JP2019116532A - Composition for sealing molding material and electronic component device - Google Patents

Abstract

To provide a composition for a sealing molding material capable of giving a cured product having a high glass transition temperature (Tg), high thermal decomposition resistance, excellent moldability, high withstand voltage, good adhesion to a semiconductor insert component, and high reliability, and to provide an electronic component device using the composition for a sealing molding material.SOLUTION: The composition for a sealing molding material contains (A) a maleimide resin having a specific structure, (B) a nadimide resin having a specific skeleton, (C) a phenolic curing agent, (D) an epoxy resin, (E) a curing accelerator, and (F) a filler containing (F-1) a hollow-structured filler. The component (C) and the component (D) each contain a triphenylmethane skeleton and/or a naphthalene skeleton. The component (E) contains (E-1) a phosphorus-based curing accelerator, (E-2) an imidazole-based curing accelerator, and (E-3) an acid-based curing accelerator.SELECTED DRAWING: None

Description

  The present invention relates to a composition for a sealing molding material and an electronic component device.

  Conventionally, epoxy resin molding materials are widely used in the field of electronic component sealing such as transistors and ICs. This is because the epoxy resin is excellent in the balance of the electrical properties, moisture resistance, mechanical properties, adhesion to the insert part, and the like.

In recent years, momentum of energy saving has been increasing worldwide on the background of concern about future depletion of resource energy and so-called global warming problem etc., control and conversion of electric power, and it is said to be "key device of energy saving technology" Power devices (power semiconductors) to be used are attracting attention.
Power conversion efficiency is a very important item to determine its performance for power semiconductors, but now, compound semiconductors such as silicon carbide (SiC) and gallium nitride (GaN) that have higher conversion efficiency than conventional Si devices Research and development and distribution in the market are booming.

  As a major feature of the power semiconductor, in particular, the SiC device has higher withstand voltage characteristics than the Si device, so that application of this enables realization of a power semiconductor module having a higher withstand voltage. Accordingly, high withstand voltage characteristics such as tracking resistance and high breakdown voltage are also required for peripheral members other than the power semiconductor element.

On the other hand, another major feature is that high temperature operation is possible compared to the conventional Si device. Having high withstand voltage characteristics as described above means that the heat generation of the element itself is also greater than before, and along with enabling high temperature operation, the peripheral members are required to have more heat resistance than before. become.
There is also an operation report at 300 ° C. or higher for the SiC element, and the molding material for sealing is required to have high heat decomposition resistance as well as high glass transition temperature.

  An epoxy resin, a phenol resin, a compound having a maleimide group, and a phenol compound having an alkenyl group are essential components as a technique for imparting a high glass transition temperature to a sealing molding material and providing reliability at high temperature There is a report of epoxy resin composition for sealing (for example, patent document 1), resin composition for sealing (for example, patent document 2) etc. which compounded a maleimide compound, a nadiimide compound, an amine compound, and a catalyst in a specific ratio. .

JP, 2006-299246, A JP, 2015-147850, A

  In order to ensure high temperature reliability, high adhesion to the semiconductor insert part is required together with high glass transition temperature (Tg), but in general, it is often difficult to achieve both of these, and There are also many problems such as peeling of It is also difficult to achieve compatibility with the moldability of the molding material related to the productivity of semiconductor parts after securing sufficient adhesion to the semiconductor insert parts, and these problems are sufficiently solved by the prior art. It is hard to say that it is being done. In Patent Document 2, a nadiimide compound is added to ensure adhesion, but since an amine compound is used as a curing agent, it is insufficient in electrical characteristics to seal a SiC device or the like to which a high voltage is applied. It is concerned that it is.

  The present invention has been made in view of such circumstances, and has high glass transition temperature (Tg), high thermal decomposition resistance, excellent moldability, high voltage resistance, and semiconductor insert parts It is an object of the present invention to provide a composition for a sealing molding material capable of obtaining a cured product having excellent adhesion and high reliability, and an electronic component device using the composition for a sealing molding material.

As a result of intensive studies to solve the above problems, the present inventors have found that a maleimide resin having a specific structure, a nadiimide resin having a specific skeleton, a phenolic curing agent having a specific skeleton, and a specific skeleton It has been found that a composition for a sealing molding material containing an epoxy resin having the following, a specific curing accelerator, and a filler containing a hollow structural filler solves the above-mentioned problems.
The present invention has been completed based on such findings.

That is, the present invention provides the following [1] to [9].
[1] (A) Maleimide resin represented by the following general formula (I), (B) allyl group-containing nadiimide resin represented by the following general formula (II), (C) phenolic curing agent, (D) epoxy A filler containing a resin, (E) a curing accelerator, and (F) (F-1) hollow structural filler, wherein the (C) component and the (D) component respectively have a triphenylmethane skeleton and / or A sealing molding material comprising a naphthalene skeleton, wherein the component (E) comprises (E-1) a phosphorus-based curing accelerator, (E-2) an imidazole-based curing accelerator, and (E-3) an acid-based curing accelerator. Composition.

(Wherein R ¹ is each independently a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may be substituted with a halogen atom. When a plurality of R ¹ are present, the plurality of R ¹ may be substituted. P may be the same as or different from each other, p is independently an integer of 0 to 4, q is an integer of 0 to 3, and z is an integer of 0 to 10.)

(Wherein, R ² is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a divalent aromatic group having 6 to 18 carbon atoms, a general formula “-A ¹ -C ₆ H ₄ - ^(a _{1) m} - ^(provided that, m is an integer of 0 or 1, each ^{a 1} is independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms. Or a group represented by the general formula “—C ₆ H ₄ —A ² —C ₆ H ₄ — (wherein A ² is“ —CH ₂ — ”,“ —C (CH ₃ ) ₂ — ”, A group represented by “—CO—”, “—O—”, “—S—” or “—SO ₂ —”))

[2] The composition for a sealing molding material as described in the above [1], wherein the average particle diameter of the (F-1) hollow structure filler is 3 to 100 μm.
[3] The (F-1) hollow structural filler is at least one selected from the group consisting of silica, alumina, and a silica-alumina compound, and the content of the (F-1) hollow structural filler is the above (F) The composition for a sealing molding material as described in said [1] or [2] which is 1-50 mass% with respect to the filler whole quantity.
[4] The (F-1) hollow structural filler is made of an organic compound, and the content of the (F-1) hollow structural filler is 0.5 to 10% by mass based on the total amount of the (F) filler. The composition for a sealing molding material as described in said [1] or [2] which is it.
[5] The (F-1) hollow structural filler is a silsesquioxane compound, and the content of the (F-1) hollow structural filler is 0.5 to the total amount of the (F) filler. The composition for a sealing molding material as described in said [1] or [2] which is 10 mass%.
[6] The composition for a sealing molding material according to any one of the above [1] to [5], wherein the content of the component (B) is 30 to 250 parts by mass with respect to 100 parts by mass of the component (A) object.
[7] Any of the above-mentioned [1] to [6], wherein the component (E-3) is at least one selected from the group consisting of p-toluenesulfonic acid, its amine salt and boron trifluoride amine complex A composition for a sealing molding material according to any one of the above.
[8] The seal according to any one of the above [1] to [7], wherein the content of the component (E-3) is 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (B) Composition for molding material.
[9] An electronic component device comprising an element sealed by the composition for a sealing molding material according to any one of the above [1] to [8].

