TWI783133B - Hardening composition and hardened product thereof - Google Patents

Abstract

The present invention provides a curable composition excellent in heat resistance and dielectric properties of the cured product, a cured product of the curable composition, a printed wiring board using the curable composition, a semiconductor packaging material, and a buildup film. Specifically, the invention provides a curable composition containing an aromatic ester compound (A) containing a polymerizable unsaturated bond and a polyaryl ether resin (B), a cured product of the aforementioned curable composition, and a cured product using the aforementioned Printed wiring boards of curable compositions, semiconductor packaging materials, and build-up films.

Description

Hardening composition and hardened product thereof

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

In recent years, the miniaturization and high performance of electronic devices have progressed, and the required performance of various materials used has been improved accordingly. For example, with respect to semiconductor packaging substrates, high-speed and high-frequency signals are progressing, and materials with low power loss, that is, materials with low dielectric dissipation factors are required.

As a material with such a low dielectric dissipation factor, there are provided, for example, a resin composition containing (A) epoxy resin, (B) active ester compound, (C) stain inhibiting component, and (D) inorganic filler invention (for example, refer to Patent Document 1). In this case, when the non-volatile content of the resin composition is 100% by mass, the (B) active ester compound, the (C) stain inhibiting component, and the (D) inorganic filler are characterized in that Each is a predetermined content rate, and the aforementioned (C) stain-inhibiting component is rubber particles.

The aforementioned Patent Document 1 discloses that the cured product of this resin composition can achieve a low dielectric dissipation factor. In addition, it is also described that smear (resin residue) in the through-hole after drilling and roughening the above-mentioned cured product can be suppressed.

In addition, the (B) active ester compound described in the aforementioned Patent Document 1 is a compound having one or more active ester groups in one molecule, and it is described that the dielectric loss factor of the cured product of the resin composition is reduced.

[Prior Art Literature] [Patent Document]

[Patent Document 1] JP-A-2016-156019

It is described in the aforementioned Patent Document 1 that the dielectric dissipation factor of the obtained cured product can be reduced by using an active ester compound. However, it has been confirmed that such cured products may not necessarily have sufficient heat resistance.

The inventors of the present invention have intensively studied to solve the above-mentioned problems. As a result, it has been found that a cured product of a curable composition containing an aromatic ester compound having a polymerizable unsaturated bond in its molecular structure and a polyaryl ether resin is exceptionally excellent in heat resistance and dielectric properties, and further completed the present invention .

That is, the present invention provides a curable composition containing a polymerizable unsaturated bond-containing aromatic ester compound (A) and a polyaryl ether resin (B), its cured product, and a curable composition using Printed wiring substrates, semiconductor packaging materials, and build-up films.

According to the present invention, there can be provided a curable composition excellent in heat resistance and dielectric properties of the cured product, a cured product of the curable composition, a printed wiring board using the curable composition, a semiconductor packaging material, and a buildup film .

[Mode of Implementing the Invention]

Hereinafter, aspects for implementing the present invention will be described in detail.

The polymerizable unsaturated bond-containing aromatic ester compound (A) used in the present invention has one to a plurality of polymerizable unsaturated bonds in the molecular structure, and has a structure in which aromatic rings are bonded to each other by ester bonds As the aromatic ester compound at the moiety, a wide variety of compounds can be used regardless of other specific structures, molecular weights, and the like.

As a specific example of the aforementioned polymerizable unsaturated bond-containing aromatic ester compound (A), for example, the following chemical formula (1):

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

The polymerizable unsaturated bond-containing aromatic ester compound (A-1), the polymerizable unsaturated bond-containing aromatic ester compound (A-2), etc., wherein the polymerizable unsaturated bond-containing aromatic ester compound (A-2) A first aromatic compound having two or more phenolic hydroxyl groups, a second aromatic compound having a phenolic hydroxyl group, and a third aromatic compound having two or more carboxyl groups and/or its acid In the reaction product of halides and esterifications, at least one of the first aromatic compound, the second aromatic compound, and the third aromatic compound and/or its acid halides or esterifications has a polymerizable unsaturated bond substituents.

As the aforementioned polymerizable unsaturated bond-containing aromatic ester compound (A), it is considered that it is more excellent in balance between properties when adjusted as a curable composition described later, heat resistance of the cured product, and dielectric properties. , preferably a liquid at normal temperature (25°C), or a softening point in the range of 40°C to 200°C.

Regarding the aforementioned polymerizable unsaturated bond-containing aromatic ester compound (A-1), Ar ¹ in the aforementioned chemical formula (1) is a substituted or unsubstituted first aromatic ring group. As described later, because n in the chemical formula (1) is an integer of 2 or 3, 2 or 3 of the hydrogen atoms constituting the aromatic ring of the first aromatic ring group become replaced by "-C(O )OAr ² ” instead.

唑、異

唑、噻唑、異噻唑、吡啶、嘧啶、嗒

、吡

、三

等之單環芳香族化合物中移除2個或3個氫原子而成者；從萘、蒽、萉、菲、喹啉、異喹啉、喹唑啉、 呔

、喋啶、香豆素、吲哚、苯并咪唑、苯并呋喃、吖啶等之稠環芳香族化合物移除2個或3個氫原子者等之從芳香族化合物移除2個或3個氫原子而成者。此外，亦可為組合複數個此等的芳香族化合物而成者，可列舉例如：從聯苯、聯萘、聯吡啶、聯噻吩、苯基吡啶、苯基噻吩、三聯苯、二苯基噻吩、聯四苯等之環集合芳香族化合物中移除2個或3個氫原子而成者；從二苯基甲烷、二苯基乙烷、1,1-二苯基乙烷、2,2-二苯基丙烷、萘基苯基甲烷、三苯基甲烷、二萘基甲烷、二萘基丙烷、苯基吡啶基甲烷、茀、二苯基環戊烷等之藉由伸烷基鍵結之芳香族化合物中移除2個或3個氫原子而成者等。 The aforementioned first aromatic ring group is not particularly limited, but examples include: benzene, furan, pyrrole, thiophene, imidazole, pyrazole,

azole, iso

Azole, Thiazole, Isothiazole, Pyridine, Pyrimidine, Pyridine

, pyri

,three

Monocyclic aromatic compounds such as those obtained by removing 2 or 3 hydrogen atoms; from naphthalene, anthracene, anthracene, phenanthrene, quinoline, isoquinoline, quinazoline, and

, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine and other condensed ring aromatic compounds that remove 2 or 3 hydrogen atoms, etc., remove 2 or 3 hydrogen atoms from the aromatic compound made of hydrogen atoms. In addition, a plurality of these aromatic compounds may be combined, for example: biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene , Tetraphenyl, etc. ring set of aromatic compounds by removing 2 or 3 hydrogen atoms; from diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2 - Diphenylpropane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fennel, diphenylcyclopentane, etc. Those obtained by removing 2 or 3 hydrogen atoms from aromatic compounds, etc.

Among them, Ar ¹ is preferably a substituted or unsubstituted benzene ring or a naphthalene ring, more preferably a substituted or unsubstituted benzene ring, in view of obtaining a cured product with better dielectric properties.

The first aromatic ring group of Ar ¹ may have a substituent. In this case, the "substituent of the first aromatic ring group" refers to a substituent for at least one of the hydrogen atoms constituting the aromatic ring of the first aromatic ring group. Specific examples of the substituent of the first aromatic ring group are not particularly limited, but examples thereof include an alkyl group, an alkoxy group, an alkyloxycarbonyl group, an alkylcarbonyloxy group, and a halogen atom.

The aforementioned alkyl group is not particularly limited, but examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, and isopentyl. Base, tertiary pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, cyclohexyl, etc.

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

The aforementioned alkyloxycarbonyl group is not particularly limited, but examples include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, n-butyl Oxycarbonyl, isobutyloxycarbonyl, secondary butyloxycarbonyl, tertiary butyloxycarbonyl and the like.

