 0.0 to 1.2 mol. In addition, since the desired benzoxazine resin is produced more efficiently, the phenol compound or the phenol resin and the formaldehyde are mixed with formaldehyde in an amount of 2 mol per 1 mol of the hydroxyl group in the phenol compound or the phenol resin. It is more preferable to react in the range of 0.0 to 2.2 mol.

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

  The reaction of the phenol compound or the phenol resin with the monoamine compound and formaldehyde may be carried out in an organic solvent, if necessary. Examples of the organic solvent used here include water, alcohol compounds such as 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 and methyl isobutyl ketone, Ketone compounds such as cyclohexanone; acetic ester 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 , Chlorobenzene and other chlorinated hydrocarbon compounds; cyclohexane, benzene, toluene, xylene and other hydrocarbon compounds; 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 kinds.

  The reaction of the phenol compound or the phenol resin with the monoamine compound and formaldehyde can be performed, for example, under a temperature condition of 50 to 150 ° C. After the reaction is completed, 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 the desired benzoxazine compound or benzoxazine resin. The benzoxazine compound can be obtained from the benzoxazine resin by, for example, purifying the mixture by a well-known crystallization or solvent washing technique, or isolating by a chromatography method.

  The benzoxazine compound of the present invention has a diarylene [b, d] furan structure, and at least one of the two arylene groups forming the diarylene [b, d] furan structure has a naphthylene skeleton, In any case, the two arylene groups are compounds obtained by reacting a phenol compound having a hydroxyl group on its aromatic ring or a phenol resin containing such a phenol compound with a monoamine compound and formaldehyde. Also, the obtained cured product is excellent in various physical properties such as heat resistance, thermal decomposition resistance, flame retardancy and dielectric properties. Hereinafter, the phenol compound used to obtain the benzoxazine compound of the present invention and the phenol resin containing the phenol compound will be described in more detail.

<Phenolic compound, phenol resin>
As the phenol compound, a phenol compound having a predetermined diarylene [b, d] furan structure as described above can be used. As such a phenol compound, specifically, the phenol compounds represented by the following structural formulas (I) and (II) can be used.

In formulas (I) and (II), each R ¹ is independently a hydrogen atom, 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. It is. Ar ¹ is a structural moiety represented by the following structural formula (i), and Ar ² is a structural moiety represented by the following structural formula (i) or (ii).

In formulas (i) and (ii), R ² is independently 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 m Is an integer of 0 to 4, and n is an integer of 0 to 3. When m or n is 2 or more, R ² may be the same or different. x and y represent the bonding points with the naphthalene ring, and represent that they are bonded to adjacent carbon atoms of the naphthalene ring so as to form a furan ring with the oxygen atom. In the formula (i), R ² and the hydroxyl group bonded to the naphthalene ring may be bonded to any aromatic ring among the aromatic rings forming the naphthalene ring.

  More specifically, the phenol compounds represented by any of the following structural formulas (1) to (4) described above can be mentioned.

In formulas (1) to (4), each R ² is independently 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 0 to 4, and n is an integer of 0 to 3. When m or n is 2 or more, R ² may be the same or different. x and y represent the bonding points with the naphthalene ring, and represent that they are bonded to adjacent carbon atoms of the naphthalene ring so as to form a furan ring with the oxygen atom. In formulas (1) to (3), R ² bonded to the naphthalene ring and the hydroxyl group bonded to the naphthalene ring to which R ² is linked are each an aromatic ring among the aromatic rings forming the naphthalene ring. May be bound to.

  Specific examples of the phenol compound represented by the structural formula (1) include phenol compounds represented by the following structural formulas (1-1) to (1-9).

  Examples of the phenol compound represented by the above (1) represented by the structural formulas (1-1) to (1-9) include parabenzoquinone as the compound (Q) having a quinone structure in the molecular structure, The compound (P) having a phenolic hydroxyl group in the molecular structure can be produced by the above-mentioned method using various dihydroxynaphthalene. At this time, the reaction ratio of parabenzoquinone and dihydroxynaphthalene is 0.1 to 10.0 mol of dihydroxynaphthalene to 1 mol of parabenzoquinone because the compound represented by the structural formula (1) can be produced with high efficiency. The ratio is preferably within the range.

  Among the phenol compounds represented by any of the structural formulas (1-1) to (1-9), by reacting with a monoamine compound and formaldehyde, the cured product has heat resistance, heat decomposition resistance, flame retardancy and The compound represented by the structural formula (1-8) or (1-9) is preferable because a benzoxazine compound excellent in various physical properties of dielectric properties can be obtained. That is, a phenol compound obtained by using 2,7-dihydroxynaphthalene as the compound (P) having a phenolic hydroxyl group in the molecular structure is preferable.

  The phenol resin may contain a phenol compound other than the phenol compound represented by the structural formula (1). Among them, a benzoxazine resin having particularly high heat resistance can be obtained by reacting with a monoamine compound and formaldehyde. Therefore, it is preferable to contain a polyfunctional compound represented by the following structural formula (1 ′).

  In formula (1 '), k is an integer of 1-2. The hydroxyl group bonded to the naphthalene ring may be bonded to any of the aromatic rings forming the naphthalene ring.

  In this case, the content ratio of each component in the phenol resin is such that the content ratio of the dinaphtho [b, d] furan compound represented by the structural formula (1) is 5 to 60% in terms of area ratio in GPC measurement. Further, the content of the polyfunctional compound represented by the structural formula (1 ′) is preferably in the range of 10 to 70% in terms of area ratio in GPC measurement.

