JP7114987B2 - Curable composition and cured product thereof - 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, a semiconductor sealing material, and a build-up film using the curable composition.

2. Description of the Related Art In recent years, the miniaturization and performance enhancement of electronic devices have progressed, and along with this, the required performance of various materials used has increased. For example, in semiconductor package substrates, the speed and frequency of signals are increasing, and materials with low electrical energy loss, that is, materials with low dielectric loss tangent are required.

As such a low dielectric loss tangent material, for example, there is provided an invention relating to a resin composition containing (A) an epoxy resin, (B) an active ester compound, (C) a smear suppressing component, and (D) an inorganic filler. (See Patent Document 1, for example). At this time, when the nonvolatile component of the resin composition is 100% by mass, the (B) active ester compound, the (C) smear suppressing component, and the (D) inorganic filler each have a predetermined content rate. and the smear suppressing component (C) is rubber particles.

Patent Literature 1 describes that a cured product of the resin composition can achieve a low dielectric loss tangent. It is also described that smears (resin residues) in via holes after the hardened material is roughened by drilling can be suppressed.

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

JP 2016-156019 A

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

The present inventors have conducted intensive research in order to solve the above problems. As a result, it was found that a curable composition containing an aromatic ester compound having a polymerizable unsaturated bond in the molecular structure and a diene polymer exhibits remarkably excellent heat resistance and dielectric properties in the cured product. I have completed my invention.

That is, the present invention uses a curable composition containing a polymerizable unsaturated bond-containing aromatic ester compound (A) and a diene polymer (B), a cured product thereof, and a curable composition. We provide printed wiring boards, semiconductor encapsulation materials, and build-up films.

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 board using the curable composition, a semiconductor encapsulating material, and a build-up film can be provided.

DETAILED DESCRIPTION OF THE INVENTION Embodiments for carrying out the present invention will be described in detail below.

The polymerizable unsaturated bond-containing aromatic ester compound (A) used in the present invention has one or more polymerizable unsaturated bonds in its molecular structure, and has a structural site in which aromatic rings are bonded to each other via an ester bond. A wide variety of compounds can be used as long as they are aromatic ester compounds having a specific structure, molecular weight, and the like, without particular limitation.

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 each independently a substituted or unsubstituted second aromatic ring group. , where at least one of Ar ¹ and 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, It is a reaction product with a third aromatic compound having two or more carboxyl groups and/or acid halides and esters thereof, wherein the first aromatic compound, the second aromatic compound, and the second A polymerizable unsaturated bond-containing aromatic ester compound (A-2), wherein at least one of the aromatic compounds and/or acid halides and esters thereof of 3 has a polymerizable unsaturated bond-containing substituent, and the like. be done.

As the polymerizable unsaturated bond-containing aromatic ester compound (A), from the viewpoint of excellent balance with handling properties when preparing a curable composition described later, heat resistance of the cured product, and dielectric properties, It is preferably liquid at (25°C) or has a softening point in the range of 40°C to 200°C.

Regarding 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 ”.

The first aromatic ring group is not particularly limited, but is monocyclic such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Aromatic compounds from which two or three hydrogen atoms have been removed; condensed ring aromatics such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine aromatic compounds with two or three hydrogen atoms removed, such as aromatic compounds with two or three hydrogen atoms removed. A combination of a plurality of these aromatic compounds may also be used, for example, ring-assembled aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. from which two or three hydrogen atoms are removed; 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 aromatic compounds linked by alkylene, such as pyridylmethane, fluorene, and diphenylcyclopentane.

Among them, Ar ¹ is preferably a substituted or unsubstituted benzene ring structure or naphthalene ring structure, more preferably a substituted or unsubstituted benzene ring structure, since a cured product with more excellent dielectric properties can be obtained. .

The first aromatic ring group for Ar ¹ may have a substituent. In this case, the "substituent of the first aromatic ring group" 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 are not particularly limited, but include alkyl groups, alkoxy groups, alkyloxycarbonyl groups, alkylcarbonyloxy groups, halogen atoms and the like.

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

Examples of the alkoxy group include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, and hexyloxy groups.

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

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, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group and the like.

Halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

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

The alkenyl group is not particularly limited, but vinyl group, allyl group, propenyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-hexenyl group, 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-pentadecenyl 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 group group, pentadeca-4,7-dienyl group, hexa-1,3,5-trienyl group, pentadeca-1,4,7-trienyl group and the like.

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

The polymerizable unsaturated bond-containing substituent may further have a substituent. In this case, the "substituent of the polymerizable unsaturated bond-containing substituent" 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, the alkylcarbonyloxy group, and the halogen atom include those described above.

Among 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, a substituted or unsubstituted alkenyl group having 2 to 5 carbon atoms, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a 1-propenyl group, a 1-butenyl group, Particularly preferred are 2-butenyl, 3-butenyl and 1,3-butadienyl groups, and most preferred are allyl, propenyl, isopropenyl and 1-propenyl groups.

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 the position of bonding to "--C(O)OAr ² ". Note that "-*" may be bonded to any position on the aromatic ring.

Among these, formulas (2-1) to (2-11) are preferable, and formulas (2-1), (2-2), (2-6), (2-7), (2- 9), and more preferably formulas (2-1), (2-2), (2-6) and (2-7).

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

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

The second aromatic ring group is not particularly limited, but is monocyclic such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Aromatic compounds from which one hydrogen atom has been removed; condensed aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine Examples include aromatic compounds from which one hydrogen atom has been removed, such as those from which one hydrogen atom has been removed. A combination of a plurality of these aromatic compounds may also be used, for example, ring-assembled aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. from which one hydrogen atom is removed; diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, Examples thereof include aromatic compounds such as fluorene and diphenylcyclopentane, which are linked by alkylene and have one hydrogen atom removed.

