JP6955232B2 - Curable composition and its cured product - Google Patents

Description

The present invention relates to a curable composition having excellent heat resistance and dielectric properties in a cured product, a cured product of the curable composition, a printed wiring board using the curable composition, a semiconductor encapsulant material, and a build-up film.

In recent years, electronic devices have become smaller and more sophisticated, and along with this, the required performance of various materials used has improved. For example, in semiconductor package substrates, signals are becoming faster and higher in frequency, and materials with low electrical energy loss, that is, materials with low dielectric loss tangent are required.

Provided are an invention relating to a resin composition containing, for example, (A) epoxy resin, (B) active ester compound, (C) smear-suppressing component, and (D) inorganic filler as such a low dielectric loss tangent material. (See, for example, Patent Document 1). At this time, when the non-volatile component of the resin composition is 100% by mass, the active ester compound (B), the smear-suppressing component (C), and the inorganic filler (D) each have a predetermined content. Moreover, the smear-suppressing component (C) is characterized by being rubber particles.

Patent Document 1 describes that a cured product of the resin composition can achieve low dielectric loss tangent. It is also described that smear (resin residue) in the via hole after the cured product is drilled and roughened can be suppressed.

The active ester compound (B) described in Patent Document 1 is a compound having one or more active ester groups in one molecule, and may lower the dielectric loss tangent of the cured product of the resin composition. Have been described.

Japanese Unexamined Patent Publication No. 2016-156019

Patent Document 1 describes that the dielectric loss tangent of the obtained cured product can be lowered by using the active ester compound. However, it has been found that such a cured product may not always have sufficient heat resistance.

The present inventors have conducted diligent research in order to solve the above problems. As a result, it was found that the curable composition containing the aromatic ester compound having a polymerizable unsaturated bond in the molecular structure and the polyarylene ether resin is remarkably excellent in heat resistance and dielectric properties in the cured product. The present invention has been completed.

That is, the present invention uses a curable composition containing a polymerizable unsaturated bond-containing aromatic ester compound (A) and a polyarylene ether resin (B), a cured product thereof, and a curable composition. It provides a printed wiring substrate, a semiconductor encapsulating material, and a build-up film.

According to the present invention, a curable composition having excellent heat resistance and dielectric properties in a cured product, a cured product of the curable composition, a printed wiring substrate using the curable composition, a semiconductor encapsulant material, and a build-up film. Can be provided.

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

The polymerizable unsaturated bond-containing aromatic ester compound (A) used in the present invention has one or more polymerizable unsaturated bonds in the molecular structure, and has a structural site in which aromatic rings are bonded to each other by an ester bond. As long as it is an aromatic ester compound, a wide variety of compounds can be used regardless of other specific structures, molecular weights, and the like.

Specific examples of the polymerizable unsaturated bond-containing aromatic ester compound (A) include the following chemical formula (1):

（上記化学式（１）中、Ａｒ^１が、置換または非置換の第１の芳香族環基であり、Ａｒ^２が、それぞれ独立して、置換または非置換の第２の芳香族環基であり、この際、前記Ａｒ^１および前記Ａｒ^２の少なくとも１つが重合性不飽和結合含有置換基を有し、ｎが、２または３の整数である。）
で表される重合性不飽和結合含有芳香族エステル化合物（Ａ−１）や、２以上のフェノール性水酸基を有する第１の芳香族化合物と、フェノール性水酸基を有する第２の芳香族化合物と、２以上のカルボキシ基を有する第３の芳香族化合物および／またはその酸ハロゲン化物、エステル化物との反応生成物であり、前記第１の芳香族化合物、前記第２の芳香族化合物、並びに前記第３の芳香族化合物および／またはその酸ハロゲン化物、エステル化物の少なくとも１つが重合性不飽和結合含有置換基を有するものである重合性不飽和結合含有芳香族エステル化合物（Ａ−２）等が挙げられる。

(In the above chemical formula (1), Ar ¹ is a substituted or unsubstituted first aromatic ring group, and Ar ² is an independently substituted or unsubstituted second aromatic ring group. At this time, ^{at least one of the Ar 1} and the Ar ² has a polymerizable unsaturated bond-containing substituent, and n is an integer of 2 or 3).
A polymerizable unsaturated bond-containing aromatic ester compound (A-1) represented by, a first aromatic compound having two or more phenolic hydroxyl groups, and a second aromatic compound having a phenolic hydroxyl group. A reaction product with a third aromatic compound having two or more carboxy groups and / or an acid halide or esterified product thereof, the first aromatic compound, the second aromatic compound, and the second. Examples thereof include the polymerizable unsaturated bond-containing aromatic ester compound (A-2) in which at least one of the aromatic compound of 3 and / or its acid halide and esterified product has a polymerizable unsaturated bond-containing substituent. Be done.

The polymerizable unsaturated bond-containing aromatic ester compound (A) is at room temperature from the viewpoint of being excellent in handleability when prepared as a curable composition described later, heat resistance of the cured product, and dielectric properties. It is preferably liquid at (25 ° C.) or its softening point is in the range of 40 ° C. to 200 ° C.

With respect to the polymerizable unsaturated bond-containing aromatic ester compound (A-1), Ar ¹ in the chemical formula (1) is a substituted or unsubstituted first 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 of the hydrogen atoms of the aromatic ring constituting the first aromatic ring group are "-C (". O) OAr ² ”will be replaced.

The first aromatic ring group is not particularly limited, but is a single ring of benzene, furan, pyrrol, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine and the like. Aromatic compounds from which two or three hydrogen atoms have been removed; condensed ring fragrances such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indol, benzimidazole, benzofuran, acrydin, etc. Examples thereof include those obtained by removing two or three hydrogen atoms from an aromatic compound, and those obtained by removing two or three hydrogen atoms from an aromatic compound. Further, a plurality of these aromatic compounds may be combined, and for example, a ring-assembled aromatic compound such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl and the like. With 2 or 3 hydrogen atoms removed from it; diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenyl Examples thereof include those obtained by removing two or three hydrogen atoms from an aromatic compound linked by an alkylene such as pyridylmethane, fluorene, and diphenylcyclopentane.

^{Among them, Ar 1} is preferably a substituted or unsubstituted benzene ring or a naphthalene ring, and more preferably a substituted or unsubstituted benzene ring, because a cured product having more excellent dielectric properties can be obtained.

The first aromatic ring group according to Ar ^{1 may have a substituent.} At this time, the "substituent of the first aromatic ring group" is one that is substituted with at least one hydrogen atom of the aromatic ring constituting the first aromatic ring group. Specific examples of the substituent of the first aromatic ring group include, but are not limited to, an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, a halogen atom and the like.

The alkyl group is not particularly limited, but is a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert. -Pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, cyclohexyl group and the like can be mentioned.

The alkoxy group 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, and a hexyloxy group.

The alkyloxycarbonyl group is not particularly limited, but is a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, a butyloxycarbonyl group, an n-butyloxycarbonyl group, an isobutyloxycarbonyl group, and the like. Examples thereof include a sec-butyloxycarbonyl group and a tert-butyloxycarbonyl group.

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

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

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

The alkenyl group is not particularly limited, but is limited to a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-hexenyl group, and 2 −Hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-octenyl group, 2-octenyl group, 1-undecenyl group, 1-pentadecenyl group, 3-pentadecenyl group, 7-pentadesenyl group, 1 -Octadecenyl group, 2-octadecenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, 1,3-butadienyl group, 1,4-butadienyl group, hexa-1,3-dienyl group, hexa-2,5-dienyl Examples thereof include a group, a pentadeca-4,7-dienyl group, a hexa-1,3,5-trienyl group, a pentadeca-1,4,7-trienyl group and the like.

