WO2021070416A1

WO2021070416A1 - Thermosetting resin composition, cured product thereof, and structural body including said cured product

Info

Publication number: WO2021070416A1
Application number: PCT/JP2020/023639
Authority: WO
Inventors: 千佳峯崎
Original assignee: 昭和電工株式会社
Priority date: 2019-10-09
Filing date: 2020-06-16
Publication date: 2021-04-15
Also published as: TWI747338B; JPWO2021070416A1; TW202116908A; JP7367766B2

Abstract

[Problem] To provide a thermosetting resin composition that has excellent adherence and adhesiveness with respect to metals without compromising moldability. [Solution] This thermosetting resin composition contains a poly alkenyl phenol compound (A), a poly maleimide compound (B), a compound (C) having a structure set forth in formula (1), and a radical initiator (D). (In the formula, R¹ and R² each represent a hydrogen atom, a halogen atom, an alkyl group having 1-3 carbon atoms, a hydroxyl group, a carboxy group, or an amino group, at least one of R¹ and R² represents an amino group, R³ represents a hydrogen atom, an alkyl group having 1-3 carbon atoms, an alkenyl group having 2-3 carbon atoms, or a cyano group, and R⁴ represents a hydrogen atom or an alkyl group having 1-3 carbon atoms.)

Description

A thermosetting resin composition, a cured product thereof, and a structure containing the cured product.

The present invention relates to a thermosetting resin composition, a cured product thereof, a method for producing a structure using the thermosetting resin composition, and a structure containing the cured product.

In recent years, semiconductor packages used in electronic devices and industrial devices have been required to have high-density wiring, miniaturization, thinning, high heat resistance, high heat dissipation, and other performances due to the high-density integration of electronic components. There is. Therefore, the encapsulant, which is a plastic material, is also required to have high heat resistance.

In transfer molding, the material is heated and softened in the plunger, and the heated and softened material is pushed into the heated mold cavity through the flow path in the mold such as a gate, sprue, and runner, and inside the mold cavity. It is a method of curing with. Since the material is injected into the cavity in a highly fluid state, it can be molded at low pressure. Transfer molding is characterized in that it is less likely to damage the insert than other molding methods that require high pressure. Transfer molding is known as a typical molding method in sealing molding of power semiconductors and ICs because it can be miniaturized and microfabricated and has high productivity.

Conventionally, an epoxy-phenolic thermosetting resin material has been used as a sealing material used in transfer molding. However, it is difficult to meet the recent demand for high heat resistance with conventional materials. In order to meet the demand for high heat resistance, encapsulants with various resin systems, such as thermosetting resin compositions containing a large amount of polyfunctional epoxy resin, bismaleimide, triazine skeleton, benzoxazine skeleton, and silsesquioki Thermosetting resin compositions and the like containing a highly heat-resistant structure such as a sun skeleton have been proposed.

Patent Document 1 (Japanese Unexamined Patent Publication No. 11-14277) describes (A) a phenol resin containing 30 to 100 parts by mass of a novolak-structured phenol resin containing a biphenyl derivative and / or a naphthalene derivative in the molecule. (B) An epoxy resin containing 30 to 100 parts by mass of a novolak-structured epoxy resin containing a biphenyl derivative and / or a naphthalene derivative in the molecule, (C) an inorganic filler, and (D) a curing accelerator. Describes an epoxy resin composition for encapsulating a semiconductor, which is characterized by being an essential component.

Patent Document 2 (Japanese Unexamined Patent Publication No. 5-43630) describes an aromatic bismaleimide containing N, N'-(alkyl-substituted diphenylmethane) bismaleimide and polyallylphenol from condensed polyphenol of salicylaldehyde and phenol. Describes the resin composition.

Patent Document 3 (Japanese Unexamined Patent Publication No. 5-6869) describes (A) a maleimide compound having two or more maleimide groups in one molecule, (B) an allylated phenol resin having a specific repeating unit, and (C). A semiconductor device in which a semiconductor element is sealed using a resin composition containing a curing catalyst is described.

Patent Document 4 (Japanese Unexamined Patent Publication No. 6-93047) describes a curable resin composition in which a maleimide compound, an alkenylphenol compound having a specific structure, and an epoxy group-containing organic silane compound are blended in a specific ratio.

Japanese Unexamined Patent Publication No. 11-14277 Japanese Unexamined Patent Publication No. 5-43630 Japanese Unexamined Patent Publication No. 5-6869 Japanese Unexamined Patent Publication No. 6-93047

It is known that the heat resistance of the molded product is improved by using the bismaleimide resin as compared with the epoxy-phenolic thermosetting resin material which has been conventionally used (Patent Documents 2 to 4). However, the conventional encapsulant using bismaleimide resin has a drawback that the adhesion to other members, particularly metal materials, is very low as compared with the epoxy-phenolic thermosetting resin material. The electronic device contains metal parts such as a conductor and copper that is responsible for cooling, and if peeling occurs between the metal and the sealing material, there is a problem in terms of internal protection. Therefore, it is an issue to improve the adhesion between the metal and the sealing material. On the other hand, if the adhesion to the molding die is improved, the mold cannot be separated without being separated, which poses a problem in production. Therefore, it is strongly desired to realize a sealing material that is easy to mold and has a high adhesion to a metal.

In the present disclosure, a thermosetting resin composition having excellent adhesion to a metal and adhesiveness without impairing moldability is described.

The present invention includes the following aspects.
[1]
A thermosetting resin composition containing a polyalkenylphenol compound (A), a polymaleimide compound (B), a compound (C) having the structure according to the formula (1), and a radical initiator (D).

