CN111936526B - Curable composition and cured product thereof - Google Patents

Abstract

A curable composition excellent in heat resistance and dielectric properties of a cured product, a cured product of the aforementioned curable composition, a printed circuit board, a semiconductor sealing material, and a laminate film using the aforementioned curable composition are provided. Specifically, a curable composition containing a polymerizable unsaturated bond-containing aromatic ester compound (A) and a polyarylene ether resin (B), a cured product of the aforementioned curable composition, and a curable composition using the aforementioned curable composition are provided. A printed circuit board, a semiconductor sealing material, and a laminated film of the composition.

Description

Curable composition and cured product thereof

technical field

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

Background technique

In recent years, the miniaturization and high performance of electronic devices have progressed, and the required performance of various materials used has been increased accordingly. For example, with regard to semiconductor package substrates, the speed and frequency of signals are increasing, and materials with low power loss, that is, materials with low dielectric loss tangent, are being sought.

As such a low dielectric loss tangent material, for example, there is provided an invention involving a resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) a smear inhibitor components, and (D) an inorganic filler (for example, refer to Patent Document 1). In this case, when the nonvolatile content of the resin composition is set to 100% by mass, the (B) active ester compound, the (C) smear inhibitor, and the (D) inorganic filler are each It is a predetermined content rate, and the said (C) smear suppressing component is a rubber particle.

The aforementioned Patent Document 1 describes that the cured product of the resin composition can achieve low dielectric loss tangent. In addition, it is described that the smear (resin residue) in the through hole after the above-mentioned cured product is drilled and roughened can be suppressed.

In addition, it is described that the (B) active ester compound described in the said patent document 1 is a compound which has one or more active ester groups in 1 molecule, and can reduce the dielectric loss tangent of the hardened|cured material of a resin composition.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Laid-Open No. 2016-156019

SUMMARY OF THE INVENTION

Invention to solve problem

The aforementioned Patent Document 1 describes that by using an active ester compound, the dielectric loss tangent of the obtained cured product can be reduced. However, it became clear that such a cured product may not necessarily be said to have sufficient heat resistance.

solution to the problem

The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems. As a result, it was found that a curable composition containing an aromatic ester compound having a polymerizable unsaturated bond in the molecular structure and a polyarylene ether resin is particularly excellent in heat resistance and dielectric properties of the cured product, thereby completing the present invention. invention.

That is, the present invention provides a curable composition containing a polymerizable unsaturated bond-containing aromatic ester compound (A) and a polyarylene ether resin (B), a cured product thereof, and further printing using the curable composition Circuit boards, semiconductor sealing materials, laminated films.

effect of invention

According to the present invention, a curable composition having excellent heat resistance and dielectric properties of a cured product, a cured product of the aforementioned curable composition, a printed circuit board, a semiconductor sealing material, and a build-up layer using the aforementioned curable composition can be provided film.

Detailed ways

Hereinafter, the form for implementing this invention is demonstrated in detail.

The polymerizable unsaturated bond-containing aromatic ester compound (A) used in the present invention only has one or more polymerizable unsaturated bonds in the molecular structure, and has a structure in which aromatic rings are bonded to each other through an ester bond The aromatic ester compound of the moiety is not particularly limited in other specific structures, molecular weights, etc., and various compounds can be used.

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

(In the above chemical formula (1), Ar ¹ is a substituted or unsubstituted first aromatic ring group, and Ar ² is each independently a substituted or unsubstituted second aromatic ring group. In this case, the aforementioned Ar ¹ and the aforementioned Ar At least one of ² has a polymerizable unsaturated bond-containing substituent, and n is an integer of 2 or 3.)

The polymerizable unsaturated bond-containing aromatic ester compound (A-2) is a reaction product of: a first aromatic compound having two or more phenolic hydroxyl groups; a second aromatic compound having a phenolic hydroxyl group; and A third aromatic compound having two or more carboxyl groups and/or an acid halide or ester thereof. At least one of the first aromatic compound, the second aromatic compound, and the third aromatic compound and/or its acid halide and ester product has a polymerizable unsaturated bond-containing substituent.

The above-mentioned polymerizable unsaturated bond-containing aromatic ester compound (A) is more excellent in the balance between the handleability when preparing the curable composition described later, the heat resistance of the cured product, and the dielectric properties. From the standpoint, it is preferable to be a liquid at normal temperature (25°C), or to have a softening point in the range of 40°C to 200°C.

About the said polymerizable unsaturated bond containing aromatic ester compound (A-1), Ar ¹ in the said chemical formula (1) is a substituted or unsubstituted 1st aromatic ring group. As will be described later, since n in the chemical formula (1) is an integer of 2 or 3, two or three hydrogen atoms of the aromatic ring constituting the first aromatic ring group are substituted with "—C(O) OAr ² ".

The first aromatic ring group is not particularly limited, and examples thereof include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, and pyridine. Monocyclic aromatic compounds such as oxazine and triazine by removing 2 or 3 hydrogen atoms; from naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine , pteridine, coumarin, indole, benzimidazole, benzofuran, acridine and other fused-ring aromatic compounds by removing 2 or 3 hydrogen atoms from aromatic compounds, etc. made of hydrogen atoms. In addition, it may be obtained by combining a plurality of these aromatic compounds, for example, biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, It is obtained by removing 2 or 3 hydrogen atoms from ring-collected aromatic compounds such as tetraphenyl; from diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenyl Remove from aromatic compounds linked by alkylene such as phenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fluorene, diphenylcyclopentane, etc. 2 or 3 hydrogen atoms, etc.

Among them, Ar ¹ is preferably a substituted or unsubstituted benzene ring or naphthalene ring, and more preferably a substituted or unsubstituted benzene ring, from the viewpoint of obtaining a cured product with more excellent dielectric properties.

The first aromatic ring group represented by Ar ¹ may have a substituent. In this case, the "substituent of the first aromatic ring group" refers to a group that substitutes at least one hydrogen atom of the aromatic ring constituting the first aromatic ring group. It does not specifically limit as a specific example of the substituent of a 1st aromatic ring group, An alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a halogen atom, etc. are mentioned.

It does not specifically limit as said alkyl group, Methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-butyl group Pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, cyclohexyl, etc.

Although it does not specifically limit as said alkoxy group, A methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, etc. are mentioned.

The alkoxycarbonyl group is not particularly limited, and examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, n-butoxycarbonyl, and isobutoxy Carbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, etc.

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

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

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

The alkenyl group is not particularly limited, and examples thereof include vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-butenyl, and 1-butenyl. - 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, cyclo Octenyl, 1,3-butadienyl, 1,4-butadienyl, 1,3-hexadienyl, 2,5-hexadienyl, 4,7-pentadecadienyl , 1,3,5-hexatrienyl, 1,4,7-pentadecatrienyl, etc.

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

The aforementioned polymerizable unsaturated bond-containing substituent may further have a substituent. In this case, the "substituent of the polymerizable unsaturated bond-containing substituent" is a group that replaces at least one hydrogen atom constituting the aforementioned polymerizable unsaturated bond-containing substituent. Specific examples of the substituent of the polymerizable unsaturated bond-containing substituent include an alkoxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom. In this case, the examples described above as an alkoxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom can be mentioned.

Among these, as the substituent containing a polymerizable unsaturated bond, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms is preferable, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms is more preferable, Further preferred are substituted or unsubstituted alkenyl groups having 2 to 5 carbon atoms, particularly preferred are vinyl groups, allyl groups, propenyl groups, isopropenyl groups, 1-propenyl groups, 1-butenyl groups, and 2-butene groups group, 3-butenyl, 1,3-butadienyl, most preferably allyl, propenyl, isopropenyl, and 1-propenyl.

Preferred structures of Ar ¹ include the following formulae (2-1) to (2-17).

In this case, in the above formulae (2-1) to (2-17), "*" represents a position where "-C(O)OAr ² " is bonded. In addition, "-*" may couple|bond with arbitrary positions of an aromatic ring.

Among these, the formulae (2-1) to (2-11) are preferable, and the formulae (2-1), (2-2), (2-6), (2-7), (2- 9), more preferably formulas (2-1), (2-2), (2-6), and (2-7). In addition, from the viewpoint of high handleability and low viscosity of the aromatic ester compound (A-1), (2-1) and (2-2) are preferable, and on the other hand, from the heat resistance of the obtained cured product More preferably, from the viewpoint of being excellent in balance with low dielectric properties, (2-6) and (2-7) are preferred.

In addition, at least one of hydrogen atoms in the aromatic rings of the formulae (2-1) to (2-17) may be substituted with an unsaturated bond-containing group.

