JP7593402B2 - Thermosetting resin composition - Google Patents

Description

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, with the increasing density of electronic components, semiconductor packages used in electronic and industrial equipment are required to have higher wiring density, be more compact, thinner, more heat resistant, and have better heat dissipation. For this reason, the plastic encapsulating material is also required to have higher heat resistance.

Transfer molding is a method in which the material is heated and softened inside a plunger, then the heated and softened material is forced into a heated mold cavity through passages inside the mold such as gates, sprues, and runners, and hardened inside the mold cavity. Since the material is injected into the cavity in a highly fluid state, molding can be done 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 allows for miniaturization and fine processing, and is highly productive, so it is known as a representative molding method for encapsulating power semiconductors and ICs.

Epoxy-phenolic thermosetting resin materials have traditionally been used as sealing materials in transfer molding. However, it is difficult for conventional materials to meet the recent demand for higher heat resistance. To meet the demand for higher heat resistance, sealing materials with various resin systems have been proposed, such as thermosetting resin compositions containing large amounts of multifunctional epoxy resins, and thermosetting resin compositions containing highly heat-resistant structures such as bismaleimide, triazine skeletons, benzoxazine skeletons, and silsesquioxane skeletons.

Patent Document 1 (JP Patent Publication No. 11-140277) describes an epoxy resin composition for semiconductor encapsulation, characterized in that the essential components are (A) a phenolic resin containing 30 to 100 parts by mass of a phenolic resin having a novolac structure containing a biphenyl derivative and/or a naphthalene derivative in the molecule, based on the total amount of phenolic resin; (B) an epoxy resin containing 30 to 100 parts by mass of an epoxy resin having a novolac structure containing a biphenyl derivative and/or a naphthalene derivative in the molecule, based on the total amount of epoxy resin; (C) an inorganic filler; and (D) a curing accelerator.

Patent Document 2 (JP Patent Publication 5-43630) describes an aromatic bismaleimide resin composition containing N,N'-(alkyl-substituted diphenylmethane) bismaleimide and polyallylphenol obtained from a condensed polyphenol of salicylaldehyde and phenol.

Patent Document 3 (JP Patent Publication 5-6869 A) describes a semiconductor device in which a semiconductor element is encapsulated using a resin composition containing (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) a curing catalyst.

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

Japanese Patent Application Publication No. 11-140277 Japanese Patent Application Publication No. 5-43630 Japanese Patent Application Publication No. 5-6869 Japanese Patent Application Publication No. 6-93047

In material development, when the resin system is significantly changed, problems may arise in balancing the performance of multiple trade-off relationships. For example, methods for increasing the heat resistance of materials include increasing the number of functional groups in epoxy resins to increase the crosslink density (Patent Document 1) and using maleimide resins as other resins (Patent Documents 2 to 4). The more the heat resistance of a material is increased by these methods, the denser the crosslink structure of the cured thermosetting resin becomes, so the material becomes harder and stronger, and the elastic modulus of the cured material tends to increase. As a result, when a thermosetting resin is used as an encapsulant, for example, when the cured material is used in close contact with a different material, problems such as peeling of the material due to stress generated at the interface are likely to occur. In particular, in devices that are repeatedly and intensely subjected to stress and/or thermal stress, peeling is likely to occur between the cured material that constitutes them and other components.

In addition, in resin molding that includes metal inserts, a trade-off often occurs between moldability, such as bleed-out and releasability, and adhesion to internal parts. These properties tend to change significantly when the structure and polarity of the main resin change.

Therefore, there is a demand for materials that have excellent adhesion to other components such as metals, and excellent reflow resistance and heat cycle resistance without compromising heat resistance and moldability. In order to resolve the above trade-off, it is useful to use additives that are suitable for the resin system.

This disclosure describes a thermosetting resin composition that gives a cured product that has excellent adhesion to metals and excellent reflow resistance without compromising moldability and heat resistance of the cured product.

［２］
前記ポリエチレングリコール化合物（Ｃ）の含有量が、前記ポリアルケニルフェノール化合物（Ａ）、前記ポリマレイミド化合物（Ｂ）、及び前記ポリエチレングリコール化合物（Ｃ）の合計に対して１～１０質量％である、［１］に記載の熱硬化性樹脂組成物。
［３］
前記ポリエチレングリコール化合物（Ｃ）の数平均分子量Ｍｎが、２０００～５００００である、［１］又は［２］に記載の熱硬化性樹脂組成物。
［４］
前記ポリアルケニルフェノール化合物（Ａ）の含有量が、前記ポリマレイミド化合物（Ｂ）１００質量部に対して５～２００質量部である、［１］～［３］のいずれかに記載の熱硬化性樹脂組成物。
［５］
前記ポリエチレングリコール化合物（Ｃ）が、ポリエチレングリコールである、［１］～［４］のいずれかに記載の熱硬化性樹脂組成物。
［６］
前記ポリアルケニルフェノール化合物（Ａ）が、式（２）－１：

及び任意に式（２）－２：

で表される構造単位を有するポリアルケニルフェノール化合物であり、
式（２）－１及び式（２）－２において、Ｒ¹はそれぞれ独立に、水素原子、炭素原子数１～５のアルキル基、又は炭素原子数１～５のアルコキシ基を表し、Ｒ²はそれぞれ独立に、式（３）：

