JP2018095690A - Thermosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which is simple and does not affect moldability, which gives a cured product having low elasticity and improved adhesion to a metal. SOLUTION: A 2-alkenyl group represented by the formula (1) is bonded to a part or all of an aromatic ring having at least two phenolic skeletons in the molecule and forming the phenolic skeleton in the molecule. At least one functional group selected from the group consisting of a polyalkenylphenol resin containing a polyalkenylphenol compound, (B) an aromatic polymaleimide compound, and (C) an amino group, a hydroxyalkyl group, and a mercapto group. A thermocurable resin composition containing a polyorganosiloxane having a functional group equivalent of 400 to 8000. [Selection diagram] None

Description

  The present invention relates to a thermosetting resin composition that provides a cured product having low elasticity and excellent adhesion to a metal.

  In recent years, resin compositions having excellent heat resistance, crack resistance, low stress properties and the like have been demanded in the fields of electric / electronic parts, semiconductors and the like. In the field of semiconductors in particular, switching from conventional Si (silicon) to SiC (silicon carbide) or GaN (gallium nitride) is being promoted in order to achieve further lower on-resistance or lower loss. Since SiC and GaN have higher heat resistance than Si and can be used in a high frequency environment, when these semiconductor materials are used, the peripheral members are also required to have high heat resistance.

  On the other hand, maleimide resin is known as a thermosetting resin having high heat resistance. When only the maleimide resin is cured, the rigid skeleton increases the crosslinking point density, resulting in a hard and brittle cured product. For this reason, a method of combining a maleimide resin and a curing agent such as diamine or phenol to obtain a cured resin is common. It is known that when a polyalkenylphenol compound is used as a curing agent, the alkenyl group of the polyalkenylphenol compound and the unsaturated group of the maleimide resin are radically polymerized with each other and highly crosslinked, thereby improving the brittleness of the cured product.

  However, when a resin composition containing a combination of a maleimide resin and a polyalkenylphenol compound is used as a sealing material, problems such as insufficient elasticity of the cured product and cracks in the cured product occur. Furthermore, since the adhesiveness between the cured product and the metal is not sufficient, peeling between the substrate and the cured product is likely to occur due to a change in the coefficient of thermal expansion accompanying the heat generation of the element.

  It is known that the addition of a plasticizer or the like is effective for realizing low elasticity of the cured product. In addition, it is known that the addition of a material having a polar functional group such as an epoxy resin or the addition of a coupling agent capable of forming a coordinate bond with a metal is effective for improving the adhesion.

  For example, in Patent Document 1, two types of additives, a polyorganosiloxane having an epoxy group at a side chain or a terminal, and γ-ureidopropylethoxysilane are added to a thermosetting resin mainly composed of a polymaleimide compound. It is described that a low elastic modulus and a low coefficient of thermal expansion can be imparted.

JP-A-6-93085

  In order to achieve low elasticity and high adhesion to metal, it is necessary to add additives that bring out the respective effects, which is not only complicated, but also has a problem with formability. Moreover, in patent document 1, since polyorganosiloxane and a polymaleimide compound do not react, hardening becomes slow, There exists a possibility that the mold release property after a shaping | molding and product external appearance may deteriorate because these components bleed out at the time of shaping | molding. there were.

  In view of the above-mentioned present situation, an object of the present invention is to provide a thermosetting resin composition that gives a cured product that has low elasticity and improved adhesion to a metal, and that does not affect moldability. It is.

  As a result of intensive studies to solve the above problems, the inventors have at least one functional group selected from the group consisting of an amino group, a hydroxyalkyl group, and a mercapto group, and a functional group equivalent of 400 By using a thermosetting resin composition containing a polyorganosiloxane of ˜8000 and obtaining a reaction mixture thereof, not only can low elasticity be achieved in the cured product, but it cannot be achieved without adding conventional additives. The present inventors have found that high adhesion to a metal can be realized and have completed the present invention.

（式（１）において、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５はそれぞれ独立に水素原子、炭素数１〜５のアルキル基、炭素数５〜１０のシクロアルキル基、又は炭素数６〜１２のアリール基を表す。式（１）の＊は、芳香環を構成する炭素原子との結合部を表す。）
［２］
前記（Ｂ）芳香族ポリマレイミド化合物の反応性二重結合に対して、前記（Ｃ）ポリオルガノシロキサンの前記官能基が１ｍｏｌ％〜２０ｍｏｌ％となる量で前記（Ｃ）ポリオルガノシロキサンを含む、［１］に記載の熱硬化性樹脂組成物。
［３］
前記（Ｃ）ポリオルガノシロキサンの官能基当量が４００〜６０００である、［１］又は［２］のいずれかに記載の熱硬化性樹脂組成物。
［４］
前記（Ａ）ポリアルケニルフェノール樹脂を１００質量部としたとき、前記（Ｂ）芳香族ポリマレイミド化合物を５０〜３５０質量部含む［１］〜［３］のいずれかに記載の熱硬化性樹脂組成物。
［５］
（Ｇ）カップリング剤をさらに含む、［１］〜［４］のいずれかに記載の熱硬化性樹脂組成物。
［６］
（Ａ）分子内に少なくとも２つのフェノール骨格を有し、かつ分子内のフェノール骨格を形成する芳香環の一部又は全部に式（１）で表される２−アルケニル基が結合しているポリアルケニルフェノール化合物を含むポリアルケニルフェノール樹脂、及び
（Ｄ）ポリオルガノシロキサンと芳香族ポリマレイミド化合物の付加物を含む熱硬化性樹脂組成物であって、前記（Ｄ）ポリオルガノシロキサンと芳香族ポリマレイミド化合物の付加物が（Ｂ）芳香族ポリマレイミド化合物、及び（Ｃ）アミノ基、ヒドロキシアルキル基、及びメルカプト基からなる群より選択される少なくとも１種の官能基を有し、官能基当量が４００〜８０００であるポリオルガノシロキサンの反応生成物である熱硬化性樹脂組成物。

（式（１）において、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５はそれぞれ独立に水素原子、炭素数１〜５のアルキル基、炭素数５〜１０のシクロアルキル基、又は炭素数６〜１２のアリール基を表す。式（１）の＊は、芳香環を構成する炭素原子との結合部を表す。）
［７］
前記（Ｄ）ポリオルガノシロキサンと芳香族ポリマレイミド化合物の付加物が式（３）又は（４）に表される化合物である［６］に記載の熱硬化性樹脂組成物。

