JP2018188611A - Composition for sealing and molding material and electronic component apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cured product having a high glass transition temperature (Tg), excellent moldability, high withstand voltage resistance, and good adhesion to semiconductor insert parts, and a composition for a sealing molding material. , And an electronic component apparatus using the composition for a sealing molding material. SOLUTION: (A) at least one selected from a maleimide resin having a specific structure, (B) a phenol-based curing agent having a specific skeleton, and a benzoxazine resin having a specific structure, and (C) specifying. At least one selected from epoxy resins having the above skeleton, (D-1) organic phosphorus-based curing accelerator, (D-2) imidazole-based curing accelerator, and (E) (e-1) hollow structure filling. A filler containing a material, and a composition for a sealing molding material containing the material. [Selection diagram] None

Description

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

  Conventionally, epoxy resin molding materials have been widely used in the field of sealing electronic components such as transistors and ICs. This is because the epoxy resin has an excellent balance of electrical properties, moisture resistance, mechanical properties, adhesion to inserts, and the like.

In recent years, there has been an increase in energy-saving momentum around the world against the background of concerns over the future depletion of resource energy and the so-called global warming problem. Power devices (power semiconductors) are attracting attention.
For power semiconductors, power conversion efficiency is a very important item that determines its performance. Here, compound semiconductors such as silicon carbide (SiC) and gallium nitride (GaN) have higher conversion efficiency than conventional Si devices. Research and development and distribution in the market have become booming.

  As a major feature of power semiconductors, SiC elements, in particular, have higher withstand voltage characteristics than Si elements. Therefore, by applying this, it is possible to realize 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 it can operate at a higher temperature than conventional Si elements. Having the above-mentioned high withstand voltage characteristics means that the element itself generates more heat than before, and coupled with the fact that high-temperature operation is possible, the peripheral members are required to have higher heat resistance than before. become.
Regarding SiC, there is an operation report at 300 ° C. or higher, and the molding material for sealing is required to have high thermal decomposition resistance with a high glass transition temperature.

  As a technology for giving a high glass transition temperature to a molding material for sealing and ensuring reliability at high temperatures, an epoxy resin, a phenol resin, a compound having a maleimide group, and a phenol compound having an alkenyl group are essential components. Sealing epoxy resin composition (for example, Patent Document 1), sealing resin composition (for example, Patent Document 2) in which a maleimide compound and a benzoxazine compound are blended at a specific ratio and a triazole compound is added. There is a report. There is also a report on an organic-inorganic nanohybrid resin using a copolymer of maleimide resin and cyanate ester resin as a resin component and inorganic nanoparticles as an inorganic component (for example, Patent Document 3).

Japanese Patent No. 4793565 Japanese Patent Laying-Open No. 2015-101667 Japanese Patent No. 5358623

  In order to ensure reliability at high temperatures, a high glass transition temperature (Tg) and a high adhesion to semiconductor insert parts are necessary. In general, it is often difficult to achieve both of these, It is not uncommon to have problems such as the occurrence of peeling. In addition, it is difficult to achieve sufficient compatibility with the moldability of molding materials related to the productivity of semiconductor components while ensuring sufficient adhesion to semiconductor insert components. It is hard to say that it has been solved.

  The present invention has been made in view of such circumstances, has a high glass transition temperature (Tg), is excellent in moldability, has high voltage resistance, and has good adhesion to semiconductor insert components. It aims at providing the composition for sealing molding materials which can obtain hardened | cured material, and the electronic component apparatus using this composition for sealing molding materials.

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

That is, the present invention provides the following [1] to [8].
[1] (A) A maleimide resin represented by the following general formula (I), (B) a phenolic curing agent represented by the following general formula (II), and a phenol represented by the following general formula (III) At least one selected from phenolic curing agents that are one or two of the above-mentioned hardeners, and a benzoxazine resin represented by the following general formula (IV), and (C) the following general formulas (V) to (VII) ), At least one selected from epoxy resins represented by: (D-1) an organophosphorus curing accelerator, (D-2) an imidazole curing accelerator, and (E) (e-1) a hollow structure. A composition for encapsulating molding material, comprising a filler containing a filler.

(In the formula, each R ¹ is 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 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 x is 0-10)

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

(In the formula, X1 is an alkylene group having 1 to 10 carbon atoms, an oxygen atom, or a direct bond. R ² and R ³ are each independently a hydrocarbon group having 1 to 10 carbon atoms. R ² and R When a plurality of ³ are present, the plurality of R ² and the plurality of R ³ may be the same or different, and m1 and m2 are each independently an integer of 0 to 4.)

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

(In the formula, n2 is 0 to 10.)


[2] The composition for encapsulating material according to [1], wherein the average particle diameter of the (e-1) hollow structure filler is 3 to 100 μm.
[3] A value obtained by dividing the ratio of the (e-1) hollow structure filler to the total amount of the sealing molding material composition by the elastic modulus of the (e-1) hollow structure filler is 0.002 to 0. 250. The composition for encapsulating molding material according to claim [1] or [2].
[4] The (e-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 (e-1) hollow structure filler is ( E) The composition for encapsulating molding material according to any one of the above [1] to [3], which is 1 to 50% by mass relative to the total amount of the filler.
[5] The (e-1) hollow structure filler is made of an organic compound, and the content of the (e-1) hollow structure filler is 0.5 to 10% by mass with respect to the total amount of the (E) filler. The composition for encapsulating molding material according to any one of the above [1] to [3].
[6] The (e-1) hollow structure filler is made of a silsesquioxane compound, and the content of the (e-1) hollow structure filler is 0.5 to 10 with respect to the total amount of the (E) filler. The composition for encapsulating material according to any one of [1] to [3], wherein the composition is mass%.
[7] The reaction start temperature when the component (D-2) is reacted with bisphenol A type epoxy resin (liquid) at a mass ratio of 1/20 is 85 ° C. or more and less than 175 ° C. The composition for sealing molding materials according to any one of the above [1] to [6], which is an imidazole-based curing accelerator.
[8] An electronic component device including an element sealed with a cured product of the composition for sealing molding material according to any one of [1] to [7].