In addition, in this invention, the content rate of each component in a phenol resin is the ratio of the peak area of each said component with respect to the total peak area of a phenol resin calculated from the GPC measurement data on condition of the following.
<GPC measurement conditions>
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Tosoh Co., Ltd. guard column "HXL-L"
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
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 according to the measurement manual of "GPC-8020 Model II Version 4.10".
(Polystyrene used)
Tosoh Corporation "A-500"
Tosoh Corporation "A-1000"
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
Tosoh Corporation "F-10"
Tosoh Corporation "F-20"
Tosoh Corporation "F-40"
Tosoh Corporation “F-80”
Tosoh Corporation "F-128"
Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solid content filtered through a microfilter (50 μl).

  Specific examples of the phenol compound represented by the structural formula (2) include phenol compounds represented by any of the following structural formulas (2-1) to (2-9).

  The phenol compound represented by the structural formula (2) represented by the structural formulas (2-1) to (2-9) is, for example, 2,2 as the compound (Q) having a quinone structure in the molecular structure. 3,5-Trimethyl-parabenzoquinone can be produced by the above-mentioned method using various dihydroxynaphthalene as the compound (P) having a phenolic hydroxyl group in the molecular structure. At this time, the reaction ratio of 2,3,5-trimethyl-parabenzoquinone and dihydroxynaphthalene is 2,3,5-trimethyl-parabenzoquinone 1 since the compound represented by the structural formula (2) can be produced with high efficiency. It is preferable that the ratio of dihydroxynaphthalene is in the range of 0.1 to 10.0 mol per mol.

  Among the phenol compounds represented by any of the structural formulas (2-1) to (2-9), by reacting with a monoamine compound and formaldehyde, the cured product has heat resistance, heat decomposition resistance, flame retardancy and The compound represented by the structural formula (2-8) or (2-9) is preferable because a benzoxazine compound excellent in various physical properties of dielectric properties can be obtained. That is, a phenol compound obtained by using 2,7-dihydroxynaphthalene as the compound (P) having a phenolic hydroxyl group in the molecular structure is preferable.

  The phenol resin may contain a phenol compound other than the phenol compound represented by the structural formula (2). Among them, a benzoxazine resin having particularly high heat resistance can be obtained by reacting with a monoamine compound and formaldehyde. Therefore, it is preferable to contain a polyfunctional compound represented by the following structural formula (2 ′).

  In formula (2 '), the hydroxyl group bonded to the naphthalene ring may be bonded to any aromatic ring among the aromatic rings forming the naphthalene ring.

  In this case, the content ratio of each component in the phenol resin is such that the content ratio of the dinaphtho [b, d] furan compound represented by the structural formula (2) is in the range of 50 to 95% in terms of area ratio in GPC measurement. Further, the content of the polyfunctional compound represented by the structural formula (2 ′) is preferably in the range of 1 to 50% in terms of area ratio in GPC measurement.

  Specific examples of the phenol compound represented by the structural formula (3) include phenol compounds represented by any of the following structural formulas (3-1) to (3-9).

  The phenol compound represented by the structural formula (3) represented by the structural formulas (3-1) to (3-9) is, for example, 1, 1 as a compound (Q) having a quinone structure in the molecular structure. 4-naphthoquinone can be produced by the above-mentioned method using various dihydroxynaphthalene as the compound (P) having a phenolic hydroxyl group in the molecular structure. At this time, the reaction ratio between 1,4-naphthoquinone and dihydroxynaphthalene is such that since the compound represented by the structural formula (1) can be produced with high efficiency, dihydroxynaphthalene is 0.1 with respect to 1 mol of 1,4-naphthoquinone. The ratio is preferably in the range of up to 10.0 mol.

  Among the phenol compounds represented by any of the structural formulas (3-1) to (3-9), by reacting with a monoamine compound and formaldehyde, heat resistance, heat decomposition resistance, flame retardancy and The compound represented by the structural formula (3-8) or (3-9) is preferable because a benzoxazine compound excellent in various physical properties of dielectric properties can be obtained. That is, a phenol compound obtained by using 2,7-dihydroxynaphthalene as the compound (P) having a phenolic hydroxyl group in the molecular structure is preferable.

  The phenol resin may contain a phenol compound other than the phenol compound represented by the structural formula (3). When the phenol resin contains another phenol compound other than the compound represented by the structural formula (3), the content of the dinaphtho [b, d] furan compound represented by the structural formula (3) in the phenol resin. Is preferably in the range of 5 to 70% in terms of area ratio in GPC measurement.

  Specific examples of other phenol compounds are represented by the following structural formula (3 ′) or (3 ″), because a benzoxazine resin having particularly high heat resistance can be obtained by reacting with a monoamine compound and formaldehyde. Polyfunctional compounds are preferred.

  In the formulas (3 ′) to (3 ″), k is an integer of 1 to 2. x and y in the formula (3 ″) represent a bonding point with the naphthalene ring and form a furan ring. Bond to adjacent carbons. In the formula (3 ′), the hydroxyl group on the naphthalene ring linked to 1,4-dihydroxynaphthalene may be bonded to any aromatic ring among the aromatic rings forming the naphthalene ring. In the formula (3 ″), the hydroxyl group on the dihydroxynaphthalene may be bonded to any aromatic ring among the aromatic rings forming the dihydroxynaphthalene. Further, the hydroxyl group on the naphthalene ring linked to the dihydroxynaphthalene may be bonded to any aromatic ring among the aromatic rings forming the naphthalene ring.

