JP6946088B2 - A composition for a cured resin, a cured product of the composition, a method for producing the composition and the cured product, and a semiconductor device. - Google Patents

Description

The present invention relates to a composition for a cured resin for obtaining a cured product having excellent physical strength, the cured product thereof, and a composition for the cured resin and a method for producing the cured product. Further, the present invention relates to a semiconductor device using the cured product as a sealing material.

The cured resin is used for various purposes such as semiconductor encapsulant and fiber reinforced plastic, and a benzoxazine compound is used as one of the raw materials.
The benzoxazine compound refers to a compound containing a benzoxazine ring having a benzene skeleton and an oxazine skeleton, and the benzoxazine resin, which is a cured product (polymer) thereof, has excellent physical properties such as heat resistance and mechanical strength, and has many properties. It is used as a high-performance material in various applications.

Patent Document 1 discloses a novel benzoxazine compound having a specific structure and a method for producing the same. The benzoxazine compound has a high thermal conductivity, and the benzoxazine resin is cured by a benzoxazine resin having a high thermal conductivity. It states that it is possible to manufacture a product.

Patent Document 2 discloses a thermosetting resin in which a part or all of the reactive ends of a polybenzoxazine resin having a specific benzoxazine ring structure in the main chain is sealed, and the thermosetting resin is used as a solvent. It describes that it is excellent in storage stability when dissolved.

Further, it is known that a cured product using a benzoxazine compound and an epoxy compound is excellent in heat resistance and mechanical properties (Patent Document 3).

Japanese Unexamined Patent Publication No. 2013-60407 Japanese Unexamined Patent Publication No. 2012-36318 Japanese Unexamined Patent Publication No. 2016-470903

In applications such as adhesives, paints, encapsulants, and matrix resins for composite materials, further high heat resistance and high mechanical strength resin cured products are still required so as to be able to meet more severe usage conditions. ing. In particular, in applications such as semiconductor devices where even higher reliability is required, a composition for a cured resin for obtaining a cured product having high physical strength is required.
However, a composition for a cured resin for obtaining a cured product having both excellent cured product performance and high mechanical strength has not yet been obtained.

Therefore, an object of the present invention is to provide a composition for a cured resin for obtaining a cured product having both high heat resistance and high mechanical strength as the cured product performance. Another object of the present invention is to provide a cured product obtained by curing the composition for a cured resin, and a composition for a cured resin and a method for producing the cured product. Another object of the present invention is to provide a semiconductor device using the cured product as a sealing material.

As a result of diligent studies to solve the above object, the present inventors have developed a composition for a cured resin containing a polyfunctional benzoxazine compound, a polyfunctional epoxy compound, a silane coupling agent, and an inorganic filler. The present invention has been completed by finding that the cured product has excellent heat resistance and mechanical strength.

［式（１）中、Ｒは、炭素数１〜１２の鎖状アルキル基、炭素数３〜８の環状アルキル基、または炭素数１〜１２の鎖状アルキル基もしくはハロゲンで置換されていてもよい炭素数６〜１４のアリール基を示す。ベンゼン環に交差して示されている二つの横線は、水素、炭素数１〜８の炭化水素基および／または連結基を表し、かつ、少なくとも一つは連結基であり、該連結基によって少なくとも二つのベンゾオキサジン環が連結している。］

［式（２）中、Ｌは、酸素および／または硫黄を含んでいてもよい、炭素数２〜１０のアルキレン基または芳香環を１〜５個有する２価の有機基である。］
［２］ 前記（Ｄ）シランカップリング剤が式（９）で示される構造を有する、［１］に記載の硬化樹脂用組成物。

（式中、Ｙはアミノ基、メルカプト基、エポキシ基、（メタ）アクリル基、ビニル基、イソシアネート基、イミダゾリル基、ウレイド基、スルフィド基、およびイソシアヌレート基からなる群から選択される官能基を含む１価の基を示し、Ｘはヒドロキシ基、アルコキシ基から選択される官能基を示し、ｌは０、１または２を示す。）
［３］ 前記（Ｄ）シランカップリング剤のＹが１級アミノ基、メルカプト基、２級アミノ基からなる群から選択される、［２］に記載の硬化樹脂用組成物。
［４］ 前記（Ｄ）シランカップリング剤の配合割合が前記（Ａ）、前記（Ｂ）、前記（Ｃ）および前記（Ｅ）の合計１００質量部に対して０．０１〜２質量部である、［１］〜［３］のいずれか一つに記載の硬化樹脂用組成物。
［５］ （Ｆ）硬化促進剤をさらに含有する、［１］〜［４］のいずれか一つに記載の硬化樹脂用組成物。
［６］ ［１］〜［５］のいずれか一つに記載の硬化樹脂用組成物を硬化させてなる硬化物。
［７］ ［１］〜［６］のいずれか一つに記載の硬化樹脂用組成物を硬化させてなる硬化物中に半導体素子が設置されている、半導体装置。
［８］ 硬化樹脂用組成物の製造方法であって、
（Ａ）ベンゾオキサジン環を少なくとも二つ有する多官能ベンゾオキサジン化合物であって、式（１）の構造単位を有する多官能ベンゾオキサジン化合物、および式（２）の構造で示される多官能ベンゾオキサジン化合物から選択される少なくとも１種の多官能ベンゾオキサジン化合物と、
（Ｂ）ノルボルナン構造を少なくとも一つ、およびエポキシ基を少なくとも二つ有するエポキシ化合物と、
（Ｃ）硬化剤と、
（Ｄ）シランカップリング剤と、
（Ｅ）無機充填剤と
を混合して混合物を得る工程、
該混合物を粉体状、ペレット状、または顆粒状の硬化樹脂用組成物に加工する工程
を有する、硬化樹脂用組成物の製造方法。

［式（１）中、Ｒは、炭素数１〜１２の鎖状アルキル基、炭素数３〜８の環状アルキル基、または炭素数１〜１２の鎖状アルキル基もしくはハロゲンで置換されていてもよい炭素数６〜１４のアリール基を示す。ベンゼン環に交差して示されている二つの横線は、水素、炭素数１〜８の炭化水素基および／または連結基を表し、かつ、少なくとも一つは連結基であり、該連結基によって少なくとも二つのベンゾオキサジン環が連結している。］

［式（２）中、Ｌは、酸素および／または硫黄を含んでいてもよい、炭素数２〜１０のアルキレン基または芳香環を１〜５個有する２価の有機基である。］
［９］ 前記混合物を得る工程において、（Ｆ）硬化促進剤をさらに混合して混合物を得る、［８］に記載の製造方法。
［１０］ ［８］または［９］に記載の方法により製造した前記硬化樹脂用組成物を１８０〜３００℃にて加熱して硬化させる工程
を有する、硬化物の製造方法。 That is, according to the present invention, the following invention is provided.
[1] (A) A polyfunctional benzoxazine compound having at least two benzoxazine rings, a polyfunctional benzoxazine compound having a structural unit of the formula (1), and a polyfunctional represented by the structure of the formula (2). At least one polyfunctional benzoxazine compound selected from benzoxazine compounds and
(B) An epoxy compound having at least one norbornane structure and at least two epoxy groups,
(C) Hardener and
(D) Silane coupling agent and
(E) A composition for a cured resin containing an inorganic filler.