（式（３）及び式（４）において、Ｒ^１０は芳香族ポリマレイミド化合物から１つのマレイミド基を除いた残基又はその誘導体を表し、Ｒ^１１はアミノ基、ヒドロキシアルキル基、及びメルカプト基からなる群より選択される少なくとも１種の官能基を表し、Ｒ^１４はＲ^１１で示される前記官能基から１つの水素原子を除いた二価基を表し、Ｒ^１２及びＲ^１３はそれぞれ独立に水素原子、アルキル基又はアリール基を表す。ｐは、１〜１００の整数である。）
［８］
前記（Ａ）ポリアルケニルフェノール樹脂１００質量部に対して、前記（Ｄ）ポリオルガノシロキサンと芳香族ポリマレイミド化合物の付加物を０．１〜１５００質量部含む、［６］又は［７］のいずれかに記載の熱硬化性樹脂組成物。
［９］
前記（Ａ）ポリアルケニルフェノール樹脂が式（２）−１及び式（２）−２に示す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に示す構造単位の一分子あたりの平均数をｍ、式（２）−２に示す構造単位の一分子あたりの平均数をｎとしたときに、ｍは１．１〜３５の実数、ｍ＋ｎは１．１〜３５の実数、ｎは０〜１．５ｍとなる実数である、［１］〜［８］のいずれかに記載の熱硬化性樹脂組成物。

（式（２）−１及び式（２）−２において、Ｒ^６はそれぞれ独立に水素原子、炭素数１〜５のアルキル基、又は炭素数１〜５のアルコキシ基を表し、Ｒ^７はそれぞれ独立に式（１）で表される２−アルケニル基を表す。Ｒ^６及びＲ^７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い。Ｑはそれぞれ独立に式−ＣＲ^８Ｒ^９−で表されるアルキレン基、炭素数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、Ｒ^８及びＲ^９はそれぞれ独立に水素原子、炭素数１〜５のアルキル基、炭素数２〜６のアルケニル基、炭素数５〜１０のシクロアルキル基、又は炭素数６〜１２のアリール基を表す。
［１０］
（Ｆ）充填材をさらに含む［１］〜［９］のいずれかに記載の熱硬化性樹脂組成物。
［１１］
前記（Ｂ）芳香族ポリマレイミド化合物と、前記（Ｃ）ポリオルガノシロキサンとを反応させて（Ｄ）ポリオルガノシロキサンと芳香族ポリマレイミド化合物の付加物を合成し、前記（Ｄ）ポリオルガノシロキサンと芳香族ポリマレイミド化合物の付加物を前記（Ａ）ポリアルケニルフェノール樹脂を含む組成物と混合することを含む、［１］〜［１０］のいずれかに記載の熱硬化性樹脂組成物の製造方法。
［１２］
［１］〜［１１］のいずれかに記載の熱硬化性樹脂組成物の硬化物。
［１３］
［１］〜［１１］のいずれかに記載の熱硬化性樹脂組成物の硬化物と金属材料とが接合された構造体。
［１４］
［１］〜［１１］のいずれかに記載の熱硬化性樹脂組成物を含む半導体用封止材。 That is, the present invention includes the following embodiments.
[1]
(A) Poly having at least two phenol skeletons in the molecule and having a 2-alkenyl group represented by the formula (1) bonded to part or all of the aromatic ring forming the phenol skeleton in the molecule A polyalkenylphenol resin containing an alkenylphenol compound,
(B) an aromatic polymaleimide compound, and (C) a poly having at least one functional group selected from the group consisting of an amino group, a hydroxyalkyl group, and a mercapto group, and having a functional group equivalent of 400 to 8000. A thermosetting resin composition containing an organosiloxane.

(In the formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ 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 number. Represents an aryl group of 6 to 12. * in the formula (1) represents a bond with a carbon atom constituting an aromatic ring.
[2]
The (C) polyorganosiloxane is contained in an amount such that the functional group of the (C) polyorganosiloxane is 1 mol% to 20 mol% with respect to the reactive double bond of the (B) aromatic polymaleimide compound. The thermosetting resin composition according to [1].
[3]
The thermosetting resin composition according to any one of [1] or [2], wherein the functional group equivalent of the (C) polyorganosiloxane is 400 to 6000.
[4]
The thermosetting resin composition according to any one of [1] to [3], which contains 50 to 350 parts by mass of the (B) aromatic polymaleimide compound when the (A) polyalkenylphenol resin is 100 parts by mass. object.
[5]
(G) The thermosetting resin composition according to any one of [1] to [4], further including a coupling agent.
[6]
(A) Poly having at least two phenol skeletons in the molecule and having a 2-alkenyl group represented by the formula (1) bonded to part or all of the aromatic ring forming the phenol skeleton in the molecule A polyalkenylphenol resin containing an alkenylphenol compound, and (D) a thermosetting resin composition containing an adduct of a polyorganosiloxane and an aromatic polymaleimide compound, the (D) polyorganosiloxane and an aromatic polymaleimide The compound adduct has (B) an aromatic polymaleimide compound, and (C) at least one functional group selected from the group consisting of an amino group, a hydroxyalkyl group, and a mercapto group, and a functional group equivalent of 400 A thermosetting resin composition which is a reaction product of polyorganosiloxane of ˜8000.

(In the formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ 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 number. Represents an aryl group of 6 to 12. * in the formula (1) represents a bond with a carbon atom constituting an aromatic ring.
[7]
The thermosetting resin composition according to [6], wherein the adduct of the (D) polyorganosiloxane and the aromatic polymaleimide compound is a compound represented by the formula (3) or (4).