The alkynyl group is not particularly limited, but includes an ethynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1,3-butadiynyl group and the like. Can be mentioned.

The polymerizable unsaturated bond-containing substituent may further have a substituent. At this time, the "substituent of the polymerizable unsaturated bond-containing substituent" is one that is substituted with at least one hydrogen atom constituting the polymerizable unsaturated bond-containing substituent. Specific examples of the substituent of the polymerizable unsaturated bond-containing substituent include an alkyloxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom. At this time, examples of the alkyloxycarbonyl group, alkylcarbonyloxy group and halogen atom include those described above.

Of these, the polymerizable unsaturated bond-containing substituent is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms. More preferably, it is a substituted or unsubstituted alkenyl group having 2 to 5 carbon atoms, and a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 1-propenyl group, a 1-butenyl group, A 2-butenyl group, a 3-butenyl group, and a 1,3-butadienyl group are particularly preferable, and an allyl group, a propenyl group, an isopropenyl group, and a 1-propenyl group are most preferable.

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

At this time, in the above formulas (2-1) to (2-17), "*" indicates a position to be bonded to " ^{-C (O) OAr 2".} In addition, "-*" may be bonded to any position of the aromatic ring.

Of these, the formulas (2-1) to (2-11) are preferable, and the formulas (2-1), (2-2), (2-6), (2-7), (2- 9) is more preferable, and formulas (2-1), (2-2), (2-6), and (2-7) are further preferable. Further, from the viewpoint of high handling property and low viscosity of the aromatic ester compound (A-1), it is preferably (2-1) and (2-2), while the obtained cured product has higher heat resistance. Therefore, from the viewpoint of excellent balance with the low dielectric property, (2-6) and (2-7) are preferable.

At least one hydrogen atom of the aromatic ring of the formulas (2-1) to (2-17) may be substituted with an unsaturated bond-containing group.

Ar ² is an independently 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 replaced with ^{"-OC (O) Ar 1".} Become.

The second aromatic ring group is not particularly limited, but is a single ring of benzene, furan, pyrrol, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine and the like. Aromatic compounds from which one hydrogen atom has been removed; from fused aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinolin, quinazoline, phthalazine, pteridine, coumarin, indol, benzimidazole, benzofuran, acrydin, etc. Examples thereof include those in which one hydrogen atom is removed from an aromatic compound such as one in which one hydrogen atom is removed. Further, a plurality of these aromatic compounds may be combined, and for example, a ring-assembled aromatic compound such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl and the like. Diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, Examples thereof include those in which one hydrogen atom is removed from an aromatic compound linked by an alkylene such as fluorene and diphenylcyclopentane.

^{Above all, Ar 2} is preferably a substituted or unsubstituted benzene ring or naphthalene ring because a cured product having more excellent dielectric properties can be obtained. Further, from the viewpoint of high handling property and low viscosity of the aromatic ester compound (A), a benzene ring is preferable, while the obtained cured product has more heat resistance and is excellent in balance with low dielectric properties. From the viewpoint, a naphthalene ring is preferable.

The second aromatic ring group according to Ar ^{2 may have a substituent.} At this time, the "substituent of the second aromatic ring group" is one that is substituted with at least one hydrogen atom of the aromatic ring constituting the second aromatic ring group. Specific examples of the substituent of the second aromatic ring group include, but are not limited to, an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, a halogen atom and the like. At this time, examples of the alkyl group, the alkoxy group, the alkyloxycarbonyl group, the alkylcarbonyloxy group and the halogen atom include those described above.

In one embodiment of the invention, Ar ² may have the unsaturated bond-containing substituents described above. At this time, the unsaturated bond-containing substituent may be contained alone or in combination of two or more.

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

At this time, in the above formulas (3-1) to (3-17), "*" indicates a position to be bonded to " ^{-OC (O) Ar 1".} In addition, "-*" may be bonded to any position of the aromatic ring.

Of these, the formulas (3-1) to (3-11) are preferable, the formulas (3-1), (3-6), and (3-9) are more preferable, and the formula (3) is preferable. -1) and (3-6) are more preferable.

At least one hydrogen atom of the aromatic ring of the formulas (3-1) to (3-17) may be substituted with an unsaturated bond-containing group.

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

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, and Ar 1} and Ar ² may have a polymerizable unsaturated bond-containing substituent. Both may have a polymerizable unsaturated bond-containing substituent.

According to one embodiment, it is preferable to have at least one polymerizable unsaturated bond-containing substituent group of Ar ^2, more preferably with all Ar ² polymerizable unsaturated bond-containing substituent group, Ar ¹ is It is more preferable that it does not have a polymerizable unsaturated bond-containing substituent and that all Ar ² has a polymerizable unsaturated bond-containing substituent. 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 polymerizable unsaturated bond-containing aromatic ester compound (A-1) has two or three ester bonds that bond two aromatic rings.

From the above, as a more preferable form 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 used. Examples include the compounds represented.

［式中Ｒ^１は重合性不飽和結合含有置換基である。Ｒ^２はそれぞれ独立にアルキル基、アルコキシ基、アルキルオキシカルボニル基、アルキルカルボニルオキシ基、ハロゲン原子の何れかである。ｈは２又は３、ｉはそれぞれ独立に１以上の整数、ｊはそれぞれ独立に０又は１以上の整数であり、ｉ＋ｊは５以下の整数である。ｋは２又は３、ｌはそれぞれ独立に１以上の整数、ｍはそれぞれ独立に０又は１以上の整数であり、ｌ＋ｍは７以下の整数である。ｉ、ｊ、ｌ、ｍが２以上の整数である場合、複数のＲ^１或いはＲ^２は互いに同一であってもよいし、異なっていてもよい。式（１−２）においてＲ^１、Ｒ^２はナフタレン環を形成する何れの炭素原子上に置換していてもよい。］

[R ^{1 in the} formula is a polymerizable unsaturated bond-containing substituent. R ² is independently any of an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom. h is 2 or 3, i is an integer of 1 or more independently, j is an integer of 0 or 1 or more independently, and i + j is an integer of 5 or less. k is 2 or 3, l is an integer of 1 or more independently, m is an integer of 0 or 1 or more independently, and l + m is an integer of 7 or less. When i, j, l, and m are integers of 2 or more, the plurality of R ¹ or R ² may be the same as or different from each other. In formula (1-2), R ¹ and R ² may be substituted on any carbon atom forming a naphthalene ring. ]

In the above formula (1-1), ^{particularly preferable R 1} is, as described above, an allyl group, a propenyl group, an isopropenyl group, and a 1-propenyl group. i is preferably 1 or 2, more preferably 1.

In the above formula (1-2), ^{particularly preferable R 1} is, as described above, an allyl group, a propenyl group, an isopropenyl group, and a 1-propenyl group. l is preferably 1 or 2, and more preferably 1.

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

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

Further, from the viewpoint of high handling property and low viscosity of the aromatic ester compound (A), it is preferably (4-1), (4-2), (4-12), (4-13). On the other hand, (4-26), (4-32), and (4-37) are preferable from the viewpoint of having higher heat resistance in the obtained cured product and having an excellent balance with the low dielectric property.

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

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

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

(Polycarboxylic acid compound or its derivative)
The polycarboxylic acid compound or a derivative thereof has a substituted or unsubstituted aromatic ring group, and preferably has a carbon atom number in the range of 3 to 30. At this time, examples of the "derivative of the polycarboxylic acid compound" include acid halides of carboxylic acids.