  According to the present invention, it has a high glass transition temperature (Tg), high thermal decomposition resistance and excellent formability, and also has high voltage resistance, good adhesion with semiconductor insert parts, and highly reliable curing. It is possible to provide a composition for a sealing molding material from which a product can be obtained, and an electronic component device using the composition for a sealing molding material.

Hereinafter, the present invention will be described in detail.
(Composition for sealing molding material)
First, each component of the composition for a sealing molding material of the present invention will be described.
[(A) maleimide resin]
The maleimide resin of the component (A) used in the present invention is a compound having two or more maleimide groups in one molecule, which is represented by the following general formula (I), and is reacted three-dimensionally by reacting the maleimide groups by heating. It is a resin that forms a network structure and hardens. In addition, the maleimide resin gives a cured product a high glass transition temperature (Tg) by a crosslinking reaction to improve the heat resistance and the heat decomposition resistance.

In the above general formula (I), R ¹ is each independently a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may be substituted by a halogen atom. p is each independently an integer of 0 to 4, and q is an integer of 0 to 3.
As said C1-C10 hydrocarbon group, alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, for example; Chloromethyl group, 3-chloropropyl group etc. Substituted alkyl groups; alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group; aryl groups such as phenyl group, tolyl group and xylyl group; monovalent groups such as aralkyl group such as benzyl group and phenethyl group The hydrocarbon group of
In addition, when there are a plurality of R ^{1 's} , the plurality of R ¹ ' s may be the same as or different from each other.
z is an integer of 0 to 10, preferably an integer of 0 to 4;

  In the maleimide resin represented by the above general formula (I), an addition reaction occurs in the presence of a phenol-based curing agent of the component (C) described later and a phosphorus-based curing accelerator of the component (E-1) to seal It gives high heat resistance to the cured product of the composition for molding material.

Specific examples of the maleimide resin represented by the above general formula (I) include, for example, N, N ′-(4,4′-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) And methane), polyphenylmethane maleimide and the like.
Moreover, BMI-2300 (made by Daiwa Kasei Kogyo Co., Ltd.) etc. which have z = 0-2 as a main component and the said maleimide resin can be obtained as a commercial item, for example.

The maleimide resin of the component (A) may be used after being preliminarily mixed with a part or the whole of the phenolic curing agent of the component (C) to be described later. The method of premixing is not particularly limited, and known mixing methods can be used. For example, after melting the component (C) at 50 to 180 ° C. using an apparatus capable of stirring, the maleimide resin of the component (A) is gradually added and mixed while stirring, and all of the components are melted and then 10 The method etc. of stirring about 60 minutes and setting it as premixed resin are mentioned.
In the pre-mixing, two or more kinds of the phenolic curing agent of the component (C) may be used.

  Apart from the maleimide resin of the component (A), that is, the maleimide resin represented by the above general formula (I), other than the maleimide resin represented by the above general formula (I) within the range not to impair the effects of the present invention The maleimide resin of As a maleimide resin which can be used in combination, for example, m-phenylenebismaleimide, 2,2-bis [4- (4-maleimidophenoxin) phenyl] propane, 1,6-bismaleimide- (2,2,4-trimethyl) Although hexane etc. can be mentioned, you may use together conventionally well-known maleimide resin other than these. In addition, when mix | blending maleimide resin other than maleimide resin represented with the said general formula (I), it is preferable that the compounding quantity sets it as 30 mass parts or less with respect to 100 mass parts of maleimide resins of (A) component. The amount is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.

[(B) Allyl group-containing nadiimide resin]
The allyl group-containing nadiimide resin (hereinafter simply referred to as nadiimide resin) of the component (B) used in the present invention is a compound represented by the following general formula (II), which contains two allyl groups in one molecule, and is heated A three-dimensional network structure is formed by the reaction of allyl groups with each other or by the reaction of allyl groups with a maleimide group, and the resin is cured. The nadiimide resin of component (B) can be expected to have the effect of improving the adhesion derived from its resin skeleton. Further, the nadiimide resin of the component (B), like the maleimide resin of the component (A), imparts a high glass transition temperature (Tg) to the cured product by the crosslinking reaction, and improves the heat resistance and the heat decomposition resistance.

In the above general formula (II), R ² is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a divalent aromatic group having 6 to 18 carbon atoms, a general formula “−A ^{1 _{-C 6 H 4 - (a 1}} ) m - ( provided that, m is an integer of 0 or 1, each ^{a 1} is independently an alkylene group having 1 to 10 carbon atoms, cycloalkyl of 4-8 carbon atoms . an alkylene group) group represented by "or the formula" _{^{-C 6 H 4 -A 2 -C 6}} H 4 - ( wherein ^{a 2} is "-CH ₂ -", "- C (CH ₃ ) ₂ - "," - CO -, "" - O - "," - S- "or" -SO ₂ -. a group represented by ")" is a group represented by.

As a specific example of the allyl group containing nadiimide resin represented by said general formula (II), resin shown to following formula (II-1) and (II-2) is mentioned, for example. Among them, the resin represented by formula (II-1) is preferable from the viewpoint of the tracking resistance and the adhesion. This is because, in the resin represented by the formula (II-1), since the distance between the allyl groups of the resin is sufficient, the steric hindrance is small, the reaction proceeds sufficiently, and a three-dimensional network structure is densely formed; It is because the cohesive force of the resin skeleton is increased.
One of these resins may be used alone, or two or more of these resins may be used in combination.

  The content of the component (B) is preferably 30 to 250 parts by mass, preferably 50 to 200 parts by mass, with respect to 100 parts by mass of the component (A), from the viewpoint of the balance of curing shrinkage and adhesion. More preferable.

  The allyl group-containing nadiimide resin represented by the above general formula (II) is commercially available as BANI-M (manufactured by Maruzen Petrochemicals Co., Ltd.), BANI-X (manufactured by Maruzen Petrochemicals Co., Ltd.), etc. as a commercial product. Can.