Among them, Ar ² is preferably a substituted or unsubstituted benzene ring structure or naphthalene ring structure because a cured product having more excellent dielectric properties can be obtained. In addition, from the viewpoint of high handleability and low viscosity of the aromatic ester compound (A), a benzene ring is preferable, and on the other hand, the obtained cured product has higher heat resistance and is excellent in balance with low dielectric properties. From the point of view, it is preferably a naphthalene ring.

The second aromatic ring group for Ar ² may have a substituent. In this case, the "substituent of the second aromatic ring group" 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 are not particularly limited, but include alkyl groups, alkoxy groups, alkyloxycarbonyl groups, alkylcarbonyloxy groups, halogen atoms and the like. At this time, examples of the alkyl group, alkoxy group, alkyloxycarbonyl group, alkylcarbonyloxy group, and halogen atom include those mentioned above.

In one embodiment of the invention, Ar ² may have an unsaturated bond-containing substituent as described above. At this time, the unsaturated bond-containing substituent may be present singly 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 the position of bonding to "--OC(O)Ar ¹ ". Note that "-*" may be bonded to any position on the aromatic ring.

Among these, formulas (3-1) to (3-11) are preferable, and formulas (3-1), (3-6), and (3-9) are more preferable, and formula (3 -1) and (3-6) are more preferred.

At least one of the hydrogen atoms in the aromatic rings of 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 ( 3-1), (3-6), and (3-9) are more preferable, and Ar ¹ is the above formula (2-1), (2-2), (2-6), (2-7 ), Ar ² is more preferably the above formula (3-1) or (3-6), Ar ¹ is the above formula (2-1), and Ar ² is the above formula (3-1) , (3-6) are particularly preferred.

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

According to one embodiment, at least one of Ar ² preferably has an unsaturated bond-containing substituent, more preferably all Ar ² have an unsaturated bond-containing substituent, and Ar ¹ has an unsaturated bond-containing It is more preferred to have no substituents and all Ar ² have unsaturated bond-containing substituents. The presence of an unsaturated bond-containing substituent on 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 connecting 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) 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はナフタレン環上の何れの炭素原子上に置換していてもよい。］

[In the formula, R ¹ is a polymerizable unsaturated bond-containing substituent. Each ^R2 is independently an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom. h is 2 or 3, i is each independently an integer of 1 or more, j is each independently an integer of 0 or 1 or more, and i+j is an integer of 5 or less. k is 2 or 3, l is each independently an integer of 1 or more, m is each independently an integer of 0 or 1 or more, and l+m is an integer of 7 or less. When i, j, l and m are integers of 2 or more, a plurality of R ¹ or R ² may be the same or different. In formula (1-2), R ¹ and R ² may be substituted on any carbon atom on the naphthalene ring. ]

In formula (1-1) above, particularly preferred examples of R ¹ include an allyl group, a propenyl group, an isopropenyl group, and a 1-propenyl group, as described above. i is preferably 1 or 2, more preferably 1.

In formula (1-2) above, particularly preferred examples of R ¹ include allyl, propenyl, isopropenyl, and 1-propenyl groups, as described above. l is preferably 1 or 2, more preferably 1.

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

Among the 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), (4-10) ) ~ (4-13), (4-18) ~ (4-39) are more preferable, and chemical formulas (4-1) ~ (4-3), (4-12), (4-13) , (4-19) ~ (4-21), (4-23) ~ (4-26), (4-29), (4-30), (4-32) ~ (4-39) More preferably, chemical formulas (4-1), (4-2), (4-12), (4-13), (4-26), (4-32), (4-37) is particularly preferred.

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

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

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

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

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

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

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

In the chemical formulas (5-1) to (5-15) above, R ¹ is a hydroxy group or a halogen atom. Also, R ² is a polymerizable unsaturated bond-containing substituent. At this time, the polymerizable unsaturated bond-containing substituent is the same as described above. Furthermore, p is 2 or 3. Also, q is 0 or an integer of 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, still more preferably 0. ^The positions of the substituents on the aromatic rings in the above chemical formulas ^are described on the same aromatic ring for convenience. It indicates that the ring may be substituted, and the number of substituents in one molecule is p and q.

Specific polycarboxylic acid compounds or derivatives thereof are not particularly limited, but isophthalic acid, terephthalic acid, 5-allyl isophthalic acid, benzene dicarboxylic acids such as 2-allyl terephthalic acid; trimellitic acid, 5-allyl trimellit Benzenetricarboxylic acid such as acid; naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 3-allylnaphthalene-1, 4-dicarboxylic acid, naphthalenedicarboxylic acids such as 3,7-diallylnaphthalene-1,4-dicarboxylic acid; pyridinetricarboxylic acids such as 2,4,5-pyridinetricarboxylic acid; 1,3,5-triazine-2,4 triazinecarboxylic acids such as ,6-tricarboxylic acid; and acid halides thereof. Among these, benzenedicarboxylic acid and benzenetricarboxylic acid are preferred, and isophthalic acid, terephthalic acid, isophthalic acid chloride, terephthalic acid chloride, 1,3,5-benzenetricarboxylic acid and 1,3,5-benzenetricarbonyl Trichloride is more preferred, and isophthaloyl chloride, terephthaloyl chloride, and 1,3,5-benzenetricarbonyltrichloride are even more preferred.

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

(phenol compound)
The phenolic compound has a substituted or unsubstituted aromatic ring group, preferably in the range of 3-30 carbon atoms. At this time, the second aromatic ring group and the substituents of the second aromatic ring group are the same as those described above.

Specific phenol compounds 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 described above. Furthermore, q is 0 or an integer of 1 or more, preferably 1 to 3, more preferably 1 or 2, and still more preferably 1. When q is 2 or more, the bonding position on the aromatic ring is arbitrary. may be substituted on any of the benzene rings present in one molecule, and the number of substituents in one molecule is q. showing.