  According to the present invention, a sealing molding material having a high glass transition temperature (Tg), excellent moldability, high voltage resistance, and capable of obtaining a cured product having good adhesion to a semiconductor insert component. The electronic component apparatus using the composition for sealing and this composition for sealing molding materials can be provided.

Hereinafter, the present invention will be described in detail.
(Composition for sealing molding material)
First, each component of the composition for sealing molding material of this invention is described.
[(A) Maleimide resin]
The maleimide resin of the component (A) used in the present invention is a compound represented by the following general formula (I) and containing two or more maleimide groups in one molecule. It is a resin that forms a network structure and cures. Moreover, the said maleimide resin gives high glass transition temperature (Tg) to hardened | cured material by a crosslinking reaction, and improves heat resistance and heat-resistant decomposition property.

In the general formula (I), each R ¹ is independently a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group may be substituted with a halogen atom. p is each independently an integer of 0 to 4, and q is an integer of 0 to 3.
Examples of the hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a chloromethyl group and a 3-chloropropyl group Substituted alkyl groups; alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl; aryl groups such as phenyl, tolyl, and xylyl; monovalent groups such as aralkyl such as benzyl and phenethyl These hydrocarbon groups are mentioned.
Also, if the R ¹ there are a plurality, R ¹ of the plurality of it may be the same or different from each other.
z is an integer of 0 to 10, preferably an integer of 0 to 4.

  The maleimide resin represented by the general formula (I) is a phenolic curing agent and / or a benzoxazine resin as a component (B) described later, and an organic phosphorus curing accelerator as a component (D-1). Addition reaction is performed relatively easily at a temperature of 170 ° C. or higher, and high heat resistance is imparted to the cured product of the composition for sealing molding material.

Specific examples of the maleimide resin represented by the general formula (I) include, for example, N, N ′-(4,4′-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl). ) Methane, polyphenylmethanemaleimide and the like.
The maleimide resin is, for example, N, N ′-(4,4′-diphenylmethane) bismaleimide, BMI having B = 0 as a main component, BMI-70 (above, manufactured by KAI Kasei Co., Ltd.), BMI -1000 (manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI-2300 (manufactured by Yamato Kasei Kogyo Co., Ltd.), which is polyphenylmethane maleimide and has z = 0-2 as a main component, can be obtained as commercial products.

The maleimide resin of the component (A) may be used after partly or fully preliminarily mixing with the phenolic curing agent and / or benzoxazine resin of the component (B) described later. Good. The premixing method is not particularly limited, and a known mixing method can be used. For example, using a stirrable apparatus, the component (B) is melted at 50 to 180 ° C., and then the maleimide resin of the component (A) is gradually added and mixed while stirring. Examples include a method of stirring for about 60 minutes to prepare a premixed resin.
In the preliminary mixing, two or more phenolic curing agents and / or benzoxazine resins as the component (B) may be used.

In addition to the maleimide resin represented by the general formula (I), in addition to the maleimide resin represented by the general formula (I), in addition to the maleimide resin represented by the general formula (I) The maleimide resin may be used in combination. Examples of maleimide resins that can be used in combination include m-phenylene bismaleimide, 2,2-bis [4- (4-maleimidophenoxine) phenyl] propane, and 1,6-bismaleimide- (2,2,4-trimethyl). ) Hexane and the like can be mentioned, but conventionally known maleimide resins other than these may be used in combination.
In addition, when mix | blending maleimide resin other than the maleimide resin represented with the said general formula (I), it is preferable that the compounding quantity shall be 30 mass parts or less with respect to 100 mass parts of maleimide resin of (A) component. , 20 parts by mass or less, more preferably 10 parts by mass or less.

[(B) a phenolic curing agent having a specific skeleton and / or a benzoxazine resin having a specific structure]
The composition for encapsulating molding material of the present invention includes, as component (B), one of a phenolic curing agent represented by the general formula (II) and a phenolic curing agent represented by the general formula (III). It contains at least one selected from a phenolic curing agent that is a seed or two kinds, and a benzoxazine resin represented by the general formula (IV).
The component (B) undergoes an addition reaction with the component (A) relatively easily in the presence of the organophosphorus curing accelerator of the component (D-1) described later. The component (B) has the effect of indirectly suppressing the self-polymerization reaction of the maleimide resin as the component (A) and relaxing the peeling stress. Moreover, it has the function which provides adhesiveness and moldability with heat resistance to the composition for sealing molding materials.

  The phenol-based curing agent is represented by the following general formulas (II) and (III), and has at least two hydroxyl groups in one molecule.

(Wherein x is 0-10)

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

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

  The phenol resin represented by the general formula (II) is MEH-7500 (Maywa Kasei Co., Ltd.), and the phenol resin represented by the general formula (III) is SN-485 (Nippon Steel & Sumikin Chemical Co., Ltd.). ))), And can be obtained as commercial products.

  The benzoxazine resin has two benzoxazine rings in one molecule and is represented by the following general formula (IV).

In said general formula (IV), X1 is a C1-C10 alkylene group, an oxygen atom, or a direct bond. R ² and R ³ are each independently a hydrocarbon group having 1 to 10 carbon atoms.

  Carbon number of the alkylene group of X1 is 1-10, Preferably it is 1-3. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. Among them, a methylene group, an ethylene group, and a propylene group are preferable. Groups are preferred.

Examples of the hydrocarbon group having 1 to 10 carbon atoms of R ² and R ³ include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group; vinyl group, allyl group Alkenyl groups such as butenyl group, pentenyl group and hexenyl group; aryl groups such as phenyl group, tolyl group and xylyl group; and monovalent hydrocarbon groups such as aralkyl groups such as benzyl group and phenethyl group.
When a plurality of R ² and R ³ are present, the plurality of R ² and the plurality of R ³ may be the same or different.

  m1 is an integer of 0-4 each independently, Preferably it is an integer of 0-2, More preferably, it is 0. m2 is each independently an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0.