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

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

In the above chemical formulas (5-1) to (5-15), R ¹ is a hydroxy group or a halogen atom. Further, R ² is a polymerizable unsaturated bond-containing substituent. At this time, the polymerizable unsaturated bond-containing substituent is the same as that described above. Further, p is 2 or 3. Further, q is 0 or an integer of 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, and even more preferably 0. The positions of the substituents on the aromatic ring in the above chemical formula are described on the same aromatic ring for convenience. For example, in the above chemical formula (5-7), R ¹ OC and R ² are different benzenes. It may be substituted on the ring, indicating that the number of substituents in one molecule is p and q.

Specific polycarboxylic acid compounds or derivatives thereof are not particularly limited, but are benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allyl isophthalic acid, and 2-allyl terephthalic acid; trimellitic acid and 5-allyl trimellitic. Benzene tricarboxylic acids such as acids; naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 3-allylnaphthalene-1, Naphthalenedicarboxylic acids such as 4-dicarboxylic acid, 3,7-diallylnaphthalene-1,4-dicarboxylic acid; pyridinetricarboxylic acids such as 2,4,5-pyridinetricarboxylic acid; 1,3,5-triazine-2,4 , Triazine carboxylic acids such as 6-tricarboxylic acids; these acid halides and the like can be mentioned. Of these, benzenedicarboxylic acid and benzenetricarboxylic acid are preferable, and isophthalic acid, terephthalic acid, isophthalic acid chloride, terephthalic acid chloride, 1,3,5-benzenetricarboxylic acid, 1,3,5-benzenetricarbonyl. It is more preferably trichloride, and even more preferably isophthalic acid chloride, terephthalic acid chloride, and 1,3,5-benzenetricarbonyltrichloride.

The above-mentioned polycarboxylic acid compound or a derivative thereof may be used alone or in combination of two or more.

(Phenol compound)
Phenolic compounds have substituted or unsubstituted aromatic ring groups, preferably in the range of 3 to 30 carbon atoms. At this time, the substituents of the second aromatic ring group and the second aromatic ring group are the same as those described above.

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

In the above chemical formulas (6-1) to (6-17), R ² is a polymerizable unsaturated bond-containing substituent. At this time, the polymerizable unsaturated bond-containing substituent is the same as that described above. Further, q is 0 or an integer of 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, in the naphthalene ring of the chemical formula (6-6) or the heterocycle of the chemical formula (6-17), it is substituted on any ring. Also, in the chemical formula (6-9) and the like, it is shown that substitution may be performed on any ring of the benzene ring existing in one molecule, and the number of substituents in one molecule is q. Shown.

Specific phenol compounds are not particularly limited, but phenol; naphthol; 2-allylphenol, 3-allylphenol, 4-allylphenol, 4-methyl-2-allylphenol, 6-methyl-2-allylphenol, Allylphenols such as eugenol; propenylphenols such as 2- (1-propenyl) phenol, isoeugenol; butenylphenols such as 2- (3-butenyl) phenol, 2- (1-ethyl-3-butenyl) phenol; cardanol; Long-chain alkenylphenols such as 2-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-1-naphthol, 3-allyl-1-naphthol and the like. Of these, allylphenol and allylnaphthol are preferable, and 2-allylphenol, 4-methyl-2-allylphenol, 6-methyl-2-allylphenol, 2-allyl-1-naphthol, and 1-allyl- 2-naphthol is more preferable, and 2-allylphenol, 2-allyl-1-naphthol, and 1-allyl-2-naphthol are even more preferable.

Further, from the viewpoint of high handling property and low viscosity of the aromatic ester compound (A), 2-allylphenol or the like having a benzene ring skeleton is preferable, while the obtained cured product has more heat resistance and low dielectric properties. From the viewpoint of excellent balance with, 2-allyl-1-naphthol, 1-allyl-2-naphthol and the like having a naphthalene ring skeleton are preferable.

The above-mentioned phenol 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 used is not particularly limited, but the carboxy group and / or the halide acyl group of the polycarboxylic acid compound or its derivative with respect to the number of moles of the hydroxy group of the phenol compound, etc. The molar ratio of the number of moles of the inducing group [(inducing group such as carboxy group and / or acyl halide group) / (hydroxy group)] is preferably 0.8 to 3.0, and 0.9 to 2 It is more preferably 0.0, and even more preferably 1.0 to 1.2.

The reaction conditions are not particularly limited, and known methods can be appropriately adopted.

The pH at the time of reaction is not particularly limited, but is preferably 11 or more. At this time, for adjusting the pH, acids such as hydrochloric acid, sulfuric acid, nitric acid and acetic acid; and bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia can be used.

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

The polymerizable unsaturated bond-containing aromatic ester compound (A-2) includes a first aromatic compound having two or more phenolic hydroxyl groups, a second aromatic compound having a phenolic hydroxyl group, and two or more. A reaction product with a third aromatic compound having a carboxy group and / or an acid halide or esterified product thereof, the first aromatic compound, the second aromatic compound, and the third aromatic. At least one of the group compounds and / or their acid halides and esters has a polymerizable unsaturated bond-containing substituent.

[First 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.

The first aromatic compound is not particularly limited, and examples thereof include a compound having two or more phenolic hydroxyl groups in the first aromatic ring having 3 to 30 carbon atoms substituted or unsubstituted.

At this time, 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-aggregated 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, and triazine.

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

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

The first aromatic ring may have a substituent. At this time, the "substituent of the first aromatic ring" is not particularly limited, but is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, and a polymerizable unsaturated bond. Examples include containing substituents.

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

The alkoxy group having 1 to 10 carbon atoms is not particularly limited, but is limited to a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group and an octyloxy group. , Nonyloxy group and the like.

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

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

The alkenyl group is not particularly limited, but is limited to a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-hexenyl group, and 2 −Hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-octenyl group, 2-octenyl group, 1-undecenyl group, 1-pentadecenyl group, 3-pentadecenyl group, 7-pentadesenyl group, 1 -Octadecenyl group, 2-octadecenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, 1,3-butadienyl group, 1,4-butadienyl group, hexa-1,3-dienyl group, hexa-2,5-dienyl Examples thereof include a group, a pentadeca-4,7-dienyl group, a hexa-1,3,5-trienyl group, a pentadeca-1,4,7-trienyl group and the like.

The alkynyl group is not particularly limited, but includes an ethynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1,3-butadiynyl group and the like. Can be mentioned.

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

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

Then, as described above, the first aromatic compound is formed by substituting at least two hydrogen atoms constituting the above-mentioned substituted or unsubstituted first aromatic ring with a hydroxy group.

Specific examples of the compound in which the first aromatic ring is a monocyclic aromatic ring (hereinafter, may be simply referred to as “first monocyclic aromatic ring compound”) include catechol, resorcinol, hydroquinone, and hydroxynol. , Fluoroglucinol, pyrogallol, 2,3-dihydroxypyridine, 2,4-dihydroxypyridine, 4,6-dihydroxypyrimidine, 3-methylcatechol, 4-methylcatechol, 4-allylpyrocatechol and the like.

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

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

Further, the first aromatic compound may have a structure in which the first aromatic ring is linked by a linking 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 an independently substituted or unsubstituted first aromatic ring group, and Ar ⁴ is an independently substituted or unsubstituted second aromatic ring group, respectively. , X are independently oxygen atom, sulfur atom, substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, aralkylene, and n is 0 to 10. At this time, at least two of the hydrogen atoms constituting the ^{Ar 3} and the Ar ^{4 are substituted with hydroxy groups.} The X corresponds to a linking group.