[In formula (1), R may be substituted with a chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or a chain alkyl group having 1 to 12 carbon atoms or a halogen. It shows a good aryl group with 6 to 14 carbon atoms. The two horizontal lines crossed over the benzene ring represent hydrogen, hydrocarbon groups with 1 to 8 carbon atoms and / or linking groups, and at least one is a linking group, at least by the linking group. Two benzoxazine rings are linked. ]

[In formula (2), L is a divalent organic group having 1 to 5 alkylene groups or aromatic rings having 2 to 10 carbon atoms, which may contain oxygen and / or sulfur. ]
[2] The composition for a cured resin according to [1], wherein the (D) silane coupling agent has a structure represented by the formula (9).

(In the formula, Y is a functional group selected from the group consisting of an amino group, a mercapto group, an epoxy group, a (meth) acrylic group, a vinyl group, an isocyanate group, an imidazolyl group, a ureido group, a sulfide group, and an isocyanurate group. Indicates a monovalent group containing, X indicates a functional group selected from a hydroxy group and an alkoxy group, and l indicates 0, 1 or 2).
[3] The composition for a cured resin according to [2], wherein Y of the (D) silane coupling agent is selected from the group consisting of a primary amino group, a mercapto group, and a secondary amino group.
[4] The blending ratio of the (D) silane coupling agent is 0.01 to 2 parts by mass with respect to a total of 100 parts by mass of the above (A), the above (B), the above (C) and the above (E). The composition for a cured resin according to any one of [1] to [3].
[5] The composition for a cured resin according to any one of [1] to [4], which further contains (F) a curing accelerator.
[6] A cured product obtained by curing the composition for a cured resin according to any one of [1] to [5].
[7] A semiconductor device in which a semiconductor element is installed in a cured product obtained by curing the composition for a cured resin according to any one of [1] to [6].
[8] A method for producing a composition for a cured resin.
(A) A polyfunctional benzoxazine compound having at least two benzoxazine rings, a polyfunctional benzoxazine compound having a structural unit of the formula (1), and a polyfunctional benzoxazine compound represented by the structure of the formula (2). With at least one polyfunctional benzoxazine compound selected from
(B) An epoxy compound having at least one norbornane structure and at least two epoxy groups,
(C) Hardener and
(D) Silane coupling agent and
(E) Step of mixing with an inorganic filler to obtain a mixture,
A method for producing a composition for a cured resin, which comprises a step of processing the mixture into a powder-like, pellet-like, or granular composition for a cured resin.

[In formula (1), R may be substituted with a chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or a chain alkyl group having 1 to 12 carbon atoms or a halogen. It shows a good aryl group with 6 to 14 carbon atoms. The two horizontal lines crossed over the benzene ring represent hydrogen, hydrocarbon groups with 1 to 8 carbon atoms and / or linking groups, and at least one is a linking group, at least by the linking group. Two benzoxazine rings are linked. ]

[In formula (2), L is a divalent organic group having 1 to 5 alkylene groups or aromatic rings having 2 to 10 carbon atoms, which may contain oxygen and / or sulfur. ]
[9] The production method according to [8], wherein in the step of obtaining the mixture, (F) a curing accelerator is further mixed to obtain a mixture.
[10] A method for producing a cured product, which comprises a step of heating and curing the cured resin composition produced by the method according to [8] or [9] at 180 to 300 ° C.

The composition for a cured resin of the present invention is a novel composition for a cured resin containing the components (A) to (E) and optionally (F), and the cured product of the composition has high mechanical strength and heat resistance. It has good properties, is hard to be thermally decomposed, and has a high glass transition temperature. Therefore, the composition for cured resin of the present invention can be used in applications that require high mechanical strength and high heat resistance, for example, adhesives, paints, encapsulants, matrix resins for composite materials, and the like. be. In particular, it can exhibit excellent sealing performance as a semiconductor element encapsulant and contribute to high reliability of the semiconductor device.

[Composition for cured resin]
Hereinafter, the present invention will be described in detail. The "compound" in the components (A) and (B) of the present invention is not only the monomer represented by each formula, but also an oligomer in which the monomer is polymerized in a small amount, that is, a pre-form before forming a cured resin. It shall also include polymers.

(Component A)
The component (A) constituting the composition for a cured resin is at least one selected from a polyfunctional benzoxazine compound having a structural unit of the formula (1) and a polyfunctional benzoxazine compound represented by the structure of the formula (2). A species of polyfunctional benzoxazine compound having at least two benzoxazine rings. The two horizontal lines crossing the benzene ring of the above formula (1) represent hydrogen, a substituent and / or a linking group (spacer), and at least one is a linking group. At least two benzoxazine rings are linked by a linking group. Here, the linking group includes a group in which two benzoxazine rings are directly bonded without interposing another group. Further, examples of the above-mentioned substituent include a hydrocarbon group having 1 to 8 carbon atoms.
Therefore, the above formula (1) represents the structural unit of a compound in which two or more benzoxazine rings are linked at the benzene ring portion among the choices of the component (A).

［式（１ａ）中、Ｒは、炭素数１〜１２の鎖状アルキル基、炭素数３〜８の環状アルキル基、または炭素数１〜１２の鎖状アルキル基もしくはハロゲンで置換されていてもよい炭素数６〜１４のアリール基を示す。Ｘは、水素または炭素数１〜８の炭化水素基であり、各々同一であっても異なっていてもよい。Ｙは、炭素数１〜６のアルキレン基、酸素、硫黄、ＳＯ_２基、またはカルボニル基である。ｍは０または１である。ｎは１〜１０の整数である。］ More specifically, the polyfunctional benzoxazine compound of the formula (1) can be represented as a structure represented by the formula (1a).

