JP7367766B2 - Thermosetting resin composition, cured product thereof, and structure containing the cured product - 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, semiconductor packages used in electronic equipment and industrial equipment have been required to have performances such as high-density wiring, miniaturization, thinness, high heat resistance, and high heat dissipation due to the high density integration of electronic components. There is. Therefore, sealing materials that are plastic materials are also required to have high heat resistance.

Transfer molding involves heating and softening the material in a plunger, pushing the heated softened material into a heated mold cavity through channels in the mold such as gates, sprues, and runners. This is a method of curing. Since the material is injected into the cavity in a highly fluid state, molding can be performed at low pressure. Transfer molding is characterized by less damage to inserts than other molding methods that require high pressure. Transfer molding is known as a typical molding method for sealing power semiconductors and ICs because it allows miniaturization and fine processing and has high productivity.

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

Patent Document 1 (Japanese Unexamined Patent Application Publication No. 11-140277) discloses (A) a phenol resin containing 30 to 100 parts by mass of a novolac structure phenol resin containing a biphenyl derivative and/or a naphthalene derivative in the molecule, in the total amount of phenol resin; (B) an epoxy resin containing 30 to 100 parts by mass of a novolac structure epoxy resin containing biphenyl derivatives and/or naphthalene derivatives in the molecule, (C) an inorganic filler, and (D) a curing accelerator. An epoxy resin composition for semiconductor encapsulation is described, which is characterized in that the composition is an essential component.

Patent Document 2 (Japanese Unexamined Patent Publication No. 5-43630) discloses an aromatic bismaleimide containing N,N'-(alkyl-substituted diphenylmethane) bismaleimide and polyallylphenol derived from a condensed polyphenol of salicylaldehyde and phenol. The resin composition is described.

Patent Document 3 (Japanese Unexamined Patent Publication No. 5-6869) discloses (A) a maleimide compound having two or more maleimide groups in one molecule, (B) an allylated phenol resin having a specific repeating unit, and (C) A semiconductor device is described in which a semiconductor element is sealed 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 with a specific structure, and an epoxy group-containing organic silane compound 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

It has been found that the use of bismaleimide resin improves the heat resistance of molded products compared to conventionally used epoxy-phenolic thermosetting resin materials (Patent Documents 2 to 4). However, conventional sealing materials using bismaleimide resin have a drawback that their adhesion to other members, especially metal materials, is extremely low compared to epoxy-phenolic thermosetting resin materials. Electronic devices include metal parts such as copper that play a role in conductor and cooling, and peeling between the metal and the encapsulant poses a problem in terms of internal protection. Therefore, the challenge is to improve the adhesion between the metal and the sealant. On the other hand, if the adhesion to the molding die is improved, it will not separate from the mold and will become impossible to mold, which will pose a problem in production. Therefore, it is strongly desired to realize a sealing material that is easy to mold and has high adhesion to metal.

The present disclosure describes a thermosetting resin composition that has excellent adhesion and adhesion to metal without impairing moldability.

（式中、Ｒ¹及びＲ²は水素原子、ハロゲン原子、炭素原子数１～３のアルキル基、水酸基、カルボキシ基、又はアミノ基であり、Ｒ¹及びＲ²の少なくとも一方はアミノ基である。Ｒ³は水素原子、炭素原子数１～３のアルキル基、炭素原子数２～３のアルケニル基、又はシアノ基であり、Ｒ⁴は水素原子、又は炭素原子数１～３のアルキル基である。）
［２]
前記化合物（Ｃ）は、６－アミノインダゾール、５－アミノインダゾール、６－アミノ－５－メチルインダゾール、６－アミノ－５－エチルインダゾール、６－アミノ－５－ヒドロキシインダゾール、６－アミノ－５－ブロモインダゾール、６－アミノ－５－クロロインダゾール、３－シアノ－５－アミノインダゾール、５－カルボキシ－６－アミノインダゾール、及び５，６－ジアミノインダゾールから選択される少なくとも一種を含む、上記態様１に記載の熱硬化性樹脂組成物。
［３]
前記化合物（Ｃ）が５－アミノインダゾール、及び６－アミノインダゾールから選択される少なくとも一種を含む、上記態様２に記載の熱硬化性樹脂組成物。
［４]
前記化合物（Ｃ）の含有量が前記ポリアルケニルフェノール化合物（Ａ）と前記ポリマレイミド化合物（Ｂ）の合計１００質量部に対して０．０５質量部～５質量部である、上記態様１～３のいずれかに記載の熱硬化性樹脂組成物。
［５]
前記ポリアルケニルフェノール化合物（Ａ）の配合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、上記態様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し、式（２）－１及び式（２）－２において、Ｒ⁵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、Ｒ⁶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、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰及びＲ¹¹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、Ｒ⁵及びＲ⁶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、式（２）－１及び式（２）－２におけるＱはそれぞれ独立に式－ＣＲ¹²Ｒ¹³－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、Ｒ¹²及びＲ¹³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、上記態様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、上記態様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、上記態様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、上記態様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、上記態様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、上記態様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、上記態様１０又は１１に記載の熱硬化性樹脂組成物。
［１３]
上記態様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]
上記態様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]
上記態様１３に記載の硬化物を含む構造体。The present invention includes the following aspects.
[1]
A thermosetting resin composition containing a polyalkenylphenol compound (A), a polymaleimide compound (B), a compound (C) having a structure represented by formula (1), and a radical initiator (D).