(In the formula, R ¹ and R ² are hydrogen atoms, halogen atoms, alkyl groups having 1 to 3 carbon atoms, hydroxyl groups, carboxy groups, or amino groups, and ^{at least one of R 1} and R ² is an amino group. R ³ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a cyano group, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. is there.)
[2]
The compound (C) is 6-aminoindazole, 5-aminoindazole, 6-amino-5-methylindazole, 6-amino-5-ethylindazole, 6-amino-5-hydroxyindazole, 6-amino-5-. The above aspect 1 comprises at least one selected from bromoindazole, 6-amino-5-chloroindazole, 3-cyano-5-aminoindazole, 5-carboxy-6-aminoindazole, and 5,6-diaminoindazole. The thermocurable resin composition according to the above.
[3]
The thermosetting resin composition according to the above aspect 2, wherein the compound (C) contains at least one selected from 5-aminoindazole and 6-aminoindazole.
[4]
The contents of the compound (C) are 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass in total of the polyalkenylphenol compound (A) and the polymaleimide compound (B). The thermosetting resin composition according to any one of.
[5]
The thermosetting resin composition according to any one of the above aspects 1 to 4, wherein the amount of the polyalkenylphenol compound (A) is 5 to 200 parts by mass with respect to 100 parts by mass of the polymaleimide compound (B). ..
[6]
The polyalkenylphenol compound (A) is represented by the formula (2) -1 :.

And optionally equation (2) -2:

In formulas (2) -1 and (2) -2, R ⁵ independently has a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms, respectively. Represents an alkoxy group of 5, and R ⁶ is an independent formula (3):

In formula (3), R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, and carbon atoms, respectively. It is a cycloalkyl group of number 5 to 10 or an aryl group having 6 to 12 carbon atoms, where * in the formula (3) represents a bond with a carbon atom constituting an aromatic ring, and R ⁵ and R ⁶ are. or different may be the same for each phenol backbone units of the formula (2) -1 and the formula (2) wherein -CR ¹² Q are each independently of -2 R ¹³ - in the alkylene group represented, the number of carbon atoms Represents a cycloalkylene group of 5 to 10, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent organic group in which these are combined, and R ¹² and R ¹³ represent. Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. The thermosetting resin composition according to any one of the above aspects 1 to 5.
[7]
When the average number of structural units shown in formula (2) -1 per molecule is p and the average number of structural units shown in formula (2) -2 per molecule is q, p is 1.1 to The thermosetting resin according to the above aspect 6, wherein 35 is a real number, p + q is a real number of 1.1 to 35, and q is a real number having a value of the formula: p / (p + q) of 0.4 to 1. Composition.
[8]
The thermosetting resin composition according to any one of the above aspects 1 to 7, wherein the polymaleimide compound (B) is an aromatic bismaleimide compound.
[9]
The thermosetting resin composition according to any one of the above aspects 1 to 8, wherein the radical initiator (D) is an organic peroxide.
[10]
The thermosetting resin composition according to any one of the above aspects 1 to 9, further comprising a filler (E).
[11]
The thermosetting resin composition according to the above aspect 10, wherein the filler (E) is at least one selected from the group consisting of silica, alumina, magnesium oxide and solid rubber particles.
[12]
The content of the filler (E) is 100 parts by mass in total of the polyalkenylphenol compound (A), the polymaleimide compound (B), the compound (C), and the radical initiator (D). The thermosetting resin composition according to the above aspect 10 or 11, which is 200 to 1900 parts by mass.
[13]
A cured product of the thermosetting resin composition according to any one of the above aspects 1 to 12.
[14]
A method for producing a structure, wherein the thermosetting resin composition according to any one of the above aspects 1 to 12 is molded by molding.
[15]
A structure containing the cured product according to the above aspect 13.

According to the present disclosure, it is possible to obtain a thermosetting resin composition having excellent adhesion and adhesiveness to a metal without impairing moldability. The thermosetting resin composition of the present disclosure can be cured in an appropriate time and gives excellent productivity. A highly reliable cured product can be formed by using the thermosetting resin composition of the present disclosure.

The present invention will be described in detail below. The thermosetting resin composition of one embodiment contains a polyalkenylphenol compound (A), a polymaleimide compound (B), a compound (C) having the structure represented by the formula (1), and a radical initiator (D). Including.

[Polyalkenylphenol compound (A)]
The polyalkenylphenol compound (A) is a compound having at least two phenol skeletons in the molecule and having a 2-alkenyl group bonded to a part or all of the aromatic ring forming the phenol skeleton in the molecule. .. As the 2-alkenyl group, a group having a structure represented by the formula (3) is preferable.

In formula (3), R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, cycloalkyl groups having 5 to 10 carbon atoms, or carbons, respectively. It is an aryl group having 6 to 12 atoms. * In the formula (3) represents a bond with a carbon atom constituting an aromatic ring.

^{Specific examples of the alkyl group having 1 to 5 carbon atoms constituting R 7} , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ in the formula (3) include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. , N-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and the like. Specific examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cycloheptyl group and the like. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group, a naphthyl group and the like. It is preferable that the 2-alkenyl group represented by the formula (3) is an allyl group, that is, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are all hydrogen atoms.

In the polyalkenylphenol compound (A), a 2-alkenyl group is contained in preferably 40 to 100%, more preferably 60 to 100%, still more preferably 80 to 100% of the total aromatic rings forming the phenol skeleton. It is combined.

Known basic skeletons of the polyalkenylphenol compound (A) include phenol novolac resin, cresol novolac resin, triphenylmethane-type phenol resin, phenol aralkyl resin, biphenyl aralkyl phenol resin, and phenol-dicyclopentadiene copolymer resin. The skeleton of phenolic resin can be mentioned. Among them, the polyalkenylphenol compound (A) having the following formula (2) -1 and optionally the structural unit represented by the formula (2) -2 can be preferably used.

The structural units represented by the formulas (2) -1 and (2) -2 are preferable phenol skeleton units constituting the polyalkenylphenol compound (A), and the binding order of these phenol skeleton units is not particularly limited. In formulas (2) -1 and (2) -2, R ⁵ is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, respectively, and is represented by the formula (2). In) -1, R ⁶ is a 2-alkoxy group independently represented by the formula (3). R ⁵ and R ⁶ may be the same or different for each phenol skeleton unit. Equation (2) -1 and the formula (2) each Q is at -2 independently formula -CR ¹² R ¹³ - in the alkylene group represented, a cycloalkylene group having 5 to 10 carbon atoms, divalent having an aromatic ring , A divalent organic group having an alicyclic condensed ring, or a divalent organic group in combination thereof. R ¹² and R ¹³ are independently hydrogen atoms and alkyl having 1 to 5 carbon atoms, respectively. A group, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

When the average number of structural units represented by the formula (2) -1 per molecule is p and the average number of structural units represented by the formula (2) -2 per molecule is q, p is preferably 1. A real number of 1 to 35, p + q is a real number of 1.1 to 35, and q satisfies a real number in which the value of the formula: p / (p + q) is 0.4 to 1.