Ar ² is each independently a substituted or unsubstituted second aromatic ring group. As is clear from the description of the above chemical formula (1), one of the hydrogen atoms of the aromatic ring constituting the second aromatic ring group is substituted with "-OC(O)Ar ¹ ".

The second aromatic ring group is not particularly limited, and examples thereof include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, and pyridine. One hydrogen atom is removed from monocyclic aromatic compounds such as oxazine and triazine; A compound obtained by removing one hydrogen atom from an aromatic compound, such as a fused-ring aromatic compound such as an indole, indole, benzimidazole, benzofuran, and acridine. In addition, it may be obtained by combining a plurality of these aromatic compounds, for example, biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, One hydrogen atom is removed from ring-collected aromatic compounds such as tetraphenyl; from diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, One hydrogen is removed from aromatic compounds such as naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fluorene, and diphenylcyclopentane that are linked by alkylene groups Atoms, etc.

Among them, Ar ² is preferably a substituted or unsubstituted benzene ring or naphthalene ring from the viewpoint of obtaining a cured product with more excellent dielectric properties. In addition, the aromatic ester compound (A) is preferably a benzene ring from the viewpoints of high handleability and low viscosity, and on the other hand, the resulting cured product has better heat resistance and a balance with low dielectric properties From an excellent viewpoint, a naphthalene ring is preferable.

The second aromatic ring group related to Ar ² may have a substituent. In this case, the "substituent of the second aromatic ring group" is a group that substitutes at least one hydrogen atom of the aromatic ring constituting the second aromatic ring group. It does not specifically limit as a specific example of the substituent of a 2nd aromatic ring group, An alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a halogen atom, etc. are mentioned. In this case, the examples described above as an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom can be mentioned.

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

Preferred structures of Ar ² include the following formulae (3-1) to (3-17).

In this case, in the above formulae (3-1) to (3-17), "*" represents a position where "-OC(O)Ar ¹ " is bonded. In addition, "-*" may couple|bond with arbitrary positions of an aromatic ring.

Among these, formulae (3-1) to (3-11) are preferred, formulae (3-1), (3-6), and (3-9) are more preferred, and formula (3-1) is further preferred. , (3-6).

In addition, at least one of hydrogen atoms in the aromatic rings of the formulae (3-1) to (3-17) may be substituted with an unsaturated bond-containing group.

According to one embodiment, it is more preferable that Ar ¹ is the above formula (2-1), (2-2), (2-6), (2-7), (2-9), and Ar ² is the above formula (3- 1), (3-6), (3-9); more preferably Ar ¹ is the above formula (2-1), (2-2), (2-6), (2-7), and Ar ² is the above Formulas (3-1) and (3-6); particularly preferably, Ar ¹ is the above formula (2-1), and Ar ² is the above formula (3-1) and (3-6).

In the above chemical formula (1), at least one of the above-mentioned Ar ¹ and Ar ² has a polymerizable unsaturated bond-containing substituent. That is, only Ar ¹ may have a polymerizable unsaturated bond-containing substituent, only Ar ² may have a polymerizable unsaturated bond-containing substituent, or both Ar ¹ and Ar ² may have a polymerizable unsaturated bond-containing substituent .

According to one embodiment, at least one of Ar ² preferably has a polymerizable unsaturated bond-containing substituent, more preferably all Ar ² has a polymerizable unsaturated bond-containing substituent, and further preferably Ar ¹ does not have a polymerizable unsaturated bond-containing substituent A substituent of a saturated bond, and all Ar ² have a substituent containing a polymerizable unsaturated bond. The presence of a polymerizable unsaturated bond-containing substituent in Ar ² 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 above-mentioned polymerizable unsaturated bond-containing aromatic ester compound (A-1) has two or three ester bonds connecting two 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), the following chemical formula (1-1) or (1-2) can be exemplified ) shown in the compound.

[In the formula, R ¹ is a polymerizable unsaturated bond-containing substituent. R ² is each independently any one 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 0 or an integer of 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 0 or an integer of 1 or more, and l+m is an integer of 7 or less. When i, j, 1, and m are integers of 2 or more, a plurality of R ¹ or R ² may be the same or different from each other. R ¹ and R ² in formula (1-2) may be substituted on any carbon atom forming a naphthalene ring. ]

In the aforementioned formula (1-1), as a particularly preferable example of R ¹ , as described above, allyl, propenyl, isopropenyl, and 1-propenyl can be mentioned. i is preferably 1 or 2, more preferably 1.

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

The specific structure of the polymerizable unsaturated bond-containing aromatic ester compound (A-1) represented by the above-mentioned chemical formula (1) is not particularly limited, and the following chemical formulae (4-1) to (4- 43) The compound shown.

Among the above chemical formulae (4-1) to (4-43), chemical formulae (4-1) to (4-39) are preferred, and chemical formulae (4-1) to (4-3) and (4-10) are more preferred. )～(4-13), (4-18)～(4-39), more preferably chemical formulae (4-1)～(4-3), (4-12), (4-13), (4 -19)～(4-21), (4-23)～(4-26), (4-29), (4-30), (4-32)～(4-39), especially the chemical formula (4-1), (4-2), (4-12), (4-13), (4-26), (4-32), (4-37).

In addition, from the viewpoint of high handleability and low viscosity of the aromatic ester compound (A), (4-1), (4-2), (4-12), (4-13) are preferable, and the other On the other hand, from the viewpoint of better heat resistance of the obtained cured product and excellent balance with low dielectric properties, (4-26), (4-32), and (4-37) are preferred.

The manufacturing method in particular of the said polymerizable unsaturated bond containing aromatic ester compound (A-1) is not restrict|limited, It can manufacture by a well-known method suitably.

In one embodiment, the method for producing a polymerizable unsaturated bond-containing aromatic ester compound (A-1) includes mixing a polycarboxylic acid compound having a substituted or unsubstituted first aromatic ring group or a derivative thereof with a polycarboxylic acid compound having a substituted or unsubstituted first aromatic ring group. The step of reacting the phenolic compound of the substituted or unsubstituted second aromatic ring group.

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

(Polycarboxylic acid compound or its derivative)

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

The substituents of the first aromatic ring group and the first aromatic ring group are the same as those described above.

Specific polycarboxylic acid compounds or derivatives thereof include compounds represented by the following chemical formulae (5-1) to (5-15).

In the above chemical formulae (5-1) to (5-15), R ¹ is a hydroxyl group or a halogen atom. In addition, R ² is a polymerizable unsaturated bond-containing substituent. In this case, the aforementioned polymerizable unsaturated bond-containing substituent is the same as that described above. Furthermore, p is 2 or 3. In addition, q is an integer of 0 or more, preferably 0 or 1 to 3, more preferably 0 or 1, and still more preferably 0. It should be noted that the position of the substituent on the aromatic ring in the above chemical formula is described on the same aromatic ring for convenience, but for example, in the above chemical formula (5-7), etc., R ¹ OC and R ² may be Substitution is performed on different benzene rings, and the number of substituents in one molecule is represented by p and q.

The specific polycarboxylic acid compound or its derivative is not particularly limited, and examples thereof include benzene such as isophthalic acid, terephthalic acid, 5-allyl isophthalic acid, and 2-allyl terephthalic acid. Dicarboxylic acids; trimellitic acid, 5-allyl trimellitic acid and other benzene tricarboxylic acids; 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, 3,7-diallylnaphthalene-1,4-dicarboxylic acid and other naphthalene dicarboxylic acids Acids; pyridinetricarboxylic acids such as 2,4,5-pyridinetricarboxylic acid; triazinecarboxylic acids such as 1,3,5-triazine-2,4,6-tricarboxylic acid; their acid halides and the like. Among these, benzenedicarboxylic acid and benzenetricarboxylic acid are preferred, and isophthalic acid, terephthalic acid, isophthaloyl chloride, terephthaloyl chloride, and 1,3,5-benzenetricarboxylic acid are more preferred. The acid and 1,3,5-benzenetricarbonyl trichloride are more preferably isophthaloyl chloride, terephthaloyl chloride, and 1,3,5-benzenetricarbonyl trichloride.

The above-mentioned polycarboxylic acid compounds or derivatives thereof may be used alone or in combination of two or more.

(Phenolic compound)

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

Specific phenolic compounds include compounds represented by the following chemical formulae (6-1) to (6-17).