  Specific examples of the benzoxazine resin represented by the general formula (IV) include resins represented by the following formulas (IV-1) to (IV-4). These resins may be used alone or in combination of two or more.

  As the benzoxazine resin, a benzoxazine resin represented by the above formula (IV-1) is preferably used. In the benzoxazine resin, the content of the benzoxazine resin represented by the formula (IV-1) is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and still more preferably 70 to 100% by mass. %.

  The benzoxazine resin represented by the above formula (IV-1) can be obtained as a commercial product such as benzoxazine Pd (manufactured by Shikoku Kasei Kogyo Co., Ltd.).

  As the component (B), compounds represented by the general formulas (II) to (IV) may be used alone, or two or more of these may be used in combination. From the viewpoint of heat resistance, it is preferable to use a benzoxazine resin represented by general formula (IV). From the viewpoint of productivity and moldability, it is represented by general formula (II) or general formula (III). It is preferable to use a phenol resin alone or in combination. When used in combination with the benzoxazine resin represented by the general formula (IV) and the phenol resin represented by the general formula (II) and / or the general formula (III), it has an excellent balance of heat resistance and moldability. A composition for encapsulated molding material can be obtained, which is one of the preferred embodiments of the present invention.

  In the present invention, from the viewpoint of a balance between heat resistance, adhesion, and moldability, the component (B) is preferably 20 to 250 parts by mass, and 30 to 200 parts by mass with respect to 100 parts by mass of the component (A). More preferably, it is more preferable to set it as 40-150 mass parts. When using 2 or more types of (B) component together, it is preferable to make the total amount into the said range.

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

[(C) Epoxy resin having specific skeleton]
The composition for sealing molding material of this invention contains at least 1 sort (s) chosen from the epoxy resin represented by the following general formula (V)-(VII) as (C) component. The epoxy resin as component (C) has two or more epoxy groups in one molecule and includes a triphenylmethane skeleton and / or a naphthalene skeleton. The (C) component epoxy resin undergoes a crosslinking reaction with the (B) component phenolic curing agent and / or benzoxazine resin, and in the presence of the (D-2) component imidazole curing accelerator described below, ( A) It promotes the self-polymerization reaction of the maleimide resin of the component, enhances the curability of the composition for sealing molding material, and also has a function of giving good moldability. As the epoxy resin of component (C), one type may be used, or two or more types may be used in combination.

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

(In the formula, n2 is 0 to 10.)

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

  The epoxy resin represented by the general formula (V) is EPPN-502H (manufactured by Nippon Kayaku Co., Ltd.), and the epoxy resin represented by the general formula (VI) is ESN-375 (Nippon Steel & Sumikin Chemical ( The epoxy resin represented by the above general formula (VII) can be obtained as a commercial product as HP-4710 (manufactured by DIC Corporation).

  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 fluidity of the composition for sealing molding material. 60-90 degreeC, More preferably, it is 65-85 degreeC.

  In the composition for encapsulating molding material of the present invention, the content of the component (C) is a hydroxyl group of the phenol-based curing agent of the component (B) in order to balance the glass transition point, adhesion and moldability. The ratio of the epoxy group (c) of the epoxy resin of component (C) to the hydroxyl group (b-2) generated when b-1) and benzoxazine are opened, (c) / [(b-1) + ( b-2)] (equivalent ratio) is preferably 0.2 to 1.5, more preferably 0.3 to 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, heat decomposition resistance, flame retardancy, etc. are good. In addition, when using 2 or more types of (C) component, it is preferable to make the total amount into the said range.

(C) The epoxy resin of a component uses together with the epoxy resin used as a semiconductor element sealing material in the range which does not impair the effect of this invention other than resin represented by general formula (V)-(VII). Can do. Examples of the epoxy resin that can be used in combination include a phenol novolac type epoxy resin, an o-cresol novolak type epoxy resin, a biphenyl type epoxy resin, a dicyclopentadiene type epoxy resin, and the like. May be.
In addition, when using together epoxy resins other than the said (C) component, it is preferable that the compounding quantity shall be 30 mass parts or less with respect to 100 mass parts of epoxy resins of (C) component, and shall be 20 mass parts or less. Is more preferably 10 parts by mass or less.

[(D-1) Organophosphorus curing accelerator]
In the present invention, from the viewpoint of balance between adhesion and moldability, (D-1) an organophosphorus curing accelerator and (D-2) an imidazole curing accelerator described later are used in combination as a curing accelerator. is necessary.
The (D-1) component organophosphorus curing accelerator mainly promotes the crosslinking reaction between the component (A) and the component (B) and the crosslinking reaction between the component (B) and the component (C). Used. The component (D-1) promotes these reactions, thereby indirectly suppressing the self-polymerization reaction between the components (A) and suppressing the occurrence of peeling stress with the semiconductor insert component.

  Examples of the organophosphorus curing accelerator of component (D-1) include triphenylphosphine, tris (4-methylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (4-propylphenyl) phosphine, and tris. Tertiary phosphines such as (4-butylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris (2,4,6-trimethylphenyl) phosphine, tributylphosphine, methyldiphenylphosphine, tetraphenylphosphonium tetraphenyl Examples thereof include tetra-substituted phosphonium tetra-substituted borates such as borate and tetrabutylphosphonium tetrabutyl borate, and these can be used as appropriate, alone or in combination of two or more. Other than these, conventionally known organophosphorus curing accelerators may be used alone or in combination of two or more.