The aforementioned alkylcarbonyloxy group is not particularly limited, but examples include methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, butylcarbonyloxy, n-butyl Carbonyloxy, isobutylcarbonyloxy, secondary butylcarbonyloxy, tertiary butylcarbonyloxy and the like.

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

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

The alkenyl group is not particularly limited, but examples include vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, 1-Octenyl, 2-Octenyl, 1-Undecenyl, 1-pentadecenyl, 3-pentadecenyl, 7-pentadecenyl, 1-octadecenyl, 2-octadecenyl, cyclopentenyl, cyclohexenyl, Cyclooctenyl, 1,3-butadienyl, 1,4-butadienyl, hexa-1,3-dienyl, hexa-2,5-dienyl, pentadec-4,7 -dienyl, hexa-1,3,5-trienyl, pentadec-1,4,7-trienyl and the like.

The aforementioned alkynyl group is not particularly limited, but examples include ethynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, 1,3-butadiynyl, etc.

The aforementioned polymerizable unsaturated bond-containing substituent may further have a substituent. In this case, the "substituent of the polymerizable unsaturated bond-containing substituent" refers to a substituent that is substituted with at least one of the hydrogen atoms constituting the aforementioned 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, the alkylcarbonyloxy group, and the halogen atom include those mentioned above.

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

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

In this case, in the above-mentioned formulas (2-1) to (2-17), "*" represents a bonded position to "-C(O)OAr ² ". In addition, "-*" may be bonded to any position of the aromatic ring.

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

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

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

唑、異

唑、噻唑、異噻唑、吡啶、嘧啶、嗒

、吡

、三

等之單環芳香族化合物中移除1個氫原子而成者；從萘、蒽、萉、菲、喹啉、異喹啉、喹唑啉、呔

、喋啶、香豆素、吲哚、苯并咪唑、苯并呋喃、吖啶等之稠環芳香族化合物移除1個氫原子而成者等之從芳香族化合物移除1個氫原子而成者。此外，亦可為組合複數個此等的芳香族化合物而成者，可列舉例如：從聯苯、聯萘、聯吡啶、聯噻吩、苯基吡啶、苯基噻吩、三聯苯、二苯基噻吩、聯四苯等之環集合芳香族化合物中移除1個氫原子而成者；從二苯基甲烷、二苯基乙烷、1,1-二苯基乙烷、2,2-二苯基丙烷、萘基苯基甲烷、三苯基甲烷、二萘基甲烷、二萘基丙烷、苯基吡啶基甲烷、茀、二苯基環戊烷等之藉由伸烷基鍵結之芳香族化合物中移除1個氫原子而成者等。 The aforementioned second aromatic ring group is not particularly limited, but examples include: benzene, furan, pyrrole, thiophene, imidazole, pyrazole,

azole, iso

Azole, Thiazole, Isothiazole, Pyridine, Pyrimidine, Pyridine

, pyri

,three

Monocyclic aromatic compounds such as those obtained by removing one hydrogen atom; from naphthalene, anthracene, anthracene, phenanthrene, quinoline, isoquinoline, quinazoline, and

, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine and other condensed ring aromatic compounds obtained by removing one hydrogen atom, etc., obtained by removing one hydrogen atom from an aromatic compound success. In addition, a plurality of these aromatic compounds may be combined, for example: biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene , Tetraphenyl, etc. ring set aromatic compounds removed from one hydrogen atom; from diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenyl Aromatic compounds bonded by alkylene, such as propane, naphthylphenylmethane, triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fennel, diphenylcyclopentane, etc. One hydrogen atom is removed from the middle and so on.

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

The second aromatic ring group of Ar ² may have a substituent. In this case, the "substituent of the second aromatic ring group" refers to a substituent for at least one of the hydrogen atoms constituting the aromatic ring of the second aromatic ring group. Specific examples of the substituent of the second aromatic ring group are not particularly limited, but examples thereof include 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 mentioned above.

In an embodiment of the present invention, Ar ² may also have the above-mentioned substituents containing unsaturated bonds. In this case, the said unsaturated bond containing substituent may have independently, and 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-mentioned formulas (3-1) to (3-17), "*" indicates that it is bonded at the position of "-OC(O)Ar ¹ ". In addition, "-*" may be bonded to any position of the aromatic ring.

Among these, it is preferably formula (3-1) ~ (3-11), more preferably formula (3-1), (3-6), (3-9), more preferably formula (3 -1), (3-6).

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

According to an embodiment, it is preferred that Ar ¹ is the above-mentioned formula (2-1), (2-2), (2-6), (2-7), (2-9), and Ar ² is the above-mentioned formula ( 3-1), (3-6), (3-9); further preferably Ar is the above formula ( ^2-1 ), (2-2), (2-6), (2-7), Ar ² is the above formula (3-1), (3-6); particularly preferably, Ar ¹ is the above formula (2-1), Ar ² is the above formula (3-1), (3-6).

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

According to one embodiment, preferably at least one of Ar ² has a substituent containing a polymerizable unsaturated bond, more preferably all of Ar ² have a substituent containing a polymerizable unsaturated bond, further preferably Ar ¹ There is no substituent containing a polymerizable unsaturated bond, and all Ar ² have substituents containing a polymerizable unsaturated bond. When a substituent having a polymerizable unsaturated bond exists in Ar ² , it is preferable because the balance between heat resistance and dielectric loss factor is excellent.

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

In view of the above, as a better aspect of the aforementioned polymerizable unsaturated bond-containing aromatic ester compound (A-1) represented by the aforementioned chemical formula (1), the following chemical formula (1-1) or (1) can be enumerated. The compound shown in -2).

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

In the aforementioned formula (1-1), particularly preferable examples of R ¹ include the aforementioned allyl group, propenyl group, isopropenyl group, and 1-propenyl group. i is preferably 1 or 2, more preferably 1.

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

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

In above-mentioned chemical formula (4-1)～(4-43), be preferably chemical formula (4-1)～(4-39), be more preferably chemical formula (4-1)～(4-3), (4- 10)~(4-13), (4-18)~(4-39), more preferably chemical formula (4-1)~(4-3), (4-12), (4-13), (4-19)~(4-21), (4-23)~(4-26), (4-29), (4-30), (4-32)~(4-39), especially good It is chemical formula (4-1), (4-2), (4-12), (4-13), (4-26), (4-32), (4-37).

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

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

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

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

(polycarboxylic acid compound or its derivative)

The aforementioned polycarboxylic acid compound or its derivative has a substituted or unsubstituted aromatic ring group, and preferably has a range of 3 to 30 carbon atoms. In this case, examples of "derivatives of polycarboxylic acid compounds" include acid halides of carboxylic acids and the like.

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

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

In the above chemical formulas (5-1) to (5-15), R ¹ is a hydroxyl group or a halogen atom. In addition, R ² is a substituent containing a polymerizable unsaturated bond. In this case, the aforementioned polymerizable unsaturated bond-containing substituents are the same as those described above. Also, p is 2 or 3. In addition, q is an integer of 0 or 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, further preferably 0. Moreover, regarding the position of the substituent on the aromatic ring in the above chemical formula, for convenience, it is recorded on the same aromatic ring, but for example: in the above chemical formula (5-7) etc., R ^{1OC, R 2 can} also be in Substitution on different benzene rings means that the number of substituents in one molecule is p and q.

-2,4,6-三甲酸等之三

甲酸；此等的酸鹵化物等。此等之中，較佳為苯二甲酸、苯三甲酸，更佳為異酞酸、對酞酸、異酞醯氯、對酞醯氯、1,3,5-苯三甲酸、1,3,5-苯三甲醯氯，進一步較佳為異酞醯氯、對酞醯氯、1,3,5-苯三甲醯氯。 The specific polycarboxylic acid compound or its derivatives are not particularly limited, but examples include: phthalic acid such as isophthalic acid, terephthalic acid, 5-allyl isophthalic acid, and 2-allyl terephthalic acid. Formic acid; Trimellitic acid such as trimellitic acid and 5-allyl trimellitic acid; naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene Naphthalene dicarboxylic acid such as -2,7-dicarboxylic acid, 3-allylnaphthalene-1,4-dicarboxylic acid, 3,7-diallylnaphthalene-1,4-dicarboxylic acid; 2,4,5- Pyridine tricarboxylic acid such as pyridine tricarboxylic acid; 1,3,5-tris

-2,4,6-tricarboxylic acid etc.