In the above chemical formulae (6-1) to (6-17), R ² is a polymerizable unsaturated bond-containing substituent. In this case, the aforementioned polymerizable unsaturated bond-containing substituent is the same as that described above. Furthermore, q is an integer of 0 or 1 or more, preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. When q is 2 or more, the bonding position on the aromatic ring is arbitrary, for example, the naphthalene ring of the chemical formula (6-6) and the heterocyclic ring of the chemical formula (6-17) can be substituted on any ring. , in chemical formula (6-9), etc., it can be substituted on any ring of the benzene ring existing in one molecule, and the number of substituents in one molecule is shown as q.

The specific phenol compound is not particularly limited, and examples thereof include phenol; naphthol; 2-allylphenol, 3-allylphenol, 4-allylphenol, and 4-methyl-2-allylphenol , 6-methyl-2-allylphenol, eugenol and other allylphenols; 2-(1-propenyl)phenol, isoeugenol and other allylphenols; 2-(3-butenyl)phenol, Butenylphenols such as 2-(1-ethyl-3-butenyl)phenol; long-chain alkenylphenols such as cardanol; 2-allyl-1-naphthol, 1-allyl-2-naphthalene Allyl naphthols such as phenol, 3-allyl-1-naphthol, 3-allyl-1-naphthol, etc. Among these, allylphenol and allylnaphthol are preferred, and 2-allylphenol, 4-methyl-2-allylphenol, and 6-methyl-2-allylphenol are more preferred. , 2-allyl-1-naphthol, 1-allyl-2-naphthol, more preferably 2-allyl-phenol, 2-allyl-1-naphthol, 1-allyl- 2-Naphthol.

In addition, 2-allylphenol and the like having a benzene ring skeleton are preferred from the viewpoints of high handleability and low viscosity of the aromatic ester compound (A), and on the other hand, the heat resistance of the resulting cured product is better. From the viewpoint of being good and having an excellent balance with low dielectric properties, 2-allyl-1-naphthol, 1-allyl-2-naphthol and the like having a naphthalene ring skeleton are preferable.

The above-mentioned phenolic compounds may be used alone or in combination of two or more.

The amount of the polycarboxylic acid compound or its derivative and the phenol compound to be used is not particularly limited. The number of moles of derivative groups such as carboxyl group and/or halogenated acyl group of the polycarboxylic acid compound or its derivative is relative to the mole number of the hydroxyl group of the phenolic compound. The molar ratio of numbers [(derivative groups such as carboxyl group and/or halogenated acyl group)/(hydroxyl group)] is preferably 0.8 to 3.0, more preferably 0.9 to 2.0, further preferably 1.0 to 1.2.

The reaction conditions are not particularly limited, and an appropriate known method can be employed.

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

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

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

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

The polymerizable unsaturated bond-containing aromatic ester compound (A-2) is a first aromatic compound having two or more phenolic hydroxyl groups, a second aromatic compound having a phenolic hydroxyl group, and a third aromatic compound having two or more carboxyl groups A reaction product of an aromatic compound and/or its acid halide or ester, at least one of the first aromatic compound, the second aromatic compound, and the third aromatic compound and/or its acid halide and ester One of them has a polymerizable unsaturated bond-containing substituent.

[1st Aromatic Compound]

The first aromatic compound has two or more phenolic hydroxyl groups. By having two or more phenolic hydroxyl groups, a polyester structure can be formed in the polymerizable unsaturated bond-containing aromatic ester compound (A-2) by reacting with a third aromatic compound or the like described later.

Although it does not specifically limit as a 1st aromatic compound, The compound which has two or more phenolic hydroxyl groups on the C3-C30 substituted or unsubstituted 1st aromatic ring is mentioned.

In this case, the first aromatic ring having 3 to 30 carbon atoms is not particularly limited, and examples thereof include a monocyclic aromatic ring, a condensed aromatic ring, and a ring-assembled aromatic ring.

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 etc.

The aforementioned condensed aromatic ring is not particularly limited, and examples thereof include naphthalene, anthracene, phenarene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, and benzene. Imidazole, benzofuran, acridine, etc.

Although it does not specifically limit as said ring-assembled aromatic ring, Biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, tetrabiphenyl, etc. are mentioned.

The said 1st aromatic ring may have a substituent. In this case, the "substituent of the first 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 non-polymerizable Substituents for saturated bonds, etc.

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

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, and a 2- Ethylhexyloxy, octyloxy, nonyloxy, etc.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

The polymerizable unsaturated bond-containing substituent refers to a substituent having 2 to 30 carbon atoms and having at least one polymerizable unsaturated bond. In this case, the "unsaturated bond" refers to a carbon-carbon double bond and a carbon-carbon triple bond. As the said polymerizable unsaturated bond containing substituent, an alkenyl group, an alkynyl group, etc. are mentioned.

The alkenyl group is not particularly limited, and examples thereof include vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-butenyl, and 1-butenyl. - 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, cyclo Octenyl, 1,3-butadienyl, 1,4-butadienyl, 1,3-hexadienyl, 2,5-hexadienyl, 4,7-pentadecadienyl , 1,3,5-hexatrienyl, 1,4,7-pentadecatrienyl, etc.

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

Among these, as the polymerizable unsaturated bond-containing substituent, an alkenyl group having 2 to 30 carbon atoms is preferable, an alkenyl group having 2 to 10 carbon atoms is more preferable, and an alkenyl group having 2 to 5 carbon atoms is further preferable. Alkenyl, particularly preferably vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadiene group, most preferably allyl, propenyl, isopropenyl and 1-propenyl.

The substituents of the above-mentioned first aromatic ring may be contained alone or in combination of two or more.

Furthermore, as described above, in the first aromatic compound, at least two of the hydrogen atoms constituting the above-mentioned substituted or unsubstituted first aromatic ring are substituted with hydroxyl groups.

Specific examples of the compound in which the first aromatic ring is a monocyclic aromatic ring (hereinafter, may also be simply referred to as "the first monocyclic aromatic ring compound") include catechol, resorcinol, and hydroquinone. , trimerol, phloroglucinol, pyrogallol, 2,3-dihydroxypyridine, 2,4-dihydroxypyridine, 4,6-dihydroxypyrimidine, 3-methylcatechol, 4- Methyl catechol, 4-allyl catechol, etc.

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

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

Moreover, the 1st aromatic compound may have the structure which the said 1st aromatic ring was connected by the connection group. In one embodiment, the first aromatic compound is represented by the following chemical formula (7).

In the above chemical formula (7), Ar ³ is each independently a substituted or unsubstituted first aromatic ring group, Ar ⁴ is each independently a substituted or unsubstituted second aromatic ring group, and X is each independently an oxygen atom , sulfur atom, substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, aralkylene, n is 0-10. At this time, at least two of the hydrogen atoms constituting the aforementioned Ar ³ and the aforementioned Ar ⁴ are substituted with hydroxyl groups. In addition, the said X corresponds to a linking group.

The aforementioned Ar ³ is a substituted or unsubstituted first aromatic ring group. It is also clear from the description of the above-mentioned chemical formula (7) that one of the hydrogen atoms of the aromatic ring constituting the above-mentioned substituted or unsubstituted aromatic ring is bonded to "X".

The first aromatic ring group is not particularly limited, and examples thereof include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, and pyridine. One hydrogen atom is removed from monocyclic aromatic compounds such as oxazine and triazine; A compound obtained by removing one hydrogen atom from an aromatic compound, such as a fused-ring aromatic compound such as an indole, indole, benzimidazole, benzofuran, and acridine. In addition, it may be obtained by combining a plurality of these aromatic compounds, for example, biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, It is obtained by removing one hydrogen atom from ring-assembled aromatic compounds such as tetraphenyl.

In this case, the first aromatic ring group may have a substituent. Examples of the "substituent of the first aromatic ring group" include the same examples as those of the "substituent of the first aromatic ring" described above.

Among these, Ar ³ is preferably selected from benzene, naphthalene, anthracene, phenarene, phenanthrene, biphenyl, binaphthyl, tetraphenyl, allylbenzene, diallylbenzene, allylnaphthalene, diallyl phenylnaphthalene, allylbiphenyl, diallylbiphenyl by removing one hydrogen atom, more preferably selected from benzene, naphthalene, biphenyl, allylbenzene, diallylnaphthalene, diallyl It is formed by removing one hydrogen atom from the base biphenyl.

The aforementioned Ar ⁴ is each independently a substituted or unsubstituted second aromatic ring group. It is also clear from the description of the above chemical formula (1) that two of the hydrogen atoms of the aromatic ring constituting the above-mentioned substituted or unsubstituted aromatic ring are bonded to "X".