で表される２－アルケニル基を表し、式（３）において、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、及びＲ⁷はそれぞれ独立に、水素原子、炭素原子数１～５のアルキル基、炭素原子数５～１０のシクロアルキル基、又は炭素原子数６～１２のアリール基であり、式（３）の＊は、芳香環を構成する炭素原子との結合部を表し、Ｒ¹及びＲ²は各フェノール骨格単位で同じでもよく異なっていてもよく、Ｑはそれぞれ独立に、式－ＣＲ⁸Ｒ⁹－で表されるアルキレン基、炭素原子数５～１０のシクロアルキレン基、芳香環を有する二価の有機基、脂環式縮合環を有する二価の有機基、又はこれらを組み合わせた二価の有機基を表し、Ｒ⁸及びＲ⁹はそれぞれ独立に、水素原子、炭素原子数１～５のアルキル基、炭素原子数２～６のアルケニル基、炭素原子数５～１０のシクロアルキル基、又は炭素原子数６～１２のアリール基を表す、［１］～［５］のいずれかに記載の熱硬化性樹脂組成物。
［７］
式（２）－１に示す構造単位の一分子あたりの平均数をｐ、式（２）－２に示す構造単位の一分子あたりの平均数をｑとしたときに、ｐは１．１～３５の実数、ｐ＋ｑは１．１～３５の実数であり、かつｑは式：ｐ／（ｐ＋ｑ）の値が０．４～１となる実数を満たす、［６］に記載の熱硬化性樹脂組成物。
［８］
前記ポリマレイミド化合物（Ｂ）が、芳香族ビスマレイミド化合物である、［１］～［７］のいずれかに記載の熱硬化性樹脂組成物。
［９］
前記ラジカル開始剤（Ｄ）が、有機過酸化物である、［１］～［８］のいずれかに記載の熱硬化性樹脂組成物。
［１０］
さらに充填材（Ｅ）を含む、［１］～［９］のいずれかに記載の熱硬化性樹脂組成物。
［１１］
前記充填材（Ｅ）が、シリカ、アルミナ、酸化マグネシウム、及び固体ゴム粒子からなる群から選択される少なくとも一種である、［１０］に記載の熱硬化性樹脂組成物。
［１２］
前記充填材（Ｅ）の含有量が、前記ポリアルケニルフェノール化合物（Ａ）、前記ポリマレイミド化合物（Ｂ）、前記ポリエチレングリコール化合物（Ｃ）、及び前記ラジカル開始剤（Ｄ）の合計１００質量部に対して２００～１９００質量部である、［１０］又は［１１］に記載の熱硬化性樹脂組成物。
［１３］
［１］～［１２］のいずれかに記載の熱硬化性樹脂組成物の硬化物。
［１４］
［１］～［１２］のいずれかに記載の熱硬化性樹脂組成物をモールディング成形する、構造体の製造方法。
［１５］
［１３］に記載の硬化物を含む構造体。 That is, the present invention relates to the following [1] to [15].
[1]
A thermosetting resin composition comprising 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 represented by formula (1), and the structural unit represented by formula (1) accounts for 90 mol % to 100 mol % of all structural units.
Thermosetting resin composition.

[2]
The content of the polyethylene glycol compound (C) is 1 to 10 mass% based on the total content of the polyalkenylphenol compound (A), the polymaleimide compound (B), and the polyethylene glycol compound (C). [1] The thermosetting resin composition according to claim 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 2,000 to 50,000.
[4]
The thermosetting resin composition according to any one of [1] to [3], wherein the content of the polyalkenylphenol compound (A) is 5 to 200 parts by mass per 100 parts by mass of the polymaleimide compound (B).
[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 formula (2)-2:

A polyalkenylphenol compound having a structural unit represented by the formula:
In formula (2)-1 and formula (2)-2, R ¹ 's each independently represent 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 's each independently represent a group represented by formula (3):

In formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; * in formula (3) represents a bond to a carbon atom constituting an aromatic ring; R ¹ and R ² may be the same or different in each phenol skeleton unit; each Q independently represents an alkylene group represented by formula -CR ⁸ R ⁹ -, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent organic group formed by combining ^these ; Each of ⁹ 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 [1] to [5].
[7]
The thermosetting resin composition according to [6], wherein p is a real number of 1.1 to 35, p+q is a real number of 1.1 to 35, and q is a real number such that the value of the formula: p/(p+q) is 0.4 to 1, where p is an average number of the structural units represented by formula (2)-1 per molecule, and q is an average number of the structural units represented by formula (2-2) per molecule.
[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 thermosetting resin composition according to [10] or [11], wherein the content of the filler (E) is 200 to 1900 parts by mass per 100 parts by mass of the total of the polyalkenylphenol compound (A), the polymaleimide compound (B), the polyethylene glycol compound (C), and the radical initiator (D).
[13]
A cured product of the thermosetting resin composition according to any one of [1] to [12].
[14]
A method for producing a structure, comprising molding the thermosetting resin composition according to any one of [1] to [12].
[15]
A structure comprising 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 that has excellent adhesion to metals and excellent reflow resistance without impairing moldability and the heat resistance of the cured product.

