JP2016041799A - Curable composition, cured product, semiconductor sealing material, semiconductor device, prepreg, print circuit board, flexible wiring board, build-up film, build-up substrate, fiber-reinforced composite material, and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that has high adhesion and can yield a cured product with excellent properties of heat resistance, dielectric properties, and low expansion rate, and provide the cured product, a semiconductor sealing material, a semiconductor device, a prepreg, a print circuit board, a flexible wiring board, a build-up film, a build-up substrate, a fiber-reinforced composite material, and a molding.SOLUTION: A curable composition comprises one or more condensed polycyclic aromatic cyanate ester compound (A) selected from compounds represented by formula (A1) and structural formula (A2), and a monocyclic aromatic cyanate ester compound (B) wherein a plurality of monocyclic compounds having cyanato groups on aromatic nuclei are bonded together directly or through linking groups.SELECTED DRAWING: None

Description

  The present invention relates to a curable composition capable of exhibiting excellent heat resistance, dielectric properties, low thermal expansion property, and adhesion in a cured product, a cured product having the above functions, a semiconductor sealing material, a semiconductor device, and a prepreg. The present invention relates to a printed circuit board, a flexible wiring board, a build-up film, a build-up board, a fiber reinforced composite material, and a molded product.

  In recent years, frequencies used in the field of computers and the like are shifting to a high frequency region such as a gigahertz band. Resin materials used in such a high frequency region are required to exhibit functions of a low dielectric constant and a low dielectric loss tangent in a cured product in order to cope with an increase in communication speed.

  Among the above-mentioned fields, in the field of printed circuit boards, the use of high melting point solder (lead-free solder) that does not use lead has become the mainstream due to environmental regulations and the like. Therefore, the resin material used for the printed circuit board is also required to exhibit an excellent heat resistance function in the cured product.

  Further, in the field of printed circuit boards, the density of wiring has been greatly increased by narrowing the wiring pitch, and a flip chip connection method is widely used as a mounting method corresponding to this. However, in the flip-chip connection method, when the printed circuit board is created, the wiring board itself is exposed to a high heat environment, so that the printed circuit board is thermally contracted, and the wiring arranged on the printed circuit board causes poor connection. There is. Therefore, the resin material used for the printed circuit board is required to exhibit a function of low thermal expansion coefficient in the cured product.

  Such a printed circuit board can be obtained by laminating a copper foil serving as a conductor layer and a resin layer serving as an insulating layer, then thermocompression bonding, and then etching the copper foil. However, the printed circuit board manufactured by the above method may have insufficient adhesion between the copper foil and the resin layer. Therefore, the resin material used for the printed circuit board is required to exhibit an excellent adhesion function in the cured product.

  As a resin material having the above characteristics, a cyanate ester resin has attracted attention. The cyanate ester resin can exhibit functions of excellent heat resistance and dielectric properties in a cured product by a triazine ring generated during heat curing.

  Patent Document 1 describes a resin composition containing a phenol novolac-type cyanate ester resin, a bisphenol A cyanate ester resin, and an epoxy resin as a resin composition in the cyanate ester.

  However, although the resin composition of Patent Document 1 is improved to some extent with respect to heat resistance, dielectric properties, and low thermal expansion coefficient in the cured product, it has not reached the level required in recent years. Moreover, since the resin composition of patent document 1 has low adhesiveness with copper foil etc., the printed circuit board manufactured using the said resin composition also had the problem that delamination occurred in a board | substrate.

JP 2004-182850 A

  Therefore, the problem to be solved by the present invention is to provide a curable composition capable of exhibiting excellent heat resistance, dielectric properties, low expansion coefficient and adhesion in a cured product, a cured product having the above functions, and a semiconductor encapsulation. It is to provide a stopping material, a semiconductor device, a prepreg, a printed circuit board, a flexible wiring board, a buildup film, a buildup board, a fiber reinforced composite material, and a molded product.

  As a result of intensive studies to solve the above problems, the present inventors have found that a curable composition having a condensed polycyclic aromatic cyanate ester compound (A) and a monocyclic aromatic cyanate ester compound (B), In order to complete the present invention, it is found that the cured product can exhibit excellent heat resistance, dielectric properties, low expansion coefficient, and adhesion, and is highly useful as a material for electronic members such as printed circuit boards. It came.

  That is, the present invention relates to one or more condensed polycyclic aromatic cyanate ester compounds (A) selected from the group consisting of compounds represented by the following structural formula (A1) and the following structural formula (A2); The present invention relates to a curable composition having a monocyclic aromatic cyanate ester compound (B) in which a plurality of monocyclic compounds having a cyanate group are bonded directly or via a connecting group.

However, in the structural formula (A1) and the structural formula (A2),
R ¹ each independently represents a monovalent substituent other than a cyanato group, j represents an integer of 1 to 3, k represents an integer of 0 to 2j + 4, l represents an integer of 0 to 5, m Represents an integer of 0 to 2, and n represents an integer of 0 to 6 independently.

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

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

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

  The present invention further relates to a prepreg obtained by impregnating a reinforcing substrate with a solution obtained by diluting the curable composition in an organic solvent and semi-curing the resulting impregnated substrate.

  The present invention further relates to a printed circuit board obtained by laminating a prepreg shaped into a plate shape with a copper foil and heating and pressing.

  The present invention further relates to a flexible wiring board obtained by applying a mixture of an organic solvent to the curable composition to an electrically insulating film and then integrating the electrically insulating film and a metal foil.

  The present invention further relates to a buildup film obtained by applying a solution obtained by diluting the curable composition in an organic solvent onto a base film and drying it.

  The present invention is further obtained by applying the build-up film to a printed circuit board on which a circuit is formed, heat-curing the printed circuit board to form irregularities, and then subjecting the printed circuit board to plating. Related to the build-up substrate.

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

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

  According to the present invention, a curable composition capable of exhibiting excellent heat resistance, dielectric properties, low expansion coefficient, and adhesion in a cured product, a cured product having the above functions, a semiconductor sealing material, a semiconductor device, A prepreg, a printed circuit board, a buildup film, a buildup board, a fiber-reinforced composite material, and a molded product can be provided.

<Curable composition>
The curable composition of this invention has a condensed polycyclic aromatic cyanate ester compound (A) and a monocyclic aromatic cyanate ester compound (B). Hereinafter, the condensed polycyclic aromatic cyanate compound (A) and the monocyclic aromatic cyanate compound (B) will be described.

・ Condensed polycyclic aromatic cyanate compound (A)
The condensed polycyclic aromatic cyanate ester compound (A) is a cyanate ester compound having a cyanate group on a condensed aromatic ring in which a plurality of aromatic rings are condensed.

  Such a condensed polycyclic aromatic cyanate compound (A) is composed of a cyanate ester compound represented by the following structural formula (A1) or the following structural formula (A2).

However, in Structural Formulas (A1) and (A2), each R ¹ independently represents a monovalent substituent other than a cyanato group, j represents an integer of 1 to 3, and k represents an integer of 0 to 2j + 4. 1 represents an integer of 0 to 5, m represents an integer of 0 to 2, and n represents each independently an integer of 0 to 6.

In the structural formula (A1), j represents the number of repeating units of the aromatic ring in the condensed polycyclic aromatic cyanate ester compound. For example, when k is 1, the structural formula (A1) indicates a naphthalene structure, and when j is 2, an anthracene structure is indicated. k represents the total number of R ¹ substituted on the condensed aromatic ring. In Structural Formula (A2), m represents the number of repeating units. For example, when m is 0, the structural formula (A2) indicates a binaphthalene structure, and when k is 1, it indicates a tanaphthalene structure. l and n each represent the total number of R ¹ substituted with condensed aromatic rings. In the structural formulas (A1) and (A2), the cyanate group is located at any position of the condensed aromatic ring in which the aromatic ring is condensed.

R ¹ represents a monovalent substituent other than the cyanate group as described above. Examples of the substituent represented by R ¹ include a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an aryl group, an aralkyl group, a halogen atom, or the number of carbon atoms. Is a structure in which one or more hydrogen atoms contained in a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an aryl group, or an aralkyl group are substituted with either a hydroxyl group or a halogen atom Any of these can be mentioned.

When R ¹ is composed of a hydrocarbon group having 1 to 6 carbon atoms, examples of R ¹ include an alkyl group, an alkenyl group, and an alkynyl group.

As the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, secondary butyl group, tertiary butyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl Group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, cyclohexyl group and the like.
Examples of the alkenyl group include a vinyl group, 1-methylvinyl group, propenyl group, butenyl group, butenyl group, pentenyl group, pentenyl group and the like.
Examples of the alkynyl group include ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group and the like.

When R ¹ is composed of an alkoxy group having 1 to 6 carbon atoms, R ¹ includes methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, secondary butoxy group, tertiary butoxy Group, pentanoxy group, 1-methylbutoxy group, 2-methylbutoxy group, 3-methylbutoxy group, 1,1-dimethylpropoxy group, 1,2-dimethylpropoxy group, hexanoxy group, 1-methylpentanoxy group 2-methylpentanoxy group, 3-methylpentanoxy group, 4-methylpentanoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, cyclohexene Examples include a sanoxy group.

When R ¹ is composed of an aryl group, examples of R ¹ include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

When R ¹ is composed of an aralkyl group, R ¹ includes benzyl, phenylethyl, phenylpropyl, tolylmethyl, tolylethyl, tolylpropyl, xylylmethyl, xylylethyl, xylylpropyl, naphthyl. A methyl group, a naphthylethyl group, a naphthylpropyl group, etc. are mentioned.

When R ¹ is composed of a substituent in which one or more hydrogen atoms contained in an alkyl group having 1 to 6 carbon atoms is substituted with either a hydroxyl group or a halogen atom, R ¹ contains a hydroxyl group Examples thereof include an alkyl group, a halogenated alkyl group, a hydroxyl group-containing alkenyl group, a halogenated alkenyl group, a hydroxyl group-containing alkynyl group, and a halogenated alkynyl group.

  Examples of the hydroxyl group-containing alkyl group include a hydroxyethyl group and a hydroxypropyl group. Examples of the halogenated alkyl group include a chloromethyl group, a chloroethyl group, a chloropropyl group, a bromomethyl group, a bromoethyl group, a bromopropyl group, a fluoromethyl group, a fluoroethyl group, and a fluoropropyl group. Examples of the hydroxyl group-containing alkenyl group include 1-hydroxy-2,3-propenyl group and 2-hydroxy-4,5-pentenyl group. Examples of the halogenated alkenyl group include a 1-chloro-3,4-butenyl group and a 2-bromo-4,5-hexenyl group. Examples of the hydroxyl group-containing alkynyl group include 2-hydroxy-4,5-pentynyl group and 2-hydroxy-3,4-hexynyl. Examples of the halogenated alkynyl group include a 1-chloro-3,4-butynyl group and a 3-bromo-5,6-hexynyl group.