  When the phenol resin contains the polyfunctional compound represented by the structural formula (3 ′), the content ratio thereof is preferably in the range of 2 to 60% in terms of area ratio in GPC measurement. When the phenol resin contains the polyfunctional compound represented by the structural formula (3 ″), the content ratio is preferably in the range of 2 to 40% in terms of area ratio in GPC measurement.

  Specific examples of the phenol compound represented by the structural formula (4) include phenol compounds represented by any of the following structural formulas (4-1) to (4-4).

  The phenol compound represented by the structural formula (4) represented by the structural formulas (4-1) to (4-4) is, for example, 1, 1 as a compound (Q) having a quinone structure in the molecular structure. 4-naphthoquinone can be produced by the above-mentioned method using various dihydroxybenzenes as the compound (P) having a phenolic hydroxyl group in the molecular structure. At this time, the reaction ratio of 1,4-naphthoquinone and dihydroxybenzene is 0.1% of dihydroxybenzene per mol of 1,4-naphthoquinone because the compound represented by the structural formula (1) can be produced with high efficiency. The ratio is preferably in the range of up to 10.0 mol.

  Among the phenol compounds represented by any of the structural formulas (4-1) to (4-4), by reacting with a monoamine compound and formaldehyde, the cured product has heat resistance, heat decomposition resistance, flame retardancy and The compound represented by the structural formula (4-2) or (4-3) is preferable because a benzoxazine compound excellent in various physical properties of dielectric properties can be obtained. That is, a phenol compound obtained by using 1,3-dihydroxybenzene as the compound (P) having a phenolic hydroxyl group in the molecular structure is preferable.

  The phenol resin may contain a phenol compound other than the phenol compound represented by the structural formula (4). Among them, a benzoxazine resin having particularly high heat resistance can be obtained by reacting with a monoamine compound and formaldehyde, and thus it is preferable to contain a polyfunctional compound represented by the following structural formula (4 ′).

  In formula (4 '), k and i are each an integer of 1-2.

  In this case, the content ratio of each component in the phenol resin is such that the content ratio of the dinaphtho [b, d] furan compound represented by the structural formula (4) is in the range of 5 to 70% in terms of area ratio in GPC measurement. Further, the content of the polyfunctional compound represented by the structural formula (4 ′) is preferably in the range of 1 to 60% in terms of area ratio in GPC measurement.

  Among these exemplified phenolic compounds, by reacting with a monoamine compound and formaldehyde, a benzoxazine compound having an excellent balance of heat resistance, thermal decomposition resistance and flame retardancy in a cured product can be obtained. ) To (3) are preferred, and the phenol compound represented by the structural formula (3) is particularly preferred.

  Next, the curable resin composition of the present invention will be described. The curable resin composition of the present invention contains the benzoxazine compound or benzoxazine resin of the present invention described in detail above as an essential component. Since the benzoxazine compound or the benzoxazine resin can be cured by itself, in the curable resin composition of the present invention, the resin component may be composed of only the benzoxazine compound or the benzoxazine resin. , And other resins may be used together.

  Examples of other resins include epoxy resins, phenolic hydroxyl group-containing resins, active ester resins, cyanate ester resins, vinylbenzyl 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, tetramethylbiphenyl 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 novolac type epoxy resin, naphthol aralkyl type epoxy resin Resin, naphthol-phenol cocondensed novolac type epoxy resin, naphthol-cresol cocondensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, biphenyl modified novolac type epoxy resin, anthracene type epoxy resin and the like. . These may be used alone or in combination of two or more.

  Among these epoxy resins, tetramethylbiphenol-type epoxy resin, biphenylaralkyl-type epoxy resin, naphthylene ether-type epoxy resin, polyhydroxynaphthalene-type epoxy resin, and novolac are particularly preferable in that a cured product having excellent flame retardancy can be obtained. A type epoxy resin is preferably used, 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 of the total number of moles (a) of the oxazine structure and the phenolic hydroxyl group in the benzoxazine resin to the number of moles of the epoxy group (b) in the epoxy resin. [(A) / (b)] is a ratio of 1.0 / 0.1 to 1.0 / 1.0, more preferably 1.0 / 0.1 to 1.0 / 0.5 It is preferable that the cured product has excellent heat resistance and thermal decomposition resistance.

  The phenolic hydroxyl group-containing compound, for example, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, naphthylene ether resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, tri Methylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-convoluted novolac resin, biphenyl modified phenol resin (polyphenol compound in which phenol nuclei are linked by bismethylene groups), 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 preferable because they have excellent dielectric properties and moisture absorption resistance. Specifically, phenol novolac resin, cresol novolac resin, aromatic carbon Hydrogen formaldehyde resin modified phenol resin, naphthylene ether resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-convoluted novolac 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 novolac type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolac type cyanate ester resin, naphthol-cresol co-condensed novolac type cyanate Examples thereof include ester resins, aromatic hydrocarbon formaldehyde resin-modified phenol resin type cyanate ester resins, biphenyl modified novolac type cyanate ester resins and anthracene type cyanate ester resins. These may be used alone or in combination of two or more.

