TWI794455B - 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, a curable composition containing an aromatic ester compound (A), a maleimide compound (B), and an epoxy compound (C) represented by the following structural formula (1) is provided.

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

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.

It is described in the aforementioned Patent Document 1 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 documents

Patent Document 1 Japanese Patent Laid-Open No. 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 was found that a cured product of a curable composition containing an aromatic ester compound having a specific molecular structure, a maleimide compound, and an epoxy compound is exceptionally excellent in heat resistance and dielectric properties, and thus completed the present invention.

That is, the present invention provides: containing the following structural formula (1)

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

Curable compositions of the aromatic ester compound (A), maleimide compound (B), and epoxy compound (C) shown, their cured products, and printed wiring using the curable composition Substrates, semiconductor packaging materials, 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 for carrying out the invention

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

The aromatic ester compound (A) used in the present invention is represented by the following structural formula (1).

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

As the above-mentioned aromatic ester compound (A), it is preferable to use it at room temperature ( 25°C) is a liquid, or its softening point is in the range of 40°C to 200°C.

Regarding the aforementioned aromatic ester compound (A), 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. Also, Ar ¹ is preferably in the range of 3 to 30 carbonyl atoms.

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,

, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc., condensed ring aromatic compounds with 2 or 3 hydrogen atoms removed, etc., 2 or 3 hydrogen atoms removed from the aromatic compound Made up of 3 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 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), but on the other hand, the obtained hardened product is more From the viewpoint of excellent balance between heat resistance and low dielectric properties, (2-6) and (2-7) are preferable.

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 ". Also, Ar ² is preferably in the range of 3 to 30 carbon atoms.

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 successful. 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 obtained hardened product 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 one embodiment of the present invention, Ar ² may also have the above-mentioned substituents containing polymerizable unsaturated bonds. In this case, the said polymerizable 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), "*" represents a bonded position to "-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 aromatic ester compound (A) has two or three ester bonds connecting two aromatic rings.

From the above, as a more preferable aspect of the aromatic ester compound (A) represented by the chemical formula (1), a compound represented by the following chemical formula (1-1) or (1-2) can be mentioned.

[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) represented by the above chemical formula (1) is not particularly limited, but compounds represented by the following chemical formulas (4-1) to (4-43) are exemplified.

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 aromatic ester compound (A) 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) comprises making a polycarboxylic acid compound having a substituted or unsubstituted first aromatic ring group or a derivative thereof, and a polycarboxylic acid compound having a substituted or unsubstituted The step of reacting the phenolic compound of the substituted 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, 3-allyl-1-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 maleimide compound (B) used in the present invention is not particularly limited as long as it has a maleimide group in the molecule, and other specific structures are not particularly limited, and various compounds can be used. Among them, a compound having two or more maleimide groups in one molecule is preferable from the standpoint of excellent curability of the curable composition, heat resistance of the cured product, and excellent dielectric properties. Specifically, bismaleimide compounds having two maleimide groups in one molecule, polymaleimide compounds having three or more maleimide groups in one molecule, etc. . The maleimide compound (B) may be used alone or in combination of two or more.

As a specific example of the said maleimide compound (B), the compound etc. which are represented by following structural formula (7) are mentioned, for example.

(In the formula, X is a divalent organic group. ^R3 is any one of a hydrogen atom, an aliphatic hydrocarbon group, or a halogen atom. The multiple ^R3s present in the formula can be the same or different.)

R ³ in the aforementioned structural formula (7) is any one of a hydrogen atom, an aliphatic hydrocarbon group, and a halogen atom. Examples of the aforementioned aliphatic hydrocarbon group include: alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; cycloalkyl groups such as cyclohexyl; vinyl, allyl, propenyl, iso Polymerizable unsaturated bond-containing groups such as propenyl and 1-propenyl, etc. Examples of the aforementioned halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The specific structure of X in the aforementioned structural formula (7) is not particularly limited, and may be any structural part. In particular, X is preferably a structural site containing an aromatic ring, from the standpoint of being a curable composition that is more excellent in heat resistance and dielectric properties of the cured product. Specific examples of the aromatic ring-containing structural site include, for example, those represented by any one of the following structural formulas (X-1) to (X-10).

