WO2019188331A1

WO2019188331A1 - Curable composition and cured product thereof

Info

Publication number: WO2019188331A1
Application number: PCT/JP2019/010503
Authority: WO
Inventors: 和久矢本; 泰佐藤; 弘司林
Original assignee: Dic株式会社
Priority date: 2018-03-29
Filing date: 2019-03-14
Publication date: 2019-10-03
Also published as: JPWO2019188331A1; KR20200128092A; TWI783133B; CN111936526B; TW201942166A; CN111936526A; KR102388192B1; JP6955232B2

Abstract

Provided are: a curable composition which exhibits excellent heat resistance and dielectric properties in a cured product; a cured product of the curable composition; and a printed circuit board, a semiconductor sealing material, and a build-up film that use the curable composition. Specifically, provided are: a curable composition which comprises a polymerizable unsaturated bond-containing aromatic ester compound (A) and a polyarylene ether resin (B); a cured product of the curable composition; and a printed circuit board, a semiconductor sealing material, and a build-up film that use the curable composition.

Description

Curable composition and cured product thereof

The present invention relates to a curable composition excellent in 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 sealing material, and a build-up film.

In recent years, electronic devices have been reduced in size and performance, and the required performance of various materials used has been improved accordingly. For example, in a semiconductor package substrate, the signal speed and the frequency are increasing, and a material having a low electric energy loss, that is, a material having a low dielectric loss tangent is required.

As such a low dielectric loss tangent material, for example, 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 is provided. (For example, refer to Patent Document 1). Under the present circumstances, when the non-volatile component of the said resin composition is 100 mass%, the said (B) active ester compound, the said (C) smear suppression component, and the said (D) inorganic filler are respectively predetermined | prescribed content rate And the (C) smear suppressing component is rubber particles.

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

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

JP 2016-156019 A

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

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

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

According to the present invention, a curable composition excellent in 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 sealing material, and a build-up film Can be provided.

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

The polymerizable unsaturated bond-containing aromatic ester compound (A) used in the present invention has a structural site in which one or more polymerizable unsaturated bonds are contained in the molecular structure and aromatic rings are bonded by an ester bond. Other specific structures and molecular weights are not particularly limited as long as they have aromatic ester compounds, and a wide variety of compounds can be used.

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

(In the above chemical formula (1), Ar ¹ is a substituted or unsubstituted first aromatic ring group, and Ar ² is each independently a substituted or unsubstituted second aromatic ring group. In this case, 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 represented by (A-1), 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 a reaction product thereof with an acid halide or esterified product thereof, wherein the first aromatic compound, the second aromatic compound, and the second aromatic compound And a polymerizable unsaturated bond-containing aromatic ester compound (A-2) in which at least one of the aromatic compounds 3 and / or acid halides and esterified products thereof has a polymerizable unsaturated bond-containing substituent. It is done.

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

In 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 represented by “—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, triazine and the like. Aromatic compounds with 2 or 3 hydrogen atoms removed; condensed aromatics such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine And aromatic compounds in which 2 or 3 hydrogen atoms are removed, such as those in which 2 or 3 hydrogen atoms are removed from an aromatic compound. Moreover, it may be a combination of a plurality of these aromatic compounds, for example, ring-aggregated aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc. From which 2 or 3 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 an aromatic compound linked by alkylene such as pyridylmethane, fluorene and diphenylcyclopentane.

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

The first aromatic ring group according to Ar ¹ may have a substituent. 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, and examples thereof include an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom.

The alkyl group is not particularly limited, but is 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.

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

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

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

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

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

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, 2-octadecenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, 1,3-butadienyl, 1,4-butadienyl, hexa-1,3-dienyl, hexa-2,5-dienyl 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 group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1,3-butadiynyl group and the like. Can be 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. In this case, examples of the alkyloxycarbonyl group, alkylcarbonyloxy group, and 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, it is more preferably a substituted or unsubstituted alkenyl group having 2 to 5 carbon atoms, vinyl group, allyl group, propenyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, A 2-butenyl group, a 3-butenyl group, and a 1,3-butadienyl group are particularly preferable, and an allyl group, a propenyl group, an isopropenyl group, and a 1-propenyl group are most preferable.

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

In this case, in the above formulas (2-1) to (2-17), “*” represents a position bonded to “—C (O) OAr ² ”. “-*” May be bonded to any position of the aromatic ring.

Of these, the formulas (2-1) to (2-11) are preferable, and the formulas (2-1), (2-2), (2-6), (2-7), (2- 9) is more preferred, and formulas (2-1), (2-2), (2-6), and (2-7) are more preferred. In addition, from the viewpoint of high handling property and low viscosity of the aromatic ester compound (A-1), (2-1) and (2-2) are preferable. On the other hand, the obtained cured product has more heat resistance. From the viewpoint of excellent balance with low dielectric properties, (2-6) and (2-7) are preferable.

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

Ar ² is each independently a substituted or unsubstituted second aromatic ring group. As is clear from the description of the chemical formula (1), one of the hydrogen atoms of the aromatic ring constituting the second aromatic ring group is substituted with “—OC (O) Ar ¹ ”. 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, triazine and the like. Aromatic compounds with one hydrogen atom removed; from condensed aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine Examples thereof include those obtained by removing one hydrogen atom from an aromatic compound such as one obtained by removing one hydrogen atom. Moreover, it may be a combination of a plurality of these aromatic compounds, for example, ring-aggregated aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc. From which one hydrogen atom is removed; diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, Examples thereof include those obtained by removing one hydrogen atom from an aromatic compound linked by alkylene such as fluorene and diphenylcyclopentane.