The Ar ³ is a substituted or unsubstituted first aromatic ring group. As is clear from the description of the above chemical formula (7), 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, but is a single ring of benzene, furan, pyrrol, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine and the like. Aromatic compounds from which one hydrogen atom has been removed; from fused aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinolin, quinazoline, phthalazine, pteridine, coumarin, indol, benzimidazole, benzofuran, acrydin, etc. Examples thereof include those in which one hydrogen atom is removed from an aromatic compound such as one in which one hydrogen atom is removed. Further, a plurality of these aromatic compounds may be combined, and for example, a ring-assembled aromatic compound such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl and the like. One is the one in which one hydrogen atom is removed from.

At this time, the first aromatic ring group may have a substituent. Examples of the "substituent of the first aromatic ring group" include the same as the above-mentioned "substituent of the first aromatic ring group".

Of these, Ar ³ has one hydrogen atom removed from benzene, naphthalene, anthracene, phenalene, phenanthrene, biphenyl, binaphthalene, quaterphenyl, allylbenzene, diallylbenzene, allylnaphthalene, diallylnaphthalene, allylbiphenyl, and diallylbiphenyl. It is preferably obtained by removing one hydrogen atom from benzene, naphthalene, biphenyl, allylbenzene, diallylnaphthalene and diallylbiphenyl.

The Ar ⁴ is an independently substituted or unsubstituted second aromatic ring group. As is clear from the description of the chemical formula (1), two of the hydrogen atoms of the aromatic ring constituting the substituted or unsubstituted aromatic ring described above are bonded to "X".

The second aromatic ring group is not particularly limited, but is a single ring of benzene, furan, pyrrol, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine and the like. Aromatic compounds from which two hydrogen atoms have been removed; from fused aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinolin, quinazoline, phthalazine, pteridine, coumarin, indol, benzimidazole, benzofuran, acrydin, etc. Examples thereof include those in which two hydrogen atoms are removed from an aromatic compound such as one in which two hydrogen atoms are removed. Further, a plurality of these aromatic compounds may be combined, and for example, a ring-assembled aromatic compound such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl and the like. The one in which two hydrogen atoms are removed from the above can be mentioned.

At this time, the second aromatic ring group may have a substituent. Examples of the "substituent of the second aromatic ring group" include the same as the above-mentioned "substituent of the first aromatic ring group".

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

The alkylene is not particularly limited, but is methylene, ethylene, propylene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, propylene, butylene. , 1-Methylpropylene, 2-Methylpropylene, pentylene, hexylene and the like.

The cycloalkylene is not particularly limited, but is represented by cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and the following chemical formulas (8-1) to (8-4). Cycloalkylene and the like can be mentioned.

In the above chemical formulas (8-1) to (8-4), "*" represents a site that binds to ^{Ar 3} or Ar ^4.

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

なお、上記化学式（９−１）〜（９−８）において、「＊」はＡｒ^３またはＡｒ^４と結合する部位を表す。

In the above chemical formulas (9-1) to (9-8), "*" represents a site that binds to ^{Ar 3} or Ar ^4.

The alkylene, the cycloalkylene, and the aralkylene may have a substituent. At this time, as the "substituent of X", the same as the above-mentioned "substituent of the first aromatic ring" can be mentioned.

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

Then, at least two of the hydrogen atoms constituting the ^{Ar 3} and the Ar ^{4 are substituted with hydroxy groups.}

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

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

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

In one embodiment, in the case where the above-mentioned first aromatic ring is represented by the above chemical formula (7), at least one of the hydrogen atoms constituting the first aromatic ring is substituted with a hydroxy group. It can be synthesized by reacting the compound with a divinyl compound or a dialkyloxymethyl compound.

At this time, the divinyl compound and the dialkyloxymethyl compound are not particularly limited, but are 1,3-butadiene, 1,5-hexadiene, dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, pentacyclopentadiene, and hexacyclopentadiene. And other aliphatic diene compounds; aromatic diene compounds such as divinylbenzene and divinylbiphenyl; dimethoxymethylbenzene, dimethoxymethylbiphenyl, bisphenol A methoxy adduct, bisphenol A ethoxy adduct, bisphenol F methoxy adduct, bisphenol Fethoxy adduct Such as dialkyloxymethyl compounds and the like.

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 group equivalent of the first aromatic compound is preferably 130 to 500 g / equivalent, and more preferably 130 to 400 g / equivalent. When the hydroxyl group 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.

When the first aromatic compound is represented by the above chemical formula (7) and n is an oligomer or a polymer, the weight average molecular weight is preferably 200 to 3000, preferably 200 to 2000. Is more preferable. When the weight average molecular weight of the first aromatic compound is 200 or more, it is preferable because it is excellent in dielectric loss tangent. On the other hand, when the weight average molecular weight of the first aromatic compound is 3000 or less, it is preferable because the moldability is excellent. In this specification, the value of "weight average molecular weight" shall be the value measured by the following method. That is, the value obtained by measuring gel permeation chromatography (GPC) under the following conditions is adopted.

GPC measurement conditions Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "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 EcoSEC-WorkStation" manufactured by Tosoh Corporation
Column temperature: 40 ° C
Developing solvent: Tetrahydrofuran Flow velocity: 1.0 ml / min Standard: Polystyrene used using the following monodisperse polystyrene with a known molecular weight in accordance with the measurement manual of the above "GPC-8320 GPC" Polystyrene used "A-500" manufactured by Tosoh Corporation "
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: A solution obtained by filtering 1.0 mass% of a tetrahydrofuran solution in terms of resin solid content 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.

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

The second aromatic ring is not particularly limited, and examples thereof include a monocyclic aromatic ring, a condensed aromatic ring, a ring-aggregated aromatic ring, and an aromatic ring linked by an alkylene. Examples of the monocyclic aromatic ring, the condensed aromatic ring, and the ring-aggregated aromatic ring include the same as the first aromatic ring described above.

The aromatic rings linked by alkylene include diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane and phenylpyridyl. Examples thereof include methane, fluorene and diphenylcyclopentane.

The second aromatic ring according to the second aromatic compound may have a substituent. At this time, examples of the "substituent of the second aromatic ring" include the same as the above-mentioned "substituent of the first aromatic ring".

Then, 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 hydroxy group.

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

In the above chemical formulas (11-1) to (11-17), R ¹ is a polymerizable unsaturated bond-containing substituent. At this time, the polymerizable unsaturated bond-containing substituent is the same as that described above. Further, p is 0 or an integer of 1 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, in the naphthalene ring of the chemical formula (11-6) or the heterocycle of the chemical formula (11-17), it is substituted on any ring. Also, in the chemical formula (11-9) and the like, it is shown that substitution may be performed on any ring of the benzene ring existing in one molecule, and the number of substituents in one molecule is p. Shown.

The specific second aromatic compound is not particularly limited, but is not particularly limited, but is phenol, cresol, xylenol, orthoallylphenol, metaallylphenol, paraallylphenol, 2,4-dialylphenol, 2,6-diallylphenol, 2 -Aromatic rings such as allyl-4-methylphenol, 2-allyl-6-methylphenol, 2-allyl-4-methoxy-6-methylphenol, 2-propargylphenol, 3-propargylphenol, 4-propargylphenol Compounds that are monocyclic aromatic rings (hereinafter, may be simply referred to as "second monocyclic aromatic ring 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, diallylnaphthol, 2-allyl-4-methoxy-1-naphthol, Compounds such as 2-propargyl-1-naphthol, 3-propargyl-1-naphthol, 1-propargyl-2-naphthol, and 3-propargyl-2-naphthol in which the aromatic ring is a fused aromatic ring (hereinafter, simply "" (Sometimes referred to as a "second fused aromatic ring compound"); a compound in which an aromatic ring such as allyl hydroxybiphenyl or hydroxypropargyl biphenyl is a ring-aggregated aromatic ring (hereinafter, simply "second ring-assembled aromatic"). (Sometimes referred to as "ring compound") and the like.