Formic acid; acid halides of these, etc. Among these, phthalic acid and benzenetricarboxylic acid are preferred, and isophthalic acid, terephthalic acid, isophthaloyl chloride, terephthaloyl chloride, 1,3,5-benzenetricarboxylic acid, 1,3 , 5-benzenetriformyl chloride, more preferably isophthaloyl chloride, terephthaloyl chloride, 1,3,5-benzenetriformyl chloride.

The said polycarboxylic acid compound or its derivative(s) may be used individually, and may use it in combination of 2 or more types.

(phenolic compound)

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

Specific phenolic 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 substituent containing a polymerizable unsaturated bond. In this case, the aforementioned polymerizable unsaturated bond-containing substituents are the same as those described above. In addition, q is an integer of 0 or more, preferably 1-3, more preferably 1 or 2, further preferably 1. When q is 2 or more, the bonding position on the aromatic ring can be arbitrary, for example: in the naphthalene ring of chemical formula (6-6), the heterocyclic ring of chemical formula (6-17) can be substituted on any ring, In terms of chemical formula (6-9) etc., it can be substituted on any one of the benzene rings present in one molecule, which means that the number of substituents in one molecule is q.

The specific phenolic compound is not particularly limited, but examples include: phenol; naphthol; 2-allylphenol, 3-allylphenol, 4-allylphenol, 4-methyl-2-allyl 2-(1-propenyl)phenol, isoeugenol and other allylphenols; 2-(3-butene Butenylphenols such as phenol and 2-(1-ethyl-3-butenyl)phenol; long-chain alkenylphenols such as cardanol; 2-allyl-1-naphthol, Allyl naphthols such as 1-allyl-2-naphthol and 3-allyl-1-naphthol. Among these, allyl phenol and allyl naphthol are preferred, and 2-allyl phenol, 4-methyl-2-allyl phenol, 6-methyl-2-allyl phenol are more preferred. 2-allyl phenol, 2-allyl-1-naphthol, 1-allyl-2-naphthol, more preferably 2-allyl phenol, 2-allyl-1-naphthol, 1-ene Propyl-2-naphthol.

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

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

The amount of the polycarboxylic acid compound or its derivative and the phenolic compound used is not particularly limited, but the carboxyl group and/or halogenated acyl group of the polycarboxylic acid compound or its derivative relative to the molar number of the hydroxyl group of the phenolic compound The molar ratio [(derivatives of carboxyl and/or haloacyl, etc.)/(hydroxyl)] of the molar number of derivatives is preferably 0.8~3.0, more preferably 0.9~2.0, further preferably 1.0~ 1.2.

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

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

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

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

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

The aforementioned polymerizable unsaturated bond-containing aromatic ester compound (A-2) is a first aromatic compound having two or more phenolic hydroxyl groups, a second aromatic compound having two or more phenolic hydroxyl groups, and a second aromatic compound having two or more phenolic hydroxyl groups. The reaction product of the third aromatic compound of the carboxyl group and/or its acid halide, esterification; and the aforementioned first aromatic compound, the aforementioned second aromatic compound, and the aforementioned third aromatic compound and/or its acid halide 1. At least one of the esterified compounds has a substituent having a polymerizable unsaturated bond.

[The first aromatic compound]

The first aromatic compound has two or more phenolic hydroxyl groups. By having 2 or more phenolic hydroxyl groups, it reacts with the 3rd aromatic compound etc. mentioned later, and can form a polyester structure in the aromatic ester compound (A-2) containing a polymerizable unsaturated bond.

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

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

唑、異

唑、噻唑、異噻唑、吡啶、嘧啶、嗒

、吡

、三

等。 The aforementioned monocyclic aromatic ring is not particularly limited, but examples include benzene, furan, pyrrole, thiophene, imidazole, pyrazole,

azole, iso

Azole, Thiazole, Isothiazole, Pyridine, Pyrimidine, Pyridine

, pyri

,three

Wait.

、喋啶、香豆素、吲哚、苯并咪唑、苯并呋喃、吖啶等。 The condensed aromatic ring is not particularly limited, but examples include naphthalene, anthracene, anthracene, phenanthrene, quinoline, isoquinoline, quinazoline, and

, Pteridine, Coumarin, Indole, Benzimidazole, Benzofuran, Acridine, etc.

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

The first aromatic ring may have a substituent. In this case, the "substituent of the first aromatic ring" is not particularly limited, but examples include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, halogen atoms, polymerizable Substituents for unsaturated bonds, etc.

The alkyl group having 1 to 10 carbon atoms is not particularly limited, but examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, n-nonyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclo Hexyl, cycloheptyl, cyclooctyl, cyclononyl.

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

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

The so-called polymerizable unsaturated bond-containing substituent refers to a substituent having at least one polymerizable unsaturated bond and having 2 to 30 carbon atoms. In this case, the "unsaturated bond" refers to a carbon atom-carbon atom double bond and a carbon atom-carbon atom triple bond. Examples of the polymerizable unsaturated bond-containing substituent include alkenyl groups, alkynyl groups, and the like.

The alkenyl group is not particularly limited, but examples include vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, 1-Octenyl, 2-Octenyl, 1-Undecenyl, 1-pentadecenyl, 3-pentadecenyl, 7-pentadecenyl, 1-octadecenyl, 2-octadecenyl, cyclopentenyl, cyclohexenyl, Cyclooctenyl, 1,3-butadienyl, 1,4-butadienyl, hexa-1,3-dienyl, hexa-2,5-dienyl, pentadec-4,7 -dienyl, hexa-1,3,5-trienyl, pentadec-1,4,7-trienyl and the like.

The aforementioned alkynyl group is not particularly limited, but examples include ethynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4-pentynyl, 1,3-butadiynyl, etc.

Among them, as the substituent having a polymerizable unsaturated bond, an alkenyl group having 2 to 30 carbon atoms is preferred, an alkenyl group having 2 to 10 carbon atoms is more preferred, and an alkenyl group having 2 to 10 carbon atoms is further preferred. ~5 alkenyl, particularly preferably vinyl, allyl, propenyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3- Butadienyl, most preferably allyl, propenyl, isopropenyl, 1-propenyl.

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

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

Specific examples of compounds in which the first aromatic ring is a monocyclic aromatic ring (hereinafter referred to simply as "the first monocyclic aromatic ring compound") include catechol, resorcinol, hydrogen Quinone, 1,2,4-glucinol, phloroglucinol, gallicol, 2,3-dihydroxypyridine, 2,4-dihydroxypyridine, 4,6-dihydroxypyrimidine, 3-methyl catechin Phenol, 4-methylcatechol, 4-allylpyrocatechol (4-allylpyrocatechol) and the like.

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

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

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

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

唑、異

唑、噻唑、異噻唑、吡啶、嘧啶、嗒

、吡

、三

等之單環芳香族化合物中移除1個氫原子而成者；從萘、蒽、萉、菲、喹啉、異喹啉、喹唑啉、呔

、喋啶、香豆素、吲哚、苯并咪唑、苯并呋喃、吖啶等之稠環芳香族化合物移除1個氫原子而成者等之從芳香族化合物移除1個氫原子而成者。此外，亦可為組合複數 個此等的芳香族化合物而成者，可列舉例如：從聯苯、聯萘、聯吡啶、聯噻吩、苯基吡啶、苯基噻吩、三聯苯、二苯基噻吩、聯四苯等之環集合芳香族化合物中移除1個氫原子而成者。 The aforementioned first aromatic ring group is not particularly limited, but examples include: benzene, furan, pyrrole, thiophene, imidazole, pyrazole,

azole, iso

Azole, Thiazole, Isothiazole, Pyridine, Pyrimidine, Pyridine

, pyri

,three

Monocyclic aromatic compounds such as those obtained by removing one hydrogen atom; from naphthalene, anthracene, anthracene, phenanthrene, quinoline, isoquinoline, quinazoline, and

, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine and other condensed ring aromatic compounds obtained by removing one hydrogen atom, etc., obtained by removing one hydrogen atom from an aromatic compound winner. In addition, a plurality of these aromatic compounds may be combined, for example: biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene , Tetraphenyl, etc., are formed by removing one hydrogen atom from the ring collection of aromatic compounds.