Among these, Ar ² is preferably a substituted or unsubstituted benzene ring or naphthalene ring because a cured product having more excellent dielectric properties can be obtained. Further, from the viewpoint of high handling property and low viscosity of the aromatic ester compound (A), a benzene ring is preferable. On the other hand, the obtained cured product is more heat resistant and excellent in balance with low dielectric properties. From the viewpoint, a naphthalene ring is preferable.

The second aromatic ring group according to Ar ² may have a substituent. 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 for the second aromatic ring group include, but are not limited to, an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom. In this case, examples of the alkyl group, alkoxy group, alkyloxycarbonyl group, alkylcarbonyloxy group, and halogen atom include those described above.

In one embodiment of the present invention, Ar ² may have the above-described unsaturated bond-containing substituent. Under the present circumstances, the said unsaturated bond containing substituent may have individually, or may have it in combination of 2 or more types.

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

In this case, in the above formulas (3-1) to (3-17), “*” represents a position bonded to “—OC (O) Ar ¹ ”. “-*” May be bonded to any position of the aromatic ring.

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

Note that at least one of the hydrogen atoms of the aromatic rings in the formulas (3-1) to (3-17) may be substituted with an unsaturated bond-containing group.

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

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

According to one embodiment, it is preferable to have at least one polymerizable unsaturated bond-containing substituent group of Ar ^2, more preferably with all Ar ² polymerizable unsaturated bond-containing substituent group, Ar ¹ is More preferably, it does not have a polymerizable unsaturated bond-containing substituent, and all Ar ² have a polymerizable unsaturated bond-containing substituent. The presence of a polymerizable unsaturated bond-containing substituent in Ar ² is preferable because the balance between heat resistance and dielectric loss tangent is excellent.

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

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

[Wherein R ¹ is a polymerizable unsaturated bond-containing substituent. R ² is each 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 independently 0 or an integer of 1 or more, and i + j is an integer of 5 or less. k is 2 or 3, l is independently an integer of 1 or more, m is independently 0 or an integer of 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 as or different from each other. In the formula (1-2), R ¹ and R ² may be substituted on any carbon atom forming a naphthalene ring. ]

In the formula (1-1), particularly preferable 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, and more preferably 1.

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

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

Of 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) ) To (4-13), (4-18) to (4-39), and more preferred are chemical formulas (4-1) to (4-3), (4-12), (4-13) , (4-19) to (4-21), (4-23) to (4-26), (4-29), (4-30), (4-32) to (4-39). More preferably, the chemical formulas are (4-1), (4-2), (4-12), (4-13), (4-26), (4-32), and (4-37). Is particularly preferred.

Further, from the viewpoint of high handling property and low viscosity of the aromatic ester compound (A), (4-1), (4-2), (4-12), and (4-13) are preferable. On the other hand, from the viewpoint that the obtained cured product is more heat resistant and has an excellent balance with low dielectric properties, (4-26), (4-32), and (4-37) are preferable.

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

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

At this time, at least one of the polycarboxylic acid compound or a derivative thereof and the phenol compound has a substituted or unsubstituted polymerizable 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 “derivative of the polycarboxylic acid compound” include an acid halide of carboxylic acid.

The first aromatic ring group and the substituent 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 above chemical formulas (5-1) to (5-15), R ¹ is a hydroxy group or a halogen atom. 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. Q 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. The position of the substituent on the aromatic ring in the above chemical formula is described on the same aromatic ring for convenience. For example, in the above chemical formula (5-7), R ¹ OC and R ² are different benzenes. It may be substituted on the ring, indicating that the number of substituents in one molecule is p and q.

Specific polycarboxylic acid compounds or derivatives thereof are not particularly limited, but benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, 2-allylterephthalic acid; trimellitic acid, 5-allyltrimellitic Benzene tricarboxylic 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, Naphthalenedicarboxylic acid such as 4-dicarboxylic acid and 3,7-diallylnaphthalene-1,4-dicarboxylic acid; pyridinetricarboxylic acid such as 2,4,5-pyridinetricarboxylic acid; 1,3,5-triazine-2,4 , 6-tricarboxylic acid and other triazine carboxylic acids; these acid halides It is. Of these, benzenedicarboxylic acid and benzenetricarboxylic acid are preferable, and isophthalic acid, terephthalic acid, isophthalic acid chloride, terephthalic acid chloride, 1,3,5-benzenetricarboxylic acid, 1,3,5-benzenetricarbonyl Trichloride is more preferable, and isophthalic acid chloride, terephthalic acid chloride, and 1,3,5-benzenetricarbonyl trichloride are further preferable.

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

(Phenol compound)
The phenol compound has a substituted or unsubstituted aromatic ring group, and preferably has 3 to 30 carbon atoms. At this time, the second aromatic ring group and the substituent 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. Further, q is 0 or an integer of 1 or more, preferably 1 to 3, more preferably 1 or 2, and further preferably 1. When q is 2 or more, the bonding position on the aromatic ring is arbitrary. For example, in the naphthalene ring of the chemical formula (6-6) or the heterocyclic ring of the chemical formula (6-17), any ring is substituted. In chemical formula (6-9) and the like, this indicates that the benzene ring existing in one molecule may be substituted on any ring, and the number of substituents in one molecule is q. Show.

Specific phenol compounds are not particularly limited, but include 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. Of these, allylphenol and allylnaphthol are preferable, and 2-allylphenol, 4-methyl-2-allylphenol, 6-methyl-2-allylphenol, 2-allyl-1-naphthol, and 1-allyl- 2-naphthol is more preferable, and 2-allylphenol, 2-allyl-1-naphthol, and 1-allyl-2-naphthol are more preferable.

