JP2017110051A - Resin composition for encapsulation, semiconductor device and on-vehicle electronic control unit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for encapsulation having high adhesiveness and capable of improving reliability of a device.SOLUTION: A resin composition 50 for encapsulation comprises the following components (A), (B) and (C). The components are: (A) a maleimide compound; (B) an amino group-containing heterocyclic compound having a specific structural formula; and (C) a thermosetting resin (excluding a compound corresponding to component (A)). The (B) amino group-containing heterocyclic compound is preferably a compound selected from an amino group-containing triazole compound, an amino group-containing triazine compound, an amino group-containing imidazole compound and an amino group-containing benzimidazole compound.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a sealing resin composition, a semiconductor device, and an on-vehicle electronic control unit.

  Various investigations have been made on resin compositions used to seal semiconductor elements. Examples of such a technique include those described in Patent Document 1 and Patent Document 2.

Patent Document 1 discloses a technique related to a resin composition for a sealing material containing an epoxy resin. Specifically, it comprises at least one selected from the group consisting of epoxy resins, acid anhydrides, amine compounds and phenolic compounds, organic group-containing silsesquioxane, silica and composite metal hydroxide, and A resin composition for a sealing material is described in which at least one selected from the group consisting of the epoxy resin, acid anhydride, amine compound and phenol compound has a melting point of 100 ° C. or higher.
On the other hand, Patent Document 2 includes a bismaleimide compound, an allyl compound, and a polymerization initiator having a specific structure as a resin composition for semiconductor encapsulation that can sufficiently suppress wafer warpage and has excellent moldability. A resin composition for encapsulating a semiconductor is disclosed.

  In recent years, a vehicle-mounted electronic control unit in which a substrate on which electronic components and the like are mounted is sealed with a sealing resin has been studied. An example of such a technique is described in Patent Document 3.

  Patent Document 3 discloses an electrical connection between a wiring board provided with a through hole, an electronic component mounted on the wiring board, a metal base on which the wiring board is mounted, and the wiring board and the outside attached to the metal base. This is a technology related to a resin-sealed electronic control device that includes a connector to be connected and in which a front surface of a wiring board and a part of a metal base are integrally sealed with a thermosetting resin.

JP 2014-028928 A JP 2014-001289 A JP 2009-147014 A

As described above, the encapsulating resin composition is used to form a sealing material for encapsulating a semiconductor element, a wiring board on which an electronic component or the like is mounted.
Here, in general, when configuring a semiconductor device, this semiconductor element is bonded to another metal member using a metal wire such as copper, and electrical connection is achieved. Here, when the semiconductor device is used for a long period of time, there is a concern that the reliability of the semiconductor device is impaired unless the adhesion between the metal and the sealing material is sufficient.
In particular, in recent years, a semiconductor device including a power semiconductor element using a wide band gap material such as SiC, GaN, Ga ₂ O ₃ , or diamond has been proposed.
Since such a power semiconductor element generates a large amount of heat during use, there is a tendency that the reliability during use of the semiconductor device tends to be lowered, and the adhesion of the resin composition for semiconductor encapsulation should be set to a higher level. Is required.

  In addition, the on-vehicle electronic control unit as described above is often placed in an engine room and exposed to high temperature conditions, and in this case, there is a concern that the adhesion between the wiring board and the sealing resin is lowered. is there.

  From such a background, an object of the present invention is to provide a sealing resin composition that has high adhesion and can improve the reliability of the device.

（式（１）中、Ａは、環を構成する原子の１つ以上が窒素原子であり、かつ、全体として芳香族性を有する複素環である。Ｂは複素環を構成する炭素原子に結合する二価の基または単結合を表す。ｍは１以上３以下の整数である。Ｒａは水素原子、炭素数１以上１２以下の有機基、水酸基、アミノ基またはカルボキシル基である。ｎは０以上の整数であり、ｍ＋ｎはＡに結合しうる基の数の総数である。） According to this invention, the resin composition for sealing containing the following components (A), (B) and (C) is provided.
(A) Maleimide compound (B) Amino group-containing heterocyclic compound represented by general formula (1) (C) Thermosetting resin (however, excluding those corresponding to component (A))

(In Formula (1), A is a heterocyclic ring in which one or more of the atoms constituting the ring is a nitrogen atom and has aromaticity as a whole. B is bonded to the carbon atom constituting the heterocyclic ring. M is an integer of 1 to 3. Ra is a hydrogen atom, an organic group having 1 to 12 carbon atoms, a hydroxyl group, an amino group, or a carboxyl group, and n is 0. (It is an integer above, and m + n is the total number of groups that can be bonded to A.)

According to the present invention,
A semiconductor element;
A cured product of the sealing resin composition;
A semiconductor device is provided.

Moreover, according to the present invention,
A wiring board;
A plurality of electronic components mounted on at least one surface of the wiring board;
A sealing resin which is formed by curing the sealing resin composition and seals the electronic component;
An in-vehicle electronic control unit is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition for sealing which has high adhesiveness and can improve the reliability of an apparatus can be provided.

It is sectional drawing which shows an example of the semiconductor device which concerns on this embodiment. It is sectional drawing which shows an example of the semiconductor device which concerns on this embodiment. It is a cross-sectional schematic diagram which shows an example of the vehicle-mounted electronic control unit which concerns on this embodiment.