FIG. 2 is a schematic diagram of a molding die, a top plate, and a bottom plate used in evaluating demolding properties. FIG. 2 is a schematic diagram of a sample used for evaluating 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 2-alkenyl groups bonded to some or all of the aromatic rings forming the phenol skeletons in the molecule. As the 2-alkenyl group, a group having a structure represented by formula (3) is preferable.

In formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms. * in formula (3) represents a bond to a carbon atom constituting an aromatic ring.

Specific examples of the alkyl group having 1 to 5 carbon atoms constituting R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ in formula (3) 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 an n-pentyl group. Specific examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cycloheptyl group. 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, and a naphthyl group. The 2-alkenyl group represented by formula (3) is preferably an allyl group, that is, R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are all hydrogen atoms.

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

Examples of the basic skeleton of the polyalkenylphenol compound (A) include the skeletons of known phenol resins such as phenol novolac resin, cresol novolac resin, triphenylmethane type phenol resin, phenol aralkyl resin, biphenyl aralkyl phenol resin, and phenol-dicyclopentadiene copolymer resin. Among these, polyalkenylphenol compounds (A) having structural units shown in the following formula (2)-1 and, optionally, formula (2)-2, can be preferably used.

The structural units shown in formula (2)-1 and formula (2)-2 are preferred phenol skeleton units constituting the polyalkenylphenol compound (A), and the bonding order of these phenol skeleton units is not particularly limited. In formula (2)-1 and formula (2)-2, R ¹ is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and in formula (2)-1, R ² is each independently a 2-alkenyl group represented by formula (3). R ¹ and R ² may be the same or different in each phenol skeleton unit. Each Q is independently an alkylene group represented by ^{the formula -CR8R9- ,} a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic fused ring, or a divalent organic group consisting of a combination thereof; and each of ^R8 and ^R9 is independently 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.

When the average number of structural units per molecule shown in formula (2)-1 is p and the average number of structural units per molecule shown in formula (2)-2 is q, preferably, p is a real number from 1.1 to 35, p+q is a real number from 1.1 to 35, and q is a real number such that 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 ^R1 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, an n-pentyl group, etc. 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, etc.

In ^R8 and ^R9 of the alkylene group represented by the formula ^-CR8R9- , specific examples of the alkyl group having ¹ to 5 carbon atoms 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 an n-pentyl group, specific examples of the alkenyl group having 2 to 6 carbon atoms include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group, specific examples of the cycloalkyl group having 5 to 10 carbon atoms include a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a cycloheptyl group, and 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, and a naphthyl group.

Specific examples of the cycloalkylene group having 5 to 10 carbon atoms constituting Q include a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group, and a cycloheptylene group. Specific examples of the divalent organic group having an aromatic ring include a phenylene group, a tolylene group, a naphthylene group, a biphenylene group, a fluorenylene group, an anthracenylene group, a xylylene group, and a 4,4-methylenediphenyl group. The number of carbon atoms in 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. The number of carbon atoms in 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. It is preferable that Q is _--CH.sub.2-- because the viscosity of the polyalkenylphenol compound (A) is low and it is advantageous for mixing with the polymaleimide compound (B).

p is preferably a real number from 1.1 to 35, more preferably a real number from 2 to 30, and even more preferably a real number from 3 to 10. If p is 1.1 or more, the thermal decomposition onset temperature when the cured product of the thermosetting resin composition is placed in a high-temperature environment is appropriate, and if p is 35 or less, the viscosity of the thermosetting resin composition is in a range suitable for processing during molding.

p + q is preferably a real number from 1.1 to 35, more preferably a real number from 2 to 30, and even more preferably a real number from 3 to 10. If p + q is 1.1 or more, the thermal decomposition onset temperature when the cured product of the thermosetting resin composition is placed in a high-temperature environment is appropriate, and if it is 35 or less, the viscosity of the thermosetting resin composition is in a range suitable for processing during molding.

q is preferably a real number that gives a value of 0.4 to 1 in the formula p/(p+q), more preferably a real number that gives a value of 0.6 to 1 in the formula p/(p+q), and even more preferably a real number that gives a value of 0.8 to 1 in the formula p/(p+q). 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 shown in formula (2)-2. The polyalkenylphenol compound (A) can have only the structural unit shown in formula (2)-1. If q is a value that satisfies the above conditions, the degree of curing of the thermosetting resin composition can be 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. If the number average molecular weight Mn is 300 or more, the thermal decomposition onset temperature is appropriate when the cured product of the thermosetting resin composition is placed in a high-temperature environment, and if it is 5000 or less, the viscosity of the thermosetting resin composition is in a range suitable for processing during molding.

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

Specific examples of the raw phenol resin for polyalkenylphenol compound (A) include phenol novolac resin, cresol novolac resin, triphenylmethane type phenol resin, phenol aralkyl resin, biphenyl aralkyl resin, phenol-dicyclopentadiene copolymer resin, etc.

As the 2-alkenyl etherification reaction of the raw phenolic resin, there can be mentioned two examples: (i) a known method of reacting a halogenated 2-alkenyl compound such as allyl chloride, methallyl chloride, or allyl bromide with a phenolic compound, and (ii) a known method of reacting a 2-alkenyl carboxylate compound such as allyl acetate with a phenolic compound. For the 2-alkenyl etherification reaction using a halogenated 2-alkenyl compound, the method described in JP-A-2-91113 can be used. For the method of reacting a 2-alkenyl carboxylate compound with a phenolic resin, the method described in JP-A-2011-26253 can be used.