Specific examples of the alkyl group having 1 to 5 carbon atoms constituting R ⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, and n. -Pentyl group and the like can be mentioned. Specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group and the like. Can be mentioned.

Formula -CR ¹² R ¹³ - in R ¹² and R ¹³ of the alkylene group represented by, specific examples of the alkyl group having 1 to 5 carbon atoms, a methyl group, an ethyl group, n- propyl group, an isopropyl group, Examples thereof include n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and specific examples of the alkyl group having 2 to 6 carbon atoms include vinyl group, allyl group, butenyl group, and pentenyl. Groups, hexenyl groups and the like can be mentioned, and specific examples of cycloalkyl groups having 5 to 10 carbon atoms include cyclopentyl groups, cyclohexyl groups, methylcyclohexyl groups, cycloheptyl groups and the like, and have carbon atoms. Specific examples of the aryl groups 6 to 12 include a phenyl group, a methylphenyl group, an ethylphenyl group, a biphenyl group, a naphthyl group and the like.

Specific examples of the cycloalkylene group having 5 to 10 carbon atoms constituting Q include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, a cycloheptylene group and the like. Specific examples of the divalent organic group having an aromatic ring include a phenylene group, a tolylen group, a naphthylene group, a biphenylene group, a fluorenylene group, an anthracenylene group, a xylylene group, a 4,4-methylenediphenyl group and the like. The number of carbon atoms of the divalent organic group having an aromatic ring can be 6 to 20 or 6 to 14. Specific examples of the divalent organic group having an alicyclic condensed ring include a dicyclopentadienylene group and the like. The number of carbon atoms of the divalent organic group having an alicyclic condensed ring can be 7 to 20 or 7 to 10.

It is preferable that Q is a dicyclopentadienylene group, a phenylene group, a methylphenylene group, a xylylene group, or a biphenylene group in terms of high mechanical strength of the cured product. Since the viscosity of the polyalkenylphenol compound (A) is low and it is advantageous for mixing with the polymaleimide compound (B), it is preferable that _{Q is −CH 2−.}

P is preferably a real number of 1.1 to 35, more preferably a real number of 2 to 30, and even more preferably a real number of 3 to 10. When p is 1.1 or more, the thermal decomposition start temperature when the cured product of the thermosetting resin composition is placed in a high temperature environment is appropriate, and when p is 35 or less, the viscosity of the thermosetting resin composition Is in a suitable range depending on the processing at the time of molding.

P + q is preferably a real number of 1.1 to 35, more preferably a real number of 2 to 30, and even more preferably a real number of 3 to 10. When p + q is 1.1 or more, the thermal decomposition start temperature when the cured product of the thermosetting resin composition is placed in a high temperature environment is appropriate, and when it is 35 or less, the viscosity of the thermosetting resin composition Is in a suitable range depending on the processing at the time of molding.

q is preferably a real number having a value of the formula: p / (p + q) of 0.4 to 1, and more preferably a real number having a value of the formula: p / (p + q) of 0.6 to 1. More preferably, it is a real number in which the value of the formula: p / (p + q) is 0.8 to 1. Equation: When the value of p / (p + q) is 1, q is 0. That is, in this embodiment, the polyalkenylphenol compound (A) does not contain the structural unit represented by the formula (2) -2. The polyalkenylphenol compound (A) can consist of the structural units represented by the formula (2) -1. When q is a value satisfying the above conditions, the degree of curing of the thermosetting resin composition can be made sufficient depending on the application.

The preferred number average molecular weight Mn of the polyalkenylphenol compound (A) is 300 to 5000, more preferably 400 to 4000, and even more preferably 500 to 3000. When the number average molecular weight Mn is 300 or more, the thermal decomposition start temperature is appropriate when the cured product of the thermosetting resin composition is placed in a high temperature environment, and when it is 5000 or less, the viscosity of the thermosetting resin composition. Is in a suitable range depending on the processing at the time of molding.

The polyalkenylphenol compound (A) can be obtained by converting a part of the hydroxyl groups of the raw material phenol resin into alkenyl ether and then rearranging the 2-alkenyl group by the Claisen rearrangement reaction. As the raw material phenol resin, a known phenol resin having a structural unit represented by the following formula (2) -2 can be preferably used.

Specific examples of the raw material phenol resin of the polyalkenylphenol compound (A) include phenol novolac resin, cresol novolac resin, triphenylmethane type phenol resin, phenol aralkyl resin, biphenyl aralkyl resin, phenol-dicyclopentadiene copolymer resin and the like. Can be mentioned.

The 2-alkenyl etherification reaction of the raw material phenol resin includes (i) a known method for reacting a halogenated 2-alkenyl compound such as allyl chloride, methallyl chloride, and allyl bromide with a phenol compound, and (ii) allyl acetate. Two known methods of reacting such a carboxylic acid 2-alkenyl compound with a phenol compound can be exemplified. For the 2-alkenyl etherification reaction using a halogenated 2-alkenyl compound, for example, the method described in JP-A-2-91113 can be used. As a method for reacting the carboxylic acid 2-alkenyl compound with the phenol resin, for example, the method described in JP-A-2011-26253 can be used.

The amount of the halogenated 2-alkenyl compound or the carboxylic acid 2-alkenyl compound used with respect to the phenolic hydroxyl group is preferably 0.4 to 5.0 equivalents, more preferably 0.6 to 4.0 equivalents. When the amount is 0.4 equivalent or more, the amount of the reaction site with the polymaleimide compound (B) after the Claisen rearrangement is more appropriate, and a cured product having more excellent heat resistance can be obtained. The 2-alkenyl etherification reaction is carried out by mixing the 2-alkenyl compound with the raw material phenol resin and reacting for 4 to 40 hours. In the 2-alkenyl etherification reaction, a solvent in which the raw material phenol resin dissolves can be used. The reaction can also be carried out without a solvent using a carboxylic acid 2-alkenyl compound capable of dissolving the raw material phenol resin. The 2-alkenyl etherification rate of the raw material phenol resin is determined by using a larger amount of the halogenated 2-alkenyl compound or the carboxylic acid 2-alkenyl compound than the above amount and adjusting the reaction time to be shorter than the above reaction time. It can also be controlled by suppressing the reaction rate (conversion rate) of the 2-alkenyl compound to a low level.

