CN111936526B

CN111936526B - Curable composition and cured product thereof

Info

Publication number: CN111936526B
Application number: CN201980023247.6A
Authority: CN
Inventors: 矢本和久; 佐藤泰; 林弘司
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2018-03-29
Filing date: 2019-03-14
Publication date: 2022-09-30
Anticipated expiration: 2039-03-14
Also published as: CN111936526A; WO2019188331A1; JP6955232B2; JPWO2019188331A1; KR20200128092A; TWI783133B; TW201942166A; KR102388192B1

Abstract

Provided are a curable composition which gives a cured product having excellent heat resistance and dielectric properties, a cured product of the curable composition, and a printed circuit board, a semiconductor sealing material, and a multilayer film each using the curable composition. Specifically disclosed are a curable composition containing an aromatic ester compound (A) having a polymerizable unsaturated bond and a poly (arylene ether) resin (B), a cured product of the curable composition, and a printed circuit board, a semiconductor sealing material and a multilayer film each using the curable composition.

Description

Curable composition and cured product thereof

Technical Field

The present invention relates to a curable composition having a cured product excellent in heat resistance and dielectric properties, a cured product of the curable composition, and a printed circuit board, a semiconductor sealing material, and a multilayer film each using the curable composition.

Background

In recent years, electronic devices have been reduced in size and improved in performance, and the performance of various materials used for the devices has been required to be improved. For example, signals are being increased in speed and frequency for semiconductor package substrates, and materials with low power loss, that is, materials with low dielectric loss tangent are being demanded.

As such a material having a low dielectric loss tangent, for example, an invention is provided which relates to a resin composition containing (a) an epoxy resin, (B) an active ester compound, (C) a scum inhibiting component, and (D) an inorganic filler (for example, see patent document 1). In this case, the active ester compound (B), the scum inhibiting component (C), and the inorganic filler (D) are each contained at a predetermined ratio, and the scum inhibiting component (C) is rubber particles, when the nonvolatile content of the resin composition is 100 mass%.

Patent document 1 describes that a cured product of the resin composition can achieve a low dielectric loss tangent. Further, it is described that smear (resin residue) in the through hole after roughening treatment by drilling the cured product can be suppressed.

It is described that the active ester compound (B) described in patent document 1 is a compound having 1 or more active ester groups in 1 molecule, and lowers the dielectric loss tangent of the cured product of the resin composition.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2016-156019

Disclosure of Invention

Problems to be solved by the invention

Patent document 1 describes that the dielectric loss tangent of the resulting cured product can be reduced by using an active ester compound. However, it is clear that such a cured product may not necessarily have sufficient heat resistance.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems. As a result, they have found that a curable composition containing an aromatic ester compound having a polymerizable unsaturated bond in the molecular structure and a poly (arylene ether) resin is particularly excellent in heat resistance and dielectric characteristics of a cured product, and have completed the present invention.

That is, the present invention provides a curable composition containing an aromatic ester compound (a) having a polymerizable unsaturated bond and a poly (arylene ether) resin (B), a cured product thereof, and a printed circuit board, a semiconductor sealing material, and a multilayer film using the curable composition.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a curable composition which gives a cured product having excellent heat resistance and dielectric characteristics, a cured product of the curable composition, and a printed circuit board, a semiconductor sealing material, and a multilayer film each using the curable composition can be provided.

Detailed Description

Hereinafter, embodiments for carrying out the present invention will be described in detail.

The aromatic ester compound (a) containing a polymerizable unsaturated bond used in the present invention is not particularly limited in terms of other specific structure, molecular weight, and the like, and various compounds can be used as long as it is an aromatic ester compound having one or more polymerizable unsaturated bonds in the molecular structure and having a structural site in which aromatic rings are bonded to each other via an ester bond.

Specific examples of the polymerizable unsaturated bond-containing aromatic ester compound (A) include a polymerizable unsaturated bond-containing aromatic ester compound (A-1) represented by the following chemical formula (1), a polymerizable unsaturated bond-containing aromatic ester compound (A-2), and the like.

(in the above chemical formula (1), Ar ¹ Is a substituted or unsubstituted 1 st aromatic ring radical, Ar ² Each independently is a substituted or unsubstituted 2 nd aromatic ring group, in which case Ar is as defined above ¹ And Ar mentioned above ² At least 1 of them has a substituent containing a polymerizable unsaturated bond, and n is 2Or an integer of 3. )

The aromatic ester compound (A-2) having a polymerizable unsaturated bond is a reaction product of: a1 st aromatic compound having 2 or more phenolic hydroxyl groups; a 2 nd aromatic compound having a phenolic hydroxyl group; and a 3 rd aromatic compound having 2 or more carboxyl groups and/or an acid halide or an ester thereof. At least 1 of the 1 st aromatic compound, the 2 nd aromatic compound, and the 3 rd aromatic compound and/or the acid halide or ester thereof has a substituent having a polymerizable unsaturated bond.

The aromatic ester compound (a) containing a polymerizable unsaturated bond is preferably a liquid at room temperature (25 ℃) or has a softening point in the range of 40 to 200 ℃ from the viewpoint of more excellent balance between handling properties in preparing a curable composition described later, heat resistance of a cured product thereof, and dielectric characteristics.

Ar in the chemical formula (1) is Ar in the polymerizable unsaturated bond-containing aromatic ester compound (A-1) ¹ Is a substituted or unsubstituted 1 st aromatic cyclic group. As described later, since n in formula (1) is an integer of 2 or 3, 2 or 3 of the hydrogen atoms of the aromatic ring constituting the 1 st aromatic ring group are replaced with "-C (O) OAr ² ”。

The 1 st aromatic ring group is not particularly limited, and examples thereof include those obtained by removing 2 or 3 hydrogen atoms from a monocyclic aromatic compound such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, or triazine; 2 or 3 hydrogen atoms are removed from an aromatic compound, such as a fused aromatic compound obtained by removing 2 or 3 hydrogen atoms from naphthalene, anthracene, Phenalene (Phenalene), phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, or acridine. In addition, a plurality of these aromatic compounds may be combined, and examples thereof include compounds obtained by removing 2 or 3 hydrogen atoms from a ring-assembly aromatic compound such as biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, tetraphenyl, and the like; and those obtained by removing 2 or 3 hydrogen atoms from an aromatic compound linked via an alkylene group, such as diphenylmethane, diphenylethane, 1-diphenylethane, 2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fluorene, diphenylcyclopentane, and the like.

Among them, Ar is Ar for obtaining a cured product having more excellent dielectric characteristics ¹ Preferred are substituted or unsubstituted benzene rings or naphthalene rings, and more preferred are substituted or unsubstituted benzene rings.

Ar ¹ The 1 st aromatic ring group may have a substituent. In this case, the "substituent for the 1 st aromatic ring group" means a group in which at least 1 of the hydrogen atoms in the aromatic ring constituting the 1 st aromatic ring group is substituted. Specific examples of the substituent of the 1 st aromatic ring group are not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a halogen atom and the like.

The alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a1, 2-dimethylpropyl group, a n-hexyl group, an isohexyl group, and a cyclohexyl group.

The alkoxy group is not particularly limited, and examples thereof include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, and the like.

The alkoxycarbonyl group is not particularly limited, and includes a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, and the like.

The alkylcarbonyloxy group is not particularly limited, and examples thereof include methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, butylcarbonyloxy group, n-butylcarbonyloxy group, isobutylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

In one embodiment of the present invention, Ar ¹ May have a substituent having a polymerizable unsaturated bond. Specific examples of the substituent having a polymerizable unsaturated bond include an alkenyl group and an alkynyl group.

The alkenyl group is not particularly limited, and there may be mentioned vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-octenyl, 2-octenyl, 1-undecenyl, 1-pentadecenyl, 3-pentadecenyl, 7-pentadecenyl, 1-octadecenyl, 2-octadecenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, 1, 3-butadienyl, 1, 4-butadienyl, 1, 3-hexadienyl, 2, 5-hexadienyl, 4, 7-pentadecadienyl, 1,3, 5-hexanetrienyl, 1,4, 7-pentadecatrienoyl, and the like.

The alkynyl group is not particularly limited, and examples thereof include ethynyl, propynyl, 1-butynyl, 2-butynyl, 3-pentynyl, 4-pentynyl, and 1, 3-butadiynyl.

The substituent having a polymerizable unsaturated bond may have a substituent. In this case, the "substituent containing a polymerizable unsaturated bond" is a group substituting at least 1 of hydrogen atoms constituting the substituent containing a polymerizable unsaturated bond. Specific examples of the substituent having a polymerizable unsaturated bond include an alkoxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom. In this case, there may be mentioned the above-mentioned examples as the alkoxycarbonyl group, alkylcarbonyloxy group and halogen atom.

Among these, the substituent containing the polymerizable unsaturated bond is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, more preferably a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, still more preferably a substituted or unsubstituted alkenyl group having 2 to 5 carbon atoms, and particularly preferably a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a1, 3-butadienyl group, and most preferably an allyl group, a propenyl group, an isopropenyl group, or a 1-propenyl group.

As Ar ¹ Preferable examples of the structure of (B) include the following formulas (2-1) to (2-17).

In this case, in the above formulae (2-1) to (2-17), "" represents a symbol "and" -C (O) OAr ² "bonding position". It should be noted that "-" may be bonded to any position of the aromatic ring.

Among these, preferred are the formulae (2-1) to (2-11), more preferred are the formulae (2-1), (2-2), (2-6), (2-7) and (2-9), and still more preferred are the formulae (2-1), (2-2), (2-6) and (2-7). Further, (2-1) and (2-2) are preferable from the viewpoint of high processability and low viscosity of the aromatic ester compound (A-1), and (2-6) and (2-7) are preferable from the viewpoint of better heat resistance and excellent balance between low dielectric characteristics of the resulting cured product.