  The content of the organophosphorus curing accelerator as the component (D-1) is preferably 0.1 to 100 parts by mass of the component (A) from the viewpoint of balance between curability and adhesion with the semiconductor insert component. It is 10 mass parts, More preferably, it is 0.3-5 mass parts, More preferably, it is 0.5-3 mass parts. When two or more organic phosphorus curing accelerators are used in combination, the total amount is preferably within the above range.

[(D-2) Imidazole-based curing accelerator]
The (D-2) component imidazole curing accelerator is mainly used to ensure the moldability of the composition for encapsulating molding material by mainly promoting the self-polymerization reaction of the component (A). The action of the component (D-2) is promoted by the presence of the epoxy resin of the component (C), and it becomes possible to give good curability and moldability to the composition for sealing molding material of the present invention.
In the present invention, the “imidazole curing accelerator” is synonymous with an imidazole compound containing a nitrogen atom at the 1,3-position on a 5-membered ring.

  Examples of the imidazole curing accelerator of component (D-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- Examples include 4-methyl-5-hydroxymethylimidazole, and these may be used alone or in combination of two or more. Moreover, you may apply conventionally well-known imidazole type hardening accelerators other than the above.

In the present invention, the component (D-2) can be appropriately selected and used as necessary, but the moldability of the composition for encapsulating molding material, the cured product of the composition, and the semiconductor insert part 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2-phenyl-4-methyl-5-hydroxymethylimidazole It is particularly preferable to use a compound having a relatively high active temperature alone or in combination of two or more. Specifically, the reaction start temperature when the imidazole compound is reacted with bisphenol A type epoxy resin (liquid) at a mass ratio of 1/20 is preferably 85 ° C. or more and less than 175 ° C., more preferably It is particularly preferable to use a compound exhibiting 100 ° C. or more and less than 160 ° C., more preferably 100 ° C. or more and 150 ° C. or less alone or in combination of two or more.
Here, the reaction start temperature is a rising curve of an exothermic or endothermic peak when a composition containing an imidazole compound and a bisphenol A type epoxy resin is heated at a heating rate of 10 ° C./min using DSC. The temperature at the intersection of the tangent and temperature axis where the peak is the steepest.
(D-2) If the reaction start temperature of a component is 85 degreeC or more, peeling with a semiconductor insert component can be suppressed, and if it is less than 175 degreeC, the moldability of the composition for sealing molding materials is favorable. Can be.

  In the present invention, the self-polymerization reaction of the component (A), the crosslinking reaction of the component (A) and the component (B), the crosslinking reaction of the component (B) and the component (C), etc. are controlled, and the sealing molding material The content ratio of the component (D-1) and the component (D-2) is optimized in order to balance the curability of the composition for use and the stress generated at the time of curing, and to suppress separation from the semiconductor insert component. It is preferable. Specifically, the content ratio [(D-1) / (D-2)] of the component (D-1) and the component (D-2) is 3/1 to 1/3 in terms of mass ratio. Preferably, 2/1 to 1/3 is more preferable. When there are many (D-1) components, moldability will be sufficient, and when there are many (D-2) components, the adhesiveness of the hardened | cured material of the composition for sealing molding materials and semiconductor insert components may each become inadequate. is there.

[(E) Filler]
The filler of component (E) in the present invention includes (e-1) a hollow structure filler, and further contains (e-2) an inorganic filler that is usually used in a molding material for sealing. Is preferred. In order to prevent peeling between the cured product of the composition for encapsulating material and the semiconductor insert component, which is an effect of the present invention, the content of the filler of component (E) from the viewpoint of mechanical strength, linear expansion coefficient, etc. Is preferably 60 to 95% by mass, more preferably 65 to 90% by mass, and still more preferably 70 to 85% by mass based on the total amount of the composition for encapsulating material. If the filler content is 60% by mass or more, an increase in the coefficient of linear expansion can be suppressed and sufficient mechanical strength can be maintained, and if it is 95% by mass or less, good fluidity can be obtained.

(E-1) Hollow structure filler The hollow structure filler of component (e-1) used in the present invention mainly relieves stress during curing caused by the self-polymerization reaction of component (A) itself, and seals By lowering the elastic modulus of the cured product of the composition for a molding material, the stress associated with the heat shrinkage is also reduced, and the cured product and the semiconductor insert part are prevented from being peeled off. It is preferable that the elasticity modulus of the hardened | cured material of the composition for sealing molding materials is 10-15GPa. When it is 15 GPa or less, peeling between the cured product and the insert part can be suppressed, and when it is 10 GPa or more, the moldability is good.
Here, the “hollow structure filler” in the present invention refers to a filler having one or more hollow structures inside the filler. There are no particular limitations on the hollow structure filler, soda lime glass, borosilicate glass, aluminum silicate, mullite, inorganic hollow structure filler such as hollow silica mainly composed of quartz, etc., and siloxane bonds. A silicone-based hollow structure filler mainly composed of a silicone compound such as a silsesquioxane compound having a structure crosslinked in a three-dimensional network represented by (CH ₃ SiO _3/2 ) n, thermoplastic or thermosetting An organic hollow structure filler mainly composed of an organic compound synthesized from a resin as a starting material can be used.
The “silsesquioxane compound” in this 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 in the side chain. Among compounds having an organic functional group such as a group, a compound in which the ratio of the side chain being a methyl group is 80% or more.
Among the “hollow structure fillers”, the inorganic hollow structure filler and the silicone hollow structure filler, in particular, have a higher heat resistance, so the composition for the sealing molding material has higher heat resistance. It can be used for things.

  From the viewpoint of preventing peeling from the insert part, the ratio (e-1) of the hollow structure filler to the total amount of the composition for sealing molding material (α), and the elastic modulus (unit: GPa) of the hollow structure filler ( When β), it is preferable to select the hollow structure filler and the amount of addition so that (α) / (β) is 0.002 to 0.250, so that 0.003 to 0.150 is obtained. It is particularly preferred to select the type of hollow structure filler and the amount added. If (α) / (β) is 0.002 or more, the stress relaxation effect upon curing of the composition for encapsulating molding material and the stress relaxation effect accompanying thermal shrinkage are sufficiently obtained, and if it is 0.250 or less. Reliability such as withstand voltage and tracking resistance is sufficiently obtained.