The target polyalkenylphenol compound (A) can be obtained by subjecting the polyalkenyl ether compound produced by the method according to (i) or (ii) above to a Claisen rearrangement reaction. The Claisen rearrangement reaction can be carried out by heating the polyalkenyl ether compound to a temperature of 100 to 250 ° C. and reacting it for 1 to 20 hours. The Claisen rearrangement reaction may be carried out using a solvent having a high boiling point, or may be carried out without a solvent. Inorganic salts such as sodium thiosulfate and sodium carbonate can also be added to promote the rearrangement reaction. Details are disclosed in, for example, Japanese Patent Application Laid-Open No. 2-911113.

[Polymaleimide compound (B)]
The polymaleimide compound (B) is a compound having two or more maleimide groups represented by the formula (4).

In the formula (4), * represents an aromatic ring or a bond with an organic group containing a straight chain, a branched chain or a cyclic aliphatic hydrocarbon group.

Examples of the polymaleimide compound (B) include bismaleimide such as bis (4-maleimidephenyl) methane, trismaleimide such as tris (4-maleimidephenyl) methane, and tetraxmaleimide such as bis (3,4-dimaleimidephenyl) methane. And polymaleimide such as poly (4-maleimide styrene). Examples of the polymaleimide compound include an aromatic polymaleimide compound and an aliphatic polymaleimide compound, and the aromatic polymaleimide compound is preferable in that the obtained cured product has particularly excellent flame retardancy.

An aromatic polymaleimide compound is a compound having two or more maleimide groups represented by the formula (4), and these maleimide groups are bonded to the same or different aromatic rings. Specific examples of the aromatic ring include a monocyclic ring such as benzene, a condensed ring such as naphthalene and anthracene, and the like. The polymaleimide compound (B) is preferably an aromatic bismaleimide compound and an aliphatic bismaleimide compound, and more preferably an aromatic bismaleimide compound because it mixes well in the thermosetting resin composition. .. Specific examples of the aromatic bismaleimide compound include bis (4-maleimidephenyl) methane, bis (3-maleimidephenyl) methane, bis (3-methyl-4-maleimidephenyl) methane, and bis (3,5-dimethyl-). 4-maleimidephenyl) methane, bis (3-ethyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane, bis (3-propyl-4-maleimidephenyl) methane, bis ( 3,5-Dipropyl-4-maleimidephenyl) methane, bis (3-butyl-4-maleimidephenyl) methane, bis (3,5-dibutyl-4-maleimidephenyl) methane, bis (3-ethyl-4-maleimide) -5-Methylphenyl) methane, 2,2-bis (4-maleimidephenyl) propane, 2,2-bis [4- (4-maleimidephenyloxy) phenyl] propane, bis (4-maleimidephenyl) ether, bis (3-Maleimidephenyl) ether, bis (4-maleimidephenyl) ketone, bis (3-maleimidephenyl) ketone, bis (4-maleimidephenyl) sulfone, bis (3-maleimidephenyl) sulfone, bis [4- (4) -Maleimidephenyloxy) phenyl] sulfone, bis (4-maleimidephenyl) sulfide, bis (3-maleimidephenyl) sulfide, bis (4-maleimidephenyl) sulfoxide, bis (3-maleimidephenyl) sulfoxide, 1,4-bis (4-Maleimidephenyl) Cyclohexane, 1,4-Dimareimidenaphthalene, 2,3-Dimareimidenaphthalene, 1,5-Dimareimidenaphthalene, 1,8-Dimareimidenaphthalene, 2,6-Dimareimidenaphthalene, 2, 7-Dimareimide naphthalene, 4,4'-Dimareimide biphenyl, 3,3'-Dimareimide biphenyl, 3,4'-Dimareimide biphenyl, 2,5-Dimareimide-1,3-xylene, 2,7-di Maleimide fluorene, 9,9-bis (4-maleimidephenyl) fluorene, 9,9-bis (4-maleimide-3-methylphenyl) fluorene, 9,9-bis (3-ethyl-4-maleimidephenyl) fluorene, 3,7-Dimareimide-2-methoxyfluorene, 9,10-Dimareimide phenanthrene, 1,2-Dimareimide anthraquinone, 1,5-Dimareimide anthraquinone, 2,6-Dimareimide anthraquinone, 1,2-Zimarei Midbenzene, 1,3-dimaleimidebenzene, 1,4-dimaleimidebenzene, 1,4-bis (4-maleimidephenyl) benzene, 2-methyl-1,4-dimaleimidebenzene, 2,3-dimethyl-1 , 4-dimaleimidebenzene, 2,5-dimethyl-1,4-dimaleimidebenzene, 2,6-dimethyl-1,4-dimaleimidebenzene, 4-ethyl-1,3-dimaleimidebenzene, 5-ethyl -1,3-dimaleimidebenzene, 4,6-dimethyl-1,3-dimaleimidebenzene, 2,4,6-trimethyl-1,3-dimaleimidebenzene, 2,3,5,6-tetramethyl- Examples thereof include 1,4-dimaleimidebenzene and 4-methyl-1,3-dimaleimidebenzene. Specific examples of the aliphatic bismaleimide compound include bis (4-maleimidecyclohexyl) methane and bis (3-maleimidecyclohexyl) methane. Of these, bis (4-maleimidephenyl) methane and 2,2-bis [4- (4-maleimidephenyloxy) phenyl] propane are preferable. Examples of commercially available products include the BMI (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) series.

When the polymaleimide compound (B) is 100 parts by mass, the blending amount of the polyalkenylphenol compound (A) is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and 20 to 20 to 150 parts by mass. It is more preferably 130 parts by mass. When the compounding amount is 5 parts by mass or more, the fluidity at the time of molding is better. On the other hand, when the compounding amount is 200 parts by mass or less, the heat resistance of the cured product is better.

[Compound (C)]
Compound (C) is represented by the formula (1).