  Hereinafter, embodiments will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

（式（１）中、Ａは、環を構成する原子の１つ以上が窒素原子であり、かつ、全体として芳香族性を有する複素環である。Ｂは複素環を構成する炭素原子に結合する二価の基または単結合を表す。ｍは１以上３以下の整数である。Ｒａは水素原子、炭素数１以上１２以下の有機基、水酸基、アミノ基またはカルボキシル基である。ｎは０以上の整数であり、ｍ＋ｎはＡに結合しうる基の数の総数である。） First, the sealing resin composition according to this embodiment will be described.
The sealing resin composition of this embodiment contains the following components (A), (B), and (C).
(A) Maleimide compound (B) Amino group-containing heterocyclic compound represented by general formula (1) (C) Thermosetting resin (however, excluding those corresponding to component (A))

(In Formula (1), A is a heterocyclic ring in which one or more of the atoms constituting the ring is a nitrogen atom and has aromaticity as a whole. B is bonded to the carbon atom constituting the heterocyclic ring. M is an integer of 1 to 3. Ra is a hydrogen atom, an organic group having 1 to 12 carbon atoms, a hydroxyl group, an amino group, or a carboxyl group, and n is 0. (It is an integer above, and m + n is the total number of groups that can be bonded to A.)

The sealing resin composition of the present embodiment has high adhesion and can improve the reliability of the device. Therefore, it is preferably used for a purpose of sealing a semiconductor element or a purpose of sealing a wiring board.
Hereinafter, each component which comprises the resin composition for sealing in this embodiment is demonstrated.

((A) Maleimide compound)
The sealing resin composition of the present embodiment contains (A) a maleimide compound.
This (A) maleimide compound is a compound having two or more maleimide groups.

  (A) A maleimide compound can contain the compound shown, for example in following formula (10). Thereby, a glass transition temperature can be raised and the high temperature long-term storage characteristic as a sealing material can be improved more effectively.

（式（１０）中、ｎ_１は０以上１０以下の整数であり、Ｘ_１はそれぞれ独立に炭素数１以上１０以下のアルキレン基、下記式（１０ａ）で表される基、式「−ＳＯ_２−」で表される基、「−ＣＯ−」で表される基、酸素原子または単結合であり、Ｒ_１はそれぞれ独立に炭素数１以上６以下の炭化水素基であり、ａはそれぞれ独立に０以上４以下の整数であり、ｂはそれぞれ独立に０以上３以下の整数である。）

（式（１０ａ）中、Ｙは芳香族環を有する炭素数６以上３０以下の炭化水素基であり、ｎ_２は０以上の整数である。）

(In formula (10), n ₁ is an integer of 0 or more and 10 or less, X ₁ is each independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following formula (10a), a formula “—SO A group represented by “ _2- ”, a group represented by “—CO—”, an oxygen atom or a single bond, each R ₁ is independently a hydrocarbon group having 1 to 6 carbon atoms, and a is each Independently an integer of 0 or more and 4 or less, and b is an integer of 0 or more and 3 or less independently.)

(In formula (10a), Y is a hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring, and n ₂ is an integer of 0 or more.)

In the present embodiment, the upper limit value of n ₂ in the above formula (10a) can be set to 20, for example.

  Moreover, as the (A) maleimide compound, for example, the following compounds can be preferably used.

In the present embodiment, the content of the (A) maleimide compound in the sealing resin composition is preferably 5% by mass or more, for example, 8% by mass or more with respect to the entire sealing resin composition. More preferably, it is more preferably 10% by mass or more. (A) By setting the content of the maleimide compound to the above lower limit or more, the heat resistance as a sealing material can be effectively improved, and the moisture resistance reliability and reflow resistance of a semiconductor device and the like are improved. Can be made.
Moreover, it is preferable that content of (A) maleimide compound is 30 mass% or less with respect to the whole resin composition for sealing, for example, it is more preferable that it is 25 mass% or less, and it is 20 mass% or less. Particularly preferred. (A) By making content of a maleimide compound below the said upper limit, the fluidity | liquidity as a resin composition for sealing can be improved.

((B) Amino group-containing heterocyclic compound)
The sealing resin composition of this embodiment contains an amino group-containing heterocyclic compound represented by the following general formula (1).

（式（１）中、Ａは、環を構成する原子の１つ以上が窒素原子であり、かつ、全体として芳香族性を有する複素環である。Ｂは複素環を構成する炭素原子に結合する二価の基または単結合を表す。ｍは１以上３以下の整数である。Ｒａは水素原子、炭素数１以上１２以下の有機基、水酸基、アミノ基またはカルボキシル基である。ｎは０以上の整数であり、ｍ＋ｎはＡに結合しうる基の数の総数である。）

(In Formula (1), A is a heterocyclic ring in which one or more of the atoms constituting the ring is a nitrogen atom and has aromaticity as a whole. B is bonded to the carbon atom constituting the heterocyclic ring. M is an integer of 1 to 3. Ra is a hydrogen atom, an organic group having 1 to 12 carbon atoms, a hydroxyl group, an amino group, or a carboxyl group, and n is 0. (It is an integer above, and m + n is the total number of groups that can be bonded to A.)

In formula (1), examples of the heterocyclic ring constituting A include monocyclic 5-membered rings such as pyrrole ring, imidazole ring, pyrazole ring and triazole ring, pyridine ring, pyrimidine ring and triazine ring. A member ring is mentioned. Examples of the bicyclic ring include an indole ring, a benzimidazole ring, a benzotriazole ring, a quinoline ring, a bipyridyl ring, and a phenanthroline ring.
These heterocycles may be condensed with an allocyclic ring composed only of aromatic carbon such as a benzene ring and a naphthalene ring.
Note that all of the carbon atoms constituting the heterocyclic ring are substituted with either the group “Ra” or “B—NH ₂ ”. Moreover, when the nitrogen atom which comprises a heterocyclic ring has a bond outside a ring, the group couple | bonded with this nitrogen atom may be a hydrogen atom or a C1-C12 organic group.