In addition, 2-allylphenol having a benzene ring skeleton is preferable from the viewpoint of high handling property and low viscosity of the aromatic ester compound (A). On the other hand, the resulting cured product is more heat resistant and has low dielectric properties. And 2-allyl-1-naphthol having a naphthalene ring skeleton, 1-allyl-2-naphthol and the like are preferable from the viewpoint of excellent balance.

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

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

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

The pH during the reaction is not particularly limited, but is preferably 11 or more. At this time, the pH can be adjusted by using an acid such as hydrochloric acid, sulfuric acid, nitric acid or acetic acid; a base such as sodium hydroxide, potassium hydroxide, calcium hydroxide or ammonia.

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

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

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

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

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

At this time, the first aromatic ring having 3 to 30 carbon atoms is not particularly limited, and examples thereof include a monocyclic aromatic ring, a condensed aromatic ring, and a ring assembly aromatic ring.

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

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

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

The first aromatic ring may have a substituent. In this case, the “substituent of the first aromatic ring” is not particularly limited, but is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogen atom, a polymerizable unsaturated bond. A containing substituent.

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

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

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

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. More preferably, it is an alkenyl group of 1 to 5, and is preferably a vinyl group, allyl group, propenyl group, isopropenyl group, 1-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl. And particularly preferably an allyl group, a propenyl group, an isopropenyl group, or a 1-propenyl group.

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

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

Specific examples of the compound in which the first aromatic ring is a monocyclic aromatic ring (hereinafter 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 “first condensed aromatic ring compound”) include 1,3-naphthalenediol, , 5-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, 1,2,4-naphthalenetriol, 1,4,5-naphthalenetriol, 9,10-dihydroxyanthracene, 1,4,9 , 10-tetrahydroxyanthracene, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 5,6-dihydroxyindole, 2-methylnaphthalene-1,4-diol and the like.

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

Further, the first aromatic compound may have a structure in which the first aromatic rings are connected by a linking group. In one embodiment, the first aromatic compound is represented by the following chemical formula (7).

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

Ar ³ is a substituted or unsubstituted first aromatic ring group. As is clear from the description of the chemical formula (7), one of the hydrogen atoms of the aromatic ring constituting the above-described substituted or unsubstituted aromatic ring is bonded 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, triazine and the like. Aromatic compounds with one hydrogen atom removed; from condensed aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine Examples thereof include those obtained by removing one hydrogen atom from an aromatic compound such as one obtained by removing one hydrogen atom. Moreover, it may be a combination of a plurality of these aromatic compounds, for example, ring-aggregated aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc. From which one hydrogen atom is removed.

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

Of these, Ar ³ is one hydrogen atom removed from benzene, naphthalene, anthracene, phenalene, phenanthrene, biphenyl, binaphthalene, quaterphenyl, allylbenzene, diallylbenzene, allylnaphthalene, diallylnaphthalene, allylbiphenyl, diallylbiphenyl. It is preferable that the hydrogen atom be removed from benzene, naphthalene, biphenyl, allylbenzene, diallylnaphthalene, or diallylbiphenyl.

Ar ⁴ is each independently a substituted or unsubstituted second aromatic ring group. As is clear from the description of the above chemical formula (1), two of the hydrogen atoms of the aromatic ring constituting the above-described 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, triazine and the like. Aromatic compounds with two hydrogen atoms removed; from condensed aromatic compounds such as naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine Examples include aromatic compounds in which two hydrogen atoms have been removed from aromatic compounds such as those in which two hydrogen atoms have been removed. Moreover, it may be a combination of a plurality of these aromatic compounds, for example, ring-aggregated aromatic compounds such as biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc. From which two hydrogen atoms are removed.

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

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 the following chemical formulas (8-1) to (8-4) Examples include cycloalkylene.

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

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

In the 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, examples of the “substituent of X” include those similar to the “substituent of the first aromatic ring” described above.

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

And at least two of the hydrogen atoms constituting the Ar ³ and the Ar ⁴ are substituted with hydroxy groups.

Specific examples of the compound represented by the following chemical formula (7) are not particularly limited. For example, various bisphenol compounds, compounds represented by the following chemical formulas (10-1) to (10-8), and these And those 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, and bisphenol Z.

In the above chemical formulas (10-1) to (10-8), n is 0 to 10, preferably 0 to 5. In this case, when the compounds represented by the chemical formulas (10-1) to (10-8) are oligomers or polymers, n means an average value thereof. In the present specification, “oligomer” means a compound containing a compound having 1 to 5 repeating units, and “polymer” means a compound containing a compound having 6 or more repeating units. Further, 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 bonded to another structure or a ring not bonded.

In one embodiment, the above-mentioned first aromatic ring represented by the chemical formula (7) is formed by substituting at least one hydrogen atom constituting the first aromatic ring with a hydroxy group. Can be synthesized by a reaction between the compound and a divinyl compound or a dialkyloxymethyl compound.

In this case, the divinyl compound or dialkyloxymethyl compound is not particularly limited, but 1,3-butadiene, 1,5-hexadiene, dicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, pentacyclopentadiene, hexacyclopentadiene. Aliphatic diene compounds such as divinylbenzene, divinylbiphenyl and the like; dimethoxymethylbenzene, dimethoxymethylbiphenyl, bisphenol A methoxy adduct, bisphenol A ethoxy adduct, bisphenol F methoxy adduct, bisphenol F ethoxy adduct And the like, and the like.