(In the formula, R ¹ and R ² are hydrogen atoms, halogen atoms, alkyl groups having 1 to 3 carbon atoms, hydroxyl groups, carboxy groups, or amino groups, and ^{at least one of R 1} and R ² is an amino group. R ³ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a cyano group, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. It is a compound represented by). Of these, one of R ¹ and R ² is preferably a hydrogen atom, and both ^{R 3} and R ^{4 are preferably hydrogen atoms.}

Specific examples of the halogen atom constituting R ¹ or R ² include a chlorine atom, a bromine atom, an iodine atom and the like. Specific examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like.
^{As R 1} or R ² other than the amino group, a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, a hydroxyl group and a carboxy group are preferable, and a hydrogen atom, a methyl group, an ethyl group, a hydroxyl group and a carboxy group are more preferable. , Hydrogen atom is more preferable.

Specific examples of the alkyl group having 1 to 3 carbon atoms constituting R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like. Specific examples of the alkenyl group having 2 to 3 carbon atoms include a vinyl group and an allyl group.
As R ³ , a hydrogen atom, a methyl group, an ethyl group, a vinyl group, an allyl group, and a cyano group are preferable, a hydrogen atom, a methyl group, an ethyl group, and a cyano group are more preferable, and a hydrogen atom is further preferable.

Specific examples of the alkyl group having 1 to 3 carbon atoms constituting R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like.
As R ⁴ , a hydrogen atom, a methyl group, and an ethyl group are preferable, a hydrogen atom and a methyl group are more preferable, and a hydrogen atom is further preferable.

Examples of the compound (C) include 6-aminoindazole, 5-aminoindazole, 6-amino-5-methylindazole, 6-amino-5-ethylindazole, 6-amino-5-hydroxyindazole, and 6-amino-5. Examples thereof include -bromoindazole, 6-amino-5-chloroindazole, 3-cyano-5-aminoindazole, 5-carboxy-6-aminoindazole, and 5,6-diaminoindazole. Of these, 6-aminoindazole and 5-aminoindazole are preferable because they are excellent in adjusting the gel time and having an affinity for the metal surface, particularly copper. By controlling the gel time within an appropriate range, it is considered that the wetting of the thermosetting resin composition with respect to the substrate can be improved.

Since ^{at least one of R 1} and R ² is an amino group, the curing rate of compound (C) can be adjusted in the curing reaction by radical polymerization. Without being bound by any theory, it is believed that the aniline moiety of compound (C) temporarily traps and stabilizes radicals, thereby adjusting the curing rate of the thermosetting resin composition. The radical polymerization rate is generally adjusted by the amount of the radical polymerization initiator. If the radical polymerization reaction rate of the composition is too fast, the initial curing of, for example, 0 to 30 seconds after the start of molding and curing proceeds in a state where sufficient wetting with respect to the base material cannot be ensured, and the distance between the cured product and the base material is increased. Sufficient adhesion is not obtained. However, if the amount of the radical polymerization initiator is reduced in order to slow down the radical polymerization, not only the initial curing but also the reaction rate in the middle stage of curing, for example, 30 seconds to 180 seconds after the start of molding curing, becomes slow, which is sufficient for removing the molded product from the mold. It takes longer to reach the desired hardness and productivity is reduced. By adding the compound (C), it is possible to prevent a decrease in productivity due to a delay in the curing rate while sufficiently ensuring wetting with respect to the base material. The pyrazole ring has higher chemical stability than the imidazole ring, which has a similar heterocyclic structure, and has a very high polymerization activity on the polymaleimide compound (B), which is catalyzed by the imidazole ring and causes a polymerization reaction. Low. This point is also excellent in terms of adjusting the curing speed.

Furthermore, compound (C) has a high affinity for metals, and the ^{amino group, which is at least one of R 1} and R ² , is an ethylenically unsaturated bond contained in the maleimide group of the polymaleimide compound (B). By the Michael addition reaction, compound (C) is covalently fixed in the molded product. By these actions, the compound (C) can act as a coupling agent between the resin and the metal surface, and can develop a strong adhesive force between the cured product and the metal base material.

The content of the compound (C) can be appropriately determined depending on the intended use, but is 0.05 parts by mass to 0.05 parts by mass with respect to 100 parts by mass in total of the polyalkenylphenol compound (A) and the polymaleimide compound (B). It is preferably 5 parts by mass, more preferably 0.2 parts by mass to 3 parts by mass, and further preferably 0.3 parts by mass to 2.5 parts by mass. If it is 0.05 part by mass or more, the adhesion to copper is better, and if it is 5 parts by mass or less, the function of adjusting the curing speed can be fully exhibited and the quick curing property can be maintained. Thereby, the appearance of the molded product and the moldability of the thermosetting resin composition can be improved.

[Radical initiator (D)]
Curing of the thermosetting resin composition can be promoted by blending the radical initiator (D) with the thermosetting resin composition. The radical initiator (D) is preferably a thermal radical initiator. Examples of the thermal radical initiator include organic peroxides. The organic peroxide is preferably an organic peroxide having a 10-hour half-life temperature of 100 to 170 ° C., specifically, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-). Butylperoxy) hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, and cumenehydroperoxide can be mentioned. The preferable amount of the radical initiator (D) to be used is 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the polyalkenylphenol compound (A), the polymaleimide compound (B), and the compound (C). , More preferably 0.05 to 7.5 parts by mass, and even more preferably 0.1 to 5 parts by mass. When the amount of the radical initiator (D) used is 0.01 parts by mass or more, the curing reaction proceeds sufficiently, and when it is 10 parts by mass or less, the storage stability of the thermosetting resin composition is better.

[Filler (E)]
The thermosetting resin composition may further contain a filler (E). The type of the filler (E) is not particularly limited, and examples thereof include solid rubber particles such as solid silicone rubber particles, organic fillers such as silicone powder, and inorganic fillers such as silica, alumina, magnesium oxide, and boron nitride. It can be appropriately selected depending on the intended use. The filler (E) is preferably at least one selected from the group consisting of silica, alumina, magnesium oxide, and solid rubber particles.

For example, when a thermosetting resin composition is used for semiconductor encapsulation, it is preferable to add an insulating inorganic filler in order to obtain a cured product having a low coefficient of thermal expansion. The inorganic filler is not particularly limited, and known materials can be used. Specific examples of the inorganic filler include silica such as amorphous silica and crystalline silica, and particles such as alumina, boron nitride, aluminum nitride, and silicon nitride. From the viewpoint of reducing the viscosity, spherical amorphous silica is desirable. The inorganic filler may be surface-treated with a silane coupling agent or the like, but may not be surface-treated.