(In the formula, R ¹ and R ² are a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, a carboxy group, or an amino group, and at least one of R ¹ and R ² is an amino group. .R ³ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a cyano group, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. be.)
[2]
The compound (C) is 6-aminoindazole, 5-aminoindazole, 6-amino-5-methylindazole, 6-amino-5-ethylindazole, 6-amino-5-hydroxyindazole, 6-amino-5- The above embodiment 1 contains at least one selected from bromoindazole, 6-amino-5-chloroindazole, 3-cyano-5-aminoindazole, 5-carboxy-6-aminoindazole, and 5,6-diaminoindazole. The thermosetting resin composition described.
[3]
The thermosetting resin composition according to the above aspect 2, wherein the compound (C) contains at least one selected from 5-aminoindazole and 6-aminoindazole.
[4]
Embodiments 1 to 3 above, wherein the content of the compound (C) is 0.05 parts by mass to 5 parts by mass based on a total of 100 parts by mass of the polyalkenylphenol compound (A) and the polymaleimide compound (B). The thermosetting resin composition according to any one of the above.
[5]
The thermosetting resin composition according to any one of aspects 1 to 4, wherein the polyalkenylphenol compound (A) is blended in an amount of 5 to 200 parts by mass based on 100 parts by mass of the polymaleimide compound (B). .
[6]
The polyalkenylphenol compound (A) has the formula (2)-1:

and optionally formula (2)-2:

In formula (2)-1 and formula (2)-2, R ⁵ is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a structural unit having 1 to 5 carbon atoms. 5 represents an alkoxy group, and each R ⁶ independently represents the formula (3):

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

According to the present disclosure, a thermosetting resin composition having excellent adhesion and adhesion to metal can be obtained without impairing moldability. The thermosetting resin composition of the present disclosure can be cured in an appropriate amount of time and provides excellent productivity. A highly reliable cured product can be formed using the thermosetting resin composition of the present disclosure.

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

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

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

Specific examples of the alkyl group having 1 to 5 carbon atoms constituting R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ in formula (3) include methyl group, ethyl group, n-propyl group, and isopropyl group. , n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, etc. 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 phenyl group, methylphenyl group, ethylphenyl group, biphenyl group, and naphthyl group. The 2-alkenyl group represented by formula (3) is preferably an allyl group, that is, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are all hydrogen atoms.

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

As the basic skeleton of the polyalkenylphenol compound (A), known compounds such as phenol novolac resin, cresol novolac resin, triphenylmethane type phenol resin, phenol aralkyl resin, biphenylaralkyl phenol resin, phenol-dicyclopentadiene copolymer resin, etc. An example is a phenolic resin skeleton. Among them, polyalkenylphenol compounds (A) having structural units shown in the following formula (2)-1 and optionally in the formula (2)-2 can be preferably used.

The structural units represented by formulas (2)-1 and (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 ⁵ 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; )-1, each R ⁶ is independently a 2-alkenyl group represented by formula (3). R ⁵ and R ⁶ may be the same or different in each phenol skeleton unit. Q in formulas (2)-1 and (2)-2 each independently represents an alkylene group represented by the formula -CR ¹² R ¹³ -, a cycloalkylene group having 5 to 10 carbon atoms, or a divalent group having an aromatic ring. , a divalent organic group having an alicyclic condensed ring, or a combination thereof, and R ¹² and R ¹³ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, group, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

When the average number of structural units 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, preferably p is 1. p+q is a real number from 1 to 35, and q satisfies a real number such that the value of the formula: p/(p+q) is from 0.4 to 1.

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

In R ¹² and R ¹³ of the alkylene group represented by the formula -CR ¹² R ¹³ -, specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, Examples include n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, etc. Specific examples of alkenyl groups having 2 to 6 carbon atoms include vinyl group, allyl group, butenyl group, and pentenyl group. Specific examples of the cycloalkyl group having 5 to 10 carbon atoms include cyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, etc. Specific examples of the 6-12 aryl group include phenyl group, methylphenyl group, ethylphenyl group, biphenyl group, and naphthyl group.