Of the above, the second aromatic compound is preferably a second monocyclic aromatic ring compound or a second condensed ring aromatic ring compound, and is preferably orthoallylphenol, metaallylphenol, paraallylphenol, 2 -Allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, 6-allyl-1-naphthol. More preferred.

Further, in another embodiment, the second aromatic compound is preferably a second fused aromatic ring compound (condensed aromatic ring compound), 2-allyl-1-naphthol, 3-. More preferably, they are allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, and 6-allyl-1-naphthol. When the second aromatic compound is a fused aromatic ring compound, it is preferable because the molecular motion is suppressed by steric hindrance and the dielectric loss tangent can be lowered. Further, from the viewpoint of high handling property and low viscosity of the aromatic ester compound (A), 2-allylphenol or the like having a benzene ring skeleton is preferable, while the obtained cured product is more heat resistant and has low dielectric properties. 2-allyl-1-naphthol, 1-allyl-2-naphthol and the like having a naphthalene ring skeleton are preferable from the viewpoint of excellent balance.

The above-mentioned second aromatic compound may be used alone or in combination of two or more.

[Third aromatic compound and / or its acid halide, esterified product]
The third aromatic compound and / or an acid halide or esterified product thereof is a carboxylic acid having two or more carboxy groups, or a derivative thereof, specifically an acid halide or an esterified product (in the present specification). The third aromatic compound and / or its acid halide and esterified product may be collectively referred to as "third aromatic compound and the like"). The third aromatic compound or the like has a polymerizable unsaturated bond-containing aromatic ester compound (A-2) by reacting with the above-mentioned first aromatic compound by having two or more carboxy groups or the like. It can form a polyester structure. By reacting with the above-mentioned second aromatic compound, the polyesterification reaction is stopped.

The third aromatic compound and the like are not particularly limited, and examples thereof include compounds having two or more carboxy groups in the third aromatic ring having 3 to 30 carbon atoms substituted or substituted.

The "carboxy group, etc." refers to a carboxy group; an acyl halide group such as an acyl fluoride group, an acyl chloride group, and an acyl bromide group; an alkyloxycarbonyl group such as a methyloxycarbonyl group and an ethyloxycarbonyl group; phenyl. Examples thereof include an aryloxycarbonyl group such as an oxycarbonyl group and a naphthyloxycarbonyl group. If it has an acyl halide group, the third aromatic compound is an acid halide, and if it has an alkyloxycarbonyl group or an aryloxycarbonyl group, the third aromatic compound can be an esterified product. Of these, the third aromatic compound preferably has a carboxy group, an acyl halide group, and an aryloxycarbonyl group, more preferably a carboxy group and an acyl halide group, and a carboxy group, an acyl chloride group, and the like. It is more preferable to have an acyl group bromide.

The third aromatic compound and the like are not particularly limited, and examples thereof include compounds having two or more carboxy groups in the third aromatic ring having 3 to 30 carbon atoms substituted or unsubstituted.

The third aromatic ring is not particularly limited, and examples thereof include a monocyclic aromatic ring, a condensed aromatic ring, a ring-aggregated aromatic ring, and an aromatic ring linked by an alkylene. The aromatic ring linked by the monocyclic aromatic ring, the condensed aromatic ring, the ring-assembled aromatic ring, and the alkylene is the same as the first aromatic ring and the second aromatic ring described above. Things can be mentioned.

The third aromatic ring according to the third aromatic compound or the like may have a substituent. At this time, examples of the "substituent of the third aromatic ring" include the same as the above-mentioned "substituent of the first aromatic ring".

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

In the above chemical formulas (12-1) to (12-15), R ¹ is a polymerizable unsaturated bond-containing substituent. At this time, the polymerizable unsaturated bond-containing substituent is the same as that described above. Further, R ² is a hydroxy group, a halogen atom, an alkyloxy group, and an aryloxy group. Further, p is 0 or an integer greater than or equal to 1, preferably 0 or 1-3, 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, in the naphthalene ring of the chemical formula (12-5) or the heterocycle of the chemical formula (12-15), it is substituted on any ring. In the chemical formula (12-7) and the like, it is shown that the benzene ring existing in one molecule may be substituted on any ring, and the number of substituents in one molecule is p, q. It shows that.

The specific third aromatic compound and the like are not particularly limited, but are benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid and 2-allylterephthalic acid; trimellitic acid and 5-allyltrimerit. Benzenetricarboxylic acids such as acids; naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 3-allylnaphthalene-1, Naphthalenedicarboxylic acids such as 4-dicarboxylic acid, 3,7-diallylnaphthalene-1,4-dicarboxylic acid; pyridinetricarboxylic acids such as 2,4,5-pyridinetricarboxylic acid; 1,3,5-triazine-2,4 , 6-Tricarboxylic acid such as tricarboxylic acid; these acid halides, esterified products and the like can be mentioned. Of these, benzenedicarboxylic acid and benzenetricarboxylic acid are preferable, and isophthalic acid, terephthalic acid, isophthalic acid chloride, terephthalic acid chloride, 1,3,5-benzenetricarboxylic acid, 1,3,5-benzenetricarbonyl. It is more preferably trichloride, and even more preferably isophthalic acid chloride, terephthalic acid chloride, and 1,3,5-benzenetricarbonyltrichloride.

Among the above, it is preferable that the aromatic ring is a monocyclic aromatic ring, such as a third aromatic compound, and the aromatic ring is a condensed aromatic ring, such as a third aromatic compound, and a benzenedicarboxylic acid. , Benzenetricarboxylic acid, naphthalenedicarboxylic acid, preferably acid halides thereof, more preferably benzenedicarboxylic acid, naphthalenedicarboxylic acid, acid halides thereof, isophthalic acid, terephthalic acid, naphthalene-1, 5-Dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, and acid halides thereof are more preferable.

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

[Structure of Aromatic Ester Compound (A-2) Containing Polymerizable Unsaturated Bonds]
At least one of the above-mentioned first aromatic compound, second aromatic compound, and third aromatic compound and / or an acid halide or esterified product thereof (third aromatic compound, etc.) is non-polymerizable. It has a saturated bond-containing 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, or the first aromatic compound and the first aromatic compound. The aromatic compound 2 may have a polymerizable unsaturated bond-containing substituent, or only the second aromatic compound may have a polymerizable unsaturated bond-containing substituent. Further, when two or more kinds of the first aromatic compound, the second aromatic compound, the third aromatic compound and the like are used, only a part thereof has a polymerizable unsaturated bond-containing substituent. You may. The number of carbon atoms of the polymerizable unsaturated bond-containing substituent is preferably in the range of 2 to 30.

In one embodiment, it is preferred that at least the second aromatic compound has a polymerizable unsaturated bond-containing substituent. As described above, the structure derived from the second aromatic compound is located at the molecular end of the polymerizable unsaturated bond-containing aromatic ester compound (A-2). As a result, the polymerizable unsaturated bond-containing substituent of the second aromatic compound is also arranged at the molecular end of the polymerizable unsaturated bond-containing aromatic ester compound (A-2). In this case, the balance between the heat resistance and the dielectric loss tangent of the obtained cured product can be improved, 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, the third aromatic compound, and the like. And may contain various compounds. Regarding the composition of the polymerizable unsaturated bond-containing aromatic ester compound (A-2), the amount of the first aromatic compound, the second aromatic compound, the third aromatic compound, etc. used, the reaction conditions, etc. It can be controlled by changing it as appropriate.