(In the formulas (3) and (4), R ¹⁰ represents a residue obtained by removing one maleimide group from an aromatic polymaleimide compound or a derivative thereof, and R ¹¹ represents an amino group, a hydroxyalkyl group, and a mercapto group. comprising represents at least one functional group selected from the group, R ¹⁴ represents a divalent group obtained by removing one hydrogen atom from the functional group represented by R ^11, hydrogen R ¹² and R ¹³ are each independently Represents an atom, an alkyl group or an aryl group, and p is an integer of 1 to 100.)
[8]
Either [6] or [7] containing 0.1 to 1500 parts by mass of the adduct of the (D) polyorganosiloxane and the aromatic polymaleimide compound with respect to 100 parts by mass of the (A) polyalkenylphenol resin. The thermosetting resin composition according to claim 1.
[9]
The (A) polyalkenylphenol resin is a polyalkenylphenol compound having a structural unit represented by formula (2) -1 and formula (2) -2, and is per molecule of the structural unit represented by formula (2) -1. When the average number is m, and the average number per molecule of the structural unit represented by formula (2) -2 is n, m is a real number from 1.1 to 35, m + n is a real number from 1.1 to 35, n Is a real number which becomes 0-1.5 m, The thermosetting resin composition in any one of [1]-[8].

(In Formula (2) -1 and Formula (2) -2, R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R ⁷ represents each Independently represents a 2-alkenyl group represented by the formula (1), wherein R ⁶ and R ⁷ may be the same or different in each phenol skeleton unit, and Q is independently represented by the formula —CR ⁸ R ⁹ —. An alkylene group, 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 obtained by combining these R ⁸ and R ⁹ are each 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 having 6 to 12 carbon atoms. Represents a group.
[10]
(F) The thermosetting resin composition according to any one of [1] to [9], further including a filler.
[11]
The (D) aromatic polymaleimide compound and the (C) polyorganosiloxane are reacted to synthesize an adduct of (D) the polyorganosiloxane and the aromatic polymaleimide compound; The method for producing a thermosetting resin composition according to any one of [1] to [10], comprising mixing an adduct of an aromatic polymaleimide compound with a composition containing the (A) polyalkenylphenol resin. .
[12]
Hardened | cured material of the thermosetting resin composition in any one of [1]-[11].
[13]
[1] A structure in which a cured product of the thermosetting resin composition according to any one of [11] and a metal material are joined.
[14]
[1] A semiconductor encapsulant comprising the thermosetting resin composition according to any one of [11].

  ADVANTAGE OF THE INVENTION According to this invention, the low elasticity of hardened | cured material and the adhesiveness improvement to a metal are possible, suppressing the bleed-out at the time of shaping | molding, the deterioration of the mold release property after shaping | molding, and the deterioration of a product external appearance. That is, according to the present invention, it is possible to obtain a thermosetting resin composition that gives a cured product having low elasticity and excellent adhesion to a metal.

  The present invention is described in detail below.

  The thermosetting resin composition of one embodiment of the present invention comprises (A) a polyalkenylphenol resin, (B) an aromatic polymaleimide compound, and (C) (B) an amino group, a hydroxyalkyl group, and a mercapto group. It contains a polyorganosiloxane having at least one selected functional group and having a functional group equivalent of 400 to 8000. The thermosetting resin composition of another embodiment contains (A) a polyalkenyl phenol resin, and (D) an adduct of a polyorganosiloxane and an aromatic polymaleimide compound.

(A) Polyalkenylphenol resin The polyalkenylphenol resin has at least two phenol skeletons in the molecule and is represented by the formula (1) in a part or all of the aromatic rings forming the phenol skeleton in the molecule. A resin containing a polyalkenylphenol compound to which 2-alkenyl groups are bonded.

In Formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ 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 6 carbon atoms. ˜12 aryl groups. * In the formula (1) represents a bond with a carbon atom constituting the aromatic ring.

Specific examples of the alkyl group having 1 to 5 carbon atoms constituting R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples thereof include an n-butyl group, a sec-butyl group, a t-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 the formula (1) is preferably an allyl group, that is, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are all hydrogen atoms.

  As the basic skeleton of the compound constituting the polyalkenylphenol resin, a phenol novolak resin, a cresol novolak resin, a triphenylmethane type phenol resin, a phenol aralkyl resin, a biphenyl aralkyl phenol resin, a phenol-dicyclopentadiene copolymer resin, and the like are known. The skeleton of a phenol resin is mentioned. In the polyalkenylphenol resin, it is preferable that 2-alkenyl groups are bonded to 40 to 100%, 60 to 100%, or 80 to 100% of aromatic rings among all aromatic rings forming a phenol skeleton. Among them, a polyalkenylphenol resin containing a polyalkenylphenol compound having a structural unit represented by the following formula (2) -1 and formula (2) -2 can be preferably used.

The structural units represented by the formula (2) -1 and the formula (2) -2 are phenol skeleton units constituting the polyalkenylphenol compound contained in the polyalkenylphenol resin, and the bonding order of these phenol skeleton units is particularly limited. Not. In Formula (2) -1 and Formula (2) -2, R ⁶ 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 R ⁷ is each independently Is a 2-alkenyl group represented by formula (1). R ⁶ and R ⁷ may be the same or different in each phenol skeleton unit. Q is each independently an alkylene group represented by the formula —CR ⁸ R ⁹ —, a cycloalkylene group having 5 to 10 carbon atoms, a divalent organic group having an aromatic ring, or a divalent organic having an alicyclic condensed ring. Group, or a divalent organic group obtained by combining these, R ⁸ and R ⁹ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 5 to 10 carbon atoms. Or an aryl group having 6 to 12 carbon atoms. When the average number per molecule of the structural unit represented by formula (2) -1 is m, and the average number per molecule of the structural unit represented by formula (2) -2 is n, m is 1.1 to A real number of 35, m + n is a real number of 1.1 to 35, and n is a real number of 0 to 1.5 m. (M + n) can be measured using gel filtration chromatography (GPC), and the ratio of m to n can be measured using ¹ H-NMR.

Specific examples of the alkyl group having 1 to 5 carbon atoms constituting R ⁶ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n- A pentyl group etc. can be mentioned. 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, t-butoxy group, n-pentoxy group and the like. It is done.