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

It is preferable that Q is a dicyclopentadienylene group, a phenylene group, a methylphenylene group, a xylylene group, or a biphenylene group from the viewpoint of high mechanical strength of the cured product. Q is preferably -CH ₂ - because the polyalkenylphenol compound (A) has a low viscosity and is advantageous for mixing with the polymaleimide compound (B).

p is preferably a real number from 1.1 to 35, more preferably from 2 to 30, still more preferably from 3 to 10. If p is 1.1 or more, the temperature at which thermal decomposition starts 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 is in a suitable range depending on the processing during molding.

p+q is preferably a real number from 1.1 to 35, more preferably from 2 to 30, still more preferably from 3 to 10. If p+q is 1.1 or more, the temperature at which thermal decomposition starts 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 appropriate. is in a suitable range depending on the processing during molding.

q is preferably a real number such that the value of the formula: p/(p+q) is 0.4 to 1, more preferably a real number such that the value of the formula: p/(p+q) is 0.6 to 1, More preferably, the value of the formula: p/(p+q) is a real number of 0.8 to 1. When the value of the formula: 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 formula (2)-2. The polyalkenylphenol compound (A) can consist of a structural unit shown in formula (2)-1. If q has a value that satisfies the above conditions, the degree of curing of the thermosetting resin composition can be made sufficient depending on the application.

The polyalkenylphenol compound (A) preferably has a number average molecular weight Mn of 300 to 5,000, more preferably 400 to 4,000, and even more preferably 500 to 3,000. If the number average molecular weight Mn is 300 or more, the thermal decomposition initiation 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 is in a suitable range depending on the processing during molding.

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

Specific examples of the raw material phenol resin for the polyalkenylphenol compound (A) include phenol novolak resin, cresol novolak resin, triphenylmethane type phenol resin, phenol aralkyl resin, biphenylaralkyl resin, phenol-dicyclopentadiene copolymer resin, etc. can be mentioned.

The 2-alkenyl etherification reaction of the raw material phenolic resin includes (i) a known method of reacting a halogenated 2-alkenyl compound such as allyl chloride, methallyl chloride, allyl bromide, etc. with a phenol compound, and (ii) a method of reacting allyl acetate with a phenol compound. Two known methods for reacting such a 2-alkenyl carboxylic acid compound with a phenol compound can be exemplified. For the 2-alkenyl etherification reaction using a halogenated 2-alkenyl compound, for example, the method described in JP-A-2-91113 can be used. As a method for reacting a 2-alkenyl carboxylic acid compound and a phenol resin, for example, the method described in JP-A No. 2011-26253 can be used.

The amount of the halogenated 2-alkenyl compound or carboxylic acid 2-alkenyl compound to be used relative 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 reaction sites with the polymaleimide compound (B) after Claisen rearrangement is more appropriate, and a cured product with 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 2-alkenyl carboxylic acid compound that can dissolve the raw material phenol resin. The 2-alkenyl etherification rate of the raw material phenol resin can be determined by using a halogenated 2-alkenyl compound or a carboxylic acid 2-alkenyl compound in a larger amount than the above-mentioned amount, and by adjusting the reaction time to be shorter than the above-mentioned reaction time. It can also be controlled by keeping the reaction rate (conversion rate) of the 2-alkenyl compound low.

The desired polyalkenylphenol compound (A) can be obtained by subjecting the polyalkenyl ether compound produced by the method described in (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 for 1 to 20 hours. The Claisen rearrangement reaction may be carried out using a high boiling point solvent, or may be carried out without a solvent. In order to promote the rearrangement reaction, inorganic salts such as sodium thiosulfate and sodium carbonate can also be added. Details are disclosed in, for example, Japanese Patent Laid-Open No. 2-91113.