The second aromatic ring group is not particularly limited, and examples thereof include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, and pyridine. Monocyclic aromatic compounds such as oxazine and triazine by removing 2 hydrogen atoms; from naphthalene, anthracene, phenarene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin It is a product obtained by removing two hydrogen atoms from an aromatic compound, such as those obtained by removing two hydrogen atoms from fused-ring aromatic compounds such as indole, indole, benzimidazole, benzofuran, and acridine. In addition, it may be obtained by combining a plurality of these aromatic compounds, for example, biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, It is formed by removing two hydrogen atoms from ring-collected aromatic compounds such as tetraphenyl.

In this case, the second aromatic ring group may have a substituent. Examples of the "substituent of the second aromatic ring group" include the same examples as the "substituent of the first aromatic ring" described above.

The aforementioned X is each independently an oxygen atom, a sulfur atom, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or an aralkylene group.

It does not specifically limit as said alkylene group, Methylene group, ethylene group, propylene group, 1-methylmethylene group, 1, 1- dimethylmethylene group, 1-methylethylene group are mentioned base, 1,1-dimethylethylene, 1,2-dimethylethylene, propylene, butylene, 1-methylpropylene, 2-methylpropylene, pentylene , Axe, etc.

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

In addition, in the said chemical formula (8-1) - (8-4), "*" represents the site|part which is bonded to Ar ³ or Ar ⁴ .

Although it does not specifically limit as said aralkylene group, The aralkylene group etc. which are represented by following chemical formula (9-1)-(9-8) are mentioned.

In addition, in the said chemical formula (9-1) - (9-8), "*" shows the site|part which is bonded to Ar ³ or Ar ⁴ .

The aforementioned alkylene group, the aforementioned cycloalkylene group, and the aforementioned aralkylene group may have a substituent. In this case, as the "substituent of X", the same examples as the above-mentioned "substituent of the first aromatic ring" can be given.

n in the above chemical formula (7) is an integer of 0 to 10, preferably 0 to 8, and preferably 0 to 5. In addition, when the compound represented by the said chemical formula (7) is an oligomer or a polymer, n means the average value.

Furthermore, at least two of the hydrogen atoms constituting the aforementioned Ar ³ and the aforementioned Ar ⁴ are substituted with 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 formulae (10-1) to (10-8), and Compounds having one or more polymerizable unsaturated bond-containing substituents on their aromatic nucleus.

As said various bisphenol compounds, bisphenol A, bisphenol AP, bisphenol B, bisphenol E, bisphenol F, bisphenol Z etc. are mentioned, for example.

In the above chemical formulae (10-1) to (10-8), n is 0-10, preferably 0-5. In this case, when the compounds represented by chemical formulae (10-1) to (10-8) are oligomers or polymers, n means the average value thereof. In addition, in this specification, "oligomer" means the compound which contains 1-5 repeating units, and "polymer" means the compound which contains 6 or more repeating units. In addition, the substituent on the aromatic ring, that is, the substitution position of the hydroxyl group is arbitrary, and in the case of the naphthalene ring, it may be any of a ring bonded to another structure or an unbonded ring.

It should be noted that, in one embodiment, the above-mentioned first aromatic ring is represented by the above-mentioned chemical formula (7), wherein at least one of the hydrogen atoms constituting the first aromatic ring may be substituted with a hydroxyl group and two It is synthesized by the reaction of a vinyl compound and a dialkoxymethyl compound.

In this case, the dienyl compound and the dialkoxymethyl compound are not particularly limited, and examples thereof include 1,3-butadiene, 1,5-hexadiene, dicyclopentadiene, and tricyclopentadiene. Aliphatic diene compounds such as diene, tetracyclopentadiene, pentacyclopentadiene, and hexacyclopentadiene; aromatic diene compounds such as dienylbenzene and divinylbiphenyl; dimethoxymethyl Benzene, dimethoxymethyl biphenyl, bisphenol A methoxy adduct, bisphenol A ethoxy adduct, bisphenol F methoxy adduct, bisphenol F ethoxy adduct and other dialkoxymethyl compounds.

The above-mentioned first aromatic compound having two or more phenolic hydroxyl groups may be used alone or in combination of two or more.

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

The first aromatic compound is represented by the above-mentioned chemical formula (7), and the weight average molecular weight when n is an oligomer or a polymer is preferably 200 to 3,000, and more preferably 200 to 2,000. When the weight average molecular weight of the first aromatic compound is 200 or more, the dielectric loss tangent is excellent, which is preferable. On the other hand, when the weight-average molecular weight of the first aromatic compound is 3,000 or less, the moldability is excellent, which is preferable. In addition, in this specification, the value measured by the following method is employ|adopted for the value of "weight average molecular weight". That is, the value obtained by gel permeation chromatography (GPC) measurement under the following conditions is used.

Measurement conditions for GPC

Measuring device: "HLC-8320GPC" manufactured by Tosoh Corporation

Column: Tosoh Co., Ltd. guard column "HXL-L"

+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

Detector: RI (differential refractometer)

Data processing: "GPC Workstation EcoSECWorkStation" manufactured by Tosoh Corporation

Column temperature: 40℃

Developing solvent: tetrahydrofuran

Flow rate: 1.0ml/min

Standard: According to the aforementioned "GPC-8320GPC" measurement manual, the following monodisperse polystyrene with known molecular weight is used

Use polystyrene

Tosoh Corporation "A-500"

Tosoh Corporation "A-1000"

Tosoh Corporation "A-2500"

Tosoh Corporation "A-5000"

Tosoh Corporation "F-1"

Tosoh Corporation "F-2"

Tosoh Corporation "F-4"

Tosoh Corporation "F-10"

Tosoh Corporation "F-20"

Tosoh Corporation "F-40"

Tosoh Corporation "F-80"

Tosoh Corporation "F-128"

Use: A tetrahydrofuran solution of 1.0 mass % in terms of resin solid content was filtered with a microfilter (50 μl).

[Second aromatic compound]

The second aromatic compound has a phenolic hydroxyl group. Since the second aromatic compound has one phenolic hydroxyl group, it has a function of stopping the polyesterification reaction of the first aromatic compound described above and the third aromatic compound described later.

Although it does not specifically limit as a 2nd aromatic compound, The compound which has one phenolic hydroxyl group on the 2nd aromatic ring of substituted or unsubstituted C3-C30 is mentioned.

Although it does not specifically limit as said 2nd aromatic ring, A monocyclic aromatic ring, a condensed-ring aromatic ring, a ring-assembled aromatic ring, an aromatic ring connected by an alkylene group, etc. are mentioned. Examples of the monocyclic aromatic ring, the condensed aromatic ring, and the ring-aggregated aromatic ring include the same examples as those of the first aromatic ring described above.

Moreover, diphenylmethane, diphenylethane, 1, 1- diphenyl ethane, 2, 2- diphenyl propane, naphthyl phenyl are mentioned as an aromatic ring connected by an alkylene group Methane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fluorene, diphenylcyclopentane, etc.

The second aromatic ring related to the second aromatic compound may have a substituent. In this case, as the "substituent of the second aromatic ring", the same examples as the above-mentioned "substituent of the first aromatic ring" can be given.

Furthermore, as described above, in the second aromatic compound, one of the hydrogen atoms constituting the above-mentioned substituted or unsubstituted second aromatic ring is substituted with a hydroxyl group.

Examples of the second aromatic compound include compounds represented by the following chemical formulae (11-1) to (11-17).

In the above chemical formulae (11-1) to (11-17), R ¹ is a polymerizable unsaturated bond-containing substituent. In this case, the aforementioned polymerizable unsaturated bond-containing substituent is the same as that described above. Furthermore, p is an integer of 0 or more, preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. When p is 2 or more, the bonding position on the aromatic ring is arbitrary. For example, the naphthalene ring of the chemical formula (11-6) and the heterocyclic ring of the chemical formula (11-17) can be substituted on any ring. , in the chemical formula (11-9), etc., it can be substituted on any ring of the benzene ring existing in one molecule, and the number of substituents in one molecule is shown as p.

The specific second aromatic compound is not particularly limited, and examples thereof include phenol, cresol, xylenol, o-allyl phenol, m-allyl phenol, p-allyl phenol, and 2,4-diallyl phenol, 2,6-diallylphenol, 2-allyl-4-methylphenol, 2-allyl-6-methylphenol, 2-allyl-4-methoxy-6 - Compounds in which the aromatic ring is a monocyclic aromatic ring such as methylphenol, 2-propynylphenol, 3-propynylphenol, and 4-propynylphenol (hereinafter, sometimes abbreviated as "second monocyclic aromatic ring") cyclic compounds"); 1-naphthol, 2-naphthol, 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3- Allyl-2-naphthol, 5-allyl-1-naphthol, 6-allyl-1-naphthol, diallyl-naphthol, 2-allyl-4-methoxy- Aromatics such as 1-naphthol, 2-propynyl-1-naphthol, 3-propynyl-1-naphthol, 1-propynyl-2-naphthol, 3-propynyl-2-naphthol Compounds in which the aromatic ring is a fused aromatic ring (hereinafter, sometimes abbreviated as "second fused aromatic ring compound"); aromatic rings such as allyl hydroxy biphenyl and hydroxypropynyl biphenyl are ring-aggregated aromatic rings A ring compound (hereinafter, it may be abbreviated as a "second ring aggregated aromatic ring compound") and the like.