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 anthranylene group, a xylylene group, and a 4,4-methylenediphenyl group. Carbon number of the divalent organic group which has an aromatic ring can be 6-20 or 6-14. Specific examples of the divalent organic group having an alicyclic fused ring include a dicyclopentadienylene group. Carbon number of the bivalent organic group which has an alicyclic condensed ring can be 7-20 or 7-10. Specific examples of the alkyl group having 1 to 5 carbon atoms in R ⁸ and R ⁹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, Specific examples of the alkenyl group having 2 to 6 carbon atoms include vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group and the like, and 5 to 10 carbon atoms. Specific examples of the cycloalkyl group 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 and a methylphenyl group. , Ethylphenyl group, biphenyl group, naphthyl group and the like. Q is preferably a dicyclopentadienylene group, a phenylene group, a methylphenylene group, or a biphenylene group in terms of high mechanical strength of the cured product when a curable resin mixture or a curable resin composition is obtained. Since the viscosity of the polyalkenyl phenol resin is low and advantageous for mixing with the aromatic polymaleimide compound, Q is preferably —CH ₂ —.

  m is a real number of 1.1 to 35, preferably a real number of 2 to 30, and more preferably a real number of 3 to 10. If m is 1.1 or more, the thermal decomposition starting temperature when the cured product of the curable resin mixture or curable resin composition is placed in a high temperature environment is appropriate, and if it is 35 or less, the curable resin mixture. Alternatively, the viscosity of the curable resin composition is in a range suitable for processing during molding.

  m + n is a real number of 1.1 to 35, preferably a real number of 2 to 30, and more preferably a real number of 3 to 10. If m + n is 1.1 or more, the thermal decomposition starting temperature when the cured product of the curable resin mixture or curable resin composition is placed in a high temperature environment is appropriate, and if it is 35 or less, the curable resin mixture. Alternatively, the viscosity of the curable resin composition is in a range suitable for processing during molding.

  n is a real number where the value of the formula: m / (m + n) is 0.4 to 1, that is, n is a real number of 0 to 1.5 m. n is preferably a real number of 0 to 0.67 m, more preferably a real number of 0 to 0.25 m. If n is a value that satisfies the above conditions, the curability of the curable resin mixture or curable resin composition can be made sufficient depending on the application.

An example of the polyalkenylphenol resin is a compound having a structure represented by the following formula (5). In the formula, m is as described above.

  The preferred number average molecular weight of the polyalkenylphenol resin is 300 to 5000, more preferably 400 to 4000, and still more preferably 500 to 3000. If the number average molecular weight is 300 or more, the thermal decomposition starting temperature is appropriate when the cured product of the curable resin mixture or curable resin composition is placed in a high temperature environment, and if it is 5000 or less, the curable resin mixture or The viscosity of the curable resin composition is in a range suitable for processing during molding.

(B) Aromatic polymaleimide compound An aromatic polymaleimide compound means a compound having two or more maleimide groups, and these maleimide groups are bonded to the same or different aromatic rings. Examples of the aromatic ring include a single ring such as benzene and a condensed ring such as naphthalene and anthracene. Specific examples of the aromatic polymaleimide compound include bismaleimide such as bis (4-maleimidophenyl) methane, trismaleimide such as tris (4-maleimidophenyl) methane, and bis (3,4-dimaleimidophenyl) methane. And polymaleimides such as tetrakismaleimide and poly (4-maleimidostyrene). The aromatic polymaleimide compound is preferably a bismaleimide compound because it mixes well in the curable resin mixture and the curable resin composition. Specific examples of the bismaleimide compound include bis (4-maleimidophenyl) methane (4,4′-bismaleimidediphenylmethane), 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-mer Reimidophenyl) propane, 2,2-bis [4- (4-maleimidophenyloxy) phenyl] propane (bisphenol A-diphenyl ether bismaleimide), 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) cyclo Xanthone, 1,4-dimaleimidonaphthalene, 2,3-dimaleimidonaphthalene, 1,5-dimaleimidonaphthalene, 1,8-dimaleimidonaphthalene, 2,6-dimaleimidonaphthalene, 2,7-dimaleimidonaphthalene, 4,4′-dimaleimidobiphenyl, 3,3′-dimaleimidobiphenyl, 3,4′-dimaleimidobiphenyl, 2,5-dimaleimide-1,3-xylene, 2,7-dimaleimidofluorene, 9,9 -Bis (4-maleimidophenyl) fluorene, 9,9-bis (4-maleimido-3-methylphenyl) fluorene, 9,9-bis (3-ethyl-4-maleimidophenyl) fluorene, 3,7-dimaleimide- 2-methoxyfluorene, 9,10-dimaleimidophenanthrene, 1,2-dimaleimidoanthraquinone, , 5-dimaleimidoanthraquinone, 2,6-dimaleimidoanthraquinone, 1,2-dimaleimidobenzene, 1,3-dimaleimidobenzene, 1,4-dimaleimidobenzene, 1,4-bis (4-maleimidophenyl) Benzene, 2-methyl-1,4-dimaleimidobenzene, 2,3-dimethyl-1,4-dimaleimidobenzene, 2,5-dimethyl-1,4-dimaleimidobenzene, 2,6-dimethyl-1, 4-dimaleimidobenzene, 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-dimale And imidobenzene. Examples of commercially available products include BMI (trade name, manufactured by Daiwa Kasei Kogyo Co., Ltd.) series.

  When (A) the polyalkenylphenol resin is 100 parts by mass, the blending amount of the (B) aromatic polymaleimide compound is preferably 50 to 350 parts by mass, more preferably 65 to 250 parts by mass. More preferably, it is -200 mass parts. If the said compounding quantity is 50 mass parts or more, mechanical characteristics, such as an elastic modulus of hardened | cured material, are an appropriate range, and hardened | cured material has sufficient intensity | strength. On the other hand, if the said compounding quantity is 350 mass parts or less, the heat resistance and mechanical strength of hardened | cured material are favorable.

(C) Polyorganosiloxane having at least one functional group selected from the group consisting of an amino group, a hydroxyalkyl group, and a mercapto group, and having a functional group equivalent of 400 to 8000. Is a compound having at least one functional group selected from the group consisting of an amino group, a hydroxyalkyl group, and a mercapto group. In the present specification, “at least one functional group selected from the group consisting of an amino group, a hydroxyalkyl group, and a mercapto group” may be referred to as a “reactive functional group”.

In one embodiment, the (C) polyorganosiloxane is a compound represented by the following formula (6).