Specific phenol compounds include, but are not limited to, 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 and isoeugenol; butenylphenols such as 2-(3-butenyl)phenol and 2-(1-ethyl-3-butenyl)phenol; cardanol long-chain alkenylphenols such as 2-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-1-naphthol and 3-allyl-1-naphthol. Among these, allylphenol and allylnaphthol are preferable, and 2-allylphenol, 4-methyl-2-allylphenol, 6-methyl-2-allylphenol, 2-allyl-1-naphthol, 1-allyl- 2-naphthol is more preferred, and 2-allylphenol, 2-allyl-1-naphthol and 1-allyl-2-naphthol are even more preferred.

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

The above phenol compounds may be used alone or in combination of two or more.

The amounts of the polycarboxylic acid compound or derivative thereof and the phenol compound used are not particularly limited, but the amount of carboxy groups and/or acyl halide groups, etc. of the polycarboxylic acid compound or derivative thereof relative to the number of moles of hydroxy groups of the phenol compound. The molar ratio of the number of moles of the derivative group [(the derivative group such as a carboxy group and/or a halogenated acyl group)/(hydroxy group)] is preferably from 0.8 to 3.0, more preferably from 0.9 to 2. It is more preferably 0.0, more preferably 1.0 to 1.2.

Reaction conditions are not particularly limited, and known techniques can be employed as appropriate.

Although the pH during the reaction is not particularly limited, it is preferably 11 or higher. At this time, pH can be adjusted by using acids such as hydrochloric acid, sulfuric acid, nitric acid and acetic acid; and bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia.

The reaction temperature is also 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 normal pressure is more preferable.

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

The polymerizable unsaturated bond-containing aromatic ester compound (A-2) comprises a first aromatic compound having two or more phenolic hydroxyl groups, a second aromatic compound having a phenolic hydroxyl group, and two or more It is a reaction product with a third aromatic compound having a carboxy group and/or an acid halide or ester thereof, wherein the first aromatic compound, the second aromatic compound, and the third aromatic compound 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.

Examples of the first aromatic compound include, but are not particularly limited to, compounds having two or more phenolic hydroxyl groups in a substituted or unsubstituted first aromatic ring having 3 to 30 carbon atoms.

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

Examples of the monocyclic aromatic ring include, but are not limited to, benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, and the like.

Examples of the condensed aromatic ring include, but are not limited to, naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine.

Examples of the ring-assembled aromatic ring include, but are not limited to, biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, and the like.

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

The alkyl group having 1 to 10 carbon atoms is not particularly limited, but methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl. group, isopentyl group, tert-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 , a cyclooctyl group, and a cyclononyl group.

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

Halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

A substituent containing a polymerizable unsaturated bond means a substituent having 2 to 30 carbon atoms and having at least one polymerizable unsaturated bond. In this case, 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 alkenyl groups and alkynyl groups.

The alkenyl group is not particularly limited, but vinyl group, allyl group, propenyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-hexenyl group, 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-pentadecenyl 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 group group, pentadeca-4,7-dienyl group, hexa-1,3,5-trienyl group, pentadeca-1,4,7-trienyl group and the like.

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

Among 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. is more preferably an alkenyl group of 1 to 5, vinyl group, allyl group, propenyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group is particularly preferred, and allyl, propenyl, isopropenyl and 1-propenyl groups are most preferred.

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

As described above, in the first aromatic compound, at least two of the hydrogen atoms constituting the substituted or unsubstituted first aromatic ring are substituted with hydroxy groups.

Specific examples of compounds in which the first aromatic ring is a monocyclic aromatic ring (hereinafter sometimes simply referred to as "first monocyclic aromatic ring compound") include catechol, resorcinol, hydroquinone, and hydroxynol. , phloroglucinol, 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 condensed aromatic ring (hereinafter sometimes simply referred to as the "first condensed 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 compounds in which the first aromatic ring is a ring-assembled aromatic ring (hereinafter sometimes simply referred to as a "first ring-assembled aromatic ring compound") include 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 3,4,4'-trihydroxybiphenyl, 2,2',3-trihydroxybiphenyl and the like.

Moreover, the first aromatic compound may have a structure in which the first aromatic rings are 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), each Ar ³ is independently a substituted or unsubstituted first aromatic ring group, and each Ar ⁴ is independently a substituted or unsubstituted second aromatic ring group. , X are each independently oxygen atom, sulfur atom, substituted or unsubstituted alkylene, substituted or unsubstituted cycloalkylene, or aralkylene, and n is 0-10. At this time, at least two of the hydrogen atoms constituting Ar ³ and Ar ⁴ are substituted with hydroxy groups. In addition, said X corresponds to a coupling group.

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 rings constituting the above-mentioned substituted or unsubstituted aromatic ring is bound to "X".

The first aromatic ring group is not particularly limited, but is monocyclic such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Aromatic compounds from which one hydrogen atom has been removed; condensed aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine Examples include aromatic compounds from which one hydrogen atom has been removed, such as those from which one hydrogen atom has been removed. A combination of a plurality of these aromatic compounds may also be used, for example, ring-assembled aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. from which one hydrogen atom is removed.

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

Among these, Ar ³ is benzene, naphthalene, anthracene, phenalene, phenanthrene, biphenyl, binaphthalene, quaterphenyl, allylbenzene, diallylbenzene, allylnaphthalene, diallylnaphthalene, allylbiphenyl, and diallylbiphenyl with one hydrogen atom removed. and more preferably benzene, naphthalene, biphenyl, allylbenzene, diallylnaphthalene, diallylbiphenyl from which one hydrogen atom has been removed.

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

The second aromatic ring group is not particularly limited, but is monocyclic such as benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Aromatic compounds from which two hydrogen atoms have been removed; condensed aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine Examples include aromatic compounds from which two hydrogen atoms have been removed, such as those from which two hydrogen atoms have been removed. A combination of a plurality of these aromatic compounds may also be used, for example, ring-assembled aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. from which two hydrogen atoms are removed.