[wherein R ⁴ are each independently any one of a group containing a polymerizable unsaturated bond, an alkyl group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. R ⁵ is any one of a hydrogen atom, an alkyl group, a halogenated alkyl group, and a halogen atom. Y is any one of an alkylene group, a halogenated alkylene group, a carbon group, a carbonyloxy group, a sulfonyl group, an oxygen atom, and a sulfur atom. In the formula (X-4), a plurality of Ys may be the same as or different from each other. Z is a carbon atom or a nitrogen atom. However, Z in the formula (X-8) is a carbon atom. i is an integer of 0 or 1~4, 1 is an integer of 0 or 1~6, m is an integer of 0 or 1~5, n is an integer of 0 or 1~7, and o is an integer of 0 or 1~3. j and k are integers of 2 or more. The position of the bonding point and the substituent on the naphthalene ring can be on any carbon atom forming the naphthalene ring. ]

R in the aforementioned structural formulas (X-1) to (X-10) is any ^one of a group containing a polymerizable unsaturated bond, an alkyl group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group. The polymerizable unsaturated bond in the above-mentioned polymerizable unsaturated bond-containing group includes, for example, a double bond between carbons, a triple bond between carbons, and the like. Among the groups containing polymerizable unsaturated bonds, specific examples of those having a double bond between carbons include, for example, vinyl, vinyloxy, (meth)allyl, (meth)allyl Oxygen, 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, (meth)acryl, (meth)acryloxy, (meth)acryloxy(poly)alkyleneoxy, etc. Also, as specific examples of those having a triple bond between carbons, for example: ethynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 3-pentynyl, 4 -pentynyl, 1,3-butadiynyl, etc.

Examples of the aforementioned alkyl group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; and cycloalkyl groups such as cyclohexyl. Examples of the aforementioned alkoxy group include methoxy, ethoxy, propoxy, butoxy and the like. Examples of the aforementioned halogen atom include fluorine atom, chlorine atom, bromine atom and the like. Examples of the aryl group include phenyl, naphthyl, anthracenyl, and structural sites substituted with the aforementioned polymerizable unsaturated bond-containing groups, alkyl groups, alkoxy groups, halogen atoms, etc. on the aromatic nuclei thereof. The aforementioned aralkyl group includes benzyl, phenylethyl, naphthylmethyl, naphthylethyl, and the above-mentioned polymerizable unsaturated bond-containing group, alkyl, alkoxy, Structural sites substituted by halogen atoms, etc.

Among these, ^R4 is preferably vinyl, vinyloxy, (meth)allyl, (meth)allyloxy, Any of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and an aralkyl group having a polymerizable unsaturated bond-containing group.

Y in the aforementioned structural formulas (X-3) and (X-4) is any one of an alkylene group, a halogenated alkylene group, a carbonyl group, a carbonyloxy group, a sulfonyl group, an oxygen atom, and a sulfur atom. The number of carbon atoms in the aforementioned alkylene group and halogenated alkylene group is not particularly limited, but is preferably in the range of 1 to 4 carbon atoms.

j in the aforementioned structural formula (X-2) is preferably 2 or 3. Also, k in the aforementioned structural formula (X-4) is preferably 2 or 3.

R ⁵ in the aforementioned structural formulas (X-6) and (X-7) is any one of a hydrogen atom, an alkyl group, a halogenated alkyl group, and a halogen atom. The number of carbon atoms in the aforementioned alkyl group and halogenated alkyl group is not particularly limited, but is preferably in the range of 1 to 4 carbon atoms.

Specific examples of the aforementioned bismaleimide compound include, for example, those represented by the following structural formulas (7-1) to (7-19).