Among the above, the second aromatic compound is preferably the second monocyclic aromatic ring compound and the second condensed aromatic ring compound, 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, 6-allyl-1-naphthol.

In addition, in another embodiment, the second aromatic compound is preferably a second condensed aromatic ring compound (condensed aromatic ring compound), more preferably 2-allyl-1-naphthol and 3-allyl Alkyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, 6-allyl-1-naphthol . When the second aromatic compound is a condensed aromatic ring compound, molecular motion is suppressed due to steric hindrance, whereby the dielectric loss tangent can be reduced, which is preferable. Moreover, 2-allylphenol etc. which have a benzene ring skeleton are preferable from the viewpoint of high handleability and low viscosity of the aromatic ester compound (A). 2-allyl-1-naphthol, 1-allyl-2-naphthol, etc. having a naphthalene ring skeleton are preferable from the viewpoint of better properties and excellent balance with low dielectric properties.

In addition, the said 2nd aromatic compound may be used individually, and may be used in combination of 2 or more types.

[The third aromatic compound and/or its acid halide, ester compound]

The third aromatic compound and/or its acid halide and ester are carboxylic acids having two or more carboxyl groups, or derivatives thereof, specifically acid halides and esters (in this specification, the third aromatic compound may be referred to as The aromatic compounds and/or their acid halides and esters are collectively referred to as "third aromatic compounds, etc."). The polymerizable unsaturated bond-containing aromatic ester compound (A-2) can be formed by reacting with the above-mentioned first aromatic compound by making the third aromatic compound etc. have two or more carboxyl groups or the like. Polyester structure. In addition, polyesterification reaction stops by reacting with the said 2nd aromatic compound.

Although it does not specifically limit as a 3rd aromatic compound etc., The compound etc. which have 2 or more carboxyl groups on a substituted or unsubstituted C3-C30 aromatic ring are mentioned.

In addition, "carboxyl group etc." include: carboxyl group; halogenated acyl groups such as fluorinated acyl groups, chlorinated acyl groups, and brominated acyl groups; alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups; phenoxycarbonyl groups, Aryloxycarbonyl such as naphthoxycarbonyl, etc. In addition, when it has a halogenated acyl group, the third aromatic compound is an acid halide, and when it has an alkoxycarbonyl group or an aryloxycarbonyl group, the third aromatic compound can be an esterified compound. Among these, the third aromatic compound preferably has a carboxyl group, a halogenated acyl group, or an aryloxycarbonyl group, more preferably a carboxyl group or a halogenated acyl group, and still more preferably a carboxyl group, a chloroacyl group, or a brominated acyl group.

Although it does not specifically limit as a 3rd aromatic compound etc., The compound etc. which have 2 or more carboxyl groups on a substituted or unsubstituted C3-C30 aromatic ring are mentioned.

Although it does not specifically limit as said 3rd aromatic ring, A monocyclic aromatic ring, a condensed-ring aromatic ring, a ring-assembled aromatic ring, an aromatic ring connected by an alkylene group, etc. are mentioned. Examples of the monocyclic aromatic ring, the condensed aromatic ring, the ring-aggregated aromatic ring, and the aromatic ring linked by an alkylene group include the same as the above-mentioned first aromatic ring and second aromatic ring example of.

The third aromatic ring related to the third aromatic compound and the like may have a substituent. In this case, as the "substituent of the third aromatic ring", the same examples as the above-mentioned "substituent of the first aromatic ring" can be given.

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

In the above chemical formulae (12-1) to (12-15), R ¹ is a polymerizable unsaturated bond-containing substituent. In this case, the aforementioned polymerizable unsaturated bond-containing substituent is the same as that described above. In addition, R ² is a hydroxyl group, a halogen atom, an alkoxy group, or an aryloxy group. Furthermore, p is an integer of 0 or 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, and even more preferably 0. q is 2 or 3. When p and q are 2 or more, the bonding position on the aromatic ring is arbitrary. For example, the naphthalene ring of the chemical formula (12-5) and the heterocyclic ring of the chemical formula (12-15) may be on any ring. Substitution is carried out, and in chemical formula (12-7) and the like, any ring of the benzene ring existing in one molecule may be substituted, and the number of substituents in one molecule is shown as p and q.

The specific third aromatic compound and the like are not particularly limited, and examples thereof include phthalic acid such as isophthalic acid, terephthalic acid, 5-allyl isophthalic acid, and 2-allyl terephthalic acid. Acid; trimellitic acid, 5-allyl trimellitic acid and other benzene tricarboxylic acids; naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid Acid, naphthalene-2,7-dicarboxylic acid, 3-allylnaphthalene-1,4-dicarboxylic acid, 3,7-diallylnaphthalene-1,4-dicarboxylic acid and other naphthalene dicarboxylic acids; Pyridinetricarboxylic acids such as 2,4,5-pyridinetricarboxylic acid; triazinecarboxylic acids such as 1,3,5-triazine-2,4,6-tricarboxylic acid; their acid halides, esters, and the like. Among these, benzenedicarboxylic acid and benzenetricarboxylic acid are preferred, and isophthalic acid, terephthalic acid, isophthaloyl chloride, terephthaloyl chloride, and 1,3,5-benzenetricarboxylic acid are more preferred. The acid and 1,3,5-benzenetricarbonyl trichloride are more preferably isophthaloyl chloride, terephthaloyl chloride, and 1,3,5-benzenetricarbonyl trichloride.

Among the above, the third aromatic compound etc. whose aromatic ring is a monocyclic aromatic ring, the third aromatic compound etc. whose aromatic ring is a condensed aromatic ring are preferable, and benzenedicarboxylic acid and benzenetricarboxylic acid are preferable. Acid, naphthalene dicarboxylic acid, and their acid halides, more preferably phthalic acid, naphthalene dicarboxylic acid, and their acid halides, still more preferably isophthalic acid, terephthalic acid, naphthalene-1,5 -Dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, their acid halides.

The above-mentioned third aromatic compound and the like may be used alone or in combination of two or more.

[Configuration of Polymerizable Unsaturated Bond-Containing Aromatic Ester Compound (A-2)]

At least one of the above-mentioned first aromatic compound, second aromatic compound, and third aromatic compound and/or its acid halide, ester product (third aromatic compound, etc.) has a polymerizable unsaturated bond the substituent. That is, the first aromatic compound, the second aromatic compound, the third aromatic compound and the like may all have a polymerizable unsaturated bond-containing substituent, and the first aromatic compound and the second aromatic compound may have a polymerizable unsaturated bond-containing substituent. As for the substituent of the saturated bond, only the second aromatic compound may have a substituent containing a polymerizable unsaturated bond. Moreover, when using 2 or more types of 1st aromatic compound, a 2nd aromatic compound, a 3rd aromatic compound, etc., only a part of them may have the substituent containing a polymerizable unsaturated bond. The number of carbon atoms of the polymerizable unsaturated bond-containing substituent is preferably in the range of 2 to 30.

In one embodiment, at least the second aromatic compound preferably has a polymerizable unsaturated bond-containing substituent. As described above, the structure derived from the second aromatic compound is located at the molecular terminal of the polymerizable unsaturated bond-containing aromatic ester compound (A-2). As a result, the polymerizable unsaturated bond-containing substituent which the second aromatic compound has is also arranged at the molecular terminal 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 cured product obtained can be made higher, which is preferable.

As described above, the polymerizable unsaturated bond-containing aromatic ester compound (A-2) is a reaction product of the first aromatic compound, the second aromatic compound, and the third aromatic compound, and may include various compounds. The composition of the polymerizable unsaturated bond-containing aromatic ester compound (A-2) can be appropriately changed by appropriately changing the amounts of the first aromatic compound, the second aromatic compound, the third aromatic compound, and the like, the reaction conditions, and the like. control.

In addition, the polymerizable unsaturated bond containing aromatic ester compound (A-2) of this aspect does not have a hydroxyl group in the molecule|numerator of the resin obtained as a principle. However, the compound having a hydroxyl group may be contained as a by-product of the reaction product within a range that does not inhibit the effect of the present invention.