The elastic modulus of the hollow structure filler of the component (e-1) is preferably 0.1 to 15 GPa, more preferably 0.2 to 12 GPa. Among them, inorganic hollow structure fillers such as hollow glass and hollow silica having a relatively high elastic modulus have a relatively high effect of suppressing shrinkage at the time of curing of the sealing resin, and a high effect of suppressing stress generated at the time of curing. Therefore, it is preferable. In addition, a silicone-based hollow structure filler such as a silsesquioxane compound having a relatively low elastic modulus is preferable because it can reduce the elastic modulus of the sealing material with a small amount of addition and has a high stress relaxation effect at the time of heat shrinkage. When an inorganic hollow structure filler such as hollow glass or silica and a silicone hollow structure filler such as a silsesquioxane compound are used in combination, the effect of suppressing separation from insert parts is high even with a relatively small amount of addition. The present invention is also applicable to a sealing resin that requires high heat resistance, and is a preferred embodiment in the present invention.
The elastic modulus of the hollow structure filler in the present invention is, for example, a dynamic ultra-small hardness meter (manufactured by Shimadzu Corporation, device name: DUH-211SR, load-unloading test, load: 5.0 mN, speed: 1. 5 mN / s).

The hollow structure filler (e-1) is an inorganic hollow structure containing at least one selected from the group consisting of silica, alumina and silica-alumina compounds from the viewpoint of achieving both insulation properties such as tracking resistance. It is preferably a silicone-based hollow structure filler containing a filler and / or a silsesquioxane compound, and among them, an inorganic hollow structure containing at least one selected from the group consisting of a silica-alumina compound and alumina. A silicone-based hollow structure filler containing a filler and / or a silsesquioxane compound is more preferable.
In the case of an organic component, an organic hollow structure filler formed from an acrylic resin, a polyester resin, or the like can be selected.

  Since the hollow structure filler of the component (e-1) has an air layer inside, the thermal conductivity tends to be lower than that of a normal filler. Since tracking resistance is greatly influenced by thermal conductivity, a decrease in thermal conductivity is often accompanied by a decrease in tracking resistance. When the hollow structure filler is an inorganic component, the (e-1) component can contain a silica-alumina compound and / or alumina having a good thermal conductivity, thereby suppressing a decrease in tracking resistance. Become. In addition, the silsesquioxane compound is presumed to have a small effect on tracking resistance because it exhibits a delamination suppressing effect with a relatively small amount of addition.

  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. When mixing cannot be prevented, it is desirable to reduce as much as possible.

  The (e-1) component hollow structure filler contains at least one selected from the group consisting of silica, alumina, and silica-alumina compounds, and has a low content of alkali metals, alkaline earth metals, and the like. For example, as Kinospheres (trade name, manufactured by Kansai Matec Co., Ltd.) mainly composed of aluminum silicate and mullite (a compound of silica and alumina), also as Spheres (trade name, manufactured by Taiheiyo Cement Co., Ltd.) Available on the market. Moreover, as a silicone type hollow structure filler (silsesquioxane compound type filler) containing a silsesquioxane compound, for example, NH-SBN04 (Nikko Rica Co., Ltd.) containing polymethylsilsesquioxane as a main component is used. Product name, etc.).

  The hollow structure filler of the component (e-1) has an average particle size of 3 to 3 from the viewpoint of coexistence of the peeling prevention effect with the semiconductor insert component and the productivity and moldability of the composition for sealing molding material. It is preferable to set it as 100 micrometers, and it is more preferable to set it as 3-60 micrometers. When the average particle size is 3 μm or more, a peeling prevention effect is obtained, and when the average particle size is 100 μm or less, the productivity and moldability of the composition for encapsulating molding material are improved. Here, the average particle diameter refers to the median value (D50) measured by a laser diffraction scattering method (for example, manufactured by Shimadzu Corporation, apparatus name: SALD-3100).

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

The content of the (e-1) component hollow structure filler is the inorganic component such as hollow glass or hollow silica, and the silicone component such as a silsesquioxane compound. Preferably it is 1-50 mass% with respect to the whole quantity, More preferably, it is 2-45 mass%. If it is 1% by mass or more, an anti-peeling effect can be obtained, and if it is 50% by mass or less, insulation performance such as withstand voltage and formability are good. In particular, when the hollow structure filler of the component (e-1) is a silsesquioxane compound, the content thereof is preferably 0.5 to 10% by mass, more preferably based on the total amount of the filler of the component (E). It is 1.0-6 mass%, More preferably, it is 1.2-5 mass%.
Moreover, when (e-1) component is an organic component, the content becomes like this. Preferably it is 0.5-10 mass% with respect to the filler whole quantity of (E) component, More preferably, it is 1.5-7 mass%. . When the content is 0.5% by mass or more, an anti-peeling effect is obtained, and when the content is 10% by mass or less, insulation performance such as a withstand voltage and formability are improved.

(E-2) Inorganic filler In this invention, a conventionally well-known inorganic filler 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 fluidity and reliability, crystalline silica, fused silica, and synthetic silica are preferred, and fused spherical silica and synthetic silica are particularly preferred as the main component. In addition, the addition of silicone powder containing polymethylsilsesquioxane or the like as the main component is effective in suppressing peeling.

  The content of the inorganic filler as the component (e-2) is preferably 50 to 99.5% by mass, more preferably 55 to 98% by mass with respect to the total amount of the filler as the component (E).