At this time, the second aromatic ring group may have a substituent. Examples of the "substituent for the second aromatic ring group" include those similar to the aforementioned "substituent for the first aromatic ring".

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

The alkylene is not particularly limited, but 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 chemical formulas (8-1) to (8-4) below. cycloalkylene and the like.

In the above chemical formulas (8-1) to (8-4), “*” represents a site that binds to Ar ³ or Ar ⁴ .

Examples of the aralkylene include, but are not particularly limited to, 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. In this case, the "substituent of X" includes the same as the above-mentioned "substituent of the first aromatic ring".

n in the above chemical formula (7) is an integer of 0-10, preferably 0-8, preferably 0-5. When the compound represented by the above chemical formula (7) is an oligomer or polymer, n means its average value.

At least two hydrogen atoms constituting Ar ³ and Ar ⁴ are substituted with hydroxy groups.

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

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 0-10, preferably 0-5. At this time, when the compounds represented by formulas (10-1) to (10-8) are oligomers or polymers, n means their average value. As used herein, the term "oligomer" means a compound containing 1 to 5 repeating units, and the term "polymer" means a compound containing 6 or more repeating units. Moreover, the substitution position of the hydroxy group, which is a substituent on the aromatic ring, is arbitrary, and in the case of the naphthalene ring, it may be either a ring that is bonded to another structure or a ring that is not bonded.

In one embodiment, the above 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 a compound with a divinyl compound or a dialkyloxymethyl compound.

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

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

The hydroxyl equivalent weight of the first aromatic compound is preferably 130 to 500 g/equivalent, more preferably 130 to 400 g/equivalent. It is preferable that the first aromatic compound has a hydroxyl equivalent weight of 130 g/equivalent or more because heat resistance can be imparted. On the other hand, when the hydroxyl equivalent of the first aromatic compound is 500 g/equivalent or less, it is preferable because the balance between heat resistance and dielectric loss tangent is excellent.

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

GPC measurement conditions Measurement device: Tosoh Corporation "HLC-8320 GPC"
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 rate: 1.0 ml / min Standard: According to the measurement manual of "GPC-8320 GPC", using the following monodisperse polystyrene with known molecular weight Polystyrene used Tosoh Corporation "A-500 ”
"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 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through 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 the function of stopping the polyesterification reaction of the first aromatic compound described above and the third aromatic compound described later.

Examples of the second aromatic compound include, but are not particularly limited to, compounds having one phenolic hydroxyl group in the second aromatic ring of substituted or unsubstituted 3 to 30 carbon atoms.

The second aromatic ring having 3 to 30 carbon atoms is not particularly limited, but includes a monocyclic aromatic ring, a condensed ring aromatic ring, a ring-assembled aromatic ring, an alkylene-linked aromatic ring, and the like. mentioned. Examples of the monocyclic aromatic ring, the condensed aromatic ring, and the ring-assembled aromatic ring include those similar to the first aromatic ring described above.

Aromatic rings linked by alkylene include diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, and phenylpyridyl. methane, fluorene, diphenylcyclopentane and the like.

The second aromatic ring of the second aromatic compound may have a substituent. In this case, the "substituents for the second aromatic ring" include those similar to the above-mentioned "substituents for the first aromatic ring".

Then, as described above, in the second aromatic compound, one of the hydrogen atoms constituting the above-described 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 described above. Furthermore, p is an integer of 0 or 1 or more, preferably 1 to 3, more preferably 1 or 2, and still more preferably 1. When p is 2 or more, the bonding position on the aromatic ring is arbitrary. Also, in chemical formula (11-9) etc., it indicates that any of the benzene rings present in one molecule may be substituted, and the number of substituents in one molecule is p. showing.

Specific examples of the second aromatic compound include, but are not limited to, phenol, cresol, xylenol, orthoallylphenol, methallylphenol, p-allylphenol, 2,4-diallylphenol, 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 and 4-propargylphenol Compounds that are monocyclic aromatic rings (hereinafter sometimes 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-allylu-4-methoxy-1-naphthol, Compounds in which the aromatic ring is a condensed aromatic ring such as 2-propargyl-1-naphthol, 3-propargyl-1-naphthol, 1-propargyl-2-naphthol and 3-propargyl-2-naphthol (hereinafter simply referred to as " Sometimes referred to as "second condensed aromatic ring compound"); compounds in which the aromatic ring is a ring-aggregated aromatic ring such as allylhydroxybiphenyl, hydroxypropargylbiphenyl (hereinafter simply referred to as "second ring-aggregated aromatic may be referred to as a "cyclic compound") and the like.

Among the above, the second aromatic compound is preferably a second monocyclic aromatic ring compound, a second condensed ring aromatic ring compound, ortho-allylphenol, meta-allylphenol, para-allylphenol, 2 - allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, 6-allyl-1-naphthol more preferred.

In another embodiment, the second aromatic compound is preferably a second condensed aromatic ring compound (condensed aromatic ring compound), 2-allyl-1-naphthol, 3- More preferred are allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol and 6-allyl-1-naphthol. It is preferable that the second aromatic compound is a condensed aromatic ring compound, because steric hindrance suppresses molecular motion, thereby reducing the dielectric loss tangent. In addition, from the viewpoint of high handleability and low viscosity of the aromatic ester compound (A), 2-allylphenol or the like having a benzene ring skeleton is preferable. 2-allyl-1-naphthol, 1-allyl-2-naphthol, etc. having a naphthalene ring skeleton are preferable from the viewpoint of excellent balance of .