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

In formula (4), * represents a bonding portion with an aromatic ring or an organic group containing 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, and tetrakismaleimides such as bis(3,4-dimaleimidophenyl)methane. and polymaleimides such as poly(4-maleimidostyrene). Examples of the polymaleimide compound include aromatic polymaleimide compounds and aliphatic polymaleimide compounds, and aromatic polymaleimide compounds are 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 the aromatic ring include monocyclic rings such as benzene, and fused rings such as naphthalene and anthracene. In order to mix well in the thermosetting resin composition, the polymaleimide compound (B) is preferably an aromatic bismaleimide compound and 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, and 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-maleimide) -5-methylphenyl)methane, 2,2-bis(4-maleimidophenyl)propane, 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-dimaleimidnaphthalene, 2,3-dimaleimidnaphthalene, 1,5-dimaleimidnaphthalene, 1,8-dimaleimidonaphthalene, 2,6-dimaleimidnaphthalene, 2, 7-dimaleimidonaphthalene, 4,4'-dimaleimidobiphenyl, 3,3'-dimaleimidobiphenyl, 3,4'-dimaleimidobiphenyl, 2,5-dimalimido-1,3-xylene, 2,7-dimaleimidobiphenyl Maleimidofluorene, 9,9-bis(4-maleimidophenyl)fluorene, 9,9-bis(4-maleimido-3-methylphenyl)fluorene, 9,9-bis(3-ethyl-4-maleimidophenyl)fluorene, 3,7-dimalimido-2-methoxyfluorene, 9,10-dimalimidophenanthrene, 1,2-dimalimidoanthraquinone, 1,5-dimalimidoanthraquinone, 2,6-dimalimidoanthraquinone, 1,2-dimalimidobenzene , 1,3-dimaleimidobenzene, 1,4-dimaleimidobenzene, 1,4-bis(4-maleimidophenyl)benzene, 2-methyl-1,4-dimaleimidobenzene, 2,3-dimethyl-1, 4-dimalimidobenzene, 2,5-dimethyl-1,4-dimaleimidobenzene, 2,6-dimethyl-1,4-dimalimidobenzene, 4-ethyl-1,3-dimaleimidobenzene, 5-ethyl- 1,3-dimaleimidobenzene, 4,6-dimethyl-1,3-dimaleimidobenzene, 2,4,6-trimethyl-1,3-dimaleimidobenzene, 2,3,5,6-tetramethyl-1 , 4-dimaleimidobenzene, 4-methyl-1,3-dimaleimidobenzene, and the like. Specific examples of aliphatic bismaleimide compounds include bis(4-maleimidocyclohexyl)methane, bis(3-maleimidocyclohexyl)methane, and the like. Among them, bis(4-maleimidophenyl)methane and 2,2-bis[4-(4-maleimidophenyloxy)phenyl]propane are preferred. Examples of commercially available products include the BMI (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) series.

When the polymaleimide compound (B) is 100 parts by mass, the amount of the polyalkenylphenol compound (A) is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and 20 to 200 parts by mass. More preferably, the amount is 130 parts by mass. If the above blending amount is 5 parts by mass or more, fluidity during molding will be better. On the other hand, if the above blending amount is 200 parts by mass or less, the heat resistance of the cured product will be better.

（式中、Ｒ¹及びＲ²は水素原子、ハロゲン原子、炭素原子数１～３のアルキル基、水酸基、カルボキシ基、又はアミノ基であり、Ｒ¹及びＲ²の少なくとも一方はアミノ基である。Ｒ³は水素原子、炭素原子数１～３のアルキル基、炭素原子数２～３のアルケニル基、又はシアノ基であり、Ｒ⁴は水素原子、又は炭素原子数１～３のアルキル基である。）で表される化合物である。このうちＲ¹及びＲ²の一方が水素原子であることが好ましく、Ｒ³、Ｒ⁴はいずれも水素原子であることが望ましい。[Compound (C)]
Compound (C) has the formula (1)

(In the formula, R ¹ and R ² are a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, a carboxy group, or an amino group, and at least one of R ¹ and R ² is an amino group. .R ³ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a cyano group, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ) is a compound represented by Among these, it is preferable that one of R ¹ and R ² is a hydrogen atom, and it is desirable that both R ³ and R ⁴ are hydrogen atoms.

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

Specific examples of the alkyl group having 1 to 3 carbon atoms constituting R ³ include methyl group, ethyl group, n-propyl group, and isopropyl group. Specific examples of alkenyl groups having 2 to 3 carbon atoms include vinyl groups and allyl groups.
R ³ is preferably a hydrogen atom, a methyl group, an ethyl group, a vinyl group, an allyl group, or a cyano group, more preferably a hydrogen atom, a methyl group, an ethyl group, or a cyano group, and even more preferably a hydrogen atom.

Specific examples of the alkyl group having 1 to 3 carbon atoms constituting R ⁴ include methyl group, ethyl group, n-propyl group, and isopropyl group.
R ⁴ is preferably a hydrogen atom, a methyl group, or an ethyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.

Examples of compound (C) include 6-aminoindazole, 5-aminoindazole, 6-amino-5-methylindazole, 6-amino-5-ethylindazole, 6-amino-5-hydroxyindazole, 6-amino-5 -bromoindazole, 6-amino-5-chloroindazole, 3-cyano-5-aminoindazole, 5-carboxy-6-aminoindazole, and 5,6-diaminoindazole. Among these, 6-aminoindazole and 5-aminoindazole are preferred in terms of their excellent gel time adjustment and affinity for metal surfaces, especially copper. It is thought that by controlling the gel time within an appropriate range, it is possible to improve the wetting of the thermosetting resin composition to the base material.