As a specific example of the polymaleimide compound having 3 or more maleimide groups in the aforementioned molecule, for example, any of the following structural formulas (8-1) to (8-3) can be enumerated. The compounds shown by those, etc.

(In the formula, ^R3 is any one of a hydrogen atom, an aliphatic hydrocarbon group, or a halogen atom, and the multiple ^R3s present in the formula may be the same as or different from each other. ^R4 is independently of each other and contains polymerizable unsaturated bonds. any one of radical, alkyl, alkoxy, halogen atom, aryl, and aralkyl. i is an integer of 0 or 1 to 4, and o is an integer of 0 or 1 to 3. V is an integer of 1 to 3 carbon atoms. Any of 4 alkylene, arylmethylene, alkylene arylylene, alkylene biphenylene alkylene, cycloalkylene, oxygen atom, sulfur atom, carbonyl group ^R5 is any one of a hydrogen atom, an alkyl group, a halogenated alkyl group, or a halogen atom. Z is a carbon atom or a nitrogen atom. t is an integer of 2 or more, and p is an integer of 3 to 6.)

As these maleimide compounds (B), commercially available ones can be used as they are, for example: BMI series manufactured by Daiwa Chemical Industry Co., Ltd. (BMI-1000, 2000, 2300, 3000, 4000, 6000, 7000 , 8000, TMH, etc.), BMI, BMI-70, BMI-80, etc. manufactured by K.I Chemical Industry Co., Ltd., B1109, N1971, B4807, P0778, P0976, etc. manufactured by Tokyo Chemical Industry Co., Ltd.

Among the aforementioned maleimide compounds (B), the aforementioned bismaleimide compound is preferred from the viewpoints of curability of the curable composition, viscosity, heat resistance of the cured product, and dielectric properties. . Furthermore, X in the aforementioned structural formula (6) is preferably any one of the aforementioned structural formulas (X-1) to (X-4), more preferably (X-3) or (X-4).

In the curable composition of the present invention, the mixing ratio of the aforementioned aromatic ester compound (A) and the aforementioned maleimide compound (B) is not particularly limited, and can be appropriately adjusted according to the desired properties of the cured product. Among them, it is preferable to use in the range of 5 to 300 parts by mass relative to 100 parts by mass of the above-mentioned aromatic ester compound (A) from the viewpoint of being a curable composition having an excellent balance between heat resistance and dielectric properties of the cured product. The aforementioned maleimide compound (B) is more preferably used in the range of 20 to 200 parts by mass.

The epoxy resin (C) used in this invention is demonstrated.

型環氧樹脂等。此等可各自單獨使用，亦可併用2種以上。 Examples of the aforementioned epoxy resins include bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol E epoxy resins, bisphenol S epoxy resins, bisphenol sulfide epoxy resins, and bisphenol sulfide epoxy resins. Benzene type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin , triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin Oxygen resin, biphenyl novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co- Novolac type epoxy resin, biphenyl modified phenol type epoxy resin (polyphenol type epoxy resin with phenol skeleton and biphenyl skeleton linked by double methylene), biphenyl modified naphthol type epoxy resin Resin (poly-naphthol-type epoxy resin with naphthol skeleton and biphenyl skeleton linked by double methylene), alkoxy-containing aromatic ring modified novolak-type epoxy resin (formaldehyde-linked epoxypropylene aromatic ring and alkoxy-containing aromatic ring compounds), phenylene ether type epoxy resin, naphthyl ether type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin,

Type epoxy resin, etc. These may be used individually, respectively, and may use 2 or more types together.

型環氧樹脂等，從可得到耐熱性優異硬化物的點來看為特佳。 Among the above, phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, polyhydroxynaphthalene epoxy resins, and polyhydroxynaphthalene Type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, biphenyl novolak type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-epoxy novolac Type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenylene ether type epoxy resin, naphthyl ether type epoxy resin,

Type epoxy resin and the like are particularly preferable in that a cured product having excellent heat resistance can be obtained.