In principle, the polymerizable unsaturated bond-containing aromatic ester compound (A-2) according to this embodiment does not have a hydroxy group in the molecule of the obtained resin. However, a compound having a hydroxy group as a by-product of the reaction product may be contained as long as the effect of the present invention is not impaired.

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

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

That is, Ar ¹ has a structure in which two or more hydrogen atoms are removed from the substituted or unsubstituted first aromatic ring, or a structure in which the first aromatic ring is linked by a linking group, respectively. Examples thereof include those in which two or more hydrogen atoms are removed from those having.

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

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

At ^{least one of Ar 1} , Ar ² , and Ar ³ has a polymerizable unsaturated bond-containing substituent.

At this time, when the first aromatic compound has 3 or more phenolic hydroxyl groups, Ar ¹ may have a further branched structure.

Further, when the third aromatic compound or the like has two or more carboxy groups or the like, Ar ³ may have a further branched structure.

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

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

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

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

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

(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, those described above are used.

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

For example, the ratio of the number of moles such as the carboxy group of the third aromatic compound to the number of moles of the hydroxy group of the first aromatic compound (carboxy group etc./hydroxy group of the first aromatic compound) is 0.5. It is preferably 10 to 10, more preferably 0.5 to 6.0, and even more preferably 1.0 to 3.0. When the ratio is 0.5 or more, the heat resistance is high, which is preferable. On the other hand, when the ratio is 10 or less, the moldability is excellent, which is preferable.

The ratio of the number of moles of the third aromatic compound, such as the carboniciki group, to the number of moles of the hydroxy group of the second aromatic compound (carboxy group, etc./hydroxy group of the second aromatic compound) is 0.5. It is preferably 10 to 10, and more preferably 1.5 to 4.0. When the ratio is 0.5 or more, the moldability is excellent, which is preferable. On the other hand, when the ratio is 10 or less, the heat resistance is high, which is preferable.

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

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

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

The pH at the time of reaction is not particularly limited, but is preferably 11 or more. At this time, for adjusting the pH, acids such as hydrochloric acid, sulfuric acid, nitric acid and acetic acid; and bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia can be used.

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

The arylene group in the polyarylene ether resin (B) used in the present invention has a phenylene group, a naphthylene group, and a structure having substituents such as an aliphatic hydrocarbon group, an alkoxy group, an aryl group, and an aralkyl group on these aromatic nuclei. The site and the like can be mentioned. Among them, since the curable composition has an excellent balance between the dielectric property and the heat resistance of the cured product, the one having a phenylene group as the main skeleton is preferable, and the phenylene group having two substituents on the aromatic nucleus is preferable. Is more preferable. As the type 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 polyarylene ether resin (B) is generally an aryloxy group having a phenolic hydroxyl group. The phenolic hydroxyl group may be modified to other structural sites. Examples of the aryl group in the aryloxy group include a phenyl group, a naphthyl group, and a structural site having a substituent such as an aliphatic hydrocarbon group, an alkoxy group, an aryl group, and an aralkyl group on these aromatic nuclei. Among them, since the curable composition has an excellent balance between the dielectric property and the heat resistance of the cured product, the one having a phenyl group as the main skeleton is preferable, and two substituents are further added to the aromatic nucleus in addition to the phenolic hydroxyl group. It is more preferable that the phenylene group has one. As the type of the substituent, an aliphatic hydrocarbon group is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

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

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

（式中Ｒ^１はそれぞれ独立に水素原子、脂肪族炭化水素基、アルコキシ基、アリール基、アラルキル基の何れかである。ｍ及びｎはそれぞれ独立に０以上の整数である。Ｘは水素原子又は重合性不飽和結合含有基である。）

(In the formula, R ¹ is independently any of a hydrogen atom, an aliphatic hydrocarbon group, an alkoxy group, an aryl group, and an aralkyl group. M and n are independently integers of 0 or more. X is a hydrogen atom. Or a polymerizable unsaturated bond-containing group.)

Y in the structural formula (15) is not particularly limited as long as it is a divalent organic group, and may be any structural site. As an example thereof, the following structural formulas (Y-1) to (Y) are used. Examples thereof include those represented by any of -9).

（式中、Ｒ^２はそれぞれ独立に脂肪族炭化水素基、アルコキシ基、アリール基、アラルキル基の何れかである。Ｒ^３はそれぞれ独立に脂肪族炭化水素基、アルコキシ基、アリール基の何れかであり、ｋは０〜４の整数である。）

(In the formula, R ² is independently any of an aliphatic hydrocarbon group, an alkoxy group, an aryl group, and an aralkyl group. R ³ is independently any of an aliphatic hydrocarbon group, an alkoxy group, and an aryl group. And 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 the phenolic hydroxyl group, that is, the functional group of the structural site represented by the -OX group at the middle end of the structural formula (15). The equivalent amount is preferably in the range of 500 to 3,000 g / equivalent, preferably in the range of 500 to 1,500 g / equivalent, because the curable composition is excellent in both heat resistance and dielectric properties. Is more preferable.

In the curable composition of the present invention, the blending ratio of the polymerizable unsaturated bond-containing aromatic ester compound (A) and the polyarylene ether resin (B) is not particularly limited, and depends on the desired cured product performance and the like. Is adjusted as appropriate. Above all, since the curable composition has an excellent balance between heat resistance and dielectric properties in the cured product, 10 to 300 mass by mass of the polyarylene ether resin (B) is added to 100 parts by mass of the aromatic ester compound (A). It is preferably used in the range of 20 to 200 parts by mass, and more preferably used in the range of 20 to 200 parts by mass.

The curable composition of the present invention may contain other components in addition to the polymerizable unsaturated bond-containing aromatic ester compound (A) and the polyarylene ether resin (B). Hereinafter, examples of other components will be given. The other components that can be contained in the curable composition of the present invention are not limited to those exemplified below, and may contain components other than these.

[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, the aromatic ester compound (A) and the polyarylene ether resin (B) ) Only has curability. On the other hand, since the aromatic ester compound (A) also functions as a curing agent for the epoxy resin and can give a cured product having higher heat resistance, the curable composition of the present invention may further contain the epoxy resin. preferable.

The epoxy resin is not particularly limited, but is not particularly limited, but is phenol novolac type epoxy resin, cresol novolac type epoxy resin, α-naphthol novolac type epoxy resin, β-naphthol novolac type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl novolac type epoxy. Novorak type epoxy resin such as resin; aralkyl type epoxy resin such as phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, phenolbiphenyl 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, tetrabromo bisphenol A type epoxy resin, etc. Biphenyl-type epoxy resin such as biphenyl-type epoxy resin, tetramethylbiphenyl-type epoxy resin, biphenyl skeleton and epoxy resin having diglycidyloxybenzene skeleton; naphthalene-type epoxy resin; binaphthol-type epoxy resin; binaphthyl-type epoxy resin; dicyclopentadiene Dicyclopentadiene type epoxy resin such as phenol type epoxy resin; glycidylamine type epoxy resin such as tetraglycidyldiaminodiphenylmethane type epoxy resin, triglycidyl-p-aminophenol type epoxy resin, glycidylamine type epoxy resin of diaminodiphenylsulfone; 2 , 6-Naphthalenedicarboxylic acid diglycidyl ester type epoxy resin, diglycidyl ester type epoxy resin such as glycidyl ester type epoxy resin of hexahydrophthalic anhydride; benzopyran such as dibenzopyran, hexamethyldibenzopyran, 7-phenylhexamethyldibenzopyran Examples include type epoxy resin. Each of these may be used alone, or two or more thereof may be used in combination.