At least 1 of the hydrogen atoms of the aromatic rings of the formulae (2-1) to (2-17) may be substituted with an unsaturated bond-containing group.

Ar ² Each independently is a substituted or unsubstituted 2 nd aromatic ring group. As is clear from the description of the above chemical formula (1), 1 of the hydrogen atoms of the aromatic ring constituting the 2 nd aromatic ring group is substituted by-OC (O) Ar ¹ ”。

The 2 nd aromatic ring group is not particularly limited, and examples thereof include those obtained by removing 1 hydrogen atom from a monocyclic aromatic compound such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine; and (2) a compound obtained by removing 1 hydrogen atom from an aromatic compound, such as a fused aromatic compound obtained by removing 1 hydrogen atom from naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, or acridine. In addition, a plurality of these aromatic compounds may be combined, and examples thereof include compounds obtained by removing 1 hydrogen atom from a ring-assembly aromatic compound such as biphenyl, binaphthyl, bipyridyl, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, and the like; and those obtained by removing 1 hydrogen atom from an aromatic compound linked by an alkylene group such as diphenylmethane, diphenylethane, 1-diphenylethane, 2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fluorene, diphenylcyclopentane, etc.

Among them, Ar is Ar for obtaining a cured product having more excellent dielectric characteristics ² Preferably a substituted or unsubstituted benzene or naphthalene ring. In addition, the aromatic ester compound (a) is preferably a benzene ring from the viewpoint of high processability and low viscosity, and is preferably a naphthalene ring from the viewpoint of better heat resistance of the resulting cured product and excellent balance between low dielectric characteristics.

Ar ² The 2 nd aromatic ring group may have a substituent. In this case, the "substituent for the 2 nd aromatic ring group" is a group that substitutes at least 1 of hydrogen atoms in the aromatic ring constituting the 2 nd aromatic ring group. Specific examples of the substituent of the 2 nd aromatic ring group are not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a halogen atom and the like. In this case, examples of the alkyl group, alkoxy group, alkoxycarbonyl group, alkylcarbonyloxy group and halogen atom are mentioned above.

In one embodiment of the present invention, Ar ² May have the unsaturated bond-containing substituent described above. In this case, the unsaturated bond-containing substituent may be present alone or in combination of 2 or more.

As Ar ² Preferable examples of the structure of (B) include the following formulas (3-1) to (3-17).

In this case, "+" indicates the presence of "-OC (O) Ar" in the above formulas (3-1) to (3-17) ¹ "bonding position". It should be noted that "-" mayTo bond to any position of the aromatic ring.

Among these, the formulae (3-1) to (3-11) are preferable, the formulae (3-1), (3-6) and (3-9) are more preferable, and the formulae (3-1) and (3-6) are still more preferable.

At least 1 of the hydrogen atoms of the aromatic rings of the formulae (3-1) to (3-17) may be substituted with an unsaturated bond-containing group.

According to an embodiment, Ar is more preferred ¹ Is represented by the above formula (2-1), (2-2), (2-6), (2-7), (2-9), Ar ² Is represented by the above formula (3-1), (3-6) or (3-9); further preferred is Ar ¹ Is represented by the above formula (2-1), (2-2), (2-6), (2-7), Ar ² The above-mentioned formulas (3-1) and (3-6); particularly preferably Ar ¹ Is represented by the formula (2-1), Ar ² The above-mentioned formulae (3-1) and (3-6).

In the above chemical formula (1), Ar is ¹ And Ar ² At least 1 of them has a substituent having a polymerizable unsaturated bond. That is, only Ar may be used ¹ Having a substituent containing a polymerizable unsaturated bond, may be Ar alone ² Having a substituent containing a polymerizable unsaturated bond, and may be Ar ¹ And Ar ² Each having a substituent having a polymerizable unsaturated bond.

According to an embodiment, Ar is preferred ² At least 1 of them has a substituent having a polymerizable unsaturated bond, and more preferably all Ar ² Has a substituent having a polymerizable unsaturated bond, and is more preferably Ar ¹ Having no substituent containing polymerizable unsaturated bond and all Ar ² Has a substituent having a polymerizable unsaturated bond. If Ar is present ² The presence of a substituent containing a polymerizable unsaturated bond in (b) is preferable because the balance between heat resistance and dielectric loss tangent is excellent.

In the above chemical formula (1), n is an integer of 2 or 3. That is, the aromatic ester compound (a-1) containing a polymerizable unsaturated bond has 2 or 3 ester bonds connecting 2 aromatic rings.

From the above, as a more preferable embodiment of the polymerizable unsaturated bond-containing aromatic ester compound (A-1) represented by the chemical formula (1), a compound represented by the following chemical formula (1-1) or (1-2) can be mentioned.

[ in the formula, R ¹ Is a substituent containing a polymerizable unsaturated bond. R ² Each independently is any of an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom. h is 2 or 3, i is each independently an integer of 1 or more, j is each independently an integer of 0 or 1 or more, and i + j is an integer of 5 or less. k is 2 or 3, l is each independently an integer of 1 or more, m is each independently an integer of 0 or 1 or more, and l + m is an integer of 7 or less. i. When j, l and m are integers of 2 or more, a plurality of R ¹ Or R ² May be the same as or different from each other. R in the formula (1-2) ¹ 、R ² Substitution may be made at any carbon atom forming a naphthalene ring.]

In the above formula (1-1), as R ¹ As described above, a particularly preferable example of (a) is allyl group, propenyl group, isopropenyl group, or 1-propenyl group. i is preferably 1 or 2, more preferably 1.

In the above formula (1-2), as R ¹ As described above, a particularly preferable example of (a) is allyl group, propenyl group, isopropenyl group, or 1-propenyl group. l is preferably 1 or 2, more preferably 1.

Specific structures of the polymerizable unsaturated bond-containing aromatic ester compound (a-1) represented by the above chemical formula (1) are not particularly limited, and compounds represented by the following chemical formulas (4-1) to (4-43) can be mentioned.

Of the above-mentioned chemical formulas (4-1) to (4-43), the chemical formulas (4-1) to (4-39) are preferable, the chemical formulas (4-1) to (4-3), (4-10) to (4-13) and (4-18) to (4-39) are more preferable, the chemical formulas (4-1) to (4-3), (4-12), (4-13), (4-19) to (4-21), (4-23) to (4-26), (4-29), (4-30) and (4-32) to (4-39) are further preferable, and the chemical formulas (4-1), (4-2), (4-12), (4-13), (4-26) and (4-32) are particularly preferable, (4-37).

Further, (4-1), (4-2), (4-12) and (4-13) are preferable from the viewpoint of high processability and low viscosity of the aromatic ester compound (a), and (4-26), (4-32) and (4-37) are preferable from the viewpoint of better heat resistance and excellent balance between low dielectric characteristics of the resulting cured product.

The method for producing the polymerizable unsaturated bond-containing aromatic ester compound (a-1) is not particularly limited, and can be produced by a known method.

In one embodiment, a method for producing the aromatic ester compound (a-1) containing a polymerizable unsaturated bond includes: a step of reacting a polycarboxylic acid compound having a substituted or unsubstituted 1 st aromatic ring group or a derivative thereof with a phenol compound having a substituted or unsubstituted 2 nd aromatic ring group.

In this case, at least 1 of the polycarboxylic acid compound or the derivative thereof and the phenol compound has a substituted or unsubstituted substituent containing a polymerizable unsaturated bond.

(polycarboxylic acid compound or derivative thereof)

The polycarboxylic acid compound or a derivative thereof has a substituted or unsubstituted aromatic ring group, and the number of carbon atoms is preferably in the range of 3 to 30. In this case, examples of the "derivative of the polycarboxylic acid compound" include an acid halide of a carboxylic acid.

The substituents for the 1 st aromatic ring group and the 1 st aromatic ring group are the same as those described above.

Specific examples of the polycarboxylic acid compound or its derivative include compounds represented by the following chemical formulas (5-1) to (5-15).

In the above chemical formulas (5-1) to (5-15), R ¹ Is hydroxyl and halogen atom. In addition, R ² Is a substituent containing a polymerizable unsaturated bond. In this case, the substituent containing the polymerizable unsaturated bond is the same as in the above case. Further, p is 2 or 3. Q is an integer of 0 or 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, and further preferably 0. For example, in the above chemical formula (5-7), R is represented by the same aromatic ring for convenience, but the position of the substituent on the aromatic ring is shown on the same aromatic ring ¹ OC、R ² The substitution may be carried out on different benzene rings, and the number of substituents in 1 molecule is represented by p and q.

Specific polycarboxylic acid compounds or derivatives thereof are not particularly limited, and include benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, and 2-allylterephthalic acid; benzene tricarboxylic acids such as trimellitic acid and 5-allyl trimellitic acid; naphthalenedicarboxylic acids such as naphthalene-1, 5-dicarboxylic acid, naphthalene-2, 3-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid, naphthalene-2, 7-dicarboxylic acid, 3-allylnaphthalene-1, 4-dicarboxylic acid, and 3, 7-diallylnaphthalene-1, 4-dicarboxylic acid; pyridine tricarboxylic acids such as 2,4, 5-pyridine tricarboxylic acid; triazine carboxylic acids such as 1,3, 5-triazine-2, 4, 6-tricarboxylic acid; acid halides thereof, and the like. Among these, benzene dicarboxylic acid and benzene tricarboxylic acid are preferable, isophthalic acid, terephthalic acid, isophthaloyl chloride, terephthaloyl chloride, 1,3, 5-benzenetricarboxylic acid, and 1,3, 5-benzenetricarbonyl trichloride are more preferable, and isophthaloyl chloride, terephthaloyl chloride, and 1,3, 5-benzenetricarbonyl trichloride are still more preferable.