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

In the above chemical formula (13), Ar ¹ is a structure derived from a first aromatic compound, Ar ² is a structure derived from a second aromatic compound, and Ar ³ is a structure derived from a third aromatic compound or the like. In addition, n is 0-10. In addition, when the polymerizable unsaturated bond-containing aromatic ester compound (A-2) is an oligomer or a polymer, n represents the average value.

That is, Ar ¹ each independently includes those obtained by removing two or more hydrogen atoms from a substituted or unsubstituted first aromatic ring, or those obtained by connecting with a connecting group from a first aromatic ring having a first aromatic ring. A compound with a structure that removes two or more hydrogen atoms.

In addition, Ar ² independently includes one obtained by removing one hydrogen atom from the substituted or unsubstituted second aromatic ring.

Ar ³ includes those obtained by removing two or more hydrogen atoms from the substituted or unsubstituted third aromatic ring.

In addition, at least one of Ar ¹ , Ar ² , and Ar ³ has a polymerizable unsaturated bond-containing substituent.

In this case, when the first aromatic compound has three or more phenolic hydroxyl groups, Ar ¹ may further have a branched structure.

Moreover, when a 3rd aromatic compound etc. have 2 or more carboxyl groups etc., Ar ³ may further have a branched structure.

In one embodiment, the compounds represented by the following chemical formulae (14-1) to (14-10) are exemplified as compounds contained in the polymerizable unsaturated bond-containing aromatic ester compound (A-2).

In the above chemical formulae (14-1) to (14-10), s is 0 to 10, preferably 0 to 5, and r is 1 to 10. At this time, when the compounds represented by chemical formulae (14-1) to (14-10) are oligomers or polymers, s1, s2, and r mean the average values thereof. In addition, the dotted line in a chemical formula is a structure obtained by reacting the compound corresponding to Ar ³ and Ar ¹ and/or Ar ² .

The weight average molecular weight of the aromatic ester compound (A-2) is preferably 150 to 3,000, and more preferably 200 to 2,000. When the weight average molecular weight is 800 or more, the dielectric loss tangent is excellent, which is preferable. On the other hand, when the weight average molecular weight is 500 or less, the moldability is excellent, which is preferable. Moreover, as a number average molecular weight, the range of 150-1500 is preferable for the same reason.

<Method for producing a polymerizable unsaturated bond-containing aromatic ester compound (A-2)>

The production method of the polymerizable unsaturated bond-containing aromatic ester compound (A-2) is not particularly limited, and it can be produced by an appropriate known method.

In one embodiment, the method for producing a polymerizable unsaturated bond-containing aromatic ester compound (A-2) includes a step of reacting a first aromatic compound, a second aromatic compound, a third aromatic compound, and the like.

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

As the first aromatic compound, the second aromatic compound, the third aromatic compound, and the like, the above-mentioned compounds can be used.

In one embodiment, the amount of the obtained polymerizable unsaturated bond-containing aromatic ester compound (A-2) can be controlled by appropriately adjusting the amounts of the first aromatic compound, the second aromatic compound, the third aromatic compound, and the like. constitute.

For example, the ratio of the number of moles of carboxyl groups and the like of the third aromatic compound to the number of moles of hydroxyl groups of the first aromatic compound (carboxyl group and the like/hydroxyl group of the first aromatic compound) is preferably 0.5 to 10, and more preferably 0.5 to 10. 6.0, and more preferably 1.0 to 3.0. When the said ratio is 0.5 or more, since heat resistance becomes high, it is preferable. On the other hand, when the said ratio is 10 or less, since it is excellent in formability, it is preferable.

In addition, the ratio of the number of moles of carboxyl groups and the like of the third aromatic compound to the number of moles of hydroxyl groups of the second aromatic compound (carboxyl group etc./hydroxyl group of the second aromatic compound) is preferably 0.5 to 10, more preferably 1.5 to 10. 4.0. When the said ratio is 0.5 or more, it is excellent in formability, and it is preferable. On the other hand, when the said ratio is 10 or less, since heat resistance becomes high, it is preferable.

Moreover, in one embodiment, by controlling the reaction sequence, the structure of the obtained polymerizable unsaturated bond-containing aromatic ester compound (A-2) can be controlled.

The method for producing a polymerizable unsaturated bond-containing aromatic ester compound (A-2) includes the step (1) of reacting the first aromatic compound and the third aromatic compound, and the step (1) obtained by reacting the The step (2) in which the product and the second aromatic compound are reacted. According to the above-mentioned production method, since the reaction can be controlled after the polyester structure is constructed, the polymerizable unsaturated bond-containing aromatic ester compound (A-2) having a uniform molecular weight distribution can be obtained.

Moreover, by controlling the reaction conditions, the structure of the obtained polymerizable unsaturated bond-containing aromatic ester compound (A-2) can be controlled.

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

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

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

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

Examples of the arylene group in the polyarylene ether resin (B) used in the present invention include a phenylene group, a naphthylene group, and an aliphatic hydrocarbon group, an alkoxy group, an aryl group, and an aryl group on their aromatic nucleus. Structural sites of substituents such as alkyl groups, etc. Among them, from the viewpoint of forming a curable composition excellent in the balance between the dielectric properties and heat resistance of the cured product, a phenylene group is preferred as the main skeleton, and a phenylene group having two substituents on an aromatic nucleus is more preferred . As the kind of the substituent, an aliphatic hydrocarbon group is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

The terminal structure of the aforementioned polyarylene ether resin (B) is usually an aryloxy group having a phenolic hydroxyl group. The aforementioned phenolic hydroxyl groups may be modified into 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, and an aralkyl group on their aromatic nucleus. Among them, from the viewpoint of forming a curable composition excellent in the balance between the dielectric properties and heat resistance of the cured product, a phenyl group is preferably used as the main skeleton, and it is more preferable that the aromatic nucleus has two substituents in addition to the phenolic hydroxyl group. of phenylene. As the kind of substituent, an aliphatic hydrocarbon group is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

As a structural moiety obtained by modifying the aforementioned phenolic hydroxyl group, for example, a polymerizable unsaturated bond-containing group such as a (meth)acryloyloxy group, an allyloxy group, a vinyloxy group, and the like, A structural site obtained by reacting a phenolic hydroxyl group with an epoxy compound, etc. Among them, a phenolic hydroxyl group or the aforementioned polymerizable unsaturated bond-containing group is preferable from the viewpoint of forming a curable composition excellent in the balance between the dielectric properties and heat resistance of the cured product.

As said polyarylene ether resin (B), the example etc. which are shown by following structural formula (15) are mentioned, for example.

(wherein R ¹ is each independently any one of a hydrogen atom, aliphatic hydrocarbon group, alkoxy group, aryl group, and aralkyl group. m and n are each independently an integer of 0 or more. X is a hydrogen atom or a polymer-containing groups with unsaturated bonds.)

Y in the aforementioned structural formula (15) is not particularly limited as long as it is a divalent organic group, and may be any structural moiety, and examples thereof include those in the following structural formulae (Y-1) to (Y-9). The structure shown by any one of , etc.

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

The functional group equivalent of the phenolic hydroxyl group of the polyarylene ether resin (B) or the structural site obtained by modifying it, that is, the functional group equivalent of the structural site represented by the terminal -OX group in the structural formula (15) is preferably in the range of 500 to 3,000 g/equivalent, and 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 compounding ratio of the above-mentioned polymerizable unsaturated bond-containing aromatic ester compound (A) and the above-mentioned polyarylene ether resin (B) is not particularly limited, and may be determined according to the desired properties of the cured product and so on to make appropriate adjustments. Among them, it is preferable to use it in the range of 10 to 300 parts by mass with respect to 100 parts by mass of the aromatic ester compound (A) from the viewpoint of forming a curable composition excellent in the balance of heat resistance and dielectric properties of the cured product It is more preferable to use the said polyarylene ether resin (B) in the range of 20-200 mass parts.

The curable composition of the present invention may contain other components in addition to the above-mentioned polymerizable unsaturated bond-containing aromatic ester compound (A) and polyarylene ether resin (B). Hereinafter, an example of other components will be given. In addition, the other components which the curable composition of this invention can contain are not limited to the components illustrated below, You may contain other components.

[Epoxy resin]

In the curable composition of the present invention, since the polymerizable unsaturated bond-containing aromatic ester compound (A) contains a polymerizable unsaturated bond, even if only the aromatic ester compound (A) and the polyarylene ether resin ( B), also has curability. On the other hand, since the said aromatic ester compound (A) also functions as a hardening|curing agent of an epoxy resin, and can obtain the hardened|cured material with higher heat resistance, it is preferable that the curable composition of this invention further contains an epoxy resin.