[(C) Phenolic curing agent]
The composition for a sealing molding material of the present invention is a phenolic curing agent containing a triphenylmethane skeleton represented by the following general formula (III) as the component (C) and a naphthalene represented by the following general formula (IV) It contains at least one selected from phenolic curing agents containing a skeleton. The phenolic curing agent of component (C) has at least two hydroxyl groups in one molecule.
The component (C) undergoes an addition reaction with the maleimide resin which is the component (A) in the presence of a phosphorus-based curing accelerator which is the component (E-1) described later, and the self-polymerization reaction of the component (A) It indirectly suppresses and has the effect of relieving peeling stress. Moreover, it has an effect | action which provides adhesiveness and a moldability with heat resistance to the composition for sealing molding materials. Further, the addition reaction is carried out in the presence of an epoxy resin which is the component (D) described later and a phosphorus-based curing accelerator which is the component (E-1) or an imidazole-based curing accelerator which is the component (E-2).

(Wherein x is 0 to 10)

(In the formula, y1 is 0 to 10.)

  In the above general formula (III), x is 0 to 10, preferably 1 to 4. Moreover, in said general formula (IV), y1 is 0-10, Preferably it is 0-3.

  The phenolic resin represented by the above general formula (III) is MEH-7500 (manufactured by Meiwa Kasei Co., Ltd.), and the phenol resin represented by the above general formula (IV) is SN-485 (Nippon Steel Sumikin Chemical Co., Ltd. ) Can be obtained as commercial products.

  As the component (C), the compounds represented by the general formulas (III) and (IV) may be used alone, or two or more of these may be used in combination.

  In the present invention, the content of the component (C) is preferably 20 to 250 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of the balance of heat resistance, adhesion and moldability. The amount is more preferably 200 parts by mass, and further preferably 40 to 150 parts by mass. When using 2 or more types of (C) components together, it is preferable to make the total amount into the said range.

  In the present invention, phenolic curing agents other than the conventionally known component (C) can be used in combination as long as the effects of the present invention are not impaired. Moreover, you may use together an acid anhydride and an amine type hardening | curing agent in the range which does not prevent the effect of this invention.

[(D) epoxy resin]
The composition for a sealing molding material of the present invention comprises, as the component (D), an epoxy resin containing a triphenylmethane skeleton represented by the following general formula (V), and a naphthalene skeleton represented by the following general formula (VI) It contains at least 1 sort (s) selected from the epoxy resin containing, and the epoxy resin containing the naphthalene structure represented by the following general formula (VII). The epoxy resin of the component (D) has two or more epoxy groups in one molecule, and by starting the reaction from a relatively low temperature, the formability is improved, and a hydroxyl group is generated during the addition reaction, and the adhesion is achieved. Have the function of In addition, the epoxy resin of the component (D) has a function of performing crosslinking reaction with the phenol-based curing agent of the component (C) to improve moldability and adhesion, as well as the self-polymerization reaction of the maleimide resin of the component (A). It also has the functions of promoting, enhancing the curability of the composition for sealing and molding materials, and giving good formability.
The epoxy resin of (D) component may use 1 type and may use it in combination of 2 or more type.

(In the formula, n1 is 0 to 10.)

(In the formula, n2 is 0 to 10)

  In the above general formula (V), n1 is 0 to 10, preferably 0 to 3. Moreover, in the said General formula (VI), n2 is 0-10, Preferably it is 0-3.

  The epoxy resin represented by the above general formula (V) is an epoxy resin represented by the above general formula (VI) as EPPN-502H (manufactured by Nippon Kayaku Co., Ltd.), and the epoxy resin represented by the above general formula (VI) is The epoxy resin represented by the said General formula (VII) can be obtained as HP-4710 (made by DIC Corporation) as a commercial item as a stock company make).

  The softening point of the epoxy resin represented by the general formulas (V) to (VII) is preferably 55 to 100 ° C., more preferably from the viewpoint of improving the productivity and the flowability of the composition for a sealing molding material. 60 to 90 ° C., more preferably 65 to 85 ° C.

  In the composition for a sealing molding material of the present invention, the content of the component (D) is to the hydroxyl group of the phenolic curing agent of the component (C) in order to balance the glass transition point, adhesion and moldability. It is preferable that ratio (equivalent ratio) of the epoxy group which the epoxy resin of (D) component has is 0.2-1.5, and it is more preferable that it is 0.3-1.2. If the equivalent ratio is 0.2 or more, the moldability is good, and if it is 1.5 or less, the heat resistance, the heat decomposition resistance, the flame retardance and the like become good. In addition, when using 2 or more types of (D) component, it is preferable to make the total amount into the said range.

  Further, the blending amount of the epoxy resin of the component (D) is preferably 30 to 200 parts by mass, more preferably 40 to 150 parts by mass, still more preferably 50 to 100 parts by mass with respect to 100 parts by mass of the maleimide resin of the component (A). It is a mass part. Adhesiveness becomes favorable by setting it as 30 mass parts or more, and heat resistance becomes favorable by setting it as 200 mass parts or less.

In addition to the resins represented by the general formulas (V) to (VII), the epoxy resin of the component (D) may be used in combination with an epoxy resin used as a semiconductor element sealing material as long as the effects of the present invention are not impaired. Can. As an epoxy resin which can be used together, although an o-cresol novolak type epoxy resin, a biphenyl type epoxy resin, a dicyclopentadiene type epoxy resin etc. can be mentioned, for example, You may use epoxy resins other than these together.
In addition, when using together epoxy resins other than the said (D) component, it is preferable to set it as 30 mass parts or less with respect to 100 mass parts of epoxy resins of (D) component, and to make it 20 mass parts or less. Is more preferable, and 10 parts by mass or less is more preferable.

[(E) curing accelerator]
In the present invention, (E-1) phosphorus-based curing accelerator, (E-2) imidazole-based curing accelerator, and (E-3) acid-based curing accelerator are used in combination as the curing accelerator for component (E). is necessary.

(E-1) Phosphorus-Based Curing Accelerator The phosphorus-based curing accelerator of component (E-1) used in the present invention mainly comprises the crosslinking reaction of component (A) with component (C), and component (C) with It is used to accelerate the crosslinking reaction with the component (D). The component (E-1) indirectly suppresses the self-polymerization reaction of the components (A) by promoting these reactions, and has the function of suppressing the generation of the peeling stress from the semiconductor insert part.

  Examples of the phosphorus-based curing accelerator as the component (E-1) include triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, and tris (4). Tertiary phosphines such as 4-butylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tributylphosphine, methyl diphenyl phosphine, etc., tetraphenylphosphonium tetraphenylborate Examples thereof include tetra-substituted phosphonium tetra-substituted borates such as tetrabutyl phosphonium tetra-butyl borate and the like, and these can be appropriately used singly or in combination of two or more. It is also possible to use conventionally well-known phosphorus-type hardening accelerators other than these individually or in combination of 2 or more types.