Among the above, dicyclopentadiene-phenol addition reaction type epoxy resins, naphthol novolac type epoxy resins, phenol aralkyl Type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-decylated novolak type epoxy resin Resin, biphenyl-modified phenol-type epoxy resin (polyphenol-type epoxy resin formed by linking phenol skeleton and biphenyl skeleton with double methylene), biphenyl-modified naphthol-type epoxy resin (naphthol skeleton and The biphenyl skeleton is linked by the double methylene group poly-naphthol type epoxy resin), the aromatic ring containing the alkoxy group is modified the novolac type epoxy resin (the aromatic ring containing the glycidyl group is linked with the formaldehyde and contains alkoxy aromatic ring compounds), aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, naphthyl ether type epoxy resin.

The blending ratio of each component in the curable composition of the present invention is not particularly limited, and is preferably adjusted appropriately according to the desired physical properties of the cured product, but for example, from the viewpoint of improving the physical property balance of the cured product , with respect to 100 parts by mass of the aforementioned aromatic ester compound (A), it is preferable to contain 5 to 300 parts by mass of the aforementioned maleimide compound (B), and to contain 5 to 300 parts by mass of the aforementioned epoxy compound (C) , It is particularly preferable to contain 20 to 200 parts by mass of the aforementioned maleimide compound (B), and to contain 20 to 200 parts by mass of the aforementioned epoxy compound (C).

改質酚樹脂(以三聚氰胺、苯胍

(benzoguanamine)等連結酚核而成之多元酚化合物)等之多元酚化合物。 The hardening resin composition of this invention can also use together the hardening agent for epoxy resins. As the curing agent for epoxy resins that can be used here, for example, curing agents such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds can be used. Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylene, isophoronediamine, imidazole, and BF3-amine. Complexes, guanidine derivatives, etc.; as amide compounds, dicyandiamide, polyamide resins synthesized from linolenic acid dimers and ethylenediamine, etc.; as acid anhydride compounds Compounds include phthalic anhydride, trimellitic anhydride, pyromelite anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl nadic acid anhydride, hexahydrophthalic anhydride, Methylhexahydrophthalic anhydride, etc.; examples of phenolic compounds include phenol novolak resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition resins, and phenol aralkyl resins , naphthol aralkyl resin, trimethylol methane resin, tetraphenol ethane resin, naphthol novolak resin, naphthol-phenol co-denatured novolac resin, naphthol-cresol co-distilled novolak resin, Benzene-modified phenol resin (polyphenol compound formed by linking phenol nucleus with double methylene group), biphenyl modified naphthol resin (multiple naphthol compound formed by linking phenol nucleus with double methylene group), amino three

Modified phenolic resin (based on melamine, benzoguanidine

(Benzoguanamine) and other polyphenolic compounds linked to phenolic nuclei) and other polyphenolic compounds.

改質酚樹脂，因阻燃性優異，故較佳。 Among them, those containing a large amount of aromatic skeletons in the molecular structure are particularly preferable from the viewpoint of the flame retardant effect, specifically, phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified Phenol resins, phenol aralkyl resins, naphthol aralkyl resins, naphthol novolak resins, naphthol-phenol novolak resins, naphthol-cresol novolak resins, biphenyl modified phenol resins, Biphenyl modified naphthol resin, amino three

Modified phenolic resin is preferable because of its excellent flame retardancy.

When using the above-mentioned curing agent for epoxy resin together, from the viewpoint of dielectric properties, the usage amount is preferably in the range of 10 to 50% by mass relative to the resin component of the composition.

