WO2021240879A1

WO2021240879A1 - Thermosetting resin composition

Info

Publication number: WO2021240879A1
Application number: PCT/JP2021/002807
Authority: WO
Inventors: 千佳峯崎
Original assignee: 昭和電工株式会社
Priority date: 2020-05-28
Filing date: 2021-01-27
Publication date: 2021-12-02
Also published as: JPWO2021240879A1

Abstract

Provided is a thermosetting resin composition that, without impairing molding properties or cured product thermal resistance, provides a cured product that has excellent adhesion to metal and excellent reflow resistance. The thermosetting resin composition contains: a polyalkenyl phenol compound (A); a polymaleimide compound (B); a polyethylene glycol compound (C); and a radical initiator (D). The polyethylene glycol compound (C) has a structural unit indicated in formula (1), said structural unit in formula (1) being 90–100 mol% of all structural units.

Description

Thermosetting resin composition

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 heat-softened in a plunger, and the heat-softened material is pushed into the heated mold cavity through a flow path in the mold such as a gate, sprue, runner, etc. It is a method of curing inside. Since the material is injected into the cavity with high fluidity, it is possible to mold at low pressure.

Transfer molding is characterized by being less likely to damage the insert than other molding methods that require high pressure. Transfer molding is known as a typical molding method in encapsulation 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 containing a highly heat-resistant structure such as a sun skeleton have been proposed.

Patent Document 1 (Japanese Unexamined Patent Publication No. 11-140277) describes (A) a phenol resin having a novolak structure containing a biphenyl derivative and / or a naphthalene derivative in the molecule, in an amount of 30 to 100 parts by mass in the total phenol resin amount. , (B) 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, (D) promoting curing. Described is an epoxy resin composition for encapsulating a semiconductor, which comprises an agent as 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 a polyallylphenol from a 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 phenolic resin having a specific repeating unit, and (C). Described is a semiconductor device in which a semiconductor element is sealed by using a resin composition containing a curing catalyst.

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

In material development, if the resin system is changed drastically, there may be a problem in balancing the performance that has multiple trade-offs. For example, as a method for increasing the heat resistance of the material, increasing the number of functional groups of the epoxy resin to increase the crosslink density (Patent Document 1) and using maleimide resin as another resin (Patent Documents 2 to 4) can be mentioned. However, as the heat resistance of the material is increased by these methods, the crosslinked structure of the cured product of the thermosetting resin becomes denser, so that the material becomes harder and stronger, and the elasticity of the cured product tends to increase. As a result, when a cured product is used in close contact with a different material, such as when a thermosetting resin is used as a sealing material, there is a tendency for the material to peel off due to the stress generated at the interface. In particular, in a device in which stress and / or thermal stress is repeatedly and violently applied, peeling is likely to occur between the cured product constituting them and another member.

Also, in resin molding including metal inserts, trade-offs are likely to occur between moldability such as bleed-out and releasability and adhesion to internal parts. These properties change significantly when the skeleton and polarity of the main resin change.

Therefore, there is a demand for a material having excellent adhesion to other members such as metal, and excellent reflow resistance and heat cycle resistance without impairing heat resistance and moldability. In order to eliminate the above-mentioned trade-off, it is useful to use an additive or the like suitable for the resin system.

The present disclosure describes a thermosetting resin composition that gives a cured product having excellent adhesion to a metal and excellent reflow resistance without impairing moldability and heat resistance of the cured product.

That is, the present invention relates to the following [1] to [15].
[1]
A thermosetting resin composition containing a polyalkenylphenol compound (A), a polymaleimide compound (B), a polyethylene glycol compound (C), and a radical initiator (D).
The polyethylene glycol compound (C) has a structural unit of the formula (1), and the structural unit of the formula (1) is 90 mol% to 100 mol% with respect to the total structural unit.
Thermosetting resin composition.