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 ones as those described above for the "substituent of the first aromatic ring group".

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

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

唑、異

唑、噻唑、異噻唑、吡啶、嘧啶、嗒

、吡

、三

等之單環芳香族化合物中移除2個氫原子而成者；從萘、蒽、萉、菲、喹啉、異喹啉、喹唑啉、呔

、喋啶、香豆素、吲哚、苯并咪唑、苯并呋喃、吖啶等之稠環芳香族化合物移除2個氫原子而成者等之從芳香族化合物移除2個氫原子而成者。此外，亦可為組合複數個此等的芳香族化合物而成者，可列舉例如：從聯苯、 聯萘、聯吡啶、聯噻吩、苯基吡啶、苯基噻吩、三聯苯、二苯基噻吩、聯四苯等之環集合芳香族化合物中移除2個氫原子而成者。 The aforementioned second aromatic ring group is not particularly limited, but examples include: benzene, furan, pyrrole, thiophene, imidazole, pyrazole,

azole, iso

Azole, Thiazole, Isothiazole, Pyridine, Pyrimidine, Pyridine

, pyri

,three

Monocyclic aromatic compounds such as those obtained by removing two hydrogen atoms; from naphthalene, anthracene, anthracene, phenanthrene, quinoline, isoquinoline, quinazoline, and

fused ring aromatic compounds such as , pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc. by removing 2 hydrogen atoms from aromatic compounds, etc. winner. In addition, a plurality of these aromatic compounds may be combined, for example: biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene , Tetraphenyl, etc., are formed by removing 2 hydrogen atoms from the ring collection of aromatic compounds.

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 ones as those described above for the "substituent of the first aromatic ring group".

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

The aforementioned alkylene group is not particularly limited, but examples include methylene, ethylylene, propylylene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylylene Ethyl, 1,1-Dimethylethylene, 1,2-Dimethylethylene, Propyl, Butyl, 1-Methylpropyl, 2-Methylpropyl, Pentyl, hexyl, etc.

As the aforementioned cycloalkylene group, there is no particular limitation, but cyclopropylidene, cyclobutylene, cyclopentyl, cyclohexylene, cycloheptyl, and the following chemical formulas (8-1)~( 8-4) the cycloalkylene group, etc.

In addition, in the above chemical formulas (8-1) to (8-4), "*" represents a bonded position with Ar ³ or Ar ⁴ .

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

In addition, in the above chemical formulas (9-1) to (9-8), "*" represents a bonded position with Ar ³ or Ar ⁴ .

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

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

Furthermore, at least two of the hydrogen atoms constituting the aforementioned Ar ³ and the aforementioned Ar ⁴ are substituted with hydroxyl groups.

Specific examples of the compound represented by the aforementioned chemical formula (7) are not particularly limited, but examples include: various bisphenol compounds, compounds represented by the following chemical formulas (10-1) to (10-8), and These aromatic nuclei have one to a plurality of substituents containing polymerizable unsaturated bonds.

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

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

In addition, in one embodiment, the above-mentioned first aromatic ring is represented by the above-mentioned chemical formula (7), which can be formed by substituting at least one of the hydrogen atoms constituting the first aromatic ring with a hydroxyl group, and two Synthesized by reaction of vinyl compound or dialkyloxymethyl compound.

In this case, the above-mentioned divinyl compound or dialkyloxymethyl compound is not particularly limited, but examples thereof include 1,3-butadiene, 1,5-hexadiene, dicyclopentadiene, tricyclopentadiene, Aliphatic diene compounds such as cyclopentadiene, tetracyclopentadiene, pentacyclopentadiene and hexacyclopentadiene; aromatic diene compounds such as divinylbenzene and divinylbiphenyl; dimethyl Oxymethylbenzene, dimethoxymethylbiphenyl, bisphenol A methoxy adduct, bisphenol A ethoxy adduct, bisphenol F methoxy adduct, bisphenol F ethoxy Dialkyloxymethyl compounds such as base adducts, etc.

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

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

When the first aromatic compound is represented by the above chemical formula (7), and n is an oligomer or a polymer, the weight average molecular weight is preferably 200-3000, more preferably 200-2000. When the weight average molecular weight of the said 1st aromatic compound is 200 or more, since it is excellent in dielectric loss factor, it is preferable. On the other hand, when the weight average molecular weight of the said 1st aromatic compound is 3000 or less, since moldability is excellent, it is preferable. In addition, in this specification, the value of "weight average molecular weight" shall be the value measured by the following method. That is, values obtained by measuring gel permeation chromatography (GPC) according to the following conditions are employed.

GPC measurement conditions

Measuring device: "HLC-8320 GPC" manufactured by Tosoh Co., Ltd.

Column: Guard column "HXL-L" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

+ "TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

Detector: RI (Differential Refractometer)

Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Co., Ltd.

Column temperature: 40°C

Developing solvent: tetrahydrofuran

Flow rate: 1.0ml/min

Standard: follow the aforementioned "GPC-8320 GPC" measurement manual, use the following monodisperse polystyrene with known molecular weight

use polystyrene

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

Sample: What filtered the tetrahydrofuran solution of 1.0 mass % in conversion of resin solid content with the microfilter (50 microliters).

[the second aromatic compound]

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

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

The above-mentioned second aromatic ring is not particularly limited, but examples thereof include a monocyclic aromatic ring, a fused-ring aromatic ring, a ring-integrated aromatic ring, an aromatic ring linked by an alkylene group, and the like. Examples of the monocyclic aromatic ring, the fused-ring aromatic ring, and the aggregated ring aromatic ring include the same ones as those described above for the first aromatic ring.

In addition, examples of aromatic rings linked via alkylene groups include diphenylmethane, diphenylethane, 1,1-diphenylethane, 2,2-diphenylpropane, and naphthylphenylmethane. , triphenylmethane, dinaphthylmethane, dinaphthylpropane, phenylpyridylmethane, fennel, diphenylcyclopentane, etc.

The second aromatic ring of the second aromatic compound may have a substituent. In this case, examples of the "substituent of the second aromatic ring" include the same ones as those described above for the "substituent of the first aromatic ring".

Furthermore, as in the above-mentioned second aromatic compound, one of the hydrogen atoms constituting the above-mentioned substituted or unsubstituted second aromatic ring is substituted by a hydroxyl 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 substituent containing a polymerizable unsaturated bond. In this case, the aforementioned polymerizable unsaturated bond-containing substituents are the same as those described above. In addition, p is an integer of 0 or more, preferably 1 to 3, more preferably 1 or 2, further preferably 1. When p is more than 2, the bonding position on the aromatic ring can be arbitrary, for example: the naphthalene ring represented by chemical formula (11-6), the heterocyclic ring of chemical formula (11-17) can be substituted on any ring, In terms of chemical formula (11-9) etc., it can be substituted on any one of the benzene rings present in one molecule, which means that the number of substituents in one molecule is p.