When R ¹ is composed of a substituent in which one or more hydrogen atoms contained in an alkoxy group having 1 to 6 carbon atoms is substituted with either a hydroxyl group or a halogen atom, R ¹ contains a hydroxyl group An alkoxy group, a halogenated alkoxy group, etc. are mentioned.

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

When R ¹ is composed of a substituent in which one or more hydrogen atoms contained in the aryl group are substituted with either a hydroxyl group or a halogen atom, R ¹ is a hydroxyl group-containing aryl group or a halogenated aryl group. Is mentioned. Examples of the hydroxyl group-containing aryl group include a hydroxyphenyl group and a hydroxynaphthyl group. Examples of the halogenated aryl group include a chlorophenyl group, a bromophenyl group, a fluorophenyl group, a chloronaphthyl group, a bromonaphthyl group, and a fluoronaphthyl group.

When R ¹ is composed of a halogen atom, examples of R ¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In addition to the above, R ¹ may be an alkoxy group-containing alkyl group, an alkoxy group-containing aryl group, or an unsaturated hydrocarbon group-containing aryl group. Examples of the alkoxy group-containing alkyl group include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an allyloxymethyl group, an allyloxypropyl group, a propargyloxymethyl group, and a propargyloxypropyl group. Examples of the alkoxy group-containing aryl group include a methoxyphenyl group, an ethoxyphenyl group, an allyloxyphenyl group, and a propargyloxyphenyl group. Examples of the unsaturated hydrocarbon group-containing aryl group include vinylphenyl, allylphenyl, ethynylphenyl, propargylphenyl and the like.

Among them, R ¹ is preferably a hydrogen atom, an alkyl group, or an aralkyl group, and R ¹ is composed of a hydrogen atom from the viewpoint that excellent heat resistance can be expressed in a cured product. Is more preferable.

  Examples of the condensed polycyclic aromatic cyanate ester compound (A) represented by the structural formula (A1) include 1,2-dicyanatonaphthalene, 1,3-dicyanatonaphthalene, 1,4-disi Anatonaphthalene, 1,5-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,7-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,3-dicyanatonaphthalene, 2,6-dicyanatonaphthalene Dicyanatonaphthalene such as 2,7-dicyanatonaphthalene, 1,2-dihydroanthracene, 1,3-dicyanatoanthracene, 1,4-dicyanatoanthracene, 1,5-dicyanatoanthracene, 1,6- Dicyanatoanthracene, 1,7-dicyanatoanthracene, 1,8-dicyanatoanthracene, 2,3-dicyanatoanthane Sen, 2,6-dicyanatoanthracene, 2,7-dicyanatoanthracene 9,10-dicyanatoanthracene, 1,9-dicyanatoanthracene, 1,10-dicyanatoanthracene, 2,9-dicyanatoanthracene, 2 , 10-dicyanatoanthracene and the like.

  Examples of the condensed polycyclic aromatic cyanate compound (A) represented by the structural formula (A2) include 2,2′-dicyanato-1,1′-binaphthalene and 2,3′-dicyanato-1,1′-. Binaphthalene, 2,4'-dicyanato-1,1'-binaphthalene, 2,5'-dicyanato-1,1'-binaphthalene, 2,6'-dicyanato-1,1'-binaphthalene, 2,7'-dicyanato -1,1'-binaphthalene, 2,8'-dicyanato-1,1'-binaphthalene, 2,3'-dicyanato-1,1'-binaphthalene, 2,4'-dicyanato-1,1'-binaphthalene, 2,5'-dicyanato-1,1'-binaphthalene, 2,6'-dicyanato-1,1'-binaphthalene, 2,7'-dicyanato-1,1'-binaphthalene, 2,8'-dicyanato-1 , 1'-Binaphthalene, 2,4'- Dicyanato-1,1'-binaphthalene, 3,4'-dicyanato-1,1'-binaphthalene, 4,4'-dicyanato-1,1'-binaphthalene, 4,5'-dicyanato-1,1'-binaphthalene 4,6'-dicyanato-1,1'-binaphthalene, 4,7'-dicyanato-1,1'-binaphthalene, 4,8'-dicyanato-1,1'-binaphthalene, 2,5'-dicyanato- 1,1′-binaphthalene, 3,5′-dicyanato-1,1′-binaphthalene, 4,5′-dicyanato-1,1′-binaphthalene, 5,5′-dicyanato-1,1′-binaphthalene, 5 , 6'-dicyanato-1,1'-binaphthalene, 5,7'-dicyanato-1,1'-binaphthalene, 5,8'-dicyanato-1,1'-binaphthalene, 2,6'-dicyanato-1, 1'-Binaphthalene, 3, 6 -Dicyanato-1,1'-binaphthalene, 4,6'-dicyanato-1,1'-binaphthalene, 5,6'-dicyanato-1,1'-binaphthalene, 6,6'-dicyanato-1,1'- Binaphthalene, 6,7'-dicyanato-1,1'-binaphthalene, 6,8'-dicyanato-1,1'-binaphthalene, 2,7'-dicyanato-1,1'-binaphthalene, 3,6'-dicyanato -1,1'-binaphthalene, 4,6'-dicyanato-1,1'-binaphthalene, 5,6'-dicyanato-1,1'-binaphthalene, 6,6'-dicyanato-1,1'-binaphthalene, 7,6′-dicyanato-1,1′-binaphthalene, 7,7′-dicyanato-1,1′-binaphthalene, 7,8′-dicyanato-1,1′-binaphthalene, 2,8′-dicyanato-1 , 1'-Binaphthalene, 3 8'-dicyanato-1,1'-binaphthalene, 4,8'-dicyanato-1,1'-binaphthalene, 5,8'-dicyanato-1,1'-binaphthalene, 6,8'-dicyanato-1,1 '-Binaphthalene, 7,8'-dicyanato-1,1'-binaphthalene, 8,8'-dicyanato-1,1'-binaphthalene, 2,2 ", 5'-tricyanato-1,1': 4 ' , 1 ″ -Thanaphthalene, 2,3 ″, 5′-Tricyanato-1,1 ′: 4 ′, 1 ″ -Turnaphthalene, 2,4 ″, 5′-Tricyanato-1,1 ′: 4 ′, 1 ″ -Thanaphthalene, 2,5 ′, 5 ″ -Tricyanato-1,1 ′: 4 ′, 1 ″ -Turnaphthalene, 2,5 ′, 6 ″ -Tricyanato-1,1 ': 4', 1 ″ -Thaphthalene, 2,5 ′, 7 ″ -tricyanato-1,1 ′: 4 ′, 1 ″ -Thanaphthalene, 2,5 ′, 8 ″ -Tricyanato-1,1 ′: 4 ′, 1 ″ -Turnaphthalene, 2,3 ″, 8′-Tricyanato-1,1 ′: 4 ′ , 1 ″ -Thanaphthalene, 3,3 ″, 5′-Tricyanato-1,1 ′: 4 ′, 1 ″ -Turnaphthalene, 3,4 ″, 5′-Tricyanato-1,1 ′: 4 ′, 1 ″ -Thanaphthalene, 3,5 ′, 5 ″ -Tricyanato-1,1 ′: 4 ′, 1 ″ -Turnaphthalene, 3,5 ′, 6 ″ -Tricyanato-1,1 ': 4', 1 "-Thanaphthalene, 3,5 ', 7" -Tricyanato-1, 1': 4 ', 1 "-Thanaphthalene, 3, 5', 8" -Tricyanato-1 , 1 ′: 4 ′, 1 ″ -Thanaphthalene, 2,4 ″, 8′-Tricyanato-1,1 ′: 4 ′, 1 ″ -Thanaphthalene, 3,4 ′ , 8′-tricyanato-1,1 ′: 4 ′, 1 ″ -turnaphthalene, 4,4 ″, 5′-tricyanato-1,1 ′: 4 ′, 1 ″ -turnaphthalene, 4,5 ', 5 ″ -tricyanato-1,1 ′: 4 ′, 1 ″ -turnaphthalene, 4,5 ′, 6 ″ -tricyanato-1,1 ′: 4 ′, 1 ″ -turnaphthalene, 4 , 5 ′, 7 ″ -tricyanato-1,1 ′: 4 ′, 1 ″ -turnaphthalene, 4,5 ′, 8 ″ -tricyanato-1,1 ′: 4 ′, 1 ″ -turnaphthalene 2,5 ″, 8′-tricyanato-1,1 ′: 4 ′, 1 ″ -Turnaphthalene, 3,5 ″, 8′-tricyanato-1,1 ′: 4 ′, 1 ″ − Turnaphthalene, 4,5 ″, 8′-tricyanato-1,1 ′: 4 ′, 1 ″ -Turnaphthalene, 4,5 ′, 5 ″ -tricyanato-1,1 ′ 4 ′, 1 ″ -Thanaphthalene, 5,5 ′, 5 ″ -Tricyanato-1,1 ′: 4 ′, 1 ″ -Turnaphthalene, 4,5 ′, 6 ″ -Tricyanato-1,1 ': 4', 1 ''-Thanaphthalene, 4,5 ', 7' '-Tricyanato-1,1': 4 ', 1' '-Turnaphthalene, 5,5', 8 ''-Tricyanato-1 , 1 ′: 4 ′, 1 ″ -Thanaphthalene, 2,6 ″, 8′-Tricyanato-1,1 ′: 4 ′, 1 ″ -Turnaphthalene, 3,6 ″, 8′-Tricyanato −1,1 ′: 4 ′, 1 ″ -Thanaphthalene, 4,6 ″, 8′-Tricyanato-1,1 ′: 4 ′, 1 ″ -Thanaphthalene, 5,6 ″, 8 ′ -Tricyanato-1,1 ': 4', 1 "-Turnaphthalene, 5 ', 6,6" -Tricyanato-1,1': 4 ', 1' '-Turnaphthalene 5 ′, 6,7 ″ -tricyanato-1,1 ′: 4 ′, 1 ″ -Thaphthalene, 5 ′, 6,8 ″ -Tricyanato-1,1 ′: 4 ′, 1 ″ -Tur Naphthalene, 2,7 ″, 8′-tricyanato-1,1 ′: 4 ′, 1 ″ -turnaphthalene, 3,7 ″, 8′-tricyanato-1,1 ′: 4 ′, 1 ″ Turnaphthalene, 4,7 ″, 8′-tricyanato-1,1 ′: 4 ′, 1 ″ -Thaphthalene, 5,7 ″, 8′-tricyanato-1,1 ′: 4 ′, 1 ″ -Turnaphthalene, 5 ′, 6 ″, 7-tricyanato-1,1 ′: 4 ′, 1 ″ -Turnaphthalene, 5 ′, 7,7 ″ -tricyanato-1,1 ′: 4 ′ , 1 ″ -Thanaphthalene, 5 ′, 7,8 ″ -Tricyanato-1,1 ′: 4 ′, 1 ″ -Turnaphthalene, 2,8 ′, 8 ″ -Tricyanato −1,1 ′: 4 ′, 1 ″ -Thanaphthalene, 3,8 ′, 8 ″ -Tricyanato-1,1 ′: 4 ′, 1 ″ -Thanaphthalene, 4,8 ′, 8 ″ -Tricyanato-1,1 ': 4', 1 "-Turnaphthalene, 5,8 ', 8" -Tricyanato-1,1': 4 ', 1' '-Turnaphthalene, 5', 6 '' , 8-tricyanato-1,1 ′: 4 ′, 1 ″ -turnaphthalene, 5 ′, 7 ″, 8-tricyanato-1,1 ′: 4 ′, 1 ″ -turnaphthalene, 5 ′, 8 , 8 ″ -tricyanato-1,1 ′: 4 ′, 1 ″ -turnaphthalene and the like.