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

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

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

Incidentally, the term "carboxyl group, etc." means a carboxy group; an acyl fluoride group, an acyl chloride group, an acyl bromide group and other halogenated acyl groups; a methyloxycarbonyl group, an ethyloxycarbonyl group and other alkyloxycarbonyl groups; aryloxycarbonyl groups such as oxycarbonyl group and naphthyloxycarbonyl group; When having an acyl halide group, the third aromatic compound is an acid halide, and when having an alkyloxycarbonyl group or an aryloxycarbonyl group, the third aromatic compound can be an ester compound. Among these, the third aromatic compound preferably has a carboxy group, an acyl halide group, an aryloxycarbonyl group, more preferably has a carboxy group, an acyl halide group, a carboxy group, an acyl chloride group, It is more preferred to have an acyl bromide group.

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

Examples of the third aromatic ring include, but are not particularly limited to, a monocyclic aromatic ring, a condensed ring aromatic ring, a ring-assembled aromatic ring, and an aromatic ring linked by alkylene. The monocyclic aromatic ring, the condensed aromatic ring, the ring-assembled aromatic ring, and the aromatic ring linked by alkylene are the same as the first aromatic ring and the second aromatic ring described above. things are mentioned.

The third aromatic ring of the third aromatic compound or the like may have a substituent. In this case, the "substituent for the third aromatic ring" includes those similar to the above-mentioned "substituent for the first aromatic ring".

Specific examples of the third aromatic compound, etc. 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 described above. Also, ^R2 is a hydroxy group, a halogen atom, an alkyloxy group, or an aryloxy group. Furthermore, p is 0 or an integer of 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, and still 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. In the chemical formula (12-7) and the like, it indicates that any of the benzene rings present in one molecule may be substituted, and the number of substituents in one molecule is p, q It shows that

Specific third aromatic compounds and the like are not particularly limited, but benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, and 2-allylterephthalic acid; trimellitic acid, 5-allyl trimellit; Benzenetricarboxylic acid such as acid; naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, 3-allylnaphthalene-1, 4-dicarboxylic acid, naphthalenedicarboxylic acids such as 3,7-diallylnaphthalene-1,4-dicarboxylic acid; pyridinetricarboxylic acids such as 2,4,5-pyridinetricarboxylic acid; 1,3,5-triazine-2,4 triazinecarboxylic acids such as ,6-tricarboxylic acid; and acid halides and esters thereof. Among these, benzenedicarboxylic acid and benzenetricarboxylic acid are preferred, and isophthalic acid, terephthalic acid, isophthalic acid chloride, terephthalic acid chloride, 1,3,5-benzenetricarboxylic acid and 1,3,5-benzenetricarbonyl Trichloride is more preferred, and isophthaloyl chloride, terephthaloyl chloride, and 1,3,5-benzenetricarbonyltrichloride are even more preferred.

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

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

[Structure of polymerizable unsaturated bond-containing aromatic ester compound (A-2)]
At least one of the first aromatic compound, the second aromatic compound, and the third aromatic compound and/or acid halides and esters thereof (third aromatic compound, etc.) is a polymerizable non-polymerizable compound. It has a saturated bond-containing substituent. That is, the first aromatic compound, the second aromatic compound, the third aromatic compound, etc. may all have a polymerizable unsaturated bond-containing substituent, or the first aromatic compound and the third The second aromatic compound 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, etc. are used, only some of them have a polymerizable unsaturated bond-containing substituent. may The number of carbon atoms in the polymerizable unsaturated bond-containing substituent is preferably in the range of 2-30.

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 positioned at the molecular terminal 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 terminal of the polymerizable unsaturated bond-containing aromatic ester compound (A-2). In this case, the balance between the heat resistance and the dielectric loss tangent of the obtained cured product can be improved, which is preferable.

The polymerizable unsaturated bond-containing aromatic ester compound (A-2) is a reaction product of the first aromatic compound, the second aromatic compound, and the third aromatic compound, as described above. Yes, and may contain a variety of compounds. Regarding the composition of the polymerizable unsaturated bond-containing aromatic ester compound (A-2), the amounts of the first aromatic compound, the second aromatic compound, and the third aromatic compound used, the reaction conditions, etc. are appropriately adjusted. You can control it by changing it.

In principle, the polymerizable unsaturated bond-containing aromatic ester compound (A-2) according to the present embodiment does not have a hydroxy group in the molecule of the resulting resin. However, a compound having a hydroxy group may be included as a by-product of the reaction product as long as it does not impair the effects of the present invention.

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

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

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

In addition, each Ar ² independently includes a substituted or unsubstituted second aromatic ring from which one hydrogen atom has been removed.

Ar ³ includes a substituted or unsubstituted third aromatic ring from which two or more hydrogen atoms have been removed.

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.

Also, when the third aromatic compound has two or more carboxyl groups, etc., Ar ³ may have a further branched structure.

In one embodiment, compounds 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 0-10, preferably 0-5, and r is 1-10. At this time, when the compounds represented by formulas (14-1) to (14-10) are oligomers or polymers, s1, s2 and r mean their average values. The dashed lines in the chemical formulas are structures obtained by reacting compounds corresponding to Ar ³ and Ar ¹ and/or Ar ² .

The weight average molecular weight of the aromatic ester compound (A-2) is preferably 150-3000, more preferably 200-2000. A weight average molecular weight of 800 or more is preferable because the dielectric loss tangent is excellent. On the other hand, when the weight average molecular weight is 500 or less, the moldability is excellent, which is preferable. Also, the number average molecular weight is preferably in the range of 150 to 1,500 for the same reason.

<Method for Producing 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 it can be produced by a suitable known method.

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

(First aromatic compound, second aromatic compound, third aromatic compound, etc.)
As the first aromatic compound, the second aromatic compound, the third aromatic compound, and the like, those mentioned above are used.

In one embodiment, the polymerizable unsaturated bond-containing aromatic ester compound (A -2) configuration can be controlled.

For example, the ratio of the number of moles of the carboxy group, etc. 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 from 10 to 10, more preferably from 0.5 to 6.0, even more preferably from 1.0 to 3.0. It is preferable that the ratio is 0.5 or more because the heat resistance is increased. On the other hand, when the ratio is 10 or less, the moldability is excellent, which is preferable.