[In formula (1a), R may be substituted with a chain alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, or a chain alkyl group or halogen having 1 to 12 carbon atoms. It shows a good aryl group with 6 to 14 carbon atoms. X is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and may be the same or different from each other. Y is an alkylene group having 1 to 6 carbon atoms, oxygen, sulfur, _two SO groups, or a carbonyl group. m is 0 or 1. n is an integer of 1-10. ]

The following groups can be exemplified as specific examples of R in the formulas (1) and (1a).
Examples of the chain alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group.
Examples of the cyclic alkyl group having 3 to 8 carbon atoms include a cyclopentyl group and a cyclohexyl group.
Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenanthryl group, and a biphenyl group.
The aryl group having 6 to 14 carbon atoms may be substituted, and examples of the substituent include a chain alkyl group having 1 to 12 carbon atoms or a halogen. Examples of the aryl group having 6 to 14 carbon atoms substituted with a chain alkyl group having 1 to 12 carbon atoms or a halogen include an o-tolyl group, an m-tolyl group, a p-tolyl group, a xsilyl group, and o-. Ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, ot-butylphenyl group, mt-butylphenyl group, pt-butylphenyl group, o-chlorophenyl group, o-bromophenyl group Can be mentioned.
In terms of good handleability, R is preferably selected from a methyl group, an ethyl group, a propyl group, a phenyl group, and a p-tolyl group.
Further, the component (A) may be a mixture of compounds represented by the formulas (1) or (1a), each having a different R.

Examples of the hydrocarbon group having 1 to 8 carbon atoms in the formulas (1) and (1a) include an alkyl group, an aryl group, an aralkyl group and the like, and an aryl group is preferable.

Examples of the polyfunctional benzoxazine compound represented by the formula (1) or (1a) include a compound represented by the following formula (1X) and an oligomer obtained by polymerizing a small amount of the compound.

［式（２）中、Ｌは、酸素および／または硫黄を含んでいてもよい、炭素数２〜１０のアルキレン基または芳香環を１〜５個有する２価の有機基である。］
さらに、成分（Ａ）は、各々Ｌが異なる式（２）に示す化合物の混合物であってもよい。 The polyfunctional benzoxazine compound of the formula (2), which is another option of the component (A), is a compound in which N of two benzoxazine rings are bonded to each other via a linking group L.

[In formula (2), L is a divalent organic group having 1 to 5 alkylene groups or aromatic rings having 2 to 10 carbon atoms, which may contain oxygen and / or sulfur. ]
Further, the component (A) may be a mixture of compounds represented by the formula (2), each having a different L.

When L in the formula (2) is a group having an aromatic ring, the number of aromatic rings is 1 to 5, and examples thereof include monocyclic compounds, polycyclic compounds, and condensed ring compounds. Further, L may contain at least one selected from the group consisting of oxygen and sulfur.
As a specific example, a group of functional groups represented by the following formula (3) can be mentioned.

Examples of the polyfunctional benzoxazine compound of the formula (2) include a compound represented by the following formula (2X) and an oligomer obtained by polymerizing a small amount of the compound.

When L in the formula (2) is an alkylene group, the number of carbon atoms thereof is 2 to 10, preferably 2 to 6. Specific examples of the alkylene group include a methylene group, an ethylene group, an isopropylidene group and the like, and a methylene group is preferable.

A commercially available product can also be used as the polyfunctional benzoxazine compound of the component (A). Examples of commercially available products include bisphenol F-aniline (FA) type benzoxazine and phenol-diaminodiphenylmethane (Pd) type benzoxazine (all manufactured by Shikoku Kasei Co., Ltd.).

(Component B)
The component (B) constituting the composition for a cured resin is an epoxy compound having at least one norbornane structure and at least two epoxy groups (hereinafter, also simply referred to as “polyfunctional epoxy compound”). As the polyfunctional epoxy compound, an alicyclic epoxy compound is preferable, and it is more preferable to have an epoxy structure bonded to a 5-membered ring, a 6-membered ring or a norbornane ring represented by the following formula (4).

As a specific polyfunctional epoxy compound, a compound represented by the following formula (5) can be exemplified.

An example of producing the polyfunctional epoxy compound of the component (B) will be described.
The compound of the following formula (5-1) can be produced, for example, as follows.

First, a compound (a) having the following norbornane structure was synthesized by a Diels-Alder reaction between butadiene and dicyclopentadiene, and then the compound (a) and metachloroperbenzoic acid were combined as shown in the following formula (6). Can be produced to produce the compound of formula (5-1).

The compound of the following formula (5-2) can be produced, for example, as follows.

First, the compound (b) (tricyclopentadiene) having the following norbornane structure was synthesized by the Diels-Alder reaction between cyclopentadiene and dicyclopentadiene, and then the compound (b) was synthesized as shown in the following formula (7). The compound of formula (5-2) can be produced by reacting with metachloroperbenzoic acid.

The compound of the following formula (5-3) can be produced, for example, as follows.

First, a compound (c) having the following norbornane structure is synthesized by a Diels-Alder reaction between butadiene and cyclopentadiene, and then the compound (c) and metachloroperbenzoic acid are combined as shown in the following formula (8). The compound of formula (5-3) can be produced by reacting.

The compound of the following formula (5-4) can be produced, for example, as follows.

The compound of formula (5-4) can be produced by reacting dicyclopentadiene with potassium peroxymonosulfate (oxone). The dicyclopentadiene epoxide which is the compound of the formula (5-4) may be a commercially available product, and examples of the commercially available product include dicyclopentadiene epoxide manufactured by SHANDONG QIHUAN BIOCHEMICAL CO., LTD.

The blending ratio of the component (A) polyfunctional benzoxazine compound and the component (B) polyfunctional epoxy compound is 5 parts by mass or more and 150 parts by mass or less of the component (B) with respect to 100 parts by mass of the component (A). It is preferably 10 parts by mass or more and more preferably 100 parts by mass or less.
When the blending ratio of the components (A) and (B) is within the above range, good heat resistance can be obtained.

(Component C)
The component (C) constituting the composition for a cured resin is a curing agent, and examples thereof include imidazoles, aromatic amines, and polyfunctional phenols.
Specific compounds of the component (C) include, for example, diethyltoluenediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, metaxylenediamine, and aromatic amines such as various derivatives thereof, triethylenetetramine, and isophoronediamine. And other aliphatic amines, imidazole derivatives, dicyandiamides, tetramethylguanidines, carboxylic acid anhydrides such as methylhexahydrophthalic acid anhydrides, carboxylic acid hydrazides such as adipate hydrazide, carboxylic acid amides, monofunctional phenols, bisphenol A, and Examples thereof include polyfunctional phenol compounds such as bisphenol sulfide such as bis (4-hydroxyphenyl) sulfide, polyphenol compounds, polymercaptans, carboxylates, and Lewis acid complexes such as boron trifluoride ethylamine complex. These may be used alone or as a mixture of two or more.