[2]
The content of the polyethylene glycol compound (C) is 1 to 10% by mass based on the total of the polyalkenylphenol compound (A), the polymaleimide compound (B), and the polyethylene glycol compound (C). The thermosetting resin composition according to [1].
[3]
The thermosetting resin composition according to [1] or [2], wherein the polyethylene glycol compound (C) has a number average molecular weight Mn of 2000 to 50,000.
[4]
The thermosetting according to any one of [1] to [3], wherein the content of the polyalkenylphenol compound (A) is 5 to 200 parts by mass with respect to 100 parts by mass of the polymaleimide compound (B). Resin composition.
[5]
The thermosetting resin composition according to any one of [1] to [4], wherein the polyethylene glycol compound (C) is polyethylene glycol.
[6]
The polyalkenylphenol compound (A) is represented by the formula (2) -1 :.

And optionally equation (2) -2:

It is a polyalkenylphenol compound having a structural unit represented by
In formulas (2) -1 and (2) -2, R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R ² Are independent of each other, equation (3):

Represents a 2-alkenyl group represented by, and in formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are independently hydrogen atoms and alkyl groups having 1 to 5 carbon atoms, respectively. It is a cycloalkyl group having 5 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and * in the formula (3) represents a bonding portion with a carbon atom constituting an aromatic ring, and R ¹ and R. ² may be the same or different for each phenol skeleton unit, and Q independently has ^{an alkylene group represented by the formula −CR 8} R ⁹ −, a cycloalkylene group having 5 to 10 carbon atoms, and an aromatic ring. Represents a divalent organic group having a divalent organic group, a divalent organic group having an alicyclic condensed ring, or a divalent organic group combining these, and R ⁸ and R ⁹ independently represent a hydrogen atom and one carbon atom. Any of [1] to [5] representing an alkyl group of up to 5; 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.
[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 [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 [1] to [7], wherein the polymaleimide compound (B) is an aromatic bismaleimide compound.
[9]
The thermosetting resin composition according to any one of [1] to [8], wherein the radical initiator (D) is an organic peroxide.
[10]
The thermosetting resin composition according to any one of [1] to [9], further comprising a filler (E).
[11]
The thermosetting resin composition according to [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 polyethylene glycol compound (C), and the radical initiator (D). The thermosetting resin composition according to [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 [1] to [12].
[14]
A method for producing a structure, wherein the thermosetting resin composition according to any one of [1] to [12] is molded.
[15]
A structure containing the cured product according to [13].

According to the present invention, it is possible to obtain a thermosetting resin composition that gives a cured product having excellent adhesion to a metal and excellent reflow resistance without impairing the moldability and the heat resistance of the cured product. can.

It is a schematic diagram of the molding die, the top plate and the bottom plate used for the evaluation of the releasability. It is a schematic diagram of the sample used for the evaluation of the releasability.

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 polyethylene glycol compound (C), and a radical initiator (D).

[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. be. As the 2-alkenyl group, a group having a structure represented by the formula (3) is preferable.

In formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, and cycloalkyl groups having 5 to 10 carbon atoms, respectively. Alternatively, it is an aryl group having 6 to 12 carbon atoms. * In the formula (3) represents a bond with a carbon atom constituting an aromatic ring.

^{Specific examples of the alkyl groups having 1 to 5 carbon atoms constituting R 3} , R ⁴ , R ⁵ , R ⁶ and R ⁷ in the formula (3) include methyl group, ethyl group, n-propyl group and isopropyl. Groups, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and the like can be mentioned. 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. In the 2-alkenyl group represented by the formula (3), ^{it is preferable that allyl groups, that is, R 3} , R ⁴ , R ⁵ , R ⁶ and R ⁷ are all hydrogen atoms.

In the polyalkenylphenol compound (A), 2-alkenyl is preferably 40 to 100%, more preferably 60 to 100%, still more preferably 80 to 100% of the total aromatic rings forming the phenol skeleton. The groups are bonded.