The specific second aromatic compound is not particularly limited, but examples include: phenol, cresol, xylenol, o-allylphenol, m-allylphenol, p-allylphenol, 2,4-di Allylphenol, 2,6-diallylphenol, 2-allyl-4-methylphenol, 2-allyl-6-methylphenol, 2-allyl-4-methoxy - Compounds in which the aromatic rings of 6-methylphenol, 2-propargylphenol, 3-propargylphenol, 4-propargylphenol, etc. are monocyclic aromatic rings (hereinafter referred to as "the second Monocyclic aromatic ring compound"); 1-naphthol, 2-naphthol, 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol Phenol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, 6-allyl-1-naphthol, diallyl-naphthol, 2-allyl-4- Methoxy-1-naphthol, 2-propargyl-1-naphthol, 3-propargyl-1-naphthol, 1-propargyl-2-naphthol, 3-propargyl-2- Compounds in which the aromatic ring of naphthol is a fused-ring aromatic ring (hereinafter, referred to as "the second fused-ring aromatic ring compound"); aromatic compounds such as allyl hydroxybiphenyl and hydroxypropargyl biphenyl A compound in which the ring is an aggregated aromatic ring (hereinafter, may be simply referred to as "a second ring aggregated aromatic ring compound") and the like.

Among the above, the second aromatic compound is preferably the second monocyclic aromatic ring compound, the second condensed ring aromatic ring compound, more preferably o-allylphenol, m-allylphenol, p-allylphenol, 2-allyl-1-naphthol, 3-allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl- 1-naphthol, 6-allyl-1-naphthol.

In addition, in another embodiment, the second aromatic compound is preferably the second fused-ring aromatic ring compound (fused-ring aromatic ring compound), more preferably 2-allyl-1-naphthol, 3- Allyl-1-naphthol, 1-allyl-2-naphthol, 3-allyl-2-naphthol, 5-allyl-1-naphthol, 6-allyl-1- Naphthol. If the second aromatic compound is a fused-ring aromatic ring compound, it is preferable because molecular movement is suppressed by steric hindrance, and the dielectric loss factor can be reduced. In addition, from the viewpoint of high handleability and low viscosity of the aromatic ester compound (A), 2-allylphenol having a benzene ring skeleton is preferable, and on the other hand, the obtained cured product is more From the viewpoint of heat resistance and excellent balance with low dielectric properties, 2-allyl-1-naphthol, 1-allyl-2-naphthol, and the like having a naphthalene ring skeleton are preferable.

Moreover, the said 2nd aromatic compound may be used individually, and may use it in combination of 2 or more types.

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

The third aromatic compound and/or its acid halides, esters are carboxylic acids having two or more carboxyl groups, or derivatives thereof, specifically, acid halides, esters (in this specification, the 3 aromatic compounds and/or their acid halides and esters are collectively referred to as "third aromatic compounds, etc."). The third aromatic compound, etc., can form a polymeric unsaturated bond-containing aromatic ester compound (A-2) by reacting with the above-mentioned first aromatic compound having two or more carboxyl groups, etc. ester structure. In addition, the polyesterification reaction is stopped by reacting with the above-mentioned second aromatic compound.

The third aromatic compound is not particularly limited, but examples include compounds having two or more carboxyl groups on a substituted or unsubstituted third aromatic ring having 3 to 30 carbon atoms.

In addition, examples of the "carboxyl group" include: carboxyl group; halogenated acyl group such as fluoroacyl group, chloracyl group, bromide group, etc.; alkyloxy group such as methyloxycarbonyl group, ethyloxycarbonyl group, etc. Carbonyl; aryloxycarbonyl such as phenyloxycarbonyl, naphthyloxycarbonyl, etc. In addition, when having an acyl halide group, the third aromatic compound can be an acid halide; when having an alkyloxycarbonyl group or an aryloxycarbonyl group, the third aromatic compound can be an esterified compound. Among them, the third aromatic compound preferably has a carboxyl group, an acyl halide group, or an aryloxycarbonyl group, more preferably has a carboxyl group or an acyl halide group, and still more preferably has a carboxyl group, an acyl chloride group, or a bromine group. Amyl group.

The third aromatic compound is not particularly limited, but examples include compounds having two or more carboxyl groups on a substituted or unsubstituted third aromatic ring having 3 to 30 carbon atoms.

The aforementioned third aromatic ring is not particularly limited, but examples thereof include a monocyclic aromatic ring, a condensed ring aromatic ring, an aggregated ring aromatic ring, and an aromatic ring linked by an alkylene group. Examples of the aforementioned single-ring aromatic ring, the aforementioned condensed-ring aromatic ring, the aforementioned ring-set aromatic ring, and the aromatic ring connected via an alkylene group include the same ones as those described above for the first aromatic ring and the second aromatic ring. .

The 3rd aromatic ring, such as a 3rd aromatic compound, may have a substituent. In this case, examples of the "substituent of the third aromatic ring" include the same ones as those described above for the "substituent of the first aromatic ring".

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 substituent containing a polymerizable unsaturated bond. In this case, the aforementioned polymerizable unsaturated bond-containing substituents are the same as those described above. In addition, R ² is a hydroxyl group, a halogen atom, an alkyloxy group, or an aryloxy group. In addition, p is an integer of 0 or 1 or more, preferably 0 or 1 to 3, more preferably 0 or 1, further preferably 0. q is 2 or 3. When p and q are 2 or more, the bonding position on the aromatic ring can be arbitrary, for example: in the naphthalene ring of chemical formula (12-5) and the heterocyclic ring of chemical formula (12-15), it can be on any ring Substitution, in terms of chemical formula (12-7) etc., can be substituted on any one of the benzene rings present in one molecule, and the number of substituents in one molecule is represented by p and q.

-2,4,6-三甲酸等之三

甲酸；此等的酸鹵化物、酯化物等。此等之中，較佳為苯二甲酸、苯三甲酸，更佳為異酞酸、對酞酸、異酞醯氯、對酞醯氯、1,3,5-苯三甲酸、1,3,5-苯三甲醯氯，進一步較佳為異酞醯氯、對酞醯氯、1,3,5-苯三甲醯氯。 The specific third aromatic compound and the like are not particularly limited, but include phthalic acids such as isophthalic acid, terephthalic acid, 5-allylisophthalic acid, and 2-allylterephthalic acid; Trimellitic acid, trimellitic acid, 5-allyl trimellitic acid, etc.; naphthalene-1,5-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2 ,7-dicarboxylic acid, 3-allyl naphthalene-1,4-dicarboxylic acid, 3,7-diallyl naphthalene-1,4-dicarboxylic acid, etc. naphthalene dicarboxylic acid; 2,4,5-pyridine tri Pyridine tricarboxylic acid such as formic acid; 1,3,5-tri

-2,4,6-tricarboxylic acid etc.

Formic acid; their acid halides, esters, etc. Among these, phthalic acid and benzenetricarboxylic acid are preferred, and isophthalic acid, terephthalic acid, isophthaloyl chloride, terephthaloyl chloride, 1,3,5-benzenetricarboxylic acid, 1,3 , 5-benzenetriformyl chloride, more preferably isophthaloyl chloride, terephthaloyl chloride, 1,3,5-benzenetriformyl chloride.

Among the above, the third aromatic compound whose aromatic ring is a monocyclic aromatic ring, and the third aromatic compound whose aromatic ring is a condensed aromatic ring are preferred, and phthalic acid and benzenetricarboxylic acid are preferred. , naphthalene dicarboxylic acid, acid halides of these, more preferably phthalic acid, naphthalene dicarboxylic acid, acid halides of these, further preferably isophthalic acid, terephthalic acid, naphthalene-1,5-dicarboxylic acid , naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, acid halides of these.

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

[Structure of aromatic ester compound (A-2) containing polymerizable unsaturated bond]

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

In one embodiment, it is preferable that at least the second aromatic compound has a substituent having a polymerizable unsaturated bond. As described above, the structure derived from the second aromatic compound is positioned at the molecular terminal of the polymerizable unsaturated bond-containing aromatic ester compound (A-2). As a result, the polymerizable unsaturated bond-containing substituent of the second aromatic compound is also arranged at the molecular terminal of the polymerizable unsaturated bond-containing aromatic ester compound (A-2). In this case, since the heat resistance and dielectric loss factor balance of the obtained hardened|cured material can become higher, it is preferable.

The polymerizable unsaturated bond-containing aromatic ester compound (A-2) is, as described above, a reaction product of the first aromatic compound, the second aromatic compound, and the third aromatic compound, etc., and may include various compounds . For the composition of the aromatic ester compound (A-2) containing polymerizable unsaturated bonds, the amount of the first aromatic compound, the second aromatic compound, and the third aromatic compound, etc. used and the reaction conditions can be appropriately changed Wait and control.