In the formula (1), B represents a divalent group or a single bond bonded to the carbon atom constituting the heterocyclic ring.
Here, examples of the divalent group include groups represented by the following formulas.
_{- [(CH 2) l -} (Z) m - (CH 2) n] P -
(However, Z represents an oxygen atom,-(C = O)-and-(C = O) -NH-, and a (hetero) arylene group, and l, m, n, and p represent an integer of 1-6. .)

Further, this B is preferably a single bond. Thereby, the adhesiveness of the sealing material with respect to a metal or a board | substrate can be improved more.
The reason for this is not clear, but this B is a single bond, that is, an amino group (—NH ₂ ) and a carbon atom constituting a heterocyclic ring are directly connected to each other, whereby an unshared electron pair of a nitrogen atom included in the amino group. There is a flow of electrons from to the heterocycle. Due to this, it is considered that the electron density on the heterocyclic ring can be adjusted to an appropriate value.

  In the formula (1), examples of the organic group having 1 to 12 carbon atoms constituting Ra include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an s-butyl group. Group, an alkyl group represented by t-butyl group, an aryl group such as a phenyl group and a tolyl group.

The amino group-containing heterocyclic compound represented by the general formula (1) includes an amino group-containing triazole compound represented by the following general formula (2) and an amino group-containing compound represented by the following general formula (3). It is preferably selected from the group consisting of a triazine compound, an amino group-containing imidazole compound represented by the following general formula (4), and an amino group-containing benzimidazole compound represented by the following general formula (5).
Since these compounds are easily available and have high adhesion to metals and the like, they can be preferably used in the sealing resin composition of the present embodiment.

（式（２）中、Ｒａは式（１）で示すものと同義である。）

(In formula (2), Ra has the same meaning as that shown in formula (1).)

（式（３）中、Ｒａは式（１）で示すものと同義である。）

(In formula (3), Ra has the same meaning as that shown in formula (1).)

（式（４）中、Ｒａは式（１）で示すものと同義である。Ｒｂは水素原子または炭素数１以上１２以下の有機基である。）

(In formula (4), Ra has the same meaning as that shown in formula (1). Rb is a hydrogen atom or an organic group having 1 to 12 carbon atoms.)

（式（５）中、Ｒｃは水素原子または炭素数１以上１２以下の有機基である。）

(In Formula (5), Rc is a hydrogen atom or an organic group having 1 to 12 carbon atoms.)

  An organic group having 1 to 12 carbon atoms that can be taken as Rb and Rc has the same meaning as an organic group having 1 to 12 carbon atoms that can be taken as the aforementioned group Ra.

In the present embodiment, the content of the (B) amino group-containing heterocyclic compound in the encapsulating resin composition is preferably 0.01% by mass or more with respect to the entire encapsulating resin composition, for example. 0.03 mass% or more is more preferable, and 0.05 mass% or more is particularly preferable. (B) By making content of an amino group containing heterocyclic compound more than the said lower limit, the adhesiveness as a sealing material can be improved effectively and the moisture-reliability reliability and heat-resistant characteristic of an apparatus are improved. Can be improved.
In addition, the content of the (B) amino group-containing heterocyclic compound is preferably 10% by mass or less, more preferably 7% by mass or less, for example, based on the whole sealing resin composition. % Or less is particularly preferable. (B) By making content of an amino-group-containing heterocyclic compound below the said upper limit, it can be made appropriate about sclerosis | hardenability as a resin composition for sealing.

((C) thermosetting resin)
The sealing resin composition of this embodiment contains a thermosetting resin in addition to the above-mentioned (A) maleimide compound.
Examples of such thermosetting resins include epoxy compounds (epoxy resins), benzoxazine compounds, phenol resins, urea (urea) resins, melamine resins, unsaturated polyester resins, polyurethane resins, diallyl phthalate resins, silicone resins, cyanates. Examples thereof include resins, polyimide resins, polyamideimide resins, and benzocyclobutene resins.

Among these, in this embodiment, it is preferable to include (C-1) an epoxy compound or (C-2) a benzoxazine compound as the sealing resin composition.
Thereby, the fluidity | liquidity and sclerosis | hardenability as a resin composition can be improved with sufficient balance.

  (C-1) As an epoxy compound, for example, biphenyl type epoxy resin; bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin; stilbene type epoxy resin; phenol novolac type Epoxy resin, novolac type epoxy resin such as cresol novolak type epoxy resin; polyfunctional epoxy resin such as triphenolmethane type epoxy resin and alkyl-modified triphenolmethane type epoxy resin; biphenyl novolac type epoxy resin; phenol aralkyl type having phenylene skeleton Aralkyl type epoxy resins such as epoxy resins and phenol aralkyl type epoxy resins having a biphenylene skeleton; dihydroxynaphthalene type epoxy resins, dihydride Naphthol type epoxy resins such as epoxy resins obtained by glycidyl etherification of dimers of xinaphthalene; Triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; Dicyclopentadiene modified phenol type epoxy resins, etc. One type or two or more types selected from the bridged cyclic hydrocarbon compound-modified phenol type epoxy resin can be included.

(C-1) When an epoxy compound is included, a curing agent can be included separately. Thereby, the sclerosis | hardenability of the resin composition for sealing can be improved further. As a hardening | curing agent, the 1 type (s) or 2 or more types selected from a phenol resin hardening | curing agent, an amine hardening | curing agent, and an acid anhydride hardening | curing agent can be included.
Among these, it is preferable to include at least one of a phenol resin-based curing agent and an amine-based curing agent, and it is particularly preferable to include at least a phenol resin-based curing agent.
In the present specification, since this curing agent is also crosslinked with the (C-1) epoxy compound to form a network, this curing agent itself is treated as a part of the “thermosetting resin”.