Known basic skeletons of the polyalkenylphenol compound (A) include phenol novolac resin, cresol novolak resin, triphenylmethane-type phenol resin, phenol aralkyl resin, biphenyl aralkyl phenol resin, and phenol-dicyclopentadiene copolymer resin. Examples include the skeleton of phenolic resin. 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 the formula (2) -2 are preferable phenol skeleton units constituting the polyalkenylphenol compound (A), and the bonding order of these phenol skeleton units is not particularly limited. In formulas (2) -1 and (2) -2, R ¹ 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 of the formula (2). In 2) -1, R ^{2 is independently a 2-} alkoxy group represented by the formula (3). R ¹ and R ² may be the same or different for each phenol skeleton unit. Q is independently of the formula -CR ⁸ R ⁹ - in the alkylene group represented, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent having an alicyclic fused ring R ⁸ and R ⁹ are independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, and alkenyl groups having 2 to 6 carbon atoms, respectively. It is 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 the structural units represented by the formula (2) -2 per molecule is q, p is preferably 1. .1 to 35 real numbers, p + q are 1.1 to 35 real numbers, and q satisfies the 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 ¹ 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. -The 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 ⁸ R ⁹ - in which R ⁸ and R ⁹ 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 an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and specific examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, and a butenyl group. Examples of the cycloalkyl group having 5 to 10 carbon atoms include a pentenyl group, a hexenyl group, and the like, and examples thereof include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cycloheptyl group, and a carbon atom. Specific examples of the aryl group having the number 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 trilene group, a naphthylene group, a biphenylene group, a fluorenylene group, an anthrasenylene 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), Q is preferably _{−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 appropriate. Is a suitable range for processing during 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 appropriate. Is a suitable range for processing during molding.

q is preferably a real number in which the value of the formula: p / (p + q) is 0.4 to 1, and more preferably is a real number in which the value of the formula: p / (p + q) is 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 have only the structural unit 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 a suitable range for processing during molding.

The polyalkenylphenol compound (A) can be obtained by rearranging a 2-alkenyl group by a Claisen rearrangement reaction after partially converting a part of the hydroxyl group of the phenol resin as a raw material into an alkenyl ether. 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 novolak 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) acetic acid. Two known methods of reacting a carboxylic acid 2-alkenyl compound such as allyl with a phenol compound can be exemplified. For the 2-alkenyl etherification reaction using the 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 to be 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 is dissolved 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 reaction time. , The reaction rate (conversion rate) of the 2-alkenyl compound can be suppressed to a low level and controlled.

The target polyalkenylphenol compound (A) can be obtained by subjecting the polyalkenyl ether compound produced by the method according to (i) or (ii) 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. 2-91113.

[Polymaleimide compound (B)]
The polymaleimide compound (B) is a compound having two or more maleimide groups represented by the formula (4). By blending the polymaleimide compound (B), the heat resistance of the cured product can be improved.

In the formula (4), * represents a bond with an aromatic ring or 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 polymaleimides such as poly (4-maleimide styrene). Examples of the polymaleimide compound (B) include aromatic polymaleimide compounds and aliphatic polymaleimide compounds, and aromatic polymaleimide compounds are preferable because the obtained cured product has particularly excellent flame retardancy.

The 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 or an aliphatic bismaleimide compound, and more preferably an aromatic bismaleimide compound, because it mixes well in the curable 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-Dimareimide naphthalene, 2,3-Dimareimide naphthalene, 1,5-Dimareimide naphthalene, 1,8-Dimareimide naphthalene, 2,6-Dimareimide naphthalene, 2, 7-Dimareimidenaphthalene, 4,4'-Dimareimidebiphenyl, 3,3'-Dimareimidebiphenyl, 3,4'-Dimareimidebiphenyl, 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-Zimare Iimidebenzene, 1,3-dimareimidebenzene, 1,4-dimaleimidebenzene, 1,4-bis (4-maleimidephenyl) benzene, 2-methyl-1,4-dimaleimidebenzene, 2,3-dimethyl- 1,4-Dimareimidebenzene, 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, 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 30 to 30 parts by mass. It is more preferably 100 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.

[Polyethylene glycol compound (C)]
The polyethylene glycol compound (C) has a structural unit of the formula (1), and the structural unit of the formula (1) is 90 mol% to 100 mol% with respect to the total structural unit.

The structural unit of the formula (1) is preferably 95 mol% to 100 mol%, more preferably 97 mol% to 100 mol%.