The polycarboxylic acid compounds or derivatives thereof may be used alone or in combination of 2 or more.

(phenol Compound)

The phenol compound has a substituted or unsubstituted aromatic ring group, and preferably has 3 to 30 carbon atoms. In this case, the substituents for the 2 nd aromatic ring group and the 2 nd aromatic ring group are the same as those described above.

Specific examples of the phenol compound include compounds represented by the following chemical formulas (6-1) to (6-17).

In the above chemical formulas (6-1) to (6-17), R ² Is a substituent containing a polymerizable unsaturated bond. In this case, the substituent containing the polymerizable unsaturated bond is the same as in the above case. Further, q is an integer of 0 or 1 or more, preferably 1 to 3, more preferably 1 or 2, and further preferably 1. When q is 2 or more, the bonding position on the aromatic ring is arbitrary, and for example, it is shown that the naphthalene ring of the chemical formula (6-6) or the heterocyclic ring of the chemical formula (6-17) may be substituted on an arbitrary ring, and that the benzene ring present in 1 molecule may be substituted on an arbitrary ring in the chemical formula (6-9) or the like, and that the number of substituents in 1 molecule is q.

Specific examples of the phenol compound include, but are not particularly limited to, phenol; naphthol; allylphenols such as 2-allylphenol, 3-allylphenol, 4-methyl-2-allylphenol, 6-methyl-2-allylphenol, and eugenol; propenyl phenols such as 2- (1-propenyl) phenol and isoeugenol; butenyl phenols such as 2- (3-butenyl) phenol and 2- (1-ethyl-3-butenyl) phenol; cardanol and other long alkenyl phenols; allylnaphthols such as 2-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-1-naphthol, and 3-allyl-1-naphthol. Among these, allyl phenol and allyl naphthol are preferable, 2-allyl phenol, 4-methyl-2-allyl phenol, 6-methyl-2-allyl phenol, 2-allyl-1-naphthol, and 1-allyl-2-naphthol are more preferable, and 2-allyl phenol, 2-allyl-1-naphthol, and 1-allyl-2-naphthol are even more preferable.

In addition, from the viewpoint of high processability and low viscosity of the aromatic ester compound (a), 2-allylphenol having a benzene ring skeleton is preferable, and from the viewpoint of better heat resistance of the resulting cured product and excellent balance between low dielectric characteristics, 2-allyl-1-naphthol, 1-allyl-2-naphthol, and the like having a naphthalene ring skeleton are preferable.

The above phenol compounds may be used alone, or 2 or more thereof may be used in combination.

The amount of the polycarboxylic acid compound or derivative thereof and the phenol compound to be used is not particularly limited, but the molar ratio of the number of moles of a derivative group such as a carboxyl group and/or a halogenated acyl group in the polycarboxylic acid compound or derivative thereof to the number of moles of a hydroxyl group in the phenol compound [ (derivative group such as a carboxyl group and/or a halogenated acyl group)/(hydroxyl group) ] is preferably 0.8 to 3.0, more preferably 0.9 to 2.0, and still more preferably 1.0 to 1.2.

The reaction conditions are not particularly limited, and any known method can be suitably used.

The pH during the reaction is not particularly limited, but is preferably 11 or more. In this case, acids such as hydrochloric acid, sulfuric acid, nitric acid, and acetic acid; sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, and the like.

The reaction temperature is not particularly limited, and is preferably 20 to 100 ℃ and more preferably 40 to 80 ℃.

The reaction pressure is also not particularly limited, and normal pressure is more preferable.

The reaction time is also not particularly limited, but is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.

The polymerizable unsaturated bond-containing aromatic ester compound (A-2) is a reaction product of a1 st aromatic compound having 2 or more phenolic hydroxyl groups, a 2 nd aromatic compound having a phenolic hydroxyl group, and a 3 rd aromatic compound having 2 or more carboxyl groups and/or an acid halide or an ester thereof, and at least 1 of the 1 st aromatic compound, the 2 nd aromatic compound, and the 3 rd aromatic compound and/or an acid halide or an ester thereof has a polymerizable unsaturated bond-containing substituent.

[1 st aromatic Compound ]

The 1 st aromatic compound has 2 or more phenolic hydroxyl groups. Having 2 or more phenolic hydroxyl groups allows the aromatic ester compound (a-2) having a polymerizable unsaturated bond to form a polyester structure by reacting with a 3 rd aromatic compound or the like described later.

The 1 st aromatic compound is not particularly limited, and examples thereof include compounds having 2 or more phenolic hydroxyl groups on the 1 st aromatic ring having 3 to 30 carbon atoms which may be substituted or unsubstituted.

In this case, the 1 st aromatic ring having 3 to 30 carbon atoms is not particularly limited, and examples thereof include monocyclic aromatic rings, condensed ring aromatic rings, ring-aggregated aromatic rings, and the like.

The monocyclic aromatic ring is not particularly limited, and examples thereof include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine and the like.

The fused aromatic ring is not particularly limited, and examples thereof include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine.

The ring-assembled aromatic ring is not particularly limited, and examples thereof include biphenyl, binaphthyl, bipyridyl, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl.

The 1 st aromatic ring may have a substituent. In this case, the "substituent for the 1 st aromatic ring" is not particularly limited, and examples thereof include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a substituent having a polymerizable unsaturated bond, and the like.

The alkyl group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a1, 2-dimethylpropyl group, a n-hexyl group, an isohexyl group, a n-nonyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclononyl group.

The alkoxy group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group.

The substituent containing a polymerizable unsaturated bond means a substituent having 2 to 30 carbon atoms and having at least 1 polymerizable unsaturated bond. In this case, "unsaturated bond" means a carbon-carbon double bond or a carbon-carbon triple bond. Examples of the substituent having a polymerizable unsaturated bond include an alkenyl group and an alkynyl group.

The alkynyl group is not particularly limited, and examples thereof include ethynyl, propynyl, 1-butynyl, 2-butynyl, 3-pentynyl, 4-pentynyl, 1, 3-butadiynyl, and the like.

Among these, the substituent containing the polymerizable unsaturated bond is preferably an alkenyl group having 2 to 30 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, still more preferably an alkenyl group having 2 to 5 carbon atoms, particularly preferably a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, or a1, 3-butadienyl group, and most preferably an allyl group, a propenyl group, an isopropenyl group, or a 1-propenyl group.

The 1 st aromatic ring substituent may be contained alone or in combination of 2 or more.

As described above, in the 1 st aromatic compound, at least 2 of the hydrogen atoms constituting the substituted or unsubstituted 1 st aromatic ring are substituted with hydroxyl groups.

Specific examples of the compound in which the 1 st aromatic ring is a monocyclic aromatic ring (hereinafter, may be abbreviated as "the 1 st monocyclic aromatic ring compound") include catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, pyrogallol, 2, 3-dihydroxypyridine, 2, 4-dihydroxypyridine, 4, 6-dihydroxypyrimidine, 3-methylcatechol, 4-allylcatechol, and the like.

Specific examples of the compound in which the 1 st aromatic ring is a condensed ring aromatic ring (hereinafter, may be simply referred to as "1 st condensed ring aromatic ring compound") include 1, 3-naphthalenediol, 1, 5-naphthalenediol, 2, 6-naphthalenediol, 2, 7-naphthalenediol, 1,2, 4-naphthalenediol, 1,4, 5-naphthalenediol, 9, 10-dihydroxyanthracene, 1,4,9, 10-tetrahydroxyanthracene, 2, 4-dihydroxyquinoline, 2, 6-dihydroxyquinoline, 5, 6-dihydroxyindole, 2-methylnaphthalene-1, 4-diol, and the like.

Specific examples of the compound in which the 1 st aromatic ring is a ring-assembled aromatic ring (hereinafter, may be simply referred to as "the 1 st ring-assembled aromatic ring compound") include 2,2 '-dihydroxybiphenyl, 4, 4' -dihydroxybiphenyl, 3,4,4 '-trihydroxybiphenyl, 2', 3-trihydroxybiphenyl, and the like.

The 1 st aromatic compound may have a structure in which the 1 st aromatic rings are linked by a linking group. In one embodiment, the 1 st aromatic compound is represented by the following chemical formula (7).

In the above chemical formula (7), Ar ³ Each independently is a substituted or unsubstituted 1 st aromatic ring radical, Ar ⁴ Each independently is a substituted or unsubstituted 2 nd aromatic cyclic group, each X independently is an oxygen atom, a sulfur atom, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or an aralkylene group, and n is 0 to 10. At this time, the aforementioned Ar is constituted ³ And Ar mentioned above ⁴ At least 2 of the hydrogen atoms of (a) are substituted by hydroxyl groups. In addition, X corresponds to a linking group.

Ar above ³ Is a substituted or unsubstituted 1 st aromatic ring group. As is clear from the description of the above chemical formula (7), the above substitution or non-substitution is made1 of the hydrogen atoms of the aromatic ring of the substituted aromatic ring is bonded to "X".

The 1 st aromatic ring group is not particularly limited, and examples thereof include those obtained by removing 1 hydrogen atom from a monocyclic aromatic compound such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine; and (2) a compound obtained by removing 1 hydrogen atom from an aromatic compound, such as a fused aromatic compound obtained by removing 1 hydrogen atom from naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, or acridine. In addition, a plurality of these aromatic compounds may be combined, and examples thereof include those obtained by removing 1 hydrogen atom from a ring-assembled aromatic compound such as biphenyl, binaphthyl, bipyridyl, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl.

In this case, the 1 st aromatic ring group may have a substituent. Examples of the "substituent for the 1 st aromatic ring" include the same ones as those of the "substituent for the 1 st aromatic ring" described above.