The amount of the halogenated 2-alkenyl compound or the 2-alkenyl carboxylate compound used relative to the phenolic hydroxyl group is preferably 0.4 to 5.0 equivalents, more preferably 0.6 to 4.0 equivalents. If it is 0.4 equivalents or more, the amount of reaction sites with the polymaleimide compound (B) after the Claisen rearrangement is more appropriate, and a cured product with better heat resistance can be obtained.

The 2-alkenyl etherification reaction is carried out by mixing a 2-alkenyl compound with the raw phenolic resin and reacting for 4 to 40 hours. In the 2-alkenyl etherification reaction, a solvent in which the raw phenolic resin dissolves can be used. The reaction can also be carried out without a solvent by using a 2-alkenyl carboxylic acid compound in which the raw phenolic resin can be dissolved.

The 2-alkenyl etherification rate of the raw material phenolic resin can also be controlled by using a larger amount of a halogenated 2-alkenyl compound or a 2-alkenyl carboxylate compound than the above-mentioned amount and adjusting the reaction time to be shorter than the above-mentioned reaction time, thereby suppressing the reaction rate (conversion rate) of the 2-alkenyl compound to a low level.

The desired polyalkenylphenol compound (A) can be obtained by subjecting the polyalkenyl ether compound produced by the method described in (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 can be carried out using a high-boiling point solvent or without a solvent. In order to promote the rearrangement reaction, an inorganic salt such as sodium thiosulfate or sodium carbonate can be added. Details are disclosed, for example, in JP-A-2-91113.

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

In formula (4), * represents a bond to an organic group containing an aromatic ring or a linear, branched, or cyclic aliphatic hydrocarbon group.

Examples of the polymaleimide compound (B) include bismaleimides such as bis(4-maleimidophenyl)methane, trismaleimides such as tris(4-maleimidophenyl)methane, tetrakismaleimides such as bis(3,4-dimaleimidophenyl)methane, and polymaleimides such as poly(4-maleimidostyrene). Examples of the polymaleimide compound (B) include aromatic polymaleimide compounds and aliphatic polymaleimide compounds, with aromatic polymaleimide compounds being preferred since the resulting cured product has particularly excellent flame retardancy.

An aromatic polymaleimide compound is a compound having two or more maleimide groups represented by formula (4), and these maleimide groups are bonded to the same or different aromatic rings. Specific examples of aromatic rings include single rings such as benzene, and condensed rings such as naphthalene and anthracene. Since they are well mixed in the curable resin composition, the polymaleimide compound (B) is preferably an aromatic bismaleimide compound or an aliphatic bismaleimide compound, and more preferably an aromatic bismaleimide compound.

Specific examples of aromatic bismaleimide compounds include bis(4-maleimidophenyl)methane, bis(3-maleimidophenyl)methane, bis(3-methyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3-ethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane, bis(3-propyl-4-maleimidophenyl)methane, bis(3,5-dipropyl-4-maleimidophenyl)methane, bis(3-butyl-4-maleimidophenyl)methane, bis(3,5-dibutyl-4-maleimidophenyl)methane, bis(3-ethyl-4-maleimido-5-methylphenyl)methane, 2,2-bis(4-maleimidophenyl)propane Pan, 2,2-bis[4-(4-maleimidophenyloxy)phenyl]propane, bis(4-maleimidophenyl)ether, bis(3-maleimidophenyl)ether, bis(4-maleimidophenyl)ketone, bis(3-maleimidophenyl)ketone, bis(4-maleimidophenyl)sulfone, bis(3-maleimidophenyl)sulfone, bis[4-(4-maleimidophenyloxy)phenyl]sulfone, bis(4-maleimidophenyl)sulfide, bis(3-maleimidophenyl)sulfide, bis(4-maleimidophenyl)sulfoxide, bis(3-maleimidophenyl)sulfoxide, 1,4-bis(4-maleimidophenyl)cyclohexane, 1,4-dimaleimidonaphthalene, 2,3-dimaleimide Naphthalene, 1,5-dimaleimido naphthalene, 1,8-dimaleimido naphthalene, 2,6-dimaleimido naphthalene, 2,7-dimaleimido naphthalene, 4,4'-dimaleimido biphenyl, 3,3'-dimaleimido biphenyl, 3,4'-dimaleimido biphenyl, 2,5-dimaleimido-1,3-xylene, 2,7-dimaleimido fluorene, 9,9-bis(4-maleimido phenyl) fluorene, 9,9-bis(4-maleimido-3-methyl phenyl) fluorene, 9,9-bis(3-ethyl-4-maleimido phenyl) fluorene, 3,7-dimaleimido-2-methoxy fluorene, 9,10-dimaleimido phenanthrene, 1,2-dimaleimido anthraquinone, 1,5-dimaleimido anthraquinone, 2,6- Dimaleimide anthraquinone, 1,2-dimaleimide benzene, 1,3-dimaleimide benzene, 1,4-dimaleimide benzene, 1,4-bis(4-maleimidephenyl)benzene, 2-methyl-1,4-dimaleimide benzene, 2,3-dimethyl-1,4-dimaleimide benzene, 2,5-dimethyl-1,4-dimaleimide benzene, 2,6-dimethyl-1,4-dimaleimide benzene, 4-ethyl-1,3-dimaleimide benzene, 5-ethyl-1,3-dimaleimide benzene, 4,6-dimethyl-1,3-dimaleimide benzene, 2,4,6-trimethyl-1,3-dimaleimide benzene, 2,3,5,6-tetramethyl-1,4-dimaleimide benzene, 4-methyl-1,3-dimaleimide benzene, and the like.