[Other ingredients]
(Silane coupling agent)
It is preferable to add a silane coupling agent to the composition for sealing molding material of the present invention from the viewpoints of moisture resistance, mechanical strength, adhesion to semiconductor insert parts, and the like. In the present invention, epoxy silanes such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N- 2- (aminoethyl) -3-aminopropyltrimethoxysilane, aminosilane such as 3-aminopropyltriethoxysilane, mercaptosilane such as 3-mercaptopropyltrimethoxysilane, and isocyanate silane such as 3-isocyanatopropyltriethoxysilane A conventionally known silane coupling agent can be appropriately used. From the viewpoint of adhesion, it is preferable to use epoxy silanes such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane, secondary aminosilanes, and isocyanate silanes alone or in combination. . In addition, a silane coupling agent may be used by simply mixing with the component (E), or a part or all of the silane coupling agent may be used after surface treatment in advance. Moreover, you may add an aluminate coupling agent and a titanate coupling agent in the range which does not inhibit the effect of this invention.

  The addition amount of the silane coupling agent is preferably 0.01 to 1% by mass, more preferably 0.03 to 0.7% by mass, and still more preferably 0.05 to 0.1% by mass with respect to the total amount of the composition for sealing molding material. 0.5% by mass. By setting it as 0.01 mass% or more, adhesiveness with a semiconductor insert component can be improved, and the hardening property 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 further preferable to add a release agent in order to realize good productivity of the composition for encapsulating material. Examples of release agents that can be added include natural waxes such as carnauba wax, fatty acid ester waxes, fatty acid amide waxes, non-oxidizing polyethylene release agents, oxidized polyethylene release agents, and silicone release agents. However, a release agent other than these may be added. Moreover, a mold release agent may be used individually or may be used in combination of 2 or more type. From the standpoint of achieving both adhesion and mold releasability, a relatively small molecular weight wax such as carnauba wax or fatty acid ester wax is used in combination with a relatively large molecular weight wax such as oxidized polyethylene. And is particularly effective.

  The composition for sealing molding material of the present invention includes, in addition to the above-mentioned components, a low stress agent such as silicone and a flame retardant generally blended in this type of composition as long as the effects of the present invention are not impaired. Further, colorants such as carbon black, organic dyes, titanium oxide, and bengara can be blended as necessary.

  In addition, an ion trapping agent such as an anion exchanger can be blended with the composition for encapsulating material of the present invention from the viewpoint of improving the moisture resistance of the semiconductor element and the high temperature storage property. Examples of the anion exchanger include hydrotalcites, hydrated 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.

  In the composition for sealing molding material of the present invention, the contents of the component (A), the component (B), the component (C), the component (D-1), the component (D-2), and the component (E) are as follows. , 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 encapsulating material of the present invention can be prepared by uniformly dispersing and mixing the above-mentioned components in a predetermined amount. The preparation method is not particularly limited, but as a general method, for example, a mixture of the above-mentioned components in a predetermined amount is sufficiently mixed with a mixer or the like, then melt-mixed with a mixing roll or an extruder, and then cooled. And crushing method.

The composition for encapsulating molding material thus obtained has a high glass transition temperature (Tg), is excellent in moldability, has high voltage resistance, and has good adhesion to semiconductor insert components. You can get things. Moreover, it is preferable that the glass transition temperature of the hardened | cured material of the said composition for sealing molding materials is 250 degreeC or more, and it is more preferable that it is 255 degreeC or more.
In addition, the said glass transition temperature can be measured by the method as described in an Example.

(Electronic component equipment)
The electronic component device of the present invention includes an element sealed with a cured product of the composition for sealing molding material. The electronic component device is a support member such as a lead frame, a single crystal silicon semiconductor element or a compound semiconductor element such as SiC or GaN, a member such as a wire or a bump for electrically connecting them, and other components. It is an electronic component device in which a necessary part is sealed with a cured product of the above-mentioned composition for sealing molding material for one set.
Moreover, by using the composition for encapsulating molding material, it is possible to provide an electronic component device that has excellent heat resistance, excellent adhesion to semiconductor insert components, and is less likely to be peeled off or cracked even after being left at high temperature. .

As a method for sealing using the composition for sealing molding material of the present invention, the transfer molding method is the most common, but an injection molding method, a compression molding method, or the like may be used.
The molding temperature is preferably 150 to 250 ° C, more preferably 160 to 220 ° C, and still more preferably 170 to 200 ° C. The molding time is preferably 30 to 600 seconds, more preferably 45 to 300 seconds, and still more preferably 60 to 200 seconds. Moreover, when post-curing, although heating temperature is not specifically limited, For example, it is preferable that it is 150-250 degreeC, and it is more preferable that it is 180-220 degreeC. Moreover, although heating time is not specifically limited, For example, it is preferable that it is 0.5 to 10 hours, and it is more preferable that it is 1 to 8 hours.

  EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited at all by these examples.

(Examples 1 to 23 and Comparative Examples 1 to 7)
Components of the types and blending amounts shown in Table 1-1, Table 1-2, and Table 2 were kneaded with a mixing biaxial roll to prepare a composition for a sealing molding material. The kneading temperature in each example and comparative example was set to about 120 ° C. In Table 1-1, Table 1-2, and Table 2, the blank represents no blending.

  The detail of each component of Table 1-1, Table 1-2, and Table 2 used for preparation of the composition for sealing molding materials is as follows.