In Formula (6), R ¹¹ represents at least one functional group selected from the group consisting of an amino group, a hydroxyalkyl group, and a mercapto group, and R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group, or Represents an aryl group. p is an integer of 1-100. In the formula (6), R ^{11 to} R ¹³ each preferably represents a substituent wherein R ¹¹ is an amino group or a hydroxyalkyl group, and R ¹² and R ¹³ are alkyl groups having 1 to 6 carbon atoms such as a methyl group and an ethyl group. Group or an aryl group such as a phenyl group. More preferably, from the viewpoint of easy procurement and physical properties of the molded product, R ¹¹ is an amino group, and R ¹² and R ¹³ are groups selected from a methyl group or a phenyl group.

  1-10 are preferable and, as for carbon number of a hydroxyalkyl group, More preferably, it is 1-5. Among reactive functional groups, an amino group is preferred because of its high reactivity with an aromatic polymaleimide compound and easy modification control.

  The functional group equivalent of the polyorganosiloxane is 400 or more and 8000 or less, preferably 400 or more and 6000 or less, more preferably 800 or more and 5500 or less, and still more preferably 1000 or more and 5000 or less. If the functional group equivalent is 400 or more, sufficient low elasticity can be imparted to the cured product, and if it is 8000 or less, a cured product having sufficient strength can be obtained. The functional group equivalent is a value obtained by dividing the molecular weight of the polyorganosiloxane of the present invention by the reactive functional group value per molecule. The molecular weight of the polyorganosiloxane can be measured by GPC, and the reactive functional group value can be measured by titration or the like.

  (C) The addition amount of polyorganosiloxane is preferably 1 mol% or more and 20 mol% or less of the reactive functional group of the polyorganosiloxane with respect to the reactive double bond of (B) the aromatic polymaleimide compound. The amount is preferably 1.5 mol% to 15 mol%, more preferably 2 mol% to 10 mol%. If polyorganosiloxane is added so that the amount is 1 mol% or more, it is advantageous to give the cured product low elasticity and high adhesion to a metal, and if the amount is 20 mol% or less, the cured product is obtained. Has good heat resistance and strength.

(D) Addition product of polyorganosiloxane and aromatic polymaleimide compound (D) Addition product of polyorganosiloxane and aromatic polymaleimide compound includes (B) aromatic polymaleimide compound, (C) amino group, and hydroxyalkyl. It can be synthesized from a polyorganosiloxane having at least one functional group selected from the group consisting of a group and a mercapto group and having a functional group equivalent of 400 to 8000. Specifically, (D) polyorganosiloxane and aromatic are added by Michael addition of the reactive functional group of (C) polyorganosiloxane to the reactive double bond of maleimide group of (B) aromatic polymaleimide compound. Adducts of polymaleimide compounds can be synthesized.

In one embodiment, the adduct of (D) polyorganosiloxane and aromatic polymaleimide compound is a compound represented by the following formula (3) or (4).

In the formulas (3) and (4), R ¹⁰ represents a residue obtained by removing one maleimide group from an aromatic polymaleimide compound or a derivative thereof, and R ¹¹ includes an amino group, a hydroxyalkyl group, and a mercapto group. It represents at least one functional group selected from the group, R ¹⁴ represents a divalent group obtained by removing one hydrogen atom from the functional group represented by R ^11, R ¹² and R ¹³ each independently represent a hydrogen atom Represents an alkyl group or an aryl group. p is an integer of 1-100. Derivatives of residues obtained by removing one maleimide group from an aromatic polymaleimide compound include those in which other maleimide groups of the aromatic polymaleimide compound are further reacted with a polyorganosiloxane having a reactive functional group It is. In the formulas (3) and (4), R ^{10 to} R ¹³ each preferably represents a substituent in which R ¹⁰ is a residue obtained by removing one maleimide group from an aromatic polymaleimide compound, and R ¹¹ is an amino group or hydroxyalkyl. Group R ¹⁴ is —NH— or —OR— (R is an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms), R ¹² and R ¹³ is an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group, or an aryl group such as a phenyl group. More preferably, from the viewpoint of easy procurement and physical properties of the molded product, R ¹¹ is an amino group, R ¹⁴ is —NH—, and R ¹² and R ¹³ are groups selected from a methyl group or a phenyl group.

  (A) When the polyalkenylphenol resin is 100 parts by mass, the blending amount of the adduct of (D) polyorganosiloxane and aromatic polymaleimide compound is preferably 0.1 to 1500 parts by mass, It is more preferable to set it as -1100 mass parts, and it is still more preferable that it is 1.0-850 mass parts. If the said compounding quantity is 0.1 mass part or more, mechanical characteristics, such as an elasticity modulus of hardened | cured material, are an appropriate range, and hardened | cured material has sufficient intensity | strength. On the other hand, if the said compounding quantity is 1500 mass parts or less, the heat resistance and mechanical strength of hardened | cured material are favorable.

<Reaction conditions>
The addition reaction is preferably performed in a temperature range of 10 ° C to 200 ° C, more preferably performed in a temperature range of 30 ° C to 150 ° C, and further preferably performed in a temperature range of 50 ° C to 120 ° C. The raw material can be diluted and reacted with a solvent in which the raw material dissolves. When diluting the raw material with a solvent, the total mass of (B) and (C) is in the range of 1 to 30% by mass with respect to the total of the solvent, (B) aromatic polymaleimide compound and (C) polyorganosiloxane. More preferably, it is the range of 5-20 mass%, More preferably, it is the range of 8-15 mass%. By setting it as the said range, side reactions, such as superposition | polymerization, can be controlled favorably.

  (D) During the synthesis of the adduct of polyorganosiloxane and aromatic polymaleimide compound, (C) polyorganosiloxane is (B) the above polyorganosiloxane with respect to the reactive double bond of aromatic polymaleimide compound. It is preferable that at least one functional group selected from the group consisting of an amino group, a hydroxyalkyl group, and a mercapto group is used in an amount of 1 mol% to 20 mol%, more preferably 1.5 mol% to 15 mol. %, More preferably in an amount of 2 mol% to 10 mol%. (B) If the amount of the reactive functional group of (C) polyorganosiloxane is 1 mol% or more with respect to the reactive double bond of the aromatic polymaleimide compound, the cured product has low elasticity and high adhesion to metal. If it is 20 mol% or less, the heat resistance and strength of the cured product are good.

  Various additives may be mixed with the thermosetting resin composition containing the above components as long as the curing characteristics are not impaired.

  Examples of the additive include (E) a polymerization initiator, (F) a filler, and (G) a coupling agent.