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

The weight average molecular weight of the epoxy resin is preferably 200 to 5000, more preferably 300 to 3000. When the weight average molecular weight of the epoxy resin is 200 or more, it is preferable because it can have quick curability. On the other hand, when the weight average molecular weight of the epoxy resin is 5000 or less, it is preferable because the moldability is excellent. As the weight average molecular weight, the value measured by the above method (GPC) is adopted.

[Other hardeners]
When the curable composition of the present invention contains the epoxy resin, in addition to the aromatic ester compound (A), another curing agent capable of curing the epoxy resin may be used in combination.

Examples of other curing agents include, but are not limited to, 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, but is diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), diproprenedamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethyl. Aliphatic amines such as piperazine, mensendiamine (MDA), isofuronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N, N, -dimethylpiperazin, triethylenediamine; m-xylene diamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethyl) Examples include aromatic amines such as aminomethyl) phenol.

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

Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, ethylene glycol bistrimerite, glycerol tristrimerite, maleic anhydride, and tetrahydrophthalic anhydride. Methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylphthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, Examples thereof include methylcyclohexene dicarboxylic acid anhydride.

Examples of the phenol resin curing agent include phenol novolac resin, cresol novolac resin, naphthol novolac resin, bisphenol novolac resin, biphenyl novolac resin, dicyclopentadiene-phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, and triphenol methane type resin. , Tetraphenol ethane type resin, aminotriazine modified phenol resin and the like.

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

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

In the curable composition of the present invention, the blending ratio of the aromatic ester compound (A), the epoxy resin, and other curing agents is not particularly limited, and is appropriately adjusted according to the desired cured product performance and the like. The total number of functional groups capable of reacting with the epoxy groups in the aromatic ester compound (A) and other curing agents is in the range of 0.7 to 1.5 mol with respect to a total of 1 mol of epoxy groups. Is preferable.

[Other resins]
Specific examples of other resins are not particularly limited, but are limited to maleimide resin, bismaleimide resin, polyimide resin, cyanate ester resin, benzoxazine resin, triazine-containing cresol novolac resin, cyanate ester resin, styrene-maleic anhydride resin, and the like. Examples thereof include allyl group-containing resins such as diallyl bisphenol and triallyl isocyanurate, polyphosphate esters, phosphate ester-carbonate copolymers, and polybutadiene resins. 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 solvent has a function of adjusting the viscosity of the composition and the like.

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

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

[Additive]
In one embodiment, the composition may include additives. Examples of the additive include a curing accelerator, a flame retardant, a filler and the like.

(Curing accelerator)
The curing accelerator is not particularly limited, and examples thereof include phosphorus-based curing accelerator, amine-based curing accelerator, imidazole-based curing accelerator, guanidine-based curing accelerator, urea-based curing accelerator, peroxide, and azo compound. Be done.

Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, triparatrilphosphine, diphenylcyclohexylphosphine and tricyclohexylphosphine; organic phosphine compounds such as trimethylphosphine and triethylphosphine; ethyltriphenyl. Phosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-trilborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium disianamide, Examples thereof include phosphonium salts such as butylphenylphosphonium disianamide and tetrabutylphosphonium decanoate.

As amine-based curing accelerators, triethylamine, tributylamine, N, N-dimethyl-4-aminopyridine (DMAP), 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo [5,4] , 0] -Undecene-7 (DBU), 1,5-diazabicyclo [4,3,0] -Nonene-5 (DBN) and the like.

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, and 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-undecyl imidazolium trimerite, 1-cyanoethyl-2-phenylimidazolium trimerite, 2-phenylimidazole isocyanuric acid adduct, 2-Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2- Examples thereof include methyl-3-benzylimidazolium chloride, 2-methylimidazoline and the like.

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

Examples of the urea-based curing accelerator include 3-phenyl-1,1-dimethylurea, 3- (4-methylphenyl) -1,1-dimethylurea, chlorophenylurea, and 3- (4-chlorophenyl) -1,1. -Dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea and the like can be mentioned.

Examples of the peroxide and azo compound include benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropylperoxycarbonate, di-2-ethylhexylperoxycarbonate, azobisisobutyronitrile and the like. Can be mentioned.

Among the above-mentioned curing accelerators, it is preferable to use 2-ethyl-4-methylimidazole and dimethylaminopyridine.

The above-mentioned curing accelerator may be used alone or in combination of two or more.

The amount of the curing accelerator used is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 with respect to 100 parts by mass of the resin solid content of the curable composition. When the amount of the curing accelerator used is 0.01 parts by mass or more, it is preferable because the curability is excellent. On the other hand, when the amount of the curing accelerator used is 5 parts by mass or less, it is preferable because the moldability is excellent.

(Flame retardants)
The flame retardant is not particularly limited, and examples thereof include an inorganic phosphorus flame retardant, an organic phosphorus flame retardant, and a halogen flame retardant.

The inorganic phosphorus-based flame retardant is not particularly limited, and examples thereof include red phosphorus; ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphoric acid amide.

The organophosphorus flame retardant is not particularly limited, but is limited to methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, and bis (2-ethylhexyl). Phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butylpyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, (2-hydroxyethyl). ) Phosphoric acid esters such as methacrylate acid phosphate; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxides and the like diphenylphosphine; 10- (2,5-dihydroxyphenyl) -10H- 9-Oxa-10-phosphaphenanthrene-10-oxide, 10- (1,4-dioxynaphthalene) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinyl hydroquinone, diphenylphos Phosphorus-containing compounds such as phenyl-1,4-dioxynaphthalin, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol, 1,5-cyclooctylenephosphinyl-1,4-phenyldiol 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10 -Cyclic phosphorus compounds such as-(2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; said phosphoric acid ester, said diphenylphosphine, said phosphorus-containing phenol, and epoxy resin. Examples thereof include aldehyde compounds and compounds obtained by reacting with phenol compounds.

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

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, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the resin solid content of the curable composition. When the amount of the flame retardant used is 0.1 parts by mass or more, flame retardancy can be imparted, which is preferable. On the other hand, when the amount of the flame retardant used is 50 parts by mass or less, flame retardancy can be imparted while maintaining the dielectric property, which is preferable.

(filler)
Examples of the filler include an organic filler and an inorganic filler. The filler has a function of improving elongation, a function of improving mechanical strength, and the like.

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

The inorganic filler is not particularly limited, but is limited to silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and nitrided. Boron, aluminum hydroxide, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate, barium zirconate , Calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black and the like.

Of these, it is preferable to use silica. At this time, as the silica, amorphous silica, molten silica, crystalline silica, synthetic silica, hollow silica and the like can be used.

Further, the filler may be surface-treated if necessary. The surface treatment agent that can be used at this time is not particularly limited, but is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilazane compound, and a titanate-based coupling. Agents and the like can be used. Specific examples of the surface treatment agent include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and hexamethyldi. Silazan and the like can be mentioned.

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

The average particle size of the filler is not particularly limited, and is preferably 0.01 to 10 μm, more preferably 0.03 to 5 μm, and even more preferably 0.05 to 3 μm. In addition, in this specification, "particle size" means the maximum length among the distances between two points on the contour line of a particle. Further, the "average particle size" is measured by measuring the particle size of any 100 particles in one screen in an image obtained by a scanning electron microscope (SEM) and calculating the average value thereof. The value shall be adopted.