The average particle size of the filler (E) is preferably 0.1 to 30 μm, and more preferably the maximum particle size is 100 μm or less, particularly 75 μm or less. When the average particle size is in this range, the viscosity of the thermosetting resin composition is appropriate at the time of use, and the injectability into a narrow pitch wiring portion or a narrow gap portion is also appropriate. The average particle size referred to here is a volume cumulative particle size D ₅₀ measured by a laser diffraction / scattering type particle size distribution measuring device.

The content of the filler (E) in the thermosetting resin composition can be appropriately determined according to the application. The content of the filler (E) in the thermosetting resin composition is 100 parts by mass in total of the polyalkenylphenol compound (A), the polymaleimide compound (B), the compound (C), and the radical initiator (D). On the other hand, it is preferably 200 to 1900 parts by mass, more preferably 300 to 1000 parts by mass, and further preferably 300 to 600 parts by mass.

As other additives, a defoaming agent, a coloring agent, a phosphor, a denaturing agent, a leveling agent, a light diffusing agent, a flame retardant, an adhesion imparting agent, a mold release agent, a coupling agent, etc. are blended in the thermosetting resin composition. It is also possible to do.

For example, as the release agent, various waxes such as ester waxes such as carnauba wax and montanic acid ester wax, amide-based waxes such as lauric acid amide, stearic acid amide, and N-stearyl erucate amide, polyethylene, and polyethylene oxide are appropriately selected. can do.

For example, examples of the coupling agent include vinyl triethoxysilane, vinyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and N-phenyl-3. -A silane coupling agent such as aminopropyltrimethoxysilane can be mentioned. The coupling agent may be used alone or in combination of two or more. The blending amount of the coupling agent in the thermosetting resin composition is preferably 0.1 to 5% by mass. When the blending amount is 0.1% by mass or more, the effect of the coupling agent is sufficiently exhibited, and when it is 5% by mass or less, the melt viscosity, the hygroscopicity and the strength of the cured product are more good.

[Method for preparing thermosetting resin composition]
The method for preparing the thermosetting resin composition is as long as the polyalkenylphenol compound (A), the polymaleimide compound (B), the compound (C), the radical initiator (D), and other optional components can be uniformly mixed and dispersed. There is no particular limitation. The method of first melting and mixing the polyalkenylphenol compound (A), the polymaleimide compound (B), and the compound (C), and then adding the radical initiator (D) and any additive is to make each material uniform. It is preferable because it is easy to mix.

The mixing method of each component is not particularly limited. Reaction vessel, pot mill, two-roll mill, three-roll mill, rotary mixer, twin-screw mixer, dispenser, single-screw or twin-screw (same direction or different direction) extruder, kneader, etc. It can be mixed by putting it in a mixer and stirring or kneading it. On a lab scale, a rotary mixer is preferable because the stirring conditions can be easily changed, and industrially, a twin-screw mixer is preferable from the viewpoint of productivity. Each mixer can be used by appropriately changing the stirring conditions.

When powdering the thermosetting resin composition, the method is not particularly limited as long as the resin is not melted by the heat generated in the work process, but it is convenient to use an agate mortar if the amount is small. When a commercially available crusher is used, it is preferable that the amount of heat generated during crushing is small in order to suppress the melting of the mixture. The particle size of the powder is preferably 1 mm or less.

[Method of manufacturing the structure]
The thermosetting resin composition can be melted by heating. A structure can be produced by molding the melted thermosetting resin composition into an arbitrary preferable shape, curing it if necessary, and removing the mold. As a method for producing the structure, molding molding, particularly transfer molding and compression molding are preferable. As preferable conditions for transfer molding, for example, in the case of a mold having a size of 10 mm × 75 mm × 3 mm, the temperature of the top plate and the mold is 170 to 190 ° C., the holding pressure is 50 to 150 kg / cm ² , and the holding time is set. It can be 1.5 to 10 minutes. As preferable conditions for compression molding, for example, in the case of a mold having a size of 100 mm × 75 mm × 3 mm, the temperature of the top plate and the mold is 170 to 190 ° C., the molding pressure is 5 to 20 MPa, and the pressurizing time is 1. It can be 5 to 10 minutes.

[Method for producing cured product]
The thermosetting resin composition can be cured by heating. The curing temperature is preferably 130 to 300 ° C, more preferably 150 to 230 ° C, and even more preferably 150 to 200 ° C. When the curing temperature is 130 ° C. or higher, the thermosetting resin composition before curing can be sufficiently melted and easily filled in the mold, and the mold can be easily removed after curing. When the curing temperature is 300 ° C. or lower, thermal deterioration or volatilization of the material can be avoided. The heating time can be appropriately changed depending on the thermosetting resin composition and the curing temperature, but 0.1 to 24 hours is preferable from the viewpoint of productivity. This heating may be performed in a plurality of times. When a particularly high degree of curing is required, the final curing temperature is preferably 250 ° C. or lower, preferably 230 ° C. or lower, without curing at an excessively high temperature, for example, by raising the temperature as the curing progresses. Is more preferable.

[Use of cured product]
The cured product of the thermosetting resin composition can be used, for example, in applications such as semiconductor encapsulants, prepregs, interlayer insulating resins, solder resists, and die attaches.

Hereinafter, the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited to this Example.

The analysis method and characteristic evaluation method used in the examples and comparative examples are as follows.

[Characteristic evaluation method]
[Molecular weight]
The measurement conditions of GPC are as follows.
Device name: JASCO LC-2000 plus (manufactured by JASCO Corporation)
Column: Shodex (registered trademark) LF-804 (manufactured by Showa Denko KK)
Mobile phase: tetrahydrofuran Flow velocity: 1.0 mL / min
Detector: JASCO RI-2031 plus (manufactured by JASCO Corporation)
Temperature: 40 ° C
Under the above measurement conditions, the number average molecular weight Mn and the weight average molecular weight Mw are calculated using a calibration curve prepared using a polystyrene standard substance.

[Degree of polymerization]
The degree of polymerization P is calculated by the following formula, where Mn is the number average molecular weight calculated from GPC and M is the molecular weight of the repeating structure of the polyalkenylphenol compound (A).
P = Mn / M

[Gel time]
1 g of a powdery thermosetting resin composition is placed on a copper substrate whose surface temperature has been adjusted to 180 ° C., and kneaded with a spatula until it hardens. The time (seconds) required for the material to lose its tackiness is measured with a stopwatch and used as the gel time.