Further, the ratio of the number of moles of the carboxyl group of the third aromatic compound 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 from 10 to 10, more preferably from 1.5 to 4.0. It is preferable that the ratio is 0.5 or more because moldability is excellent. On the other hand, when the ratio is 10 or less, the heat resistance is increased, which is preferable.

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

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

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

Although the pH during the reaction is not particularly limited, it is preferably 11 or higher. At this time, pH can be adjusted by using acids such as hydrochloric acid, sulfuric acid, nitric acid and acetic acid; and bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia.

The reaction temperature is also 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 normal pressure is more preferable.

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

The diene-based polymer (B) used in the present invention specifically refers to a polymer containing a diene compound such as a butadiene monomer or an isoprene monomer as an essential constituent monomer. The diene polymer (B) generally has double bonds in the polymer chain and is reactive. Among them, a polybutadiene-based polymer containing a butadiene monomer as an essential constituent monomer is preferable.

Examples of the butadiene monomer include 1,3-butadiene, butadiene compounds having a substituent such as 2-methyl-1,3-butadiene. Each of these may be used alone, or two or more of them may be used in combination.

The diene-based polymer (B) may be obtained by copolymerizing a diene compound such as a butadiene monomer or an isoprene monomer, or other polymerizable monomers. Said other polymerizable monomers, for example, ethylene, propylene, butylene, pentene, 2-methyl-1-pentene, hexene, 3-methyl-1-hexene, 3-methyl-2-hexene aliphatic monoolefin compounds ; alicyclic monoolefin compounds such as cyclohexene; styrene compounds such as styrene, 4-methylstyrene, α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) Acrylic ester compounds such as acrylate, 2-ethylhexyl (meth)acrylate, 2-(dimethylamino)ethyl (meth)acrylate; vinyl ester compounds such as vinyl acetate and vinyl propionate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether Vinyl methyl ketone, vinyl ketone compounds such as methyl isopropenyl ketone; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, ethylenically unsaturated carboxylic acids such as itaconic anhydride; (meth) acrylonitrile, (meth ) nitrogen atom-containing compounds such as acrylamide, vinylpyridine and vinylpyrrolidone; and halogen atom-containing compounds such as vinyl chloride, vinylidene chloride and vinyl fluoride. Each of these may be used alone, or two or more of them may be used in combination.

The diene-based polymer (B) is modified using a double bond in the polymer chain or a functional group derived from the other polymerizable monomer, or modified by reacting with a compound for introducing a functional group. can be anything. Specifically, those in which a part of the vinyl group is modified to an epoxy group; those in which the carboxy groups in the polymer are reacted with epoxy group-containing compounds or resins; and those in which the oxirane compounds such as ethylene oxide and propylene oxide are reacted. Hydroxy groups in the polymer are reacted with a polyisocyanate compound; Hydroxyl groups in the polymer are reacted with a polyisocyanate compound to introduce an isocyanate group, and then a urethanization reaction is used. (meth)acryloyl groups or other functional groups introduced therein; and those modified with polyesters by reacting hydroxyl groups in the polymer with lactone compounds.

A commercially available product may be used as the diene polymer (B). Examples of commercially available products include "NISSO-PB" B series manufactured by Nippon Soda Co., Ltd. ("B-1000" number average molecular weight (Mn) 1,200, "B-2000" number average molecular weight (Mn) 2 , 100, "B-3000" number average molecular weight (Mn) 3,200, both polybutadiene homopolymer), G series ("G-1000" number average molecular weight (Mn) 1,400, hydroxyl value 68 to 78 mgKOH / g , "G-2000" number average molecular weight (Mn) 1,900, hydroxyl value 35 to 55 mgKOH / g, "G-3000" number average molecular weight (Mn) 3,000, hydroxyl value 27 mgKOH / g or more, both terminal hydroxyl groups Polybutadiene), JP series (“JP-100” number average molecular weight (Mn) 1,300, epoxy group equivalent 190 to 210 g / equivalent, “JP-200” number average molecular weight (Mn) 2,200, epoxy group equivalent 210 to 240 g / equivalent, "JP-400" number average molecular weight (Mn) 3,500, epoxy group equivalent 230 g / equivalent, both epoxidized polybutadiene), TE series ("TP-1000" number average molecular weight (Mn) 2,000 , (meth) acryloyl group equivalent 1,200 to 1,600 g / equivalent, "TE-2000" number average molecular weight (Mn) 2,500, (meth) acryloyl group equivalent 1,600 to 2,300 g / equivalent, both urethane (meth)acrylate-modified polybutadiene), TP series (“TP-1000”, isocyanate group-containing polybutadiene), GQ series (“GQ-1000”, hydroxyl group- and carboxy group-containing polybutadiene), and the like.

The diene polymer (B) preferably has a number average molecular weight (Mn) of 500 to 5,000, more preferably 800 to 4,000. For the number average molecular weight (Mn) of the diene polymer (B), the value published by the manufacturer or the value obtained by measuring gel permeation chromatography (GPC) under the conditions described above is adopted.

When an epoxy-modified diene polymer (B) is used, the epoxy group equivalent is preferably in the range of 180 to 300 g/equivalent.

In the curable composition of the present invention, the blending ratio of the polymerizable unsaturated bond-containing aromatic ester compound (A) and the diene polymer (B) is not particularly limited, depending on desired cured product performance etc. adjusted accordingly. Among them, 10 to 300 parts by mass of the diene-based polymer (B) with respect to 100 parts by mass of the aromatic ester compound (A), since the resulting curable composition has an excellent balance between heat resistance and dielectric properties in the cured product. It is preferably used in the range of , more preferably 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 diene polymer (B). Examples of other components are given below. In addition, other components that the curable composition of the present invention may contain 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 diene polymer (B ) alone has curability. On the other hand, since the aromatic ester compound (A) functions also as a curing agent for epoxy resins and can give cured products with higher heat resistance, the curable composition of the present invention may further contain an epoxy resin. preferable.