  The content of the phosphorus-based curing accelerator as the component (E-1) is preferably 0.1 to 6 parts per 100 parts by mass of the component (A) from the viewpoint of the balance between the curability and the adhesion to the semiconductor insert part. It is a mass part, More preferably, it is 0.3-5 mass parts, More preferably, it is 0.5-3 mass parts. When using 2 or more types of phosphorus-based hardening accelerators together, it is preferable that the total amount becomes in the said range.

(E-2) Imidazole-based curing accelerator The imidazole-based curing accelerator of the component (E-2) used in the present invention mainly promotes the self-polymerization reaction of the component (A) to form a composition for a sealing molding material It is used to secure the formability of The function of the component (E-2) is promoted by the presence of the epoxy resin of the component (D), and the composition for a sealing molding material of the present invention can be provided with good curability and moldability. In addition, the moldability and adhesion are improved by promoting the addition reaction of the phenolic curing agent of component (C) and the epoxy resin of component (D) and the self-polymerization reaction of the epoxy resin of component (D). It works.
In the present invention, the term "imidazole-based curing accelerator" has the same meaning as the imidazole compound containing a nitrogen atom at the 1,3 position on the 5-membered ring.

  Examples of the imidazole-based curing accelerator as the component (E-2) include 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2- Phenyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2-phenyl- 4-methyl-5-hydroxymethylimidazole and the like can be exemplified, and these may be used alone or in combination of two or more. Moreover, you may apply the conventionally well-known imidazole type hardening accelerator other than the above.

  The content of the imidazole-based curing accelerator as the component (E-2) is preferably 0.1 to 4 with respect to 100 parts by mass of the component (A) from the viewpoint of the balance between the curability and the adhesion to the semiconductor insert part. It is a mass part, More preferably, it is 0.3-3 mass parts, More preferably, it is 0.5-2 mass parts. When using 2 or more types of imidazole series hardening accelerators together, it is preferable that the total amount becomes in the said range.

(E-3) Acid-based curing accelerator The acid-based curing accelerator of the component (E-3) used in the present invention mainly promotes the reactivity of the allyl group-containing nadiimide resin of the component (B), the component (A) And the allyl group-containing nadiimide resin of component (B) to promote the curing property of the resin and to start the reaction from a relatively low temperature. In addition, by promoting the reaction of the phenolic curing agent of the component (C) and the epoxy resin of the component (D), it has the function of improving moldability and adhesion. Although maleimide resins generally have high heat resistance, they require high temperatures for the curing reaction. The reaction can be initiated at a relatively low temperature by reacting the maleimide resin of component (A), the allyl group-containing nadiimide resin of component (B), and the acid curing accelerator of component (E-3), and molding Improves the quality.

  Examples of the acid-based curing accelerator as the component (E-3) include p-toluenesulfonic acid, trifluoromethanesulfonic acid, or an amine salt thereof, pyridine sulfate, phosphoric acid, boron trifluoride ether complex, trifluorene An example is borohydride amine complex and the like. Among these, in the present invention, it is preferable to use at least one selected from the group consisting of p-toluenesulfonic acid, its amine salt and boron trifluoride amine complex from the viewpoint of reactivity and resin physical properties. Further, p-toluenesulfonic acid is more preferable from the viewpoint of adhesion, and boron trifluoride amine complex is more preferable from the viewpoint of curability. These may be used alone or in combination of two or more.

  The content of the acid-based curing accelerator as the component (E-3) is preferably 0.1 to 10 parts by mass, more preferably 100 parts by mass of the component (B), from the viewpoint of the balance between curability and thermal decomposition. Preferably it is 0.3-5 mass parts, More preferably, it is 0.5-3 mass parts. When using 2 or more types of acid system hardening accelerators together, it is preferable that the total amount becomes in the said range.

[(F) filler]
The filler of the component (F) used in the present invention comprises (F-1) a hollow structural filler, and further comprises (F-2) an inorganic filler which is usually used in a molding material for sealing. Is preferred. The content of the filler of the component (F) from the viewpoint of mechanical strength, linear expansion coefficient, etc., in order to prevent peeling between the cured product of the composition for a sealing molding material and the semiconductor insert part, which is the effect of the present invention Is preferably 60 to 95% by mass, more preferably 65 to 90% by mass, still more preferably 70 to 85% by mass, based on the total amount of the composition for a sealing molding material. When the content of the filler is 60% by mass or more, an increase in the linear expansion coefficient can be suppressed, sufficient mechanical strength can be maintained, and when the content is 95% by mass or less, good flowability can be obtained.

(F-1) Hollow Structured Filler The hollow structure filler of the component (F-1) used in the present invention mainly relieves the stress during curing, and the elastic modulus of the cured product of the composition for sealing and molding material By lowering it, it also relieves the stress associated with heat shrinkage, and works to prevent peeling between the cured product and the semiconductor insert part. It is preferable that the elastic modulus of the hardened | cured material of the composition for sealing molding materials is 10-15 GPa. Peeling of a hardened material and an insert part can be controlled as it is 15 GPa or less, and moldability is good as it is 10 GPa or more.
Here, the "hollow structure filler" in the present invention refers to a filler having one or more hollow structures inside the filler. The hollow structured filler is not particularly limited, and soda lime glass, borosilicate glass, inorganic hollow structured filler such as so-called hollow glass or hollow silica mainly composed of aluminum silicate, mullite, quartz etc., siloxane bond, etc. Thermoplastic or thermosetting in addition to silicone-based hollow structural fillers mainly composed of silicone compounds such as silsesquioxane compounds such as silsesquioxane compounds having a cross-linked structure represented by (CH ₃ SiO _3/2 ) _n in a three-dimensional network shape Organic hollow structure filler etc. which have as a main component an organic compound etc. which were synthesized using an acid resin as a starting material can be used.
The “silsesquioxane compound” in the present specification has a structure in which a siloxane bond is cross-linked in a three-dimensional network represented by (CH ₃ SiO _3/2 ) _n , and a methyl group or phenyl group is used as a side chain. Among compounds having organic functional groups such as groups, it refers to compounds in which the proportion of methyl groups in the side chains is 80% or more.
Among the above-mentioned "hollow structural fillers", in particular, inorganic hollow structural fillers and silicone hollow structural fillers have higher heat resistance of the hollow structural fillers themselves, so the composition for a sealing molding material having higher heat resistance It is possible to use for the thing.