  Among these cyanate ester resins, a bisphenol A type cyanate ester resin, a bisphenol F type cyanate ester resin, a bisphenol E type cyanate ester resin, a polyhydroxynaphthalene type cyanate ester resin is particularly preferable in that a cured product having excellent heat resistance can be obtained. , A naphthylene ether type cyanate ester resin and a novolac type cyanate ester resin are preferably used, and a 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 formula (Z1), 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 (Z2), 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, m is an average of repeating units of 0 to It is 10.

  In formula (Z3), 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, m is an average of repeating units of 0 to It is 10.

  The active ester resin is not particularly limited, but generally, an ester group having high reaction activity such as phenol ester, thiophenol ester, N-hydroxyamine ester, and ester of heterocyclic hydroxy compound is contained in one 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. Particularly, 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 preferable, 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 More preferable. 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 halides 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, and 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 type resin and the like.

  As the active ester resin, specifically, an active ester resin containing a dicyclopentadiene-phenol addition structure, an active ester resin containing a naphthalene structure, an active ester resin which is an acetylation product of phenol novolac, and a benzoylation product of phenol novolak. Ester resins and the like are preferable, and among them, active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferable because they are excellent in improving the peel strength. Specific examples of the active ester resin containing a dicyclopentadiene-phenol addition structure include compounds represented by the following structural formula (iv).

  In formula (d), R is a phenyl group or a naphthyl group, u represents 0 or 1, and n is 0.05 to 2.5 in average of repeating units. From the viewpoint of decreasing the dielectric loss tangent of the cured product of the 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 without a catalyst, but a catalyst can be used together. These catalysts include tertiary amine compounds such as imidazole and dimethylaminopyridine; phosphorus compounds such as triphenylphosphine; boron trifluoride, boron trifluoride amine complex such as boron trifluoride monoethylamine complex; thiodipropionic acid. Examples thereof include organic acid compounds such as; benzoxazine compounds such as thiodiphenolbenzoxazine and sulfonylbenzoxazine; sulfonyl compounds; compounds containing a phenolic hydroxyl group. 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, aromatic compound. Hydrocarbon formaldehyde resin-modified phenol resin, naphthylene ether resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-shrink novolak Resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenolic resin (with a bismethylene group Polyphenol compounds with linked nuclei), biphenyl-modified naphthol resins (polynaphthol compounds with linked phenol nuclei with bismethylene groups), aminotriazine-modified phenolic resins (phenolic compounds linked with melamine, benzoguanamine, etc.) (Phenolic compounds) and the like. These may be used alone or in combination of two or more. The addition amount of these catalysts is preferably in the range of 0.001 to 15 parts by mass in 100 parts by mass of the curable resin composition.

  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 atom may be added.

  The non-halogen flame retardant includes, for example, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc., and there is no limitation in using them. However, the flame retardants of the same type may be used alone, or the flame retardants of different types may be used in combination.

  The phosphorus-based flame retardant may be either inorganic or organic. Examples of the inorganic compound include red phosphorus, ammonium monophosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like, and examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide and 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 or titanium hydroxide, and Method of coating with a mixture of thermosetting resin such as phenol resin, (iii) Thermosetting of phenol resin or the like on a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide or titanium hydroxide Examples include a method of double coating with a resin.

  Examples of the organophosphorus compounds include general-purpose organophosphorus compounds such as phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds, as well as 9,10-dihydro. -9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7- Examples thereof include cyclic organic phosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and derivatives obtained by reacting the same with a compound such as a phenol resin or a phenol resin.

  The compounding amount of these phosphorus-based flame retardants is preferably, for example, in the range of 0.1 to 2.0 parts by mass when red phosphorus is used in 100 parts by mass of the curable resin composition. When it is used, it is preferably blended in the range of 0.1 to 10.0 parts by mass, more preferably 0.5 to 6.0 parts by mass.

  When the phosphorus-based flame retardant is used, hydrotalcite, magnesium hydroxide, boride compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. may be used in combination with the phosphorus-based flame retardant. Good.

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

  The triazine compound is, for example, melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, guanylmelamine sulfate, melem sulfate, melam sulfate, and other sulfates. Examples thereof include an aminotriazine compound, the aminotriazine-modified phenol resin, and the aminotriazine-modified phenol resin further modified with tung oil, isomerized linseed oil and the like.

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

  The blending amount of the nitrogen-based flame retardant is preferably, for example, 0.05 to 10 parts by mass, and 0.1 to 5 parts by mass in 100 parts by mass of the curable resin composition. Is more preferable.

  When using the nitrogen-based flame retardant, a metal hydroxide, a molybdenum compound or the like may be used together.

  The silicone-based flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone-based flame retardant compounded is preferably, for example, 0.05 to 20 parts by mass in 100 parts by mass of the curable resin composition. When using the silicone-based flame retardant, a molybdenum compound, alumina or the like may be used together.

  Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, low melting point glass, and the like.

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

  The metal oxide is, for example, 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, tungsten oxide and the like.

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

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

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

Examples of the low melting point glass include Sipley (Bokusui Brown Co., Ltd.), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O. ₅ -B ₂ O ₃ -PbO-MgO-based, _{P-Sn-O-F-based, PbO-V 2 O 5 -TeO} 2 _system, Al ₂ O 3 -H ₂ O system, lead borosilicate-based glass or the like shaped A compound can be mentioned.

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

  The organic metal salt flame retardant is, for example, 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 ionic bond or coordination Examples include compounds having a position bond.