  Furthermore, as the condensed polycyclic aromatic cyanate compound (A) represented by the structural formulas (A1) and (A2), cyanic acid represented by the following structural formulas (A1-a) and (A2-a) More preferably, it is an ester compound. The curable composition containing the condensed polycyclic aromatic cyanate compound (A) has excellent fluidity during molding.

However, in Structural Formulas (A1-a) and (A2-a), R ¹ independently represents a monovalent substituent other than a cyanato group, k represents an integer of 0 to 6, and n represents each independently. The integer of 0-6 is shown. Specific types of substituents represented by R ¹ are as described above.

Furthermore, similarly for the condensed polycyclic aromatic cyanate compound (A) represented by the structural formulas (A1-a) and (A2-a), R ¹ is a hydrogen atom, an alkyl group, or an aralkyl group. It is preferable that R ¹ is a hydrogen atom because it is possible to develop excellent heat resistance in the cured product. That is, when the condensed polycyclic aromatic cyanate compound (A) is a compound represented by the structural formulas (A1-a) and (A2-a), when R ¹ is a hydrogen atom, The curable composition containing the condensed polycyclic aromatic cyanate ester compound is excellent in fluidity during molding and can exhibit excellent heat resistance in the cured product.

-Method for Producing Condensed Polycyclic Aromatic Cyanate Compound (A) The condensed polycyclic aromatic cyanate ester compound (A) described above includes a condensed polycyclic aromatic hydroxy compound (a) and a cyanogen halide. Can be obtained by reacting with. Specifically, in the above reaction, the cyanogen halide is reacted at a ratio of 1.05 mol to 1.5 mol with respect to 1 mol of the hydroxy group in the condensed polycyclic aromatic hydroxy compound (a). . Thereafter, an appropriate amount of water is added to the reaction solution to dissolve the produced salt, and after washing with water repeatedly to remove the produced salt in the system, it is further purified by dehydration and filtration, and the organic solvent is removed by distillation. A condensed polycyclic aromatic cyanate compound (A) can be obtained.

  The cyanate ester (A) thus obtained preferably has a cyanato group equivalent in the range of 80 g / eq to 250 g / eq, and more preferably in the range of 100 g / eq to 200 g / eq. When the cyanate group equivalent of the obtained cyanate ester (A) is in the range of 80 g / eq to 250 g / eq, the resulting cured product can exhibit excellent heat resistance, dielectric properties, and low thermal expansion. Thus, when it is in the range of 100 g / eq to 200 g / eq, the obtained cured product can exhibit further excellent heat resistance, dielectric properties, and low thermal expansion.

Examples of the condensed polycyclic aromatic hydroxy compound (a) include compounds represented by the following structural formula (a1) and the following structural formula (a2).

In Structural Formulas (a1) and (a2), R ¹ independently represents a monovalent substituent other than a hydroxyl group, j represents an integer of 1 to 3, and k represents an integer of 0 to 2j + 4. , L represents an integer of 0-5, m represents an integer of 0-2, and n independently represents an integer of 0-6. Note that the substituent represented by R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, a halogen atom, or a carbon atom number. One or more hydrogen atoms contained in a 1-6 hydrocarbon group, an alkoxy group having 1-6 carbon atoms, an aryl group, or an aralkyl group are substituted with a halogen atom. The specific structure shown by these is as described above.

  Examples of the condensed polycyclic aromatic hydroxy compound (a) represented by the structural formula (a1) include 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, and 1,5-dihydroxy. Dihydroxynaphthalene such as naphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1, 2-dihydroanthracene, 1,3-dihydroxyanthracene, 1,4-dihydroxyanthracene, 1,5-dihydroxyanthracene, 1,6-dihydroxyanthracene, 1,7-dihydroxyanthracene, 1,8-dihydroxyanthracene, 2, -Dihydroxyanthracene, 2,6-dihydroxyanthracene, 2,7-dihydroxyanthracene 9,10-dihydroxyanthracene, 1,9-dihydroxyanthracene, 1,10-dihydroxyanthracene, 2,9-dihydroxyanthracene, 2,10-dihydroxy And dihydroxyanthracene such as anthracene.

  Among the above, dihydroxynaphthalene is preferred from the viewpoint that the flame retardancy of the cured product finally obtained is further improved and the dielectric loss tangent in the cured product is low, and among the dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene or 2,7-dihydroxynaphthalene is more preferable, and 2,7-dihydroxynaphthalene is particularly preferable among them.

  Examples of the condensed polycyclic aromatic hydroxy compound (a) represented by the structural formula (a2) include [1,1′-binaphthalene] -2,2′-diol and [1,1′-binaphthalene] -2. , 3′-diol, [1,1′-binaphthalene] -2,4′-diol, [1,1′-binaphthalene] -2,5′-diol, [1,1′-binaphthalene] -2,6 '-Diol, [1,1'-binaphthalene] -2,7'-diol, [1,1'-binaphthalene] -2,8'-diol, [1,1'-binaphthalene] -3,2'- Diol, [1,1′-Binaphthalene] -3,3′-diol, [1,1′-Binaphthalene] -3,4′-diol, [1,1′-Binaphthalene] -3,5′-diol, [1,1′-binaphthalene] -3,6′-diol, [1,1 ′ Binaphthalene] -3,7'-diol, [1,1'-binaphthalene] -3,8'-diol, [1,1'-binaphthalene] -4,2'-diol, [1,1'-binaphthalene] -4,3'-diol, [1,1'-binaphthalene] -4,4'-diol, [1,1'-binaphthalene] -4,5'-diol, [1,1'-binaphthalene] -4 , 6′-diol, [1,1′-binaphthalene] -4,7′-diol, [1,1′-binaphthalene] -4,8′-diol, [1,1′-binaphthalene] -5,2 '-Diol, [1,1'-binaphthalene] -5,3'-diol, [1,1'-binaphthalene] -5,4'-diol, [1,1'-binaphthalene] -5,5'- Diol, [1,1′-Binaphthalene] -5,6′-diol, [1,1 -Binaphthalene] -5,7'-diol, [1,1'-Binaphthalene] -5,8'-diol, [1,1'-Binaphthalene] -6,2'-diol, [1,1'-Binaphthalene ] -6,3'-diol, [1,1'-binaphthalene] -6,4'-diol, [1,1'-binaphthalene] -6,5'-diol, [1,1'-binaphthalene]- 6,6′-diol, [1,1′-binaphthalene] -6,7′-diol, [1,1′-binaphthalene] -6,8′-diol, [1,1′-binaphthalene] -7, 2'-diol, [1,1'-binaphthalene] -7,3'-diol, [1,1'-binaphthalene] -7,4'-diol, [1,1'-binaphthalene] -7,5 ' -Diol, [1,1'-binaphthalene] -7,6'-diol, [1,1 '-Binaphthalene] -7,7'-diol, [1,1'-Binaphthalene] -7,8'-diol, [1,1'-Binaphthalene] -8,2'-diol, [1,1'- Binaphthalene] -8,3′-diol, [1,1′-binaphthalene] -8,4′-diol, [1,1′-binaphthalene] -8,5′-diol, [1,1′-binaphthalene] -8,6'-diol, [1,1'-binaphthalene] -8,7'-diol, [1,1'-binaphthalene] -8,8'-diol, [1,1 ': 4', 1 '' -Thanaphthalene] -2,2 '', 5′-triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -2,3 ″, 5′-triol, [1,1 ': 4', 1 ″ -Turnaphthalene] -2,4 ″, 5′-triol, [1,1 ′: 4 ′, 1 ″ -Turnaphthalate ] -2,5 ′, 5 ″ -triol, [1,1 ′: 4 ′, 1 ″ -turnaphthalene] -2,5 ′, 6 ″ -triol, [1,1 ′: 4 ′ , 1 ″ -Thanaphthalene] -2,5 ′, 7 ″ -triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -2,5 ′, 8 ″ -triol, [1 , 1 ′: 4 ′, 1 ″ -Thanaphthalene] -3,3 ″, 5′-triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -3,4 ″, 5 '-Triol, [1,1': 4 ', 1 "-turnaphthalene] -3,5', 5" -triol, [1,1 ': 4', 1 "-turnaphthalene] -3 , 5 ′, 6 ″ -triol, [1,1 ′: 4 ′, 1 ″ -turnaphthalene] -3,5 ′, 7 ″ -triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -3,5 ', 8' '-triol, [ 1,1 ′: 4 ′, 1 ″ -turnaphthalene] -2,4 ″, 8′-triol, [1,1 ′: 4 ′, 1 ″ -turnaphthalene] -3,4 ″, 8′-triol, [1,1 ′: 4 ′, 1 ″ -turnaphthalene] -4,4 ″, 5′-triol, [1,1 ′: 4 ′, 1 ″ -turnaphthalene] − 4,5 ′, 5 ″ -triol, [1,1 ′: 4 ′, 1 ″ -turnaphthalene] -4,5 ′, 6 ″ -triol, [1,1 ′: 4 ′, 1 ′ '-Thanaphthalene] -4,5', 7 "-triol, [1,1 ': 4', 1" -Thanaphthalene] -4,5 ', 8 "-triol, [1,1' : 4 ', 1 "-Thanaphthalene] -2,5", 8'-triol, [1,1': 4 ', 1 "-Thanaphthalene] -3,5", 8'-triol , [1,1 ': 4', 1 ''-Tannaphthalene ] -4,5 ″, 8′-triol, [1,1 ′: 4 ′, 1 ″ -turnaphthalene] -5,5 ′, 6 ″ -triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -5,5 ′, 7 ″ -triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -5,5 ′, 8 ″ -triol, [1, 1 ′: 4 ′, 1 ″ -Thanaphthalene] -2,6 ″, 8′-triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -3,6 ″, 8 ′ Triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -4,6 ″, 8′-Triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -5 6 ″, 8′-triol, [1,1 ′: 4 ′, 1 ″ -turnaphthalene] -5 ′, 6,7 ″ -triol, [1,1 ′: 4 ′, 1 ″- Turnaphthalene] -5 ′, 6,8 ″ -triol, [1 1 ′: 4 ′, 1 ″ -Thanaphthalene] -2,7 ″, 8′-triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -3,7 ″, 8 ′ Triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -4,7 ″, 8′-Triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -5 7 ″, 8′-triol, [1,1 ′: 4 ′, 1 ″ -turnaphthalene] -5 ′, 7,7 ″ -triol, [1,1 ′: 4 ′, 1 ″- Turnaphthalene] -5 ′, 7,8 ″ -triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -2,8 ′, 8 ″ -triol, [1,1 ′: 4 ', 1 ″ -Thanaphthalene] -3,8 ′, 8 ″ -triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -4,8 ′, 8 ″ -triol, [ 1,1 ′: 4 ′, 1 ″ -Tannaphthalene] − , 8 ′, 8 ″ -triol, [1,1 ′: 4 ′, 1 ″ -turnaphthalene] -5 ′, 6 ″, 8-triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -5 ′, 7 ″, 8-triol, [1,1 ′: 4 ′, 1 ″ -Thanaphthalene] -5 ′, 8,8 ″ -triol and the like.