Moreover, a hardening accelerator can also be used together suitably as needed. Various hardening accelerators can be used, and examples thereof include phosphorus-based compounds, amine-based compounds, imidazoles, organic acid metal salts, Lewis acids, and amine zirconium salts. In particular, when used as a buildup material or a circuit board, dimethylaminopyridine and imidazole are preferable from the viewpoint of excellent heat resistance, dielectric properties, solder resistance, and the like. In particular, when used as a semiconductor encapsulating material, triphenylphosphine is preferable for phosphorus compounds, and triphenylphosphine is preferable for amines from the viewpoint of excellent curability, heat resistance, electrical characteristics, and moisture resistance reliability. It is preferably 1,8-diacribicyclo-[5.4.0]-undecene (DBU).

Examples of the aforementioned phosphorus-based compounds include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; trimethyl phosphite, phosphorous acid Organic phosphite compounds such as triethyl esters; ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenyl tetraphenyl borate phosphonium, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, dicyanamide butylphenyl Phosphonium, phosphonium salts such as tetrabutylphosphonium decanoate, etc.

Examples of the aforementioned amine compounds include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (DMAP), 2,4,6-para(dimethylaminomethyl)phenol , 1,8-diacribicyclo[5,4,0]-undecene-7(DBU), 1,5-diacribicyclo[4,3,0]-nonene-5(DBN), etc.

Examples of the aforementioned imidazole include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl Imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyano Ethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, trimellitic acid-1-cyanoethyl- 2-undecylimidazolium salt, trimellitic acid-1-cyanoethyl-2-phenylimidazolium salt, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5 -Dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 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 and the like.

The curable composition of the present invention may contain other components in addition to the aforementioned aromatic ester compound (A), the aforementioned maleimide compound (B), and the aforementioned epoxy compound (C). 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.

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、聚伸苯基醚樹脂、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 resin components are not particularly limited, but include polyester resins other than the aforementioned aromatic ester compound (A), imide resins other than the aforementioned maleimide compound (B), and cyanate esters. (cyanate ester) resin, 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, polyphenylene ether resin, polybutadiene resin, etc. These other resins may be used alone or in combination of two or more.

The polyester resin other than the aromatic ester compound (A) is not particularly limited, but generally, phenolic esters, thiophenolic esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc. are preferably used. A compound having two or more highly reactive ester groups in one molecule. The aforementioned polyester resin is preferably obtained by condensation reaction of carboxylic acid compound and/or thiocarboxylic acid compound with hydroxyl compound and/or mercapto compound. In particular, from the viewpoint of improving heat resistance, polyester resins derived from carboxylic acid compounds or their halides, and hydroxyl compounds are preferred, more preferably polyester resins derived from carboxylic acid compounds or their halides, and phenol compounds and/or Or polyester resin of naphthol compound. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromeltaric acid, and the like, or their halides. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, phenol peptide, methylated bisphenol A, formazan Hydroxylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxy Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadiene-phenol addition type resin, etc.

Specifically, the polyester resin is preferably a polyester resin containing a dicyclopentadiene-phenol addition structure, a polyester resin containing a naphthalene structure, a polyester resin that is an acetylated product of phenol novolak, a polyester resin that is a phenol novolac Benzoyl polyester resins of novolaks, etc. Among them, polyester resins containing a dicyclopentadiene-phenol addition structure and polyester resins containing a naphthalene structure are more preferable because they are excellent in improving peel strength. More specifically, the compound represented by following general formula (iv) is mentioned as a polyester resin containing a dicyclopentadiene-phenol addition structure.

[wherein, R ^b is phenyl or naphthyl, d represents 0 or 1, and h is 0.05 to 2.5 in terms of the average value of repeating units. ]

From the viewpoint of reducing the dielectric dissipation factor of the cured product of the resin composition and improving heat resistance, Rb is preferably a naphthyl group, d is preferably 0, and h is preferably 0.25 to 1.5.