  The amount of the organic metal salt-based flame retardant compounded is preferably, for example, 0.005 to 10 parts by mass in 100 parts by mass of the curable resin composition.

  The curable resin composition of the present invention may contain an inorganic filler if necessary. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like. Fused silica is preferably used when the amount of the inorganic filler compounded is particularly large. The fused silica may be used in either a crushed form or a spherical form, but 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 the spherical form. In order to further increase the compounding 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 considering flame retardancy, and particularly preferably 20% by mass or more based on the total mass of the curable resin composition. In addition, when used for applications such as conductive paste, a conductive filler such as silver powder or copper powder can be used.

  The curable resin composition of the present invention may further contain, if necessary, reinforcing fibers, for example, glass, quartz, carbon, oriented fibers and synthetic fibers in the usual form of short fibers, staple fibers, twine, cloth or mat. (Keflar, Nomex), natural fibers such as flax, jute, sisal, hemp: silane coupling agent: release agent: pigment: dye: emulsifier and the like may be added.

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

  The curable resin composition of the present invention is a known process for thermosetting resins such as phenol formaldehyde resin or epoxy resin, for example, hot pressing of prepreg, 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 a hard printed wiring board material, which is excellent in heat resistance, thermal decomposition resistance, flame retardancy and dielectric properties in a cured product, Resin compositions for flexible wiring boards, circuit board insulation materials such as interlayer insulation materials for build-up boards, semiconductor encapsulation materials, conductive pastes, build-up adhesive films, resin casting materials, adhesives, FRP materials, etc. It can be suitably used as various materials.

  When applied to a semiconductor encapsulating material, a compounding agent such as an inorganic filler is added to the curable resin composition as needed using an extruder, a kneader, a roll, etc. until the mixture is uniform. The semiconductor encapsulation material can be manufactured by melt mixing. At that time, fused silica is usually used as the inorganic filler, but when it is used as a high thermal conductive semiconductor encapsulating material for power transistors and power ICs, crystalline silica, alumina, nitride having higher thermal conductivity than fused silica is used. It is preferable to use highly filled silicon, fused silica, crystalline silica, alumina, silicon nitride, or the like. 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, flame retardancy, moisture resistance, solder crack resistance, and linear expansion. In order to reduce the coefficient, it is more preferably 70 to 95 parts by mass, further preferably 80 to 95 parts by mass.

  When applied to a circuit board application, the curable resin composition of the present invention is added to an organic solvent to form a plate-shaped varnish, which is laminated with a copper foil, and heat-pressed to form a circuit board. Can be manufactured. When applied to hard printed wiring board applications, a reinforcing base material is impregnated with a varnish obtained by adding an organic solvent to a curable resin composition, and semi-cured to obtain a prepreg, which is overlaid with a copper foil. It can be manufactured by a method of thermocompression bonding.

  As the organic solvent used when the curable resin composition of the present invention is varnished, for example, a polar solvent having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol can be preferably used, and cured. It is preferable to use the resin composition in such a proportion that the nonvolatile content thereof is 40 to 80% by mass. Examples of the reinforcing base material used for printed wiring board applications include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. If this method is described in further detail, first, the varnish-like curable resin composition is heated at a heating temperature according to the solvent type used, preferably at 50 to 170 ° C. to obtain a prepreg that is a cured product. obtain. At this time, the mass ratio of the curable resin composition to be used and the reinforcing base material is not particularly limited, but it is usually preferable to prepare the resin content in the prepreg to be 20 to 60 mass%. Then, the prepregs obtained as described above are laminated by a conventional method, copper foils are appropriately laminated, and the resulting prepregs are thermocompression bonded at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa, The desired circuit board can be obtained.

To produce a flexible wiring board from the curable resin composition of the present invention, the curable resin composition containing an organic solvent is applied to the electrically insulating film using a coating machine such as a reverse roll coater or a comma coater. Then, using a heater, it is heated at 60 to 170 ° C. for 1 to 15 minutes to volatilize the solvent and B-stage the curable resin composition. Then, the metal foil is thermocompression bonded to the resin layer using a heating roll or the like. At that time, the pressure bonding pressure is preferably ^{2 to} 200 N / cm ² , and the pressure bonding temperature is preferably 40 to 200 ° C. If sufficient adhesion performance can be obtained with this, it may be finished here, but when complete curing is required, it is preferable to further post-cure under conditions of 100 to 200 ° C. for 1 to 24 hours. The thickness of the resin layer after the final 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 in which rubber, a filler and the like are appropriately mixed, is spray-coated on a substrate such as a wiring substrate on which a circuit is formed, a spray coating method, After coating using a curtain coating method or the like, it is cured. After that, a predetermined through-hole portion or the like is bored as needed, and then treated with a roughening agent, and the surface thereof is washed with hot water to form irregularities, and a metal such as copper is plated. The plating method is preferably electroless plating or electrolytic plating, and examples of the roughening agent include oxidizing agents, alkalis and organic solvents. A build-up substrate can be obtained by sequentially repeating such operations as desired and alternately building up the resin insulating layer and the conductor layer of a predetermined circuit pattern to form. However, the through holes are drilled after the outermost resin insulating layer is formed. Further, a resin-coated copper foil obtained by semi-curing a curable resin composition on a copper foil is heat-pressed at 170 to 250 ° C. onto a circuit board-formed wiring substrate to form a roughened surface and plating treatment. It is also possible to manufacture the build-up substrate by omitting the step.