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

The hydroxyl equivalent of the first aromatic compound is preferably 130 to 500 g / equivalent, and more preferably 130 to 400 g / equivalent. It is preferable that the hydroxyl group equivalent of the first aromatic compound is 130 g / equivalent or more because heat resistance can be imparted. On the other hand, the hydroxyl group equivalent of the first aromatic compound is preferably 500 g / equivalent or less 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, and preferably 200 to 2000. Is more preferable. When the weight average molecular weight of the first aromatic compound is 200 or more, it is preferable because the dielectric loss tangent is excellent. On the other hand, it is preferable that the weight average molecular weight of the first aromatic compound is 3000 or less because of excellent moldability. In the present specification, the value measured by the following method is adopted as the value of “weight average molecular weight”. That is, the value obtained by measuring gel permeation chromatography (GPC) under the following conditions is employed.

GPC measurement conditions Measuring device: “HLC-8320 GPC” manufactured by Tosoh Corporation
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ “TSK-GEL G4000HXL” manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ "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: Based on the above-mentioned measurement manual “GPC-8320 GPC”, the following monodispersed polystyrene having a known molecular weight is used. “A-500” manufactured by Tosoh Corporation "
“A-1000” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 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 a function of stopping the polyesterification reaction of the first aromatic compound described above and the third aromatic compound described later.

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

The second aromatic ring is not particularly limited, and examples thereof include a monocyclic aromatic ring, a condensed aromatic ring, a ring assembly aromatic ring, and an aromatic ring connected by alkylene. Examples of the monocyclic aromatic ring, the condensed aromatic ring, and the ring assembly aromatic ring include those similar to the first aromatic ring described above.

The aromatic rings connected by alkylene include diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, and phenylpyridyl. Methane, fluorene, diphenylcyclopentane, etc. are mentioned.

The second aromatic ring related to the second aromatic compound may have a substituent. In this case, examples of the “substituent of the second aromatic ring” include those similar to the “substituent of the first aromatic ring” described above.

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. Further, p is 0 or an integer of 1 or more, preferably 1 to 3, more preferably 1 or 2, and further preferably 1. When p is 2 or more, the bonding position on the aromatic ring is arbitrary. For example, in the naphthalene ring of the chemical formula (11-6) or the heterocyclic ring of the chemical formula (11-17), any ring is substituted. In the chemical formula (11-9), etc., it may be substituted on any ring of the benzene ring existing in one molecule, and the number of substituents in one molecule is p. Show.

Specific examples of the second aromatic compound include, but are not limited to, phenol, cresol, xylenol, orthoallylphenol, methallylphenol, paraallylphenol, 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, 4-propargylphenol A compound which is a monocyclic aromatic ring (hereinafter sometimes simply referred to as “second monocyclic aromatic ring compound”); 1-naphthol, 2-naphthol, 2-allyl-1-naphthol, 3-allyl- 1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5- Ryl-1-naphthol, 6-allyl-1-naphthol, diallylnaphthol, 2-allyl-4-methoxy-1-naphthol, 2-propargyl-1-naphthol, 3-propargyl-1-naphthol, 1-propargyl-2- Compounds in which the aromatic ring is a condensed aromatic ring, such as naphthol and 3-propargyl-2-naphthol (hereinafter sometimes referred to simply as “second condensed aromatic ring compound”); allyl hydroxybiphenyl, hydroxy Examples thereof include compounds in which an aromatic ring such as propargylbiphenyl is a ring-aggregated aromatic ring (hereinafter sometimes simply referred to as “second ring-aggregated aromatic ring compound”).

Among the above, the second aromatic compound is preferably a second monocyclic aromatic ring compound or a second condensed aromatic ring compound, such as orthoallylphenol, methallylphenol, paraallylphenol, 2 -Allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, 6-allyl-1-naphthol More preferred.

In another embodiment, the second aromatic compound is preferably a second condensed aromatic ring compound (condensed aromatic ring compound), such as 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. The second aromatic compound is preferably a condensed-ring aromatic ring compound because the dielectric loss tangent can be reduced by suppressing molecular motion due to steric hindrance. In addition, 2-allylphenol having a benzene ring skeleton is preferable from the viewpoint of high handling property and low viscosity of the aromatic ester compound (A), while the cured product obtained is more heat resistant and has low dielectric properties. From the viewpoint of excellent balance, 2-allyl-1-naphthol and 1-allyl-2-naphthol having a naphthalene ring skeleton are preferable.

In addition, the above-mentioned 2nd aromatic compound may be used independently or may be used in combination of 2 or more type.

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

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

The term “carboxy group” means a carboxy group; an acyl halide group such as an acyl fluoride group, an acyl chloride group or an acyl bromide group; an alkyloxycarbonyl group such as a methyloxycarbonyl group or an ethyloxycarbonyl group; Examples thereof include aryloxycarbonyl groups such as oxycarbonyl group and naphthyloxycarbonyl group. In addition, when it has a halogenated acyl group, the third aromatic compound is an acid halide, and when it has an alkyloxycarbonyl group or an aryloxycarbonyl group, the third aromatic compound can be an esterified product. Of these, the third aromatic compound preferably has a carboxy group, an acyl halide group, or an aryloxycarbonyl group, more preferably has a carboxy group or an acyl halide group, a carboxy group, an acyl chloride group, More preferably, it has an acyl bromide group.

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

The third aromatic ring is not particularly limited, and examples thereof include a monocyclic aromatic ring, a condensed aromatic ring, a ring assembly aromatic ring, and an aromatic ring connected by alkylene. The monocyclic aromatic ring, the condensed aromatic ring, the ring assembly aromatic ring, and the aromatic ring connected by alkylene are the same as the first aromatic ring and the second aromatic ring described above. Things.