Although not bound by any theory, since the polyethylene glycol compound (C) has good compatibility with both the polyalkenylphenol compound (A) and the polymaleimide compound (B), the polyethylene glycol compound (C) is used. By adding the compound, the compatibility of the polyalkenylphenol compound (A) and the polymaleimide compound (B) can be improved. Further, when a mold release agent is used, the surface separability of the mold release agent can be controlled while the polyethylene glycol compound (C) itself is appropriately compatible with the mold release agent. This effect can suppress the bleed-out of the release agent and other components. Further, since the high molecular weight polyethylene glycol compound (C) is a stable component even at a high temperature, the fluidity of the thermosetting resin composition and the adjustment of the surface wettability of the thermosetting resin composition with respect to the mold during molding are adjusted. Can also be. Due to these effects, bleed-out can be further suppressed by adding the high molecular weight polyethylene glycol compound (C).

The number average molecular weight Mn of the polyethylene glycol compound (C) is preferably 2000 to 50000, more preferably 2500 to 30000, and further preferably 3000 to 25000. When the number average molecular weight Mn is 2000 or more, the bleed-out of the polyethylene glycol compound (C) to the surface of the cured product after molding can be further suppressed. On the other hand, when the number average molecular weight Mn is 50,000 or less, the viscosity of the thermosetting resin composition falls within a range suitable for molding.

The structural units of the polyethylene glycol compound (C) other than the formula (1) are 0 to 10 mol%, preferably 0 to 5 mol%, and more preferably 0 to 3 mol% with respect to the total structural units. be. The structural unit other than the formula (1) includes a structural unit constituting a branched structure; an amino group, a carboxy group, a sulfonic acid group, a hydroxy group, a glycidyl group, an azido group, a cyano group, a thiol group, and a non-substituted amino group. A structural unit containing a terminal functional group such as a saturated hydrocarbon group; a by-produced structural unit during compound synthesis can be mentioned.

Examples of the polyethylene glycol compound (C) include polyethylene glycol and polyethylene glycol derivatives. Specific examples of polyethylene glycol include PEG-4000 and PEG-6000 of Toho Chemical Industry Co., Ltd., PEG-10000 and PEG-20000 of Sanyo Chemical Industries, Ltd. Examples of the polyethylene glycol derivative include polyethylene glycol fatty acid esters such as polyethylene glycol oleic acid monoester and polyethylene glycol-di-2-ethylhexoate.

The content of the polyethylene glycol compound (C) is preferably 1 to 10% by mass, more preferably 1 to 10% by mass, based on the total of the polyalkenylphenol compound (A), the polymaleimide compound (B), and the polyethylene glycol compound (C). It is 1.3 to 7% by mass, more preferably 1.5 to 5% by mass. When the content of the polyethylene glycol compound (C) is 1% by mass or more, the wet adhesion to the metal surface can be further improved. On the other hand, when the content of the polyethylene glycol compound (C) is 10% by mass or less, the melting point or softening point of the thermosetting resin composition before molding can be appropriately adjusted to improve the handleability. Bleedout of the polyethylene glycol compound (C) after curing can be further suppressed.

[Radical initiator (D)]
By blending the radical initiator (D) with the thermosetting resin composition, the curing of the thermosetting resin composition can be promoted. Examples of the radical initiator (D) include a thermal radical initiator. 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 polyethylene glycol compound (C). It is more preferably 0.05 to 7.5 parts by mass, and further 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. be.

[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. In one embodiment, the filler (E) is 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 the narrow pitch wiring portion or the narrow gap portion is also appropriate. The average particle size referred to here is the 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 intended use. The content of the filler (E) in the thermosetting resin composition is 100% by mass in total of the polyalkenylphenol compound (A), the polymaleimide compound (B), the polyethylene glycol compound (C), and the radical initiator (D). 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 with respect to the parts.

[Other additives]
As other additives, a coupling agent, 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, etc. are blended in the thermosetting resin composition. It is also possible to do. The other additives do not include the polyalkenylphenol compound (A), the polymaleimide compound (B), the polyethylene glycol compound (C), the radical initiator (D), and the compound corresponding to the filler (E).