Since at least one of R ¹ and R ² is an amino group, the curing rate of compound (C) can be adjusted in the curing reaction by radical polymerization. Without being bound by any theory, it is believed that the aniline moiety of compound (C) temporarily captures and stabilizes radicals, thereby adjusting the curing rate of the thermosetting resin composition. The rate of radical polymerization is generally adjusted by the amount of radical polymerization initiator. If the radical polymerization reaction rate of the composition is too fast, the initial curing, for example, from 0 seconds to 30 seconds after the start of molding and curing, will proceed without sufficient wettability to the substrate, and the gap between the cured product and the substrate will progress. There is not enough adhesion force. However, if the amount of radical polymerization initiator is reduced in order to slow down radical polymerization, not only the initial curing but also the reaction rate in the middle of curing, for example from 30 seconds to 180 seconds after the start of molding curing, will slow down, and the reaction rate will be slow enough to take out the molded product from the mold. It takes longer to reach the desired hardness, which reduces productivity. By adding the compound (C), it is possible to prevent a decrease in productivity due to a delay in the curing speed while ensuring sufficient wetting to the base material. The pyrazole ring has higher chemical stability than the imidazole ring, which has a similar heterocyclic structure, and has very high polymerization activity toward the polymaleimide compound (B) that undergoes a polymerization reaction catalyzed by the imidazole ring. low. This point is also excellent in terms of curing speed adjustment.

Furthermore, the compound (C) has a high affinity for metals, and the amino group that is at least one of R ¹ and R ² is bonded to an ethylenically unsaturated bond contained in the maleimide group of the polymaleimide compound (B). The Michael addition reaction causes compound (C) to be covalently fixed in the molded product. Due to these functions, the compound (C) can function as a coupling agent between the resin and the metal surface, and can develop strong adhesion between the cured product and the metal base material.

The content of compound (C) can be determined as appropriate depending on the application, but it is 0.05 parts by mass to 100 parts by mass of the total of polyalkenylphenol compound (A) and polymaleimide compound (B). The amount is preferably 5 parts by weight, more preferably 0.2 parts by weight to 3 parts by weight, and even more preferably 0.3 parts by weight to 2.5 parts by weight. When it is 0.05 parts by mass or more, the adhesion to copper is better, and when it is 5 parts by mass or less, it is possible to sufficiently exhibit the function of adjusting the curing rate and maintain fast curing properties. Thereby, the appearance of the molded product and the moldability of the thermosetting resin composition can be improved.

[Radical initiator (D)]
By blending the radical initiator (D) into the thermosetting resin composition, curing of the thermosetting resin composition can be promoted. The radical initiator (D) is preferably a thermal radical initiator. Examples of thermal radical initiators include organic peroxides. The organic peroxide is preferably an organic peroxide with a 10-hour half-life temperature of 100 to 170°C, and specifically, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert- Mention may be made of (butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide. The preferable amount of the radical initiator (D) used is 0.01 to 10 parts by mass based on a total of 100 parts by mass of the polyalkenylphenol compound (A), the polymaleimide compound (B), and the compound (C). , more preferably 0.05 to 7.5 parts by weight, and even more preferably 0.1 to 5 parts by weight. If the amount of the radical initiator (D) used is 0.01 parts by mass or more, the curing reaction will proceed sufficiently, and if it is 10 parts by mass or less, the storage stability of the thermosetting resin composition will be better.

[Filler (E)]
The thermosetting resin composition may further contain a filler (E). There is no particular restriction on the type of filler (E), and examples 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 selected as appropriate depending on the purpose. The filler (E) is preferably at least one selected from the group consisting of silica, alumina, magnesium oxide, and solid rubber particles.

For example, when a thermosetting resin composition is used for semiconductor encapsulation, it is preferable to include an insulating inorganic filler in order to obtain a cured product with a low coefficient of thermal expansion. The inorganic filler is not particularly limited, and any known inorganic filler can be used. Specific examples of the inorganic filler include particles of silica such as amorphous silica and crystalline silica, alumina, boron nitride, aluminum nitride, and silicon nitride. From the viewpoint of lowering the viscosity, true 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 the maximum particle size is preferably 100 μm or less, particularly 75 μm or less. When the average particle size is within this range, the viscosity of the thermosetting resin composition is appropriate during use, and the injectability into narrow pitch wiring portions or narrow gap portions is also appropriate. The average particle size here refers to the volume cumulative particle size D ₅₀ measured by a laser diffraction scattering particle size distribution analyzer.