Among these, Ar ³ Preferably, the compound is one obtained by removing 1 hydrogen atom from benzene, naphthalene, anthracene, phenalene, phenanthrene, biphenyl, binaphthyl, quaterphenyl, allylbenzene, diallylbenzene, allylnaphthalene, diallylnaphthalene, allylbiphenyl, and diallylbiphenyl, and more preferably, one obtained by removing 1 hydrogen atom from benzene, naphthalene, biphenyl, allylbenzene, diallylnaphthalene, and diallylbiphenyl.

Ar above ⁴ Each independently is a substituted or unsubstituted 2 nd aromatic ring group. As is clear from the description of the above chemical formula (1), 2 of the hydrogen atoms of the aromatic ring constituting the above substituted or unsubstituted aromatic ring are bonded to "X".

The 2 nd aromatic ring group is not particularly limited, and examples thereof include those obtained by removing 2 hydrogen atoms from a monocyclic aromatic compound such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine; and (2) hydrogen atoms are removed from aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine and other fused ring aromatic compounds. In addition, a plurality of these aromatic compounds may be combined, and examples thereof include compounds obtained by removing 2 hydrogen atoms from a ring-assembled aromatic compound such as biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, and the like.

In this case, the 2 nd aromatic ring group may have a substituent. Examples of the "substituent for the 2 nd aromatic ring" include the same ones as those for the "substituent for the 1 st aromatic ring" described above.

Each of the aforementioned xs is independently an oxygen atom, a sulfur atom, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or an aralkylene group.

The alkylene group is not particularly limited, and examples thereof include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a1, 1-dimethylmethylene group, a 1-methylethylene group, a1, 1-dimethylethylene group, a1, 2-dimethylethylene group, a propylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, and a hexylene group.

The cycloalkylene group is not particularly limited, and examples thereof include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and cycloalkylene groups represented by the following chemical formulae (8-1) to (8-4).

In the above chemical formulas (8-1) to (8-4), "+" represents the same as Ar ³ Or Ar ⁴ The site of bonding.

The aralkylene group is not particularly limited, and examples thereof include aralkylene groups represented by the following chemical formulae (9-1) to (9-8).

In the above chemical formulas (9-1) to (9-8), "+" represents the same as Ar ³ Or Ar ⁴ The site of bonding.

The alkylene group, the cycloalkylene group and the aralkylene group may have a substituent. In this case, examples of the "substituent for X" include the same ones as those of the "substituent for the 1 st aromatic ring".

N in the chemical formula (7) is an integer of 0 to 10, preferably 0 to 8, and preferably 0 to 5. When the compound represented by the above chemical formula (7) is an oligomer or a polymer, n represents an average value thereof.

And, the aforementioned Ar is constituted ³ And Ar mentioned above ⁴ At least 2 of the hydrogen atoms of (a) are substituted by hydroxyl groups.

Specific examples of the compound represented by the following chemical formula (7) are not particularly limited, and examples thereof include various bisphenol compounds, compounds represented by the following chemical formulas (10-1) to (10-8), and compounds having one or more substituents containing a polymerizable unsaturated bond on the aromatic nucleus thereof.

Examples of the various bisphenol compounds include bisphenol a, bisphenol AP, bisphenol B, bisphenol E, bisphenol F, bisphenol Z, and the like.

In the above chemical formulas (10-1) to (10-8), n is 0 to 10, preferably 0 to 5. In this case, when the compounds represented by the chemical formulas (10-1) to (10-8) are oligomers or polymers, n is an average value thereof. In the present specification, "oligomer" refers to a compound containing 1 to 5 repeating units, and "polymer" refers to a compound containing 6 or more repeating units. The substitution position of a hydroxyl group as a substituent on the aromatic ring is arbitrary, and in the case of a naphthalene ring, the ring may be either a ring bonded to another structure or a ring not bonded thereto.

In one embodiment, the 1 st aromatic ring represented by the formula (7) may be synthesized by a reaction of a compound in which at least 1 of hydrogen atoms constituting the 1 st aromatic ring is substituted with a hydroxyl group, a divinyl compound, or a dialkoxymethyl compound.

In this case, the diene-based compound and the dialkoxymethyl compound are not particularly limited, and examples thereof include aliphatic diene compounds such as 1, 3-butadiene, 1, 5-hexadiene, dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, pentacyclopentadiene and hexacyclopentadiene; aromatic diene compounds such as divinylbenzene and divinylbiphenyl; and dialkoxymethyl compounds such as dimethoxymethylbenzene, dimethoxymethylbiphenyl, bisphenol A methoxy adduct, bisphenol A ethoxy adduct, bisphenol F methoxy adduct, and bisphenol F ethoxy adduct.

The 1 st aromatic compound having 2 or more phenolic hydroxyl groups may be used alone or in combination of 2 or more.

The hydroxyl equivalent of the 1 st aromatic compound is preferably 130 to 500 g/equivalent, more preferably 130 to 400 g/equivalent. The 1 st aromatic compound is preferable because heat resistance can be imparted when the hydroxyl equivalent is 130 g/equivalent or more. On the other hand, when the hydroxyl group equivalent of the 1 st aromatic compound is 500 g/equivalent or less, the balance between the heat resistance and the dielectric loss tangent is excellent, and therefore, it is preferable.

The 1 st aromatic compound is represented by the above chemical formula (7), and when n is an oligomer or a polymer, the weight average molecular weight is preferably 200 to 3000, more preferably 200 to 2000. The 1 st aromatic compound preferably has a weight average molecular weight of 200 or more because of excellent dielectric loss tangent. On the other hand, the 1 st aromatic compound preferably has a weight average molecular weight of 3000 or less because of its excellent moldability. In the present specification, the value of the "weight average molecular weight" is a value measured by the following method. That is, the values obtained by Gel Permeation Chromatography (GPC) measurement under the following conditions were used.

Measurement conditions of GPC

A measuring device: HLC-8320GPC, manufactured by Tosoh corporation "

Column: "HXL-L" protective column available from Tosoh corporation "

"TSK-GEL G4000 HXL", manufactured by Tosoh corporation "

+ TSK-GEL G3000HXL manufactured by Tosoh corporation "

+ TSK-GEL G2000HXL manufactured by Tosoh corporation "

"TSK-GEL G2000 HXL", manufactured by Tosoh corporation "

A detector: RI (differential refractometer)

Data processing: "GPC workstation EcoECWorkStation" manufactured by Tosoh corporation "

Column temperature: 40 deg.C

Developing solvent: tetrahydrofuran (THF)

Flow rate: 1.0 ml/min

The standard is as follows: the following monodisperse polystyrene having a known molecular weight was used according to the manual of GPC-8320GPC

Using polystyrene

"A-500" made by Tosoh corporation "

"A-1000" made by Tosoh corporation "

"A-2500" made by Tosoh corporation "

"A-5000" manufactured by Tosoh corporation "

"F-1" manufactured by Tosoh corporation "

"F-2" made by Tosoh corporation "

"F-4" made by Tosoh corporation "

"F-10" made by Tosoh corporation "

"F-20" made by Tosoh corporation "

"F-40" made by Tosoh corporation "

"F-80" made by Tosoh corporation "

"F-128" made by Tosoh corporation "

Use of: the resulting tetrahydrofuran solution (1.0 mass% in terms of resin solid content) was filtered through a microfilter to obtain a filtrate (50. mu.l).

[ 2 nd aromatic Compound ]

The 2 nd aromatic compound has a phenolic hydroxyl group. The 2 nd aromatic compound has 1 phenolic hydroxyl group, and therefore has a function of stopping a reaction of polyesterification of the 1 st aromatic compound and a 3 rd aromatic compound and the like described later.

The 2 nd aromatic compound is not particularly limited, and examples thereof include a substituted or unsubstituted 2 nd aromatic compound having 3 to 30 carbon atoms and having 1 phenolic hydroxyl group on the 2 nd aromatic ring.

The 2 nd aromatic ring is not particularly limited, and examples thereof include monocyclic aromatic rings, fused ring aromatic rings, ring-assembly aromatic rings, and aromatic rings connected by an alkylene group. Examples of the monocyclic aromatic ring, the condensed ring aromatic ring, and the ring-aggregated aromatic ring include those similar to the 1 st aromatic ring.

Examples of the aromatic ring linked via an alkylene group include diphenylmethane, diphenylethane, 1-diphenylethane, 2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fluorene, and diphenylcyclopentane.

The 2 nd aromatic ring related to the 2 nd aromatic compound may have a substituent. In this case, examples of the "substituent for the 2 nd aromatic ring" include the same ones as those of the "substituent for the 1 st aromatic ring" described above.

As described above, in the 2 nd aromatic compound, 1 of the hydrogen atoms constituting the above-mentioned substituted or unsubstituted 2 nd aromatic ring is substituted with a hydroxyl group.

As the 2 nd aromatic compound, compounds represented by the following chemical formulas (11-1) to (11-17) may be mentioned.

In the above chemical formulas (11-1) to (11-17), R ¹ Is a substituent containing a polymerizable unsaturated bond. In this case, the substituent having a polymerizable unsaturated bondThe same as described above. Further, p is an integer of 0 or 1 or more, preferably 1 to 3, more preferably 1 or 2, and still more preferably 1. When p is 2 or more, the bonding position on the aromatic ring is arbitrary, and for example, it is shown that the naphthalene ring of the chemical formula (11-6) or the heterocyclic ring of the chemical formula (11-17) may be substituted on an arbitrary ring, and that the substitution may be performed on an arbitrary ring of the benzene rings existing in 1 molecule in the chemical formula (11-9) or the like, and that the number of the substituents in 1 molecule is p.