The aforementioned cyanate resins include, for example: bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol E type cyanate resin, bisphenol S type cyanate resin, bisphenol M type Cyanate resin, bisphenol P cyanate resin, bisphenol Z cyanate resin, bisphenol AP cyanate resin, bisphenol thioether cyanate resin, phenylene ether cyanate Resin, naphthyl ether type cyanate resin, biphenyl type cyanate resin, tetramethylbiphenyl type cyanate resin, polyhydroxynaphthalene type cyanate resin, phenol novolac type cyanate resin, formazan Phenol novolak type cyanate resin, triphenylmethane type cyanate resin, tetraphenylethane type cyanate resin, dicyclopentadiene-phenol addition reaction type cyanate resin, phenol aralkyl type Cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol novolak type cyanate ester resin, naphthol-cresol novolak type Cyanate resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate resin, biphenyl modified novolac type cyanate resin, anthracene type cyanate resin, etc. These may be used individually, respectively, and may use 2 or more types together.

Among these cyanate resins, bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol E type cyanate resin, bisphenol E type cyanate resin, etc. Ester resins, polyhydroxynaphthalene-type cyanate resins, naphthyl ether-type cyanate resins, and novolac-type cyanate resins, dicyclopentadiene is preferred because a hardened product with excellent dielectric properties can be obtained. Alkene-phenol addition reaction type cyanate ester resin.

樹脂，並沒有特別限制，可列舉例如：雙酚F與福馬林與苯胺之反應生成物(F-a型苯并

樹脂)、二胺基二苯基甲烷與福馬林與苯酚之反應生成物(P-d型苯并

樹脂)、雙酚A與福馬林與苯胺之反應生成物、二羥基二苯基醚與福馬林與苯胺之反應生成物、二胺基二苯基醚與福馬林與苯酚之反應生成物、雙環戊二烯-苯酚加成型樹脂與福馬林與苯胺之反應生成物、酚肽與福馬林與苯胺之反應生成物、二苯基硫醚與福馬林與苯胺之反應生成物等。此等可各自單獨使用，亦可併用2種以上。 As the aforementioned benzo

The resin is not particularly limited, for example: the reaction product of bisphenol F, formalin and aniline (Fa type benzo

resin), diaminodiphenylmethane and the reaction product of formalin and phenol (Pd type benzo

Resin), the reaction product of bisphenol A and formalin and aniline, the reaction product of dihydroxy diphenyl ether and formalin and aniline, the reaction product of diamino diphenyl ether and formalin and phenol, bicyclic The reaction product of pentadiene-phenol addition type resin and formalin and aniline, the reaction product of phenol peptide and formalin and aniline, the reaction product of diphenyl sulfide and formalin and aniline, etc. These may be used individually, respectively, and may use 2 or more types together.

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.

In one embodiment, the composition may also contain additives. Examples of such additives include hardening accelerators, flame retardants, fillers, and the like other than the hardening accelerators described above for epoxy resins.

The curing accelerator is not particularly limited, but examples thereof include guanidine-based curing accelerators, urea-based curing accelerators, peroxides, and azo compounds.

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.

、過氧化苯甲醯、過氧化對氯苯甲醯、過氧化二(三級丁基)、過氧化碳酸二異丙酯(diisopropyl peroxycarbonate)、過氧化碳酸二(2-乙基己基)酯(di-2-ethylhexyl peroxycarbonate)、偶氮雙異丁腈等。 Examples of the aforementioned peroxides and azo compounds include diperoxides,

, benzoyl peroxide, p-chlorobenzoyl peroxide, bis(tertiary butyl) peroxide, diisopropyl peroxycarbonate (diisopropyl peroxycarbonate), bis(2-ethylhexyl) peroxycarbonate ( di-2-ethylhexyl peroxycarbonate), azobisisobutyronitrile, etc.

、2-乙基-4-甲基咪唑、二甲基胺基吡啶。 Among the above-mentioned hardening accelerators, it is preferable to use diperoxide

, 2-ethyl-4-methylimidazole, 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.