The third aromatic ring related to the third aromatic compound or the like may have a substituent. In this case, examples of the “substituent of the third aromatic ring” include those similar to the “substituent of the first aromatic ring” described above.

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

In the above chemical formulas (12-1) to (12-15), R ¹ is a polymerizable unsaturated bond-containing substituent. At this time, the polymerizable unsaturated bond-containing substituent is the same as described above. R ² 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. For example, in the naphthalene ring of the chemical formula (12-5) or the heterocyclic ring of the chemical formula (12-15), any ring is substituted. In the chemical formula (12-7) and the like, this indicates that the benzene ring existing in one molecule may be substituted on any ring, and the number of substituents in one molecule is p, q It is shown that.

Specific examples of the third aromatic compound include, but are not limited to, benzenedicarboxylic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, and 2-allylterephthalic acid; trimellitic acid, 5-allyltrimellitic Benzene tricarboxylic 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, Naphthalenedicarboxylic acid such as 4-dicarboxylic acid and 3,7-diallylnaphthalene-1,4-dicarboxylic acid; pyridinetricarboxylic acid such as 2,4,5-pyridinetricarboxylic acid; 1,3,5-triazine-2,4 , 6-tricarboxylic acid and other triazine carboxylic acids; these acid halides, esterified products, etc. It is. Of these, benzenedicarboxylic acid and benzenetricarboxylic acid are preferable, and isophthalic acid, terephthalic acid, isophthalic acid chloride, terephthalic acid chloride, 1,3,5-benzenetricarboxylic acid, 1,3,5-benzenetricarbonyl Trichloride is more preferable, and isophthalic acid chloride, terephthalic acid chloride, and 1,3,5-benzenetricarbonyl trichloride are further preferable.

Of the above, the aromatic ring is preferably a monocyclic aromatic ring such as a third aromatic compound, and the like, and preferably the aromatic ring is a condensed aromatic ring such as a third aromatic compound. Benzenetricarboxylic acid, naphthalenedicarboxylic acid, and acid halides thereof are preferable, benzenedicarboxylic acid, naphthalenedicarboxylic acid, and acid halides thereof are more preferable, and 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 or the like may be used alone or in combination of two or more.

[Configuration of polymerizable unsaturated bond-containing aromatic ester compound (A-2)]
At least one of the first aromatic compound, the second aromatic compound, and the third aromatic compound and / or an acid halide or esterified product thereof (such as the third aromatic compound) is not polymerizable. Has a saturated bond-containing substituent. That is, all of the first aromatic compound, the second aromatic compound, the third aromatic compound, etc. may have a polymerizable unsaturated bond-containing substituent, and the first aromatic compound and the first aromatic compound The two aromatic compounds may have a polymerizable unsaturated bond-containing substituent, or only the second aromatic compound may have a polymerizable unsaturated bond-containing substituent. Moreover, when using 2 or more types of 1st aromatic compounds, 2nd aromatic compounds, 3rd aromatic compounds, etc., only one part has a polymerizable unsaturated bond containing substituent. May be. The number of carbon atoms of the polymerizable unsaturated bond-containing substituent is preferably in the range of 2-30.

In one embodiment, it is preferable that at least the second aromatic compound has a polymerizable unsaturated bond-containing substituent. As described above, the structure derived from the second aromatic compound is located at the molecular end of the polymerizable unsaturated bond-containing aromatic ester compound (A-2). As a result, the polymerizable unsaturated bond-containing substituent of the second aromatic compound is also arranged at the molecular end of the polymerizable unsaturated bond-containing aromatic ester compound (A-2). In this case, it is preferable because the balance of heat resistance and dielectric loss tangent of the obtained cured product can be further increased.

As described above, the polymerizable unsaturated bond-containing aromatic ester compound (A-2) is a reaction product of the first aromatic compound, the second aromatic compound, the third aromatic compound, and the like. And can include various compounds. Regarding the constitution of the polymerizable unsaturated bond-containing aromatic ester compound (A-2), the use amount of the first aromatic compound, the second aromatic compound, the third aromatic compound, etc., the reaction conditions, etc. It can control by changing suitably.

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

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 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 a structure derived from the third aromatic compound. It is a derived structure. N is 0-10. In addition, when the polymerizable unsaturated bond-containing aromatic ester compound (A-2) is an oligomer or a polymer, n represents an average value thereof.

That is, each Ar ¹ independently represents a structure in which two or more hydrogen atoms have been removed from a substituted or unsubstituted first aromatic ring, or a structure in which the first aromatic rings are linked by a linking group. What has two or more hydrogen atoms removed from what it has.

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

Ar ³ includes those in which two or more hydrogen atoms are removed from a substituted or unsubstituted third aromatic ring.

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

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

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

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

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

The weight average molecular weight of the aromatic ester compound (A-2) is preferably 150 to 3000, and more preferably 200 to 2000. A weight average molecular weight of 800 or more is preferable because of excellent dielectric loss tangent. On the other hand, a weight average molecular weight of 500 or less is preferable because of excellent moldability. Similarly, the number average molecular weight is preferably in the range of 150 to 1500 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 can be suitably produced by a known method.

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

(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 described above are used.