  From the viewpoint of preventing peeling with the insert part, the ratio of (F-1) hollow structural filler to the total amount of the composition for a sealing molding material is (α), the elastic modulus (unit: GPa) of the hollow structural filler is It is preferable to select the hollow structure filler species and the addition amount thereof such that (α) / (β) becomes 0.002 to 0.250 when β), and 0.003 to 0.150 It is particularly preferred to select the hollow structural filler species and the amount added. If (α) / (β) is 0.002 or more, the stress relaxation effect at the time of curing of the composition for a sealing molding material and the stress relaxation effect accompanying heat shrinkage can be sufficiently obtained, and if it is 0.250 or less Reliability such as withstand voltage or tracking resistance can be sufficiently obtained.

Moreover, the elasticity modulus of the hollow structure filler of (F-1) component becomes like this. Preferably it is 0.1-15 GPa, More preferably, it is 0.2-12 GPa. Among them, inorganic hollow structured fillers such as the above-mentioned hollow glass and hollow silica having a relatively high elastic modulus are relatively high in the effect of suppressing shrinkage during curing of the sealing resin, and high in the effect of suppressing stress generated during curing. Because it is preferable. In addition, a silicone-based hollow structural filler having a relatively low elastic modulus can reduce the elastic modulus of the sealing material with a small amount of addition, and is preferable because the stress relaxation effect at the time of heat contraction is high. When an inorganic hollow structural filler such as hollow glass or hollow silica and a silicone hollow structural filler are used in combination, the effect of suppressing peeling from the insert part is high even with a relatively small amount of addition, and high heat resistance is required. It is applicable also to sealing resin and is a preferred embodiment in the present invention.
The elastic modulus of the hollow structured filler in the present invention is, for example, a dynamic ultra-microhardness tester (manufactured by Shimadzu Corporation, device name: DUH-211SR, load-unload test, load: 5.0 mN, velocity 1. It can measure by 5 mN / s.

In the case of the inorganic component, the hollow structured filler of the component (F-1) contains at least one member selected from the group consisting of silica, alumina, and a silica-alumina compound, from the viewpoint of achieving both insulation properties such as tracking resistance. Inorganic hollow structural filler, and / or a silicone hollow structural filler containing a silsesquioxane compound, preferably containing at least one selected from the group consisting of silica-alumina compounds and alumina. More preferably, they are inorganic hollow structural fillers and / or silicone hollow structural fillers containing a silsesquioxane compound.
In the case of an organic component, it is possible to select an organic hollow structural filler made of an acrylic resin, a polyester resin or the like.

  The hollow structured filler of the component (F-1) tends to have a lower thermal conductivity than ordinary fillers because it has an air layer inside. Since the tracking resistance is greatly affected by the thermal conductivity, the decrease in the thermal conductivity often involves the decrease in the tracking resistance. When the hollow structural filler is an inorganic component, it is possible to suppress the decrease in tracking resistance by containing the thermally conductive silica-alumina compound and / or alumina as the component (F-1). Become. In addition, with regard to the silsesquioxane compound, it is presumed that the effect on the tracking resistance is reduced because the peeling suppression effect is exhibited by the addition of a relatively small amount.

  The hollow structure filler that can be suitably used in the present invention preferably contains no alkali metal or alkaline earth metal from the viewpoint of preventing corrosion of the semiconductor insert due to ionic impurities. If contamination can not be prevented, it is desirable to reduce as much as possible.

  The hollow structured filler of the component (F-1) contains at least one member selected from the group consisting of silica, alumina, and silica-alumina compounds, and has a small content of alkali metal, alkaline earth metal, etc. For example, Kainos Fears (trade name of Kansai Matek Co., Ltd., trade name) mainly composed of aluminum silicate and mullite (compound of silica and alumina), Es Fears (trade name of Pacific Cement Co., Ltd.), etc. It is available on the market. In addition, as a silicone-based hollow structural filler (silsesquioxane compound-based filler) containing a silsesquioxane compound, for example, NH-SBN04 (manufactured by Nikko Rica Co., Ltd.) containing polymethylsilsesquioxane as a main component It is available on the market as manufactured goods, brand names, etc.

  The hollow structured filler of the component (F-1) has an average particle diameter of 3 to 3 from the viewpoint of coexistence with the peeling prevention effect with the semiconductor insert part, productivity of the composition for a sealing molding material, moldability and the like. The thickness is preferably 100 μm, and more preferably 3 to 60 μm. When the average particle size is 3 μm or more, the peeling prevention effect is obtained, and when the average particle size is 100 μm or less, the productivity and the moldability of the composition for a sealing molding material become good. Here, the average particle diameter refers to a median (D50) measured by a laser diffraction scattering method (for example, device name: SALD-3100, manufactured by Shimadzu Corporation).

  As hollow structured fillers having an average particle size of 3 to 100 μm, Einospheres 75 (average particle size 35 μm) and the like as the above-mentioned Kinospheres (manufactured by Kansai Matec Co., Ltd., trade name) series, E.Spheres SL75 (average particle diameter 55 μm), and the same E. Sphers SL125 (average particle diameter 80 μm), etc. are available in the market. In addition, Glass Bubbles K37 (average particle diameter 45 μm), Glass Bubbles iM30K (average particle diameter 16 μm) (above, 3M Japan Co., Ltd. product), NH-SBN04 (average particle diameter 4 μm, Nikko Rica Co., Ltd. product), ADVANCELL HB-2051 (average particle size 20 μm, manufactured by Sekisui Chemical Co., Ltd.) and the like can also be obtained on the market.

The content of the hollow structure filler of the component (F-1) is an inorganic hollow structure filler containing at least one selected from the group consisting of silica, alumina, and a silica-alumina compound, and a silsesquioxane compound In the case of an inorganic component such as a silicone-based hollow structure filler containing the above, it is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, still more preferably 5 to 20 based on the total amount of the filler of the component (F). It is mass%. If it is 1 mass% or more, the peeling prevention effect will be acquired, and if it is 50 mass% or less, insulation performance such as withstand voltage and moldability will be good. In particular, in the case where the hollow structural filler of the component (F-1) is a silicone-based hollow structural filler containing a silsesquioxane compound, the content thereof is preferably 0. to the total amount of the filler of the component (F). The content is 5 to 10% by mass, more preferably 1.0 to 6% by mass, and still more preferably 1.2 to 5% by mass.
When the component (F-1) is an organic component, the content is preferably 0.5 to 10% by mass, more preferably 1.5 to 7% by mass, based on the total amount of the filler of the component (F). . If it is 0.5 mass% or more, the peeling prevention effect will be acquired, and if it is 10 mass% or less, insulation performance, such as withstand voltage, etc. and moldability will become favorable.