Specific examples of aliphatic bismaleimide compounds include bis(4-maleimidocyclohexyl)methane, bis(3-maleimidocyclohexyl)methane, etc. Among these, bis(4-maleimidophenyl)methane and 2,2-bis[4-(4-maleimidophenyloxy)phenyl]propane are preferred. Commercially available products include, for example, the BMI (trade name, Daiwa Kasei Kogyo Co., Ltd.) series.

When the polymaleimide compound (B) is taken as 100 parts by mass, the amount of the polyalkenylphenol compound (A) is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 30 to 100 parts by mass. If the amount is 5 parts by mass or more, the flowability during molding is better. On the other hand, if the amount is 200 parts by mass or less, the heat resistance of the cured product is better.

式（１）の構造単位は、好ましくは９５モル％～１００モル％であり、より好ましくは９７モル％～１００モル％である。 [Polyethylene glycol compound (C)]
The polyethylene glycol compound (C) is a compound having a structural unit of the formula (1), in which the structural unit of the formula (1) accounts for 90 mol % to 100 mol % of all structural units.

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

Without being bound by any theory, the polyethylene glycol compound (C) has good miscibility with both the polyalkenylphenol compound (A) and the polymaleimide compound (B), so adding the polyethylene glycol compound (C) can improve the compatibility of the polyalkenylphenol compound (A) and the polymaleimide compound (B). In addition, when a release agent is used, the polyethylene glycol compound (C) itself is moderately compatible and can control the surface separation property of the release agent. This effect can suppress the bleeding out of the release agent and other components. Furthermore, since the high molecular weight polyethylene glycol compound (C) is a stable component even at high temperatures, it can also adjust the fluidity of the thermosetting resin composition and the surface wettability of the thermosetting resin composition to the mold during molding. Due to these effects, the addition of the high molecular weight polyethylene glycol compound (C) can further suppress bleeding out.

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

The structural units other than formula (1) of the polyethylene glycol compound (C) are 0 to 10 mol %, preferably 0 to 5 mol %, and more preferably 0 to 3 mol %, based on the total structural units. Examples of structural units other than formula (1) include structural units constituting a branched structure; structural units containing terminal functional groups such as optionally substituted amino groups, carboxy groups, sulfonic acid groups, hydroxy groups, glycidyl groups, azide groups, cyano groups, thiol groups, and unsaturated hydrocarbon groups; and structural units produced as by-products during compound synthesis.

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

The content of the polyethylene glycol compound (C) is preferably 1 to 10% by mass, more preferably 1.3 to 7% by mass, and even more preferably 1.5 to 5% by mass, based on the total of the polyalkenylphenol compound (A), the polymaleimide compound (B), and the polyethylene glycol compound (C). If 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, if 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, and the bleeding out of the polyethylene glycol compound (C) after curing can be further suppressed.

[Radical initiator (D)]
By blending the radical initiator (D) in the thermosetting resin composition, the curing of the thermosetting resin composition can be promoted. Examples of the radical initiator (D) include thermal radical initiators. 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, and specific examples thereof include dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide.

The preferred amount of radical initiator (D) used is 0.01 to 10 parts by mass, more preferably 0.05 to 7.5 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of the polyalkenylphenol compound (A), the polymaleimide compound (B), and the polyethylene glycol compound (C). If the amount of radical initiator (D) used is 0.01 parts by mass or more, the curing reaction proceeds sufficiently, and if 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 include 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, and can be appropriately selected depending on the application. 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 the thermosetting resin composition is used for semiconductor sealing, it is preferable to blend an insulating inorganic filler in order to obtain a cured product with a low thermal expansion coefficient. The inorganic filler is not particularly limited, and known fillers can be used. Specific examples of inorganic fillers include particles of silica such as amorphous silica and crystalline silica, alumina, boron nitride, aluminum nitride, silicon nitride, and the like. From the viewpoint of reducing viscosity, spherical amorphous silica is preferable. 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 the maximum particle size is preferably 100 μm or less, particularly preferably 75 μm or less. When the average particle size is within this range, the viscosity of the thermosetting resin composition during use is appropriate, and the injectability into narrow-pitch wiring parts or narrow gap parts is also appropriate. The average particle size referred to here is the volume cumulative particle size _D50 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 depending on the application. The content of the filler (E) in the thermosetting resin composition is preferably 200 to 1900 parts by mass, more preferably 300 to 1000 parts by mass, and even more preferably 300 to 600 parts by mass, per 100 parts by mass of the total of the polyalkenylphenol compound (A), the polymaleimide compound (B), the polyethylene glycol compound (C), and the radical initiator (D).