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), diphenylphosphine benzene Base-1,4-dioxynaphthalene, 1,4-cyclooctylene phosphinyl-1,4-phenyldiol (1,4-cyclooctylene phosphinyl-1,4-phenyldiol), 1,5- Phosphorus-containing phenols such as cyclooctylphosphine oxide-1,4-phenyldiol; 9,10-dihydro-9-oxa-10-phosphinephenanthrene-10-oxide, 10-(2,5- Dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10- Cyclic phosphorus compounds such as oxides; 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 thereof include brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2, -bis(tetrabromophthalimide), 2,4,6-paraffin(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.

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.

According to an embodiment of the present invention, there is provided a cured product, which is a curable composition containing the above-mentioned aromatic ester compound (A), maleimide compound (B) and epoxy compound (C) Hardened.

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

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) has a low dielectric loss factor because of its own low dielectric loss factor, so the hardened product has a low dielectric loss factor, and because it is mixed with a maleimide compound (B) and an epoxy compound ( C) It reacts to become a hardened product with better heat resistance, so it can be used in electronic materials such as semiconductor packaging substrates, printed 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.

Synthesis Example 1

In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, fill 268g (2.0 moles) of o-allylphenol and 1200g of toluene, and replace the system with nitrogen under reduced pressure to dissolve it. Next, 203 g (1.0 mol) of isophthaloyl chloride was charged, and nitrogen substitution was performed in the system to dissolve it. Thereafter, 0.6 g of tetrabutylammonium bromide was dissolved, the inside of the system was controlled to 60° C. or lower while nitrogen flushing, and 412 g of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Next, stirring was continued for 1.0 hour under the same conditions. After the reaction, the liquid was separated and the water layer was removed. Water was further added into the toluene phase in which the reactant was dissolved, stirred and mixed for about 15 minutes, left to stand for liquid separation, and the water layer was removed. This operation was repeated until the pH of the aqueous layer became 7. Thereafter, it was heated and dried under reduced pressure to obtain 370 g of active ester resin (A-1) represented by the following structural formula. The ester group equivalent weight of this active ester resin (A-1) was 199 g/eq, the allyl group equivalent weight was 199 g/eq, and the E-type viscosity (25° C.) was 6000 mPa.s.

Synthesis Example 2-1 (Synthesis of Allylated Form of 1-Naphthol)

In a flask equipped with a stirring device, a reflux condenser, and a thermometer, fill 144g (1 mol) of 1-naphthol, 200g of methyl isobutyl ketone, and 99.5g (1.3 mol) of allyl chloride, and heat to 80°C After uniformly dissolving, a 10% aqueous solution of sodium hydroxide (1.3 mol) was added dropwise through a dropping funnel over 2 hours while stirring, and after the addition was completed, the reaction was further stirred for 1 hour. After the reaction, the reaction solution separated into two layers was transferred to a separatory funnel, and the lower water layer was separated and removed, and the organic layer was washed 5 times with 500 ml of distilled water. Next, methyl isobutyl ketone was completely distilled off under reduced pressure to obtain a reddish-brown liquid reactant. Next, this reaction product was transferred to a flask, heated to 150° C. and stirred for 2 hours to perform a rearrangement reaction. As a result, an allylated body of 1-naphthol represented by the following structural formula was obtained. The hydroxyl equivalent of the allylated body of 1-naphthol was 195 g/eq.

Synthesis example 2-2

In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, fill 390 g (2.0 moles) of the allylated body of 1-naphthol obtained above and 1,560 g of toluene, and decompose in the system. Pressurized nitrogen was replaced to dissolve it. Next, 203 g (1.0 mol) of isophthaloyl chloride was charged, and nitrogen substitution was performed in the system to dissolve it. Thereafter, 0.8 g of tetrabutylammonium bromide was dissolved, the inside of the system was controlled to 60° C. or lower while purging with nitrogen, and 412 g of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Next, stirring was continued for 1.0 hour under the same conditions. After the reaction, the liquid was separated and the water layer was removed. Water was further added into the toluene phase in which the reactant was dissolved, stirred and mixed for about 15 minutes, left to stand for liquid separation, and the water layer was removed. This operation was repeated until the pH of the aqueous layer became 7. Thereafter, it was heated and dried under reduced pressure to obtain 510 g of active ester resin (A-2) represented by the following structural formula. The ester group equivalent weight of this active ester resin (A-2) was 259 g/eq, the allyl group equivalent weight was 259 g/eq, and the softening point was 62°C.