The blending ratio of the component (C) is preferably in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the total of the components (A) and (B). More than parts by mass and 25 parts by mass or less are more preferable. By containing the component (C) in this range, the curing reaction can proceed efficiently, and a cured product having high heat resistance can be obtained.

（式中、Ｙはアミノ基、メルカプト基、エポキシ基、（メタ）アクリル基、ビニル基、イソシアネート基、イミダゾリル基、ウレイド基、スルフィド基、およびイソシアヌレート基からなる群から選択される官能基を含む１価の基を示し、Ｘはヒドロキシ基、アルコキシ基から選択される官能基を示し、ｌは０、１または２を示す。） (Component D)
The (D) silane coupling agent used in the present invention has reactivity with both (A) polyfunctional benzoxazine compound and (B) polyfunctional epoxy compound and (C) inorganic filler, which are organic components, and has reactivity. It is a component that improves the affinity between the two. The (D) silane coupling agent of the present invention has a functional group Y that contributes to the bond with the organic component and a functional group X that contributes to the bond with the (C) inorganic filler, according to the following formula (9). Examples include compounds having the structures shown.

(In the formula, Y is a functional group selected from the group consisting of an amino group, a mercapto group, an epoxy group, a (meth) acrylic group, a vinyl group, an isocyanate group, an imidazolyl group, a ureido group, a sulfide group, and an isocyanurate group. Indicates a monovalent group containing, X indicates a functional group selected from a hydroxy group and an alkoxy group, and l indicates 0, 1 or 2).

In the present invention, X in the formula (9) is preferably an alkoxy group. The alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 or 2. The alkoxy group is preferably a methoxy group or an ethoxy group. The silane coupling agent has 1 to 3, preferably 2 or 3 functional groups X in one molecule that contribute to binding to the inorganic filler. Therefore, l in the formula (9) is preferably 1 or 2. When there are two or more functional groups X that contribute to the bond with the inorganic filler, the functional groups X may be the same functional group or a combination of different functional groups.

In the present invention, the monovalent group represented by Y in the formula (9) is selected from the group consisting of an amino group, a mercapto group, an epoxy group, a (meth) acrylic group, a vinyl group, an isocyanate group, an imidazolyl group and a ureido group. It is preferable to contain one or more functional groups (Y ₁ ), and it is more preferable to contain one or more functional groups selected from the group consisting of an amino group and a mercapto group. Here, the amino group may be any of a primary, secondary and tertiary amino group, and is preferably a primary or secondary amino group. Here, the secondary amino group is preferably an anirino group.

（式中、Ｙ_１は、アミノ基、メルカプト基、エポキシ基、（メタ）アクリル基、ビニル基、イソシアネート基、イミダゾリル基、ウレイド基、スルフィド基およびイソシアヌレート基からなる群から選択される１種以上の官能基を示し、Ｒは炭化水素基を示す。） Further, as a monovalent group represented by Y in the formula (9), the structure of the following formula (9-1) can be mentioned.

(In the formula, Y ₁ is one selected from the group consisting of an amino group, a mercapto group, an epoxy group, a (meth) acrylic group, a vinyl group, an isocyanate group, an imidazolyl group, a ureido group, a sulfide group and an isocyanurate group. The above functional groups are shown, and R represents a hydrocarbon group.)

The Y ₁ in the present invention, an amino group, a mercapto group, an epoxy group, (meth) acryl group, a vinyl group, an isocyanate group, an imidazolyl group, one or more functional selected from the group consisting of ureido groups and isocyanurate groups Groups are preferred, and one or more functional groups selected from the group consisting of primary amino groups, mercapto groups, and secondary amino groups are more preferred.
Examples of the "hydrocarbon group" represented by R in the formula (9-1) include an alkylene group, and the alkylene group may be substituted and the substituent is not particularly limited, but has 1 carbon number. Examples thereof include a chain alkyl group of ~ 12 or an aryl group having 6 to 14 carbon atoms. Examples of the chain alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group. Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenanthryl group, and a biphenyl group.
The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The alkylene group may be linear or branched. As the alkylene group, an unsubstituted alkylene group is preferable.

Specific examples of the monovalent group represented by Y include an N- (phenyl) -amino C _1-10 alkyl group (here, the C _1-10 alkyl group represents an alkyl group having 1 to 10 carbon atoms. Similar), Mercapto C _1-10 Alkyl Group, Amino C _1-10 Alkyl Group, N- (Amino C _1-10 Alkyl) -Amino C _1-10 Alkyl Group, N- (C _1-10 Alkylidene) -Amino C _1-10 alkyl group, (epoxy C _3-10 cycloalkyl) C _1-10 alkyl group, glycidoxy C _1-10 alkyl group, glycidyl C _1-10 alkyl group, acrylicoxy C _1-10 alkyl group, methacryloxy C _1-10 alkyl group, vinyl group, styryl group, isocyanate C _1-10 alkyl group, imidazolyl C _1-10 alkyl group, ureido C _1-10 alkyl group, tri (C _1-10 alkoxy) silyl C _1-10 alkyl Examples thereof include a tetrasulfide C _1-10 alkyl group and a di [tri (C _1-10 alkoxy) silyl C _1-10 alkyl] isocyanurate C _1-10 alkyl group. Preferably, it is an N- (phenyl) -amino C _1-10 alkyl group, a mercapto C _1-10 alkyl group, or an amino C _1-10 alkyl group.

Specific examples of the (D) silane coupling agent used in the present invention are shown below. Examples of the silane coupling agent having an amino group (hereinafter, also referred to as aminosilane) include γ-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane (also referred to as γ-aminopropyltrimethoxysilane), and N-. Phenyl-3-aminopropyltrimethoxysilane (also referred to as N-phenyl-γ-aminopropyltrimethoxysilane, anilinosilane) and the like can be mentioned. Examples of the silane coupling agent having a mercapto group (hereinafter, also referred to as mercaptosilane) include 3-mercaptopropyltrimethoxysilane (also referred to as γ-mercaptopropyltrimethoxysilane) and 3-mercaptopropylmethyldimethoxysilane. be able to. Examples of the silane coupling agent having an epoxy group (hereinafter, also referred to as epoxysilane) include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β- (3,4 epoxycyclohexyl). Ethyltrimethoxysilane and the like can be mentioned.
These (D) silane coupling agents may be used alone or in combination of two or more.