  Among these, from the point that the flame retardancy of the cured product in the finally obtained curable composition is further improved, and the dielectric loss tangent of the cured product is lowered to improve the dielectric properties [1,1. '-Binaphthalene] -2,2'-diol is particularly preferred.

  Examples of the cyanogen halide include cyanogen chloride and cyanogen bromide.

  In addition, it is preferable to perform the said reaction in presence of a basic catalyst from the point that reactivity becomes favorable. Examples of the basic catalyst used here include basic substances such as tertiary amines such as triethylamine and trimethylamine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide;

  The above reaction is preferably performed in the presence of an organic solvent. Examples of the organic solvent used here include aromatic solvents such as benzene, toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and ether solvents such as THF.

・ Monocyclic aromatic cyanate compound (B)
Next, the monocyclic aromatic cyanate ester compound (B) will be described.

  The monocyclic aromatic cyanate ester compound (B) is a compound in which a plurality of monocyclic compounds having a cyanate group on an aromatic ring are bonded directly or via a connecting group.

  As such a monocyclic aromatic cyanate ester compound (B), a cyanate ester compound represented by the following structural formula (B1) or the following structural formula (B2) can be given.

However, in Structural Formulas (B1) and (B2), L represents a divalent linking group, R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or 1 carbon atom. -6 alkoxy groups, hydroxyl groups, aryl groups, aralkyl groups, halogen atoms, hydrocarbon groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aryl groups, or aralkyl groups. One of the structures in which one or more hydrogen atoms are substituted with either a hydroxyl group or a halogen atom, and p independently represents an integer of 0 to 4.

  As described above, L represents a divalent linking group. As the divalent linking group represented by L, a divalent hydrocarbon group, a divalent group in which one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with a hydroxyl group, an alkoxy group, or a halogen atom, Examples thereof include a divalent heteroatom or a divalent atomic group containing a heteroatom. The “divalent hydrocarbon group” referred to in the present invention refers to a hydrocarbon obtained by removing two hydrogens from a hydrocarbon group, and represents “—R— (R is a hydrocarbon)”. The “hydrocarbon” indicates an aliphatic saturated hydrocarbon, an aliphatic unsaturated hydrocarbon, an aromatic hydrocarbon, or a combination thereof.

  When L represents a divalent hydrocarbon group, L is an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, an arylene group, an aralkylene group (a divalent group having an alkylene group and an arylene group, for example, “ -R-Ar-R- (wherein R is an aliphatic hydrocarbon, Ar is an aromatic hydrocarbon) "and the like.

  In this case, as the alkylene group, methylene group, ethylene group, ethylidene group, propylidene group, propylene group, trimethylene group, isopropylidene group, butylidene group, butylene group, isobutylidene group, pentylene group, pentylidene group, isopentylidene group, Examples include a hexylene group, a hexylidene group, and an isohexylidene group. Examples of the alkenylene group include a vinylene group, a 1-methylvinylene group, a propenylene group, a butenylene group, a butenylene group, a pentenylene group, and a pentenylene group. Examples of the alkynylene group include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, and a hexynylene group. Examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group. Examples of the arylene group include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group. The aralkylene group is represented by “—R—Ar—R— (wherein R is an alkylene group, Ar is an arylene)”, and examples thereof include an aralkylene group having 7 to 20 carbon atoms having the alkylene group and the arylene group.

  When L represents a divalent group in which one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with a hydroxyl group, an alkoxy group, or a halogen atom, L is a hydroxyl group-containing alkylene group or an alkoxy group. Containing alkylene group, halogenated alkylene group, hydroxyl group-containing alkenylene group, alkoxy group-containing alkenylene group, halogenated alkenylene group, hydroxyl group-containing alkynylene group, alkoxy group-containing alkynylene group, halogenated alkynylene group, hydroxyl group-containing cycloalkylene group, alkoxy group-containing Examples include cycloalkylene groups, halogenated cycloalkylene groups, hydroxyl group-containing arylene groups, alkoxy group-containing arylene groups, halogenated arylene groups, hydroxyl group-containing aralkylene groups, alkoxy group-containing aralkylene groups, and halogenated aralkylene groups.

  Examples of the hydroxyl group-containing alkylene group include a hydroxymethylene group, a hydroxyethylene group, and a hydroxypropylene group. Examples of the alkoxy group-containing alkylene group include a methoxymethylene group, a methoxyethylene group, a methoxypropylene group, an allyloxymethylene group, an allyloxypropylene group, a propargyloxymethylene group, and a propargyloxypropylene group. Examples of the halogenated alkylene group include a chloromethylene group, a chloroethylene group, a chloropropylene group, a bromomethylene group, a bromoethylene group, a bromopropylene group, a fluoromethylene group, a fluoroethylene group, and a fluoropropylene group. Examples of the hydroxyl group-containing alkenylene group include a hydroxybutenylene group and a hydroxypentenylene group. Examples of the alkoxy group-containing alkenylene group include a methoxybutenylene group and an ethoxyhexenylene group. Examples of the halogenated alkenylene group include a chloropropenylene group and a bromopentenylene group. Examples of the hydroxyl group-containing alkynylene group include a hydroxypentynylene group and a hydroxyhexynylene group. Examples of the alkoxy group-containing alkynylene group include an ethoxyhexynylene group and a methoxyheptynylene group. Examples of the halogenated alkynylene group include a chlorohexynylene group and a fluorooctynylene group. Examples of the hydroxyl group-containing cycloalkylene group include a hydroxycyclohexanylene group. Examples of the alkoxy group-containing cycloalkylene group include a methoxycyclopentanylene group. Examples of the halogenated cycloalkylene group include a dichlorocyclopentanylene group. Examples of the hydroxyl group-containing arylene group include a hydroxyphenylene group. Examples of the alkoxy group-containing arylene group include a methoxyphenylene group, an ethoxyphenylene group, an allyloxyphenylene group, and a propargyloxyphenylene group. Examples of the halogenated arylene group include a chlorophenylene group, a bromophenylene group, a fluorophenylene group, a chloronaphthylene group, a bromonaphthylene group, and a fluoronaphthylene group. In addition to the above, L may be an unsaturated hydrocarbon group-containing arylene group. Examples of the unsaturated hydrocarbon group-containing arylene group include a vinylphenylene group, an allylphenylene group, an ethynylphenylene group, and a propargylphenylene group.

When L represents a divalent hetero atom or a divalent atomic group containing a hetero atom, L may be an ether bond group (—O— group), a carbonyl group (—CO— group), an ester group (—COO). - group), amide groups (-CONH- group), an imino group (-CCN- group), an azo group (-N = N-group), sulfide groups (-S- group), a sulfonyl group _(-SO 2 -) Etc.

  Among these, the divalent linking group L is preferably a methylene group, an ethylidene group, or an isopropylidene group. The hardened | cured material obtained from the curable composition containing the above monocyclic aromatic cyanate ester compounds (B) can express the outstanding heat resistance.

R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an aryl group, an aralkyl group, a halogen atom, or carbon. A structure in which one or more hydrogen atoms contained in a hydrocarbon group having 1 to 6 atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, or an aralkyl group are substituted with either a hydroxyl group or a halogen atom As such R ^{2, the same} as those described for R ¹ can be mentioned.

  Specific examples of the monocyclic aromatic cyanate compound (B) described above include, for example, bisphenol A type cyanate ester compound, bisphenol F type cyanate ester compound, bisphenol E type cyanate ester compound, and bisphenol S. Type cyanate ester compound, bisphenol M type cyanate ester compound, bisphenol P type cyanate ester compound, bisphenol Z type cyanate ester compound, bisphenol AP type cyanate ester compound, bisphenol sulfide type cyanate ester compound, phenylene ether type cyanide Acid ester compound, biphenyl type cyanate ester compound, tetramethyl biphenyl type cyanate ester compound, benzyl modified tetramethyl biphenyl type cyanate ester compound, tetramethyl Bisphenol F type cyanate ester compound, dicyclopentadiene - phenol addition type cyanate ester compound, and the like bisphenol fluorene type cyanate ester compound.

  Specific examples include monocyclic aromatic cyanate ester compounds (B) represented by the following structural formulas (B1-1) to (B1-20).

In the structural formulas (B1-1) to (B1-20), p represents an integer of 1 to 4, and the specific structure represented by R ² is as described above.

  Furthermore, as the monocyclic aromatic cyanate compound (B) represented by structural formulas (B1) and (B2), cyanate esters represented by the following structural formulas (B1-a) and (B2-a) More preferred are compounds. The curable composition containing the monocyclic aromatic cyanate compound (B) can exhibit excellent low thermal expansibility in the obtained cured product.

However, in Structural Formulas (B1-a) and (B2-a), L is a divalent linking group, R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, or a carbon atom. Included in an alkoxy group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, or an aralkyl group 1 or more hydrogen atoms are substituted with halogen atoms, and p is an integer of 1 to 4. Specific structures of the substituents represented by L and R ² are as described above.