(F-2) Inorganic Filler In the present invention, conventionally known inorganic fillers can be used. Examples of such inorganic fillers include crystalline silica, fused silica, synthetic silica, alumina, aluminum nitride, boron nitride, zircon, calcium silicate, calcium carbonate, barium titanate and the like. From the viewpoint of flowability and reliability, crystalline silica, fused silica and synthetic silica are preferable, and fused spherical silica and synthetic silica are particularly preferable as the main component. Further, the addition of silicone powder containing polymethylsilsesquioxane or the like as a main component is effective in suppressing peeling.

  The content of the inorganic filler of the component (F-2) is preferably 50 to 99.5% by mass, more preferably 55 to 98% by mass, based on the total amount of the filler of the component (F).

[Other ingredients]
(Silane coupling agent)
It is preferable to add a silane coupling agent to the composition for a sealing molding material of the present invention from the viewpoints of moisture resistance, mechanical strength, adhesion to a semiconductor insert part, and the like. In the present invention, epoxysilane such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- Aminosilanes such as 2- (aminoethyl) -3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, and isocyanate silanes such as 3-isocyanatopropyltriethoxysilane It is possible to appropriately use conventionally known silane coupling agents. From the viewpoint of adhesion, it is preferable to use epoxysilane such as 3-glycidoxypropyltrimethoxysilane or 3-glycidoxypropyltriethoxysilane, secondary aminosilane, and isocyanate silane alone or in combination. . The silane coupling agent may be used by simply mixing it with the component (F), or it may be subjected to surface treatment of a part or the whole thereof in advance. In addition, an aluminate coupling agent or a titanate coupling agent may be added as long as the effects of the present invention are not impaired.

  The amount of the silane coupling agent added is preferably 0.01 to 1% by mass, more preferably 0.03 to 0.7% by mass, still more preferably 0.05 to 1% by mass, based on the total amount of the composition for a sealing molding material. It is 0.5 mass%. Adhesiveness with a semiconductor insert part can be improved by setting it as 0.01 mass% or more, and the fall of the hardenability at the time of shaping | molding can be suppressed by setting it as 1 mass% or less.

(Release agent)
In the present invention, it is preferable to further add a release agent in order to realize good productivity of the composition for a sealing molding material. As the releasing agent which can be added, for example, natural wax such as carnauba wax, fatty acid ester wax, fatty acid amide wax, non-oxidized polyethylene type releasing agent, oxidized polyethylene type releasing agent, silicone type releasing agent Although etc. can be mentioned, you may add a mold release agent other than these. In addition, these release agents may be used alone or in combination of two or more. From the viewpoint of achieving both adhesion and mold releasability, a wax having a relatively small molecular weight such as carnauba wax and a fatty acid ester wax and a wax having a relatively large molecular weight such as oxidized polyethylene are used in combination. And especially effective.

  In the composition for a sealing molding material of the present invention, in addition to the above components, a low stress agent such as silicone generally blended in a composition of this type, a flame retardant, to the extent that the effects of the present invention are not inhibited. Carbon black, organic dyes, titanium oxide, colorants such as bengal, and the like can be blended as required.

  In addition, in the composition for a sealing molding material of the present invention, an ion trap agent such as an anion exchanger can be blended from the viewpoint of improving the moisture resistance of the semiconductor element and the high temperature storage characteristics. Examples of the anion exchanger include hydrotalcites, hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, bismuth and the like, and other conventionally known anion exchangers. May be used. These may be used alone or in combination of two or more.

  Component (A), (B), (C), (D), (E-1), (E-2), (E-3) in the composition for a sealing molding material of the present invention The content of the component (F-1) and the component (F-2) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more.

  The composition for a sealing molding material of the present invention can be prepared by uniformly dispersing and mixing the above-described components in a predetermined amount. The preparation method is not particularly limited, but as a general method, for example, a mixture of a predetermined amount of each of the above components is sufficiently mixed by a mixer or the like, and then melt mixed by a mixing roll, an extruder or the like, and then cooled. And the method of crushing can be mentioned.

The composition for a sealing molding material thus obtained has a high glass transition temperature (Tg), has high thermal decomposition resistance, is excellent in moldability, has high withstand voltage, It is possible to obtain a cured product having high adhesion and high reliability.
The glass transition temperature of the cured product of the composition for a sealing molding material is preferably 230 ° C. or more, more preferably 240 ° C. or more, and still more preferably 250 ° C. or more.
Moreover, the thermal decomposition temperature of the hardened | cured material of the said composition for sealing molding materials becomes like this. Preferably it is 380 degreeC or more, More preferably, it is 385 degreeC or more.
In addition, the glass transition temperature and thermal decomposition temperature of hardened | cured material can be measured by the method as described in an Example.

(Electronic component device)
The electronic component device of the present invention comprises an element sealed by the cured product of the above composition for sealing and molding material. The above electronic component devices include supporting members such as lead frames, single crystal silicon semiconductor elements or compound semiconductor elements such as SiC and GaN, members such as wires and bumps for electrically connecting them, and other constituent members It is an electronic component device in which the necessary part is sealed with the cured product of the above-mentioned composition for a sealing molding material with respect to one set.
Moreover, by using the composition for a sealing molding material, it is possible to obtain an electronic component device which is excellent in heat resistance, excellent in adhesion to a semiconductor insert part, and less likely to peel or crack even after being left at high temperature. .

As a method of sealing using the composition for a sealing molding material of the present invention, a transfer molding method is the most general, but an injection molding method, a compression molding method or the like may be used.
The molding temperature is preferably 150 to 220 ° C, more preferably 170 to 210 ° C. The molding time is preferably 45 to 300 seconds, more preferably 60 to 200 seconds. Moreover, when carrying out post-hardening, although heating temperature is not specifically limited, For example, Preferably it is 150-220 degreeC, More preferably, it is 170-210 degreeC. The heating time is not particularly limited, but is preferably 0.5 to 10 hours, and more preferably 1 to 8 hours.

  EXAMPLES The present invention will next be described in detail by way of examples, which should not be construed as limiting the invention thereto.

(Examples 1 to 10, Comparative Examples 1 to 5)
Each component of the kind and compounding quantity of Table 1 was knead | mixed with a mixing biaxial roll, and the composition for sealing molding materials was prepared. The kneading temperature in each example and comparative example was set to about 120 ° C. In addition, the blank in the table represents no blending.

  The detail of each component of Table 1 used for preparation of the composition for sealing molding materials is as follows.