By adding the (D) silane coupling agent used in the present invention to the resin composition containing the inorganic filler, it is possible to improve the mechanical strength and reduce the viscosity of the resin composition at the time of melting. Become.

Here, the blending ratio of the (D) silane coupling agent used in the present invention is not particularly limited, but from the viewpoint of improving the mechanical strength of the cured product, the components (A), (B), and (C). ) And (E) totaling 100 parts by mass, preferably 0.01 to 2 parts by mass, and more preferably 0.05 to 2 parts by mass. The blending ratio of the (D) silane coupling agent may be 0.1 to 0.6 parts by mass with respect to 100 parts by mass in total of the components (A), (B), (C) and (E). More preferably, in the case of the blending ratio, an excellent balance between mechanical strength and fluidity is obtained, and a good cured resin composition can be obtained.

(Component E)
The component (E) constituting the cured resin composition is an inorganic filler. The inorganic filler used in the present invention is not particularly limited, and can be selected in consideration of the use of the composition for a cured resin or the cured product thereof or the properties to be imparted. Examples of such inorganic fillers include oxides such as silica, alumina, titanium oxide, zirconium oxide, magnesium oxide, cerium oxide, ittium oxide, calcium oxide, antimony trioxide, zinc oxide and iron oxide; calcium carbonate, Carbonates such as magnesium carbonate, barium carbonate and strontium carbonate; sulfates such as barium sulfate, aluminum sulfate and calcium sulfate; nitrides such as aluminum nitride, silicon nitride, titanium nitride, boron nitride and manganese nitride; calcium hydroxide and water Hydroxides such as aluminum oxide and magnesium hydroxide; silicon compounds such as calcium silicate, magnesium silicate and aluminum silicate; boron compounds such as aluminum borate, zirconium compounds such as barium zirconate and calcium zirconate; phosphoric acid Phosphor compounds such as zirconium and magnesium phosphate; titanium compounds such as strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, barium titanate, potassium titanate; mica, talc, kaolin, kaolin clay, kaolinite , Halloysite, cordierite, pyrophyllite, montmorillonite, cericite, amesite, bentonite, asbestos, wollastonite, sepiolite, zonolite, zeolite, hydrotalcite, hydrated plaster, myoban, kaolin, boehmite, etc. Minerals, fly ash, dehydrated sludge, glass beads, glass fiber, kaolin, carbon black, magnesium oxysulfate, silicon oxide, silicon carbide, etc .; including metals such as copper, iron, cobalt, nickel, or any of them. Alloys; magnetic materials such as sentust, alnico magnets, ferrite, etc., and the like, preferably silica or alumina. Here, examples of silica include fused silica, spherical silica, crystalline silica, amorphous silica, synthetic silica, hollow silica, and the like, and spherical silica and crystalline silica are preferable. The inorganic filler may be used alone or in combination of two or more.

The inorganic filler used in the present invention may be granular, and the average particle size in that case is not particularly limited, but examples thereof include 0.01 μm or more and 150 μm or less, preferably 0.1 μm or more. It is 120 μm or less, more preferably 0.5 μm or more and 75 μm or less. Within this range, for example, when used as a sealing material for semiconductor elements, the filling property into the mold cavity becomes good. The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction type particle size distribution measuring device, "LA-500", "LA-750", "LA-950", "LA-960", etc. manufactured by HORIBA, Ltd. can be used.

The blending ratio of the component (E) is not particularly limited as long as a highly heat-resistant cured product of the composition for a cured resin can be obtained, and can be appropriately set according to the intended use. For example, when the composition is used for semiconductor encapsulation, the compounding ratio shown below is preferable.
The lower limit of the blending ratio of the component (E) is, for example, 150 parts by mass or more with respect to 100 parts by mass in total of the components (A), (B), (C), and (D), and 400 parts by mass. The above is preferable, and 500 parts by mass or more is more preferable. The upper limit of the blending ratio of the component (F) is 1300 parts by mass or less, preferably 1150 parts by mass or less, and more preferably 950 parts by mass or less. When it is 400 parts by mass or more, an increase in the amount of moisture absorbed and a decrease in strength due to curing of the cured resin assembly composition can be suppressed, and therefore a cured product having good solder crack resistance can be obtained. Further, when the amount is 1300 parts by mass or less, the cured resin assembly composition has fluidity, is easily filled in the mold, and the cured product exhibits good sealing performance.

(Component F)
The composition for a cured resin of the present invention may further contain (F) a curing accelerator, if desired.
As the curing accelerator, a known curing accelerator can be used, and amine compounds such as tributylamine, 1,8-diazabicyclo (5,4,0) undecene-7, 2-methylimidazole, and 2-ethyl can be used. Imidazole compounds such as imidazole and 1,2-dimethylimidazole, organophosphorus compounds in which phosphorus is bound only by covalent bonds such as triphenylphosphine, and phosphorus is bound by covalent bonds and ionic bonds such as tetraphenylphosphonium tetraphenylborate. Examples thereof include, but are not limited to, organic phosphorus compounds such as salt-type organic phosphorus compounds. Further, the above-mentioned curing accelerator may be used alone or in combination of two or more. Of these, organophosphorus compounds such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate are preferable because they have a large effect of improving the curing rate.
As described in JP-A-55-157594, the organic phosphorus compound exerts a function of promoting a cross-linking reaction between an epoxy group and a phenolic hydroxyl group. Further, it also exerts a function of accelerating the reaction between the hydroxyl group and the epoxy group generated when the polyfunctional benzoxazine compound (A) undergoes a cleavage reaction at a high temperature. The organic phosphorus compound of the present invention is not particularly limited as long as it has the above-mentioned function.
The blending ratio of the component (F) is preferably in the range of 0.01 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the total of the components (A) and (B). .. It is more preferably in the range of 0.1 part by mass or more and 7 parts by mass or less. By containing the component (F) in this range, a composition for a cured resin having good fast-curing properties can be obtained.