The phenol resin-based curing agent is not particularly limited. For example, a novolak resin such as a phenol novolak resin, a cresol novolak resin, or a bisphenol novolac; a polyvinyl phenol; a polyfunctional phenol resin such as a trismethane phenol resin; a terpene-modified phenol resin; Modified phenol resins such as dicyclopentadiene-modified phenol resin; Aralkyl resins such as phenol aralkyl resins having phenylene skeleton and / or biphenylene skeleton, naphthol aralkyl resins having phenylene and / or biphenylene skeleton; bisphenols such as bisphenol A and bisphenol F Compound; One or two or more compounds selected from resol type phenol resins and the like can be contained.
The amine-based curing agent is not particularly limited. For example, aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylylenediamine (MXDA), diaminodiphenylmethane (DDM), and m-phenylenediamine (MPDA). ), Aromatic polyamines such as diaminodiphenylsulfone (DDS), tertiary amine compounds such as benzyldimethylamine (BDMA), 2,4,6-trisdimethylaminomethylphenol (DMP-30), dicyandiamide (DICY), organic One or more selected from other amine compounds including acid dihydralazide and the like can be included.
Examples of the acid anhydride curing agent include alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA), trimellitic anhydride (TMA), and pyromellitic anhydride (PMDA). 1 type, or 2 or more types selected from aromatic acid anhydrides, such as benzophenone tetracarboxylic acid (BTDA), can be included.

(C-2) Examples of the benzoxazine compound include compounds having two or more benzoxazine rings.
For example, at least one of a compound represented by the following formula (6) and a compound represented by the following formula (7) can be contained, and at least a compound represented by the following formula (6) is more preferably contained. Thereby, the high temperature long-term storage characteristic of a sealing material can be improved more effectively. It is also possible to contribute to the improvement of the mechanical properties of the sealing material.

In the above formula (6), R ₃ is a divalent organic group having 1 to 30 carbon atoms, and may contain one or more of an oxygen atom and a nitrogen atom. From the viewpoint of improving the high-temperature storage characteristics of the encapsulant, R ₃ is more preferably an organic group containing an aromatic ring. In the present embodiment, for example, the following compounds can be used as the compound represented by the above formula (6).

In the above formula (7), R ₄ is a divalent organic group having 1 to 30 carbon atoms, and may contain one or more of an oxygen atom, a nitrogen atom, and a sulfur atom. Two R _{5 s} are each independently an aromatic hydrocarbon group having 1 to 12 carbon atoms.

In the present embodiment, the content of (C) thermosetting resin in the sealing resin composition (excluding those corresponding to (A)) is, for example, relative to the entire sealing resin composition. It is preferably 2% by mass or more, more preferably 4% by mass or more, and particularly preferably 6% by mass or more. (C) By making content of a thermosetting resin more than the said lower limit, the fluidity | liquidity and sclerosis | hardenability as a resin composition can be improved with sufficient balance.
In addition, the content of (C) the thermosetting resin (excluding those corresponding to (A)) is preferably 20% by mass or less, for example, with respect to the entire sealing resin composition. More preferably, it is less than or equal to 15% by weight, particularly preferably less than or equal to 15% by weight. (C) By making content of a thermosetting resin below the said upper limit, handling as a resin composition for sealing can be improved.
In addition, regarding content of this (C) thermosetting resin, when using (C-1) an epoxy compound, it can define as the value which also combined the hardening | curing agent corresponding to this epoxy compound.

((D) inorganic filler)
The sealing resin composition of the present embodiment can contain (D) an inorganic filler. Thereby, the rigidity of the sealing material obtained from the resin composition for sealing can be further improved.
This (D) inorganic filler is, for example, one or more selected from titanium oxide, zirconium oxide, silica, calcium carbonate, boron carbide, clay, mica, talc, wollastonite, glass beads, milled carbon, graphite and the like. Is used.
Among these, it is preferable to use silica, and one or more selected from fused spherical silica, fused crushed silica, and crystalline silica can be included. Among these, it is more preferable to contain fused spherical silica from the viewpoint of improving the filling property of the encapsulating resin composition, the high-temperature long-term storage characteristics of the encapsulant, and the like.

The silica preferably has, for example, a SiO ₂ content of 99.8% by mass or more. By using such high-purity silica, it becomes easy to realize a sealing material having good heat resistance and mechanical properties while reducing the amount of ionic impurities such as metal impurities. From the viewpoint of more effectively improving the high-temperature long-term storage characteristics of the sealing material, the content of SiO ₂ in silica is preferably 99.9% by mass or more.

In the present embodiment, the content of the (D) inorganic filler in the sealing resin composition is preferably 60% by mass or more, for example, 65% by mass or more with respect to the entire sealing resin composition. It is more preferable that it is 70 mass% or more. (D) By making content of an inorganic filler more than the said lower limit, the rigidity as a sealing material can be improved effectively.
Further, the content of the (D) inorganic filler is, for example, preferably 85% by mass or less, more preferably 83% by mass or less, and 80% by mass or less, with respect to the entire sealing resin composition. It is particularly preferred that there is. (D) By making content of an inorganic filler below the said upper limit, the reliability of an apparatus etc. can be improved further.

((E) Curing accelerator)
The sealing resin composition of the present embodiment can contain, for example, (E) a curing accelerator. (E) A hardening accelerator should just be what accelerates | stimulates hardening of (A) maleimide compound or (C) thermosetting resin.
In this embodiment, the (E) curing accelerator contains phosphorus atoms such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds. Compounds: Amidines such as 2-phenylimidazole and 2-methylimidazole; amidines and tertiary amines exemplified by 1,8-diazabicyclo [5.4.0] undecene-7, benzyldimethylamine, and the like. 1 type or 2 types or more selected from nitrogen atom containing compounds, such as quaternary salt of these.