  Furthermore, in the monocyclic aromatic cyanate ester compound (B) represented by the structural formula (B1-a), the divalent linking group L is composed of a methylene group, an ethylidene group, an isopropylidene group, and an alkylidene group. The divalent linking group L is more preferably composed of a methylene group, an ethylidene group, and an isopropylidene group because the resulting cured product can exhibit excellent heat resistance.

Furthermore, regarding the monocyclic aromatic cyanate ester compound (B) represented by the structural formulas (B1-a) and (B2-a), the substituent R ² is a hydrogen atom, an alkyl group, or an aralkyl group. It is more preferable that it is composed of hydrogen atoms because a curable composition that exhibits excellent heat resistance in the cured product can be obtained. That is, when the monocyclic aromatic cyanate compound (B) is a compound represented by the structural formulas (B1-a) and (B2-a), the substituent R ² is composed of a hydrogen atom. In addition to the excellent heat resistance, the resulting cured product can exhibit an excellent low thermal expansion property.

-Manufacturing method of monocyclic aromatic cyanate ester (B) The monocyclic aromatic cyanate ester (B) described above is obtained by reacting a monocyclic aromatic hydroxy compound (b) with cyanogen halide. Can be obtained. Specifically, cyanogen halide is reacted at a ratio of 1.05 mol to 1.5 mol with respect to 1 mol of the hydroxy group in the monocyclic aromatic hydroxy compound (b). Thereafter, an appropriate amount of water is added to the reaction solution to dissolve the produced salt, and after washing with water repeatedly to remove the produced salt in the system, it is further purified by dehydration and filtration, and the organic solvent is removed by distillation. A monocyclic aromatic cyanate ester compound (B) can be obtained.

  The monocyclic aromatic cyanate ester compound (B) thus obtained has excellent heat resistance and dielectric properties in a cured product obtained by having a cyanate group equivalent in the range of 80 g / eq to 250 g / eq, and has low heat It is preferable from the viewpoint of excellent expandability. More preferably, it is in the range of 100 g / eq to 200 g / eq.

Examples of the monocyclic aromatic hydroxy compound (b) include compounds represented by the following structural formula (b1) and the following structural formula (b2).

In Structural Formulas (b1) and (b2), R ² represents a monovalent substituent other than a hydroxyl group, and p represents an integer of 0 to 4. Specific substituents represented by R ² are as described above.

  Examples of the monocyclic aromatic hydroxy compound (b) represented by the structural formula (b1) include 2,2′-methylenediphenol, 2- (3-hydroxybenzyl) phenol, and 2- (4-hydroxybenzyl). Phenol, 3,3′-methylenediphenol, 3- (4-hydroxybenzyl) phenol, 4,4′-methylenediphenol, 2,2 ′-(ethane-1,2-dinyl) diphenol, 2- ( 3-hydroxyphenethyl) phenol, 2- (4-hydroxyphenethyl) phenol, 3,3 ′-(ethane-1,2-dinyl) diphenol, 3- (4-hydroxyphenethyl) phenol, 4,4 ′-( Ethane-1,2-dinyl) diphenol, and the like.

  Examples of the monocyclic aromatic hydroxy compound (b) represented by the structural formula (b2) include [1,1′-biphenyl] -2,2′-diol, [1,1′-biphenyl] -2, 3′-diol, [1,1′-biphenyl] -2,4′-diol, [1,1′-biphenyl] -3,3′-diol, [1,1′-biphenyl] -3,4 ′ -Diol, [1,1'-biphenyl] -4,4'-diol and the like.

  Among these, [1,1′-biphenyl] -4,4′-diol is preferable because a curable composition can be obtained in which the flame retardancy and dielectric properties of the cured product are further improved.

  In addition, the curable composition of this invention is the condensed polycyclic aromatic cyanate ester compound (A) 1 in the condensed polycyclic aromatic cyanate ester compound (A) and the monocyclic aromatic cyanate ester compound (B). It is preferable that the monocyclic aromatic cyanate ester compound (B) is contained in an amount of 0.1 to 5 parts by mass with respect to parts by mass. When the condensed polycyclic aromatic cyanate ester compound (A) and the monocyclic aromatic cyanate ester compound (B) are contained in the above range, the resulting cured product has a thermal conductivity and a thermal decomposition resistance. Will improve.

As the curable composition of the present invention, a fused polycyclic aromatic cyanate ester compound (A) and a monocyclic aromatic cyanate ester compound (B) are melt-mixed and prepolymerized (condensed polycyclic A part of the cyanate group of the aromatic cyanate ester compound (A) or the aromatic cyanate ester compound (B) may be trimerized to form a triazine ring). In such a case, if a compound in which the trimerization reaction of cyanate group has proceeded excessively is used, the curable composition is gelled and loses fluidity. Therefore, the curable composition may be a condensed polycyclic aromatic. It is preferable to use a cyanate ester compound (A) or an aromatic cyanate ester compound (B) having a cyanate group reaction rate in the range of 10% to 70%. More preferably, the range of 20% to 60% is used. In addition, the reaction rate of the said cyanato group is the absorption peak (the aromatic ring origin which does not change by reaction with the absorption peak intensity | strength of the cyanate group (2270cm < ^-1 >) in a infrared spectrometer (IR) and a triazine ring (1370cm < ^-1 >)). For example, it is computable on the basis of 1500cm < ^-1 >).

・ Bismaleimide (C)
Furthermore, the curable composition of the present invention may contain bismaleimide (C) in addition to the condensed polycyclic aromatic cyanate compound (A) and monocyclic aromatic cyanate compound (B). Good. In such a case, in the curable composition, the monocyclic aromatic cyanate ester compound (B) is 0.1 parts by mass to 5 parts by mass with respect to 1 part by mass of the condensed polycyclic aromatic cyanate ester compound (A). It is preferable that maleimide (C) is contained in a proportion of 0.1 to 5 parts by mass. In the curable composition, the condensed polycyclic aromatic cyanate compound (A), the monocyclic aromatic cyanate compound (B), and the bismaleimide (C) are contained in the above ratio. The heat resistance and heat decomposition resistance of the resulting cured product are improved.

  The bismaleimide is not particularly limited as long as it is a compound having two or more maleimide groups in one molecule. Specific examples thereof include 4,4′-diphenylmethane bismaleimide, 4,4′-diphenylsulfone bismaleimide, m-phenylene bismaleimide, bis (3-methyl-4-maleimidophenyl) methane, bis (3- Ethyl-4-maleimidophenyl) methane, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4 -Bismaleimides such as -maleimidophenyl) methane.

  Among these, since the heat resistance of the cured product is particularly good, as bismaleimide (C), 4,4′-diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidophenyl) methane, Bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and bis (3,5-diethyl-4-maleimidophenyl) methane are preferred.

・ Epoxy resin (D)
Furthermore, the curable composition of the present invention may contain an epoxy resin (D) in addition to the condensed polycyclic aromatic cyanate compound (A) and the monocyclic aromatic cyanate compound (B). In such a case, in the curable composition, the monocyclic aromatic cyanate ester compound (B) is 0.1 to 5 parts by mass with respect to 1 part by mass of the condensed polycyclic aromatic cyanate ester compound (A). It is preferable that the resin (D) is contained in a proportion of 0.1 to 5 parts by mass. When the curable composition contains the condensed polycyclic aromatic cyanate ester compound (A), the monocyclic aromatic cyanate ester compound (B), and the epoxy resin (D) at the above-mentioned ratios, it is obtained. The mechanical strength of the cured product is improved.

  Furthermore, the curable composition of the present invention comprises an epoxy resin (D) in addition to the condensed polycyclic aromatic cyanate ester compound (A), monocyclic aromatic cyanate ester compound (B), and bismaleimide (C). May be included. In such a case, in the curable composition, 0.1 part by mass to 5 parts by mass of the monocyclic aromatic cyanate ester compound (B) is added to 1 part by mass of the condensed polycyclic aromatic cyanate ester compound (A). It is preferable to contain maleimide (C) in a proportion of 0.1 to 5 parts by mass and epoxy resin (D) in a proportion of 0.1 to 5 parts by mass. The curable composition comprises the condensed polycyclic aromatic cyanate compound (A), the monocyclic aromatic cyanate compound (B), the bismaleimide (C), and the epoxy resin (D) at the above ratio. When it contains, the heat-resistant decomposition property and mechanical strength improve in the hardened | cured material obtained.

  The epoxy resin (D) used here is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolak type. Epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type Epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, biphenyl modified phen Type epoxy resin (polyhydric phenol compound in which phenol skeleton and biphenyl skeleton are linked by bismethylene group), biphenyl-modified naphthol type epoxy resin (polyvalent naphthol compound in which phenol skeleton and biphenyl skeleton are linked by bismethylene group), aromatic And aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, biphenyl novolac type epoxy resin, xanthene type epoxy resin, naphthylene ether type epoxy resin and the like.

  Among these, phenol aralkyl type epoxy resins, biphenyl novolak type epoxy resins, naphthol novolak type epoxy resins containing a naphthalene skeleton, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolacs. Type epoxy resin, crystalline biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, xanthene type epoxy resin, alkoxy group-containing aromatic ring-modified novolak type epoxy resin (formaldehyde glycidyl group-containing aromatic ring and alkoxy group-containing aromatic ring Are particularly preferable in that a cured product having excellent heat resistance can be obtained.

・ Curing accelerator (E)
Furthermore, the curable composition of this invention may contain the hardening accelerator (E) as needed. Various curing accelerators (E) can be used, and examples thereof include phenols, amines, Lewis acids, tertiary sulfonium salts, quaternary ammonium salts, quaternary phosphonium salts, and epoxy group-containing compounds. . Among these, when the curable composition is composed of the condensed polycyclic aromatic cyanate compound (A) and the monocyclic aromatic cyanate compound (B), nonylphenol, 2,4,6-tris ( Dimethylaminomethyl) Phenol, copper, lead, tin, manganese, nickel, iron, zinc, cobalt and other carboxylates, titanium tetra-n-butoxide and its polymers, copper, nickel, cobalt and other pentadionate salts, odor Tetrabutylammonium chloride, tetrabutylphosphonium chloride, tetraphenylphosphonium tetra (methylphenyl) borate and zinc octylate are preferred. When the curing accelerator is configured as described above, the curing accelerator is highly compatible with the condensed polycyclic aromatic cyanate compound (A) and the monocyclic aromatic cyanate compound (B). The curing reaction proceeds smoothly. Further, among these, tetraphenylphosphonium tetra (methylphenyl) borate is particularly preferable as the curing accelerator. When the curing accelerator is composed of tetraphenylphosphonium tetra (methylphenyl) borate, the curing reaction proceeds faster. In this case, it is preferable that the usage-amount of a hardening accelerator (B) is 0.001 mass part-1.00 mass part per 100 mass parts of cyanate ester compound (A), for example.