(Other ingredients)
When the composition for a cured resin of the present invention is desired to reduce the viscosity of the composition, it is a monofunctional compound having one benzoxazine ring as a benzoxazine compound other than the component (A) as long as its performance is not impaired. It may contain a benzoxazine compound.
Further, for example, nanocarbon, a flame retardant, a mold release agent and the like can be blended in the composition for a cured resin of the present invention as long as its performance is not impaired.
Examples of nanocarbons include carbon nanotubes, fullerenes, and derivatives thereof.
Examples of the flame retardant include phosphate esters such as red phosphorus, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresil diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol bisphenyl phosphate, and bisphenol A bisdiphenyl phosphate. , Boric acid ester and the like.
Examples of the release agent include silicone oil, stearic acid ester, carnauba wax and the like.

When the composition for cured resin of the present invention is used for semiconductor encapsulation, carbon black, paraffin, and oxidation are used in addition to the components (A) to (F) as long as the performance of the composition for cured resin is not impaired. Colorants such as titanium; natural waxes such as carnauba wax, synthetic waxes such as polyethylene oxide wax, higher fatty acids such as stearic acid, metal salts such as zinc stearate, and mold release agents such as paraffin; silicone oil and silicone rubber. Such as low stress additives; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; and flame retardants such as phosphazene may be appropriately blended.

(Characteristics of composition for cured resin)
The melt viscosity of the composition for a cured resin of the present invention can be measured as the minimum melting torque at 200 ° C. and 100 rpm, and is not particularly limited as long as the effect of the present invention is exhibited, but the minimum melting torque is 6.5 gf. -Cm or less, and from the viewpoint of fluidity, it is preferably 6.2 gf · cm or less, more preferably 6.1 gf · cm or less, and further preferably 6.0 gf · cm or less. The minimum melting torque is indicated by the minimum value of the torque curve drawn under a constant temperature and a constant rotation speed, and can be measured by a gel time measuring machine, a lab plast mill, or the like. Specifically, it can be easily performed by using a commercially available gel time measuring machine (for example, manufactured by Matsuo Sangyo).

[Manufacturing method of composition for cured resin]
Next, a method for producing the composition for a cured resin of the present invention will be described.
The composition for a cured resin of the present invention is produced by adding the components (A) to (E), and if desired, the component (F), other additives, and a solvent as appropriate and mixing them by a kneading or mixing device. can do.
The kneading and mixing methods are not particularly limited, and for example, kneading can be performed using a kneader, a planetary mixer, a twin-screw extruder, a kneader such as a hot roll or a kneader, or the like. Further, if necessary, the mixture may be heated and kneaded, or may be kneaded under pressurized or reduced pressure conditions. The heating temperature is preferably 80 to 120 ° C. Further, since the component (D) is generally in a liquid state at room temperature, it may be mixed with the component (E) in advance, or may be mixed with the components (A), (B), (C), (F) and the like. ..
Since the composition for a cured resin containing the component (E) is in a solid state at room temperature, it may be cooled and pulverized after heating and kneading to form a powder, and the powder may be tableted into pellets. May be good. Further, the powder may be granulated into granules.

[Cured product]
The cured product of the composition for a cured resin of the present invention has features that it has good heat resistance, is hard to be thermally decomposed, has a high glass transition temperature, and has high mechanical strength. The reason why the composition for a cured resin of the present invention forms such an excellent cured product is considered as follows.
First, in the homopolymerization of benzoxazine, a phenolic hydroxyl group is generated by the polymerization. It is considered that this phenolic hydroxyl group has low heat resistance and a low glass transition temperature because the polymer chain is cleaved by the ketoenol tautomer at a high temperature, for example, 200 ° C. or higher. Has been done.
On the other hand, the epoxy compound having the norbornan structure of the present application and having two or more epoxy groups is difficult to homopolymerize, and reacts with the phenolic hydroxyl group derived from benzoxazine to prevent the breakage of the polymer chain. Conceivable. Therefore, a cured product having high heat resistance can be obtained.
Further, since the component (D) has both the reactivity with the polyfunctional benzoxazine compound (A) and the polyfunctional epoxy compound (B) and the reactivity with the inorganic filler (E), the affinity between the organic substance and the inorganic filler It is considered that the reactivity can be improved, the mechanical strength can be improved, and the melt viscosity of the cured resin can be reduced.

The mechanical strength of the cured product of the present invention can be evaluated by measuring the bending strength by a bending test. The bending strength is not particularly limited as long as the effect of the present invention is exhibited, but 100 MPa or more is mentioned, and preferably 105 MPa or more, more preferably 110 MPa or more. Bending strength can be measured according to JIS K 6911. Such measurement can be easily performed by using a commercially available precision universal testing machine (for example, manufactured by Shimadzu Corporation).

The heat resistance of the cured product of the present invention can be evaluated by measuring the glass transition temperature. The glass transition temperature is not particularly limited as long as the effects of the present invention are exhibited, but may be 200 ° C. or higher, preferably 210 ° C. or higher, and more preferably 220 ° C. or higher. The glass transition temperature can be measured by differential scanning calorimetry (DSC). Such measurement can be easily performed by using a commercially available differential scanning calorimeter (for example, manufactured by Hitachi High-Tech Science Corporation).

[Manufacturing method of cured product]
The cured product of the present invention can be produced, for example, as follows. That is, ring-opening polymerization can be performed and cured under the same curing conditions as known benzoxazine compounds and / or epoxy compounds. For example, the following methods can be mentioned.
First, the composition for a cured resin of the present invention is produced by the above method. Subsequently, the obtained cured resin composition is heated at 180 to 300 ° C. for 1 minute to 1 hour to obtain a cured product. In terms of continuous production of the cured product, a curing time of 1 to 3 minutes is sufficient, but in terms of obtaining sufficient strength, heating is preferably about 5 minutes to 1 hour.
Further, a cured product can be obtained by blending other benzoxazine compounds and / or other epoxy compounds as long as the effects of the present invention are not impaired.

[Semiconductor device]
The semiconductor device of the present invention is a semiconductor device in which a semiconductor element is installed in a cured product obtained by curing the composition for a cured resin of the present invention containing the components (A) to (E) and, if desired, (F). Is. Here, the semiconductor element is usually supported and fixed by a lead frame which is a thin plate of a metal material. "The semiconductor element is installed in the cured product" means that the semiconductor element is sealed with the cured product of the above-mentioned cured resin composition, and the semiconductor element is coated with the cured product. Represents a state. In this case, the entire semiconductor element may be covered, or the surface of the semiconductor element installed on the substrate may be covered.