In the present embodiment, the content of the (E) curing accelerator in the encapsulating resin composition is preferably 0.01% by mass or more, for example, relative to the entire encapsulating resin composition. The content is more preferably 03% by mass or more, and particularly preferably 0.05% by mass or more. (E) By making content of a hardening accelerator more than the said lower limit, sclerosis | hardenability of a resin composition can be improved effectively.
In addition, the content of (E) the curing accelerator is, for example, preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass or less with respect to the entire sealing resin composition. It is particularly preferred that there is. (E) By making content of a hardening accelerator into the said upper limit or less, handling of the resin composition for sealing can be improved.

((F) Silane coupling agent)
The sealing resin composition of the present embodiment can contain, for example, (F) a silane coupling agent.
Thereby, the further improvement of the adhesiveness of the resin composition for sealing can be aimed at.
The (F) silane coupling agent may be included in the sealing resin composition by, for example, mixing (D) an inorganic filler surface-treated with the (F) silane coupling agent with a multicomponent. it can. On the other hand, (D) the inorganic filler is not subjected to the above-mentioned surface treatment, and (F) the silane coupling agent is added to a mixer or the like together with the respective components, and mixed to obtain (F) the silane coupling agent. You may include in the resin composition for sealing.

(F) As the silane coupling agent, for example, various silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane and methacryl silane can be used.
Examples of these include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane , Vinyltriacetoxysilane, phenylaminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilyl) Propyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ -Chloropropyltrime Hydrolysis of toxisilane, hexamethyldisilane, vinyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine Examples include silane coupling agents such as decomposition products.
These may be used individually by 1 type and may be used in combination of 2 or more type.

In the present embodiment, the content of the (F) silane coupling agent in the sealing resin composition is preferably 0.01% by mass or more with respect to the entire sealing resin composition, for example. 0.03% by mass or more is more preferable, and 0.05% by mass or more is particularly preferable. (F) By making content of a silane coupling agent more than the said lower limit, the fluidity | liquidity and adhesiveness of a resin composition can be improved effectively.
Further, the content of (F) the silane coupling agent is, for example, preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass or less, with respect to the entire sealing resin composition. Is particularly preferred. (F) By making content of a silane coupling agent below the said upper limit, sclerosis | hardenability of the resin composition for sealing can be improved.

(Other ingredients)
In the sealing resin composition of the present embodiment, if necessary, ion scavengers exemplified by inorganic ion exchangers such as hydrotalcites and polyvalent metal acid salts; low stress materials such as silicone rubber Natural oils such as carnauba wax, synthetic waxes, higher fatty acids such as zinc stearate and release agents such as metal salts thereof or paraffin; colorants such as carbon black and bengara; aluminum hydroxide, magnesium hydroxide, zinc borate Flame retardants such as zinc molybdate and phosphazene; various additives such as antioxidants may be appropriately blended. These compounding amounts are arbitrary.

The sealing resin composition of the present embodiment is obtained, for example, by mixing the above-described components by a known means, further melt-kneading with a kneader such as a roll, a kneader, or an extruder, pulverizing after cooling. be able to. Furthermore, those obtained by tableting these into tablets can also be used as the sealing resin composition.
By using such a tablet-molded composition, it becomes easy to seal-mold using a known molding method such as transfer molding, injection molding, and compression molding.

  The encapsulating resin composition of the present embodiment preferably satisfies the following characteristics.

That is, the glass transition temperature of the cured product obtained by curing the sealing resin composition of the present embodiment under the conditions of 175 ° C. and 180 seconds is preferably 250 ° C. or higher, and more preferably 255 ° C. or higher. More preferably, the temperature is 260 ° C. or higher.
By doing in this way, the heat resistance as an apparatus can be improved and reliability can be improved further.
Moreover, the glass transition temperature of the hardened | cured material of this sealing resin composition is although it does not specifically limit, For example, it is 350 degrees C or less.

Further, the encapsulating resin composition of the present embodiment, 175 ° C. on a copper plate, when to obtain a cured product obtained by curing under conditions of 180 seconds, die shear strength DS ₁ and the copper plate and the cured product 5MPa or more and The die shear strength DS ₁ is more preferably 7 MPa or more, and further preferably 8.5 MPa or more.
By setting in this way, the adhesiveness with the metal member etc. which comprise an apparatus is improved, and the reliability of an apparatus can be improved further.
The upper limit value of the die shear strength DS ₁ is not particularly limited, but is, for example, 30 MPa or less.
Incidentally, the die shear strength DS _1, for example can be measured as follows.
That is, using a low pressure transfer molding machine (“AV-600-50-TF” manufactured by Yamashiro Seiki Co., Ltd.), a strip shape of 9 × 29 mm under conditions of a mold temperature of 175 ° C., an injection pressure of 10 MPa, and a curing time of 180 seconds. Ten adhesion strength test pieces of 3.6 mmφ × 3 mm are formed on the test copper lead frame. About this test piece, die-shear intensity | strength is measured at room temperature using an automatic die-shear measuring apparatus (The Nordson Advanced Technology company make, DAGE4000 type | mold).

Moreover, when the hardened | cured material which hardened the resin composition for sealing of this embodiment on the conditions of 175 degreeC and 180 second on a copper plate was further heated at 250 degreeC for 3 hours, a copper plate and hardened | cured material The die shear strength DS ₂ is preferably 4.5 MPa or more, the die shear strength DS ₂ is more preferably 6 MPa or more, and further preferably 7 MPa or more.
By setting in this way, for example, even when an element that generates a large amount of heat is used as a semiconductor device or when a device that is exposed to a higher temperature condition is manufactured, higher reliability can be ensured. .
Upper limit of the die shear strength DS ₂ is not particularly limited, for example, or less 30 MPa.
The die shear strength DS ₂ is obtained by measuring the die shear strength at room temperature for a sample cured at 250 ° C. for 3 hours after molding the adhesion strength test piece in the measurement of the die shear strength DS ₁ described above. be able to.