[Other additives]
As other additives, it is also possible to blend in the thermosetting resin composition a coupling agent, a defoaming agent, a colorant, a phosphor, a modifier, a leveling agent, a light diffusing agent, a flame retardant, an adhesion imparting agent, a mold release agent, etc. The other additives do not include compounds corresponding to the polyalkenylphenol compound (A), the polymaleimide compound (B), the polyethylene glycol compound (C), the radical initiator (D), and the filler (E).

For example, a coupling agent may be added from the viewpoint of improving adhesion. The coupling agent is not particularly limited, and examples thereof include silane coupling agents such as vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. The coupling agent may be used alone or in combination of two or more. The amount of the coupling agent in the thermosetting resin composition is preferably 0.1 to 5% by mass. If the amount is 0.1% by mass or more, the effect of the coupling agent is fully exerted, and if it is 5% by mass or less, the melt viscosity, the moisture absorption property and the strength of the cured product are better.

For example, a release agent may be blended from the viewpoint of improving releasability. The release agent is not particularly limited, and examples thereof include carnauba wax, amide wax, Montan acid ester wax, Montan acid partially saponified ester wax, metal soaps such as calcium stearate, polyethylene wax, polypropylene wax, etc. Among these, carnauba wax, Montan acid ester wax, and polyethylene wax are preferred. The release agent may be used alone or in combination of two or more. The amount of the release agent blended in the thermosetting resin composition is preferably 0.01 to 0.5% by mass. If the blending amount is 0.01% by mass or more, the effect of the release agent is fully exerted, and if it is 0.5% by mass or less, bleeding out of mold stains and the like does not occur and the appearance is good.

[Method for preparing thermosetting resin composition]
The method for preparing the thermosetting resin composition is not particularly limited as long as the polyalkenylphenol compound (A), the polymaleimide compound (B), the polyethylene glycol compound (C), the radical initiator (D), and other optional components can be uniformly mixed and dispersed. A method in which the polyalkenylphenol compound (A), the polymaleimide compound (B), and the polyethylene glycol compound (C) are first melt-mixed, and then the radical initiator (D) and optional additives are added is preferred because each material can be easily mixed uniformly.

The method of mixing each component is not particularly limited. Each component can be mixed in a predetermined mixing ratio by adding it to a mixer such as a reaction vessel, a pot mill, a two-roll mill, a three-roll mill, a rotary mixer, a twin-screw mixer, a disperser, a single-screw or twin-screw (same-direction or different-direction) extruder, or a kneader, and stirring or kneading it. On a laboratory scale, a rotary mixer is preferred because the stirring conditions can be easily changed, and industrially, a twin-screw mixer is preferred from the viewpoint of productivity. Each mixer can be used by changing the stirring conditions as appropriate.

When powdering a thermosetting resin composition, there are no particular limitations on the method as long as the resin does not melt due to the heat generated during the work process, but if the amount is small, a method using an agate mortar is convenient. When using a commercially available grinder, one that generates less heat during grinding is preferred in order to prevent the mixture from melting. The particle size of the powder is preferably 1 mm or less.

[Method of fabricating the structure]
The thermosetting resin composition can be melted by heating to a temperature at which the curing reaction does not proceed rapidly. The molten thermosetting resin composition can be molded into any desired shape, cured as necessary, and demolded to produce a structure. As a method for producing the structure, molding, particularly transfer molding and compression molding, are preferred.

Preferred conditions for transfer molding, for example, in the case of a mold having dimensions of 10 mm×75 mm×3 mm thickness, are a top plate and mold temperature of 170 to 190° C., a holding pressure of 50 to 150 kg/cm ² , and a holding time of 1.5 to 10 minutes. Preferred conditions for compression molding, for example, in the case of a mold having dimensions of 100 mm×75 mm×3 mm thickness, are a top plate and mold temperature of 170 to 190° C., a molding pressure of 5 to 20 MPa, and a pressure time of 1.5 to 10 minutes.

[Method of 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. If the curing temperature is 130°C or higher, the thermosetting resin composition before curing can be sufficiently melted and easily filled into a mold, and it is also easy to demold after curing. If the curing temperature is 300°C or lower, thermal deterioration or volatilization of the material can be avoided.

The heating time can be changed as appropriate depending on the thermosetting resin composition and the curing temperature, but from the viewpoint of productivity, 0.1 to 24 hours is preferable. This heating may be performed in multiple steps. When a particularly high degree of curing is required, it is preferable not to cure at an excessively high temperature, but to raise the temperature as the curing progresses, for example, so that the final curing temperature is 250°C or less, and more preferably 230°C or less.

[Applications of the cured product]
The cured product of the thermosetting resin composition can be used for applications such as semiconductor encapsulation materials, prepregs, interlayer insulating resins, solder resists, and die attach.

The present invention will be described in detail below based on examples and comparative examples, but the present invention is not limited to these examples.

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

<Analysis and Characterization Methods>
[Molecular weight]
The measurement conditions for GPC are as follows.
Device name: JASCO LC-2000 plus (JASCO Corporation)
Column: Shodex (registered trademark) LF-804 (Showa Denko K.K.)
Mobile phase: tetrahydrofuran Flow rate: 1.0 mL/min
Detector: JASCO RI-2031 plus (JASCO Corporation)
Temperature: 40°C
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 under the above measurement conditions.