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

For example, the ratio of the number of moles of the carboxy group of the third aromatic compound to the number of moles of the hydroxy group of the first aromatic compound (carboxy group etc./hydroxy group of the first aromatic compound) is 0.5. Is preferably 10 to 10, more preferably 0.5 to 6.0, and still more preferably 1.0 to 3.0. It is preferable that the ratio is 0.5 or more because heat resistance becomes high. On the other hand, it is preferable that the ratio is 10 or less because the moldability is excellent.

The ratio of the number of moles of the third aromatic compound such as a carboxyl group to the number of moles of the hydroxy group of the second aromatic compound (carboxy group or the like / hydroxy group of the second aromatic compound) is 0.5. Is preferably ˜10, more preferably 1.5˜4.0. It is preferable that the ratio is 0.5 or more because the moldability is excellent. On the other hand, when the ratio is 10 or less, the heat resistance is preferably increased.

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

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

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

The arylene group in the polyarylene ether resin (B) used in the present invention has a phenylene group, a naphthylene group, and a structure having a substituent such as an aliphatic hydrocarbon group, an alkoxy group, an aryl group or an aralkyl group on the aromatic nucleus. A site | part etc. are mentioned. Especially, since it becomes a curable composition which is excellent in the balance of the dielectric property and heat resistance in hardened | cured material, what has a phenylene group as a main skeleton is preferable, and is a phenylene group which has two substituents on an aromatic nucleus. Is more preferable. As the kind of the substituent, an aliphatic hydrocarbon group is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

The terminal structure of the polyarylene ether resin (B) is generally an aryloxy group having a phenolic hydroxyl group. The phenolic hydroxyl group may be modified to other structural sites. Examples of the aryl group in the aryloxy group include a phenyl group, a naphthyl group, and a structural site having a substituent such as an aliphatic hydrocarbon group, an alkoxy group, an aryl group, and an aralkyl group on the aromatic nucleus. Especially, since it becomes a curable composition which is excellent in the balance of the dielectric property and heat resistance in hardened | cured material, what has a phenyl group as a main skeleton is preferable, and 2 substituents are further added to an aromatic nucleus other than a phenolic hydroxyl group. More preferred is a phenylene group having two. As the kind of the substituent, an aliphatic hydrocarbon group is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

Examples of the structural portion obtained by modifying the phenolic hydroxyl group include a polymerizable unsaturated bond-containing group such as a (meth) acryloyloxy group, an allyloxy group, and a vinyloxy group, or an epoxy compound reacted with the phenolic hydroxyl group. Examples of the structural site to be obtained are given. Especially, since it becomes a curable composition excellent in the balance of the dielectric property and heat resistance in hardened | cured material, it is preferable that it is a phenolic hydroxyl group or the said polymerizable unsaturated bond containing group.

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

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

Y in the structural formula (15) is not particularly limited as long as it is a divalent organic group, and may be any structural site. Examples thereof include the following structural formulas (Y-1) to (Y -9) and the like.

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

The functional group equivalent of the phenolic hydroxyl group of the polyarylene ether resin (B) or the structural part obtained by modifying it, that is, the functional group of the structural part represented by the —OX group at the end in the structural formula (15) The equivalent is preferably in the range of 500 to 3,000 g / equivalent, and more preferably in the range of 500 to 1,500 g / equivalent because a curable composition having both excellent heat resistance and dielectric properties is obtained. Is more preferable.

In the curable composition of the present invention, the blending ratio of the polymerizable unsaturated bond-containing aromatic ester compound (A) and the polyarylene ether resin (B) is not particularly limited, depending on the desired cured product performance and the like. Are adjusted accordingly. In particular, the polyarylene ether resin (B) is added in an amount of 10 to 300 parts by mass with respect to 100 parts by mass of the aromatic ester compound (A) because the curable composition has an excellent balance between heat resistance and dielectric properties in the cured product. It is preferably used in the range of parts by weight, and more preferably in the range of 20 to 200 parts by weight.

The curable composition of the present invention may contain other components in addition to the polymerizable unsaturated bond-containing aromatic ester compound (A) and the polyarylene ether resin (B). Hereinafter, examples of other components will be given. In addition, the other component which the curable composition of this invention can contain is not limited to what was illustrated below, You may contain components other than these.

[Epoxy resin]
Since the polymerizable unsaturated bond-containing aromatic ester compound (A) contains a polymerizable unsaturated bond, the curable composition of the present invention contains the aromatic ester compound (A) and the polyarylene ether resin (B ) Alone is curable. On the other hand, since the aromatic ester compound (A) also functions as a curing agent for the epoxy resin and can give a cured product 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 is a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, an α-naphthol novolak type epoxy resin, a β-naphthol novolak type epoxy resin, a bisphenol A novolak type epoxy resin, a biphenyl novolak type epoxy resin. Novolak type epoxy resins such as resins; Aralkyl type epoxy resins such as phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, phenol biphenyl aralkyl type epoxy resins; bisphenol A type epoxy resins, bisphenol AP type epoxy resins, bisphenol AF type epoxy resins , Bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type Bisphenol type epoxy resins such as epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy resin; biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, biphenyl skeleton and diglycidyloxybenzene skeleton Biphenyl type epoxy resin such as epoxy resin; naphthalene type epoxy resin; binaphthol type epoxy resin; binaphthyl type epoxy resin; dicyclopentadiene type epoxy resin such as dicyclopentadiene phenol type epoxy resin; Glycidyl amino such as glycidyl-p-aminophenol type epoxy resin, glycidylamine type epoxy resin of diaminodiphenylsulfone, etc. Type epoxy resin; diglycidyl ester type epoxy resin such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resin, glycidyl ester type epoxy resin of hexahydrophthalic anhydride; dibenzopyran, hexamethyldibenzopyran, 7-phenylhexamethyl Examples include benzopyran-type epoxy resins such as dibenzopyran. These may be used alone or in combination of two or more.