Moreover, after making the resin composition for sealing of this embodiment into the hardened | cured material hardened on the conditions of 175 degreeC and 180 second on a copper plate, when further heating at 250 degreeC for 3 hours, hardening after the heating It is preferable that the 5% weight reduction temperature of the product is set to a specific value or more.
More specifically, the 5% weight reduction temperature of the cured product after heating is preferably 400 ° C or higher, more preferably 420 ° C or higher, and further preferably 440 ° C or higher.
By satisfying such conditions, even higher reliability can be ensured even when an element that generates a large amount of heat is used in a semiconductor device or when a device that is exposed to higher temperature conditions is manufactured. .

Further, the sealing resin composition of the present embodiment preferably has a curast torque value of 200 kg after starting measurement at 175 ° C. of 80 kgf / cm or more, more preferably 90 kgf / cm or more.
By setting in this way, a resin composition having excellent curability can be realized.

  The above characteristics can be achieved by appropriately adjusting the type and blending amount of each component constituting the sealing resin composition of the present embodiment.

Next, a semiconductor device will be described.
FIG. 1 is a cross-sectional view showing an example of a semiconductor device 100 according to the present embodiment. The semiconductor device 100 according to this embodiment includes a semiconductor element 20 mounted on a substrate 30 and a sealing material 50 that seals the semiconductor element 20. The semiconductor element 20 is a power semiconductor element formed of, for example, SiC, GaN, Ga ₂ O ₃ , or diamond. Moreover, the sealing material 50 is comprised by the hardened | cured material obtained by hardening | curing the resin composition for semiconductor sealing which concerns on this embodiment.

In the semiconductor device 100 according to the present embodiment, the semiconductor element 20 is a power semiconductor element formed of SiC, GaN, Ga ₂ O ₃ , or diamond as described above, and can operate at a high temperature of 200 ° C. or higher. it can. Even in such a long-time use in a high-temperature environment, the sealing material 50 formed using the resin composition for semiconductor encapsulation according to the present embodiment can exhibit sufficient adhesion. For this reason, the reliability of the semiconductor device 100 can be improved. The semiconductor element 20 can be a power semiconductor element having an input power of 1.7 W or more, for example.

In FIG. 1, the case where the board | substrate 30 is a circuit board is illustrated. In this case, as shown in FIG. 1, for example, a plurality of solder balls 60 are formed on the other surface of the substrate 30 opposite to the surface on which the semiconductor element 20 is mounted. The semiconductor element 20 is mounted on, for example, the substrate 30 and is electrically connected to the substrate 30 through the wire 40. On the other hand, the semiconductor element 20 may be flip-chip mounted on the substrate 30.
Here, the wire 40 is made of, for example, copper.

  For example, the sealing material 50 seals the semiconductor element 20 so as to cover the other surface of the semiconductor element 20 opposite to the one surface facing the substrate 30. In the example shown in FIG. 1, a sealing material 50 is formed so as to cover the other surface and the side surface of the semiconductor element 20. The sealing material 50 can be formed, for example, by sealing and molding a semiconductor sealing resin composition using a known method such as a transfer molding method or a compression molding method.

FIG. 2 is a cross-sectional view showing an example of the semiconductor device 100 according to the present embodiment, and shows an example different from FIG. A semiconductor device 100 shown in FIG. 2 uses a lead frame as the substrate 30. In this case, the semiconductor element 20 is mounted on, for example, the die pad 32 of the substrate 30 and electrically connected to the outer lead 34 via the wire 40. The semiconductor element 20 is a power semiconductor element formed of SiC, GaN, Ga ₂ O ₃ , or diamond, as in the example shown in FIG. Moreover, the sealing material 50 is formed using the resin composition for semiconductor sealing which concerns on this embodiment similarly to the example shown in FIG.

Next, the manufacturing method of the vehicle-mounted electronic control unit 10 is demonstrated based on FIG.
The on-vehicle electronic control unit 10 according to the present embodiment is manufactured as follows, for example. First, a plurality of electronic components 16 are mounted on at least one surface of the wiring board 12. Next, the plurality of electronic components 16 are encapsulated using an encapsulating resin composition. As the resin composition for sealing, those exemplified above can be used.
Hereinafter, the manufacturing method of the vehicle-mounted electronic control unit 10 will be described in detail.

  First, a plurality of electronic components 16 are mounted on at least one surface of the wiring board 12. In the present embodiment, for example, a plurality of electronic components 16 can be mounted on one surface of the wiring board 12 and another surface opposite to the one surface. Thereby, the vehicle-mounted electronic control unit 10 in which the electronic components 16 are mounted on both surfaces of the wiring board 12 as shown in FIG. 3 can be formed. On the other hand, the electronic component 16 may be mounted on only one surface of the wiring board 12 and the electronic component 16 may not be mounted on the other surface. In addition, as the wiring board 12 and the electronic component 16, what is normally used in this technical field is applicable.

  As shown in FIG. 3, the wiring board 12 has, for example, a flat plate shape. In the present embodiment, for example, an organic substrate formed of an organic material such as polyimide can be used as the wiring substrate 12. The wiring board 12 may have a through hole 120 that penetrates the wiring board 12 and connects one surface to the other surface, for example. In this case, the wiring provided on one surface of the wiring board 12 and the wiring provided on the other surface are electrically connected via the conductor pattern provided in the through hole 120.