Specific 2 nd aromatic compounds are not particularly limited, and examples thereof include compounds in which the aromatic ring is a monocyclic aromatic ring, such as phenol, cresol, xylenol, o-allylphenol, m-allylphenol, p-allylphenol, 2, 4-diallylphenol, 2, 6-diallylphenol, 2-allyl-4-methylphenol, 2-allyl-6-methylphenol, 2-allyl-4-methoxy-6-methylphenol, 2-propynyl phenol, 3-propynyl phenol, and 4-propynyl phenol (hereinafter, may be simply referred to as "2 nd monocyclic aromatic ring compounds"); 1-naphthol, 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, compounds having an aromatic ring as a condensed ring aromatic ring (hereinafter, may be referred to simply as "2 nd condensed ring aromatic ring compound"), such as 6-allyl-1-naphthol, diallylnaphthol, 2-allyl-4-methoxy-1-naphthol, 2-propynyl-1-naphthol, 3-propynyl-1-naphthol, 1-propynyl-2-naphthol, and 3-propynyl-2-naphthol; and compounds in which an aromatic ring such as allylhydroxybiphenyl or hydroxypropynyl biphenyl is a ring-assembled aromatic ring (hereinafter, may be simply referred to as "ring-2-assembled aromatic ring compounds").

Among the above, the 2 nd aromatic compound is preferably a 2 nd monocyclic aromatic ring compound or a 2 nd fused ring aromatic ring compound, and more preferably o-allylphenol, m-allylphenol, p-allylphenol, 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, or 6-allyl-1-naphthol.

In another embodiment, the 2 nd aromatic compound is preferably a 2 nd fused aromatic ring compound (fused aromatic ring compound), and more preferably 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, or 6-allyl-1-naphthol. When the 2 nd aromatic compound is a fused ring aromatic ring compound, the dielectric loss tangent can be reduced because molecular movement is suppressed by steric hindrance, which is preferable. Further, from the viewpoint of high processability and low viscosity of the aromatic ester compound (a), 2-allylphenol having a benzene ring skeleton and the like are preferable, and from the viewpoint of better heat resistance of the resultant cured product and excellent balance between low dielectric characteristics, 2-allyl-1-naphthol, 1-allyl-2-naphthol and the like having a naphthalene ring skeleton are preferable.

The above-mentioned 2 nd aromatic compound may be used alone, or 2 or more thereof may be used in combination.

[ 3 rd aromatic Compound and/or acid halide or ester thereof ]

The 3 rd aromatic compound and/or its acid halide or ester is a carboxylic acid having 2 or more carboxyl groups, or a derivative thereof, specifically an acid halide or ester (in the present specification, the 3 rd aromatic compound and/or its acid halide or ester may be collectively referred to as "the 3 rd aromatic compound or the like"). The 3 rd aromatic compound or the like having 2 or more carboxyl groups or the like is reacted with the 1 st aromatic compound, whereby a polyester structure can be formed in the aromatic ester compound (a-2) having a polymerizable unsaturated bond. The polyesterification reaction is stopped by the reaction with the 2 nd aromatic compound.

The 3 rd aromatic compound and the like are not particularly limited, and examples thereof include compounds having 2 or more carboxyl groups on a 3 rd aromatic ring having 3 to 30 carbon atoms which may be substituted or unsubstituted.

The "carboxyl group and the like" include: a carboxyl group; halogenated acyl groups such as fluorinated acyl groups, chlorinated acyl groups, and brominated acyl groups; alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl; and an aryloxycarbonyl group such as a phenoxycarbonyl group and a naphthyloxycarbonyl group. When the aromatic compound has an acyl halide group, the aromatic compound of the 3 rd group is an acid halide compound, and when the aromatic compound has an alkoxycarbonyl group or an aryloxycarbonyl group, the aromatic compound of the 3 rd group may be an ester compound. Among these, the 3 rd aromatic compound preferably has a carboxyl group, an acyl halide group, and an aryloxycarbonyl group, more preferably has a carboxyl group and an acyl halide group, and further preferably has a carboxyl group, an acyl chloride group, and an acyl bromide group.

The 3 rd aromatic ring is not particularly limited, and monocyclic aromatic ring, fused ring aromatic ring, ring-assembly aromatic ring, aromatic ring linked by an alkylene group, and the like can be given. Examples of the monocyclic aromatic ring, the fused ring aromatic ring, the ring-aggregated aromatic ring, and the aromatic ring connected via an alkylene group include the same ones as those of the 1 st aromatic ring and the 2 nd aromatic ring.

The 3 rd aromatic ring related to the 3 rd aromatic compound and the like may have a substituent. In this case, examples of the "substituent for the 3 rd aromatic ring" include the same ones as those of the "substituent for the 1 st aromatic ring" described above.

Specific examples of the 3 rd aromatic compound include compounds represented by the following chemical formulas (12-1) to (12-15).

In the above chemical formulas (12-1) to (12-15), R ¹ Is a substituent containing a polymerizable unsaturated bond. In this case, the substituent containing the polymerizable unsaturated bond is the same as in the above case. In addition, R ² Hydroxyl, halogen atom, alkoxy and aryloxy. Further, p is an integer of 0 or 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, and further preferably 0. q is 2 or 3. When p and q are 2 or more, the bonding position on the aromatic ring is arbitrary, and for example, a naphthalene ring of the formula (12-5) or a heterocyclic ring of the formula (12-15) may be on an arbitrary ringThe substitution may be carried out on any ring of the benzene rings present in 1 molecule in the chemical formula (12-7) and the like, and the number of substituents in 1 molecule is represented by p and q.

Specific examples of the 3 rd aromatic compound include, but are not particularly limited to, benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, and 2-allylterephthalic acid; benzene tricarboxylic acids such as trimellitic acid and 5-allyl trimellitic acid; naphthalenedicarboxylic acids such as naphthalene-1, 5-dicarboxylic acid, naphthalene-2, 3-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid, naphthalene-2, 7-dicarboxylic acid, 3-allylnaphthalene-1, 4-dicarboxylic acid, and 3, 7-diallylnaphthalene-1, 4-dicarboxylic acid; pyridine tricarboxylic acids such as 2,4, 5-pyridine tricarboxylic acid; triazine carboxylic acids such as 1,3, 5-triazine-2, 4, 6-tricarboxylic acid; acid halides and esters thereof. Among these, benzene dicarboxylic acid and benzene tricarboxylic acid are preferable, isophthalic acid, terephthalic acid, isophthaloyl chloride, terephthaloyl chloride, 1,3, 5-benzenetricarboxylic acid, and 1,3, 5-benzenetricarbonyl trichloride are more preferable, and isophthaloyl chloride, terephthaloyl chloride, and 1,3, 5-benzenetricarbonyl trichloride are still more preferable.

Among the above, the 3 rd aromatic compound and the like in which the aromatic ring is a monocyclic aromatic ring and the 3 rd aromatic compound and the like in which the aromatic ring is a condensed ring aromatic ring are preferable, the benzene dicarboxylic acid, the benzene tricarboxylic acid, the naphthalene dicarboxylic acid, and acid halides thereof are preferable, the benzene dicarboxylic acid, the naphthalene dicarboxylic acid, and acid halides thereof are more preferable, and the isophthalic acid, the terephthalic acid, the naphthalene-1, 5-dicarboxylic acid, the naphthalene-2, 3-dicarboxylic acid, the naphthalene-2, 6-dicarboxylic acid, the naphthalene-2, 7-dicarboxylic acid, and acid halides thereof are further preferable.

The above-mentioned 3 rd aromatic compound and the like may be used alone, or 2 or more thereof may be used in combination.

[ constitution of the aromatic ester Compound (A-2) having polymerizable unsaturated bond ]

At least 1 of the 1 st aromatic compound, the 2 nd aromatic compound, and the 3 rd aromatic compound and/or the acid halide or ester thereof (e.g., the 3 rd aromatic compound) has a substituent having a polymerizable unsaturated bond. That is, all of the 1 st aromatic compound, the 2 nd aromatic compound, the 3 rd aromatic compound, and the like may have a substituent having a polymerizable unsaturated bond, the 1 st aromatic compound and the 2 nd aromatic compound may have a substituent having a polymerizable unsaturated bond, or only the 2 nd aromatic compound may have a substituent having a polymerizable unsaturated bond. When 2 or more kinds of the 1 st aromatic compound, the 2 nd aromatic compound, the 3 rd aromatic compound, and the like are used, only a part thereof may have a substituent having a polymerizable unsaturated bond. The number of carbon atoms of the substituent containing the polymerizable unsaturated bond is preferably in the range of 2 to 30.

In one embodiment, at least the 2 nd aromatic compound preferably has a substituent having a polymerizable unsaturated bond. As described above, the structure derived from the 2 nd aromatic compound is located at the molecular end of the aromatic ester compound (A-2) having a polymerizable unsaturated bond. As a result, the substituent having a polymerizable unsaturated bond in the 2 nd aromatic compound is also arranged at the molecular end of the polymerizable unsaturated bond-containing aromatic ester compound (a-2). In this case, the balance between the heat resistance and the dielectric loss tangent of the resulting cured product can be further improved, which is preferable.

As described above, the aromatic ester compound (a-2) containing a polymerizable unsaturated bond is a reaction product of the 1 st aromatic compound, the 2 nd aromatic compound, the 3 rd aromatic compound, and the like, and may contain various compounds. The composition of the aromatic ester compound (a-2) having a polymerizable unsaturated bond can be controlled by appropriately changing the amounts of the 1 st aromatic compound, the 2 nd aromatic compound, the 3 rd aromatic compound and the like to be used, the reaction conditions and the like.

In the aromatic ester compound (a-2) having a polymerizable unsaturated bond of the present embodiment, the obtained resin has no hydroxyl group in the molecule as a principle. However, a compound having a hydroxyl group may be contained as a by-product of the reaction product within a range not hindering the effect of the present invention.