<Maleimide resin>
[Component (A)]
BMI-1000: N, N ′-(4,4′-diphenylmethane) bismaleimide (mainly z = 0 in general formula (I)), manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name -2300: Polyphenylmethane maleimide (mainly consisting of z = 0 to 2 in general formula (I)), manufactured by Daiwa Kasei Kogyo Co., Ltd., trade name

<Phenolic curing agent having a specific skeleton and benzoxazine resin having a specific structure>
[(B) component]
MEH-7500: triphenylmethane type phenol resin (phenol resin having x = 1 to 4 in general formula (II) as a main component), manufactured by Meiwa Kasei Co., Ltd., trade name, hydroxyl group equivalent 97, softening point 110 ℃
SN-485: naphthol aralkyl resin (phenol resin having y1 = 0 to 3 in general formula (III) as a main component), manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name, hydroxyl group equivalent 215, softening point 87 ° C.
Benzoxazine Pd: benzoxazine resin (benzoxazine resin represented by formula (IV-1)), manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name

<Epoxy resin having specific skeleton>
[Component (C)]
EPPN-502H: triphenylmethane type epoxy resin (epoxy resin in which n1 = 0 to 3 in general formula (V) is a main component), manufactured by Nippon Kayaku Co., Ltd., trade name, epoxy equivalent 168, softening point 67 ° C
ESN-375: naphthol aralkyl-type epoxy resin (mainly an epoxy resin having n2 = 0 to 3 in the general formula (VI)), manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name, epoxy equivalent 172, softening point 75 ℃
HP-4710: dihydroxynaphthalene novolak type epoxy resin (epoxy resin represented by general formula (VII)), manufactured by DIC Corporation, trade name, epoxy equivalent 161, softening point 82 ° C.

<Organic phosphorus accelerator>
[(D-1) component]
-PP-200: Triphenylphosphine, manufactured by Hokuko Chemical Industry Co., Ltd., trade name-TPTP: Tris (4-methylphenyl) phosphine, manufactured by Hokuko Chemical Industry Co., Ltd., trade name

<Imidazole-based curing accelerator>
[(D-2) component]
2E4MZ: 2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name (reaction start temperature with bisphenol A type epoxy resin: 90 ° C.)
2MZ-A: 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name (with bisphenol A type epoxy resin (Reaction starting temperature: 120 ° C.)
2P4MHZ-PW: 2-phenyl-4-methyl-5-hydroxymethylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name (reaction start temperature with bisphenol A type epoxy resin: 129 ° C.)
2PHZ-PW: 2-phenyl-4,5-dihydroxymethylimidazole, manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name (reaction start temperature with bisphenol A type epoxy resin: 155 ° C.)

<Filler>
[(E) component]
(E-1) Component: Hollow structure filler / Kinospheres 75: Inorganic hollow structure filler mainly composed of amorphous aluminum (30 to 70%) and mullite (30 to 70%), average particle size 35 μm , Manufactured by Kansai Matec Co., Ltd., trade name, elastic modulus 8GPa
-Spheres SL75: inorganic hollow structure filler mainly composed of amorphous aluminum (65 to 85%) and mullite (20 to 30%), average particle size 55 μm, Taiheiyo Cement Co., Ltd., trade name, Elastic modulus 10GPa
-Spheres SL125: inorganic hollow structure filler mainly composed of amorphous aluminum (65 to 85%) and mullite (20 to 30%), average particle size of 80 μm, product name, Taiheiyo Cement Co., Ltd. Elastic modulus 10GPa
Glass bubbles K37: Soda lime glass, borosilicate glass, synthetic silica mixture type inorganic hollow structure filler, average particle size 45 μm, manufactured by 3M Japan Ltd., trade name, elastic modulus 7 GPa
・ Glass Bubbles iM30K: Soda-lime glass, borosilicate glass, synthetic silica mixture type inorganic hollow structure filler, average particle size 16 μm, manufactured by 3M Japan Ltd., trade name, elastic modulus 7 GPa
ADVANCEL HB-2051: Acrylic porous hollow structure filler, average particle size 20 μm, manufactured by Sekisui Chemical Co., Ltd., trade name, elastic modulus 0.3 GPa
NH-SBN04: Polymethylsilsesquioxane-based single-hole hollow structure filler, average particle size 4 μm, manufactured by Nikko Rica Co., Ltd., trade name, elastic modulus 1.0 GPa
The value of elastic modulus here is a dynamic ultra micro hardness meter (manufactured by Shimadzu Corporation, device name: DUH-211SR, load-unloading test, load: 5.0 mN, speed 1.5 mN / s, indenter Is the average value of the values measured five times by a triangular indenter).

(E-2) Component: Inorganic filler. EP-5518: Silicone elastomer mainly composed of polymethylsilsesquioxane, manufactured by Toray Dow Corning Co., Ltd., trade name, average particle size 3 μm
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-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., trade name · HW-4252E: Release agent (oxidized polyethylene having a number average molecular weight of 1,000) Release agent), manufactured by Mitsui Chemicals, Inc., trade name / MA-600: Colorant (carbon black), manufactured by Mitsubishi Chemical Corporation, trade name

  Under the measurement conditions shown below, the properties of the compositions for sealing molding materials prepared in Examples 1 to 23 and Comparative Examples 1 to 7 were measured and evaluated. The evaluation results are shown in Tables 1 and 2. The molding material was molded by a transfer molding machine under the 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.

<Evaluation items>
(1) Glass transition temperature (Tg)
The glass transition temperature (Tg) was measured as one measure of heat resistance of the cured product of the composition for sealing molding material. First, the composition for encapsulating molding material was molded under the above conditions using a mold having a length of 4 mm × width of 4 mm × height of 20 mm, and further post-cured under the above conditions to form a molded product (length 4 mm × width 4 mm × A thickness of 20 mm) was produced. A sample obtained by cutting the molded product into a necessary size is used as a test piece, and the glass transition temperature (Tg) of the test piece is measured by a thermal analysis apparatus (manufactured by Seiko Instruments Inc., trade name: SSC / 5200) by the TMA method. It measured using. In addition, 250 degreeC or more was set as the pass.

(2) Flexural modulus The elastic modulus of the composition for sealing molding material at normal temperature (20 ° C.) was measured by a three-point bending method using a test piece having a size of 100 mm long × 10 mm wide × 4 mm thick. For the measurement, Autograph AG-X manufactured by Shimadzu Corporation was used. The span length was 64 mm and the head speed was mm / min. The average value of N = 4 was defined as the flexural modulus, and the flexural modulus was determined to be 15 GPa or less.