(E) Polymerization initiator Curing can be accelerated by using a polymerization initiator. Examples of the polymerization initiator include radical initiators such as a photo radical initiator and a thermal radical initiator. The polymerization initiator is preferably a thermal radical initiator. More preferable thermal radical initiators include organic peroxides. Among the organic peroxides, an organic peroxide having a 10-hour half-life temperature of 100 to 170 ° C. is more preferable. Specifically, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 1,1,3, Examples thereof include 3-tetramethylbutyl hydroperoxide and cumene hydroperoxide. The preferable usage-amount of a polymerization initiator is 0.1-5 mass parts with respect to 100 mass parts of sum total of a polyalkenyl phenol resin and an aromatic polymaleimide compound, More preferably, it is 0.2-4 mass parts. More preferably, it is 0.5 to 3 parts by mass. If the usage-amount of a polymerization initiator is 0.1 mass part or more, hardening reaction will fully advance, and if it is 5 mass parts or less, the storage stability of a thermosetting resin composition is favorable.

(F) Filler There is no restriction | limiting in particular in the kind of filler, Organic fillers, such as silicone powder, inorganic fillers, such as a silica and boron nitride, etc. are mentioned, It can select suitably by a use.

For example, when the thermosetting resin composition is used for semiconductor sealing applications, it is preferable to blend an insulating inorganic filler in order to reduce the thermal expansion coefficient of the cured product. An inorganic filler is not specifically limited, A well-known thing can be used. Specific examples of the inorganic filler include particles of amorphous silica, crystalline silica, alumina, boron nitride, aluminum nitride, silicon nitride, and the like. Spherical amorphous silica is desirable from the viewpoint of lowering the viscosity. The inorganic filler may be subjected to surface treatment with a silane coupling agent or the like, but may not be subjected to surface treatment. The average particle size of the inorganic filler is preferably 0.1 to 100 μm, and the maximum particle size is preferably 70 μm or less, and more preferably 50 μm or less. When the average particle size is in this range, the viscosity of the thermosetting resin composition is appropriate at the time of use, and the injection property to the narrow pitch wiring part or the narrow gap part is also appropriate. The average particle diameter referred to here is the volume cumulative particle diameter D ₅₀ measured by a laser diffraction scattering particle size distribution measuring apparatus. Content of the inorganic filler of a thermosetting resin composition can be suitably determined according to a use. For example, in semiconductor sealing applications, the content of the inorganic filler in the thermosetting resin composition is preferably 50 to 95% by mass, more preferably 55 to 90% by mass, and still more preferably 65 to 90% by mass. %.

(G) Coupling agent Although a coupling agent may be mix | blended from a viewpoint of adhesiveness provision, the structure is not specifically limited, For example, vinyltriethoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltri Examples include silane coupling agents such as methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane. A coupling agent may be used independently and 2 or more types may be used together. (F) As for the compounding quantity of the (G) coupling agent to a filler, 0.1-5 mass% is preferable. When the blending amount is 0.1% by mass or more, the blending effect of the coupling agent is sufficiently exhibited. When the blending amount is 5% by mass or less, the melt viscosity, the hygroscopic property of the cured product, and the strength are good.

(H) Other additives As other additives, antifoaming agents, colorants, phosphors, modifiers, leveling agents, light diffusing agents, flame retardants, and the like can be used.

  The method for preparing the thermosetting resin composition is not particularly limited. (A) a polyalkenylphenol resin, (B) an aromatic polymaleimide compound, (C) at least one functional group selected from the group consisting of an amino group, a hydroxyalkyl group, and a mercapto group, and a functional group equivalent Predetermined blending of polyorganosiloxane having a ratio of 400 to 8000, (D) adduct of polyorganosiloxane and aromatic polymaleimide compound, (E) polymerization initiator, (F) filler, (G) coupling agent Put in a mixer such as pot mill, two-roll, three-roll mill, rotary mixer, twin screw mixer, disper, half or twin screw (same direction or different direction) extruder, kneader and mix Can be prepared. When the thermosetting resin composition is pulverized, it is not particularly limited as long as the resin is not melted by the heat generated in the work process, but if it is a small amount, it is easy 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 can be about 1 mm or less.

  Total content of (A) polyalkenylphenol resin, (B) aromatic polymaleimide compound, (C) polyorganosiloxane, and (D) adduct of polyorganosiloxane and aromatic polymaleimide compound of thermosetting resin composition The amount can be, for example, 5% by mass or more, 10% by mass or more, or 20% by mass or more, 99.9% by mass or less, 95% by mass or less, or 90% by mass or less.

(3) Manufacturing method of hardened | cured material The thermosetting resin composition of this invention can be fuse | melted by heating, and can be shape | molded in arbitrary preferable shapes. The molding temperature of the thermosetting resin composition may vary depending on the blending amount, molecular weight, molecular weight distribution, and the like of the resin, but is preferably 120 to 250 ° C, more preferably 130 to 220 ° C, and still more preferably 140. ~ 200 ° C. Examples of the molding method include injection and coating, and transfer molding and compression molding are particularly preferable.

  The thermosetting resin composition of the present invention can be cured by additional heating after the molding step to complete the curing reaction. In this post-molding curing step, the mechanical strength of the cured product can be increased, or the internal stress can be relaxed. 110-300 degreeC is preferable for thermosetting conditions, More preferably, it is 120-280 degreeC, More preferably, it is 130-250 degreeC. If it is 110 degreeC or more, hardening will fully progress within an appropriate time, and if it is 300 degrees C or less, deterioration or volatilization of a component can be prevented and the safety | security of an installation is also maintained. Although the heating time depends on the curing temperature, the heating for 0.5 to 48 hours is preferable from the viewpoint of productivity. This heating may be performed in a plurality of times. In particular, when a high degree of curing is required, the final curing temperature can be 250 ° C. or lower, preferably 230 ° C. or lower, without being cured at an excessively high temperature, for example, by raising the temperature with the progress of curing.

  The thermosetting resin composition of the present invention can be used to form a structure in which the cured product and a metal material are joined. In one embodiment, a thermosetting resin composition can be used for the semiconductor sealing material.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to this Example.