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

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

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

That is, Ar ¹ are each independently, and may include those obtained by removing two or more hydrogen atoms from a substituted or unsubstituted first aromatic ring, or those obtained by having a first aromatic ring linked by a linking group. The structure obtained by removing two or more hydrogen atoms.

In addition, Ar ² is each independently, and one hydrogen atom is removed from the substituted or unsubstituted 2nd aromatic ring.

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

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

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

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

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

In the above chemical formulas (14-1)~(14-10), s is 0~10, preferably 0~5, and r is 1~10. 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. In addition, the wavy line in the chemical formula is a structure obtained by reacting compounds corresponding to Ar ³ and Ar ¹ and/or Ar ² .

The weight average molecular weight of the aromatic ester compound (A-2) is preferably 150-3000, more preferably 200-2000. When the weight average molecular weight is 800 or more, since the dielectric loss factor is excellent, it is preferable. On the other hand, when the weight average molecular weight is 500 or less, since formability is excellent, it is preferable. Moreover, similarly, as a number average molecular weight, it is preferable that it is the thing in the range of 150-1500 for the same reason.

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

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

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

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

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

In one embodiment, the obtained aromatic ester compound containing polymerizable unsaturated bonds (A- 2) Composition.

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

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

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

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

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

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

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

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

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

The aryl groups in the polyaryl ether resin (B) used in the present invention include phenylene groups, naphthylene groups, and those having aliphatic hydrocarbon groups, alkoxy groups, aryl groups on the aromatic nucleus. , aralkyl and other substituents, etc. Among them, from the standpoint of being a curable composition having an excellent balance between the dielectric properties and heat resistance of the cured product, those having a phenylene group as the main skeleton are preferable, and those having two substituents on the aromatic nucleus are more preferable. phenyl. The type of the substituent is more preferably an aliphatic hydrocarbon group, particularly preferably an alkyl group having 1 to 4 carbon atoms.

The terminal structure of the polyarylether resin (B) is generally an aryloxy group having a phenolic hydroxyl group. The aforementioned phenolic hydroxyl group can also be modified into other structural parts. The aryl group in the aryloxy group includes phenyl, naphthyl, and structural sites having substituents such as aliphatic hydrocarbon groups, alkoxy groups, aryl groups, and aralkyl groups on the aromatic nuclei thereof. Among them, from the standpoint of being a curable composition having an excellent balance between the dielectric properties and heat resistance of the cured product, those having a phenyl group as the main skeleton are preferred, and those having a phenyl group in addition to a phenolic hydroxyl group on the aromatic nucleus are more preferable. A phenylene group with 2 substituents. The type of the substituent is more preferably an aliphatic hydrocarbon group, particularly preferably an alkyl group having 1 to 4 carbon atoms.

As the structural site obtained by modifying the above-mentioned phenolic hydroxyl group, for example, a polymerizable unsaturated bond-containing group such as (meth)acryloxy group, allyloxy group, vinyloxy group, or Structural sites obtained by reacting epoxy compounds with phenolic hydroxyl groups, etc. Among them, a phenolic hydroxyl group or a polymerizable unsaturated bond-containing group is preferable from the standpoint of being a curable composition having an excellent balance between the dielectric properties and heat resistance of the cured product.

As said polyarylether resin (B), what is represented by following structural formula (15) etc. are mentioned, for example.

(In the formula, R1 is each independently ^a hydrogen atom, an aliphatic hydrocarbon group, an alkoxyl 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 polymer containing base of sexually unsaturated bonds.)

As long as Y in the aforementioned structural formula (15) is a divalent organic group, it is not particularly limited, although it can be any structural position, but as an example, the following structural formulas (Y-1) to (Y-9 ) as indicated by any one of them, etc.

(wherein, R ² are each independently any one of aliphatic hydrocarbon group, alkoxyl group, aryl group, and aralkyl group. R ³ systems are each independently any one of aliphatic hydrocarbon group, alkoxyl group, and aryl group, k is an integer from 0 to 4.)

From the point of view of being able to form a curable composition excellent in both heat resistance and dielectric properties, the functional group equivalent of the phenolic hydroxyl group of the aforementioned polyarylether resin (B) or the structural part obtained by modifying it, That is, the functional group equivalent weight of the structural site represented by the terminal -OX group in the aforementioned structural formula (15) is preferably in the range of 500 to 3,000 g/equivalent, more preferably in the range of 500 to 1,500 g/equivalent.

In the curable composition of the present invention, the blending ratio of the above-mentioned aromatic ester compound (A) containing a polymerizable unsaturated bond (A) to the above-mentioned polyaryl ether resin (B) is not particularly limited. Physical performance and other appropriate adjustments. Among these, it is preferable to use in the range of 10 to 300 parts by mass relative to 100 parts by mass of the above-mentioned aromatic ester compound (A) from the viewpoint of forming a curable composition having an excellent balance between heat resistance and dielectric properties of the cured product. The polyaryl ether resin (B) is more preferably used in the range of 20 to 200 parts by mass.

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

[epoxy resin]

In the curable composition of the present invention, since the above-mentioned aromatic ester compound (A) containing a polymerizable unsaturated bond contains a polymerizable unsaturated bond, even if only the above-mentioned aromatic ester compound (A) and polyaryl ether resin ( B) It is also hardening. On the other hand, since the aforementioned aromatic ester compound (A) also functions as a curing agent for epoxy resins, and can impart a cured product with higher heat resistance, the curable composition of the present invention preferably further contains epoxy resin.

The epoxy resin is not particularly limited, but examples include: phenol novolak type epoxy resin, cresol novolac type epoxy resin, α-naphthol novolak type epoxy resin, β-naphthol novolac type epoxy resin, and β-naphthol novolak type epoxy resin. Epoxy resins, bisphenol A novolac epoxy resins, biphenyl novolak epoxy resins, etc. novolac epoxy resins; phenol aralkyl epoxy resins, naphthol aralkyl epoxy resins, Aralkyl type epoxy resins such as phenol biphenyl aralkyl type epoxy resins; bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin Resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy Bisphenol-type epoxy resins such as resins; biphenyl-type epoxy resins such as biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, epoxy resins having a biphenyl skeleton and a diecidyloxybenzene skeleton, etc. Epoxy resins; naphthalene type epoxy resins; binaphthol type epoxy resins; binaphthyl type epoxy resins; dicyclopentadiene type epoxy resins such as dicyclopentadiene phenol type epoxy resins; tetrapropylene oxide Glycidyl diaminodiphenylmethane type epoxy resin, triglycidyl p-aminophenol type epoxy resin, glycidylamine type epoxy resin of diaminodiphenylsulfone, etc. Amine type epoxy resin; Diglycidyl ester type epoxy resin of 2,6-naphthalene dicarboxylate type epoxy resin, glycidyl ester type epoxy resin of hexahydrophthalic anhydride, etc. ; Benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. These may be used individually, respectively, and may use 2 or more types together.

The epoxy equivalent of the epoxy resin is preferably 150-500 g/equivalent, more preferably 200-350 g/equivalent. When the epoxy group equivalent of the epoxy resin is 150g/equivalent or more, it is better because of excellent heat resistance; on the other hand, when the epoxy group equivalent of the epoxy resin is 500g/equivalent or less, due to heat resistance and dielectric loss The balance of factors is more excellent, so it is preferable.

The weight average molecular weight of the epoxy resin is preferably 200-5000, more preferably 300-3000. When the weight-average molecular weight of the epoxy resin is 200 or more, it is preferable because it can also have rapid curing properties. On the other hand, when the weight average molecular weight of an epoxy resin is 5000 or less, since moldability is excellent, it is preferable. In addition, the weight average molecular weight can employ the value measured according to the aforementioned method (GPC).