The content of the filler (E) in the thermosetting resin composition can be determined as appropriate depending on the application. The content of the filler (E) in the thermosetting resin composition is 100 parts by mass in total of the polyalkenylphenol compound (A), the polymaleimide compound (B), the compound (C), and the radical initiator (D). On the other hand, it is preferably 200 to 1,900 parts by weight, more preferably 300 to 1,000 parts by weight, and even more preferably 300 to 600 parts by weight.

Other additives include antifoaming agents, colorants, phosphors, modifiers, leveling agents, light diffusing agents, flame retardants, adhesion agents, mold release agents, coupling agents, etc., added to the thermosetting resin composition. It is also possible to do so.

For example, as a mold release agent, various waxes such as ester-based waxes such as carnauba wax and montanic acid ester wax, amide-based waxes such as lauric acid amide, stearic acid amide, and N-stearyl erucic acid amide, polyethylene, and polyethylene oxide may be appropriately selected. can do.

For example, coupling agents include vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-3 Examples include silane coupling agents such as -aminopropyltrimethoxysilane. The coupling agents may be used alone or in combination of two or more. The content of the coupling agent in the thermosetting resin composition is preferably 0.1 to 5% by mass. When the amount is 0.1% by mass or more, the effect of the coupling agent is fully exhibited, and when it is 5% by mass or less, the melt viscosity, hygroscopicity and strength of the cured product are better.

[Method for preparing thermosetting resin composition]
The method for preparing the thermosetting resin composition is as follows, if the polyalkenylphenol compound (A), the polymaleimide compound (B), the compound (C), the radical initiator (D), and other optional components can be uniformly mixed and dispersed. Not particularly limited. The method of first melt-mixing the polyalkenylphenol compound (A), the polymaleimide compound (B), and the compound (C), and then adding the radical initiator (D) and any additives is to uniformly mix each material. It is preferred because it is easy to mix.

The method of mixing each component is not particularly limited. Mix each component in a predetermined proportion in a reaction vessel, pot mill, two-roll mill, three-roll mill, rotary mixer, twin-screw mixer, disper, single-screw or twin-screw (same direction or different directions) extruder, kneader, etc. Mixing can be achieved by charging the mixture into a mixer and stirring or kneading. On a laboratory scale, a rotary mixer is preferred because stirring conditions can be easily changed, and on an industrial scale, a twin-shaft mixer is preferred from the viewpoint of productivity. Each mixer can be used by changing the stirring conditions as appropriate.

When powderizing a thermosetting resin composition, there is no particular limitation as long as the method does not melt the resin due to the heat generated during the work process, but if the amount is small, it is convenient to use an agate mortar. When using a commercially available pulverizer, one that generates a small amount of heat during pulverization is preferred in order to suppress melting of the mixture. The particle size of the powder is preferably 1 mm or less.

[Method for manufacturing structure]
The thermosetting resin composition can be melted by heating. A structure can be produced by molding a molten thermosetting resin composition into any desired shape, curing it as necessary, and removing the mold. As a method for producing the structure, molding, particularly transfer molding and compression molding is preferred. Preferred conditions for transfer molding include, for example, in the case of a mold with a size of 10 mm x 75 mm x 3 mm thick, the temperature of the top plate and mold should be 170 to 190°C, the holding pressure should be 50 to 150 kg/cm ² , and the holding time. The time can be 1.5 to 10 minutes. Preferred conditions for compression molding are, for example, in the case of a mold with a size of 100 mm x 75 mm x 3 mm thick, the temperature of the top plate and the mold is 170 to 190°C, the molding pressure is 5 to 20 MPa, and the pressing time is 1. It can be for 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, 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 into a mold, and it can also be easily demolded 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 curing temperature, but from the viewpoint of productivity, it is preferably 0.1 to 24 hours. This heating may be performed in multiple steps. When a particularly high degree of curing is desired, it is preferable to raise the temperature as the curing progresses, without curing at an excessively high temperature, so that the final curing temperature is 250°C or lower, preferably 230°C or lower. is more preferable.

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

The present invention will be specifically described below based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

The analysis methods and characteristic evaluation methods used in Examples and Comparative Examples are as follows.

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

[Degree of polymerization]
The degree of polymerization P is determined 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 polyalkenylphenol compound (A).
P=Mn/M

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

[Curing time]
Structures of 30 mm x 30 mm x 5 mm were fabricated using compression molding at 180°C with longer molding times of 30 s, 60 s, and 15 s, respectively, and the structures obtained using a type D durometer in accordance with JIS K 7215 (1986). The hardness of the body was measured at 180°C. The time (seconds) required until the hardness exceeds 85 is defined as the curing time.