The amount of the filler used is preferably 0.5 to 95 parts by mass and more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the resin solid content of the curable composition. When the amount of the filler used is 0.5 parts by mass or more, low thermal expansion can be imparted, which is preferable. On the other hand, when the amount of the filler used is 95 parts by mass or less, it is preferable because the balance between the characteristics and the moldability is excellent.

<Curing 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 polyarylene ether resin (B). Will be done.

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

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

Since the polymerizable unsaturated bond-containing aromatic ester compound (A) itself has a low dielectric loss tangent, the cured product has a low dielectric loss tangent and is more excellent in heat resistance. It can be used for electronic materials such as substrates, build-up adhesive films, and semiconductor encapsulation materials. In addition, it can also be applied to applications such as adhesives and paints.

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

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to the description of Examples.

Production Example 1 Production of a polymerizable unsaturated bond-containing aromatic ester compound (A-1-1) 268 g of orthoallylphenol and 1200 g of toluene are placed in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer. Was charged, and the contents were dissolved while substituting nitrogen under reduced pressure in the system. Next, 203 g of isophthalic acid chloride was charged, and the contents were dissolved while substituting nitrogen under reduced pressure in the system. 0.6 g of tetrabutylammonium bromide was added to dissolve the bromide, and while purging with nitrogen gas, the temperature inside the system was controlled to 60 ° C. or lower, and 412 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, stirring was continued for 1 hour under the same temperature conditions. The reaction mixture was allowed to stand to separate liquids, and the aqueous layer was removed. Water was added to the obtained organic phase, and the mixture was stirred for about 15 minutes, allowed to stand to separate liquids, and the aqueous layer was removed. This washing operation was repeated until the pH of the aqueous layer reached 7. The organic phase after washing with water 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) has an ester group equivalent of 199 g / equivalent, an allyl group equivalent of 199 g / equivalent, and an E-type viscosity (25 ° C.) of 6000 mPa. It was s.

Production Example 2 Production of polymerizable unsaturated bond-containing aromatic ester compound (A-2-1) Dicyclopentadiene and phenol are added to a flask equipped with a thermometer, a dropping funnel, a cooling tube, a distillate tube, and a stirrer. 165 g of a heavy addition reaction resin (hydroxyl equivalent 165 g / equivalent, softening point 85 ° C.), 134 g of orthoallyl phenol, and 1200 g of toluene were charged, and the contents were dissolved while substituting nitrogen under reduced pressure in the system. Next, 203 g of isophthalic acid chloride was charged and dissolved while substituting nitrogen under reduced pressure in the system. 0.6 g of tetrabutylammonium bromide was added to dissolve the bromide, and while purging with nitrogen gas, the temperature inside the system was controlled to 60 ° C. or lower, and 412 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, stirring was continued for 1 hour under the same temperature conditions. The reaction mixture was allowed to stand to separate liquids, and the aqueous layer was removed. Water was added to the obtained organic phase, and the mixture was stirred for about 15 minutes, allowed to stand to separate liquids, and the aqueous layer was removed. This washing operation was repeated until the pH of the aqueous layer reached 7. The organic phase after washing with water 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 group equivalent of 428 g / equivalent, and a softening point of 82 ° C.

Production Example 3 Production of polymerizable unsaturated bond-containing aromatic ester compound (A-2-2) Production example except that 165 g of the polyaddition reaction resin of dicyclopentadiene and phenol in Production Example 2 was changed to 160 g of diallyl bisphenol A. In the same manner as in No. 2, 402 g of a polymerizable unsaturated bond-containing aromatic ester compound (A-2-2) was obtained. 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 group equivalent of 212 g / equivalent, and a softening point of 51 ° C.

Comparative Production Example 1 Production of Aromatic Ester Compound (A') A double addition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g) in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer. / Equivalent, softening point 85 ° C.) 165 g, 1-naphthol 72 g, and toluene 630 g were charged, and the contents were dissolved while replacing the inside of the system with reduced pressure nitrogen. Next, 152 g of isophthalic acid chloride was charged and dissolved while substituting nitrogen under reduced pressure in the system. 0.6 g of tetrabutylammonium bromide was added, and while performing nitrogen gas purging treatment, the inside of the system was controlled to 60 ° C. or lower, and 315 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After completion of the dropping, stirring was continued for 1 hour under the same temperature conditions. The reaction mixture was allowed to stand to separate liquids, and the aqueous layer was removed. Water was added to the obtained organic phase, and the mixture was stirred for about 15 minutes, allowed to stand to separate liquids, and the aqueous layer was removed. This washing operation was repeated until the pH of the aqueous layer reached 7. The organic phase after washing with water was dried under heating and reduced pressure conditions 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 1-9 and Comparative Example 1
Each component was blended in the proportions shown in Tables 1 and 2 below to obtain a curable composition. With respect to the obtained curable composition, the heat resistance of the cured product was evaluated and the dielectric loss tangent value was measured as follows. 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): "NORYL SA90" manufactured by SABIC, hydroxyl group equivalent 850 g / equivalent, theoretical structure is as follows.

・ポリアリーレンエーテル樹脂（Ｂ−２）：ＳＡＢＩＣ社製「ＮＯＲＹＬ ＳＡ９０００」、メタクリロイル基当量８５０ｇ/当量、理論構造は以下の通り。

Polyarylene ether resin (B-2): "NORYL SA9000" manufactured by SABIC, methacrylyl group equivalent 850 g / equivalent, theoretical structure is as follows.

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

Production of Cured Product The curable composition was poured into a mold of 11 cm × 9 cm × 2.4 mm and molded using a press at 150 ° C. for 60 minutes, then at 175 ° C. for 90 minutes, and further at 200 ° C. for 90 minutes. The molded product was taken out from the mold and 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 cured product having a thickness of 2.4 mm obtained above. Using the "solid viscoelasticity measuring device RSAII" manufactured by Leometric, the temperature at which the change in elastic modulus of the test piece is maximum (the rate of change in tan δ is the largest) is measured by DMA (dynamic viscoelasticity) measurement by the rectangular tension method. It was measured as the transition temperature. The measurement conditions were a frequency of 1 Hz and a heating rate of 3 ° C./min.

Measurement of Dissipation Factor The cured product obtained at the destination was vacuum-dried by heating at 105 ° C. for 2 hours, and then stored in a room at a temperature of 23 ° C. and a humidity of 50% for 24 hours as a test piece. The dielectric loss tangent of the test piece at 1 GHz was measured by the cavity resonance method using a “network analyzer E8632C” manufactured by Agilent Technologies, Inc.

Claims (6)

A curable composition containing a polymerizable unsaturated bond-containing aromatic ester compound (A) and a polyarylene ether resin (B).
The polymerizable unsaturated bond-containing aromatic ester compound (A) has the following chemical formula (1):

(In the above chemical formula (1),
Ar ¹ is a substituted or unsubstituted first aromatic ring group,
Ar ² is an independently substituted or unsubstituted second aromatic ring group, respectively.
At this time, ^{at least one of the Ar 1} and the Ar ² has a polymerizable unsaturated bond-containing substituent, and n is an integer of 2 or 3. ) Is a curable composition. The curable composition according to claim 1, further comprising an epoxy resin. A cured product of the curable composition according to claim 1 or 2. A printed wiring board using the curable composition according to claim 1 or 2. A semiconductor encapsulating material using the curable composition according to claim 1 or 2. A build-up film using the curable composition according to claim 1 or 2.