<Maleimide resin>
[(A) component]
BMI-2300: polyphenylmethane maleimide (having z = 0 to 2 in the general formula (I) as a main component), manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name

<Allyl group-containing nadiimide resin>
[(B) component]
BANI-M: N, N '-(methylenedi-p-phenylene) -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), Maruzen Petrochemicals Co., Ltd. Trade name • BANI-X: N, N′-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), Maruzen Petrochemical Co., Ltd., Product name

<Phenolic curing agent>
[(C) component]
MEH-7500: Triphenylmethane-type phenol resin (Phenol resin with x = 1 to 4 in the general formula (III) as a main component), manufactured by Meiwa Kasei Co., Ltd., trade name, hydroxyl equivalent 97, softening point 110 ° C
SN-485: Naphthol aralkyl resin (Phenol resin with y 1 = 0 to 3 in general formula (IV) as the main component), Nippon Steel Sumikin Chemical Co., Ltd., trade name, hydroxyl equivalent 215, softening point 87 ° C.

<Epoxy resin>
[(D) component]
-EPPN-502H: Triphenylmethane type epoxy resin (epoxy resin with n1 = 0 to 3 in general formula (V) as the main component), Nippon Kayaku Co., Ltd., trade name, epoxy equivalent 168, softening point 67 ° C
-ESN-375: Naphthol aralkyl type epoxy resin (epoxy resin with n2 = 0 to 3 in general formula (VI) as main component), Nippon Steel Sumikin Chemical Co., Ltd. product name, trade name, epoxy equivalent 172, softening point 75 ° C
HP-4710: dihydroxy naphthalene novolac epoxy resin (epoxy resin represented by the general formula (VII)), manufactured by DIC Corporation, trade name, epoxy equivalent 161, softening point 82 ° C.

<Hardening accelerator>
[(E-1) component: phosphorus-based curing accelerator]
PP-200: triphenyl phosphine, manufactured by Hokuko Chemical Industry Co., Ltd., trade name, TPTP: tris (4-methylphenyl) phosphine, manufactured by Hokuko Chemical Industry Co., Ltd., trade name

[(E-2) component: imidazole-based curing accelerator]
· 2MZ-A: 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] -ethyl-s-triazine, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name · 2P4 MHZ-PW: 2-phenyl -4-Methyl-5-hydroxymethylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name

[(E-3) component: acid curing accelerator]
AC-4B50: Boron trifluoride imidazole complex, manufactured by Stella Chemifa Co., Ltd., trade name, p-toluenesulfonic acid: manufactured by Tokyo Chemical Industry Co., Ltd.

<Amine curing agent>
・ 4,4'-diaminodiphenylmethane: made by Tokyo Chemical Industry Co., Ltd.

<Filler>
[(F-1) component: hollow structure filler]
・ E-spheres SL 75: Inorganic hollow structure filler mainly composed of amorphous aluminum (65 to 85%) and mullite (20 to 30%), average particle diameter 55 μm, manufactured by Pacific Cement Co., Ltd., trade name, Elastic modulus 10GPa
・ ADVANCELL HB-2051: Acrylic porous hollow structure filler, average particle diameter 20 μm, Sekisui Chemical Co., Ltd. product name, trade name, elastic modulus 0.3 GPa
· NH-SBN 04: Polymethylsilsesquioxane based single-hole hollow structural filler, average particle diameter 4 μm, manufactured by Nikko Rika Co., Ltd., trade name, elastic modulus 1.0 GPa
Here, the value of the elastic modulus is a dynamic ultra-microhardness tester (manufactured by Shimadzu Corporation, device name: DUH-211SR, load-reload test, load: 5.0 mN, speed 1.5 mN / s, indenter) : The average value of the values measured five times with a triangular indenter.

[(F-2) component: inorganic filler]
· FB-105: fused spherical silica, manufactured by Denki Kagaku Kogyo Co., Ltd., trade name, average particle diameter 18 μm, specific surface area 4.5 m ² / g

<Other ingredients>
· KBM-403: Silane coupling agent, 3-glycidoxypropyl trimethoxysilane, Shin-Etsu Chemical Co., Ltd., trade name · HW-4252 E: Releasing agent (Oxidized polyethylene of number average molecular weight 1,000 Release agent), Mitsui Chemicals Co., Ltd., trade name, MA-600: Colorant (carbon black), Mitsubishi Chemical Co., Ltd., trade name

  The measurement of the characteristic of the composition for sealing molding materials prepared by Examples 1-10 and Comparative Examples 1-5, and evaluation were performed on the measurement conditions shown below. The evaluation results are shown in Table 1. The molding material was molded using a transfer molding machine under conditions of a mold temperature of 185 ° C., a molding pressure of 10 MPa, and a curing time of 180 seconds unless otherwise specified. Further, post curing was performed at 200 ° C. for 8 hours unless otherwise specified.

(1) Glass transition temperature (Tg)
The glass transition temperature (Tg) was measured as one of the standard of the heat resistance of the hardened | cured material of the composition for sealing molding materials. First, using a mold of 4 mm long x 4 mm wide x 20 mm high, the composition for a sealing molding material is molded under the above conditions, and further after 2 hours at 185 ° C. or 8 hours at 200 ° C. It was made to harden and a cast (4 mm long x 4 mm wide x 20 mm in thickness) was produced. The molded product is cut into pieces of necessary dimensions to obtain a test piece, and the glass transition temperature (Tg) of the test piece is measured by a TMA method using a thermal analyzer (manufactured by Seiko Instruments Inc., trade name: SSC / 5200). ) Was used. The low temperature reactivity was evaluated as follows: those having a Tg of 185 ° C. for post-curing and those having a Tg difference of 200 ° C. of less than 15 ° C. were 〇 and those having 15 ° C. or more were x.

(2) Thermal decomposition temperature (1% weight loss temperature)
The thermal decomposition temperature by TG-DTA was measured as another reference of the heat resistance of the hardened | cured material of the sealing molding material. The sealing molding material composition was molded under the above conditions and further post cured at 200 ° C. for 8 hours to prepare a molded product (long 4 mm × horizontal 4 mm × thickness 20 mm). The molded product is cut into pieces of the same size as the above (1) to obtain a test piece, and the powder obtained by sufficiently grinding the test piece in a mortar is used at room temperature (25 ° C.) at a heating rate of 10 ° C./min. To 600 ° C. The temperature at which a weight loss of 1% was observed from the weight change chart obtained was taken as the thermal decomposition temperature. As a measuring apparatus, “EXSTAR 6000” manufactured by Seiko Instruments Inc. was used. In addition, 385 ° C or more is a pass.