  The curable composition contains bismaleimide (C) and epoxy resin (D) in addition to the condensed polycyclic aromatic cyanate compound (A) and monocyclic aromatic cyanate compound (B). From the point that the obtained cured product can express excellent curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., as the curing accelerator, triphenylphosphine, 1,8- Diazabicyclo- [5.4.0] -undecene (DBU), benzyldimethylamine, and imidazole are preferably used.

-Curing agent Furthermore, the curable composition of this invention may contain the hardening | curing agent suitably as needed. Examples of curing agents that can be used here include curing agents such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds. Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivatives. Examples of the amide compound include dicyandiamide, Examples include polyamide resins synthesized from dimer of linolenic acid and ethylenediamine. Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and tetrahydrophthalic anhydride. , Methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., and phenolic compounds include phenol novolac resins, cresol novolac resins, Aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene-phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, Naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol skeleton and biphenyl skeleton are linked by bismethylene group), biphenyl modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group) , Aminotriazine modified phenolic resin (polyhydric phenol compound with phenolic nuclei linked by melamine, benzoguanamine, etc.) and alkoxy group-containing aromatic ring modified Rack resin (polyhydric phenol compound phenol nucleus and an alkoxy group-containing aromatic ring are connected by formaldehyde), polyhydric phenol compounds such as naphthylene ether resins.

  Among the above, it is preferable to use a resin containing a large amount of an aromatic skeleton in the molecular structure when it is desired to develop an excellent flame retardant effect in the obtained cured product. Such resins include phenol novolac resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed. Examples thereof include novolak resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, aminotriazine-modified phenol resins, and naphthylene ether resins. Of the above, dicyclopentadiene-phenol addition type resin is preferable when it is desired to develop excellent dielectric properties in the obtained cured product.

  When the above-described curing agent is used in combination, the amount used is preferably included in the range of 10% by mass to 50% by mass in the total curable composition because the effect exhibited by the present invention is sufficiently exhibited. .

-Thermosetting resin Furthermore, the said curable composition may contain the thermosetting resin suitably. Examples of thermosetting resins include cyanate ester resins, benzoxazine resins, monomaleimide compounds having one maleimide group per molecule, active ester resins, vinyl benzyl compounds, acrylic compounds, styrene and maleic anhydride. And the like. When the other thermosetting resins described above are used in combination, the amount used is not particularly limited as long as the effect of the present invention is not impaired, but in 100 parts by mass of the curable composition, 1 part by mass to 50 parts by mass. A range is preferable.

  Examples of the cyanate ester resins include naphthylene ether type cyanate ester resins, polyhydroxynaphthalene type cyanate ester resins, phenol novolac type cyanate ester resins, cresol novolac type cyanate ester resins, and triphenylmethane type cyanate esters. Resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol- Phenol-condensed novolac-type cyanate ester resin, naphthol-cresol co-condensed novolak-type cyanate ester resin, aromatic hydrocarbon formaldehyde resin-modified phenolic tree Type cyanate ester resin, biphenyl-modified novolak type cyanate ester resins, anthracene type cyanate ester resins. These may be used alone or in combination of two or more.

  Among these cyanate ester resins, polyhydroxynaphthalene-type cyanate ester resins, naphthylene ether-type cyanate ester resins, phenol novolac-type cyanate ester resins, and cresols are particularly useful in that cured products having excellent heat resistance can be obtained. Use novolak-type cyanate ester resin, naphthol novolak-type cyanate ester resin, naphthol-phenol co-condensed novolak-type cyanate ester resin, naphthol-cresol co-condensed novolac-type cyanate ester resin, biphenyl-modified novolac-type cyanate ester resin In terms of obtaining a cured product having excellent dielectric properties, a dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable.

  The benzoxazine resin is not particularly limited. For example, a reaction product of bisphenol F, formalin and aniline (Fa type benzoxazine resin) or a reaction product of diaminodiphenylmethane, formalin and phenol (Pd type). Benzoxazine resin), reaction product of bisphenol A, formalin and aniline, reaction product of dihydroxydiphenyl ether, formalin and aniline, reaction product of diaminodiphenyl ether, formalin and phenol, dicyclopentadiene-phenol addition resin and formalin and aniline Reaction products of phenolphthalein, formalin and aniline, reaction products of diphenyl sulfide, formalin and aniline, and the like. These may be used alone or in combination of two or more.

  Examples of the monomaleimide compound having one maleimide group in one molecule include various compounds represented by the following structural formula (i).

  In the above formula (i), R is a monovalent substituent other than a cyanato group, and x and y each represent a hydrogen atom, a halogen atom, an alkyl group, or an aryl group.

Examples of R include the same substituents as those described for R ¹ and R ² , and in particular, a hydroxyphenyl group, a propenyl group, a propynyl group, an allylphenyl group, a propargylphenyl group, and an allylhydroxyphenyl group. It is preferably a propargyl hydroxyphenyl group. As described above, when R is configured, the heat resistance of the obtained cured product is improved.

  Although there is no restriction | limiting in particular as active ester resin, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of a heterocyclic hydroxy compound, are 2 in 1 molecule. A compound having at least one is preferably used. The other active ester resin is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound or a halide thereof and a hydroxy compound is preferred, and an active ester resin obtained from a carboxylic acid compound or a halide thereof and a phenol compound and / or a naphthol compound is preferred. More preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, and the like, or a halide thereof. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadiene-phenol addition resin and the like. Specific examples of the active ester resin include an active ester resin containing a dicyclopentadiene-phenol addition structure, an active ester resin containing a naphthalene structure, an active ester resin that is an acetylated product of phenol novolac, and an activity that is a benzoylated product of phenol novolac. An ester resin or the like is preferable, and an active ester resin including a dicyclopentadiene-phenol addition structure and an active ester resin including a naphthalene structure are more preferable because they are excellent in improving peel strength. More specifically, examples of the active ester resin containing a dicyclopentadiene-phenol addition structure include compounds represented by the following general formula (ii).

  In formula, R is a phenyl group or a naphthyl group, k represents 0 or 1, and n shows 0.05-2.5 on the average of a repeating unit.

  From the viewpoint of reducing the dielectric loss tangent of the cured product and improving the heat resistance, R is preferably a naphthyl group, k is preferably 0, and n is preferably 0.25 to 1.5.

-Flame retardant Moreover, in order to exhibit a flame retardance, the said curable composition may contain the non-halogen-type flame retardant which does not contain a halogen atom substantially in the range which does not reduce reliability.

  Examples of the non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. The flame retardants may be used alone or in combination, and a plurality of flame retardants of the same system may be used, or different types of flame retardants may be used in combination.

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

  The red phosphorus is preferably surface-treated for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (1) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (2) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and Method of coating with a mixture of thermosetting resins such as phenolic resin, (3) Thermosetting of phenolic resin on a film of inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide For example, a method of double coating with a resin may be used.

  Examples of the organic phosphorus compound include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phospholane compounds, organic nitrogen-containing phosphorus compounds, and 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 organophosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected according to the type of the phosphorus-based flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. For example, a condensed polycyclic aromatic cyanate ester Red phosphorus is non-halogenated in 100 parts by mass of the curable composition containing the compound (A), monocyclic aromatic cyanate ester compound (B), non-halogen flame retardant, and other fillers and additives. When used as a system flame retardant, it is preferably blended in the range of 0.1 parts by mass to 2.0 parts by mass, and when an organic phosphorus compound is used, it is similarly 0.1 parts by mass to 10.0 parts by mass. It is preferable to mix | blend in the range, and it is preferable to mix | blend especially in the range of 0.5 mass part-6.0 mass parts.

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

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

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (1) guanylmelamine sulfate, melem sulfate, sulfate Aminotriazine sulfate compounds such as melam, (2) cocondensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (3) Mixtures of the above (2) cocondensates and phenol resins such as phenol formaldehyde condensates, (4) (2) and (3) further modified with tung oil, isomerized linseed oil, etc. .

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The compounding amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. In 100 parts by mass of curable composition containing all of aromatic cyanate ester compound (A), monocyclic aromatic cyanate ester compound (B), non-halogen flame retardant, and other fillers and additives, etc. It is preferable to mix | blend in the range of 0.05 mass part-10 mass parts, and it is preferable to mix | blend especially in the range of 0.1 mass part-5 mass parts.

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

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

  The amount of the silicone flame retardant is appropriately selected depending on the type of the silicone flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. In 100 parts by mass of curable composition containing all of aromatic cyanate ester compound (A), monocyclic aromatic cyanate ester compound (B), non-halogen flame retardant, and other fillers and additives, etc. It is preferable to blend in the range of 0.05 parts by mass to 20 parts by mass. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

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

  Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

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

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

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

Specific examples of the low-melting-point glass include, for example, Sheepley (Bokusui Brown), 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, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned.

  The blending amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. In 100 parts by mass of curable composition containing all of aromatic cyanate ester compound (A), monocyclic aromatic cyanate ester compound (B), non-halogen flame retardant, and other fillers and additives, etc. It is preferable to mix | blend in the range of 0.05 mass part-20 mass parts, and it is preferable to mix | blend especially in the range of 0.5 mass part-15 mass parts.

  Examples of the organometallic salt flame retardant include ferrocene, acetylacetonate metal complex, organometallic carbonyl compound, organocobalt salt compound, organosulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organometallic salt-based flame retardant is appropriately selected depending on the type of the organometallic salt-based flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. 100 mass of curable composition containing all of condensed polycyclic aromatic cyanate compound (A), monocyclic aromatic cyanate compound (B), non-halogen flame retardant, and other fillers and additives It is preferable to mix | blend in 0.005 mass part-10 mass parts in a part.

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

-Organic solvent Furthermore, the curable composition of this invention may contain the organic solvent suitably. Examples of the organic solvent that can be used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The amount used can be appropriately selected depending on the application.

-Compounding agent The curable composition of this invention may contain various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, and an emulsifier, as needed.

-Hardened | cured material The curable composition of this invention can be easily made into hardened | cured material by the method similar to the method known conventionally. Examples of such cured products include molded cured products such as laminates, cast products, adhesive layers, coating films, and films. In addition, as a method for obtaining a cured product, it may be in accordance with a curing method of a general curable composition, for example, the heating temperature condition may be appropriately selected depending on the type of curing agent to be combined and the use, What is necessary is just to heat the composition obtained by the said method in the temperature range of about 20 degreeC-300 degreeC.