(1) Raw materials The raw materials used in Examples and Comparative Examples are as follows.
(A) Polyalkenylphenol resin / Phenol novolac resin Shonoll (registered trademark) BRG-558 (Showa Denko KK) resin in which the para position of the phenolic hydroxyl group is allylated (hydroxyl equivalent 159, number average molecular weight Mn 1600, weight) Average molecular weight Mw 5400, melting point 55 ° C., m = 10, n = 0). The manufacturing method is described in Example 3 of JP-A-2016-28129.
(B) Polymaleimide compound BMI-4000 (bisphenol A-diphenyl ether bismaleimide, melting point 165 ° C., Daiwa Kasei Kogyo Co., Ltd.)
(C) a polyorganosiloxane / KF-8010 having at least one functional group selected from the group consisting of an amino group, a hydroxyalkyl group, and a mercapto group, and having a functional group equivalent of 400 to 8000 (both amino-modified) Terminal type, Shin-Etsu Chemical Co., Ltd.)
・ X-22-161A (Amino-modified both terminal type, Shin-Etsu Chemical Co., Ltd.)
・ X-22-161B (Amino-modified both terminal type, Shin-Etsu Chemical Co., Ltd.)
・ KF-8012 (Amino-modified both terminal type, Shin-Etsu Chemical Co., Ltd.)
X-22-1660B-3 (amino-modified both terminal type, R ¹² in formula (6) is a phenyl group, Shin-Etsu Chemical Co., Ltd.)
・ KF-8008 (Amino-modified both terminal type, Shin-Etsu Chemical Co., Ltd.)
・ KF-864 (amino-modified side chain type, Shin-Etsu Chemical Co., Ltd.)
・ KF-865 (amino-modified side chain type, Shin-Etsu Chemical Co., Ltd.)
・ KF-6002 (Carbinol-modified both ends, Shin-Etsu Chemical Co., Ltd.)
・ X-22-170DX (Carbinol modified one-end type, Shin-Etsu Chemical Co., Ltd.)
(E) Polymerization initiator: Park mill D (Dicumyl peroxide, NOF Corporation)
(F) Filler: MSR2212 (spherical silica, average particle size 25.5 μm, Tatsumori Co., Ltd.)
(G) Silane coupling agent: KBM-903 (3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.)
(H) Compound other than (C) having reactivity with polymaleimide compound PAM-E (amino-modified both terminal type, Shin-Etsu Chemical Co., Ltd.)
・ KF-9701 (silanol-modified both ends, Shin-Etsu Chemical Co., Ltd.)
・ 1,12-Diaminododecane (alkyl diamine, Tokyo Chemical Industry Co., Ltd.)

(2) Production of Thermosetting Resin Composition Containing (A) Polyalkenylphenol Resin, (B) Aromatic Polymaleimide Compound, and (C) Polyorganosiloxane [Example 1]
Each component was mix | blended in the ratio shown in Table 1, and it knead | mixed for 10 minutes at 110 degreeC with the Toyo Seiki Co., Ltd. two rolls (roll diameter 8 inches). Next, after cooling and solidifying at 25 ° C. for 1 hour, the mixture was pulverized using a mill mixer (Osaka Chemical Co., Ltd., model WB-1, 25 ° C., 30 seconds) to obtain a desired powdery resin composition. I got a thing.

[Examples 2 to 12, Comparative Examples 1 to 4]
A resin composition was obtained in the same manner as in Example 1 using each component in the ratio shown in Table 1.

(3) (D) Synthesis of adduct of polyorganosiloxane and aromatic polymaleimide compound [Synthesis Example 1]
BMI-4000 (functional group equivalent 285.3) 50.0 g, KF-8010 (functional group equivalent 430) 3.8 g, and toluene 570 ml were added to a 1 L eggplant-shaped flask equipped with a stirrer and a Liebig condenser. The mixture was heated and stirred for 1 hour in an oil bath. After cooling to room temperature, the solvent was distilled off with an evaporator. Then, it dried with the vacuum dryer and obtained 52.0g of yellow powder. When the product was confirmed by ¹ H-NMR, the production of a Michael adduct was confirmed.

[Synthesis Examples 2 to 16]
Using each component in the ratio shown in Table 2, a product was obtained by the same method as in Synthesis Example 1. When the product was confirmed by ¹ H-NMR, the production of a Michael adduct was confirmed in Synthesis Examples 2 to 16.

(4) Production of Thermosetting Resin Composition Containing (A) Polyalkenylphenol Resin and (D) Adduct of Polyorganosiloxane and Aromatic Polymaleimide Compound [Example 13]
Each component was mix | blended in the ratio shown in Table 2, and it knead | mixed for 10 minutes at 110 degreeC with the Toyo Seiki Co., Ltd. two rolls (roll diameter 8 inches). Next, after cooling and solidifying at 25 ° C. for 1 hour, the mixture was pulverized using a mill mixer (Osaka Chemical Co., Ltd., model WB-1, 25 ° C., 30 seconds) to obtain a desired powdery resin composition. I got a thing.

[Examples 14 to 24, Comparative Examples 5 to 8]
A resin composition was obtained in the same manner as in Example 13 using each component in the ratio shown in Table 2.

(5) Evaluation and bending elastic modulus of thermosetting resin composition 750 mm length under conditions of a mold temperature of 180 ° C., a molding pressure of 100 kgf / cm ² , and a curing time of 180 seconds using a transfer molding machine (manufactured by Matsuda Seisakusho Co., Ltd.) A sample for bending test having a width of 10 mm and a thickness of 3 mm was produced. Using an A & D Tensilon tester (model: MSAT0002RTF / RTG), in accordance with JIS K7171, a three-point bending test was performed five times at a test speed of 2 mm / min at room temperature, and the average value was bent. Elastic modulus was used. The results are shown in Tables 1 and 2.

-Bleed-out property After forming the sample for the flexural modulus test, the sample was taken out of the mold, and then the mold was visually observed. The case where there was resin leakage or cloudiness in the air vent part of the mold was defined as “Yes”, and the case where there was no resin leakage or cloudiness was defined as “None”. The results are shown in Tables 1 and 2.