The epoxy resin is not particularly limited, and examples thereof include phenol novolak epoxy resin, cresol novolak epoxy resin, α-naphthol novolak epoxy resin, and β-naphthol novolak epoxy resin. Resin, bisphenol A novolak epoxy resin, biphenyl novolak epoxy resin and other novolak epoxy resin; phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, phenol biphenyl Aralkyl type epoxy resin such as aralkyl type epoxy resin; 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 and other bisphenols type epoxy resin; biphenyl type epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, epoxy resin with biphenyl skeleton and diglycidyloxybenzene skeleton, etc. biphenyl type epoxy resin; naphthalene type ring Oxygen resin; binaphthol type epoxy resin; binaphthyl type epoxy resin; dicyclopentadiene type epoxy resin such as dicyclopentadiene phenol type epoxy resin; tetraglycidyl diaminodiphenylmethane type epoxy resin, triglycidyl-p-aminophenol type epoxy resin, glycidylamine type epoxy resin of diaminodiphenyl sulfone and other glycidylamine type epoxy resin; 2,6-naphthalene dicarboxylic acid Diglycidyl ester epoxy resins, such as glycidyl ester epoxy resins, glycidyl ester epoxy resins of hexahydrophthalic anhydride, etc.; dibenzopyran, hexamethyldibenzopyran, 7-benzene Benzopyran type epoxy resins such as hexamethyldibenzopyran, etc. These may be used independently, respectively, and may be used in combination of 2 or more types.

The epoxy equivalent of the epoxy resin is preferably 150 to 500 g/equivalent, and 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, so it is preferable. On the other hand, when the epoxy equivalent of the epoxy resin is 500 g/equivalent or less, the difference between the heat resistance and the dielectric loss tangent is Since it is more excellent in balance, it is preferable.

It is preferable that it is 200-5000, and, as for the weight average molecular weight of an epoxy resin, it is more preferable that it is 300-3000. When the weight average molecular weight of the epoxy resin is 200 or more, it is possible to have both rapid curing properties, which is preferable. On the other hand, when the weight-average molecular weight of the epoxy resin is 5,000 or less, the moldability is excellent, which is preferable. In addition, the value measured by the above-mentioned method (GPC) is employ|adopted for the weight average molecular weight.

[Other curing agents]

When the curable composition of this invention contains the said epoxy resin, in addition to the said aromatic ester compound (A), other hardening|curing agent which can be hardened with an epoxy resin can be used together.

The other curing agent is not particularly limited, and examples thereof include aromatic ester compounds that do not contain a polymerizable unsaturated bond, amine curing agents, imidazole curing agents, acid anhydride curing agents, and phenol resin curing agents.

The amine curing agent is not particularly limited, and examples thereof include diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), and dipropylenediamine (DPDA). ), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine, montanediamine (MDA), isofluranediamine (IPDA), 1,3-bisaminomethylcyclohexanone (1 ,3-BAC), piperidine, N,N-dimethylpiperazine, triethylenediamine and other aliphatic amines; m-xylylenediamine (XDA), methanephenylenediamine (MPDA), diamino Diphenylmethane (DDM), Diaminodiphenylsulfone (DDS), Benzylmethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl) ) Aromatic amines such as phenol, etc.

Examples of the imidazole curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, epoxy- Imidazole adducts, etc.

Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, glycerol trimellitate, and maleic anhydride , tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendemethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride Formic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexenedicarboxylic anhydride, and the like.

Examples of the phenolic resin curing agent include phenol novolac resins, cresol novolac resins, naphthol novolac resins, bisphenol novolac resins, biphenyl novolac resins, dicyclopentadiene-phenol addition type resins, Phenol aralkyl resin, naphthol aralkyl resin, trisphenol methane type resin, tetraphenol ethane type resin, aminotriazine modified phenolic resin, etc.

The other curing agents described above may be used alone or in combination of two or more.

Content in particular of the said other hardening|curing agent is not restrict|limited, It is preferable that it is 2-80 mass % with respect to the said aromatic ester compound (A), and it is more preferable that it is 5-70 mass %.

In the curable composition of the present invention, the compounding ratio of the aromatic ester compound (A), epoxy resin, and other curing agent is not particularly limited, and can be appropriately adjusted according to the desired properties of the cured product. As an example, relative to It is preferable that it is the range of 0.7-1.5 mol of sum total of 1 mol of epoxy groups, and the sum total of the functional groups which can react with an epoxy group in the said aromatic ester compound (A) and another hardening|curing agent.

[other resins]

Specific examples of other resins are not particularly limited, and examples thereof include maleimide resins, bismaleimide resins, polyimide resins, cyanate ester resins, benzoxazine resins, and triazine-containing resins. Cresol novolac resin, cyanate ester resin, styrene-maleic anhydride resin, diallyl bisphenol, triallyl isocyanurate and other allyl-containing resins, polyphosphate ester, phosphate ester-carbonic acid Ester copolymer, polybutadiene resin, etc. These other resins may be used alone or in combination of two or more.

[solvent]

In one embodiment, the composition may contain a solvent. The aforementioned solvent has a function of adjusting the viscosity of the composition, and the like.

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

As a usage-amount of a solvent, 10-80 mass % is preferable with respect to the whole mass of a curable composition, and 20-70 mass % is more preferable. When the usage-amount of a solvent is 10 mass % or more, since handleability is excellent, it is preferable. On the other hand, when the usage-amount of a solvent is 80 mass % or less, since the impregnation property with other base materials is excellent, it is preferable.

[additive]

In one embodiment, the composition may contain additives. As this additive, a hardening accelerator, a flame retardant, a filler, etc. are mentioned.

(curing accelerator)

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, azo compounds, and the like .

Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; trimethylphosphite, Organic phosphite compounds such as triethyl phosphite; ethyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium chloride, butyl phosphonium tetraphenyl borate, tetraphenyl phosphonium tetraphenyl borate salt, tetraphenylphosphonium tetra-p-tolyl borate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide salt, butylphenylphosphonium dicyanamide salts, phosphonium salts such as tetrabutylphosphonium decanoate, etc.

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

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-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, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazolium isocyanurate plus Product, 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 guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, and trimethylguanidine. guanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabi Cyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-butyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide and the like.

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

Examples of the aforementioned peroxides and azo compounds include benzoyl peroxide, p-chlorobenzoyl peroxide, di-tert-butyl peroxide, diisopropyl peroxycarbonate, and bis(2-peroxycarbonate) ethylhexyl) ester, azobisisobutyronitrile, etc.

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

In addition, the said hardening accelerator may be used individually or in combination of 2 or more types.

The usage-amount of a hardening accelerator is preferably 0.01-5 mass parts with respect to 100 mass parts of resin solid content of a curable composition, More preferably, it is 0.1-3. When the usage-amount of a hardening accelerator is 0.01 mass part or more, since sclerosing|hardenability is excellent, it is preferable. On the other hand, when the usage-amount of a hardening accelerator is 5 mass parts or less, it is excellent in formability, and it is preferable.

(Flame Retardant)

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

Although it does not specifically limit as said inorganic phosphorus flame retardant, Red phosphorus; Ammonium phosphates, such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; Phosphoric acid amide, etc. are mentioned.

The organic phosphorus-based flame retardant is not particularly limited, and examples include 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, tridecane base acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, behenyl acid phosphate, ethylene glycol Phosphate esters such as acid phosphate, (2-hydroxyethyl) methacrylate acid phosphate, etc.; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenyl Diphenylphosphine such as phosphine oxide; 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxaphthalene )-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylanthraquinone phosphine oxide, diphenylphosphinyl-1,4-dioxonaphthalene, 1,4-cyclooctylene Phosphosphinyl-1,4-phenyldiol, 1,5-cyclooctylenephosphinyl-1,4-phenyldiol and other phosphorus-containing phenols; 9,10-dihydro-9-oxo Hetero-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7 -Dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic phosphorus compounds; the aforementioned phosphate ester, the aforementioned diphenylphosphine, the aforementioned phosphorus-containing phenol and epoxy resin, A compound obtained by reacting an aldehyde compound and a phenol compound, etc.

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

The above-mentioned flame retardants may be used alone or in combination of two or more.

The amount of the flame retardant used is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass relative to 100 parts by mass of the resin solid content of the curable composition. When the usage-amount of a flame retardant is 0.1 mass part or more, since flame retardance can be provided, it is preferable. On the other hand, when the amount of the flame retardant used is 50 parts by mass or less, the dielectric properties can be maintained and flame retardancy can be imparted, which is preferable.