<Use of curable composition>
Applications of the curable composition of the present invention include printed wiring board materials, flexible wiring board compositions, interlayer insulating materials for build-up boards, insulating materials for circuit boards such as build-up adhesive films, and resin casting materials. , Adhesives, semiconductor sealing materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up substrates, fiber reinforced composite materials, molded products obtained by curing the composite materials, and the like. Among these various applications, for printed wiring board materials, circuit board insulation materials, and build-up adhesive film applications, passive components such as capacitors and active components such as IC chips are embedded in the substrate for so-called electronic component-embedded substrates. It can be used as an insulating material. Among the above, the curable composition of the present invention is a semiconductor encapsulating material, a semiconductor device, a prepreg, taking advantage of the characteristics that the cured product can exhibit excellent heat resistance, dielectric properties, and low expansion coefficient. It is preferably used for flexible wiring boards, circuit boards, build-up films, build-up boards, multilayer printed wiring boards, fiber reinforced composite materials, and molded products obtained by curing the composite materials. Below, the method to manufacture the said semiconductor sealing material etc. from the curable composition of this invention is demonstrated.

Semiconductor encapsulating material As a method for obtaining a semiconductor encapsulating material from the curable composition, as necessary, using an extruder, a kneader, a roll, etc., a curable composition, a curing accelerator, and Examples thereof include a method in which a compounding agent such as an inorganic filler is sufficiently melt-mixed until uniform. At that time, fused silica is usually used as the inorganic filler. However, when manufacturing a high thermal conductive semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, which has higher thermal conductivity than fused silica, High filling such as silicon nitride, or fused silica, crystalline silica, alumina, silicon nitride, or the like may be used. As for the filling rate, it is preferable to use an inorganic filler in the range of 30 to 95 parts by mass per 100 parts by mass of the curable composition, and among them, improvement in flame resistance, moisture resistance and solder crack resistance, and linear expansion. In order to reduce the coefficient, the amount is more preferably 70 parts by mass or more, and further preferably 80 parts by mass or more.

Semiconductor device As a method for obtaining a semiconductor device from the curable composition, the semiconductor sealing material is cast or molded using a transfer molding machine, an injection molding machine, and the like, and further at 50 ° C. to 200 ° C. for 2 hours. What is necessary is just to heat for 10 hours.

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

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

-Circuit board As a method of obtaining a circuit board from the said curable composition, the said prepreg is laminated | stacked by a conventional method, a copper foil is laminated | stacked suitably, and it is 170 degreeC-300 degreeC under the pressurization of 1 MPa-10 MPa-10 minutes- The method of carrying out thermocompression bonding for 3 hours is mentioned.

-Flexible wiring board As a method of obtaining a lexible wiring board from the said curable composition, the method of manufacturing from the three processes shown below is mentioned.
Step 1: Using a coating machine such as a reverse roll coater or a comma coater, the condensed polycyclic aromatic cyanate compound (A), the monocyclic aromatic cyanate compound (B), and an organic solvent are formed on the electrically insulating film. The process of forming the resin insulation layer which consists of a curable composition which mix | blended.
Step 2: Heat the electrically insulating film on which the resin insulating layer is formed at 60 ° C. to 170 ° C. for 1 minute to 15 minutes using a heater, volatilize the solvent from the electric insulating film, and resin insulating layer B-stage.
Process 3: The process of thermocompression-bonding a resin insulation layer and metal foil using a heating roll etc. (crimping pressure is 20 N / cm-200 N / cm, and crimping | compression-bonding temperature is 40 to 200 degreeC is preferable).

  In addition, if sufficient adhesion performance is obtained between the resin insulating layer and the metal foil through the above three steps, the process may be finished here, but when complete adhesion performance is required, Furthermore, it is preferable that the resin insulating layer is post-cured for 1 to 24 hours at 100 to 200 ° C. The thickness of the resin insulation layer after finally curing is preferably in the range of 5 μm to 100 μm.

-Build-up board | substrate As a method of obtaining a build-up board | substrate from the said curable composition, the method manufactured from three processes shown below is mentioned.
Step 1: The above curable composition containing rubber, filler, etc., as appropriate is applied to a circuit board on which a circuit is formed using a spray coating method, a curtain coating method, etc., and then cured to be curable on the circuit board. Forming a resin insulation layer comprising the composition;
Step 2: A step of drilling a predetermined through-hole portion and the like on the circuit board and surface treatment as necessary to form irregularities, and then plating a metal such as copper.
Process 3: The process of repeating the said operation sequentially as needed, and building up and forming a resin insulating layer and a metal plating conductive layer alternately.

  In addition, the build-up board | substrate of this invention is thermocompression-bonding at 170 to 250 degreeC on the wiring board which formed the circuit the copper foil with resin which semi-hardened the said curable composition on copper foil. It is also possible to produce.

・ Build-up film
Examples of a method for obtaining a buildup substrate from the curable composition include a method of applying the curable composition on a support film.

  When manufacturing the build-up film, the support film is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and simultaneously with the lamination to the circuit board, via holes or through holes existing in the circuit board. It is important to flow to a place where the resin can be filled, and it is preferable to blend the above-described components so as to exhibit such characteristics.

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

  Specifically, the adhesive film described above is prepared by preparing the varnish-like curable composition, coating the surface of the support film with the varnish-like composition, and further heating or blowing hot air, etc. It can manufacture by drying a solvent and forming the resin insulating layer which consists of a curable composition on a support film.

  The thickness of the resin insulating layer to be formed is usually equal to or greater 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 μm to 70 μm, the thickness of the composition layer is preferably 10 μm to 100 μm.

  In addition, the resin insulating layer in this invention may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust from adhering to the surface of the composition layer and scratches.

  The above support film and protective film are made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes referred to as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Although the thickness of a support film is not specifically limited, Usually, it is 10 micrometers-150 micrometers, Preferably it is used in the range of 25 micrometers-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1 micrometer-40 micrometers.

  The support film is peeled off after being laminated on the circuit board or after the insulating layer is formed by heat curing. If the support film is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

-Multilayer printed wiring board In addition, a multilayer printed wiring board can also be manufactured using the film obtained as mentioned above. For example, when the resin insulating layer is protected with a protective film, the method for producing such a multilayer printed wiring board is to remove these, and then directly attach the resin insulating layer to the circuit board on one or both sides of the circuit board. For example, lamination is performed by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

The lamination conditions are preferably 70 ° C. to 140 ° C. The bonding temperature (lamination temperature), the crimping pressure preferably set to ^{9.8 × 10 4 Pa~107.9 × 10 4} Pa, vacuum following 26.7hPa air pressure Laminating below is preferred.

・ Fiber reinforced composite material As a method for producing a fiber reinforced composite material (a sheet-like intermediate material in which the curable composition is impregnated in the reinforced fiber) from the curable composition, each component constituting the curable composition is uniformly used. The varnish is prepared by mixing, and then impregnated into a reinforcing substrate made of reinforcing fibers, and then subjected to a polymerization reaction.

  Specifically, the curing temperature at the time of performing the polymerization reaction is preferably in the temperature range of 50 ° C. to 250 ° C., and in particular, after curing at 50 ° C. to 100 ° C. to obtain a tack-free cured product. Furthermore, it is preferable to perform the treatment under a temperature condition of 120 ° C to 200 ° C.

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

-Molded product As a method of obtaining a molded product (one obtained by curing a sheet-like member in which the composition is impregnated with reinforcing fibers) from the curable composition of the present invention, the fiber-reinforced composite material is cut into a predetermined size, and then a predetermined size is obtained. A method of curing the curable composition while applying heat and pressure to the laminate obtained by laminating the number of sheets can be used.

  Methods for heat-curing the curable composition while applying heat and pressure include a press molding method, an autoclave molding method, a bagging molding method, a wrapping tape method, and an internal pressure molding method.

  For example, as a method of forming a plate-shaped molded article, a sheet-like fiber reinforced composite material is cut into a predetermined size and then laminated on a rigid tool in a predetermined fiber axis direction. Next, the fiber reinforced composite material is sealed with a flexible film, and the space between the rigid tool and the flexible film is sucked with a vacuum pump and degassed, then placed in an autoclave, heated and pressurized to form. Goods can be obtained.

  Here, as the material of the rigid tool, various existing materials such as metals such as steel and aluminum, fiber reinforced plastic (FRP), wood, and plaster are used. Nylon, fluorine resin, silicone resin, or the like is used as the material for the flexible film.

  As temperature which shape | molds a molded article, it is normally adjusted in the temperature range of 80 to 220 degreeC. More preferably, it is a temperature range of 50 ° C. to 250 ° C., and in particular, after pre-curing at 50 ° C. to 100 ° C. to form a tack-free cured product, it is further treated at a temperature condition of 120 ° C. to 200 ° C. It is preferable. If the molding temperature is too low, sufficient rapid curability may not be obtained. Conversely, if the molding temperature is too high, warping due to thermal strain may be likely to occur.

  Moreover, as a pressure which shape | molds a molded article, although it changes with the thickness, volume content rate, etc. of a prepreg, it is normally adjusted in the pressure range of 9.8 Pa-980 Pa. If the molding pressure is too low, heat may not be sufficiently transmitted to the inside of the fiber reinforced composite material, resulting in local uncuring or warping. On the other hand, if it is too high, the resin may flow out to the surroundings before it is cured, and an unimpregnated portion may be generated in the molded product, or the target volume content may not be obtained.

  Other methods for obtaining a molded product from the curable composition of the present invention include a hand lay-up method, a spray-up method, a male type and a female type in which a fiber aggregate is laid on a mold and multiple varnishes are laminated. Vacuum bags that are molded in a vacuum (reduced pressure) after being sealed with a flexible mold capable of applying pressure to the molded product. The varnish is impregnated with the varnish by the SMC press method in which the varnish containing the reinforcing fiber is formed into a sheet in a mold, or the RTM method in which the varnish is injected into a mating die in which the fibers are laid. For example, there is a method of producing a prepreg that has been prepared and baking it in a large autoclave. In addition, the molded article obtained above is a molded article having reinforcing fibers and a cured product of the curable composition. Specifically, the volume content of the reinforcing fibers in the molded article is 40% to 85%. %, Preferably in the range of 50% to 70% from the viewpoint of strength.

-Hardened | cured material As a method of manufacturing hardened | cured material from the said curable composition, it can manufacture by complying with the hardening method of a general curable composition. For example, the heating temperature condition may be appropriately selected depending on the type and application of the curing agent to be combined.

  The cured product thus obtained is excellent in heat resistance, dielectric properties, low expansion coefficient, and adhesion as described above, and can be used for various electronic materials.

  Accordingly, the curable composition containing the condensed polycyclic aromatic cyanate ester compound (A) and the monocyclic aromatic cyanate ester compound (B) has excellent heat resistance, dielectric properties, and low expansion in the cured product. It can exhibit efficiency and adhesion, and can be used as a state-of-the-art electronic material.