[Shear adhesive strength]
Evaluate adhesion to metal from the perspective of shear adhesive strength. A base material of oxygen-free copper (C1020) measuring 18 mm x 14 mm x 1.6 mm is used as the adherend base material. The substrate to be adhered is immersed in acetone for 5 minutes, immersed in 5% by mass sulfuric acid for 5 minutes, washed twice or more with ion-exchanged water, and dried at 50° C. for 10 minutes before use. A thermosetting resin composition is molded onto the surface of the adherent substrate using a transfer molding machine into a conical tower shape (a circle with a grounding part of 3 mm in diameter, a height of 3 mm, and an upper part of 1.5 mm in diameter). The molding conditions were a mold temperature of 180° C., a holding pressure of 100 kg/cm ² and a holding time of 3 minutes.

For the obtained test piece, the substrate to be adhered was firmly fixed, and the conical tower-shaped structure was pressurized from the lateral direction at a speed of 2 mm/s along the adhered surface, so that the conical tower-shaped structure was adhered. Measure the applied pressure when peeling from the base material. This measurement is performed for one thermosetting resin composition with N=6, and the average value (MPa) of the measured applied pressure divided by the adhesion area is calculated as the shear of the thermosetting resin composition. Adhesive force.
[Adhesion rate after molding]
Adhesion to metal is evaluated from the viewpoint of adhesion rate after molding. The material is rolled oxygen-free copper (C1020), the external dimensions are 52 mm in width, 38 mm in length, and 0.5 mm in thickness, and a lead frame with a bed of 18 mm in length and width in the center is used. The pretreatment of the lead frame is performed under the same conditions as the pretreatment of the adherend substrate in the shear adhesion test. A thermosetting resin composition is used to enclose the bed with outer dimensions of 30 mm in length, 30 mm in width, and 3 mm in thickness around the center of the lead frame. The sealing was performed by molding the 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. was post-cured at 200°C for 5 hours. Regarding the post-cured test piece, the state of peeling at the interface between the lead frame and the cured product of the thermosetting resin composition is observed using an ultrasonic flaw detection imaging device (HA-60A manufactured by Honda Electronics Co., Ltd.). Using Image-J software, the value obtained by dividing the area of the unpeeled portion by the total area is determined as the adhesion rate after molding.
[Reflow resistance]
Adhesion to metal is also evaluated from the viewpoint of reflow resistance. Using the test piece observed in the post-molding adhesion rate test, a reflow test is performed using a reflow simulator SRS-1 manufactured by Malcolm Co., Ltd. in accordance with the conditions of level 3 of IPC/JEDEC J-STD-020D. The test piece after the reflow test is analyzed in the same manner as the post-molding adhesion rate test, and the obtained value is determined as the post-reflow adhesion rate.

[raw materials]
[Polyalkenylphenol compound (A)]
・BRG-APO (R ⁵ in formula (2)-1 = hydrogen atom, Q = -CR ¹² R ¹³ -, R ¹² and R ¹³ = hydrogen atom, R ⁷ to R ¹¹ in formula (3) = hydrogen atom)
Using a 1:1 mixture of phenol novolak resins Shonol (registered trademark) BRG-556 and BRG-558 (Aica Kogyo Co., Ltd.), 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, degree of polymerization 6.6, p=6.6, q=0, p/(p+q)=0) was produced. For the manufacturing method, see Example 1 of JP-A No. 2016-28129.

・HE100C-APO (R ⁵ in formula (2)-1 and formula (2)-2 = hydrogen atom, R ⁷ to R ¹¹ in formula (3) = hydrogen atom, Q = p-xylylene group)
Using phenolic aralkyl resin HE100C-10-15 (Air Water Co., Ltd.), a resin in which the ortho or para position of the phenolic hydroxyl group was allylated (hydroxyl group Equivalent weight: 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).

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

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

[Radical initiator (D)]
・Percmil (registered trademark) D (dicumyl peroxide, NOF Corporation)

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

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

[Manufacture of thermosetting resin composition]
Example 1
35 parts by mass of BRG-APO as the polyalkenylphenol compound (A), 65 parts by mass of BMI-4000 as the polymaleimide compound (B), 1.5 parts by mass of Percyl D as the radical initiator (D), filler ( 400 parts by mass of MSR5100 treated with a coupling agent with KBM-603 as E) and 0.35 parts by mass of 5-aminoindazole as compound (C) were mixed and melt-kneaded (using two rolls manufactured by Toyo Seiki Seisakusho Co., Ltd.). 8 inches in diameter) at 110°C for 10 minutes). After solidifying by cooling at room temperature (25°C) for 1 hour, it is pulverized using a mill mixer (manufactured by Osaka Chemical Co., Ltd., model WB-1, 25°C, 30 seconds) to form a thermoset powder. A synthetic resin composition was obtained. As a raw material for transfer molding, a powdered thermosetting resin composition was pressed into a tablet shape using a tablet press (manufactured by Fuji Yakuhin Kikai Co., Ltd.). Each of the above-mentioned test pieces was prepared and evaluated using a powdered or tablet-shaped thermosetting resin composition.