Comparative Synthesis Example 1

In a flask equipped with a thermometer, dropping funnel, condenser, fractionating tube, and stirrer, fill 165g of dicyclopentadiene and phenol compound addition reaction resin (hydroxyl equivalent: 165g/eq, softening point: 85°C) 165g, α -Naphthol 72g (0.5 mol) and toluene 630g, nitrogen substitution in the system under reduced pressure to dissolve. Next, 152 g (0.75 mol) of isophthaloyl chloride was charged, and the system was replaced with nitrogen under reduced pressure to dissolve it. Thereafter, 0.6 g of tetrabutylammonium bromide was dissolved, the inside of the system was controlled to 60° C. or lower while purging with nitrogen, and 315 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Next, stirring was continued for 1.0 hour under the same conditions. After the reaction, the liquid was separated and the water layer was removed. Water was further poured into the toluene layer in which the reactants were dissolved, stirred and mixed for about 15 minutes, left to stand for liquid separation, and the water layer was removed. This operation was repeated until the pH of the aqueous layer became 7. Thereafter, it was heated and dried under reduced pressure to synthesize an active ester resin (A'). The ester group equivalent weight of this active ester resin (A') is 223g/eq, and the softening point is 150°C.

Embodiment 1~4 and comparative example 1~4

Each component was blended in the ratio shown in the following table, and the curable composition was obtained. 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. Display the results in a table.

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

‧Maleimide compound (B-1): 4,4'-diphenylmethanebismaleimide ("BMI-1000" manufactured by Daiwa Chemical Co., Ltd., maleimide equivalent weight 179g/ Equivalent)

‧Epoxy resin (C-1): Dicyclopentadiene phenol-type epoxy resin ("EPICLONHP-7200H" produced by DIC Co., Ltd. has an epoxy group equivalent of 277g/equivalent)

‧Epoxy resin (C-2): Bisphenol A type epoxy resin ("EPICLON850S" produced by DIC Co., Ltd. has an epoxy group equivalent of 188g/equivalent)

‧DABPA: Diallyl bisphenol A ("DABPA" manufactured by Daiwa Chemical Co., Ltd., allyl equivalent weight: 154g/eq)

‧DMAP:、Dimethylaminopyridine

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.

Determination 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 Technology Co., Ltd., the dielectric loss factor of the test piece at 1 GHz was measured by the cavity resonance method.

Claims (7)

A curable composition, which contains an aromatic ester compound (A), a maleimide compound (B), and an epoxy compound (C) represented by the following structural formula (1),

(In the above chemical formula (1), Ar ¹ is a substituted or unsubstituted first aromatic ring group, and Ar ² is independently substituted or unsubstituted the second aromatic ring group. At this time, the aforementioned At least one of Ar ¹ and the aforementioned Ar ² has a substituent containing a polymerizable unsaturated bond, n is an integer of 2 or 3). The curable composition according to Claim 1, which contains 5 to 300 parts by mass of the aforementioned maleimide compound (B), and 5 to 300 parts by mass of The aforementioned epoxy compound (C). The curable composition according to claim 1 or 2, which further contains peroxide. A cured product of the curable composition according to any one of claims 1 to 3. A printed wiring board formed using the curable composition according to any one of claims 1 to 3. A semiconductor packaging material formed by using the curable composition according to any one of claims 1 to 3. A build-up film formed using the curable composition according to any one of claims 1 to 3.