  Next, the plurality of electronic components 16 are encapsulated using an encapsulating resin composition. Thereby, the sealing resin 14 for sealing the electronic component 16 is formed. In this embodiment, for example, the sealing resin composition is molded so as to seal the wiring substrate 12 together with the electronic component 16. The vehicle-mounted electronic control unit 10 illustrated in FIG. 3 is obtained, for example, by sealing and molding one surface and the other surface of the wiring board 12 and the electronic component 16 mounted on the wiring board 12 with a sealing resin composition. be able to. In the present embodiment, a part or all of the wiring board 12 is sealed together with the plurality of electronic components 16 using the sealing resin composition. The in-vehicle electronic control unit 10 illustrated in FIG. 3 is sealed so that the entire other part is sealed without sealing the connection terminal 18 of the wiring board 12 so that the connection terminal 18 is exposed, for example. It is obtained by molding the resin composition for use.

  It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  Next, examples of the present invention will be described.

(Preparation of resin composition for sealing)
For each example and each comparative example, a sealing resin composition was prepared as follows.
First, the inorganic filler 1 was subjected to a surface treatment with a silane coupling agent 1 having a blending amount shown in Table 1.
Then, according to the formulation shown in Table 1, each component was mixed with a mixer. Subsequently, after roll-kneading the obtained mixture, it cooled and grind | pulverized and the resin composition for sealing which is a granular material was obtained. Details of each component in Table 1 are as follows. Moreover, the mixture ratio of each component shown in Table 1 has shown the mixture ratio (mass%) with respect to the whole resin composition.

(A) Maleimide Compound Maleimide Compound 1: Compound having two or more maleimide groups represented by the following formula (8) (“BMI-2300” manufactured by Daiwa Kasei Kogyo Co., Ltd.)

(B) Heterocyclic Compound Heterocyclic Compound 1: 3-amino-1,2,4-triazole (“A0432” manufactured by Tokyo Chemical Industry Co., Ltd.)
Heterocyclic compound 2: 2,4-diamino-1,3,5-triazine (“D2227” manufactured by Tokyo Chemical Industry Co., Ltd.)
Heterocyclic compound 3: 2-aminobenzimidazole (“A0850” manufactured by Tokyo Chemical Industry Co., Ltd.)

(B) 'heterocyclic compound heterocyclic compound 4: 3-mercapto-1,2,4-triazole (“M0814” manufactured by Tokyo Chemical Industry Co., Ltd.)
Heterocyclic compound 5: 4-amino-1,2,4-triazole (“A1037” manufactured by Tokyo Chemical Industry Co., Ltd.)
Heterocyclic compound 6: 3-nitro-1,2,4-triazole (“N0477” manufactured by Tokyo Chemical Industry Co., Ltd.)

(C) Thermosetting resin Thermosetting resin 1: Biphenyl novolac type epoxy resin (“NC-3000L” manufactured by Nippon Kayaku Co., Ltd.)
Thermosetting resin 2: Trismethanephenol type resin (“MEH-7500” manufactured by Meiwa Kasei Co., Ltd.)
Thermosetting resin 3: benzoxazine compound represented by the following formula (9) (“Pd-BO” manufactured by Shikoku Kasei Co., Ltd.)

(D) Inorganic filler Inorganic filler 1: fused spherical silica (average particle size: 15 μm)

(E) Curing accelerator Curing accelerator 1: 2-phenylimidazole (“2PZ-PW” manufactured by Shikoku Kasei Co., Ltd.)
Curing accelerator 2: 2-methylimidazole (“2MZ-H” manufactured by Shikoku Kasei Co., Ltd.)

(F) Silane coupling agent Silane coupling agent 1: Phenylaminopropyltrimethoxysilane ("CF-4083" manufactured by Toray Dow Corning Co., Ltd.)

Carbon black 1: Carbon black # 5 manufactured by Mitsubishi Chemical Corporation

  The obtained sealing resin composition was evaluated based on the following items.

(Die shear strength 1)
Using a low-pressure transfer molding machine (“AV-600-50-TF” manufactured by Yamashiro Seiki Co., Ltd.), a strip test of 9 × 29 mm under conditions of a mold temperature of 175 ° C., an injection pressure of 10 MPa, and a curing time of 180 seconds. Ten adhesion strength test pieces of 3.6 mmφ × 3 mm were molded per level on a copper lead frame for use. Subsequently, the die shear strength between the test piece and the frame was measured at room temperature using an automatic die shear measuring device (DAGE 4000 type, manufactured by Nordson Advanced Technology). Table 1 shows the average die shear strength of 10 test pieces.

(Die shear strength 2)
Using a low-pressure transfer molding machine (“AV-600-50-TF” manufactured by Yamashiro Seiki Co., Ltd.), a strip test of 9 × 29 mm under conditions of a mold temperature of 175 ° C., an injection pressure of 10 MPa, and a curing time of 180 seconds. Ten adhesion strength test pieces of 3.6 mmφ × 3 mm were molded per level on a copper lead frame for use. After curing at 250 ° C. for 3 hours, the shear strength between the test piece and the frame was measured at room temperature at room temperature using an automatic die shear measuring device (manufactured by Nordson Advanced Technology, DAGE 4000 type). Table 1 shows the average die shear strength of 10 test pieces.

(Curast torque)
Using a curast meter (Orientec Co., Ltd., JSR curast meter IVPS type), the mold temperature was 175 ° C. and the torque 200 seconds after the start of heating was determined. Table 1 shows this value with the unit kgf / cm.

(Glass-transition temperature)
About each Example and each comparative example, the glass transition temperature of the hardened | cured material of the obtained resin composition for sealing was measured as follows.
About the hardened | cured material used by the test of the above-mentioned (die shear strength 1), using a thermomechanical analyzer (the Seiko Electronics Co., Ltd. make, TMA100), measurement temperature range 0 degreeC-320 degreeC, temperature rising rate 5 degreeC / The glass transition temperature was obtained by measuring under the condition of minutes.
The unit of glass transition temperature in Table 1 is ° C.