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

In Examples 1 to 6, the structures could be easily demolded and had good moldability. Examples 1 to 6 had high shear adhesive strength, high adhesion rate after molding, and high adhesion rate after reflow, and were excellent in adhesion and adhesion to metal. The gel times of Examples 1 to 6 were within appropriate ranges. The curing times of Examples 1 to 6 were within an appropriate range, and the productivity was also excellent. On the other hand, for Comparative Examples 1 to 5, the shear adhesive strength and adhesion rate after molding, especially the adhesion rate after reflow, were low, and the adhesion and adhesion to metals, especially the adhesion after reflow test, were poor. Comparative Examples 6 and 7 had low shear adhesive strength and poor adhesion to metal. In addition, other additives having an imidazole skeleton excessively promoted the polymerization reaction, making it impossible to prepare comparatively large test pieces for evaluating the adhesion rate after molding and the adhesion rate after reflow.

Claims (13)

Contains a polyalkenylphenol compound (A), a polymaleimide compound (B), a compound (C) having the structure described in formula (1), and a radical initiator (D),
The amount of the polyalkenylphenol compound (A) is 20 to 130 parts by mass based on 100 parts by mass of the polymaleimide compound (B),
Thermosetting, wherein the content of the compound (C) is 0.3 parts by mass to 2.5 parts by mass based on 100 parts by mass of the polyalkenylphenol compound (A) and the polymaleimide compound (B). Resin composition.
(In the formula, R ¹ and R ² are a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, a carboxy group, or an amino group, and at least one of R ¹ and R ² is an amino group. .R ³ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, or a cyano group, and R ⁴ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. be.) The compound (C) is 6-aminoindazole, 5-aminoindazole, 6-amino-5-methylindazole, 6-amino-5-ethylindazole, 6-amino-5-hydroxyindazole, 6-amino-5- Claim 1 comprising at least one selected from bromoindazole, 6-amino-5-chloroindazole, 3-cyano-5-aminoindazole, 5-carboxy-6-aminoindazole, and 5,6-diaminoindazole. The thermosetting resin composition described. The thermosetting resin composition according to claim 2, wherein the compound (C) contains at least one selected from 5-aminoindazole and 6-aminoindazole. The polyalkenylphenol compound (A) has the formula (2)-1:
and optionally formula (2)-2:
In formula (2)-1 and formula (2)-2, R ⁵ is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a structural unit having 1 to 5 carbon atoms. 5 represents an alkoxy group, and each R ⁶ independently represents the formula (3):
In formula (3), R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a carbon atom. It is a cycloalkyl group having 5 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and * in formula (3) represents a bond with a carbon atom constituting an aromatic ring, and R ⁵ and R ⁶ are Each phenol skeleton unit may be the same or different, and Q in formula (2)-1 and formula (2)-2 each independently represents an alkylene group represented by the formula -CR ¹² R ¹³ -, the number of carbon atoms Represents a cycloalkylene group of 5 to 10, a divalent organic group having an aromatic ring, a divalent organic group having an alicyclic condensed ring, or a divalent organic group combining these, and R ¹² and R ¹³ are 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 3 . 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 1. The thermosetting resin according to claim 4 , wherein 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. Composition. The thermosetting resin composition according to any one of claims 1 to 5 , wherein the polymaleimide compound (B) is an aromatic bismaleimide compound. The thermosetting resin composition according to any one of claims 1 to 6 , wherein the radical initiator (D) is an organic peroxide. The thermosetting resin composition according to any one of claims 1 to 7 , further comprising a filler (E). The thermosetting resin composition according to claim 8 , 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 based on a total of 100 parts by mass of the polyalkenylphenol compound (A), the polymaleimide compound (B), the compound (C), and the radical initiator (D). The thermosetting resin composition according to claim 8 or 9 , wherein the amount is 200 to 1900 parts by mass. A cured product of the thermosetting resin composition according to any one of claims 1 to 10 . A method for manufacturing a structure, comprising molding the thermosetting resin composition according to any one of claims 1 to 10 . A structure comprising the cured product according to claim 11 .