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

The weight average molecular weight of the epoxy resin is preferably 200 to 5000, and more preferably 300 to 3000. When the weight average molecular weight of the epoxy resin is 200 or more, it is preferable because it can have fast curability. On the other hand, when the weight average molecular weight of the epoxy resin is 5000 or less, it is preferable because of excellent moldability. In addition, the value measured by the above-mentioned method (GPC) is employ | adopted for a weight average molecular weight.

[Other curing agents]
When the curable composition of this invention contains the said epoxy resin, you may use together the other hardening | curing agent which can be hardened | cured with an epoxy resin other than the said aromatic ester compound (A).

Other curing agents include, but are not limited to, aromatic ester compounds that do not contain a polymerizable unsaturated bond, amine curing agents, imidazole curing agents, acid anhydride curing agents, phenol resin curing agents, and the like.

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

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

Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol trislimitate, maleic anhydride, tetrahydrophthalic anhydride, Methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, And methylcyclohexene dicarboxylic acid 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, triphenolmethane type resin. , Tetraphenolethane type resins, aminotriazine-modified phenolic resins, and the like.

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

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

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

[Other resins]
Specific examples of other resins include, but are not limited to, maleimide resins, bismaleimide resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolac 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 polybutadiene resins. These other resins may be used alone or in combination of two or more.

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

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; cellosolve, butyl carbitol, and the like Examples thereof 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 the solvent used is preferably 10 to 80% by mass and more preferably 20 to 70% by mass with respect to the total mass of the curable composition. It is preferable that the amount of the solvent used is 10% by mass or more because of excellent handling properties. On the other hand, when the amount of the solvent used is 80% by mass or less, it is preferable because the impregnation property with another substrate is excellent.

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

(Curing accelerator)
Although it does not restrict | limit especially as a hardening accelerator, A phosphorus hardening accelerator, an amine hardening accelerator, an imidazole hardening accelerator, a guanidine hardening accelerator, a urea hardening accelerator, a peroxide, an azo compound, etc. are mentioned. It is done.

Examples of the phosphorus curing accelerators include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tripalatolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organic phosphite compounds such as trimethylphosphite and triethylphosphite; ethyltriphenyl Phosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphinetriphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, Butylphenylphosphonium dicyanamide, tetra Phosphonium salts such as chill phosphonium decanoate salts.

Examples of the amine curing accelerator 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 isocyanate Luric 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-based 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, Examples thereof include 1-ethyl biguanide, 1-butyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide 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 peroxide and azo compound include benzoyl peroxide, p-chlorobenzoyl peroxide, di-t-butyl peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, azobisisobutyronitrile, etc. Is mentioned.

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

In addition, the above-mentioned hardening accelerator may be used independently or may be used in combination of 2 or more type.

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

(Flame retardants)
Although it does not restrict | limit especially as a flame retardant, An inorganic phosphorus flame retardant, an organic phosphorus flame retardant, a halogen flame retardant, etc. are mentioned.

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

The organophosphorus flame retardant is not particularly limited, but is 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 acid such as methacrylate acid phosphate Steal; diphenylphosphine such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide; 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phospha Phenanthrene-10-oxide, 10- (1,4-dioxynaphthalene) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphenyl-1,4-dioxy Phosphorus-containing phenols such as naphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol, 1,5-cyclooctylenephosphinyl-1,4-phenyldiol; 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 0- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phospha Examples thereof include cyclic phosphorus compounds such as phenanthrene-10-oxide; compounds obtained by reacting the phosphate ester, the diphenylphosphine, the phosphorus-containing phenol with an epoxy resin, an aldehyde compound, or a phenol compound.

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

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

The amount of flame retardant used is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts per 100 parts by mass of resin solid content of the curable composition. When the amount of the flame retardant used is 0.1 part by mass or more, it is preferable because flame retardancy can be imparted. On the other hand, when the amount of 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 the filler include organic fillers and inorganic fillers. The filler has a function of improving elongation, a function of improving mechanical strength, and the like.

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

The inorganic filler is not particularly limited, but silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, nitriding 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.

Of these, it is preferable to use silica. In this case, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, or the like can be used as the silica.

Further, the filler may be surface-treated as necessary. The surface treatment agent that can be used in this case is not particularly limited, but an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an organosilazane compound, and a titanate coupling. An agent or the like can be used. Specific examples of the surface treatment agent include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilane. Silazane etc. are mentioned.

In addition, the above-mentioned filler may be used independently or may be used in combination of 2 or more type.

The average particle diameter of the filler is not particularly limited and is preferably 0.01 to 10 μm, more preferably 0.03 to 5 μm, and further preferably 0.05 to 3 μm. In the present specification, the “particle size” means the maximum length of the distance between two points on the particle outline. The “average particle size” is measured by a method of measuring the particle size of 100 arbitrary 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 and more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the resin solid content of the curable composition. 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 the filler used is 95 parts by mass or less, it is preferable because the balance between characteristics and moldability is excellent.