[Other hardeners]

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

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

、

烯二胺(MDA)、異佛酮二胺(IPDA)、1,3-雙胺基甲基環己烷(1,3-BAC)、哌啶、N,N’-二甲基哌

、三伸乙基二胺等之脂肪族胺；間二甲苯二胺(XDA)、甲烷伸苯基二胺(MPDA)、二胺基二苯基甲烷(DDM)、二胺基二苯碸(DDS)、苄基甲基胺、2-(二甲基胺基甲基)苯酚、2,4,6-參(二甲基胺基甲基)苯酚等之芳香族胺等。 The aforementioned amine hardener is not particularly limited, but examples include: diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine Amine (DPDA), Diethylaminopropylamine (DEAPA), N-Aminoethylpiper

,

Methylene diamine (MDA), isophorone diamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N'-dimethylpiper

, triethylenediamine and other aliphatic amines; m-xylylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylene ( DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-paraffin (dimethylaminomethyl)phenol and other aromatic amines.

Examples of the aforementioned imidazole hardener include 2-methylimidazole, 2-ethyl-4-methylimidazole, trimellitic acid-1-cyanoethyl-2-undecylimidazolium salt (1-cyanoethyl-2 -undecyl imidazolium trimellitate), epoxy-imidazole adducts, etc.

Examples of the aforementioned acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bis-trimellitic acid ester, glycerol paramelellitic acid ester, Maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, bridged methylene tetrahydrophthalic anhydride, methyl bridged methylene tetrahydrophthalic anhydride, methylbutenyl tetrahydrophthalic anhydride, dodeca Alkenyl succinic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, succinic anhydride, methylcyclohexenedicarboxylic anhydride, etc.

改質酚樹脂等。 Examples of the aforementioned phenolic resin hardener include phenol novolac resins, cresol novolac resins, naphthol novolak resins, biphenyl novolac resins, biphenyl novolak resins, dicyclopentadiene-phenol addition type resins, phenol Arane resin, naphthol arane resin, triphenol methane type resin, tetraphenol ethane type resin, amino three

Modified phenolic resin, etc.

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

The content of the aforementioned other hardeners is not particularly limited, but relative to the aforementioned aromatic ester compound (A), it is preferably 2-80% by mass, more preferably 5-70% by mass.

In the curable composition of the present invention, the mixing ratio of the aforementioned aromatic ester compound (A), epoxy resin, and other curing agents is not particularly limited, and can be appropriately adjusted according to the desired properties of the cured product, but as For example, it is preferable that the total amount of functional groups capable of reacting with epoxy groups in the aforementioned aromatic ester compound (A) or other hardeners is in the range of 0.7 to 1.5 mol with respect to 1 mol of epoxy groups in total.

[Other resins]

樹脂、含三

之甲 酚酚醛清漆樹脂、氰酸酯(cyanic acid ester)樹脂、苯乙烯-馬來酸酐樹脂、二烯丙基雙酚、三聚異氰酸三烯丙酯等之含烯丙基之樹脂、多磷酸酯、磷酸酯-碳酸酯共聚物、聚丁二烯樹脂等。此等的其他樹脂可單獨使用，亦可組合2種以上而使用。 Specific examples of other resins are not particularly limited, but include maleimide resins, bismaleimide resins, polyimide resins, cyanate ester resins, benzo

Resin, containing three

Allyl group-containing resins such as cresol novolak resin, cyanic acid ester resin, styrene-maleic anhydride resin, diallyl bisphenol, triallyl isocyanate, etc. Polyphosphate, phosphate-carbonate copolymer, polybutadiene resin, etc. These other resins may be used alone or in combination of two or more.

[solvent]

In one embodiment, the composition may also include a solvent. The aforementioned solvent has the function of adjusting the viscosity of the composition, etc.

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

The amount of the solvent used is preferably from 10 to 80% by mass, more preferably from 20 to 70% by mass, based on the entire mass of the curable composition. When the usage-amount of a solvent is 10 mass % or more, since handling property is excellent, it is preferable. On the other hand, when the usage-amount of a solvent is 80 mass % or less, since impregnation property with another base material is excellent, it is preferable.

[additive]

In one embodiment, the composition may also contain additives. Examples of such additives include hardening accelerators, flame retardants, fillers, and the like.

(hardening accelerator)

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

Examples of the phosphorus-based hardening accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; trimethyl phosphite, Organic phosphite compounds such as triethyl phosphite; ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetra-p-tolueneboronic acid Tetraphenylphosphonium, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, butyl dicyanamide Phosphonium salts such as phenylphosphonium and tetrabutylphosphonium decanoate, etc.

Examples of amine-based hardening accelerators include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (DMAP), 2,4,6-paraffin (dimethylaminomethyl) Phenol, 1,8-diacribicyclo[5,4,0]-undecene-7 (DBU), 1,5-diacribicyclo[4,3,0]-nonene-5 (DBN), etc.

Examples of imidazole-based hardening accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, -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, trimellitic acid-1-cyano Ethyl-2-undecylimidazolium salt, trimellitic acid-1-cyanoethyl-2-phenylimidazolium salt, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl- 4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole (2, 3-dihydro-1H-pyrrolo[1,2-a]benzimidazole), 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, etc.

Examples of the guanidine hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-benzoguanidine, metguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, Pentamethylguanidine, 1,5,7-triacridinebicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triacridinebicyclo[4.4.0]dec-5-ene, 1 - methyl biguanide, 1-ethyl biguanide, 1-butyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide and the like.

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

Examples of the aforementioned peroxides and azo compounds include benzoyl peroxide, p-chlorobenzoyl peroxide, di(tertiary butyl) peroxide, diisopropyl peroxydicarbonate, diisopropyl peroxydicarbonate, (2-Ethylhexyl) ester, azobisisobutyronitrile, etc.

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

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

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

(flame retardant)

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

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

The organophosphorus flame retardant is not particularly limited, but examples thereof include methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate Butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, acid phosphoric acid Tridecyl, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, glycolic acid phosphate , (2-hydroxyethyl) methacrylate acid phosphate and other phosphates; 9,10-dihydro-9-oxa-10-phosphinephenanthrene-10-oxide (9,10-dihydro-9 -oxa-10-phosphaphenanthrene-10-oxide), diphenylphosphine oxide and other diphenylphosphines; 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10- Oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphine-10-oxide, diphenylphosphinyl hydroquinone, diphenylphosphinyl hydroquinone -1,4-dioxynaphthalene, 1,4-cyclooctylene phosphinyl-1,4-phenyldiol (1,4-cyclooctylene phosphinyl-1,4-phenyldiol), 1,5-cycloctylene phosphinyl-1,4-phenyldiol Phosphorus-containing phenols such as octylphosphine oxide-1,4-phenyldiol; 9,10-dihydro-9-oxa-10-phosphinephenanthrene-10-oxide, 10-(2,5-di Hydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide Cyclic phosphorus compounds such as compounds; compounds obtained by reacting the aforementioned phosphoric acid esters, the aforementioned diphenylphosphine, the aforementioned phosphorus-containing phenols, and epoxy resins, aldehyde compounds, or phenolic compounds, etc.

、四溴酞酸等。 The aforementioned halogen-based flame retardant is not particularly limited, but examples include brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2- Bis(tetrabromophthalimide), 2,4,6-para(2,4,6-tribromophenoxy)-1,3,5-tri

, Tetrabromophthalic acid, etc.

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

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

(filler)

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

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

The aforementioned inorganic filler is not particularly limited, but examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, oxide Magnesium, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate (barium titanate zirconate), barium zirconate (barium zirconate), calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, talc, clay, mica powder, zinc oxide, hydrotalcite, diaspore, carbon black, etc.

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

In addition, the above-mentioned fillers may also be subjected to surface treatment as required. The surface treatment agent that can be used at this time is not particularly limited, but aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanium Ester coupling agent, etc. Specific examples of surface treatment agents include 3-glycidoxypropyl trimethoxysilane (3-glycidoxypropyl trimethoxysilane), 3-mercaptopropyl trimethoxysilane (3-mercaptopropyl trimethoxysilane), 3-aminopropyl Triethoxysilane (3-aminopropyltriethoxysilane), N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilazane, etc.