For example, a coupling agent may be blended from the viewpoint of improving the adhesiveness. The coupling agent is not particularly limited, and for example, vinyl triethoxysilane, vinyl trimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N- Examples thereof include a silane coupling agent such as phenyl-3-aminopropyltrimethoxysilane. 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.

For example, a mold release agent may be blended from the viewpoint of improving the mold release property. The release agent is not particularly limited, and examples thereof include carnauba wax, amide wax, montanic acid ester wax, montanic acid partially saponified ester wax, metal soap such as calcium stearate, polyethylene wax, and polypropylene wax. Of these, carnauba wax, montanic acid ester wax, and polyethylene wax are preferable. The release agent may be used alone or in combination of two or more. The blending amount of the release agent in the thermosetting resin composition is preferably 0.01 to 0.5% by mass. When the blending amount is 0.01% by mass or more, the effect of the mold release agent is sufficiently exhibited, and when it is 0.5% by mass or less, bleed-out such as mold stain does not occur and the appearance is good.

[Method for preparing thermosetting resin composition]
In the method for preparing a thermosetting resin composition, a polyalkenylphenol compound (A), a polymaleimide compound (B), a polyethylene glycol compound (C), a radical initiator (D), and other optional components are uniformly mixed. And, if it can be dispersed, it is not particularly limited. The method of melt-mixing the polyalkenylphenol compound (A), the polymaleimide compound (B), and the polyethylene glycol compound (C) first, and then adding the radical initiator (D) and any additive is to add each material. It is preferable because it is easy to mix uniformly.

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 the mixer of the above and stirring or kneading. In the laboratory 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 the thermosetting resin composition is powdered, the method is not particularly limited as long as the resin is not melted by the heat generated in the work process, but if the amount is small, the method using an agate mortar is convenient. 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 to a temperature at which the curing reaction does not proceed rapidly. A structure can be produced by molding the melted thermosetting resin composition into an arbitrary preferred 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.

Preferred conditions for transfer molding are, 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. 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 demolding after curing is also easy. 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 these Examples and the like.

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

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

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

[Glass-transition temperature]
The heat resistance of the cured product was evaluated from the viewpoint of the glass dislocation temperature (Tg). Specifically, a thermosetting resin composition is molded 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, and a glass transition temperature of 5 mm × 5 mm × 5 mm. A test piece for measurement was prepared. The test piece was heated at 200 ° C. for 5 hours and then cured, and then measured by thermal mechanical measurement (TMA). The measurement was carried out using a TMA / SS6100 thermomechanical analyzer manufactured by SII Nanotechnology Co., Ltd. under the conditions of a temperature range of 30 to 300 ° C., a heating rate of 5 ° C./min, and a load of 20.0 mN. The inflection point of the expansion coefficient was Tg.

[Releasability]
The moldability was evaluated from the viewpoint of mold releasability. Specifically, the molding die 1 shown in FIG. 1 (the size of the test piece is lower diameter: 25 mmφ, upper diameter: 10 mmφ, upper thickness: 7 mm, lower thickness: 7 mm, taper: 2 °), top plate. Using a transfer molding machine equipped with 2 and the bottom plate 3, a ^{thermosetting resin composition was molded 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, and as shown in FIG. The demolding force when pushed from the top with only a spring was measured. Molding was performed a plurality of times in succession, and the number of continuous moldings in which the average value of the left and right demolding forces was 40 N or less was recorded. The evaluation was completed when the average value exceeded 40 N or when the number of moldings reached 10 times.

[Appearance (bleed out)]
The moldability was also evaluated from the viewpoint of appearance. Specifically, a thermosetting resin composition is molded 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, and after taking out the obtained molded product. The mold and the molded product were visually observed. It is good that the mold is not cloudy after 10 times of molding and demolding and no resin exuded on the surface of the molded product is seen after repeating molding and demolding under the above conditions. Those in which at least one of exudation and stains on the mold were observed were acceptable, and those in which at least one of resin exudation and stains on the mold was observed in the first and second times were evaluated as defective.