  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 MS spectrum and IR spectrum were measured under the following conditions.

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

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

[Synthesis Example 1] Synthesis of Condensed Polycyclic Aromatic Cyanate Compound (A) While flowing nitrogen gas through a four-necked flask equipped with a dropping funnel, thermometer, stirring device, heating device, and cooling reflux tube, bromide 106 g (1.0 mol) of cyanide and 80.0 g (0.5 mol) of 2,7-dihydroxynaphthalene were charged and dissolved in 1000 g of acetone, and then cooled to -3 ° C. Next, 111 g (1.1 mol) of triethylamine was charged into the dropping funnel and added dropwise at a rate such that the temperature inside the flask did not exceed 10 ° C. while stirring. After completion of the dropwise addition, the mixture was stirred for 2 hours at a temperature of 10 ° C. or lower, and the resulting precipitate was removed by filtration. Then, acetone was removed, 1000 g of methylene chloride was added, and the reaction product was obtained by washing with water. Next, the obtained reaction product was subjected to IR spectrum measurement and MS spectrum measurement. As a result, although absorption of 2260 cm ⁻¹ (cyanate group) could be observed in the obtained IR spectrum, absorption derived from a hydroxyl group could not be observed. In the obtained mass spectrum, a peak of M ⁺ = 210 could be observed. From the above results, it was confirmed that the condensed polycyclic aromatic cyanate compound (A-1) could be synthesized.

Synthesis Example 2 Synthesis of Condensed Polycyclic Aromatic Cyanate Compound (A) 80.0 g (0.5 mol) of 2,7-dihydroxynaphthalene of Synthesis Example 1 was converted to 80.0 g of 1,6-dihydroxynaphthalene (0 The reaction product was obtained in the same manner as in Synthesis Example 1 except that the amount was changed to 5 mol). Next, the obtained reaction product was subjected to IR spectrum measurement and MS spectrum measurement. As a result, although absorption of 2260 cm ⁻¹ (cyanato group) could be observed in the obtained IR spectrum, absorption derived from a hydroxyl group could not be observed. In the obtained mass spectrum, a peak of M ⁺ = 210 could be observed. From the above results, it was confirmed that the reaction product was a condensed polycyclic aromatic cyanate compound (A-2).

[Example 1 to Comparative Example 2] Preparation of curable composition and cured product Next, as shown in Table 1, condensed polycyclic aromatic cyanate compound (A), monocyclic aromatic cyanate compound ( B), bismaleimide (C), epoxy resin (D), curing accelerator (E), aluminum hydroxide (F), and fused silica (G) were respectively adjusted to cure Examples 1 to Comparative Example 2. Sex composition was obtained. For each symbol shown in Table 1, the following compounds or resins are shown.
(1) Condensed polycyclic aromatic cyanate compound (A)
A-1: Cyanate ester compound obtained in Synthesis Example 1 A-2: Cyanate ester compound obtained in Synthesis Example 2 (2) Monocyclic aromatic cyanate ester compound (B)
B-1: 2,2-bis (4-cyanatophenyl) propane
B-2: 1,1-bis (4-cyanatophenyl) ethane manufactured by Tokyo Chemical Industry Co., Ltd.
“LECy” manufactured by Lonza
(3) Bismaleimide (C)
C-1: 4,4′-diphenylmethane bismaleimide
“BMI-1000” manufactured by Daiwa Kasei Kogyo Co., Ltd.
(4) Epoxy resin (D)
D-1: Bisphenol A type epoxy resin
“850-S” manufactured by DIC Corporation
D-2: Naphthalene type epoxy resin
“HP-6000” manufactured by DIC Corporation
(5) Curing accelerator (E)
E-1: Dimethylbenzylamine E-2: Tetraphenylphosphonium tetra (methylphenyl) borate
“TPP-MK” manufactured by Hokuko Chemical Co., Ltd.
(6) Aluminum hydroxide (F)
F-1: Aluminum hydroxide
“CL303” manufactured by Sumitomo Chemical Co., Ltd.
(7) Fused silica (G)
G-1: Fused silica
“FB3SDC” manufactured by Denki Kagaku Kogyo Co., Ltd.

  Next, the curable composition obtained above was molded at a temperature of 200 ° C. for 10 minutes using a press machine, and then heated at a temperature of 200 ° C. for 5 hours to obtain a cured product having a thickness of 0.8 mm. Obtained. About the obtained hardened | cured material, the glass transition temperature, thermal expansibility, dielectric loss tangent, thermal decomposition resistance, and thermal conductivity were measured. The measurement methods for the above measurements are shown below, and the results are shown in Table 1.

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

<Thermal expansion>
The cured product was cut into a size of 0.8 mm in thickness, 5 mm in width, and 5 mm in length, and this was used as test piece 2. The test piece 2 was measured for an expansion coefficient in the range of 40 ° C. to 60 ° C. using a thermomechanical analyzer (manufactured by SII Nano Technology Inc., TMA / SS 6100, heating rate: 3 ° C./min).

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

<Heat-resistant decomposition>
Using a differential thermal-thermogravimetric simultaneous measurement device ("TGA / DSC1" manufactured by METTLER TOLEDO), a test piece cut into a mass of 6 mg was held at 150 ° C for 15 minutes, and then under nitrogen gas flow conditions The temperature was raised at 5 ° C. per minute, and the temperature when 5% of the mass decreased was measured.

<Thermal conductivity>
The thermal conductivity of the test piece 1 was measured by the unsteady hot wire method using a thermal conductivity meter (QTM-500 manufactured by Kyoto Electronics Co., Ltd.).

<Adhesion>
The measurement of adhesion was performed by measuring peel strength in accordance with JIS-C6481. The results are shown in Table 1. In addition, the hardened | cured material used for the measurement of adhesiveness puts 18 micrometers copper foil (Nikko Metal Co., Ltd. TCR foil) under the curable composition obtained in Example 1-Comparative Example 2, and presses a press machine. A cured product (thickness: 0.8 mm) obtained by molding at a temperature of 200 ° C. for 10 minutes and then applying a temperature of 200 ° C. for 5 hours was used.

Claims (19)

One or more condensed polycyclic aromatic cyanate compounds (A) selected from the group consisting of compounds represented by the following structural formula (A1) and the following structural formula (A2), and a cyanate group on the aromatic nucleus A curable composition having a monocyclic aromatic cyanate ester compound (B) in which a plurality of monocyclic compounds are bonded directly or via a linking group.

[However, in the structural formula (A1) and the structural formula (A2),
R ¹ each independently represents a monovalent substituent other than a cyanato group, j represents an integer of 1 to 3, k represents an integer of 0 to 2j + 4, l represents an integer of 0 to 5, m shows the integer of 0-2, n shows the integer of 0-6 each independently. ] Each R ¹ is independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an aryl group, an aralkyl group, a halogen atom, or a carbon atom; One or more hydrogen atoms contained in a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, or an aralkyl group are substituted with either a hydroxyl group or a halogen atom. The curable composition according to claim 1, which is any one of them. The monocyclic aromatic cyanate ester compound (B) is one or more monocyclic aromatic cyanate esters selected from the group consisting of compounds represented by the following structural formula (B1) and the following structural formula (B2) The curable composition according to claim 1.

[However, in the structural formula (B1) and the structural formula (B2),
L represents a divalent linking group, and each R ² independently represents a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, an aryl group, or aralkyl. 1 or more hydrogen atoms contained in a group, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group, or an aralkyl group, Any one of the structures substituted by each is shown, and p independently represents an integer of 0 to 4. ]   L is a divalent hydrocarbon group, a divalent group in which one or more hydrogen atoms contained in the divalent hydrocarbon group are substituted with a hydroxyl group, an alkoxy group, or a halogen atom, a divalent heteroatom, or The curable composition according to claim 3, which is any one of divalent atomic groups containing a hetero atom.   The condensed polycyclic aromatic cyanate ester compound (A) and the monocyclic aromatic cyanate ester compound (B) are mixed with the monocyclic aromatic cyanate ester compound (A) per 1 part by mass of the monocyclic aromatic cyanate ester compound (A). The curable composition of Claim 1 which contains a cyclic | annular aromatic cyanate ester compound (B) in the ratio of 0.1-5 mass parts.   The curable composition according to claim 1, further comprising a bismaleimide (C) in addition to the condensed polycyclic aromatic cyanate compound (A) and the monocyclic aromatic cyanate compound (B).   The condensed polycyclic aromatic cyanate ester compound (A), the monocyclic aromatic cyanate ester (B) and the bismaleimide (C) are 1 part by mass of the condensed polycyclic aromatic cyanate ester (A). The curability according to claim 6, comprising 0.1 to 5 parts by mass of the monocyclic aromatic cyanate ester compound (B) and 0.1 to 5 parts by mass of the bismaleimide (C). Composition.   The curable composition according to claim 1, further comprising an epoxy resin (D) in addition to the condensed polycyclic aromatic cyanate compound (A) and the monocyclic aromatic cyanate compound (B).   The condensed polycyclic aromatic cyanate ester compound (A), the monocyclic aromatic cyanate ester compound (B), and the epoxy resin (D) are converted into the condensed polycyclic aromatic cyanate ester compound (A) 1. The said monocyclic aromatic cyanate ester compound (B) is 0.1-5 mass parts with respect to a mass part, The said epoxy resin (D) is included in the ratio of 0.1-5 mass parts of Claim 8. Curable composition.   Hardened | cured material obtained by hardening the curable composition as described in any one of Claims 1-9.   The semiconductor sealing material containing the curable composition as described in any one of Claims 1-9, and an inorganic filler.   A semiconductor device obtained by heat-curing the semiconductor sealing material according to claim 11.   A prepreg obtained by impregnating a reinforcing substrate with the curable composition according to any one of claims 1 to 9 diluted in an organic solvent and semi-curing the resulting impregnated substrate.   A printed circuit board obtained by laminating a prepreg according to claim 13 in a plate shape with a copper foil and molding by heating and pressing.   The curable composition according to any one of claims 1 to 9, obtained by blending an organic solvent with an electrically insulating film, and then integrating the electrically insulating film and a metal foil. Flexible wiring board   The buildup film obtained by apply | coating what dried the curable composition as described in any one of Claims 1-9 in the organic solvent on a base film, and making it dry.   A build-up film obtained by applying the build-up film according to claim 16 to a circuit board on which a circuit is formed, heat-curing the circuit board to form irregularities, and then plating the circuit board. substrate.   The fiber reinforced composite material containing the curable composition as described in any one of Claims 1-9, and a reinforced fiber.   A molded product obtained by curing the fiber-reinforced composite material according to claim 18.