The epoxy resin is not particularly limited, but phenol novolak type epoxy resin, cresol novolak type epoxy resin, α-naphthol novolak type epoxy resin, β-naphthol novolak type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl novolak type epoxy resin. Novolac type epoxy resins such as resins; aralkyl type epoxy resins such as phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin; bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin , bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy resin, etc. biphenyl-type epoxy resins such as biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, epoxy resins having a biphenyl skeleton and diglycidyloxybenzene skeleton; naphthalene-type epoxy resins; binaphthol-type epoxy resins; binaphthyl-type epoxy resins; dicyclopentadiene dicyclopentadiene-type epoxy resins such as phenol-type epoxy resins; glycidylamine-type epoxy resins such as tetraglycidyldiaminodiphenylmethane-type epoxy resins, triglycidyl-p-aminophenol-type epoxy resins, and diaminodiphenylsulfone glycidylamine-type epoxy resins;2 , 6-naphthalene dicarboxylic acid diglycidyl ester type epoxy resin, hexahydrophthalic anhydride glycidyl ester type epoxy resin, etc.; dibenzopyran, hexamethyldibenzopyran, 7-phenylhexamethyldibenzopyran, etc. benzopyran type epoxy resin and the like. 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 150-500 g/equivalent, more preferably 200-350 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. .

The weight average molecular weight of the epoxy resin is preferably 200-5000, more preferably 300-3000. It is preferable that the weight-average molecular weight of the epoxy resin is 200 or more because it can also have rapid 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. In addition, the value measured by the above-mentioned method (GPC) is adopted as the weight average molecular weight.

[Other curing agents]
When the curable composition of the present invention contains the epoxy resin, other curing agents capable of curing with the epoxy resin may be used in combination with the aromatic ester compound (A).

Other curing agents include, but are not limited to, aromatic ester compounds containing no polymerizable unsaturated bonds, amine curing agents, imidazole curing agents, acid anhydride curing agents, phenolic resin curing agents, and the like.

The amine curing agent is not particularly limited, but diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethyl Aliphatic amines such as piperazine, mencenediamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N,-dimethylpiperazine, triethylenediamine; m-xylylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethyl aromatic amines such as aminomethyl)phenol and the like.

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

Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, glycerol tri trimellitate, maleic anhydride, tetrahydro phthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexenedicarboxylic anhydride.

Examples of the phenol resin curing agent include phenol novolak resin, cresol novolak resin, naphthol novolak resin, bisphenol novolak resin, biphenyl novolak 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 other curing agents may be used alone or in combination of two or more.

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

In the curable composition of the present invention, the blending ratio of the aromatic ester compound (A), epoxy resin, and other curing agents is not particularly limited, and can be adjusted as appropriate according to the desired cured product performance. The total amount of functional groups capable of reacting with epoxy groups in the aromatic ester compound (A) or other curing agent is in the range of 0.7 to 1.5 mol per 1 mol of epoxy groups. is preferred.

[Other resins]
Specific examples of other resins include, but are not particularly limited to, maleimide resins, bismaleimide resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolak resins, cyanate ester resins, styrene-maleic anhydride resins, Examples include allyl group-containing resins such as diallyl bisphenol and triallyl isocyanurate, polyphosphate esters, phosphate ester-carbonate copolymers, and polyphenylene ether 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 include, 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 include carbitols, aromatic hydrocarbons such as toluene and xylene, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

The amount of 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. It is preferable that the amount of the solvent used is 10% by mass or more because the handleability is excellent. On the other hand, when the amount of the solvent used is 80% by mass or less, it is preferable because the impregnating property with other substrates is excellent.

[Additive]
In one embodiment, the composition may contain additives. Such additives include curing accelerators, flame retardants, fillers, and the like.

(Curing accelerator)
The curing accelerator is not particularly limited, but includes phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, urea-based curing accelerators, peroxides, azo compounds, and the like. be done.

Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tripparatolylphosphine, diphenylcyclohexylphosphine and tricyclohexylphosphine; organic phosphine compounds such as trimethylphosphite and triethylphosphite; ethyltriphenyl phosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, Examples include phosphonium salts such as butylphenylphosphonium dicyanamide and tetrabutylphosphonium decanoate.

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

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

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

Examples of the peroxides and azo compounds include benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropylperoxycarbonate, di-2-ethylhexylperoxycarbonate, azobisisobutyronitrile, and the like. are mentioned.

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

In addition, the above curing accelerators 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 parts by mass, based on 100 parts by mass of the resin solid content of the curable composition. It is preferable that the amount of the curing accelerator used is 0.01 parts by mass or more because the curability is excellent. On the other hand, when the amount of the curing accelerator used is 5 parts by mass or less, the moldability is excellent, which is preferable.

(Flame retardants)
The flame retardant is not particularly limited, but includes inorganic phosphorus flame retardants, organic phosphorus flame retardants, halogen flame retardants, and the like.

Examples of the inorganic phosphorus-based flame retardant include, but are not particularly limited to, red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate; and phosphate amides.

The organic phosphorus flame retardant is not particularly limited, but methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, (2-hydroxyethyl ) phosphoric esters such as methacrylate acid phosphate; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide and the like diphenylphosphine; 9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphine Phosphorus-containing phenols such as phenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol and 1,5-cyclooctylenephosphinyl-1,4-phenyldiol 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10 Cyclic phosphorus compounds such as -(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; Examples include compounds obtained by reacting with aldehyde compounds and phenol compounds.

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

The above 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, based on 100 parts by mass of the resin solid content of the curable composition. It is preferable that the amount of the flame retardant used is 0.1 parts by mass or more because flame retardancy can be imparted. On the other hand, when the amount of the flame retardant used is 50 parts by mass or less, it is preferable because flame retardancy can be imparted while maintaining dielectric properties.