  The method for producing a build-up adhesive film from the curable resin composition of the present invention, for example, a curable resin composition of the present invention is diluted by adding an organic solvent is applied on a support film, to form a resin layer. A method of forming the adhesive film for a multilayer printed wiring board may be mentioned.

  The organic solvent used in this case, for example, ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, acetic acid ester solvent such as carbitol acetate, ethanol, propanol, butanol, etc. Alcohol solvent, cellosolve, carbitol solvent such as butyl carbitol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and should be used in a proportion of 30 to 60% by mass of the nonvolatile content of the curable resin composition. Is preferred.

  The adhesive film made of the curable resin composition of the present invention is softened under the temperature conditions (usually 70 ° C. to 140 ° C.) of the lamination in the vacuum laminating method, and at the same time as the lamination of the circuit board, the via hole or the through hole existing in the circuit board. It is essential to show fluidity (resin flow) capable of filling the resin inside, and it is preferable to mix the above-mentioned components so as to express 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 thereof is usually 0.1 to 1.2 mm, and it is usually preferable that the resin can be filled in this range. When laminating both sides of the circuit board, it is desirable to fill about 1/2 of the through hole.

  The method for producing the above-mentioned adhesive film, specifically, after preparing the varnish-shaped curable resin composition of the present invention, the surface of the support film, the varnish-shaped curable resin composition is applied, Further, it can be produced by drying the organic solvent by heating, blowing hot air or the like to form the layer (γ) of the curable resin composition.

  The thickness of the formed layer (γ) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of 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.

  The layer (γ) may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin layer and scratches.

  The support film and the protective film described above include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter may be abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and further separated. Examples include pattern paper, copper foil, metal foil such as aluminum foil, and the like. The support film and the protective film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment.

  The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and preferably 25 to 50 μm. Further, the thickness of the protective film is preferably 1 to 40 μm.

  The support film described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heating and curing. If the support film is peeled off after the adhesive film is heat-cured, adhesion of dust or the like can be prevented in the curing step. When 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 by a protective film, after peeling them off, the layer ( One surface or both surfaces of the circuit board is laminated by, for example, a vacuum laminating method so that γ) directly contacts the circuit board. The laminating method may be a batch method or a continuous method using rolls. If necessary, the adhesive film and the circuit board may be heated (preheated) before laminating.

The lamination conditions are such that the pressure bonding temperature (lamination temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure is preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m 2). It is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or less.

  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 obtain a composition for anisotropic conductive film, which is liquid at room temperature. Examples thereof include a method of using a certain paste resin composition for circuit connection and 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 in the curable resin composition, and a cationic polymerization catalyst as a curing agent are blended, and a pigment, talc, and a filler are added to form a resist ink composition. After that, a method of forming a resist ink cured product after coating on a printed board by a screen printing method can be mentioned. Since the polyarylene ether resin alone can cause a curing reaction, the polyarylene ether resin may be used alone as the resin component in the curable resin composition of the present invention, 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. The GPC, IR, and MS were measured under the following conditions.

GPC: The measurement conditions are as follows.
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation,
Column: Tosoh Co., Ltd. guard column "HXL-L"
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
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 according to the measurement manual of "GPC-8020 Model II Version 4.10".
(Polystyrene used)
Tosoh Corporation "A-500"
Tosoh Corporation "A-1000"
Tosoh Corporation "A-2500"
Tosoh Corporation "A-5000"
Tosoh Corporation "F-1"
Tosoh Corporation "F-2"
Tosoh Corporation "F-4"
Tosoh Corporation "F-10"
Tosoh Corporation "F-20"
Tosoh Corporation "F-40"
Tosoh Corporation “F-80”
Tosoh Corporation "F-128"
Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solid content filtered through a microfilter (50 μl).

<IR measuring device>
The following apparatus was used as the IR measuring apparatus.
Equipment: "FT / IR-550" manufactured by JASCO Corporation

<MS measuring device>
The following measuring devices were used for the MS measuring device.
Device: JEOL Ltd. double focusing mass spectrometer AX505H (FD505H)

Example 1 Production of benzoxazine resin (A-1) In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer, 160 g (1.0 mol) of 2,7-dihydroxynaphthalene, 1, 158 g (1.0 mol) of 4-naphthoquinone, 6 g of paratoluenesulfonic acid and 318 g of methyl isobutyl ketone were charged, and the temperature was raised from room temperature to 120 ° C. with stirring. After reaching 120 ° C., the mixture was stirred for 3 hours to be reacted. After completion of the reaction, the mixture was neutralized and washed with 200 g of water three times. Then, it was heated to 150 ° C. and dried under reduced pressure to obtain 300 g of phenol resin (A). The GPC chart of the obtained phenol resin (A) is shown in FIG. The hydroxyl group equivalent of the phenol resin (A) was 137 g / eq. Further, the content of the component corresponding to the dinaphthofuran compound represented by the following structural formula (a) calculated from the GPC chart is 55.3%, and the value of k represented by the following structural formula (b) is 1. 2 The content of the component corresponding to the compound corresponding to the nucleophilic phenol compound was 9.7%, and the content of the component corresponding to the trinuclear phenol compound represented by the following structural formula (c) was 22.0%. It was

［ｘ、ｙはナフタレン環との結合点を示し、フラン環を形成するように互いに隣接する炭素に結合することを表す。］

[X and y represent bonding points with the naphthalene ring, and represent bonding with carbons adjacent to each other so as to form a furan ring. ]