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

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

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

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

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

Hereinafter, the present invention will be described 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) A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was equipped with 268 g of orthoallylphenol and 1200 g of toluene. The contents were dissolved while the system was purged with nitrogen under reduced pressure. Next, 203 g of isophthalic acid chloride was charged, and the contents were dissolved while the system was purged with nitrogen under reduced pressure. Tetrabutylammonium bromide (0.6 g) was added and dissolved, and the inside of the system was controlled to 60 ° C. or lower while performing a nitrogen gas purge, and 412 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropwise addition, stirring was continued for 1 hour under the same temperature condition. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. 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 water washing operation was repeated until the pH of the aqueous layer reached 7. The organic phase after washing with water was dried under heating and reduced pressure conditions to obtain 370 g of a polymerizable unsaturated bond-containing aromatic ester compound (A-1-1) represented by the following structural formula. The polymerizable unsaturated bond-containing aromatic ester compound (A-1-1) has an ester group equivalent of 199 g / equivalent, an allyl group equivalent of 199 g / equivalent, and an E-type viscosity (25 ° C.) of 6000 mPa.s. s.

Production Example 2 Production of polymerizable unsaturated bond-containing aromatic ester compound (A-2-1) A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with dicyclopentadiene and phenol. A polyaddition reaction resin (hydroxyl equivalent 165 g / equivalent, softening point 85 ° C.) 165 g, orthoallylphenol 134 g, and toluene 1200 g were charged, and the contents were dissolved while the system was purged with nitrogen under reduced pressure. Next, 203 g of isophthalic acid chloride was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. Tetrabutylammonium bromide (0.6 g) was added and dissolved, and the inside of the system was controlled to 60 ° C. or lower while performing a nitrogen gas purge, and 412 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropwise addition, stirring was continued for 1 hour under the same temperature condition. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. 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 water 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 ester group equivalent of the polymerizable unsaturated bond-containing aromatic ester compound (A-2-1) was 214 g / equivalent, the allyl group equivalent was 428 g / equivalent, and the softening point was 82 ° C.

Production Example 3 Production of polymerizable unsaturated bond-containing aromatic ester compound (A-2-2) Production Example except that 165 g of polyaddition reaction resin of dicyclopentadiene and phenol in Production Example 2 was changed to 160 g of diallyl bisphenol A In the same manner as in Example 2, 402 g of a polymerizable unsaturated bond-containing aromatic ester compound (A-2-2) was obtained. The theoretical structure of the polymerizable unsaturated bond-containing aromatic ester compound (A-2-2) is shown below. The ester group equivalent of the polymerizable unsaturated bond-containing aromatic ester compound (A-2-2) was 212 g / equivalent, the allyl group equivalent was 212 g / equivalent, and the softening point was 51 ° C.

Comparative Production Example 1 Production of Aromatic Ester Compound (A ′) Polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g) to a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer / Equivalent, softening point 85 ° C.) 165 g, 1-naphthol 72 g, and toluene 630 g were charged, and the contents were dissolved while the system was purged with nitrogen under reduced pressure. Next, 152 g of isophthalic acid chloride was charged and dissolved in the system while substituting with nitrogen under reduced pressure. While adding 0.6 g of tetrabutylammonium bromide and performing a nitrogen gas purge process, the inside of the system was controlled to 60 ° C. or lower, and 315 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of the dropwise addition, stirring was continued for 1 hour under the same temperature condition. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. 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 water washing operation was repeated until the pH of the aqueous layer reached 7. The organic phase after washing with water was dried under heating under reduced pressure to obtain an aromatic ester compound (A ′). The ester group equivalent of the aromatic ester compound (A ′) was 223 g / equivalent, and the softening point was 150 ° C.

Examples 1 to 9 and Comparative Example 1
Each component was mix | blended in the ratio shown to following Table 1, 2, and the curable composition was obtained. About the obtained curable composition, the heat resistance evaluation of the hardened | cured material and the measurement of the dielectric loss tangent value were performed in the following way. The results are shown in Tables 1 and 2.

Details of each component used in the examples are as follows.
Polyarylene ether resin (B-1): “NORYL SA90” manufactured by SABIC, hydroxyl equivalent 850 g / equivalent, theoretical structure is as follows.

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

Epoxy resin: bisphenol A type epoxy resin (“EPICLON850S” epoxy equivalent 188 g / equivalent by DIC Corporation)

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

Evaluation of heat resistance (measurement of glass transition temperature)
A test piece having a width of 5 mm and a length of 54 mm was cut out from the cured product having a thickness of 2.4 mm obtained above. Using a “solid viscoelasticity measuring device RSAII” manufactured by Rheometric Co., Ltd., the temperature at which the change in the elastic modulus of the test piece becomes the maximum (the tan δ change rate is the highest) is measured by the DMA (dynamic viscoelasticity) measurement by the rectangular tension method. The transition temperature was measured. 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 heated and vacuum dried at 105 ° C. for 2 hours, and then stored in a room at 23 ° C. and 50% humidity for 24 hours. Using a “network analyzer E8362C” manufactured by Agilent Technologies, the dielectric loss tangent of the test piece at 1 GHz was measured by the cavity resonance method.

Claims

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

(In the above chemical formula (1),
Ar 1 is a substituted or unsubstituted first aromatic ring group,
Ar 2 is each independently a substituted or unsubstituted second aromatic ring group;
At this time, 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. )
The curable composition according to claim 1, which is represented by:
The polymerizable unsaturated bond-containing aromatic ester compound (A) is
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 esterified product thereof;
The 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 esterified product thereof has a polymerizable unsaturated bond-containing substituent. Item 2. A curable composition according to Item 1.
The curable composition according to any one of claims 1 to 3, further comprising an epoxy resin.
A cured product of the curable composition according to any one of claims 1 to 4.
A printed wiring board comprising the curable composition according to any one of claims 1 to 4.
A semiconductor sealing material comprising the curable composition according to any one of claims 1 to 4.
A build-up film using the curable composition according to any one of claims 1 to 4.