[Curing time]
A structure of 30 mm × 30 mm × 5 mmt in which the molding time was lengthened by 30 s, 60 s and 15 s at 180 ° C. was prepared by a compression mold, respectively, and the structure obtained by using a type D durometer compliant with JIS K 7215 (1986). Body hardness was measured at 180 ° C. The time (seconds) required for the hardness to exceed 85 is defined as the curing time.

[Shear adhesive force]
The adhesiveness to metal is evaluated from the viewpoint of shear adhesive force. As the adherend base material, a base material of oxygen-free copper (C1020) having a size of 18 mm × 14 mm × 1.6 mmt is used. The adherend is immersed in acetone for 5 minutes, immersed in 5% by mass sulfuric acid for 5 minutes, washed twice or more with ion-exchanged water, and dried at 50 ° C. for 10 minutes before use. A thermosetting resin composition is formed on the surface of the adherend base material into a conical tower shape (a circle having a ground contact portion of 3 mmφ, a height of 3 mm, and an upper portion of 1.5 mmφ) using a transfer molding machine. The molding conditions are a mold temperature of 180 ° C., a holding pressure of 100 kg / cm ² , and a holding time of 3 minutes.

The adherend base material was firmly fixed to the obtained test piece, and the conical tower-shaped structure was pressed along the adherend surface at a speed of 2 mm / s from the lateral direction, and the conical tower-shaped structure was adhered. Measure the applied pressure when peeling from the substrate. This measurement was performed for one thermosetting resin composition at N = 6, and the value (MPa) obtained by dividing the measured applied pressure by the adherend area was the shear value of the thermosetting resin composition. Adhesive strength.
[Adhesion rate after molding]
Adhesion to metal is evaluated from the viewpoint of adhesion rate after molding. A lead frame is used in which the material is rolled oxygen-free copper (C1020), the outer dimensions are 52 mm in width, 38 mm in length, and 0.5 mm in thickness, and the bed is 18 mm in length and width in the center. The pretreatment of the lead frame is performed under the same conditions as the pretreatment of the adherend base material in the shear adhesion test. A thermosetting resin composition is used to seal the bed around the center of the lead frame with outer dimensions of 30 mm in length, 30 mm in width, and 3 mm in thickness. Sealing was performed by molding a thermosetting resin composition using a transfer molding machine under the conditions of a mold temperature of 180 ° C., a holding pressure of 100 kg / cm ^{2, and a holding time of 3 minutes.} Is post-cured at 200 ° C. for 5 hours. For the post-cured test piece, an ultrasonic flaw detection imaging device (HA-60A manufactured by Honda Electronics Corporation) is used to observe the peeling state of the interface between the lead frame and the cured product of the thermosetting resin composition. Using Image-J software, the value obtained by dividing the area of the non-peeled portion by the total area is determined as the post-molding adhesion ratio.
[Reflow resistance]
Adhesion to metal is also evaluated from the viewpoint of reflow resistance. Using the test pieces observed in the post-molding adhesion test, a reflow test is performed using a reflow simulator SRS-1 manufactured by Malcolm Co., Ltd. in accordance with the level 3 conditions of IPC / JEDEC J-STD-020D. The test piece after the reflow test is analyzed in the same manner as in the post-molding adhesion test, and the obtained value is determined as the post-reflow adhesion.

[raw materials]
[Polyalkenylphenol compound (A)]
· BRG-APO (formula (2) -1 of R ⁵ = ^{^{hydrogen, Q = -CR 12 R 13 -}} , R 12 and R ¹³ = hydrogen atom, R ⁷ ~ R ¹¹ = hydrogen atom of the formula (3))
Phenolic novolak resin A resin in which the ortho or para position of a phenolic hydroxyl group is allylated using a 1: 1 mixture of BRG-556 (registered trademark) BRG-556 and BRG-558 (Aika Kogyo Co., Ltd.) (hydroxyl equivalent 154, number). An average molecular weight Mn1000, a weight average molecular weight Mw3000, a degree of polymerization of 6.6, p = 6.6, q = 0, and p / (p + q) = 0) were produced. For the production method, refer to Example 1 of JP-A-2016-28129.

^{HE100C-APO (R 5} = hydrogen atom of formula (2) -1 and formula (2) -2 ^{, R 7} to R ¹¹ = hydrogen atom of formula (3), Q = p-xylylene group)
A resin in which the ortho-position or para-position of a phenolic hydroxyl group is allylated by a method according to Example 1 of JP2016-28129A using a phenol aralkyl resin HE100C-10-15 (Air Water Co., Ltd.) (hydroxyl group). Equivalent 222, number average molecular weight Mn900, weight average molecular weight Mw1900, degree of polymerization 4.0, p = 3.8, q = 0.2, p / (p + q) = 0.95) were produced.

[Polymaleimide compound (B)]
・ BMI-4000 (2,2-bis [4- (4-maleimidephenyloxy) phenyl] propane, Daiwa Kasei Kogyo Co., Ltd.)
・ BMI-1100H (bis (4-maleimidephenyl) methane, Daiwa Kasei Kogyo Co., Ltd.)

[Compound (C)]
・ 6-Aminoindazole (Reagent manufactured by Tokyo Kasei Co., Ltd.)
・ 5-Aminoindazole (Reagent manufactured by Tokyo Kasei Co., Ltd.)

[Radical initiator (D)]
・ Park Mill (registered trademark) D (Dikumil Peroxide, NOF Corporation)

[Filler (E)]
-Silica filler MSR5100 (spherical silica, average particle size 22.7 μm, manufactured by Ryumori Co., Ltd.) was treated with 0.5% by mass of a silane coupling agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.).

The following additives were used as other ingredients.
・ Indazole (reagent manufactured by Tokyo Kasei Co., Ltd.)
・ 5-Hydroxyindazole (manufactured by Tokyo Kasei Co., Ltd.)
・ 5-Nitroindazole (manufactured by Tokyo Kasei Co., Ltd.)
・ Pyrazoline (manufactured by Tokyo Kasei Co., Ltd.)
・ 5-Amino-2- (4-aminophenyl) benzimidazole (manufactured by Tokyo Kasei Co., Ltd.)
・ 6-Amino-1-H-benzimidazole (manufactured by Tokyo Kasei Co., Ltd.)