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

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

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

<Hardened product (hardened product of curable composition)>

According to an embodiment of the present invention, there is provided a cured product which is a curable composition comprising the above-mentioned polymerizable unsaturated bond-containing aromatic ester compound (A) and polyaryl ether resin (B) Hardened.

The above-mentioned polymerizable unsaturated bond-containing aromatic ester compound (A) can be polymerized by itself because it has a polymerizable unsaturated bond-containing substituent to obtain a cured product.

In addition, the above-mentioned hardening agent, additive, hardening accelerator, etc. may also be contained in the said hardened|cured material as needed.

The aromatic ester compound (A) containing polymerizable unsaturated bonds has a low dielectric loss factor, so the hardened product has a low dielectric loss factor and excellent heat resistance, so it can be used in semiconductor packaging substrates, printing Electronic materials such as wiring substrates, build-up adhesive films, and semiconductor packaging materials. In addition, it can also be applied to applications such as adhesives and paints.

The heating temperature during heat hardening is not particularly limited, but is preferably 150-300°C, more preferably 175-250°C.

[Example]

Hereinafter, although an Example demonstrates this invention, this invention is not limited to description of an Example.

Production Example 1 Production of Polymerizable Unsaturated Bond-Containing Aromatic Ester Compound (A-1-1)

In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, fill 268g of o-allylphenol and 1,200g of toluene, and dissolve the contents while replacing the system with nitrogen under reduced pressure. Next, 203 g of isophthaloyl chloride was charged, and the contents were dissolved while substituting nitrogen under reduced pressure in the system. 0.6 g of tetrabutylammonium bromide was added and dissolved, and the inside of the system was controlled to 60° C. or lower while flushing with nitrogen, and 412 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the dropwise addition, stirring was continued for 1 hour under the same temperature conditions. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the obtained organic phase and stirred for about 15 minutes, then allowed to stand for liquid separation, and the water layer was removed. This water washing operation was repeated until the pH of the aqueous layer became 7. The organic phase after washing with water was dried under heating and reduced pressure to obtain 370 g of an aromatic ester compound (A-1-1) containing a polymerizable unsaturated bond represented by the following structural formula. The ester group equivalent weight of the polymerizable unsaturated bond-containing aromatic ester compound (A-1-1) was 199 g/equivalent, the allyl group equivalent weight was 199 g/equivalent, and the E-type viscosity (25° C.) was 6000 mPa.s.

Production Example 2 Production of Polymerizable Unsaturated Bond-Containing Aromatic Ester Compound (A-2-1)

In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, fill 165 g of a double addition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent 165 g/equivalent, softening point 85° C.), o-olefin 134 g of propylphenol and 1,200 g of toluene were dissolved in the system while substituting nitrogen under reduced pressure. Next, 203 g of isophthaloyl chloride was charged, and dissolved while substituting nitrogen under reduced pressure in the system. 0.6 g of tetrabutylammonium bromide was added and dissolved, and the inside of the system was controlled to 60° C. or lower while flushing with nitrogen, and 412 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the dropwise addition, stirring was continued for 1 hour under the same temperature conditions. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the obtained organic phase and stirred for about 15 minutes, then allowed to stand for liquid separation, and the water layer was removed. This water washing operation was repeated until the pH of the aqueous layer became 7. The organic phase washed with water was dried under reduced pressure under heating to obtain 385 g of a polymerizable unsaturated bond-containing aromatic ester compound (A-2-1). The theoretical structure of the polymerizable unsaturated bond-containing aromatic ester compound (A-2-1) is shown below. The polymerizable unsaturated bond-containing aromatic ester compound (A-2-1) had an ester group equivalent of 214 g/equivalent, an allyl group equivalent of 428 g/equivalent, and a softening point of 82°C.

Production Example 3 Production of Polymerizable Unsaturated Bond-Containing Aromatic Ester Compound (A-2-2)

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

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

In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, fill 165 g of dicyclopentadiene and phenol compound addition reaction resin (hydroxyl equivalent: 165 g/equivalent, softening point 85° C.) 165 g, 1- 72 g of naphthol and 630 g of toluene were dissolved while nitrogen substitution was performed in the system under reduced pressure. Next, 152 g of isophthaloyl chloride was charged, and dissolved while substituting nitrogen under reduced pressure in the system. 0.6 g of tetrabutylammonium bromide was added, nitrogen flushing was performed, and the inside of the system was controlled to 60° C. or lower, and 315 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. After the dropwise addition, stirring was continued for 1 hour under the same temperature conditions. The reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the obtained organic phase and stirred for about 15 minutes, then allowed to stand for liquid separation, and the water layer was removed. This water washing operation was repeated until the pH of the aqueous layer became 7. The organic phase washed with water was dried under reduced pressure under heating 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.

Embodiment 1～9 and comparative example 1

The components were blended in the ratios shown in Tables 1 and 2 below to obtain curable compositions. With respect to the obtained curable composition, the heat resistance evaluation of the cured product and the measurement of the dielectric loss factor value were carried out according to the following points. The results are shown in Tables 1 and 2.

The details of each component used in the examples are as follows.

‧Polyaryl ether resin (B-1): "NORYL SA90" manufactured by SABIC, the hydroxyl equivalent is 850 g/equivalent, and the theoretical structure is as follows.

‧Polyaryl ether resin (B-2): "NORYL SA9000" manufactured by SABIC Corporation, methacryl group equivalent 850 g/equivalent, theoretical structure as follows.

‧Epoxy resin: bisphenol A type epoxy resin ("EPICLON850S" produced by DIC Co., Ltd. has an epoxy group equivalent of 188g/equivalent)

Manufacture of hardened

Flow the curable composition into a 11cm×9cm×2.4mm template, use a press, and mold at 150°C for 60 minutes, then at 175°C for 90 minutes, and then at 200°C for 90 minutes. The molded product was taken out from the template, 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 previously obtained hardened product having a thickness of 2.4 mm. Using the "Solid Viscoelasticity Measuring Device RSAII" manufactured by Rheometric Co., Ltd., by measuring the DMA (dynamic viscoelasticity) according to the rectangular tension method, the temperature at which the elastic modulus of the test piece changes the most (the change rate of tan δ is the largest) is measured. as the glass transition temperature. The measurement conditions were set at a frequency of 1 Hz, and at a rate of temperature increase of 3° C./min.

Measurement of Dielectric Loss Factor

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

Claims (6)

A curable composition comprising an aromatic ester compound (A) containing a polymerizable unsaturated bond and a polyaryl ether resin (B), wherein the aromatic ester compound (A) containing a polymerizable unsaturated bond is A polymerizable unsaturated bond-containing aromatic ester compound (A-1) represented by the following chemical formula (1), or a polymerizable unsaturated bond-containing aromatic ester compound (A-2):

(In the above chemical formula (1), Ar ¹ is a substituted or unsubstituted 1st aromatic ring group, Ar ² is each independently a substituted or unsubstituted 2nd aromatic ring group, at this time, the aforementioned Ar ¹ and at least one of the aforementioned Ar ² has a substituent containing a polymerizable unsaturated bond, n is an integer of 2 or 3); the aforementioned aromatic ester compound (A-2) containing a polymerizable unsaturated bond has 2 The reaction product of the above first aromatic compound with phenolic hydroxyl group, the second aromatic compound with phenolic hydroxyl group, and the third aromatic compound with two or more carboxyl groups and/or its acid halides and esters; At least one of the first aromatic compound, the second aromatic compound, and the third aromatic compound and/or its acid halide or esterified compound has a polymerizable unsaturated bond-containing substituent. The curable composition according to claim 1, which further contains epoxy resin. A cured product of the curable composition as claimed in claim 1 or 2. A printed wiring board formed using the curable composition according to claim 1 or 2. A semiconductor packaging material, which is formed using the curable composition according to claim 1 or 2. A build-up film formed using the curable composition according to claim 1 or 2.