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

[Glass transition temperature]
The heat resistance of the cured product was evaluated from the viewpoint of glass transition temperature (Tg). Specifically, a transfer molding machine was used to mold the thermosetting resin composition under conditions of a mold temperature of 180°C, a holding pressure of 100 kg/ ^cm2 , and a holding time of 3 minutes, and a test piece for measuring the glass transition temperature of 5 mm x 5 mm x 5 mm was prepared. The test piece was heated at 200°C for 5 hours to post-cure, and then measured by thermomechanical measurement (TMA). The measurement was performed using a TMA/SS6100 thermomechanical analyzer manufactured by SII Nano Technology Co., Ltd. under conditions of a temperature range of 30 to 300°C, a heating rate of 5°C/min, and a load of 20.0 mN, and the inflection point of the linear expansion coefficient was taken as Tg.

[Releasability]
The moldability was evaluated from the viewpoint of releasability from the mold. Specifically, a transfer molding machine equipped with a molding die 1 (test piece size: lower diameter: 25 mmφ, upper diameter: 10 mmφ, upper thickness: 7 mm, lower thickness: 7 mm, taper: 2°) and a top plate 2 and a bottom plate 3 shown in FIG. 1 was used to mold a thermosetting resin composition 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 the demolding force when pressed from above with a spring scale was measured as shown in FIG. Multiple moldings were performed in succession, and the number of continuous moldings at which the average value of the demolding force on the left and right sides was kept 40 N or less was recorded. When the average value exceeded 40 N, or when the number of moldings reached 10, the evaluation was terminated.

[Appearance (bleed out)]
The moldability was also evaluated from the viewpoint of appearance. Specifically, a thermosetting resin composition was molded using a transfer molding machine under conditions of a mold temperature of 180° C., a holding pressure of 100 kg/cm ² , and a holding time of 3 minutes, and the mold and molded product obtained were visually observed after removal. Molding and demolding were repeated under the above conditions, and the mold was evaluated as good when there was no clouding on the mold and no resin exuded from the surface of the molded product after 10 moldings and demoldings, fair when at least one of resin exudation and mold staining was observed after the 3rd to 10th moldings, and poor when at least one of resin exudation and mold staining was observed after the 1st to 2nd moldings.

[Adhesion rate after molding]
The lead frame used was made of rolled oxygen-free copper (C1020), with outer dimensions of 52 mm wide, 38 mm long, and 0.5 mm thick, and a bed with a length and width of 18 mm in the center. The bed was enclosed with an outer dimension of 30 mm long, 30 mm wide, and 3 mm thick, centered on the center of the lead frame. The sealing was performed by molding the thermosetting resin composition using a transfer molding machine under conditions of a mold temperature of 180°C, a holding pressure of 100 kg/cm ² , and a holding time of 3 minutes, and the obtained test piece was post-cured at 200°C for 5 hours. The post-cured test piece was observed for peeling at the interface between the lead frame and the cured product of the thermosetting resin composition 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 part by the total area was determined as the post-molding adhesion rate.

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

<Ingredients>
[Polyalkenylphenol compound (A)]
BRG-APO (in formula (2)-1, R ¹ is a hydrogen atom, Q is -CR ⁸ R ⁹ -, R ⁸ and R ⁹ are hydrogen atoms, and in formula (3) R ³ to R ⁷ are hydrogen atoms)
A 1:1 mixture of phenolic novolak resins Shownol (registered trademark) BRG-556 and BRG-558 (Aica Kogyo Co., Ltd.) was used to produce a resin in which the ortho- or para-position of the phenolic hydroxyl group was allylated (hydroxyl equivalent 154, number average molecular weight Mn 1000, weight average molecular weight Mw 3000, polymerization degree 6.6, p = 6.6, q = 0, p/(p + q) = 1). For the production method, see Example 1 of JP2016-28129A.

HE100C-APO (R ¹ in formula (2)-1 and formula (2)-2 is a hydrogen atom, Q is a p-xylylene group, and R ³ to R ⁷ in formula (3) are hydrogen atoms)
A resin (hydroxyl equivalent 222, number average molecular weight Mn 900, weight average molecular weight Mw 1900, degree of polymerization 4.0, p = 3.8, q = 0.2, p/(p + q) = 0.95) was produced in which the ortho- or para-position of the phenolic hydroxyl group was allylated using phenol aralkyl resin HE100C-10-15 (Air Water Inc.) in a manner similar to Example 1 of JP2016-28129A.

[Polymaleimide compound (B)]
BMI-4000 (2,2-bis[4-(4-maleimidophenyloxy)phenyl]propane, Daiwa Chemical Industry Co., Ltd.)
BMI-1100H (bis(4-maleimidophenyl)methane, Daiwa Chemical Industry Co., Ltd.)