When various electronic components such as semiconductor elements are sealed using the cured product of the present invention to manufacture a semiconductor device, a sealing step is performed by a conventional molding method such as transfer mold, compression mold, or injection mold. By carrying out the above, a semiconductor device can be manufactured.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

<Component (A); Polyfunctional benzoxazine compound>
The following was used as the component (A).
(A); Phenol-diaminodiphenylmethane (Pd) type benzoxazine represented by the following formula (2-1) (manufactured by Shikoku Chemicals Corporation)

<Component (B); Polyfunctional epoxy compound>
The following (B1) to (B5) were used as the component (B).
(B1) Polyfunctional epoxy compound 1; Compound of formula (5-1) The compound (a) represented by the above formula (6) was described as "Diels-Alder reaction of butadiene and cyclopentadiene-trimer" by Shoichi Tsuchida et al. It was synthesized according to the method described in "Determining the Body-", Journal of the Petroleum Society, 1972, Vol. 15, No. 3, p189-192.
Next, the reaction of the above formula (6) was carried out as follows. 23.5 kg of chloroform and 1.6 kg of compound (a) were put into the reaction vessel, and 4.5 kg of metachloroperbenzoic acid was added dropwise while stirring at 0 ° C. The temperature was raised to room temperature, and the reaction was carried out for 12 hours.
Next, after removing the metachlorobenzoic acid produced as a by-product by filtration, the filtrate was washed 3 times with a 1N aqueous sodium hydroxide solution and then with a saturated saline solution. The organic layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the filtrate was concentrated to obtain a crude product.
Toluene (2 kg) was added to the crude product, and the mixture was dissolved at room temperature. 6 kg of heptane was added dropwise thereto for crystallization, and the mixture was aged at 5 ° C. for 1 hour. The crystallized product was collected by filtration and washed with hexane. By drying under reduced pressure for 24 hours at 35 ° C., 1.4 kg of the compound represented by the following formula (5-1) was obtained as a white solid.

(B2) Polyfunctional Epoxy Compound 2; Compound of Formula (5-2) (Tricyclopentadiene Diepoxide)
Compound (b) was synthesized in the same manner as compound (a) according to the method described in the above literature.
Next, the reaction of the above formula (7) was carried out as follows. 59.2 kg of chloroform and 4.0 kg of compound (b) were added to the reaction vessel, and 10.6 kg of metachloroperbenzoic acid was added dropwise with stirring at −10 ° C. The temperature was raised to room temperature, and the reaction was carried out for 12 hours.
Next, after removing the meta-chlorobenzoic acid produced as a by-product by filtration, the filtrate was washed with 42.0 kg of a 5% aqueous sodium sulfite solution. The organic layer was further washed 4 times with 41.6 kg of 1N aqueous sodium hydroxide solution and then with 48.0 kg of saturated brine. The organic layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the filtrate was concentrated to obtain 5.1 kg of a crude product.
Toluene (3.5 kg) was added to the crude product, and the mixture was dissolved at room temperature. 13.7 kg of heptane was added dropwise thereto for crystallization, and the mixture was aged at 5 ° C. for 1 hour. The crystallized product was collected by filtration and washed with heptane. By drying under reduced pressure for 12 hours at 35 ° C., 2.8 kg of the compound represented by the following formula (5-2) was obtained as a white solid.

(B3) Polyfunctional Epoxy Compound 3; Compound of Formula (5-4) (Dicyclopentadiene Diepoxide)
10 kg of dicyclopentadiene, 68 kg of baking soda, 100 L of acetone and 130 L of ion-exchanged water were charged in the reaction vessel, cooled to 10 ° C. or lower, and then the cooling was controlled so as to maintain the temperature of the reaction solution at 30 ° C. or lower, and 84 kg of oxone. Was gradually added, and the reaction was carried out for 10 hours with stirring.
Next, the reaction product was extracted twice with 100 L of ethyl acetate, and the obtained organic layers were separated and combined. Subsequently, the organic layer was washed with 100 L of a mixed aqueous solution of salt and sodium thiosulfate (20 wt% of salt + 20 wt% of sodium thiosulfate), and then further washed twice with 100 L of ion-exchanged water.
The washed organic layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the organic solvent was distilled off from the filtrate to obtain 11 kg of the compound represented by the following formula (5-4) as a white solid.

（Ｂ５）多官能エポキシ化合物５；下記式（１１）に示す多官能エポキシ化合物（ＮＣ−３０００、日本化薬株式会社製）

The following components (B4) and (B5), which do not have a norbornane structure, were used as the (B4) polyfunctional epoxy compound for the comparative example.
(B4) Polyfunctional Epoxy Compound 4; Polyfunctional Epoxy Compound Represented by the following formula (10) (YX-4000H, manufactured by Mitsubishi Chemical Corporation)

(B5) Polyfunctional epoxy compound 5; Polyfunctional epoxy compound represented by the following formula (11) (NC-3000, manufactured by Nippon Kayaku Co., Ltd.)

<Component (C); Hardener>
The following was used as the component (C).
(C); Bis (4-hydroxyphenyl) sulfide (TDP) represented by the following formula (12) (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Component (D); Silane coupling agent>
The following (D1), (D2), and (D3) were used as the component (D).
(D1) Silane Coupling Agent 1; 3-Aminopropyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
(D2) Silane Coupling Agent 2; N-Phenyl-3-aminopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)
(D3) Silane Coupling Agent 3; 3-Mercaptopropyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Component (E); Inorganic filler>
As the component (E), molten spherical silica (FB-820, manufactured by Denka Co., Ltd.) having an average particle size D50 of 22 μm was used. Hereinafter, it will be referred to as (E).

<Component (F); Hardening accelerator>
The following was used as the component (F).
(F); Triphenylphosphine (TPP) (manufactured by Hokuko Chemical Industry Co., Ltd.)

<Other ingredients>
Carnauba wax (manufactured by Clariant Japan Co., Ltd.) was used as the release agent, and carbon black (MA600, manufactured by Mitsubishi Chemical Corporation) was used as the colorant.

(Example 1)
A composition for a cured resin (hereinafter simply referred to as a composition) and a cured product are prepared as follows, and the glass transition temperature is evaluated as heat resistance, and the strength, elastic modulus, and fluidity by bending test are evaluated as mechanical strength. As an evaluation, the melting torque was measured.
(A), (B1), (C), (D1), (E), (F), carnauba wax, and carbon black are blended in the proportions shown in Table 1 and have surface temperatures of 90 ° C and 100 ° C. After kneading under atmospheric pressure for 10 minutes using a hot roll kneader (BR-150HCV, IMEX Co., Ltd.) having this roll, the mixture was cooled to room temperature to obtain a mixture. The mixture was pulverized with a mini speed mill MS-09 (manufactured by Labonect Co., Ltd.) into a powder so that the mold could be well filled to obtain a composition.
Table 1 shows the measurement results of the glass transition temperature, the strength and elastic modulus by the bending test, and the melting torque.