[Adhesion rate after molding]
A lead frame was used in which the material was rolled oxygen-free copper (C1020), the outer dimensions were 52 mm in width, 38 mm in length, and 0.5 mm in thickness, and the bed was 18 mm in length and width in the center. The bed was sealed around the center of the lead frame with an outer dimension 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.} After curing at 200 ° C. for 5 hours. For the post-cured test piece, the peeling state of the interface between the lead frame and the cured product of the thermosetting resin composition was observed using an ultrasonic flaw detection imaging device (Honda Electronics Co., Ltd., HA-60A). Using Image-J software, the value obtained by dividing the area of the non-peeled portion by the total area was determined as the post-molding adhesion ratio.

[Reflow resistance]
The reflow resistance was evaluated by the adhesion rate after reflow. For the post-cured test piece obtained by the same method as the post-molding adhesion test, a reflow simulator SRS-1 manufactured by Malcolm Co., Ltd. was used in accordance with the level 3 conditions of IPC / JEDEC J-STD-020D. Then, a reflow test was conducted. The test piece after the reflow test was analyzed in the same manner as in the post-molding adhesion test, and the obtained value was determined as the post-reflow adhesion.

<Raw materials>
[Polyalkenylphenol compound (A)]
· BRG-APO (formula (2) -1 of R ¹ = hydrogen ^{^{atom, Q = -CR 8 R 9 -}} , R 8 and R ⁹ = hydrogen atom, R ³ ~ R ⁷ = hydrogen atom of the formula (3))
Phenolic novolak resin A resin in which the ortho-position 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) = 1) were produced. For the production method, refer to Example 1 of JP-A-2016-28129.

^{HE100C-APO (R 1} = hydrogen atom of formula (2) -1 and formula (2) -2, Q = p-xylylene group, R ³ to R ⁷ = hydrogen atom of formula (3))
A resin in which the ortho-position or para-position of the phenolic hydroxyl group is allylated by a method according to Example 1 of JP-A-2016-28129 using the 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.)

[Polyethylene glycol compound (C)]
PEG-4000 (polyethylene glycol, Mn4000, Mw5000, structural unit of formula (1) 100 mol%, Toho Chemical Industry Co., Ltd.)
PEG-6000 (polyethylene glycol, Mn6000, Mw7300, structural unit of formula (1) 100 mol%, Toho Chemical Industry Co., Ltd.)
PEG-10000 (polyethylene glycol, Mn10000, Mw14000, structural unit of formula (1) 100 mol%, Sanyo Chemical Industries, Ltd.)
PEG-20000 (polyethylene glycol, Mn21000, Mw26000, structural unit of formula (1) 100 mol%, Sanyo Chemical Industries, Ltd.)
-Rionon MO-60 (polyethylene glycol oleic acid monoester, Mn7200, Mw8000, structural unit of formula (1) 94 mol%, Lion Specialty Chemicals 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, Ryumori Co., Ltd.) was treated with 0.5% by mass of a silane coupling agent KBE-403 (Shin-Etsu Chemical Co., Ltd.).

[Release agent]
・ Carnauba No. 1 (Carnauba Wax, Nikko Rika Co., Ltd.)
-LICOWAX (registered trademark) PE520 (polyethylene wax, Clariant Chemicals Co., Ltd.)

The following compounds were used as other resins.
KF6004 (Silicone PEG, Mn3000, Mw4500, structural unit of formula (1) 50 mol%, Shin-Etsu Chemical Co., Ltd.)
・ EPPN-501H (triphenylmethane type epoxy resin, Nippon Kayaku Co., Ltd.)
・ CRG-951 (Phenol novolac resin, Aica Kogyo Co., Ltd.)
・ TPP (triphenylphosphine)