In one embodiment, the aromatic ester compound (a-2) having a polymerizable unsaturated bond includes a compound represented by the following chemical formula (13).

In the above chemical formula (13), Ar ¹ Is a structure derived from a1 st aromatic compound, Ar ² Is a structure derived from a 2 nd aromatic compound, Ar ³ Is derived from a 3 rd aromatic compound or the like. In addition, n is 0 to 10. When the aromatic ester compound (a-2) having a polymerizable unsaturated bond is an oligomer or a polymer, n represents the average value thereof.

Namely, Ar ¹ Each independently may be exemplified by: the compound having a structure in which 2 or more hydrogen atoms are removed from a substituted or unsubstituted 1 st aromatic ring, or 2 or more hydrogen atoms are removed from a compound having a structure in which 1 st aromatic rings are linked by a linking group.

In addition, Ar ² Each independently includes a 2 nd substituted or unsubstituted aromatic ring from which 1 hydrogen atom has been removed.

Ar ³ Examples thereof include those obtained by removing 2 or more hydrogen atoms from a substituted or unsubstituted 3 rd aromatic ring.

In addition, Ar is ¹ 、Ar ² And Ar ³ At least 1 of them has a substituent having a polymerizable unsaturated bond.

In this case, when the 1 st aromatic compound has 3 or more phenolic hydroxyl groups, Ar ¹ May further have a branched structure.

When the 3 rd aromatic compound has 2 or more carboxyl groups, Ar ³ May further have a branched structure.

In one embodiment, examples of the compound contained in the polymerizable unsaturated bond-containing aromatic ester compound (A-2) include compounds represented by the following chemical formulas (14-1) to (14-10).

In the above chemical formulas (14-1) to (14-10), s is 0 to 10, preferably 0 to 5, and r is 1 to 10. In this case, when the compounds represented by the chemical formulas (14-1) to (14-10) are oligomers or polymers, s1, s2 and r are average values thereof. In the formula, the dotted line corresponds to Ar ³ And Ar ¹ And/or Ar ² The compound (4) is reacted to obtain the structure.

The weight average molecular weight of the aromatic ester compound (A-2) is preferably 150 to 3000, more preferably 200 to 2000. The weight average molecular weight is preferably 800 or more because it is excellent in dielectric loss tangent. On the other hand, a weight average molecular weight of 500 or less is preferable because moldability is excellent. The number average molecular weight is preferably in the range of 150 to 1500 for the same reason.

< method for producing aromatic ester Compound (A-2) containing polymerizable unsaturated bond >

The method for producing the aromatic ester compound (a-2) containing a polymerizable unsaturated bond is not particularly limited, and can be produced by a known method.

In one embodiment, the method for producing the aromatic ester compound (a-2) containing a polymerizable unsaturated bond includes a step of reacting a1 st aromatic compound, a 2 nd aromatic compound, a 3 rd aromatic compound, and the like.

(1 st aromatic compound, 2 nd aromatic compound, 3 rd aromatic compound, etc.)

The 1 st aromatic compound, the 2 nd aromatic compound, the 3 rd aromatic compound, and the like can be the above compounds.

In one embodiment, the composition of the obtained aromatic ester compound (a-2) having a polymerizable unsaturated bond can be controlled by appropriately adjusting the amounts of the 1 st aromatic compound, the 2 nd aromatic compound, the 3 rd aromatic compound and the like to be used.

For example, the ratio of the number of moles of the carboxyl group or the like in the 3 rd aromatic compound to the number of moles of the hydroxyl group in the 1 st aromatic compound (carboxyl group or the like/hydroxyl group in the 1 st aromatic compound) is preferably 0.5 to 10, more preferably 0.5 to 6.0, and still more preferably 1.0 to 3.0. When the ratio is 0.5 or more, the heat resistance is preferably high. On the other hand, when the ratio is 10 or less, moldability is excellent, and therefore, it is preferable.

The ratio of the number of moles of the carboxyl group or the like in the 3 rd aromatic compound to the number of moles of the hydroxyl group in the 2 nd aromatic compound (carboxyl group or the like/hydroxyl group in the 2 nd aromatic compound) is preferably 0.5 to 10, and more preferably 1.5 to 4.0. When the ratio is 0.5 or more, moldability is excellent, and therefore, the ratio is preferable. On the other hand, when the ratio is 10 or less, the heat resistance is preferably high.

In one embodiment, the structure of the obtained aromatic ester compound (a-2) having a polymerizable unsaturated bond can be controlled by controlling the reaction sequence.

The method for producing the polymerizable unsaturated bond-containing aromatic ester compound (A-2) comprises: a step (1) of reacting the 1 st aromatic compound and the 3 rd aromatic compound, and a step (2) of reacting the product obtained in the step (1) with the 2 nd aromatic compound. According to the above production method, since the reaction can be controlled after the polyester structure is built, the aromatic ester compound (a-2) having a uniform molecular weight distribution and containing a polymerizable unsaturated bond can be obtained.

Further, the constitution of the obtained aromatic ester compound (A-2) having a polymerizable unsaturated bond can be controlled by controlling the reaction conditions.

The pH during the reaction is not particularly limited, but is preferably 11 or more. In this case, acids such as hydrochloric acid, sulfuric acid, nitric acid, and acetic acid; alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, etc.

The reaction temperature is also not particularly limited, but is preferably 20 to 100 ℃ and more preferably 40 to 80 ℃.

The arylene group in the poly (arylene ether) resin (B) used in the present invention includes phenylene, naphthylene, and a structural site having a substituent such as an aliphatic hydrocarbon group, an alkoxy group, an aryl group, or an aralkyl group on the aromatic nucleus thereof. Among them, in view of forming a curable composition having an excellent balance between dielectric characteristics and heat resistance of a cured product, a phenylene group is preferably used as a main skeleton, and a phenylene group having 2 substituents on an aromatic nucleus is more preferably used. The substituent is more preferably an aliphatic hydrocarbon group, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

The terminal structure of the above poly (arylene ether) resin (B) is usually an aryloxy group having a phenolic hydroxyl group. The phenolic hydroxyl group may be modified to other structural sites. Examples of the aryl group in the aryloxy group include a phenyl group, a naphthyl group, and a structural site having a substituent such as an aliphatic hydrocarbon group, an alkoxy group, an aryl group, or an aralkyl group on an aromatic nucleus thereof. Among them, from the viewpoint of forming a curable composition having an excellent balance between dielectric characteristics and heat resistance of a cured product, a phenyl group is preferably used as a main skeleton, and a phenylene group having 2 substituents in addition to a phenolic hydroxyl group on an aromatic nucleus is more preferable. The substituent is more preferably an aliphatic hydrocarbon group, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

Examples of the structural site obtained by modifying the phenolic hydroxyl group include a group having a polymerizable unsaturated bond such as a (meth) acryloyloxy group, an allyloxy group, or a vinyloxy group, and a structural site obtained by reacting a phenolic hydroxyl group with an epoxy compound. Among them, the phenolic hydroxyl group or the polymerizable unsaturated bond-containing group is preferable from the viewpoint of forming a curable composition having an excellent balance between dielectric characteristics and heat resistance of a cured product.

Examples of the poly (arylene ether) resin (B) include those represented by the following formula (15).

(in the formula, R ¹ Each independently is any of a hydrogen atom, an aliphatic hydrocarbon group, an alkoxy group, an aryl group, and an aralkyl group. m and n are each independently integers of 0 or moreAnd (4) counting. X is a hydrogen atom or a group having a polymerizable unsaturated bond. )

Y in the structural formula (15) is not particularly limited as long as it is a divalent organic group, and may be any structural site, and examples thereof include structures represented by any of the following structural formulae (Y-1) to (Y-9).

(in the formula, R ² Each independently is any of an aliphatic hydrocarbon group, an alkoxy group, an aryl group, and an aralkyl group. R ³ Each independently is any one of an aliphatic hydrocarbon group, an alkoxy group and an aryl group, and k is an integer of 0 to 4. )

The equivalent weight of the functional group of the phenolic hydroxyl group of the poly (arylene ether) resin (B) or a structural site obtained by modifying the phenolic hydroxyl group, that is, the equivalent weight of the functional group of the structural site represented by the-OX group at the end of the structure (15), is preferably in the range of 500 to 3,000 g/equivalent, more preferably in the range of 500 to 1,500 g/equivalent, from the viewpoint of forming a curable composition excellent in both heat resistance and dielectric properties.

In the curable composition of the present invention, the blending ratio of the aromatic ester compound (a) having a polymerizable unsaturated bond and the poly (arylene ether) resin (B) is not particularly limited, and may be appropriately adjusted depending on the desired properties of the cured product and the like. Among these, from the viewpoint of forming a curable composition having an excellent balance between heat resistance and dielectric properties of a cured product, the poly (arylene ether) resin (B) is preferably used in an amount of 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, based on 100 parts by mass of the aromatic ester compound (a).

The curable composition of the present invention may contain other components in addition to the polymerizable unsaturated bond-containing aromatic ester compound (a) and the poly (arylene ether) resin (B). Examples of other components are given below. The other components that can be contained in the curable composition of the present invention are not limited to the components exemplified below, and may be contained in other components.

[ epoxy resin ]

The curable composition of the present invention contains a polymerizable unsaturated bond in the aromatic ester compound (a) containing a polymerizable unsaturated bond, and therefore, even when only the aromatic ester compound (a) and the poly (arylene ether) resin (B) are used, the curable composition has curability. On the other hand, the aromatic ester compound (a) also functions as a curing agent for an epoxy resin, and a cured product having higher heat resistance can be obtained, and therefore the curable composition of the present invention preferably further contains an epoxy resin.