(3) Initial peeling An SiC chip (6 × 6 × 0.15 mm, no surface protection film) is fixed to the center of the island (8.5 × 11.5 mm) of the TO-247 package of the electroless Ni-plated lead frame. The composition for encapsulating molding material was molded under the above conditions, and further post-cured under the above conditions to produce 10 molded products. The molded product was observed using an ultrasonic imaging device (manufactured by Hitachi, Ltd., FS300II), and the presence or absence of peeling between the island around the SiC chip and the composition for sealing molding material was confirmed. The number of packages where peeling of the island portion was observed was 3 or less out of 10 packages.
The chip was fixed to the lead frame using lead-free solder in a 5% formic acid and 95% nitrogen atmosphere at 340 ° C./13 minutes. Further, the lead frame was used after being subjected to an argon plasma treatment for 60 seconds using a plasma cleaner AC-300 manufactured by Nordson, immediately before molding the composition for sealing molding material.

(4) Peeling after standing at high temperature After peeling the TO-247 package subjected to peeling observation in (3) above at 250 ° C. for 250 hours, an ultrasonic imaging apparatus (manufactured by Hitachi, Ltd., FS300II) is used. The presence or absence of peeling was confirmed. The number of packages in which the peeled area of the island portion was 20% or more was 3 or less out of 10 packages.

(5) Tracking resistance (CTI)
A test piece of φ100 mm × 2 mmt was prepared, and after post-curing, tracking resistance (CTI) was measured according to ASTM_D3638. YST-112-1S manufactured by Yamayo Tester Co., Ltd. was used as the tester. In addition, 400V or more was set as the pass.

(6) Dielectric strength (dielectric breakdown voltage)
A test piece of φ100 mm × 2 mmt was prepared, and after post-curing, the dielectric breakdown voltage at room temperature was measured according to ASTM-D149. The measurement was performed by the “short time method”. YST-243BD-100RO manufactured by Yamayo Tester Co., Ltd. was used as the tester. When the measurement was performed at n = 3, an average value of 10 kV / mm or more was regarded as acceptable.

(7) Continuous formability Using a release load measuring molding machine (trade name: GM-500, manufactured by Kyocera Corporation), PBGA (Plastic Ball Grid Array, 30 mm × 30 mm × 1 mm, t / 2 pieces) On the other hand, 300 shots of continuous molding were performed. The mold temperature was 185 ° C. and the molding time was 180 seconds. The evaluation was made according to the following criteria.
A: Continuous molding was possible up to 300 shots, and mold contamination was not observed. ○: Dust contamination was observed, but continuous molding was possible up to 300 shots. X: Due to sticking to the mold, etc. Continuous molding up to 300 shots was not possible

  In Examples 1 to 23 using the composition for encapsulating molding material containing the components (A) to (E), the glass transition temperature of the cured product is 250 ° C. or higher, and after initial peeling or standing at high temperature. Good results were shown in terms of peeling and continuous formability. Further, the tracking resistance (CTI) was 400 V or more, and the dielectric breakdown voltage at room temperature was 10 kV / m or more. On the other hand, in Comparative Examples 1 to 7 lacking any of the components (A) to (E), any of glass transition temperature, peel resistance, continuous formability, etc., or a plurality of items resulted in insufficient results. .

  The composition for sealing molding material of this invention can be utilized for an electronic component apparatus etc.

Claims (8)

(A) A maleimide resin represented by the following general formula (I), (B) a phenolic curing agent represented by the following general formula (II), and a phenolic curing agent represented by the following general formula (III) Represented by the following general formulas (V) to (VII): at least one selected from phenolic curing agents that are one or two of the above, and benzoxazine resin represented by the following general formula (IV): At least one selected from epoxy resins, (D-1) an organophosphorus curing accelerator, (D-2) an imidazole curing accelerator, and (E) (e-1) a hollow structure filler. A composition for encapsulating molding material containing the filler.

(In the formula, each R ¹ is 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 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 x is 0-10)

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

(In the formula, X1 is an alkylene group having 1 to 10 carbon atoms, an oxygen atom, or a direct bond. R ² and R ³ are each independently a hydrocarbon group having 1 to 10 carbon atoms. R ² and R When a plurality of ³ are present, the plurality of R ² and the plurality of R ³ may be the same or different, and m1 and m2 are each independently an integer of 0 to 4.)

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

(In the formula, n2 is 0 to 10.)

  2. The composition for encapsulating material according to claim 1, wherein the average particle diameter of the (e-1) hollow structure filler is 3 to 100 μm.   A value obtained by dividing the ratio of the (e-1) hollow structure filler to the total amount of the composition for sealing molding material by the elastic modulus of the (e-1) hollow structure filler is 0.002 to 0.250. The composition for sealing molding materials according to claim 1 or 2.   The (e-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 (e-1) hollow structure filler is (E) filled. It is 1-50 mass% with respect to material whole quantity, The composition for sealing molding materials as described in any one of Claims 1-3.   The (e-1) hollow structure filler is made of an organic compound, and the content of the (e-1) hollow structure filler is 0.5 to 10% by mass with respect to the total amount of the (E) filler. The composition for sealing molding materials as described in any one of 1-3.   The (e-1) hollow structure filler is made of a silsesquioxane compound, and the content of the (e-1) hollow structure filler is 0.5 to 10% by mass with respect to the total amount of the (E) filler. The composition for sealing molding materials as described in any one of Claims 1-3.   The imidazole system in which the reaction start temperature when the component (D-2) is reacted with bisphenol A type epoxy resin (liquid) at a mass ratio of 1/20 is 85 ° C. or higher and lower than 175 ° C. It is a hardening accelerator, The composition for sealing molding materials as described in any one of Claims 1-6.   An electronic component apparatus provided with the element sealed with the hardened | cured material of the composition for sealing molding materials as described in any one of Claims 1-7.