<Example 1>
[Manufacturing of thermosetting resin composition]
35 parts by mass of BRG-APO as polyalkenylphenol compound (A), 65 parts by mass of BMI-4000 as polymaleimide compound (B), 2 parts by mass of PEG-6000 as polyethylene glycol compound (C), radical initiator ( As D), 1.5 parts by mass of Park Mill D, 400 parts by mass of MSR5100 as filler (E), 0.4 parts by mass of carnauba wax as a release agent and 0.15 parts by mass of PE520 were mixed and melt-kneaded (d). Two rolls (roll diameter 8 inches) manufactured by Toyo Seiki Seisakusho Co., Ltd. were used at 110 ° C. for 10 minutes. After allowing to cool at room temperature (25 ° C) for 1 hour to solidify, it is crushed using a mill mixer (Osaka Chemical Co., Ltd., model WB-1, 25 ° C, 30 seconds) to obtain a powdery thermosetting property. A resin composition was obtained.

[Analysis and characterization]
The obtained thermosetting resin composition was subjected to the above analysis, and was transferred and molded using a tablet compacted by a tableting machine (Fuji Yakuhin Machinery Co., Ltd.) to evaluate the above characteristics. Each test piece used in the above was prepared and its characteristics were evaluated.

<Examples 2 to 8, Comparative Examples 1 to 3>
A thermosetting resin composition was produced in the same manner as in Example 1 except that the type and amount of the raw materials were changed as shown in Table 1, and the thermosetting resin composition was analyzed and evaluated for characteristics.

Examples 1 to 8 had good releasability, adhesion after molding, adhesion after reflow, and appearance. In addition, Examples 1 to 8 were also excellent in heat resistance of the cured product. On the other hand, Comparative Examples 1 and 2 containing no polyethylene glycol compound (C) had poor releasability and appearance, and the adhesion rate after reflow was remarkably low. Comparative Example 3 based on the epoxy resin had poor releasability and appearance, and had a low adhesion rate after reflow resistance.

1 Mold 2 Top plate 3 Bottom plate 4 Gate 5 Runner 6 Molded product

Claims

A thermosetting resin composition containing a polyalkenylphenol compound (A), a polymaleimide compound (B), a polyethylene glycol compound (C), and a radical initiator (D).
The polyethylene glycol compound (C) has a structural unit of the formula (1), and the structural unit of the formula (1) is 90 mol% to 100 mol% with respect to the total structural unit.
Thermosetting resin composition.
The content of the polyethylene glycol compound (C) is 1 to 10% by mass based on the total of the polyalkenylphenol compound (A), the polymaleimide compound (B), and the polyethylene glycol compound (C). The thermosetting resin composition according to claim 1.
The thermosetting resin composition according to claim 1 or 2, wherein the polyethylene glycol compound (C) has a number average molecular weight Mn of 2000 to 50,000.
The thermosetting according to any one of claims 1 to 3, wherein the content of the polyalkenylphenol compound (A) is 5 to 200 parts by mass with respect to 100 parts by mass of the polymaleimide compound (B). Resin composition.
The thermosetting resin composition according to any one of claims 1 to 4, wherein the polyethylene glycol compound (C) is polyethylene glycol.
The polyalkenylphenol compound (A) is represented by the formula (2) -1 :.

And optionally equation (2) -2:

It is a polyalkenylphenol compound having a structural unit represented by
In formulas (2) -1 and (2) -2, R 1 independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R 2 Are independent of each other, equation (3):

Represents a 2-alkenyl group represented by, and in formula (3), R 3 , R 4 , R 5 , R 6 and R 7 are independently hydrogen atoms and alkyl groups having 1 to 5 carbon atoms. It is a cycloalkyl group having 5 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and * in the formula (3) represents a bonding portion with a carbon atom constituting an aromatic ring, and R 1 and R are represented. 2 may be the same or different for each phenol skeleton unit, and Q independently has an alkylene group represented by the formula −CR 8 R 9 −, a cycloalkylene group having 5 to 10 carbon atoms, and an aromatic ring. Represents a divalent organic group having a divalent organic group, a divalent organic group having an alicyclic condensed ring, or a divalent organic group combining these, and R 8 and R 9 are independently hydrogen atoms and 1 carbon atom, respectively. One of claims 1 to 5, which represents an alkyl group having 5 to 5, 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.
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 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 polyethylene glycol 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.