The epoxy resin is not particularly limited, and examples thereof include novolac-type epoxy resins such as phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, α -naphthol novolac-type epoxy resin, β -naphthol novolac-type epoxy resin, bisphenol a novolac-type epoxy resin, and biphenol novolac-type epoxy resin; aralkyl type epoxy resins such as phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, phenol biphenyl aralkyl type epoxy resins and the like; bisphenol type epoxy resins such as bisphenol a type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol a type epoxy resin; biphenyl type epoxy resins such as biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyl oxybenzene skeleton; naphthalene type epoxy resins; binaphthol type epoxy resins; binaphthyl-type epoxy resins; dicyclopentadiene type epoxy resins such as dicyclopentadiene phenol type epoxy resins; glycidyl amine type epoxy resins such as tetraglycidyl diaminodiphenylmethane type epoxy resin, triglycidyl-p-aminophenol type epoxy resin, and diaminodiphenylsulfone glycidyl amine type epoxy resin; diglycidyl ester type epoxy resins such as 2, 6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resin and glycidyl ester type epoxy resin of hexahydrophthalic anhydride; and benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. These may be used alone or in combination of 2 or more.

The epoxy equivalent of the epoxy resin is preferably 150 to 500 g/equivalent, more preferably 200 to 350 g/equivalent. When the epoxy equivalent of the epoxy resin is 150 g/equivalent or more, the heat resistance is excellent, and therefore it is preferable, and when the epoxy equivalent of the epoxy resin is 500 g/equivalent or less, the balance between the heat resistance and the dielectric loss tangent is further excellent, and therefore it is preferable.

The weight average molecular weight of the epoxy resin is preferably 200 to 5000, and more preferably 300 to 3000. The weight average molecular weight of the epoxy resin is preferably 200 or more because it can achieve both quick curability and high curability. On the other hand, the weight average molecular weight of the epoxy resin is preferably 5000 or less because the moldability is excellent. The weight average molecular weight is a value measured by the aforementioned method (GPC).

[ other curing agents ]

When the curable composition of the present invention contains the epoxy resin, other curing agents that can be cured with the epoxy resin may be used in combination with the aromatic ester compound (a).

The other curing agent is not particularly limited, and examples thereof include an aromatic ester compound having no polymerizable unsaturated bond, an amine curing agent, an imidazole curing agent, an acid anhydride curing agent, a phenol resin curing agent, and the like.

The amine curing agent is not particularly limited, and examples thereof include aliphatic amines such as Diethylenetriamine (DTA), triethylenetetramine (TTA), Tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), Diethylaminopropylamine (DEAPA), N-aminoethylpiperazine, Menthanediamine (MDA), Isofluorodiamine (IPDA), 1, 3-bisaminomethylcyclohexanone (1,3-BAC), piperidine, N-dimethylpiperazine, and triethylenediamine; and aromatic amines such as m-Xylylenediamine (XDA), Methane Phenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2- (dimethylaminomethyl) phenol, and 2,4, 6-tris (dimethylaminomethyl) phenol.

Examples of the imidazole curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and epoxy-imidazole adduct.

Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol trimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, methylbutenyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, and the like.

Examples of the phenolic resin curing agent include phenol novolac resins, cresol novolac resins, naphthol novolac resins, bisphenol novolac resins, biphenol novolac resins, dicyclopentadiene-phenol addition type resins, phenol aralkyl resins, naphthol aralkyl resins, triphenol methane type resins, tetraphenol ethane type resins, and aminotriazine modified phenolic resins.

The above-mentioned other curing agents may be used alone, or 2 or more kinds may be used in combination.

The content of the other curing agent is not particularly limited, but is preferably 2 to 80% by mass, more preferably 5 to 70% by mass, based on the aromatic ester compound (a).

In the curable composition of the present invention, the blending ratio of the aromatic ester compound (a), the epoxy resin, and the other curing agent is not particularly limited, and may be appropriately adjusted according to the desired properties of the cured product, and for example, the total amount of functional groups reactive with epoxy groups in the aromatic ester compound (a) and the other curing agent is preferably in the range of 0.7 to 1.5 moles per 1 mole of the total amount of epoxy groups.

[ other resins ]

Specific examples of the other resin are not particularly limited, and include maleimide resins, bismaleimide resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolac resins, cyanate ester resins, styrene-maleic anhydride resins, allyl-containing resins such as diallyl bisphenol and triallyl isocyanurate, polyphosphate esters, phosphate-carbonate copolymers, polybutadiene resins, and the like. These other resins may be used alone, or 2 or more of them may be used in combination.

[ solvent ]

In one embodiment, the composition may comprise a solvent. The solvent has a function of adjusting the viscosity of the composition.

Specific examples of the solvent are not particularly limited, and include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and the like; and carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. These solvents may be used alone, or 2 or more kinds may be used in combination.

The amount of the solvent used is preferably 10 to 80% by mass, and more preferably 20 to 70% by mass, based on the total mass of the curable composition. The amount of the solvent to be used is preferably 10% by mass or more because the handling property is excellent. On the other hand, the amount of the solvent used is preferably 80% by mass or less because the impregnation with other base materials is excellent.

[ additives ]

In one embodiment, the composition may comprise an additive. Examples of the additives include a curing accelerator, a flame retardant, and a filler.

(curing accelerators)

The curing accelerator is not particularly limited, and examples thereof include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, urea-based curing accelerators, peroxides, and azo compounds.

Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organic phosphite compounds such as trimethyl phosphite and triethyl phosphite; and phosphonium salts such as ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide salt, butylphenyl phosphonium dicyanamide salt, tetrabutylphosphonium decanoate salt and the like.

Examples of the amine-based curing accelerator include triethylamine, tributylamine, N-dimethyl-4-aminopyridine (DMAP), 2,4, 6-tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo [5,4,0] -undec-7-ene (DBU), 1, 5-diazabicyclo [4,3,0] -non-5-ene (DBN), and the like.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and the like, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazolium isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and the like.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, and 1-phenylbiguanide.

Examples of the urea-based curing accelerator include 3-phenyl-1, 1-dimethylurea, 3- (4-methylphenyl) -1, 1-dimethylurea, chlorophenyl urea, 3- (4-chlorophenyl) -1, 1-dimethylurea, and 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea.

Examples of the peroxide and azo compound include benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, bis (2-ethylhexyl) peroxycarbonate, and azobisisobutyronitrile.

Among the above-mentioned curing accelerators, 2-ethyl-4-methylimidazole and dimethylaminopyridine are preferably used.

The curing accelerators may be used alone or in combination of 2 or more.

The amount of the curing accelerator used is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the resin solid content of the curable composition. The amount of the curing accelerator to be used is preferably 0.01 part by mass or more because the curability is excellent. On the other hand, the amount of the curing accelerator used is preferably 5 parts by mass or less because the moldability is excellent.

(flame retardant)

The flame retardant is not particularly limited, and examples thereof include inorganic phosphorus flame retardants, organic phosphorus flame retardants, halogen flame retardants, and the like.

The inorganic phosphorus flame retardant is not particularly limited, and red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; phosphoric acid amides, and the like.

The organic phosphorus flame retardant is not particularly limited, and examples thereof include phosphoric acid esters such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, lignoceryl acid phosphate, glycolic acid phosphate, and 2-hydroxyethyl methacrylate acid phosphate; diphenylphosphines such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and diphenylphosphine oxide; phosphorus-containing phenols such as 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (1, 4-dioxynaphthalene) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylanthraquinone phosphine oxide, diphenylphosphino-1, 4-dioxynaphthalene, 1, 4-cyclooctylenephosphino-1, 4-phenylenediol and 1, 5-cyclooctylenephosphino-1, 4-phenylenediol; cyclic phosphorus compounds such as 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10- (2, 7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; and compounds obtained by reacting the phosphoric acid ester, the diphenylphosphine, and the phosphorus-containing phenol with an epoxy resin, an aldehyde compound, and a phenol compound.

The halogen-based flame retardant is not particularly limited, and may include brominated polystyrene, bis (pentabromophenyl) ethane, tetrabromobisphenol a bis (dibromopropyl ether), 1, 2-bis (tetrabromophthalimide), 2,4, 6-tris (2,4, 6-tribromophenoxy) -1,3, 5-triazine, tetrabromobenzenedicarboxylic acid, and the like.

The flame retardants mentioned above may be used alone, or 2 or more kinds thereof may be used in combination.

The amount of the flame retardant is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, per 100 parts by mass of the resin solid content of the curable composition. The amount of the flame retardant to be used is preferably 0.1 part by mass or more because flame retardancy can be imparted. On the other hand, the amount of the flame retardant to be used is preferably 50 parts by mass or less because it can impart flame retardancy while maintaining dielectric properties.

(Filler)

Examples of the filler include an organic filler and an inorganic filler. The filler has a function of increasing the elongation and a function of increasing the mechanical strength.

The organic filler is not particularly limited, and examples thereof include polyamide particles.

The inorganic filler is not particularly limited, and examples thereof include silica, alumina, glass, panzeite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphotungstate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black, and the like.

Among these, silica is preferably used. In this case, as the silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, or the like can be used.

The filler may be surface-treated as necessary. In this case, the surface treatment agent to be used is not particularly limited, and an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilazane compound, a titanate-based coupling agent, or the like can be used. Specific examples of the surface-treating agent include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilazane and the like.

The fillers may be used alone or in combination of 2 or more.

The average particle size of the filler is not particularly limited, but is preferably 0.01 to 10 μm, more preferably 0.03 to 5 μm, and still more preferably 0.05 to 3 μm. In the present specification, the term "particle diameter" refers to the maximum length among the distances between 2 points on the contour of the particle. In addition, the "average particle diameter" takes the following value: in an image obtained by a Scanning Electron Microscope (SEM), the particle diameters of any 100 particles in 1 screen were measured, and the average value thereof was measured by a calculation method.