<Heat resistance (glass transition temperature; Tg)>
Using a transfer molding machine, the prepared composition is cured under the conditions of a mold temperature of 200 ° C., an injection pressure of 4 MPa, and a curing time of 6 minutes. A cured product having a size of 3 mm × width 3 mm × length 15 mm was prepared. Tg was measured by DSC under the following conditions using a test piece obtained by cutting the cured product into a size of 3 mm in length × 3 mm in width × 2 mm in length.
Equipment: X-DSC-7000 (manufactured by Hitachi High-Tech Science Corporation)
Measurement conditions: N ₂ flow rate; 20 mL / min, heating rate; 20 ° C / min

<Bending strength and flexural modulus>
Using a transfer molding machine, the prepared composition is cured under the conditions of a mold temperature of 200 ° C., an injection pressure of 4 MPa, and a curing time of 3 minutes, and further, as a post-curing treatment, it is heated in an oven at 240 ° C. for 4 hours. A cured product of 10 mm × length 80 mm × thickness 3 mm was prepared. The bending strength [MPa] and flexural modulus [MPa] of the cured product were measured by a precision universal testing machine (AGS-1kNX manufactured by Shimadzu Corporation) according to JIS K 6911.

<Minimum melting torque>
The minimum melting torque [gf · cm] of 0.60 g of the prepared composition at a rotation speed of 100 rpm at 200 ° C. was measured by a gel time measuring machine (Matsuo Sangyo's automatic curing time (gel time) measuring device “Madoka”).
Stirring method: Biaxial eccentric sample amount: 0.60 g

(Examples 2 to 8)
The composition of each example was prepared in the same manner as in Example 1 except that the blending ratio of each component was as shown in Table 1. The heat resistance (glass transition temperature), bending strength, flexural modulus, and melting torque of each composition were measured in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Examples 1 to 7)
The compositions of each Comparative Example were prepared in the same manner as in Example 1 except that the blending ratio of each component was as shown in Table 2. The heat resistance (glass transition temperature), bending strength, flexural modulus, and melting torque of each composition were measured in the same manner as in Example 1. The results are shown in Table 2.

The cured resin composition of each example has a heat resistance (glass transition temperature) of 220 ° C. or higher and a bending strength of 100 MPa or higher, and it can be seen that the heat resistance and high strength are highly achieved. Further, since the minimum melting torque is 6.1 gf · cm or less, it is expected that the fluidity at the time of transfer molding is good. On the other hand, Comparative Examples 1, 2 and 3 are relatively good in terms of heat resistance, but have low bending strength. In Comparative Examples 4 to 7, the glass transition temperature is low and the heat resistance is inferior.
From the above results, it was found that by using the composition for a cured resin according to the embodiment of the present invention, both high heat resistance and high bending strength of the cured product obtained by curing the composition can be achieved at the same time.

Claims (14)

(A) A polyfunctional benzoxazine compound having at least two benzoxazine rings, and at least one polyfunctional benzoxazine compound selected from the polyfunctional benzoxazine compounds represented by the formula (2X).
(B) An epoxy compound having at least one norbornane structure and at least two epoxy groups and having at least one epoxy structure selected from the epoxy structures represented by the formula (4).
(C) Hardener and
(D) Silane coupling agent and
(E) A composition for a cured resin containing an inorganic filler.

The composition for a cured resin according to claim 1, wherein the epoxy compound having at least one norbornane structure and at least two epoxy groups (B) is at least one of the compounds represented by the formula (5).

A hard claim that the blending ratio of the (A) polyfunctional benzoxazine compound and the (B) epoxy compound is 5 parts by mass or more and 150 parts by mass or less of the (B) with respect to 100 parts by mass of the (A). The composition for a cured resin according to 1 or 2. 3. The composition for a cured resin according to the above. The composition for a cured resin according to any one of claims 1 to 4, wherein the (D) silane coupling agent has a structure represented by the formula (9).

(In the formula, Y is a functional group selected from the group consisting of an amino group, a mercapto group, an epoxy group, a (meth) acrylic group, a vinyl group, an isocyanate group, an imidazolyl group, a ureido group, a sulfide group, and an isocyanurate group. Indicates a monovalent group containing, X indicates a functional group selected from a hydroxy group and an alkoxy group, and l indicates 0, 1 or 2). The composition for a cured resin according to claim 5 , wherein Y of the (D) silane coupling agent is selected from the group consisting of a primary amino group, a mercapto group, and a secondary amino group. Claimed that the blending ratio of the (D) silane coupling agent is 0.01 to 2 parts by mass with respect to a total of 100 parts by mass of the above (A), the above (B), the above (C) and the above (E). Item 6. The composition for a cured resin according to any one of Items 1 to 6. The blending ratio of the inorganic filler (E) is 150 parts by mass or more and 1300 parts by mass or less with respect to 100 parts by mass in total of (A), (B), (C) and (D). The composition for a cured resin according to any one of claims 1 to 7. (F) The composition for a cured resin according to any one of claims 1 to 8 , further containing a curing accelerator. A cured product obtained by curing the cured resin composition according to any one of claims 1 to 9. A semiconductor device in which a semiconductor element is installed in a cured product obtained by curing the composition for a cured resin according to any one of claims 1 to 10. A method for producing a composition for a cured resin.
(A) A polyfunctional benzoxazine compound having at least two benzoxazine rings, and at least one polyfunctional benzoxazine compound selected from the polyfunctional benzoxazine compounds represented by the formula (2X).
(B) An epoxy compound having at least one norbornane structure and at least two epoxy groups and having at least one epoxy structure selected from the epoxy structures represented by the formula (4).
(C) Hardener and
(D) Silane coupling agent and
(E) Step of mixing with an inorganic filler to obtain a mixture,
A method for producing a composition for a cured resin, which comprises a step of processing the mixture into a powder-like, pellet-like, or granular composition for a cured resin.

The production method according to claim 12 , wherein in the step of obtaining the mixture, (F) a curing accelerator is further mixed to obtain a mixture. A method for producing a cured product, which comprises a step of heating and curing the cured resin composition produced by the method according to claim 12 or 13 at 180 to 300 ° C.