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

Examples of the organic filler include, but are not particularly limited to, polyamide particles.

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

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

Moreover, the said filler may be surface-treated as needed. Surface treatment agents that can be used at this time are not particularly limited, but aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, and titanate coupling agents. agents and the like can be used. Specific examples of surface treatment agents include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldimethoxysilane, silazane and the like.

In addition, the above fillers 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, even more preferably 0.05 to 3 μm. As used herein, the term "particle size" means the maximum length of the distances between two points on the contour line of the particle. In addition, the "average particle size" is measured by measuring the particle size of arbitrary 100 particles in one screen in an image obtained by a scanning electron microscope (SEM) and calculating the average value. shall be adopted.

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

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

The cured product may contain the aforementioned curing agent, additive, curing accelerator, etc., 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 has excellent heat resistance. It can be used for electronic materials such as substrates, build-up adhesive films, and semiconductor sealing materials. In addition, it can also be applied to uses such as adhesives and paints.

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

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

Production Example 1 Production of Polymerizable Unsaturated Bond-Containing Aromatic Ester Compound (A-1-1) 268 g of orthoallylphenol and 1200 g of toluene were placed in a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer. was charged, and the contents were dissolved while the inside of the system was replaced with nitrogen under reduced pressure. Next, 203 g of isophthaloyl chloride was charged, and the contents were dissolved while the pressure in the system was reduced and replaced with nitrogen. 0.6 g of tetrabutylammonium bromide was added and dissolved, and while purging with nitrogen gas, the inside of the system was controlled at 60° C. or lower, and 412 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the dropwise addition was completed, stirring was continued for 1 hour under the same temperature conditions. The reaction mixture was left to separate 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 still for liquid separation, 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) had 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.s. was s.

Production Example 2 Production of Polymerizable Unsaturated Bond-Containing Aromatic Ester Compound (A-2-1) 165 g of a polyaddition reaction resin (hydroxyl equivalent weight: 165 g/equivalent, softening point: 85° C.), 134 g of orthoallylphenol, and 1200 g of toluene were charged, and the contents were dissolved while the system was decompressed and replaced with nitrogen. Then, 203 g of isophthaloyl chloride was charged and dissolved while the inside of the system was replaced with nitrogen under reduced pressure. 0.6 g of tetrabutylammonium bromide was added and dissolved, and while purging with nitrogen gas, the inside of the system was controlled at 60° C. or lower, and 412 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the dropwise addition was completed, stirring was continued for 1 hour under the same temperature conditions. The reaction mixture was left to separate 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 still for liquid separation, 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 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 weight of 214 g/equivalent, an allyl group equivalent weight 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 2 to obtain 402 g of a polymerizable unsaturated bond-containing aromatic ester compound (A-2-2). The theoretical structure of the polymerizable unsaturated bond-containing aromatic ester compound (A-2-2) is shown below. The polymerizable unsaturated bond-containing aromatic ester compound (A-2-2) had an ester group equivalent weight of 212 g/equivalent, an allyl group equivalent weight of 212 g/equivalent, and a softening point of 51°C.

Examples 1 to 12 and Comparative Example 1
Each component was blended in the proportions shown in Tables 1 to 3 below to obtain a curable composition. With respect to the resulting curable composition, the heat resistance of the cured product was evaluated and the dielectric loss tangent value was measured in the following manner. The results are shown in Tables 1-3.

The details of each component used in the examples are as follows.
· Diene polymer (B-1): Nippon Soda Co., Ltd. "B-3000", 1,2-polybutadiene homopolymer, number average molecular weight (Mn) 3,200, theoretical repeating structure is as follows.

· Diene polymer (B-2): "JP-200" manufactured by Nippon Soda Co., Ltd., epoxidized polybutadiene, epoxy equivalent 210 to 240 g/equivalent, theoretical repeating structure is as follows.

- Epoxy resin: bisphenol A type epoxy resin (manufactured by DIC Corporation "EPICLON850S" 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 from the cured product having a thickness of 2.4 mm obtained above. DMA (dynamic viscoelasticity) measurement by the rectangular tension method was performed using Rheometric Co., Ltd.'s "Solid Viscoelasticity Measuring Apparatus RSA II". Measured as the transition temperature. The measurement conditions were a frequency of 1 Hz and a heating rate of 3° C./min.

Measurement of Dielectric Loss Tangent The cured product obtained above 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 to obtain a test piece. Using "Network Analyzer E8362C" manufactured by Agilent Technologies, Inc., the dielectric loss tangent of the test piece at 1 GHz was measured by the cavity resonance method.

Claims (6)

A curable composition containing a polymerizable unsaturated bond-containing aromatic ester compound (A) and a diene polymer (B), wherein the polymerizable unsaturated bond-containing aromatic ester compound (A) is the following (i) and/or (ii), wherein the diene-based polymer (B) is 1,2-polybutadiene (including those in which some of the vinyl groups are modified with epoxy groups), and The blending ratio of the saturated bond-containing aromatic ester compound (A) and the diene polymer (B) is such that the diene polymer ( B) A curable composition of 10 to 300 parts by weight .

(i) a polymerizable unsaturated bond-containing aromatic ester compound represented by the following chemical formula (1)

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

(ii) a first aromatic compound having two or more phenolic hydroxyl groups;
a second aromatic compound having a phenolic hydroxyl group;
a third aromatic compound having two or more carboxy groups and/or an acid halide or ester thereof;
is a reaction product of
At least one of the first aromatic compound, the second aromatic compound, and the third aromatic compound and/or an acid halide or ester thereof has an allyl group as a polymerizable unsaturated bond-containing substituent. Polymerizable unsaturated bond-containing aromatic ester compound having The curable composition of 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 comprising the curable composition according to claim 1 or 2 . A build-up film using the curable composition according to claim 1 or 2 .