(filler)

As a filler, an organic filler and an inorganic filler are mentioned. The filler has a function of increasing elongation, a function of increasing mechanical strength, and the like.

It does not specifically limit as said organic filler, Polyamide particle etc. are mentioned.

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

Among these, silica is preferably used. At this time, as the silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like can be used.

Moreover, the said filler can be surface-treated as needed. In this case, the surface treating agent that can be used is not particularly limited, and aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, and organosilazane compounds can be used , titanate coupling agent, etc. Specific examples of the surface treatment agent include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl -3-aminopropyltrimethoxysilane, hexamethyldisilazane, etc.

In addition, the above-mentioned fillers may be used alone or in combination of two or more.

The average particle diameter of the filler is not particularly limited, but is preferably 0.01 to 10 μm, more preferably 0.03 to 5 μm, and further preferably 0.05 to 3 μm. In addition, in this specification, "particle diameter" means the maximum length among the distances between two points on the contour line of a particle. In addition, the "average particle size" is a value obtained by measuring the particle size of arbitrary 100 particles in one screen in an image obtained by a scanning electron microscope (SEM), and measuring the average value by a calculation method .

The usage-amount of a filler is preferably 0.5-95 mass parts with respect to 100 mass parts of resin solid content of a curable composition, More preferably, it is 5-80 mass parts. When the usage-amount of a filler is 0.5 mass part or more, since low thermal expansion property can be provided, it is preferable. On the other hand, when the usage-amount of a filler is 95 mass parts or less, since the balance of characteristics and formability is excellent, it is preferable.

<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 above-mentioned polymerizable unsaturated bond-containing aromatic ester compound (A) and poly(arylene ether) resin (B). made of.

Since the above-mentioned polymerizable unsaturated bond-containing aromatic ester compound (A) has a polymerizable unsaturated bond-containing substituent, the polymerization of itself can be realized, and a cured product can be obtained.

In addition, the said hardened|cured material may contain the above-mentioned hardening|curing agent, an additive, a hardening accelerator, etc. as needed.

The polymerizable unsaturated bond-containing aromatic ester compound (A) has a low dielectric loss tangent, so the cured product has a low dielectric loss tangent and is more excellent in heat resistance, so it can be used for semiconductor packaging substrates, Electronic materials such as printed circuit boards, build-up adhesive films, and semiconductor sealing materials. In addition, it can also be applied to applications such as adhesives and paints.

The heating temperature at the time of heating and curing is not particularly limited, but is preferably 150 to 300°C, and more preferably 175 to 250°C.

Example

Hereinafter, the present invention will be described using examples, but the present invention is not limited to the description of the examples.

Production Example 1 Production of a polymerizable unsaturated bond-containing aromatic ester compound (A-1-1)

268 g of o-allyl phenol and 1,200 g of toluene were put into a flask equipped with a thermometer, dropping funnel, condenser, fractionation tube, and stirrer, and the contents were dissolved while the inside of the system was replaced with nitrogen under reduced pressure. Next, 203 g of isophthaloyl chloride was put in, and the contents were dissolved while the inside of the system was replaced with nitrogen under reduced pressure. 0.6 g of tetrabutylammonium bromide was added and dissolved, the inside of the system was controlled to be 60° C. or lower while purging with nitrogen, and 412 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the dropwise addition, stirring was continued for 1 hour under the same temperature conditions. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the obtained organic phase, the mixture was stirred for about 15 minutes, left to stand for liquid separation, 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 water washing was dried under heating and reduced pressure conditions to obtain 370 g of a polymerizable unsaturated bond-containing aromatic ester compound (A-1-1) represented by the following structural formula. The polymerizable unsaturated bond-containing aromatic ester compound (A-1-1) had an ester group 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 a polymerizable unsaturated bond-containing aromatic ester compound (A-2-1)

Into a flask equipped with a thermometer, dropping funnel, condenser tube, fractionation tube, and agitator, put 165 g of an addition polymerization reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent 165 g/equivalent, softening point 85°C), adjacent 134 g of allyl phenol and 1200 g of toluene were dissolved in the system while the inside of the system was replaced with nitrogen under reduced pressure. Next, 203 g of isophthaloyl chloride was put in, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve it. 0.6 g of tetrabutylammonium bromide was added and dissolved, the inside of the system was controlled to be 60° C. or lower while purging with nitrogen, and 412 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the dropwise addition, stirring was continued for 1 hour under the same temperature conditions. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the obtained organic phase, the mixture was stirred for about 15 minutes, left to stand for liquid separation, 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 water washing was dried under heating and reduced pressure conditions to obtain 385 g of a polymerizable unsaturated bond-containing aromatic ester compound (A-2-1). The theoretical structure of the polymerizable unsaturated bond-containing aromatic ester compound (A-2-1) is shown below. The polymerizable unsaturated bond-containing aromatic ester compound (A-2-1) had an ester group equivalent of 214 g/equivalent, an allyl equivalent of 428 g/equivalent, and a softening point of 82°C.

Production Example 3 Production of a polymerizable unsaturated bond-containing aromatic ester compound (A-2-2)

Except having changed 165 g of the addition polymerization reaction resin of dicyclopentadiene and phenol of Production Example 2 to 160 g of diallyl bisphenol A, it was carried out in the same manner as in Production Example 2 to obtain a polymerizable unsaturated bond-containing aromatic 402 g of family ester compound (A-2-2). The theoretical structure of the polymerizable unsaturated bond-containing aromatic ester compound (A-2-2) is shown below. The polymerizable unsaturated bond-containing aromatic ester compound (A-2-2) had an ester group equivalent of 212 g/equivalent, an allyl equivalent of 212 g/equivalent, and a softening point of 51°C.

Comparative Production Example 1 Production of Aromatic Ester Compound (A')

Addition polymerization reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/equivalent, softening point 85°C) 165 g, 1- 72 g of naphthol and 630 g of toluene were dissolved in the system while the inside of the system was replaced with nitrogen under reduced pressure. Next, 152 g of isophthaloyl chloride was put in, and the inside of the system was dissolved with nitrogen under reduced pressure. 0.6 g of tetrabutylammonium bromide was added, the inside of the system was controlled to be 60° C. or lower while carrying out nitrogen purging, and 315 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the dropwise addition, stirring was continued for 1 hour under the same temperature conditions. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the obtained organic phase, the mixture was stirred for about 15 minutes, left to stand for liquid separation, and the aqueous layer was removed. This water washing operation was repeated until the pH of the aqueous layer became 7. The organic phase washed with water was dried under heating and reduced pressure to obtain an aromatic ester compound (A'). The ester group equivalent of the aromatic ester compound (A') was 223 g/equivalent, and the softening point was 150°C.

Examples 1 to 9 and Comparative Example 1

The respective components were blended in the ratios shown in the following Tables 1 and 2 to obtain a curable composition. With respect to the obtained curable composition, the heat resistance evaluation of the cured product and the measurement of the dielectric loss tangent value were performed according to the following procedures. The results are shown in Tables 1 and 2.

Details of each component used in the examples are as follows.

Polyarylene ether resin (B-1): "NORYLSA90" manufactured by SABIC Corporation, hydroxyl equivalent weight 850 g/equivalent, and the theoretical structure is as follows.

- Polyarylene ether resin (B-2): "NORYLSA9000" manufactured by SABIC, 850 g/equivalent of methacryloyl equivalent, and the theoretical structure is as follows.

Epoxy resin: Bisphenol A type epoxy resin ("EPICLON850S" manufactured by DIC Corporation, epoxy equivalent: 188 g/equivalent)

Manufacture of cured products

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

Evaluation of heat resistance (measurement of glass transition temperature)

A test piece having a width of 5 mm and a length of 54 mm was cut out from the previously obtained cured product having a thickness of 2.4 mm. Using the "solid viscoelasticity measuring apparatus RSAII" manufactured by Rheometrics, Inc., the temperature at which the change in the elastic modulus of the test piece becomes the largest (the largest tan δ change rate) is measured by DMA (dynamic viscoelasticity) measurement by the rectangular tension method. transition temperature. As for the measurement conditions, the frequency was set to 1 Hz, and the temperature increase rate was set to 3°C/min.

Determination of dielectric loss tangent

The obtained cured product was heated and vacuum-dried at 105° C. for 2 hours, and then stored in a room with a temperature of 23° C. and a humidity of 50% for 24 hours as a test piece. Using "Network Analyzer E8362C" manufactured by Agilent Technologies, Inc., the dielectric loss tangent at 1 GHz of the test piece was measured by the cavity resonance method.

[Table 1]

Table 1

[Table 2]

Table 2

Claims (6)

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.