(5% weight loss temperature)
About the hardened | cured material used by the test of the above-mentioned (die shear strength 2), the 5% weight reduction | decrease temperature in air | atmosphere was measured using the thermobalance apparatus (the Bruker AXS company make, "TG-DTA2000").

(Temperature cycle test)
Using a low-pressure transfer molding machine (“MSL-06M” manufactured by Apic Yamada), the mold temperature was 175 ° C., the injection pressure was 10 MPa, the curing time was 180 seconds, and TO-220 (package size 114 mm × 30 mm, thickness 1.3 mm, chip Is mounted, the lead frame is made of Cu), and cured at 250 ° C. for 3 hours to produce a test semiconductor device. The sealed test semiconductor device was repeated 3 cycles at −40 ° C. to 250 ° C., and the presence or absence of package cracks or peeling between members was determined (number of defects / number of samples).

  The results are summarized in Table 1 below.

As shown in Table 1, the encapsulating resin composition of each example using a heterocyclic compound having a specific structure gave good results in a temperature cycle test when applied to a semiconductor device.
On the other hand, Comparative Examples 1 and 3 having no amino group in the molecule as the heterocyclic compound, Comparative Example 2 using a heterocyclic compound in which the amino group is not bonded to a carbon atom on the heterocyclic ring, In Comparative Example 4 in which a heterocyclic compound having an amino group in the molecule was not used, the results of the temperature cycle test were inferior compared to the Examples.
From the above, it can be said that the reliability of a device to which this is applied can be improved by obtaining a sealing resin composition using a heterocyclic compound having a specific structure.

DESCRIPTION OF SYMBOLS 10 In-vehicle electronic control unit 12 Wiring board 14 Sealing resin 16 Electronic component 18 Connection terminal 20 Semiconductor element 30 Substrate 32 Die pad 34 Outer lead 40 Wire 50 Sealing material 60 Solder ball 100 Semiconductor device 120 Through hole

Claims (10)

A sealing resin composition comprising the following components (A), (B) and (C).
(A) Maleimide compound (B) Amino group-containing heterocyclic compound represented by general formula (1) (C) Thermosetting resin (however, excluding those corresponding to component (A))

(In Formula (1), A is a heterocyclic ring in which one or more of the atoms constituting the ring is a nitrogen atom and has aromaticity as a whole. B is bonded to the carbon atom constituting the heterocyclic ring. M is an integer of 1 to 3. Ra is a hydrogen atom, an organic group having 1 to 12 carbon atoms, a hydroxyl group, an amino group, or a carboxyl group, and n is 0. (It is an integer above, and m + n is the total number of groups that can be bonded to A.) The sealing resin composition according to claim 1,
B in the formula (1) is a sealing resin composition representing a single bond. The sealing resin composition according to claim 1 or 2,
The amino group-containing heterocyclic compound represented by (B) the general formula (1) is an amino group-containing triazole compound represented by the following general formula (2), an amino represented by the following general formula (3). Sealing resin selected from the group consisting of a group-containing triazine compound, an amino group-containing imidazole compound represented by the following general formula (4), and an amino group-containing benzimidazole compound represented by the following general formula (5) Composition.

(In formula (2), Ra has the same meaning as that shown in formula (1).)

(In formula (3), Ra has the same meaning as that shown in formula (1).)

(In formula (4), Ra has the same meaning as that shown in formula (1). Rb is a hydrogen atom or an organic group having 1 to 12 carbon atoms.)

(In Formula (5), Rc is a hydrogen atom or an organic group having 1 to 12 carbon atoms.) A sealing resin composition according to any one of claims 1 to 3,
The sealing resin composition, wherein the maleimide compound (A) is a maleimide compound represented by the following formula (10).

(In formula (10), n ₁ is an integer of 0 or more and 10 or less, X ₁ is each independently an alkylene group having 1 to 10 carbon atoms, a group represented by the following formula (10a), a formula “—SO A group represented by “ _2- ”, a group represented by “—CO—”, an oxygen atom or a single bond, each R ₁ is independently a hydrocarbon group having 1 to 6 carbon atoms, and a is each Independently an integer of 0 or more and 4 or less, and b is an integer of 0 or more and 3 or less independently.)

(In formula (10a), Y is a hydrocarbon group having 6 to 30 carbon atoms having an aromatic ring, and n ₂ is an integer of 0 or more.) A sealing resin composition according to any one of claims 1 to 4,
The (C) thermosetting resin is a sealing resin composition containing (C-1) an epoxy compound or (C-2) a benzoxazine compound. A sealing resin composition according to any one of claims 1 to 5,
Furthermore, (D) the resin composition for sealing containing an inorganic filler. A sealing resin composition according to any one of claims 1 to 6,
The resin composition for sealing whose glass transition temperature of the hardened | cured material which hardened the said resin composition for sealing on 175 degreeC and 180 second conditions is 250 degreeC or more and 350 degrees C or less. A sealing resin composition according to any one of claims 1 to 7,
When a cured product obtained by curing the sealing resin composition on a copper plate at 175 ° C. for 180 seconds is obtained, the die shear strength DS ₁ between the copper plate and the cured product is 5 MPa or more. Resin composition for stopping. A semiconductor element;
A cured product of the sealing resin composition according to any one of claims 1 to 8,
A semiconductor device comprising: A wiring board;
A plurality of electronic components mounted on at least one surface of the wiring board;
A sealing resin that is formed by curing the sealing resin composition according to any one of claims 1 to 8, and that seals the electronic component;
An in-vehicle electronic control unit.

Images