Then, while flowing nitrogen gas into a four-necked flask equipped with a dropping funnel, a thermometer, a stirrer, a heating device, and a cooling reflux tube, 93.1 g (1.0 mol) of aniline and 137.0 g of phenol resin (A). (Hydroxyl group 1.0 equivalent) was charged, dissolved in 400 g of toluene, 143 g (2.0 mol) of 42% formaldehyde aqueous solution was added, the temperature was raised to 80 ° C. with stirring, and the mixture was reacted at 80 ° C. for 5 hours. It was After the reaction, the mixture was transferred to a separating funnel and the aqueous layer was removed. Then, the solvent was removed from the organic layer under heating and reduced pressure to obtain 167 g of a benzoxazine resin. The IR spectrum showed absorption at 948 cm ⁻¹ derived from the oxazine ring, and the mass spectrum showed a peak such as 535, which confirmed that the desired benzoxazine resin (A-1) was obtained.

Example 2 Production of benzoxazine resin (B-1) In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 160 g (1.0 mol) of 2,7-dihydroxynaphthalene, 1, 158 g (1.0 mol) of 4-naphthoquinone, 6 g of paratoluenesulfonic acid and 333 g of isopropyl alcohol were charged, and the temperature was raised from room temperature to 80 ° C. with stirring. After reaching 80 ° C., the mixture was stirred and reacted for 3 hours. After completion of the reaction, the mixture was neutralized and washed with 200 g of water three times. Then, it was heated to 150 ° C. and dried under reduced pressure to obtain 295 g of phenol resin (B). The GPC chart of the obtained phenol resin (B) is shown in FIG. The hydroxyl equivalent of the phenol resin was 119 g / eq. Further, the content of the component corresponding to the dinaphthofuran compound represented by the structural formula (a) calculated from the GPC chart is 50.2%, and the value of k represented by the structural formula (b) is 1. 2 The content of the component corresponding to the compound corresponding to the nucleophilic phenol compound was 14.8%, and the content of the component corresponding to the trinuclear phenol compound represented by the structural formula (c) was 24.2%. It was

Then, while flowing nitrogen gas into a four-necked flask equipped with a dropping funnel, a thermometer, a stirrer, a heating device, and a cooling reflux tube, 93.1 g (1.0 mol) of aniline and 119 g of phenol resin (B) (hydroxyl group) (1.0 equivalent) was charged and dissolved in 400 g of toluene, then 143 g (2.0 mol) of 42% formaldehyde aqueous solution was added, the temperature was raised to 80 ° C. with stirring, and the mixture was reacted at 80 ° C. for 5 hours. After the reaction, the mixture was transferred to a separating funnel and the aqueous layer was removed. Then, the solvent was removed from the organic layer under heating and reduced pressure to obtain 152 g of a benzoxazine resin. The IR spectrum showed absorption at 948 cm ⁻¹ derived from the oxazine ring, and the mass spectrum showed a peak such as 535, which confirmed that the desired benzoxazine resin (B-1) was obtained.

Example 3 Production of benzoxazine resin (C-1) 160 g (1.0 mol) of 1,5-dihydroxynaphthalene, 1, 1, in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer. 158 g (1.0 mol) of 4-naphthoquinone, 6 g of paratoluenesulfonic acid and 333 g of isopropyl alcohol were charged, and the temperature was raised from room temperature to 80 ° C. with stirring. After reaching 80 ° C., the mixture was stirred and reacted for 3 hours. After completion of the reaction, the mixture was neutralized and washed with 200 g of water three times. Then, it was heated to 150 ° C. and dried under reduced pressure to obtain 292 g of phenol resin (C). The GPC chart of the obtained phenol resin (C) is shown in FIG. The hydroxyl equivalent of the phenol resin was 132 g / eq. The content of the component corresponding to the dinaphthofuran compound represented by the structural formula (a) calculated from the GPC chart was 24.1%.

Then, while flowing nitrogen gas into a four-necked flask equipped with a dropping funnel, a thermometer, a stirrer, a heater, and a cooling reflux tube, 93.1 g (1.0 mol) of aniline and 132 g of phenolic resin (C) (hydroxyl group). (1.0 equivalent) was charged and dissolved in 400 g of toluene, then 143 g (2.0 mol) of 42% formaldehyde aqueous solution was added, the temperature was raised to 80 ° C. with stirring, and the mixture was reacted at 80 ° C. for 5 hours. After the reaction, the mixture was transferred to a separating funnel and the aqueous layer was removed. After that, the solvent was removed from the organic layer under heating and reduced pressure to obtain 177 g of benzoxazine resin. The IR spectrum showed absorption at 948 cm ⁻¹ derived from the oxazine ring, and the mass spectrum showed a peak such as 535, which confirmed that the desired benzoxazine resin (C-1) was obtained.

Examples 4 to 6 Production of compositions and cured products The benzoxazine resins (A-1), (B-1) and (C-1) obtained in Examples 1 to 3 and phenol novolac resin (DIC Corporation). "TD-2131") and fused silica ("FB3SDC" manufactured by Denki Kagaku Co., Ltd.) were mixed as shown in Table 1, molded by a press at a temperature of 200 ° C for 10 minutes, and then at a temperature of 200 ° C. After curing for 5 hours, a cured product having a thickness of 0.8 mm was obtained.