The amount of the filler used is preferably 0.5 to 95 parts by mass, more preferably 5 to 80 parts by mass, per 100 parts by mass of the resin solid content of the curable composition. The amount of the filler used is preferably 0.5 part by mass or more because low thermal expansion properties can be imparted. On the other hand, the amount of the filler to be used is preferably 95 parts by mass or less because the balance between the properties and moldability is excellent.

< cured product (cured product of curable composition) >

According to one embodiment of the present invention, there is provided a cured product obtained by curing a curable composition containing the polymerizable unsaturated bond-containing aromatic ester compound (a) and the polyarylene ether resin (B).

The polymerizable unsaturated bond-containing aromatic ester compound (a) has a substituent having a polymerizable unsaturated bond, and therefore can be polymerized by itself to obtain a cured product.

The cured product may contain the above-mentioned curing agent, additive, curing accelerator, and the like as needed.

The aromatic ester compound (a) containing a polymerizable unsaturated bond has a low dielectric loss tangent of its own, and therefore the cured product has a low dielectric loss tangent and is excellent in heat resistance, and therefore, can be used for electronic material applications such as semiconductor package substrates, printed circuit substrates, build-up adhesive films, and semiconductor sealing materials. In addition, the resin composition can be applied to adhesives, paints and the like.

The heating temperature for the heat curing is not particularly limited, but is preferably 150 to 300 ℃, and more preferably 175 to 250 ℃.

Examples

The present invention will be described below with reference to examples, but the present invention is not limited to the description of the examples.

Production example 1 production of aromatic ester Compound (A-1-1) containing polymerizable unsaturated bond

268g of o-allylphenol and 1200g of toluene were put into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, and the contents were dissolved while replacing the system with nitrogen under reduced pressure. Next, 203g of isophthaloyl dichloride was charged into the system, and the contents were dissolved while replacing the system with nitrogen under reduced pressure. Then, 0.6g of tetrabutylammonium bromide was added and dissolved, and the inside of the system was controlled to 60 ℃ or lower while purging with nitrogen, and 412g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the completion of the dropwise addition, the stirring was continued for 1 hour under the same temperature condition. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. To the obtained organic phase, water was added and stirred for about 15 minutes, and the mixture was allowed to stand to separate the liquid, and the aqueous layer was removed. This water washing operation was repeated until the pH of the aqueous layer became 7. The organic phase after washing was dried under heating and reduced pressure to obtain 370g of a polymerizable unsaturated bond-containing aromatic ester compound (A-1-1) represented by the following structural formula. The aromatic ester compound (A-1-1) having a polymerizable unsaturated bond had an ester equivalent of 199 g/equivalent, an allyl equivalent of 199 g/equivalent, and an E-type viscosity (25 ℃ C.) of 6000 mPa.s.

Production example 2 production of aromatic ester Compound (A-2-1) having polymerizable unsaturated bond

165g of a dicyclopentadiene/phenol addition polymerization resin (165 g/eq hydroxyl group, 85 ℃ softening point), 134g of o-allylphenol, and 1200g of toluene were put into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, and the contents were dissolved while replacing the inside of the system with nitrogen under reduced pressure. Next, 203g of isophthaloyl dichloride was charged and dissolved while replacing the system with nitrogen under reduced pressure. Then, 0.6g of tetrabutylammonium bromide was added and dissolved, and the inside of the system was controlled to 60 ℃ or lower while purging with nitrogen, and 412g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the completion of the dropwise addition, the stirring was continued for 1 hour under the same temperature condition. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. To the obtained organic phase, water was added, stirring was carried out for about 15 minutes, and the mixture was allowed to stand for liquid separation to remove the aqueous layer. This water washing operation was repeated until the pH of the aqueous layer became 7. The organic phase after washing was dried under heating and reduced pressure to obtain 385g of an aromatic ester compound (A-2-1) containing a polymerizable unsaturated bond. The theoretical structure of the aromatic ester compound (A-2-1) having a polymerizable unsaturated bond is shown below. The aromatic ester compound (A-2-1) having a polymerizable unsaturated bond had an ester equivalent of 214 g/equivalent, an allyl equivalent of 428 g/equivalent and a softening point of 82 ℃.

Production example 3 production of aromatic ester Compound (A-2-2) containing polymerizable unsaturated bond

402g of a polymerizable unsaturated bond-containing aromatic ester compound (A-2-2) was obtained in the same manner as in production example 2, except that 165g of the dicyclopentadiene and phenol addition polymerization resin in production example 2 was changed to diallylbisphenol A160 g. The theoretical structure of the aromatic ester compound (A-2-2) having a polymerizable unsaturated bond is shown below. The aromatic ester compound (A-2-2) having a polymerizable unsaturated bond had an ester equivalent of 212 g/equivalent, an allyl equivalent of 212 g/equivalent and a softening point of 51 ℃.

Comparative production example 1 production of aromatic ester Compound (A')

165g of a dicyclopentadiene and phenol addition polymerization resin (hydroxyl equivalent: 165 g/equivalent, softening point 85 ℃ C.), 72g of 1-naphthol, and 630g of toluene were put into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, and the contents were dissolved while replacing the system with nitrogen under reduced pressure. Subsequently, 152g of isophthaloyl dichloride was charged into the system and dissolved therein while replacing the system with nitrogen under reduced pressure. After adding 0.6g of tetrabutylammonium bromide, the temperature in the system was controlled to 60 ℃ or lower while purging with nitrogen gas, and 315g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the completion of the dropwise addition, stirring was continued for 1 hour under the same temperature condition. The reaction mixture was allowed to stand to separate the liquid, and the aqueous layer was removed. To the obtained organic phase, water was added and stirred for about 15 minutes, and the mixture was allowed to stand to separate the liquid, and the aqueous layer was removed. This water washing operation was repeated until the pH of the water layer became 7. The organic phase after washing with water is dried under heating and reduced pressure to obtain an aromatic ester compound (A'). The aromatic ester compound (A') had an ester group equivalent of 223 g/equivalent and a softening point of 150 ℃.

Examples 1 to 9 and comparative example 1

The curable compositions were obtained by blending the respective components at the ratios shown in tables 1 and 2. The obtained curable composition was subjected to evaluation of heat resistance of a cured product and measurement of a dielectric loss tangent in the following manner. The results are shown in tables 1 and 2.

Details of each component used in examples are as follows.

Polyarylene ether resin (B-1): "NORYLSA 90" manufactured by SABIC corporation, hydroxyl equivalent of 850 g/equivalent, and theoretical structure are as follows.

Polyarylene ether resin (B-2): "NORYLA 9000" manufactured by SABIC corporation, methacryloyl equivalent of 850 g/equivalent, and the theoretical structure are as follows.

Epoxy resin: bisphenol A type epoxy resin (DIC corporation product "EPICLON 850S" epoxy equivalent 188 g/equivalent)

Production of cured product

The curable composition was poured into a 11cm × 9cm × 2.4mm template, and molded by a press at 150 ℃ for 60 minutes, then at 175 ℃ for 90 minutes, and further at 200 ℃ for 90 minutes. The molded article was taken out from the mold and further cured at 230 ℃ for 4 hours to obtain a cured product.

Evaluation of Heat resistance (measurement of glass transition temperature)

A test piece having a width of 5mm and a length of 54mm was cut out from the cured product having a thickness of 2.4mm obtained in the above manner. The glass transition temperature was measured as the temperature at which the change in the elastic modulus of the test piece was the largest (the change rate of tan δ was the largest) by DMA (dynamic viscoelasticity) measurement by a rectangular tension method using "solid viscoelasticity measurement device RSAII" manufactured by Rheometrics, inc. The frequency was set to 1Hz, and the temperature rise rate was set to 3 ℃/min.

Measurement of dielectric loss tangent

The cured product obtained above was dried under heating and vacuum at 105 ℃ for 2 hours, and then stored in a room at 23 ℃ and 50% humidity for 24 hours to obtain a test piece. The dielectric loss tangent at 1GHz of the test piece was measured by the cavity resonance method using "network analyzer E8362C" manufactured by Agilent Technologies, Inc.

[ Table 1]

TABLE 1

[ Table 2]

TABLE 2

Claims

1. A curable composition comprising: an aromatic ester compound (A) having a polymerizable unsaturated bond and a poly (arylene ether) resin (B),

wherein the aromatic ester compound (A) containing a polymerizable unsaturated bond is represented by the following chemical formula (1),

in the chemical formula (1),

Ar ¹ is a substituted or unsubstituted 1 st aromatic ring group,

Ar ² each independently a substituted or unsubstituted 2 nd aromatic ring group,

at this time, the Ar ¹ And said Ar ² At least 1 of them has a substituent having a polymerizable unsaturated bond, and n is an integer of 2 or 3, or

The aromatic ester compound (A) containing a polymerizable unsaturated bond is a reaction product of:

a1 st aromatic compound having 2 or more phenolic hydroxyl groups;

a 2 nd aromatic compound having a phenolic hydroxyl group; and

a 3 rd aromatic compound having 2 or more carboxyl groups and/or an acid halide or an ester thereof,

at least 1 of the 1 st aromatic compound, the 2 nd aromatic compound, and the 3 rd aromatic compound and/or an acid halide or an ester thereof has a substituent having a polymerizable unsaturated bond.

2. The curable composition according to claim 1, further comprising an epoxy resin.

3. A cured product of the curable composition according to claim 1 or 2.

4. A printed circuit board comprising the curable composition according to claim 1 or 2.

5. A semiconductor sealing material comprising the curable composition according to claim 1 or 2.

6. A multilayer film comprising the curable composition according to claim 1 or 2.