(3) Adhesion to Ni-plated surface On the electroless Ni plating (Mitsui Hitec Co., Ltd., trade name "VQFP208p"), a sealing molding material composition is molded under the above conditions, and further post curing under the above conditions Four molded articles were produced. Using a bond tester (manufactured by Nishijin Shoji Co., Ltd., SS-30 WD), a φ 3.5 mm purine-like molding formed on Ni plating was moved from a height of 0.5 mm to a speed of 0.1 mm from the bottom of the molding. The film was peeled off in the shear direction at 1 / sec, and the adhesion between the molded product and the Ni plating was measured at normal temperature (25 ° C.) or 250 ° C. This was done four times and the average value was calculated. In addition, 4 MPa or more is taken as pass at normal temperature, and 3 MPa or more is taken as pass at 250 ° C.

(4) Package observation after leaving at 250 ° C. for 250 hours SiC chip (6 × 6 × 0.15 mmt) at the center of the island (8.5 × 11.5 mm) of the electroless Ni-plated lead frame TO-247 package The surface protective film was fixed, the composition for a sealing molding material was molded under the above conditions, and post curing was further performed under the above conditions to prepare ten molded articles. The molded product was observed using an ultrasonic imaging apparatus (manufactured by Hitachi, Ltd., FS300II) to confirm the presence or absence of peeling between the island around the SiC chip and the composition for a sealing molding material. The number of packages in which peeling of the island portion was observed was 3 or less out of 10.
The chip was fixed to the lead frame using a lead-free solder under an environment of 340 ° C./13 minutes in an atmosphere of 5% formic acid and 95% nitrogen. Further, the lead frame was used by subjecting the composition for a sealing molding material to argon plasma treatment for 60 seconds using Plasma Cleaner AC-300 manufactured by Nordson Corporation immediately before molding.
The TO-247 package subjected to the peeling observation as described above was allowed to stand at 250 ° C. for 250 hours, and then the presence or absence of peeling was confirmed using an ultrasonic imaging apparatus (FS300II manufactured by Hitachi, Ltd.). The number of packages in which the peeled area of the island portion was 20% or more was regarded as 3 or less out of 10.

(5) Electrical characteristics, tracking resistance (CTI)
A test piece of φ100 mm × 2 mmt was prepared, and after post-curing, tracking resistance (CTI) was measured in accordance with ASTM-D3638. As a tester, YST-112-1S manufactured by Yamayo Test Instruments Co., Ltd. was used. In addition, 400 V or more was taken as passing.

(6) Breakdown voltage (breakdown voltage)
Test pieces of φ100 mm × 2 mmt were prepared, and after post-curing, the dielectric breakdown voltage at room temperature (25 ° C.) was measured in accordance with ASTM-D149. The measurement was performed by the "short time method". As a tester, YST-243BD- 100RO manufactured by Yamayo Test Instruments Co., Ltd. was used. An average value of 10 kV / mm or more at the time of measurement at n = 3 was taken as a pass.

(7) Continuous formability Using a mold release load measurement molding machine (manufactured by KYOCERA Corporation, trade name: GM-500), PBGA (Plastic Ball Grid Array, 30 mm × 30 mm × 1 mm, t / 2 pieces) In contrast, 300 shots were continuously formed. The mold temperature was 185 ° C., and the molding time was 180 seconds. The following criteria were evaluated.
:: Continuous molding was possible up to 300 shots, and mold stains and the like were hardly observed. ×: Continuous molding up to 300 shots was impossible due to sticking to the die etc.

(8) Storage Life The gelation time immediately after the production of the composition for a sealing molding material (initial) and after standing for 7 days at 25 ° C. was measured by the hot plate method at 185 ° C. From these gelation times, the following criteria were evaluated.
○: Change from initial gel time is less than 15% ×: Change from initial gel time is 15% or more

  The compositions for a sealing molding material of Examples 1 to 10 are all excellent in moldability, and the cured product of the composition for a sealing molding material has a high glass transition temperature (Tg), and is resistant to thermal decomposition, It was shown that the voltage resistance is high, the adhesion to the semiconductor insert part is good, and the reliability is high.

Claims (9)

(A) maleimide resin represented by the following general formula (I), (B) allyl group-containing nadiimide resin represented by the following general formula (II), (C) phenolic curing agent, (D) epoxy resin, E) containing a curing accelerator, and a filler comprising (F) (F-1) hollow structural filler,
The component (C) and the component (D) each contain a triphenylmethane skeleton and / or a naphthalene skeleton, and the component (E) is a (E-1) phosphorus-based curing accelerator, (E-2) imidazole-based The composition for sealing molding materials containing a hardening accelerator and (E-3) acid type hardening accelerator.

(Wherein R ¹ is each independently a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may be substituted with a halogen atom. When a plurality of R ¹ are present, the plurality of R ¹ may be substituted. P may be the same as or different from each other, p is independently an integer of 0 to 4, q is an integer of 0 to 3, and z is an integer of 0 to 10.)

(Wherein, R ² is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms, a divalent aromatic group having 6 to 18 carbon atoms, a general formula “-A ¹ -C ₆ H ₄ - ^(a _{1) m} - ^(provided that, m is an integer of 0 or 1, each ^{a 1} is independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 8 carbon atoms. Or a group represented by the general formula “—C ₆ H ₄ —A ² —C ₆ H ₄ — (wherein A ² is“ —CH ₂ — ”,“ —C (CH ₃ ) ₂ — ”, A group represented by “—CO—”, “—O—”, “—S—” or “—SO ₂ —”))   The composition for a sealing molding material according to claim 1, wherein the average particle diameter of the (F-1) hollow structure filler is 3 to 100 μm.   The (F-1) hollow structure filler is at least one selected from the group consisting of silica, alumina, and a silica-alumina compound, and the content of the (F-1) hollow structure filler is the above (F) The composition for a sealing molding material according to claim 1 or 2, which is 1 to 50% by mass with respect to the total amount of the filler.   The (F-1) hollow structure filler is made of an organic compound, and the content of the (F-1) hollow structure filler is 0.5 to 10% by mass with respect to the total amount of the (F) filler. The composition for sealing molding materials as described in claim 1 or 2.   Said (F-1) hollow structure filler consists of a silsesquioxane compound, and content of this (F-1) hollow structure filler is 0.5-10 mass% with respect to said (F) filler whole quantity. The composition for a sealing molding material according to claim 1 or 2.   Content for the said (B) component is 30-250 mass parts with respect to 100 mass parts of said (A) components, The composition for sealing molding materials as described in any one of Claims 1-5.   The component (E-3) is at least one selected from the group consisting of p-toluenesulfonic acid, its amine salt and boron trifluoride amine complex, according to any one of claims 1 to 6, Composition for sealing molding material.   Content of the said (E-3) component is 0.1-10 mass parts with respect to 100 mass parts of said (B) components, The composition for sealing molding materials as described in any one of Claims 1-7 object.   The electronic component apparatus provided with the element sealed by the composition for sealing molding materials as described in any one of Claims 1-8.