Comparative Example 1 Composition and Cured Product Production 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 Denki Kagaku Co., Ltd.) are mixed as shown in Table 1 and molded by a press at a temperature of 200 ° C for 10 minutes, and then at a temperature of 200 ° C for 5 minutes. After the time, it was cured to obtain a cured product having a thickness of 0.8 mm.

  The glass transition point, thermal decomposition resistance, dielectric constant, dielectric loss tangent, and flame retardancy of the cured products obtained in Examples 4 to 6 and Comparative Example 1 were measured. The results are shown in Table 1, and the measuring method is shown below.

<Measurement of glass transition point>
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, and the obtained cured product was used as a test piece 1. Using this viscoelasticity measuring device (DMA: solid viscoelasticity measuring device “RSAII” manufactured by Rheometric Co., rectangular tension method: frequency 1HZ, temperature rising rate 3 ° C./min), the change in elastic modulus was maximized. The temperature at which the maximum change rate (tan δ change) occurs was measured as the glass transition point.

<Measurement 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, an impedance material analyzer "HP4291B" manufactured by Agilent Technologies Co., Ltd. was used to test specimen 1 at 1 GHz after being stored in a room at 23 ° C and 50% humidity for 24 hours after being absolutely dried. Dielectric constant and tangent were measured.
<Measurement of flame retardancy>
From the cured product obtained above, a cured product having a thickness of 0.8 mm was cut out into a size of 12.7 mm in width and 127 mm in length, and this was used as a test piece 2. About this test piece 2, the combustion test was measured according to the UL-94 test method. The combustion test was performed using five test pieces 2 each.

Claims (13)

A diarylene [b, d] furan structure, at least one of the two arylene groups forming the diarylene [b, d] furan structure has a naphthylene skeleton, and the two arylene groups are Both are phenol compounds having a hydroxyl group on the aromatic ring,
In the aromatic ring having hydroxyl groups of both of the two arylene groups, at least one of carbon atoms of the same aromatic ring, which are located adjacent to each other when viewed from the aromatic ring carbon atom to which the hydroxyl groups in the same aromatic ring are bonded, is hydrogen. A phenolic compound bound to an atom,
The following structural formula (R)

[In the formula (R), R ³ is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or one or more hydrogen atoms contained in the aliphatic hydrocarbon group or the aromatic hydrocarbon group is a hydroxyl group, an alkoxy group, or a halogen. Any of the structures substituted with any of the atoms]
A benzoxazine compound obtained by reacting a monoamine compound represented by and formaldehyde.   Carbon to which at least one of the two arylene groups forming the diarylene [b, d] furan structure of the phenol compound is bonded to an oxygen atom forming a furan ring of the diarylene [b, d] furan structure. The benzoxazine compound according to claim 1, which has a hydroxyl group at the para-position on the same benzene ring of the atoms. The phenol compound has a molecular structure represented by the following structural formula (I) or the following structural formula (II) (provided that an aromatic ring having hydroxyl groups of both two arylene groups in the structural formulas (I) and (II)). In the above, at least one of the carbon atoms of the same aromatic ring, which is located adjacent to the carbon atom of the aromatic ring to which the hydroxyl group in the same aromatic ring is bonded, is bonded to a hydrogen atom). Benzoxazine compounds.

[In the formulas (I) and (II), each R ¹ independently represents a hydrogen atom, 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. It is either. Ar ¹ is a structural moiety represented by the following structural formula (i), and Ar ² is a structural moiety represented by the following structural formula (i) or (ii). ]

[In the formulas (i) and (ii), each R ² is independently 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 0 to 4, and n is an integer of 0 to 2 . When m or n is 2 or more, R ² may be the same or different. x and y represent the bonding points with the naphthalene ring, and represent that they are bonded to adjacent carbon atoms of the naphthalene ring so as to form a furan ring with the oxygen atom. In the formula (i), R ² and the hydroxyl group bonded to the naphthalene ring may be bonded to any aromatic ring among the aromatic rings forming the naphthalene ring. ] The benzoxazine compound according to claim 3, wherein the phenol compound has a molecular structure represented by any one of the following structural formulas (1), (3), and (4).

[In the formulas (1), (3), and (4), R ^2's each independently represent 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. Any of them, m is an integer of 0 to 4, and n is an integer of 0 to 2 . When m or n is 2 or more, R ² may be the same or different. x and y represent the bonding points with the naphthalene ring, and represent that they are bonded to adjacent carbon atoms of the naphthalene ring so as to form a furan ring with the oxygen atom. In the formulas (1) and (3), R ² bonded to the naphthalene ring and the hydroxyl group bonded to the naphthalene ring to which R ² is linked are each selected from among aromatic rings constituting the naphthalene ring. It may be bonded to an aromatic ring. ]   A benzoxazine resin containing the benzoxazine compound according to claim 1. A curable resin composition comprising the benzoxazine compound according to any one of claims 1 to 4 or the benzoxazine resin according to claim 5 as an essential component.   A cured product obtained by curing the curable resin composition according to claim 6.   An FRP material comprising the curable resin composition according to claim 6.   A semiconductor encapsulation containing the curable resin composition according to claim 6 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 6.   A circuit board obtained by stacking the varnish according to claim 10 formed into a plate shape on a copper foil, and heat-pressing.   A prepreg obtained by impregnating a reinforcing base material with the varnish according to claim 10 and then semi-curing the varnish.   A buildup film obtained by applying the curable resin composition according to claim 6 on a substrate and then curing the composition.

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