-Adhesion to Cu substrate A 3 mm diameter pudding cup on an oxygen-free Cu substrate on a transfer molding machine (manufactured by Matsuda Seisakusho Co., Ltd.) under conditions of a mold temperature of 180 ° C., a molding pressure of 100 kgf / cm ² , and a curing time of 180 seconds. A shaped molded product was obtained. This was subjected to a lateral load at a constant speed of 12 mm / min using a die shear tester (manufactured by Daisy Co., Ltd.), and the strength when sheared was measured at 3 points at 25 ° C., and the average value was defined as adhesion to Cu. . The results are shown in Tables 1 and 2.

(6) Consideration from the results From Tables 1 and 2, Examples 1 to 24 showed low elastic modulus and high adhesion to Cu. On the other hand, Comparative Examples 1-8 showed a high elastic modulus, and adhesion to Cu was not obtained. Therefore, a polyorganosiloxane having at least one functional group selected from the group consisting of an amino group, a hydroxyalkyl group, and a mercapto group, and having a functional group equivalent of 400 to 8000, or such a polyorgano It is suggested that by using a thermosetting resin composition containing an adduct of siloxane and an aromatic polymaleimide compound, low elasticity and high adhesion to metal can be achieved in the cured product.

  According to the present invention, while suppressing bleed-out during molding, deterioration of mold release after molding, and deterioration of product appearance, it has low elasticity, excellent adhesion to metal, and excellent mechanical strength. The thermosetting resin composition which gives a thing, and the electronic component obtained using it can be provided. In particular, when the thermosetting resin composition of the present invention is used for a semiconductor encapsulant, an encapsulant having high mechanical strength and high adhesion to a metal can be produced after molding.

Claims (14)

(A) Poly having at least two phenol skeletons in the molecule and having a 2-alkenyl group represented by the formula (1) bonded to part or all of the aromatic ring forming the phenol skeleton in the molecule A polyalkenylphenol resin containing an alkenylphenol compound,
(B) an aromatic polymaleimide compound, and (C) a poly having at least one functional group selected from the group consisting of an amino group, a hydroxyalkyl group, and a mercapto group, and having a functional group equivalent of 400 to 8000. A thermosetting resin composition containing an organosiloxane.

(In the formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ 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 number. Represents an aryl group of 6 to 12. * in the formula (1) represents a bond with a carbon atom constituting an aromatic ring.   The (C) polyorganosiloxane is contained in an amount such that the functional group of the (C) polyorganosiloxane is 1 mol% to 20 mol% with respect to the reactive double bond of the (B) aromatic polymaleimide compound. The thermosetting resin composition according to claim 1.   The thermosetting resin composition according to claim 1, wherein the functional group equivalent of the (C) polyorganosiloxane is 400 to 6000.   The thermosetting resin composition according to any one of claims 1 to 3, comprising 50 to 350 parts by mass of the (B) aromatic polymaleimide compound when the (A) polyalkenylphenol resin is 100 parts by mass.   (G) The thermosetting resin composition according to any one of claims 1 to 4, further comprising a coupling agent. (A) Poly having at least two phenol skeletons in the molecule and having a 2-alkenyl group represented by the formula (1) bonded to part or all of the aromatic ring forming the phenol skeleton in the molecule A polyalkenylphenol resin containing an alkenylphenol compound, and (D) a thermosetting resin composition containing an adduct of a polyorganosiloxane and an aromatic polymaleimide compound, the (D) polyorganosiloxane and an aromatic polymaleimide The compound adduct has (B) an aromatic polymaleimide compound, and (C) at least one functional group selected from the group consisting of an amino group, a hydroxyalkyl group, and a mercapto group, and a functional group equivalent of 400 A thermosetting resin composition which is a reaction product of polyorganosiloxane of ˜8000.

(In the formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ 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 number. Represents an aryl group of 6 to 12. * in the formula (1) represents a bond with a carbon atom constituting an aromatic ring. The thermosetting resin composition according to claim 6, wherein the adduct of the (D) polyorganosiloxane and the aromatic polymaleimide compound is a compound represented by the formula (3) or (4).

(In the formulas (3) and (4), R ¹⁰ represents a residue obtained by removing one maleimide group from an aromatic polymaleimide compound or a derivative thereof, and R ¹¹ represents an amino group, a hydroxyalkyl group, and a mercapto group. comprising represents at least one functional group selected from the group, R ¹⁴ represents a divalent group obtained by removing one hydrogen atom from the functional group represented by R ^11, hydrogen R ¹² and R ¹³ are each independently Represents an atom, an alkyl group or an aryl group, and p is an integer of 1 to 100.)   8. The composition according to claim 6, comprising 0.1 to 1500 parts by mass of an adduct of the polyorganosiloxane and the aromatic polymaleimide compound with respect to 100 parts by mass of the (A) polyalkenylphenol resin. The thermosetting resin composition as described. The (A) polyalkenylphenol resin is a polyalkenylphenol compound having a structural unit represented by formula (2) -1 and formula (2) -2, and is per molecule of the structural unit represented by formula (2) -1. When the average number is m, and the average number per molecule of the structural unit represented by formula (2) -2 is n, m is a real number from 1.1 to 35, m + n is a real number from 1.1 to 35, n The thermosetting resin composition according to any one of claims 1 to 8, which is a real number of 0 to 1.5 m.

(In Formula (2) -1 and Formula (2) -2, R ⁶ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and R ⁷ represents each Independently represents a 2-alkenyl group represented by the formula (1), wherein R ⁶ and R ⁷ may be the same or different in each phenol skeleton unit, and Q is independently represented by the formula —CR ⁸ R ⁹ —. An alkylene group, 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 obtained by combining these R ⁸ and R ⁹ are each 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 having 6 to 12 carbon atoms. Represents a group.   (F) The thermosetting resin composition according to any one of claims 1 to 9, further comprising a filler.   The (D) aromatic polymaleimide compound and the (C) polyorganosiloxane are reacted to synthesize an adduct of (D) the polyorganosiloxane and the aromatic polymaleimide compound; The manufacturing method of the thermosetting resin composition in any one of Claims 1-10 including mixing the adduct of an aromatic polymaleimide compound with the composition containing the said (A) polyalkenyl phenol resin.   Hardened | cured material of the thermosetting resin composition in any one of Claims 1-11.   A structure in which a cured product of the thermosetting resin composition according to claim 1 and a metal material are joined.   The semiconductor sealing material containing the thermosetting resin composition in any one of Claims 1-11.