[Polyethylene glycol compound (C)]
PEG-4000 (polyethylene glycol, Mn 4000, Mw 5000, 100 mol% of the structural unit of formula (1), Toho Chemical Industry Co., Ltd.)
PEG-6000 (polyethylene glycol, Mn 6000, Mw 7300, 100 mol% of structural unit of formula (1), Toho Chemical Industry Co., Ltd.)
PEG-10000 (polyethylene glycol, Mn 10000, Mw 14000, 100 mol% of structural unit of formula (1), Sanyo Chemical Industries, Ltd.)
PEG-20000 (polyethylene glycol, Mn 21000, Mw 26000, 100 mol% of structural unit of formula (1), Sanyo Chemical Industries, Ltd.)
Lionon MO-60 (polyethylene glycol monooleate, Mn 7200, Mw 8000, 94 mol% of the structural unit of formula (1), Lion Specialty Chemicals Co., Ltd.)

[Radical initiator (D)]
Percumyl (registered trademark) D (Dicumyl peroxide, NOF Corporation)

[Filler (E)]
Silica filler MSR5100 (spherical silica, average particle size 22.7 μm, Tatsumori 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 Rica Corporation)
LICOWAX (registered trademark) PE520 (polyethylene wax, Clariant Chemicals Co., Ltd.)

As other resins, the following compounds were used.
KF6004 (silicone PEG, Mn 3000, Mw 4500, 50 mol% of structural unit of formula (1), 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
[Production 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), 1.5 parts by mass of Parkmil D as radical initiator (D), 400 parts by mass of MSR5100 as filler (E), 0.4 parts by mass of carnauba wax as a mold release agent and 0.15 parts by mass of PE520 were mixed and melt-kneaded (2 rolls (roll diameter 8 inches) manufactured by Toyo Seiki Seisakusho Co., Ltd., 110 ° C., 10 minutes). After cooling and solidifying at room temperature (25 ° C.) for 1 hour, it was pulverized using a mill mixer (Osaka Chemical Co., Ltd., model WB-1, 25 ° C., 30 seconds) to obtain a powdered thermosetting resin composition.

[Analysis and Characterization]
The above-mentioned analyses were carried out on the obtained thermosetting resin composition, and the composition was compressed into tablets using a tableting machine (Fuji Yakuhin Kikai Co., Ltd.) and then transfer molded to prepare each test piece to be used in the above-mentioned property evaluation, and the properties were evaluated.

<Examples 2 to 8, Comparative Examples 1 to 3>
Thermosetting resin compositions were produced in the same manner as in Example 1, except that the types and amounts of raw materials were changed as shown in Table 1, and analysis and characteristic evaluation were performed.

Examples 1 to 8 were good in terms of releasability, post-molding adhesion rate, post-reflow adhesion rate, and appearance. In addition, Examples 1 to 8 also had excellent heat resistance of the cured products. On the other hand, Comparative Examples 1 and 2, which did not contain polyethylene glycol compound (C), had poor releasability and appearance, and the adhesion rate after reflow was extremely low. Comparative Example 3, which was based on an epoxy resin, had poor releasability and appearance, and also had a low adhesion rate after reflow resistance.

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

Claims (15)

A thermosetting resin composition comprising a polyalkenylphenol compound (A), a polymaleimide compound (B), a polyethylene glycol compound (C), and a radical initiator (D),
The polyalkenylphenol compound (A) is a compound having at least two phenol skeletons in the molecule, and having 2-alkenyl groups bonded to some or all of the aromatic rings forming the phenol skeletons in the molecule,
The polyethylene glycol compound (C) has a structural unit represented by formula (1), and the structural unit represented by formula (1) accounts for 90 mol % to 100 mol % of all structural units.
Thermosetting resin composition.
The thermosetting resin composition according to claim 1, wherein the content of the polyethylene glycol compound (C) is 1 to 10 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 or 2, wherein the number average molecular weight Mn of the polyethylene glycol compound (C) is 2,000 to 50,000. The thermosetting resin composition according to any one of claims 1 to 3, wherein the content of the polyalkenylphenol compound (A) is 5 to 200 parts by mass per 100 parts by mass of the polymaleimide compound (B). 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 formula (2)-2:
A polyalkenylphenol compound having a structural unit represented by the formula:
In formula (2)-1 and formula (2)-2, R ¹ 's each independently represent 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 's each independently represent a group represented by formula (3):
In formula (3), R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms; * in formula (3) represents a bond to a carbon atom constituting an aromatic ring; R ¹ and R ² may be the same or different in each phenol skeleton unit; each Q independently represents an alkylene group represented by formula -CR ⁸ R ⁹ -, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent organic group formed by combining ^these ; ⁹ 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. The thermosetting resin composition according to claim 6, wherein p is a real number between 1.1 and 35, p+q is a real number between 1.1 and 35, and q is a real number such that the value of the formula p/(p+q) is between 0.4 and 1, where p is the average number of structural units per molecule as shown in formula (2)-1, and q is the average number of structural units per molecule as shown in formula (2)-2. 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 thermosetting resin composition according to claim 10 or 11, wherein the content of the filler (E) is 200 to 1900 parts by mass per 100 parts by mass of the total of the polyalkenylphenol compound (A), the polymaleimide compound (B), the polyethylene glycol compound (C), and the radical initiator (D). A cured product of the thermosetting resin composition according to any one of claims 1 to 12. A method for manufacturing a structure, comprising molding the thermosetting resin composition according to any one of claims 1 to 12. A structure comprising the cured product according to claim 13.

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