[Manufacturing of thermosetting resin composition]
Example 1
35 parts by mass of BRG-APO as the polyalkenylphenol compound (A), 65 parts by mass of BMI-4000 as the polymaleimide compound (B), 1.5 parts by mass of Park Mill D as the radical initiator (D), filler ( 400 parts by mass of MSR5100 treated with KBM-603 as E) and 0.35 parts by mass of 5-aminoindazole as compound (C) were mixed and melt-kneaded (2 rolls manufactured by Toyo Seiki Seisakusho Co., Ltd.). At 110 ° C. for 10 minutes) at a diameter of 8 inches). After allowing to cool at room temperature (25 ° C) for 1 hour to solidify, it is pulverized using a mill mixer (manufactured by Osaka Chemical Co., Ltd., model WB-1, 25 ° C, 30 seconds) to heat-cure powder. A sex resin composition was obtained. As a raw material for transfer molding, a powdery thermosetting resin composition was compacted into a tablet shape by a tableting machine (manufactured by Fuji Yakuhin Machinery Co., Ltd.). Each of the above-mentioned test pieces was prepared and evaluated using a powdery or tablet-shaped thermosetting resin composition.

Examples 2 to 6, Comparative Examples 1 to 7
The thermosetting resin composition was produced and evaluated in the same manner as in Example 1 except that the types and amounts of the components were changed as shown in Table 1.

In Examples 1 to 6, the structure could be easily removed from the mold, and the moldability was good. In Examples 1 to 6, the shear adhesive force, the adhesion rate after molding, and the adhesion rate after reflow were high, and the adhesion to the metal and the adhesiveness were excellent. The gel times of Examples 1 to 6 were in an appropriate range. The curing times of Examples 1 to 6 were in an appropriate range, and the productivity was also excellent. On the other hand, in Comparative Examples 1 to 5, the shear adhesive force and the adhesion after molding, particularly the adhesion after reflow, were low, and the adhesiveness and adhesion to the metal, particularly the adhesion after the reflow test, were poor. In Comparative Examples 6 and 7, the shear adhesive force was low and the adhesiveness to the metal was poor. In addition, other additives having an imidazole skeleton excessively promoted the polymerization reaction, and it was not possible to prepare a test piece for evaluating the adhesion rate after molding and the adhesion rate after reflow, which are relatively large in size.

Claims

A thermosetting resin composition containing a polyalkenylphenol compound (A), a polymaleimide compound (B), a compound (C) having the structure according to the formula (1), and a radical initiator (D).

(In the formula, R 1 and R 2 are hydrogen atoms, halogen atoms, alkyl groups having 1 to 3 carbon atoms, hydroxyl groups, carboxy groups, or amino groups, and at least one of R 1 and R 2 is an amino group. R 3 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a cyano group, and R 4 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. is there.)
The compound (C) is 6-aminoindazole, 5-aminoindazole, 6-amino-5-methylindazole, 6-amino-5-ethylindazole, 6-amino-5-hydroxyindazole, 6-amino-5-. Claim 1 comprises at least one selected from bromoindazole, 6-amino-5-chloroindazole, 3-cyano-5-aminoindazole, 5-carboxy-6-aminoindazole, and 5,6-diaminoindazole. The thermocurable resin composition according to the above.
The thermosetting resin composition according to claim 2, wherein the compound (C) contains at least one selected from 5-aminoindazole and 6-aminoindazole.
Claims 1 to 3 in which the content of the compound (C) is 0.05 parts by mass to 5 parts by mass with respect to a total of 100 parts by mass of the polyalkenylphenol compound (A) and the polymaleimide compound (B). The thermosetting resin composition according to any one of the above.
The thermosetting resin according to any one of claims 1 to 4, wherein the amount of the polyalkenylphenol compound (A) is 5 to 200 parts by mass with respect to 100 parts by mass of the polymaleimide compound (B). Composition.
The polyalkenylphenol compound (A) is represented by the formula (2) -1 :.

And optionally equation (2) -2:

In formulas (2) -1 and (2) -2, R 5 independently has a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms, respectively. Represents an alkoxy group of 5, and R 6 is an independent formula (3):

In formula (3), R 7 , R 8 , R 9 , R 10 and R 11 are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, and carbon atoms, respectively. It is a cycloalkyl group of number 5 to 10 or an aryl group having 6 to 12 carbon atoms, where * in the formula (3) represents a bond with a carbon atom constituting an aromatic ring, and R 5 and R 6 are. or different may be the same for each phenol backbone units of the formula (2) -1 and the formula (2) wherein -CR 12 Q are each independently of -2 R 13 - in the alkylene group represented, the number of carbon atoms Represents a cycloalkylene group of 5 to 10, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent organic group in which these are combined, and R 12 and R 13 represent. Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. The thermosetting resin composition according to any one of claims 1 to 5.
When the average number of structural units shown in formula (2) -1 per molecule is p and the average number of structural units shown in formula (2) -2 per molecule is q, p is 1.1 to The thermocurable resin according to claim 6, wherein 35 is a real number, p + q is a real number of 1.1 to 35, and q is a real number having a value of the formula: p / (p + q) of 0.4 to 1. Composition.
The thermosetting resin composition according to any one of claims 1 to 7, wherein the polymaleimide compound (B) is an aromatic bismaleimide compound.
The thermosetting resin composition according to any one of claims 1 to 8, wherein the radical initiator (D) is an organic peroxide.
The thermosetting resin composition according to any one of claims 1 to 9, further comprising a filler (E).
The thermosetting resin composition according to claim 10, wherein the filler (E) is at least one selected from the group consisting of silica, alumina, magnesium oxide, and solid rubber particles.
The content of the filler (E) is 100 parts by mass in total of the polyalkenylphenol compound (A), the polymaleimide compound (B), the compound (C), and the radical initiator (D). The thermosetting resin composition according to claim 10 or 11, which is 200 to 1900 parts by mass.
A cured product of the thermosetting resin composition according to any one of claims 1 to 12.
A method for producing a structure, wherein the thermosetting resin composition according to any one of claims 1 to 12 is molded by molding.
A structure containing the cured product according to claim 13.